TWI406892B - Resin composition - Google Patents
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- TWI406892B TWI406892B TW95115172A TW95115172A TWI406892B TW I406892 B TWI406892 B TW I406892B TW 95115172 A TW95115172 A TW 95115172A TW 95115172 A TW95115172 A TW 95115172A TW I406892 B TWI406892 B TW I406892B
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Description
本發明係有關含安定劑之樹脂組成物。更詳言之係有關,含安定劑固溶氫氧化鈣及水滑石之樹脂組成物。本發明並係有關該樹脂組成物成形品。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.
合成樹脂尤以含鹵樹脂因對於熱、光不安定,有安定劑鉛化合物、有機錫化合物及Cd/Ba系、Ba/Zn系、Ca/Zn系等複合有機酸鹽之使用。然而,這些安定劑之毒性,這些安定劑所致之地球環境污染漸成問題,而有合成樹脂用之更安全,以氫氧化鈣為主成分之各種安定劑的開發(參考專利文獻1及2)。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). ).
可是,氫氧化鈣因於水中生石灰之溶解度高,易於長晶比表面積小(參考專利文獻3),鹵素捕集性有限。配合氫氧化鈣系安定劑於合成樹脂時,較之配合鉛化合物、有機錫化合物於合成樹脂時熱安定性差,有初期著色性非常差之缺點。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.
雖有這些缺點,但氫氧化鈣因安全性高、價廉,可望用作合成樹脂用之安定劑,其改良受到期待。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.
專利文獻1日本專利特開平6-316662號公報專利文獻2特開平11-193336號公報專利文獻3特開2001-123071號公報Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.
本發明之目的在提供,長久熱安定性優良,初期著色性優良之樹脂組成物其成形品。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.
本發明人發現,固溶矽化合物、鋁化合物或這些之混合物的氫氧化鈣與水滑石組合,雖少量亦能於合成樹脂付與優良之熱安定性而完成本發明。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.
亦即本發明係對於100重量份之合成樹脂,含有(A)0.001重量份以上,未達0.1重量份的下述式(1)Ca(OH)2 - n x (An - )x (1)(式中n表1~4之整數,x表0.001~0.2之數,An - 表來自矽化合物、鋁化合物或這些之混合物的陰離子)之氫氧化鈣(A成分)及(B)0.1重量份以上,10重量份以下之水滑石(B成分)之樹脂組成物。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.
本發明並係上述樹脂組成物之成形品。The present invention is also a molded article of the above resin composition.
以下具體說明本發明。The invention is specifically described below.
<氫氧化鈣:A成分>用於本發明之A成分係下述式(1)Ca(OH)2 - n x (An - )x (1)之氫氧化鈣。<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).
式中n表1~4之整數,x表0.001~0.2之數,An - 表來自矽化合物、鋁化合物或這些之混合物(以下或稱添加劑)的陰離子。因此,n係陰離子之價數,x係陰離子之含有率,nx係其積。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.
An - 之一價陰離子(n=1)有例如SiO(OH)3 - ,Al(OH)4 - 。2價陰離子(n=2)有例如SiO2 (OH)2 2 - ,Si2 O6 (OH)6 2 - 。4價陰離子(n=4)有例如SiO4 4 - ,Si4 O8 (OH)4 4 - 。其中,以SiO(OH)3 - 、SiO2 (OH)2 2 - 、Al(OH)4 - 為佳。An - 可同時於式(1)之化合物中有多種陰離子。此時,各陰離子之價數及含有率之積合計以nx表示。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係0.001~0.2,0.005~0.15為佳,0.01~0.1更佳。x is 0.001~0.2, 0.005~0.15 is better, and 0.01~0.1 is better.
亦即,A成分係矽化合物、鋁化合物或這些之混合物固溶而成的氫氧化鈣。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.
矽化合物以用選自矽酸鉀、矽酸鹽、含水矽酸、無水矽酸、結晶矽酸(例如石英)及有機矽化合物之群的至少一種矽化合物為佳。二氧化矽尤佳。有機矽化合物以四乙氧基矽烷、四甲氧基矽烷、聚甲氧基矽烷、矽烷耦合劑為佳。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.
鋁化合物以選自鋁鹽、結晶氫氧化鋁及不定形氫氧化鋁之群的至少一種鋁化合物為佳。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.
A成分係天然石灰或合成石灰。A成分氯元素含量以0.05重量%以下為佳,鈉元素含量以20ppm以下為佳。鈉元素含量係以原子吸光法、氯元素含量係以吸光光度法測定。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.
A成分以雷射繞射散射法測定之平均2次粒徑以0.1~10 μ m為佳,0.1~7 μ m更佳,0.5~7 μ m尤佳。A成分之BET法總面積以5~40 m2 /g為佳,10~30m2 /g更佳。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.
A成分其製程中因抑制結晶成長而有微細結晶,比表面積大活性高,酸中和性、鹵素捕集性大,適用作合成樹脂的安定劑。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.
對於100重量份之合成樹脂,含A成分0.001重量份以上,未達0.1重量份。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.
A成分可於矽化合物、鋁化合物或這些之混合物的存在下,The component A can be in the presence of a ruthenium compound, an aluminum compound or a mixture of these,
(i)使氧化鈣在水中起消化反應,或(ii)使水溶性鈣鹽及鹼金屬氫氧化物反應而製造。(i) producing a calcium oxide in a digestion reaction in water or (ii) reacting a water-soluble calcium salt with an alkali metal hydroxide.
亦即本發明之氫氧化鈣可於含矽化合物、鋁化合物或這些之混合物(添加劑)的水中,使(生石灰)氧化鈣起消化反應而製造。含合適之添加劑,於10~60℃,較佳者30~60℃水中,攪拌下供給生石灰使之起消化反應。反應溫度隨生石灰之添加,自行生熱而上升達例如90℃以上。以消化法製造時得平均2次粒徑1.0~7 μ m之氫氧化鈣。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.
第二,可於水溶性鈣鹽水溶液與鹼金屬氫氧化物水溶液之反應時有添加劑存在而製造。亦即,可使氯化鈣、硝酸鈣等水溶性鈣鹽之水溶液,在矽化合物、鋁化合物或這些之混合物的存在下反應而製造。此時,鹼金屬氫氧化物之水溶液,以對於鈣有當量以上之鹼量(較佳者1.05~1.3倍當量)為佳。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.
反應後所得白色沈澱物於約60~150℃,較佳者80~120℃加熱熟化0.5~4小時,以陰離子界面活性劑作表面處理為佳。之後,經適當選作過濾、水洗、乾燥、粉碎、分級等製成。以反應法製造時,得平均2次粒徑0.5~2 μ m左右之氫氧化鈣。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.
第三,將生石灰投入水中消化反應得之氫氧化鈣粒子懸浮液中,添加矽化合物、鋁化合物或這些之混合物,經熟化亦可得A成分。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.
對於生成之氫氧化鈣,添加劑以0.01~7重量%為佳,0.05~7重量%更佳,0.1~7重量%又更佳。少於0.01重量%則生成之氫氧化鈣化合物比表面積小。超過7重量%則有時會超出往氫氧化鈣之固溶極限。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.
這些製法中,添加劑以何作用加大氫氧化鈣粒子之BET表面積尚不明白,而應係添加劑發揮結晶成長抑制劑之作用,控制結晶成長之故。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.
因此A成分亦可謂係,於矽化合物、鋁化合物或這些之混合物的存在下(i)使氧化鈣在水中起消化反應,或(ii)使水溶性鈣鹽及鹼金屬氫氧化物反應而得之氫氧化鈣。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.
依上述方法可得高比表面積之氫氧化鈣,反應後並使反應混合物熟化,可得更高品質之氫氧化鈣。該熟化係以反應混合物可於60~170℃,較佳者80~120℃,更佳者90至100℃,實施5分鐘~3小時,10分鐘~2小時為佳,20分鐘~1小時更佳。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.
反應完後或熟化完後,必要時亦可將所得氫氧化鈣於懸浮液中以濕式球磨機等粉碎裝置粉碎。經粉碎可得平均2次粒徑小於2 μ m之粒子。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.
A成分必要時可經其習知表面處理劑作表面處理。經表面處理可改良與樹脂等之相溶性。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.
該表面處理劑有例如選自(a)高級脂肪酸、(b)高級脂肪酸之鹼金屬鹽、(c)高級醇之硫酸酯、(d)陰離子界面活性劑、(e)磷酸酯、(f)耦合劑(矽烷系、鈦酸酯系、鋁系)、(g)多元醇之脂肪酸酯及(h)矽化合物、磷化合物、鋁化合物、無機酸及有機酸之群的化合物。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.
較適用之表面處理劑例示如下。A more suitable surface treatment agent is exemplified as follows.
(a)硬脂酸、芥子酸、十六酸、月桂酸、蘿酸等碳原子數10以上之高級脂肪酸;(b)高級脂肪酸之鹼金屬鹽;(c)硬脂醇、油醇等高級醇之硫酸酯;(d)聚乙二醇醚之硫酸酯、醯胺結合硫酸酯、酯結合硫酸酯、酯結合磺酸酯、醯胺結合磺酸鹽、醚結合磺酸鹽、醚結合烷基芳基磺酸鹽、酯結合烷基芳基磺酸鹽、醯胺結合烷基芳基磺酸鹽等陰離子界面活性劑;(e)磷酸及油醇、硬脂醇等之一或二酯或兩者之混合物,而為其酸型或鹼金屬鹽或胺鹽等之磷酸酯;(f)乙烯基乙氧矽烷、乙烯基參(2-甲氧乙氧基)矽烷、γ甲基丙烯醯氧丙基三甲氧矽烷、γ-胺丙基三甲氧矽烷、β-(3,4-環氧環己基)乙基三甲氧矽烷、γ-巰丙基三甲氧矽烷等矽烷耦合劑;異丙基三異硬脂醯鈦酸酯、異丙基三(焦磷酸二辛酯)鈦酸酯、異丙基三(N-胺乙基胺乙基)鈦酸酯、異丙基三癸基苯磺醯鈦酸酯等鈦酸酯系耦合劑;乙醯烷氧基鋁合二異丙醇等鋁系耦合劑;(g)甘油一硬脂酸酯、甘油一油酸酯等多元醇之脂肪酸酯。(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)具有SiO(OH)3 - 、Al(OH)4 - 、Cl- 、NO3 - 、H2 PO4 - 、C6 H7 O7 - 、SiO2 (OH)2 2 - 、Si2 O6 (OH)6 2 - 、HPO4 2 - 、C6 H6 O7 2 - 、PO4 3 - 、C6 H5 O7 3 - 、SiO4 4 - 或Si4 O8 (OH)4 4 - 等之矽化合物、磷化合物、鋁化合物。(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.
A成分之表面處理可由其習知濕式或乾式法實施。例如,濕式法可於氫氧化鈣粒子漿體以液態或乳劑加表面處理劑,至約100℃以機械式充分混合。乾式法係以亨謝耳混合機等混合器攪拌氫氧化鈣粒子,以液態、乳劑、固態加表面處理劑,加熱或非加熱下充分混合。表面處理劑之添加量可適當選擇,基於氫氧化鈣粒子之重量以約10重量%以下為佳。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.
經表面處理之氫氧化鈣粒子必要時可適當施以例如水洗、脫水、造粒、乾燥、粉碎、分級等,成最終製品形態。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.
<水滑石:B成分>本發明之樹脂組成物,A成分外,含B成分水滑石。水滑石可係合成品或天然品。<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.
水滑石係以下述式(2){(Mg)y (Zn)z }1 - x (Al)x (OH)2 (An - )x / n .mH2 O (2)者為佳。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).
上述式(2)中An - 示n價陰離子。n以1~4之整數為佳,1或2更佳。具體例有ClO4 - 、SO4 2 - 及CO3 2 - ,以CO3 2 - 為佳。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.
上述式(2)中(y+z)係1,x滿足0.1≦x≦0.5,較佳為滿足0.2≦x≦0.4。In the above formula (2), (y+z) is 1, and x satisfies 0.1≦x≦0.5, preferably 0.2≦x≦0.4.
y滿足0.5≦y≦1,以0.7≦y≦1為佳。又z滿足0≦z≦0.5,較佳為滿足0≦z≦0.3。M滿足0≦m<1,0≦m≦0.7為佳。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.
B成分以雷射繞射散射法測定之平均2次粒徑在2 μ m以下,即幾乎所有粒子不2次凝集而為1次粒子為佳,平均2次粒徑0.4~1.0 μ m之粒子更佳。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.
B成分以BET法測定之比表面積以1~30 m2 /g為佳,5~20 m2 /g更佳。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.
B成分之製法、條件無任何限制。B成分之原料及製造條件已屬習知,基本上可依習知方法製造(參考例如特公昭46-2280號公報及其對應之美國專利第3650704號說明書;特公昭47-32198號公報其對應之美國專利第3879525號說明書;特公昭50-30039號公報;特公昭48-29477號公報;特公昭51-29129號公報等)。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.
為工業規模量產B成分所用之原料,鋁源係硫酸鋁及鋁酸鈉及氫氧化鋁,鎂源係海水、氯化鎂(鹽水、離子苦汁)、氫氧化鎂、氧化鎂,而鹼源係工業用苛性鈉,天然石灰因難以純化而不佳。碳酸離子原料可用工業上之碳酸鈉或二氧化碳。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.
B成分亦可經煅燒使用。煅燒溫度以200℃以上為佳,230℃以上更佳。The component B can also be used for calcination. The calcination temperature is preferably 200 ° C or more, more preferably 230 ° C or more.
B成分以經表面處理者為佳,表面處理劑可用如同A成分氫氧化鈣之表面處理劑,採用同樣方法。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.
對於合成樹脂100重量份,B成分係以0.1重量份以上10重量份以下,0.2重量份以上7重量份以下較佳,0.5重量份以上6重量份以下更佳。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.
A成分及B成分中多含鐵化合物、錳化合物等則配合於樹脂時,樹脂耐熱劣化性差,鐵化合物及錳化合物合計含量以金屬換算(Fe+Mn)宜在0.02重量%以下。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).
<合成樹脂>合成樹脂若係通常成形品用者即可。有例如聚乙烯、聚丙烯、乙烯/丙烯共聚物、聚丁烯、聚-4-甲基戊烯-1等之C2 ~C8 烯烴(α-烯烴)聚合物或共聚物,這些烯烴與二烯之共聚物類,乙烯-丙烯酸酯共聚物、聚苯乙烯、ABS樹脂、AAS樹脂、AS樹脂、MBS樹脂、乙烯/氯乙烯共聚樹脂、乙烯乙酸乙烯酯共聚樹脂、乙烯-氯乙烯-乙酸乙烯酯接枝共聚樹脂、二氯亞乙烯、聚氯乙烯、氯化聚乙烯、氯化聚丙烯、氯乙烯丙烯共聚物、乙酸乙烯酯樹脂、苯氧樹脂、聚縮酮、聚醯胺、聚醯亞胺、聚碳酸酯、聚碸、聚苯醚、聚苯硫醚、聚對酞酸乙二酯、甲基丙烯醯樹脂等熱塑性樹脂,環氧樹脂、酚樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、醇酸樹脂、尿素樹脂等熱固性樹脂,及EPDM、丁基橡膠、異平橡膠、SBR、NBR、氯磺化聚乙烯、NIR、氨酯橡膠、丁二烯橡膠、丙烯醯橡膠、聚矽氧橡膠、含氟橡膠等合成橡膠。<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.
本發明之樹脂組成物可將這些合成樹脂及安定劑以輥機等混練而製造。The resin composition of the present invention can be produced by kneading these synthetic resins and stabilizers by a roll machine or the like.
合成樹脂以聚氯乙烯為佳。The synthetic resin is preferably polyvinyl chloride.
本發明之樹脂組成物除上述成分外可配合以其它慣用添加劑。如此之添加劑有例如抗氧化劑、抗靜電劑、顏料、發泡劑、塑化劑、填料、強化劑、有機鹵素難燃劑、交聯劑、光安定劑、紫外線吸收劑、滑劑等。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.
<成形品>本發明包含上述樹脂組成物之成形品。該成形品有管、彎頭、薄膜、電纜線被覆材料、窗框、食品包裝容器、電子機器用之殼體或零件、汽車零件等。<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.
以下舉實施例更詳述本發明。The invention is described in more detail in the following examples.
以下實施例中,(1)平均2次粒徑、(2)BET比表面積、(3)SiO2 之分析、(4)Al2 O3 、(5)金屬分析各係依如下方法測定。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)平均2次粒徑使用MICROTRAC粒度分析計SPA型[LEEDS & amp;NORTHRUP INSTRUMENTS公司製]以雷射繞射散射法測定。亦即於70ml之水加試樣粉末700mg,以超音波(NISSEI公司製,MODEL US-300,電流300 μ A)分散處理3分鐘後,取其分散液2~4ml,加於容有250ml脫氣水之上述粒度分析計的試樣室,啟動分析計使懸浮液循環8分鐘後測定粒度分布。共測定2次,各得之50%累計2次粒徑求出算數平均,為試樣之平均2次粒徑。(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)BET比表面積以液態氮吸附法測定。亦即,使用液態氮吸附裝置(YUASAIONICS公司製NOVA2000)測定。於測定用專用池正確稱取試樣粉末0.5g,於真空度10mTorr以下,105℃前處理30分鐘(裝置:YUASAIONICS公司製Flovac Degasser)。前處理後,將池冷卻,放入測定裝置室測定比表面積。(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)SiO2 之分析以吸光光度法分析。亦即於鉑坩堝正確稱取試樣粉末0.5g,加硼酸2g及無水碳酸鈉3g混合。於950℃熔化2小時後冷卻,溶解於稀鹽酸40ml,加離子交換水250ml。取溶液25ml,移入100 ml量瓶,加鉬酸銨溶液(10%液)5ml,再加離子交換水100ml成測定用溶液,定量係以分光光度計裝置(日立製作所(股)製雙光束分光光度計150-20型)測定420nm之吸光度。(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)Al2 O3 之分析以螯合法分析。亦即於100 ml燒杯正確稱取試樣粉末0.5g,加稀鹽酸20ml及過氯酸15 ml於150~200℃加熱30分鐘。加熱後,加冷卻水將不溶物以定量用濾紙過濾.洗淨。濾液及洗液合併成正確之250ml測定用溶液。取測定用溶液25ml加離子交換水調整pH為3.0。於測定用pH調整溶液加指示劑Cu-PAN溶液,加熱至沸騰一面以0.01mol/1-EDTA2Na溶液滴定。滴定終點為加熱1分鐘以上亦不變橙黃色之點。(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)金屬分析於100 ml燒杯正確稱取試樣粉末0.5g,加稀鹽酸10ml,加熱溶解。冷卻後移入100ml量瓶加離子交換水100ml成測定用溶液。定量係用ICP發光分光分析裝置(SEIKO INSTRUMENTS公司製SPS1500VR)測定Mn=257.610nm及Fe=259.940nm之吸光度。(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.).
合成例1、2 CH22、23之合成2 m3 容積之反應槽饋入4N之NaOH 360L及表1之量的水玻璃(398g/L),加4 mol/L之CaCl2 165L,於40℃反應5分鐘。將所得產物過濾、乾燥、粉碎,得固溶氫氧化鈣CH22、23。CH22及23之組成及物性測定結果如表2。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.
合成例3 CH26之合成2 m3 容積之反應槽饋入4N之NaOH 360L及表1之量的鋁酸鈉(323g/L),加4 mol/L之CaCl2 165L,於40℃反應5分鐘。將所得產物過濾、乾燥、粉碎,得固溶氫氧化鈣CH26。CH26之組成及物性測定結果如表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.
合成例4 CH29之合成2 m3 容積之反應槽饋入水1 m3 及表1之量的水玻璃(398g/L),反應槽內調溫為60℃。之後,加生石灰27Kg。因生石灰之投入,消化熱使溫度上升至約90℃。該狀態下反應30分鐘。將所得產物過濾、乾燥、粉碎,得固溶氫氧化鈣CH29。CH29之組成及物性測定結果如表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.
參考例1 CHCE3之合成2 m3 容積之反應槽饋入4N之NaOH 360L及CaCl2 (4 mol/L)165L,於40℃反應5分鐘,過濾、乾燥、粉碎,得非固溶氫氧化鈣CHCE3。CHCE3之組成及物性測定結果如表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.
合成例5 CH39之合成2 m3容積之反應槽饋入4N之NaOH 360L及表3之量的水玻璃(398g/L),加4 mol/L之CaCl2 165L,於40℃反應5分鐘。將所得產物過濾、乾燥、粉碎,得固溶氫氧化鈣CH39。CH39之組成及物性測定結果如表4。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.
合成例6 CH40之合成合成例5中水玻璃改用表3之量的合成非晶質氧化矽(SiO2 =93重量%)外如同合成例5調製固溶氫氧化鈣CH40。CH40之組成及物性測定結果如表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.
合成例7 CH42之合成合成例5中水玻璃改用表3之量的四乙氧矽烷(SiO2 =28重量%)外如同合成例5調製固溶氫氧化鈣CH42。CH42之組成及物性測定結果如表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.
合成例8 HT1之合成將純化鹽水(MgCl2 =312.1g/L)移入濃度調整桶,加硫酸鋁(Al2 O3 =106.8 1g/L)成Mg濃度1.95mol/L、Al濃度0.847mol/L之混合水溶液(A)。其次將苛性鈉(48.7%)移入另一濃度調整桶,加碳酸鈉粉末(Na2 CO3 =99.9%)及水成含NaOH 3mol/L及Na2 CO3 0.23mol/L之水溶液(B)。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) .
以混合水溶液(A)1.18L對水溶液(B)2.2L之比率,攪拌下以滯留時間60分鐘同時注入已有水之反應槽,得水滑石反應漿體。取該反應漿體800L,攪拌下以170℃×6小時保持於熱壓器中加熱熟化。冷卻後漿體移入表面處理槽,攪拌下加溫至80℃,慢慢注入預先溶解於80℃溫水50L之硬脂酸鈉(C1 7 H3 6 COONa=93.4%)2kg,攪拌下保持30分鐘完成表面處理。將固體過濾、洗淨,熱風乾燥機乾燥後以鎚磨機粉碎成樣本。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.
所得HT1之分析結果,組成式為Mg0 . 7 Al0 . 3 (OH)2 (CO3 )0 . 1 5 .0.5H2 O。組成及物性測定結果如表5。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.
合成例9 HT2之合成於合成例8,原料中之純化鹽水改用離子苦汁,使用氯化鋅外使用同樣裝置作同樣反應。亦即,將離子苦汁(MgCl2 =168.2g/L)移入濃度調整桶,加氯化鋅(ZnCl2 =572.7g/L)、硫酸鋁(Al2 O3 =106.8 1g/L)成M g濃度1.05mol/L,Zn濃度0.42mol/L及Al濃度0.63mol/L之混合水溶液。此時,因於混合槽產生硫酸鈣沈澱物,過濾成(A)液。其次將苛性鈉(NaOH 48.7%)移入另一濃度調整桶,加碳酸鈉粉末(Na2 CO3 =99.9%)及水成含NaOH 3mol/L、Na2 CO3 0.225mol/L之水溶液(B)。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 ).
以(A)液1L對(B)液1.4L之比率,攪拌下以滯留時間60分鐘同時注入已有水之反應槽,得HT反應漿體。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.
取該反應漿體800L,攪拌下以140℃×6小時保持於熱壓器中加熱熟化。冷卻後漿體移入表面處理槽,攪拌下加溫至80℃,慢慢注入預先溶解於80℃溫水50L之硬脂酸鈉1.3 kg,攪拌下保持30分鐘完成表面處理。將固體過濾、洗淨,再乳化後噴霧乾燥成樣本。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.
所得HT2之分析結果,組成式為Mg0 . 5 Zn0 . 2 Al0 . 3 (OH)2 (CO3 )0 . 1 5 .0.55H2 O。組成及物性測定結果如表5。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.
合成例10 HT3之合成合成例8得之水滑石HT1於240℃煅燒調製水滑石HT3。組成及物性測定結果如表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.
合成例11 HT4之合成合成例9得之HT2於240℃煅燒調製水滑石HT4。組成及物性測定結果如表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.
以固溶氫氧化鈣CH39、CH23、水滑石HT1及HT2及非固溶氫氧化鈣CHCE3為安定劑,調製如下組成(A)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。安定劑之組成如表6。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.
熱安定性係切取5 cm×8 cm之該薄片,放入190℃之熟化烘箱每10分鐘取出作評估。評估係以出現著色之樹脂劣化度為之,測定變黑至一定程度之時間,並評估熱安定性初期之色澤。結果如表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.
組成(A)聚氯乙烯(聚合度700) 100PHR硬脂酸鋅 0.3PHR硬脂醯基苯甲醯甲烷 0.2PHR二新戊四醇 0.2PHR安定劑 1.0PHRComposition (A) Polyvinyl chloride (degree of polymerization 700) 100PHR zinc stearate 0.3PHR stearyl benzoyl hydrazine methane 0.2PHR dinonpentaerythritol 0.2PHR stabilizer 1.0PHR
以固溶氫氧化鈣CH39、水滑石HT2及非固溶氫氧化鈣CHCE3為安定劑,調製如下組成(B)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表7。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.
組成(B)聚氯乙烯(聚合度1000) 100PHR二苯甲醯甲烷 0.1PHR二新戊四醇 0.2PHR D KISIOL G32 0.2PHR硬脂酸鋅 0.8PHR硬脂酸鈣 0.4PHR METABLEN P-501 0.5PHR白艷華CCR(碳酸鈣、白石鈣製) 4.0PHR安定劑 1.0PHRComposition (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
以固溶氫氧化鈣CH22、CH40、CH42、水滑石HT1及非固溶氫氧化鈣CHCE3為安定劑,調製如下組成(C)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表8。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.
組成(C)聚氯乙烯(聚合度1000) 100PHR二苯甲醯甲烷 0.1PHR二新戊四醇 0.2PHR D KISIOL G32(KOGNIS製) 0.2PHR硬脂酸鋅 0.6PHR硬脂酸鈣 0.2PHR重質碳酸鈣 3.0PHR安定劑 0.5PHRComposition (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
以固溶氫氧化鈣CH39、CH23、CH26、CH40、CH42、水滑石HT1、HT2、HT3、HT4及非固溶氫氧化鈣CHCE3為安定劑,調製如下組成(D)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表9。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.
組成(D)聚氯乙烯(聚合度1300) 100PHR DOP(酞酸二辛酯) 50PHR硬脂酸鋅 0.6PHR安定劑 0.5PHRComposition (D) Polyvinyl chloride (degree of polymerization 1300) 100PHR DOP (dioctyl phthalate) 50PHR zinc stearate 0.6PHR stabilizer 0.5PHR
以固溶氫氧化鈣CH39、水滑石HT1及HT2為安定劑,調製如下組成(D-1)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表10。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.
組成(D-1)聚氯乙烯(聚合度1300) 100PHR酞酸二辛酯 50PHR硬脂酸鋅 0.4PHR安定劑 1.6PHRComposition (D-1) Polyvinyl chloride (degree of polymerization 1300) 100PHR dioctyl phthalate 50PHR zinc stearate 0.4PHR stabilizer 1.5PHR
以固溶氫氧化鈣CH39、水滑石HT1及HT2為安定劑,調製如下組成(D-2)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表11。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.
組成(D-2)聚氯乙烯(聚合度1300) 100PHR酞酸二辛酯 50PHR硬脂酸鋅 0.4PHR安定劑 4.0PHRComposition (D-2) Polyvinyl chloride (degree of polymerization 1300) 100PHR dioctyl phthalate 50PHR zinc stearate 0.4PHR stabilizer 4.0PHR
以固溶氫氧化鈣CH39、水滑石HT1及HT2為安定劑,調製如下組成(A-1)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表12。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.
組成(A-1)聚氯乙烯(聚合度700) 100PHR硬脂酸鋅 0.3PHR硬脂醯基苯甲醯甲烷 0.2PHR二新戊四醇 0.2PHR安定劑 3.0PHRComposition (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
以固溶氫氧化鈣CH39、水滑石HT1及HT2為安定劑,調製如下組成(A-2)之樹脂組成物,該樹脂組成物用輥機以180℃×5分鐘混練製成0.7 mm之捲片。如同實施例1評估熱安定性。安定劑之組成、結果如表13。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.
組成(A-2)聚氯乙烯(聚合度700) 100PHR硬脂酸鋅 0.3PHR硬脂醯基苯甲醯甲烷 0.2PHR二新戊四醇 0.2PHR安定劑 6.0PHRComposition (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
依本發明,以比表面積大,活性高,酸中和性、鹼捕集性大之固溶氫氧化鈣,及水滑石組合,可提供付與合成樹脂優良之熱安定性及初期著色性之安定劑組成物。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.
本發明之樹脂組成物及成形品熱安定性,尤以長久熱安定性優良,初期著色性優良。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.
本發明之氫氧化鈣可用作酸中和劑、鹵素捕集劑而為合成樹脂之安定劑。本發明之樹脂組成物因熱安定性、初期著色性優良,可利用於各領域。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.
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US4347353A (en) * | 1978-12-14 | 1982-08-31 | Kyowa Chemical Industry, Co., Ltd. | Method for inhibiting the corrosion-causing tendency and coloration of halogen-containing olefin resin blends |
US4761188A (en) * | 1985-09-24 | 1988-08-02 | Kyowa Chemical Industry Co., Ltd. | Filiform corrosion-resistant primer coating composition and method for preventing filiform corrosion |
JP2000309671A (en) * | 1999-04-23 | 2000-11-07 | Kaisui Kagaku Kenkyusho:Kk | Stabilized halogen-containing resin composition |
JP2001011268A (en) * | 1999-04-28 | 2001-01-16 | Kyowa Chem Ind Co Ltd | Chlorine-containing resin composition |
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US4347353A (en) * | 1978-12-14 | 1982-08-31 | Kyowa Chemical Industry, Co., Ltd. | Method for inhibiting the corrosion-causing tendency and coloration of halogen-containing olefin resin blends |
US4761188A (en) * | 1985-09-24 | 1988-08-02 | Kyowa Chemical Industry Co., Ltd. | Filiform corrosion-resistant primer coating composition and method for preventing filiform corrosion |
JP2000309671A (en) * | 1999-04-23 | 2000-11-07 | Kaisui Kagaku Kenkyusho:Kk | Stabilized halogen-containing resin composition |
JP2001011268A (en) * | 1999-04-28 | 2001-01-16 | Kyowa Chem Ind Co Ltd | Chlorine-containing resin composition |
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