TWI406892B - Resin composition - Google Patents

Abstract

A resin composition that excels in long-term thermal stability and in initial colorability; and a molded article therefrom. There is provided a resin composition comprising a synthetic resin and per 100 pts.wt. thereof, (A) 0.001 to <0.1 pt.wt. of calcium hydroxide of the formula: Ca(OH)<SUB>2-nx</SUB>(A<SUP>n-</SUP>)<SUB>x</SUB> (1) wherein n is an integer of 1 to 4; x is a numeral of 0.001 to 0.2; and A<SUP>n-</SUP> is an anion derived from a silicic compound, aluminous compound or mixture thereof (component A), and (B) 0.1 to 10 pts.wt. of hydrotalcite (component B).

Description

Resin composition

The present invention relates to a resin composition containing a stabilizer. More specifically, it relates to a resin composition containing a stabilizer dissolved in calcium hydroxide and hydrotalcite. The present invention relates to a molded article of the resin composition.

The synthetic resin, particularly a halogen-containing resin, is used as a composite organic acid salt such as a stabilizer lead compound, an organotin compound, and a Cd/Ba system, a Ba/Zn system, or a Ca/Zn system because it is unstable to heat and light. However, the toxicity of these stabilizers, the environmental pollution caused by these stabilizers is becoming a problem, and the development of various stabilizers containing calcium hydroxide as a component is more safe (see Patent Documents 1 and 2). ).

However, calcium hydroxide has a high solubility in quicklime in water and is easy to have a long crystal specific surface area (refer to Patent Document 3), and has low halogen trapping property. When a calcium hydroxide-based stabilizer is used in a synthetic resin, the thermal stability is poor when the lead compound or the organotin compound is blended with the synthetic resin, and the initial coloring property is extremely poor.

Despite these disadvantages, calcium hydroxide is expected to be used as a stabilizer for synthetic resins because of its high safety and low cost, and its improvement is expected.

Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

An object of the present invention is to provide a molded article of a resin composition which is excellent in long-term heat stability and excellent in initial coloring property.

The present inventors have found that a combination of a solid solution cerium compound, an aluminum compound or a mixture of calcium hydroxide and hydrotalcite, although a small amount can impart excellent thermal stability to a synthetic resin, completes the present invention.

That is, the present invention contains (A) 0.001 part by weight or more and less than 0.1 part by weight of the following formula (1) Ca(OH) _{2 - n x} (A ^{n -} ) _x (1) for 100 parts by weight of the synthetic resin. ) (wherein n represents an integer of 1 to 4. the, x number of tables 0.001 to 0.2 of, a ^{n -} tables from anionic silicon compound, an aluminum compound or a mixture of these sum) of calcium hydroxide (a component) and (B) 0.1 A resin composition of hydrotalcite (component B) of 10 parts by weight or less by weight or more.

The present invention is also a molded article of the above resin composition.

The invention is specifically described below.

<Hydrogen Hydroxide: Component A> The component A used in the present invention is calcium hydroxide of the following formula (1) Ca(OH) _{2 - n x} (A ^{n -} ) _x (1).

Wherein n is an integer from Tables 1 to 4, x is a number from 0.001 to 0.2, and A ^{n -} is derived from an anion of a ruthenium compound, an aluminum compound or a mixture of these (hereinafter referred to as an additive). Therefore, the valence of the n-type anion, the content of the x-based anion, and the product of nx are.

A ^{n -} one monovalent anion (n = 1) for example ^{_{SiO (OH) 3 -, Al}} (OH) 4 -. The divalent anion (n=2) is, for example, SiO ₂ (OH) ₂ ^{2 -} , Si ₂ O ₆ (OH) ₆ ^{2 -} . The tetravalent anion (n=4) is, for example, SiO ₄ ^{4 -} , Si ₄ O ₈ (OH) ₄ ^{4 -} . Among them, SiO(OH) ₃ ^- , SiO ₂ (OH) ₂ ^{2 -} , and Al(OH) ₄ ^{- are} preferred. A ^{n -} may have multiple anions in the compound of formula (1). At this time, the total of the valence number and the content rate of each anion is represented by nx.

x is 0.001~0.2, 0.005~0.15 is better, and 0.01~0.1 is better.

That is, the component A is a calcium hydroxide in which a bismuth compound, an aluminum compound or a mixture of these is solid-solved.

The ruthenium compound is preferably at least one ruthenium compound selected from the group consisting of potassium citrate, decanoate, aqueous citric acid, anhydrous citric acid, crystalline citric acid (for example, quartz), and an organic ruthenium compound. Ceria is especially preferred. The organic ruthenium compound is preferably tetraethoxy decane, tetramethoxy decane, polymethoxy decane or decane coupling agent.

The aluminum compound is preferably at least one aluminum compound selected from the group consisting of aluminum salts, crystalline aluminum hydroxide, and amorphous aluminum hydroxide.

The component A is natural lime or synthetic lime. The chlorine content of the component A is preferably 0.05% by weight or less, and the sodium element content is preferably 20 ppm or less. The sodium content is determined by spectrophotometry using atomic absorption and chlorine content.

The average secondary particle diameter of the component A measured by the laser diffraction scattering method is preferably 0.1 to 10 μm, more preferably 0.1 to 7 μm, and particularly preferably 0.5 to 7 μm. The total area of the BET method of the component A is preferably 5 to 40 m ² /g, more preferably 10 to 30 m ² /g.

In the process of the component A, fine crystals are formed by suppressing crystal growth, and the specific surface area is large, the activity is high, the acid neutralizing property and the halogen trapping property are large, and it is suitable as a stabilizer for a synthetic resin.

The 100 parts by weight of the synthetic resin contains 0.001 parts by weight or more of the component A, and is less than 0.1 part by weight.

(Method of making A component)

The component A can be in the presence of a ruthenium compound, an aluminum compound or a mixture of these,

(i) producing a calcium oxide in a digestion reaction in water or (ii) reacting a water-soluble calcium salt with an alkali metal hydroxide.

That is, the calcium hydroxide of the present invention can be produced by subjecting (calcium) calcium oxide to digestion reaction in water containing a ruthenium compound, an aluminum compound or a mixture (additive) thereof. Containing suitable additives, the lime is supplied to the digestion reaction at 10 to 60 ° C, preferably 30 to 60 ° C in water. The reaction temperature rises by self-heating with the addition of quicklime to, for example, 90 ° C or higher. When the digestive method is used, the average calcium hydroxide having a particle diameter of 1.0 to 7 μm is obtained.

Second, it can be produced by the presence of an additive in the reaction of a water-soluble calcium salt aqueous solution with an alkali metal hydroxide aqueous solution. That is, an aqueous solution of a water-soluble calcium salt such as calcium chloride or calcium nitrate can be produced by reacting in the presence of a ruthenium compound, an aluminum compound or a mixture of these. In this case, the aqueous solution of the alkali metal hydroxide is preferably an alkali amount (equivalent to 1.05 to 1.3 equivalents) which is equivalent to or more than calcium.

The white precipitate obtained after the reaction is heated and aged at about 60 to 150 ° C, preferably 80 to 120 ° C for 0.5 to 4 hours, and preferably treated with an anionic surfactant as a surface treatment. Thereafter, it is suitably selected for filtration, water washing, drying, pulverization, classification, and the like. When it is produced by the reaction method, calcium hydroxide having an average particle diameter of about 0.5 to 2 μm is obtained.

Thirdly, the quicklime is put into a suspension of calcium hydroxide particles obtained by digesting the water, and a cerium compound, an aluminum compound or a mixture thereof is added, and the component A can be obtained by aging.

For the calcium hydroxide formed, the additive is preferably 0.01 to 7% by weight, more preferably 0.05 to 7% by weight, still more preferably 0.1 to 7% by weight. When it is less than 0.01% by weight, the calcium hydroxide compound formed has a small specific surface area. When it exceeds 7% by weight, it sometimes exceeds the solid solution limit of calcium hydroxide.

In these processes, it is not known how the additive increases the BET surface area of the calcium hydroxide particles, and the additive acts as a crystal growth inhibitor to control the growth of the crystal.

Therefore, the component A can also be said to be in the presence of a ruthenium compound, an aluminum compound or a mixture of these (i) to cause the calcium oxide to undergo a digestion reaction in water, or (ii) to react a water-soluble calcium salt with an alkali metal hydroxide. Calcium hydroxide.

According to the above method, calcium hydroxide having a high specific surface area can be obtained, and after the reaction, the reaction mixture is matured to obtain higher quality calcium hydroxide. The curing can be carried out at 60-170 ° C, preferably 80-120 ° C, more preferably 90-100 ° C, for 5 minutes to 3 hours, preferably 10 minutes to 2 hours, 20 minutes to 1 hour. good.

After the completion of the reaction or after the aging, the obtained calcium hydroxide may be pulverized in a suspension by a pulverizing apparatus such as a wet ball mill if necessary. After pulverization, particles having an average secondary particle diameter of less than 2 μm can be obtained.

The component A can be surface-treated by a conventional surface treating agent as necessary. Surface treatment can improve compatibility with resins and the like.

The surface treatment agent is, for example, selected from the group consisting of (a) higher fatty acids, (b) alkali metal salts of higher fatty acids, (c) sulfates of higher alcohols, (d) anionic surfactants, (e) phosphates, (f) A coupling agent (a decane type, a titanate type, an aluminum type), (g) a fatty acid ester of a polyhydric alcohol, and (h) a compound of a ruthenium compound, a phosphorus compound, an aluminum compound, an inorganic acid, and an organic acid.

A more suitable surface treatment agent is exemplified as follows.

(a) higher fatty acids having 10 or more carbon atoms such as stearic acid, sinapic acid, palmitic acid, lauric acid, and rosin; (b) alkali metal salts of higher fatty acids; (c) stearyl alcohol, oleyl alcohol, etc. Sulfate of alcohol; (d) sulfate of polyglycol ether, guanamine-bound sulfate, ester-bound sulfate, ester-bound sulfonate, guanamine-bound sulfonate, ether-bound sulfonate, ether-bound alkane Anionic surfactant such as an alkylarylsulfonate, an ester-bound alkylarylsulfonate, a guanamine-bonded alkylarylsulfonate; (e) one or a diester of phosphoric acid, oleyl alcohol, stearyl alcohol, etc. Or a mixture of the two, which is a phosphate of an acid or alkali metal salt or an amine salt thereof; (f) vinyl ethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, γ methacryl a decane coupling agent such as methoxypropyltrimethoxy decane, γ-aminopropyltrimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane or γ-mercaptopropyltrimethoxy decane; Triisostearyl strontium titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-amineethylamineethyl) titanate, isopropyl tridecyl benzene Sulfonium titanate Titanate-based coupling agent; acetyl alkoxy aluminum diisopropylate and other aluminum-based coupling agent; (G) glyceryl monostearate, glyceryl monooleate and other fatty acid esters of polyhydric alcohols.

(h) having 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 -}矽 矽 compound, phosphorus compound, aluminum compound.

The surface treatment of component A can be carried out by conventional wet or dry methods. For example, the wet process can be mechanically mixed well in a slurry of calcium hydroxide particles in a liquid or emulsion plus a surface treatment to about 100 °C. The dry method stirs the calcium hydroxide particles with a mixer such as a Henschel mixer, and thoroughly mixes them in a liquid state, an emulsion, a solid state plus a surface treatment agent, with or without heating. The amount of the surface treatment agent to be added can be appropriately selected, and is preferably about 10% by weight or less based on the weight of the calcium hydroxide particles.

The surface-treated calcium hydroxide particles may be suitably subjected to, for example, water washing, dehydration, granulation, drying, pulverization, classification, etc., to form a final product.

<Hydrohydrotalcite: Component B> The resin composition of the present invention contains a component B hydrotalcite in addition to the component A. Hydrotalcite can be a synthetic or natural product.

The hydrotalcite is represented by the following formula (2) {(Mg) _y (Zn) _z } _{1 - x} (Al) _x (OH) ₂ (A ^{n -} ) _{x / n} . It is better for mH ₂ O (2).

In the above formula (2), A ^{n -} shows an n-valent anion. n is preferably an integer of 1 to 4, and 1 or 2 is more preferable. Specific examples are ClO ₄ ^- , SO ₄ ^{2 -} and CO ₃ ^{2 -} , with CO ₃ ^{2 - being} preferred.

In the above formula (2), (y+z) is 1, and x satisfies 0.1≦x≦0.5, preferably 0.2≦x≦0.4.

y satisfies 0.5≦y≦1, preferably 0.7≦y≦1. Further, z satisfies 0≦z≦0.5, preferably 0≦z≦0.3. M satisfies 0≦m<1, and 0≦m≦0.7 is preferable.

The average secondary particle diameter of the B component measured by the laser diffraction scattering method is 2 μm or less, that is, almost all particles are not agglomerated twice, and the primary particles are preferably primary particles, and the average secondary particle diameter is 0.4 to 1.0 μm. Better.

The specific surface area of the component B measured by the BET method is preferably 1 to 30 m ² /g, more preferably 5 to 20 m ² /g.

There are no restrictions on the preparation method and conditions of component B. The material of the component B and the manufacturing conditions thereof are conventionally known, and can be manufactured by a conventional method (refer to, for example, Japanese Patent Publication No. Sho 46-2280 and the corresponding US Pat. No. 3,650,704; U.S. Patent No. 3,879,525; Japanese Patent Publication No. Sho 50-30039; Japanese Patent Publication No. Sho 48-29477; Japanese Patent Publication No. Sho 51-29129, and the like.

For the industrial production of raw materials for the production of component B, aluminum source is aluminum sulfate and sodium aluminate and aluminum hydroxide, magnesium source is seawater, magnesium chloride (saline, ion bitum juice), magnesium hydroxide, magnesium oxide, and alkali source industry With caustic soda, natural lime is not good for purification. The carbonate ion raw material can be industrially sodium carbonate or carbon dioxide.

The component B can also be used for calcination. The calcination temperature is preferably 200 ° C or more, more preferably 230 ° C or more.

The component B is preferably a surface treatment agent, and the surface treatment agent may be the same as the surface treatment agent of the calcium component A.

The component B is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.2 parts by weight or more and 7 parts by weight or less, and more preferably 0.5 parts by weight or more and 6 parts by weight or less, based on 100 parts by weight of the synthetic resin.

When a multi-iron compound or a manganese compound in the component A and the component B is blended in a resin, the resin has poor heat deterioration resistance, and the total content of the iron compound and the manganese compound is preferably 0.02% by weight or less in terms of metal (Fe + Mn).

<Synthetic Resin> The synthetic resin may be used as a usual molded article. There are C ₂ -C ₈ olefin (α-olefin) polymers or copolymers such as polyethylene, polypropylene, ethylene/propylene copolymer, polybutene, poly-4-methylpentene-1, etc., these olefins and Copolymer of diene, ethylene-acrylate copolymer, polystyrene, ABS resin, AAS resin, AS resin, MBS resin, ethylene/vinyl chloride copolymer resin, ethylene vinyl acetate copolymer resin, ethylene-vinyl chloride-acetic acid Vinyl ester graft copolymer resin, dichloroethylene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride propylene copolymer, vinyl acetate resin, phenoxy resin, polyketal, polyamine, poly Thermoplastic resins such as phthalimide, polycarbonate, polyfluorene, polyphenylene ether, polyphenylene sulfide, polyethylene terephthalate, methacrylic resin, epoxy resin, phenol resin, melamine resin, unsaturated poly Thermosetting resins such as ester resins, alkyd resins, urea resins, and EPDM, butyl rubber, isobutyl rubber, SBR, NBR, chlorosulfonated polyethylene, NIR, urethane rubber, butadiene rubber, acryl rubber, poly Synthetic rubber such as silicone rubber or fluorine rubber.

The resin composition of the present invention can be produced by kneading these synthetic resins and stabilizers by a roll machine or the like.

The synthetic resin is preferably polyvinyl chloride.

The resin composition of the present invention may be blended with other conventional additives in addition to the above components. Such additives include, for example, antioxidants, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, organohalogen flame retardants, crosslinking agents, light stabilizers, ultraviolet absorbers, slip agents, and the like.

<Molded article> The present invention contains a molded article of the above resin composition. The molded article includes a tube, an elbow, a film, a cable covering material, a window frame, a food packaging container, a casing or a part for an electronic device, and an automobile part.

Example

The invention is described in more detail in the following examples.

In the following examples, (1) average secondary particle diameter, (2) BET specific surface area, (3) analysis of SiO ₂ , and (4) Al ₂ O ₃ and (5) metal analysis were measured by the following methods.

(1) The average secondary particle diameter was measured by a laser diffraction scattering method using a MICROTRAC particle size analyzer SPA type [manufactured by LEEDS & NORTHRUP INSTRUMENTS]. That is, 700 mg of sample powder was added to 70 ml of water, and after dispersing for 3 minutes by ultrasonic wave (MODES US-300, current 300 μA), the dispersion was taken 2 to 4 ml, and 250 ml of the dispersion was added. The sample chamber of the above-mentioned particle size analyzer of gas water was started by an analyzer to measure the particle size distribution after circulating the suspension for 8 minutes. The total measurement was performed twice, and the average particle size of each of the 50% cumulative secondary particle diameters was obtained as the average secondary particle diameter of the sample.

(2) The BET specific surface area was measured by a liquid nitrogen adsorption method. That is, it was measured using a liquid nitrogen adsorption device (NOVA 2000 manufactured by YUASAIONICS Co., Ltd.). 0.5 g of the sample powder was accurately weighed in a dedicated cell for measurement, and the vacuum was 10 mTorr or less, and pretreated at 105 ° C for 30 minutes (device: Flovac Degasser manufactured by YUASAIONICS Co., Ltd.). After the pretreatment, the cell was cooled and placed in a measuring device chamber to measure the specific surface area.

(3) Analysis of SiO ₂ was analyzed by absorption spectrophotometry. That is, 0.5 g of the sample powder was accurately weighed in platinum crucible, and 2 g of boric acid and 3 g of anhydrous sodium carbonate were mixed. After melting at 950 ° C for 2 hours, it was cooled, dissolved in 40 ml of dilute hydrochloric acid, and 250 ml of ion-exchanged water was added. Take 25ml of the solution, transfer it to a 100 ml volumetric flask, add 5 ml of ammonium molybdate solution (10% solution), and add 100 ml of ion-exchanged water to the solution for measurement. Quantitative system is divided into two beams by a spectrophotometer device (Hitachi, Ltd.) Photometer 150-20) The absorbance at 420 nm was measured.

(4) Analysis of Al ₂ O ₃ was analyzed by chelation. That is, 0.5 g of the sample powder was properly weighed in a 100 ml beaker, and 20 ml of diluted hydrochloric acid and 15 ml of perchloric acid were heated at 150 to 200 ° C for 30 minutes. After heating, add cooling water to filter the insoluble matter with quantitative filter paper. Wash. The filtrate and washings were combined to form the correct 250 ml assay solution. 25 ml of the measurement solution and ion-exchanged water were added to adjust the pH to 3.0. The pH adjustment solution and the indicator Cu-PAN solution were used for the measurement, and the mixture was heated to a boiling side and titrated with a 0.01 mol/1-EDTA2Na solution. The end point of the titration is that the point of heating for more than 1 minute does not change to orange.

(5) Metal analysis 0.5 g of the sample powder was accurately weighed in a 100 ml beaker, diluted with 10 ml of hydrochloric acid, and dissolved by heating. After cooling, 100 ml of a measuring flask and 100 ml of ion-exchanged water were transferred to a solution for measurement. The absorbance of Mn = 257.610 nm and Fe = 259.940 nm was measured by an ICP emission spectroscopic analyzer (SPS 1500VR manufactured by SEIKO INSTRUMENTS Co., Ltd.).

Synthesis Example 1, 2 CH22, 23 Synthesis 2 m ³ volume reaction tank was fed 4N NaOH 360L and Table 1 amount of water glass (398g / L), plus 4 mol / L of CaCl ₂ 165L, at 40 ° C Reaction for 5 minutes. The obtained product was filtered, dried, and pulverized to obtain solid solution of calcium hydroxide CH22 and 23. The composition and physical property measurement results of CH22 and 23 are shown in Table 2.

Synthesis Example 3 Synthesis of CH26 The reaction tank of 2 m ³ volume was fed with 4N NaOH 360L and the amount of sodium aluminate (323 g/L) of Table 1, and 4 mol/L of CaCl ₂ 165L was added, and reacted at 40 ° C for 5 minutes. . The obtained product was filtered, dried, and pulverized to obtain a solid solution of calcium hydroxide CH26. The composition and physical property measurement results of CH26 are shown in Table 2.

Synthesis Example 4 Synthesis of CH29 A reaction tank of 2 m ³ volume was fed with water glass (398 g/L) in an amount of 1 m ³ and Table 1, and the temperature in the reaction vessel was 60 °C. After that, lime was added to 27 kg. Due to the input of quicklime, the heat of digestion raises the temperature to about 90 °C. The reaction was carried out for 30 minutes in this state. The obtained product was filtered, dried, and pulverized to obtain a solid solution of calcium hydroxide CH29. The composition and physical property measurement results of CH29 are shown in Table 2.

Reference Example 1 Synthesis of CHCE3 The reaction tank of 2 m ³ volume was fed with 4N NaOH 360L and CaCl ₂ (4 mol/L) 165L, reacted at 40 ° C for 5 minutes, filtered, dried and pulverized to obtain non-solid solution calcium hydroxide. CHCE3. The composition and physical property measurement results of CHCE3 are shown in Table 2.

Synthesis Example 5 Synthesis of CH39 A reaction tank of 2 m3 volume was fed with 4N NaOH 360L and water glass (398 g/L) of Table 3, and 4 mol/L of CaCl2 165L was added, and reacted at 40 ° C for 5 minutes. The obtained product was filtered, dried, and pulverized to obtain a solid solution of calcium hydroxide CH39. The composition and physical property measurement results of CH39 are shown in Table 4.

Synthesis Example 6 Synthetic Synthesis of CH40 The water glass was changed to the amount of the synthetic amorphous cerium oxide (SiO ₂ = 93% by weight) in Table 3 except that the solid solution calcium hydroxide CH40 was prepared as in Synthesis Example 5. The composition and physical property measurement results of CH40 are shown in Table 4.

Synthesis Example 7 Synthesis of CH42 In Synthesis Example 5, water glass was changed to tetraethoxy decane (SiO ₂ = 28% by weight) in an amount shown in Table 3, and solid solution calcium hydroxide CH42 was prepared as in Synthesis Example 5. The composition and physical property measurement results 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 1 g/L) was added to have a Mg concentration of 1.95 mol/L and an Al concentration of 0.847 mol/ A mixed aqueous solution of L (A). Next, the caustic soda (48.7%) was transferred to another concentration adjustment tank, sodium carbonate powder (Na ₂ CO ₃ = 99.9%) and water to an aqueous solution containing NaOH 3 mol / L and Na ₂ CO ₃ 0.23 mol / L (B) .

The hydrotalcite reaction slurry was obtained by mixing the aqueous solution (A) with a ratio of 1.18 L to the aqueous solution (B) at a ratio of 2.2 L with stirring for 60 minutes while injecting into a reaction tank of existing water. The reaction slurry was taken up to 800 L, and heated and aged in an autoclave at 170 ° C for 6 hours while stirring. After cooling, the slurry is transferred to the surface treatment tank, heated to 80 ° C under stirring, and slowly injected with 2 kg of sodium stearate (C _{1 7} H _{3 6} COONa = 93.4%) previously dissolved in warm water of 80 ° C, and kept under stirring. Finish the surface treatment in 30 minutes. The solid was filtered, washed, dried in a hot air dryer, and pulverized into a sample by a hammer mill.

Analysis results of the obtained HT1, composition formula _{Mg 0. 7 Al 0. 3} (OH) 2 (CO 3) 0. 1 5. 0.5H ₂ O. The composition and physical property measurement results are shown in Table 5.

Synthesis Example 9 Synthesis of HT2 In Synthesis Example 8, the purified brine in the raw material was changed to ionic bitter juice, and the same apparatus was used in the same manner except using zinc chloride. That is, the ion bitter juice (MgCl ₂ = 168.2 g / L) was transferred to a concentration adjustment tank, zinc chloride (ZnCl ₂ = 572.7 g / L), aluminum sulfate (Al ₂ O ₃ = 106.8 1 g / L) into Mg A mixed aqueous solution having a concentration of 1.05 mol/L, a Zn concentration of 0.42 mol/L, and an Al concentration of 0.63 mol/L. At this time, a calcium sulfate precipitate was generated in the mixing tank, and it was filtered into (A) liquid. Next, the caustic soda (NaOH 48.7%) was transferred to another concentration adjustment tank, sodium carbonate powder (Na ₂ CO ₃ = 99.9%) and water to an aqueous solution containing NaOH 3 mol / L and Na ₂ CO ₃ 0.225 mol / L (B ).

The HT reaction slurry was obtained by injecting a ratio of 1 L of the (A) solution to the ratio of 1.4 L of the (B) solution with stirring for 60 minutes while injecting the water into the reaction vessel.

The reaction slurry was taken up to 800 L, and heated and aged in a hot press at 140 ° C for 6 hours while stirring. After cooling, the slurry was transferred to a surface treatment tank, heated to 80 ° C under stirring, and slowly injected with 1.3 kg of sodium stearate dissolved in 50 L of warm water at 80 ° C, and kept under stirring for 30 minutes to complete the surface treatment. The solid was filtered, washed, emulsified, and spray dried to form a sample.

Analysis results of the obtained HT2, composition formula _{Mg 0. 5 Zn 0. 2} Al 0. 3 (OH) 2 (CO 3) 0. 1 5. 0.55H ₂ O. The composition and physical property measurement results 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 composition and physical property measurement results are shown in Table 5.

Synthesis Example 11 Synthesis of HT4 Synthesis of HT2 obtained by calcination of HT2 at 240 ° C to prepare hydrotalcite HT4. The composition and physical property measurement results are shown in Table 5.

Examples 1 to 10 and Comparative Examples 1 to 7

The solid composition of calcium hydroxide CH39, CH23, hydrotalcite HT1 and HT2 and non-solid solution calcium hydroxide CHCE3 as a stabilizer, the resin composition of the following composition (A) was prepared, and the resin composition was rolled at 180 ° C × 5 Minutes were mixed to make a 0.7 mm roll. The composition of the stabilizer is shown in Table 6.

Thermal stability was taken by taking 5 cm × 8 cm of the sheet and taking it out in a 190 ° C curing oven every 10 minutes for evaluation. The evaluation was carried out by measuring the degree of deterioration of the resin which was colored, measuring the time to blackening to a certain extent, and evaluating the color of the initial stage of thermal stability. The results are shown in Table 6.

Composition (A) Polyvinyl chloride (degree of polymerization 700) 100PHR zinc stearate 0.3PHR stearyl benzoyl hydrazine methane 0.2PHR dinonpentaerythritol 0.2PHR stabilizer 1.0PHR

^* ) Thermal stability initial color: colorless and transparent is +, light yellow is transparent to ++++, and the color difference between them is represented by + ^{* * *} ) blackening time: the time of blackening in Comparative Example 2 is 100

The solid composition calcium hydroxide CH39, hydrotalcite HT2 and non-solid solution calcium hydroxide CHCE3 were used as stabilizers to prepare a resin composition of the following composition (B), which was prepared by a roller machine at 180 ° C for 5 minutes. A 0.7 mm roll. Thermal stability was evaluated as in Example 1. The composition and results of the stabilizer are shown in Table 7.

Composition (B) Polyvinyl chloride (degree of polymerization 1000) 100PHR Benzopyrene methane 0.1PHR dinepentaerythritol 0.2PHR D KISIOL G32 0.2PHR zinc stearate 0.8PHR calcium stearate 0.4PHR METABLEN P-501 0.5PHR Bai Yanhua CCR (calcium carbonate, white stone calcium) 4.0PHR stabilizer 1.0PHR

Examples 14 to 19 and Comparative Examples 12 to 17

The solid composition calcium hydroxide CH22, CH40, CH42, hydrotalcite HT1 and non-solid solution calcium hydroxide CHCE3 were used as stabilizers to prepare a resin composition of the following composition (C), which was rolled at 180 ° C × 5 Minutes were mixed to make a 0.7 mm roll. Thermal stability was evaluated as in Example 1. The composition and results of the stabilizer are shown in Table 8.

Composition (C) Polyvinyl chloride (degree of polymerization 1000) 100PHR benzophenone methane 0.1PHR dipentaerythritol 0.2PHR D KISIOL G32 (made by KOGNIS) 0.2PHR zinc stearate 0.6PHR calcium stearate 0.2PHR heavy Calcium carbonate 3.0PHR stabilizer 0.5PHR

Examples 20 to 45 and Comparative Examples 18 to 23

The resin composition of the following composition (D) is prepared by using solid solution calcium hydroxide CH39, CH23, CH26, CH40, CH42, hydrotalcite HT1, HT2, HT3, HT4 and non-solid solution calcium hydroxide CHCE3 as stabilizers. The composition was kneaded by a roll machine at 180 ° C for 5 minutes to make a 0.7 mm roll. Thermal stability was evaluated as in Example 1. The composition and results of the stabilizer 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 to 54 and Comparative Example 24

The solid composition calcium hydroxide CH39, hydrotalcite HT1 and HT2 were used as stabilizers to prepare a resin composition of the following composition (D-1), which was kneaded by a roll machine at 180 ° C for 5 minutes to make a roll of 0.7 mm. sheet. Thermal stability was evaluated as in Example 1. The composition and results of the stabilizer are shown in Table 10.

Composition (D-1) Polyvinyl chloride (degree of polymerization 1300) 100PHR dioctyl phthalate 50PHR zinc stearate 0.4PHR stabilizer 1.5PHR

Examples 55 to 63 and Comparative Example 25

The solid composition calcium hydroxide CH39, hydrotalcite HT1 and HT2 were used as stabilizers to prepare a resin composition of the following composition (D-2), which was kneaded by a roll machine at 180 ° C for 5 minutes to make a roll of 0.7 mm. sheet. Thermal stability was evaluated as in Example 1. The composition and results of the stabilizer are shown in Table 11.

Composition (D-2) Polyvinyl chloride (degree of polymerization 1300) 100PHR dioctyl phthalate 50PHR zinc stearate 0.4PHR stabilizer 4.0PHR

Examples 64 to 71 and Comparative Example 26

The solid composition calcium hydroxide CH39, hydrotalcite HT1 and HT2 were used as stabilizers to prepare a resin composition of the following composition (A-1), which was kneaded by a roll machine at 180 ° C for 5 minutes to make a roll of 0.7 mm. sheet. Thermal stability was evaluated as in Example 1. The composition and results of the stabilizer are shown in Table 12.

Composition (A-1) Polyvinyl chloride (degree of polymerization 700) 100PHR zinc stearate 0.3PHR stearyl benzoyl hydrazine methane 0.2PHR dinonpentaerythritol 0.2PHR stabilizer 3.0PHR

Examples 72-79 and Comparative Example 27

The solid composition calcium hydroxide CH39, hydrotalcite HT1 and HT2 were used as stabilizers to prepare a resin composition of the following composition (A-2), which was kneaded by a roll machine at 180 ° C for 5 minutes to make a roll of 0.7 mm. sheet. Thermal stability was evaluated 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 stearyl benzoyl hydrazine methane 0.2PHR dipentaerythritol 0.2PHR stabilizer 6.0PHR

Effect of the invention

According to the present invention, a combination of solid solution calcium hydroxide having a large specific surface area, high activity, acid neutralization property, and large alkali trapping property, and hydrotalcite can provide excellent thermal stability and initial coloring property to a synthetic resin. Stabilizer composition.

The resin composition and the molded article of the present invention have excellent thermal stability, and are excellent in long-term heat stability and excellent in initial coloring property.

Industrial use possibility

The calcium hydroxide of the present invention can be used as an acid neutralizing agent or a halogen trapping agent and is a stabilizer for a synthetic resin. The resin composition of the present invention is excellent in thermal stability and initial coloring property, and can be used in various fields.

Claims (9)

A resin composition containing (A) 0.001 parts by weight or more and less than 0.1 parts by weight of calcium hydroxide (component A) represented by the following formula (1), which is contained in an amount of 100 parts by weight of the synthetic resin. It is obtained by reacting a water-soluble calcium salt with an alkali metal hydroxide, Ca(OH) _2-nx (A ^n- ) _x (1) (wherein n represents an integer of 1 to 4, and x represents 0.001~ A number of 0.2, A ^n- represents an anion derived from a ruthenium 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). The resin composition of claim 1, wherein the A ^n- based 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 ^4- , Si ₄ O ₈ (OH) ₄ ^4- or a mixture of these. The resin composition of claim 1, wherein the A ^n- based SiO(OH) ₃ ^- , SiO ₂ (OH) ₂ ^2- , Al(OH) ₄ ^- or a mixture thereof. The resin composition of claim 1, wherein the component A is calcium hydroxide having an average secondary particle diameter of 0.1 to 10 μm as measured by a laser diffraction scattering method. The resin composition of 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 of claim 1, wherein the synthetic resin is polyvinyl chloride. The resin composition of claim 1, wherein the component B is hydrotalcite {(Mg) _y (Zn) _z } _1-x (Al) _x (OH) ₂ (A) represented by the following formula (2) ^N- ) _x/n ‧mH ₂ O (2) (wherein A ^n- system ClO ₄ ^- , SO ₄ ^2- or CO ₃ ^2- , or a mixture of these, n-system 1 or 2, x, y, z And m satisfies y+z=1, 0.1≦x≦0.5, 0.5≦y≦1, 0≦z≦0.5, 0≦m<1). The resin composition of claim 1, wherein the component B is hydrotalcite calcined at 200 ° C or higher. A molded article comprising the resin composition of claim 1 of the patent application.