JP2006328428A - Thermal stabilizer for halogen-including resin - Google Patents
Thermal stabilizer for halogen-including resin Download PDFInfo
- Publication number
- JP2006328428A JP2006328428A JP2006251710A JP2006251710A JP2006328428A JP 2006328428 A JP2006328428 A JP 2006328428A JP 2006251710 A JP2006251710 A JP 2006251710A JP 2006251710 A JP2006251710 A JP 2006251710A JP 2006328428 A JP2006328428 A JP 2006328428A
- Authority
- JP
- Japan
- Prior art keywords
- halogen
- weight
- parts
- containing resin
- dolomite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 239000003017 thermal stabilizer Substances 0.000 title claims abstract description 5
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 45
- 239000010459 dolomite Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000011342 resin composition Substances 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 50
- 150000002367 halogens Chemical class 0.000 claims description 50
- 239000012760 heat stabilizer Substances 0.000 claims description 15
- -1 organic acid zinc salt Chemical class 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 7
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- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
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- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- KQMBEUPSQAQIKF-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;magnesium Chemical compound [Mg].[Ca].O[Si](O)=O KQMBEUPSQAQIKF-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- HVINKLZTQUQDJO-UHFFFAOYSA-N pentadecane-2,4-dione Chemical compound CCCCCCCCCCCC(=O)CC(C)=O HVINKLZTQUQDJO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940079889 pyrrolidonecarboxylic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910001720 Åkermanite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は熱安定化されたハロゲン含有樹脂組成物に関し、更に詳しくは、ハロゲン含有樹脂に、苦灰石系化合物及び有機酸の亜鉛塩を配合してなる熱安定化されたハロゲン含有樹脂組成物に関する。 The present invention relates to a heat-stabilized halogen-containing resin composition, and more specifically, a heat-stabilized halogen-containing resin composition comprising a halogen-containing resin and a zinc salt of a dolomite compound and an organic acid. About.
塩化ビニル樹脂などのハロゲン含有樹脂は、難燃性が高く、耐光性、リサイクル性、耐薬品性等に優れた特性を有し、建材、配管、電線被覆材、各種シート、各種フィルム、容器等として極めて幅広く用いられている。 Halogen-containing resins such as vinyl chloride resin are highly flame retardant and have excellent properties such as light resistance, recyclability, chemical resistance, building materials, piping, wire covering materials, various sheets, various films, containers, etc. Is widely used.
ハロゲン含有樹脂は、加熱成形加工時において、脱ハロゲン化水素を伴った熱分解により、樹脂の熱着色、強度等の物理的性質の低下等の品質低下現象が生じる。このような問題点を解決するために、ハロゲン含有樹脂の熱安定性を改善するための安定剤を添加するのが一般的である。 The halogen-containing resin undergoes a degradation phenomenon such as thermal coloring of the resin and a decrease in physical properties such as strength due to thermal decomposition accompanied by dehydrohalogenation during the thermoforming process. In order to solve such problems, it is common to add a stabilizer for improving the thermal stability of the halogen-containing resin.
ハロゲン含有樹脂の熱安定性を改善するための安定剤（以下、「熱安定剤」という）としては、従来、脂肪酸、芳香族カルボン酸、アミノ酸等の有機酸の金属塩が使用されている。具体的には鉛塩やカドミウム塩が熱安定剤としては満足すべき機能を有し、特に鉛系安定剤は大量に使用されてきた。しかし、これらは毒性上の問題が大きいため使用が制限されている。これらに替わる熱安定剤として、安全性の高い有機酸の亜鉛塩が注目されている。 As stabilizers for improving the thermal stability of halogen-containing resins (hereinafter referred to as “thermal stabilizers”), metal salts of organic acids such as fatty acids, aromatic carboxylic acids and amino acids have been conventionally used. Specifically, lead salts and cadmium salts have satisfactory functions as heat stabilizers, and lead stabilizers have been used in large quantities. However, their use is limited due to the great toxicity problem. As a heat stabilizer alternative to these, zinc salts of organic acids with high safety are attracting attention.
しかしながら、鉛系安定剤に比べ、亜鉛系の熱安定剤の熱安定の効果は十分でなく、安全性の高い亜鉛系安定剤の配合によって鉛系安定剤と同じレベルの熱安定化効果をハロゲン含有樹脂に付与し得る熱安定化システムが求められている。 However, compared to lead-based stabilizers, zinc-based heat stabilizers do not have the sufficient heat-stabilizing effect, and the combination of highly safe zinc-based stabilizers has the same level of heat-stabilizing effect as lead-based stabilizers. There is a need for a thermal stabilization system that can be applied to the containing resin.
本発明の目的は、安全性が高く、熱安定性に優れたハロゲン含有樹脂組成物を提供することにある。 An object of the present invention is to provide a halogen-containing resin composition having high safety and excellent thermal stability.
本発明者らは上記課題を解決するために鋭意検討した結果、苦灰石系化合物を有機酸の亜鉛塩系安定剤との組み合わせで使用した場合にはハロゲン含有樹脂に対して著しい熱安定化効果を発揮することを見いだし、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have made remarkable thermal stabilization with respect to halogen-containing resins when a dolomite compound is used in combination with a zinc salt stabilizer of an organic acid. It has been found that the effect is exhibited, and the present invention has been completed.
即ち、本発明は苦灰石系化合物および有機酸の亜鉛塩を含有することを特徴とするハロゲン含有樹脂用熱安定剤、該熱安定剤を含有する熱安定化されたハロゲン含有樹脂組成物および該ハロゲン含有樹脂組成物を成形加工して得られる成形加工品である。 That is, the present invention contains a dolomite-based compound and a zinc salt of an organic acid, a heat stabilizer for a halogen-containing resin, a heat-stabilized halogen-containing resin composition containing the heat stabilizer, and This is a molded product obtained by molding the halogen-containing resin composition.
以上説明したように、本発明によれば安全性の高い熱安定剤を用い、塩化ビニル樹脂等のハロゲン含有樹脂の熱安定性を著しく向上させることができる。 As described above, according to the present invention, the heat stability of a halogen-containing resin such as a vinyl chloride resin can be remarkably improved by using a highly safe heat stabilizer.
本発明に用いる苦灰石系化合物は特に限定されるものではなく、天然に広く産出し壁材料、製鉄用耐火物等に用いられている苦灰石(すなわちドロマイト)を用いることができる。さらに、苦灰石は、その化学組成が炭酸カルシウムと炭酸マグネシウムの複塩であり、化学合成により得られる炭酸カルシウムー炭酸マグネシウムの複塩、すなわち合成苦灰石を用いることもできる。本発明に用いる合成苦灰石の組成は、カルシウムとマグネシウムがある比率で混在していれば良く、ＣａＯとＭｇＯの換算でその重量比率が５：９５〜９５：５の範囲が好ましい。この比率範囲を外れた合成ドロマイトを用いた場合、本発明による熱安定化効果が十分に得られない。 The dolomite-based compound used in the present invention is not particularly limited, and dolomite (that is, dolomite) that is widely produced in nature and used in wall materials, refractories for iron making, and the like can be used. Further, dolomite has a chemical composition of calcium carbonate and magnesium carbonate double salt, and a calcium carbonate-magnesium carbonate double salt obtained by chemical synthesis, that is, synthetic dolomite can also be used. The composition of the synthetic dolomite used in the present invention may be a mixture of calcium and magnesium in a certain ratio, and the weight ratio in terms of CaO and MgO is preferably in the range of 5:95 to 95: 5. When synthetic dolomite outside this ratio range is used, the heat stabilization effect according to the present invention cannot be sufficiently obtained.
また、これらの天然および／または合成苦灰石を焼成、消和等、金属元素組成を大きく変更させることなく変性した誘導体を用いることができ、具体的には苦灰石を７００〜８００℃にて加熱し得られるドロマイトセメント、９００〜１０００℃にて加熱し得られる軽焼ドロマイト、さらに１６００〜１８００℃の高温で硬焼した死焼ドロマイト、軽焼ドロマイトに水を加えて消化した苦土消石灰、合成マグドロクリンカー等が挙げられる。さらに、アケルマナイト（Ｃａ2ＭｇＳｉ2Ｏ7) 、透輝石（ＣａＭｇ（ＳｉＯ3）2）および各種スラグのように、カルシウムとマグネシウムの比率が上述の合成ドロマイトと同じ範囲にある天然鉱物や合成の複塩を同様に変性した誘導体も用いることができる。更に、これらの任意の混合物であっても良いことはいうまでもない。 In addition, it is possible to use derivatives obtained by modifying these natural and / or synthetic dolomite without largely changing the metal element composition, such as firing and calcination. Specifically, the dolomite is heated to 700 to 800 ° C. Dolomite cement that can be heated by heating, light-burned dolomite that can be heated at 900-1000 ° C., dead-burned dolomite hard-fired at a high temperature of 1600-1800 ° C., and bituminous slaked lime that has been digested by adding water to light-burning dolomite And synthetic magdro clinker. Furthermore, natural minerals and synthetic double salts in which the ratio of calcium to magnesium is in the same range as the above-mentioned synthetic dolomite, such as akermanite (Ca2MgSi2O7), diopside (CaMg (SiO3) 2) and various slags, were similarly modified. Derivatives can also be used. Needless to say, any mixture of these may be used.
これらの苦灰石およびその誘導体を本明細書では苦灰石系化合物と総称するが、これらの苦灰石化合物は工業的に幅広く大量に産出されており、製鋼から陶器、建材、農業等極めて幅広い産業で使用されているため、安定な品質で、容易かつ安価に入手可能なものである。中でも、軽焼ドロマイトを使用した場合、得られるハロゲン含有樹脂組成物の熱安定性が特に良好になる。 These dolomite and its derivatives are collectively referred to herein as dolomite compounds, but these dolomite compounds are produced in large quantities industrially in large quantities, such as steelmaking, pottery, building materials, agriculture, etc. Since it is used in a wide range of industries, it can be obtained easily and inexpensively with stable quality. Especially, when lightly burned dolomite is used, the thermal stability of the resulting halogen-containing resin composition becomes particularly good.
また必要に応じ、本発明の効果を阻害しない範囲で、工業的に使用されている表面処理剤を任意に併用させてもよい。具体的には、シラン系、アルミ系、リン酸系等のカップリング剤やアテアリン酸、アテアリン酸亜鉛、アテアリン酸カルシウム等のカチオン系、アニオン系、ノニオン系の界面活性剤、高分子系の分散剤等が挙げられる。ただし、本発明の処理剤による熱安定性向上効果を十分得るためには、これらの表面処理剤は、本発明において苦灰石系化合物の表面処理の用いる化合物に対し、多くとも同量ないし同量未満に止めることが好ましい。 Moreover, you may use together the surface treating agent currently used industrially in the range which does not inhibit the effect of this invention as needed. Specifically, coupling agents such as silane, aluminum and phosphoric acid, and cationic, anionic and nonionic surfactants such as atearic acid, zinc atearate and calcium atearic acid, and polymeric dispersants Etc. However, in order to sufficiently obtain the effect of improving the heat stability by the treatment agent of the present invention, these surface treatment agents are used in the present invention at most in the same amount or the same amount as the compound used for the surface treatment of the dolomite compound. It is preferable to stop below the amount.
本発明に用いられる苦灰石系化合物の使用量は、通常ハロゲン含有樹脂１００重量部に対して０.０１重量部以上、好ましくは０．０５重量部以上である。０.０１重量部未満では目的とする熱安定化効果が十分に発揮されない。一方、３０重量部より多く苦灰石系化合物を使用する場合、熱安定化効果がそれ以上向上しないことがある。また、苦灰石系化合物は２００重量部程度まで添加することができるが、好ましくは１５０重量部以下で用いられる。２００重量部より多い場合、本発明の熱安定化効果を低下させることはないが、通常の充填剤と同様でハロゲン含有樹脂組成物の物理特性を低下させる可能性がある。 The amount of the dolomite compound used in the present invention is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more with respect to 100 parts by weight of the halogen-containing resin. If the amount is less than 0.01 parts by weight, the desired heat stabilizing effect is not sufficiently exhibited. On the other hand, when more than 30 parts by weight of the dolomite compound is used, the thermal stabilization effect may not be further improved. Moreover, although a dolomite type compound can be added to about 200 weight part, Preferably it is used at 150 weight part or less. When the amount is more than 200 parts by weight, the thermal stabilization effect of the present invention is not lowered, but the physical properties of the halogen-containing resin composition may be lowered in the same manner as a normal filler.
本発明に用いられる苦灰石系化合物の平均粒径は、１００ミクロン以下が好ましく、更に好ましくは１０ミクロン以下である。１００ミクロンより大きいと、成形後の樹脂組成物の表面がざらつき、物理特性の低下等の品質の低下が起こる場合があり好ましくない。 The average particle size of the dolomite compound used in the present invention is preferably 100 microns or less, more preferably 10 microns or less. If it is larger than 100 microns, the surface of the resin composition after molding is rough, which may cause deterioration in quality such as physical properties.
本発明のハロゲン含有樹脂用熱安定剤において、苦灰石系化合物と共に用いられる有機酸の亜鉛塩について説明する。有機酸としては、例えば酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、オクタン酸、ラウリン酸、ステアリン酸、ベヘン酸、安息香酸、サリチル酸、オレイン酸、リンゴ酸、コハク酸、アジピン酸、テレフタル酸、トリメリット酸、グルタミン酸、リジン、ピロリドンカルボン酸、アスパラギン酸、グリシン等が挙げられる。 In the heat stabilizer for halogen-containing resin of the present invention, an organic acid zinc salt used together with a dolomite compound will be described. Examples of organic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, stearic acid, behenic acid, benzoic acid, salicylic acid, oleic acid, malic acid, succinic acid, adipic acid, terephthalic acid , Trimellitic acid, glutamic acid, lysine, pyrrolidonecarboxylic acid, aspartic acid, glycine and the like.
有機酸の亜鉛塩の使用量は、通常、ハロゲン含有樹脂用熱安定剤として用いられる場合の量、例えばハロゲン含有樹脂１００重量部に対して０．０１〜２０重量部でよい。 The amount of the organic acid zinc salt used is usually 0.01 to 20 parts by weight relative to 100 parts by weight of the halogen-containing resin when used as a heat stabilizer for halogen-containing resins.
本発明のハロゲン含有樹脂用熱安定剤においては、苦灰石系化合物（或いは表面処理された苦灰石系化合物）および有機酸の亜鉛塩に加え、樹脂の熱着色を更に抑制するために、多価アルコール化合物および／またはβ−ジケトン化合物を配合してもよい。 In the heat stabilizer for halogen-containing resin of the present invention, in addition to the dolomite compound (or the surface-treated dolomite compound) and the zinc salt of the organic acid, in order to further suppress the thermal coloring of the resin, You may mix | blend a polyhydric alcohol compound and / or (beta) -diketone compound.
本発明に用いることができる多価アルコール化合物としては、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、テトラペンタエリスリトール、ソルビトール、グリセリン、ポリグリセリン等が挙げられる。また、これら多価アルコールの水酸基の一部をエステル化、エーテル化等により化学修飾したものを用いることができる。 Examples of the polyhydric alcohol compound that can be used in the present invention include pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, sorbitol, glycerin, polyglycerin and the like. Further, those obtained by chemically modifying a part of hydroxyl groups of these polyhydric alcohols by esterification, etherification or the like can be used.
多価アルコール化合物のなかでも特にペンタエリスリトール、ジペンタエリスリトール、またはこれらを塩基酸でエステル化したものが好ましい。 Among the polyhydric alcohol compounds, pentaerythritol, dipentaerythritol, or those obtained by esterifying them with a basic acid are particularly preferable.
特にペンタエリスリトールおよび／またはジペンタエリスリトールを、炭素原子数１０〜２２の高級脂肪酸および／または炭素原子数４〜１０の二塩基酸でエステル化した部分エステル化物は、高分子量であるため、加熱成形加工時の昇華がなく金型汚染を起こさない、樹脂の加工性が向上する、粉体（苦灰石系化合物等）の樹脂中への分散性改善、等の付加的な長所を有するので好ましい。 In particular, since a partially esterified product obtained by esterifying pentaerythritol and / or dipentaerythritol with a higher fatty acid having 10 to 22 carbon atoms and / or a dibasic acid having 4 to 10 carbon atoms has a high molecular weight, it is thermoformed. It is preferable because it has additional advantages such as no sublimation during processing, no mold contamination, improved processability of the resin, and improved dispersibility of powders (dolomite compounds, etc.) in the resin. .
上記高級脂肪酸としては、例えば、カプリン酸、ウンデカン酸、ラウリル酸、トリデカン酸、ミリスチン酸、パルミチン酸、イソステアリン酸、ステアリン酸、１，２−ヒドロキシステアリン酸、オレイン酸、リノール酸等が挙げられる。 Examples of the higher fatty acid include capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 1,2-hydroxystearic acid, oleic acid, linoleic acid, and the like.
上記二塩基酸としては、例えば、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、セバチン酸等が挙げられる。 Examples of the dibasic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and sebacic acid.
炭素原子数４〜１０の二塩基酸は低昇華性効果および熱安定化効果に、炭素原子数１０〜２２の高級脂肪酸は処理粉体の加工性改善効果および良分散性効果に寄与する。 A dibasic acid having 4 to 10 carbon atoms contributes to a low sublimation effect and a thermal stabilization effect, and a higher fatty acid having 10 to 22 carbon atoms contributes to an effect of improving processability and good dispersibility of the treated powder.
目的とするハロゲン含有樹脂組成物の機能、配合系に合わせ任意に分子設計し用いることができる。このようなペンタエリスリトールおよび／またはジペンタエリスリトールと、炭素原子数１０〜２２の高級脂肪酸および／または炭素原子数４〜１０の二塩基酸との一部水酸基のエステル化物は、特開昭５３−６３５０号公報、特公昭５７−６１２８９号公報、特開昭５５−０６９６３９号公報等に記載された既知の方法で工業的に容易に製造することが出来、また、一部ではあるが、市販されている。 The molecule can be arbitrarily designed and used in accordance with the function and blending system of the target halogen-containing resin composition. Such partially esterified products of pentaerythritol and / or dipentaerythritol and higher fatty acids having 10 to 22 carbon atoms and / or dibasic acids having 4 to 10 carbon atoms are disclosed in JP-A 53- 6350, JP-B-57-61289, JP-A-55-066939, etc. can be easily produced industrially, and although it is a part, it is commercially available. ing.
多価アルコール化合物の使用量は、ハロゲン含有樹脂１００重量部に対して通常０．０１〜１０重量部、好ましくは０．０５〜５重量部である。０．０１重量部未満では多価アルコール化合物による相乗的熱安定化効果が十分に発揮されない場合がある。一方１０重量部を越えた場合、ハロゲン含有樹脂配合物の物理特性を低下させる可能性がある。本発明に用いる多価アルコール化合物は上記のものを単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The use amount of the polyhydric alcohol compound is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the halogen-containing resin. If it is less than 0.01 part by weight, the synergistic heat stabilization effect by the polyhydric alcohol compound may not be sufficiently exhibited. On the other hand, when it exceeds 10 parts by weight, the physical properties of the halogen-containing resin compound may be lowered. As the polyhydric alcohol compound used in the present invention, the above may be used alone, or two or more may be used in combination.
本発明に用いることができるβ−ジケトン化合物としては、例えば特公昭５２−４７９４９号公報等に開示され、工業的に製造されているものを任意に使用することができる。具体的には、ベンゾイルアセチルメタン、トリベンゾイルメタン、ジアセチルベンゾイルメタン、ステアロイルベンゾイルメタン、パルミトイルベンゾイルメタン、ベンゾイルアセチルエチルメタン、ジアセチルメタン、トリアセチルメタン、ジベンゾイルメタン、ジステアロイルメタン、ステアロイルアセチルメタン、ラウロイルアセチルメタン、ベンゾイルホルミルメタン等が挙げられる。 As the β-diketone compound that can be used in the present invention, for example, those disclosed in Japanese Patent Publication No. 52-47949 and manufactured industrially can be arbitrarily used. Specifically, benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, benzoylacetylethylmethane, diacetylmethane, triacetylmethane, dibenzoylmethane, distearoylmethane, stearoylacetylmethane, lauroyl Acetylmethane, benzoylformylmethane, etc. are mentioned.
更に、これらβ−ジケトンの金属塩、例えばリチウム、ナトリウム、マグネシウム、アルミニウム、カリウム、カルシウム、亜鉛、等の塩を用いても良い。 Further, metal salts of these β-diketones such as lithium, sodium, magnesium, aluminum, potassium, calcium, zinc and the like may be used.
β−ジケトン化合物の使用量は、ハロゲン含有樹脂１００重量部に対して通常０．０１〜１０重量部、好ましくは０．０５〜５重量部である。０．０１重量部未満ではβ−ジケトンによる相乗的熱安定化効果が十分に発揮されない場合がある。一方１０重量部を越えた場合、ハロゲン含有樹脂配合物の物理特性を低下させる可能性がある。これらのβ−ジケトン化合物は、各々単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The usage-amount of (beta) -diketone compound is 0.01-10 weight part normally with respect to 100 weight part of halogen containing resin, Preferably it is 0.05-5 weight part. If it is less than 0.01 part by weight, the synergistic heat stabilization effect by β-diketone may not be sufficiently exhibited. On the other hand, when it exceeds 10 parts by weight, the physical properties of the halogen-containing resin compound may be lowered. These β-diketone compounds may be used alone or in combination of two or more.
また、本発明の熱安定剤またはハロゲン含有樹脂組成物においては、必要に応じて本発明の効果を阻害しない範囲で、各種の添加剤を配合してもよい。例えば、通常ハロゲン含有樹脂組成物に用いられる可塑剤、充填剤、酸化防止剤、紫外線吸収剤、難燃剤、滑剤、顔料、帯電防止剤、防曇剤等を配合することができる。有機リン化合物やエポキシ化合物等も配合することができる。 Moreover, in the heat stabilizer or halogen-containing resin composition of this invention, you may mix | blend various additives in the range which does not inhibit the effect of this invention as needed. For example, plasticizers, fillers, antioxidants, ultraviolet absorbers, flame retardants, lubricants, pigments, antistatic agents, antifogging agents, etc. that are usually used in halogen-containing resin compositions can be blended. An organophosphorus compound, an epoxy compound, etc. can also be mix | blended.
本発明で用いられるハロゲン含有樹脂としては、例えば、ポリ塩化ビニル、ポリ臭化ビニル、ポリフッ化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−ブタジエン共重合体等が挙げられ、これらのアロイであっても良い。またこれらのハロゲン含有樹脂と、ポリエチレン、ポリプロピレン、ポリスチレン、ポリフェニレンエーテル、ポリアミド、ポリカーボネート等の非含ハロゲン樹脂とのアロイであっても良い。また、チーグラー型触媒を用いて製造されるオレフィン樹脂中には、ハロゲン含有触媒残渣を含むが、かかるハロゲン含有触媒残渣を含んだオレフィン樹脂も本発明のいうハロゲン含有樹脂に包含する。 Examples of the halogen-containing resin used in the present invention include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-butadiene copolymer. Etc., and these alloys may be used. An alloy of these halogen-containing resins and non-halogen-containing resins such as polyethylene, polypropylene, polystyrene, polyphenylene ether, polyamide, and polycarbonate may also be used. The olefin resin produced using a Ziegler-type catalyst contains a halogen-containing catalyst residue. The olefin resin containing such a halogen-containing catalyst residue is also included in the halogen-containing resin referred to in the present invention.
本発明の熱安定化されたハロゲン含有樹脂組成物を混練・成形・加工する場合、その配合方法、混練方法、順序、成形方法等に特に制限はない。 When kneading / molding / processing the heat-stabilized halogen-containing resin composition of the present invention, there are no particular limitations on the blending method, kneading method, order, molding method, and the like.
さらに本発明の特徴をより明らかにすべく、実施例にて説明するが、本発明はこの実施例に限定されるものではない。 Further, in order to clarify the characteristics of the present invention, examples will be described. However, the present invention is not limited to the examples.
［製造例１］
水酸化マグネシウム５８．３部（部は重量部を表す。以下同じ）と水酸化カルシウム７４．１部を水２０００部に懸濁、溶解させ、１０℃にて攪拌しつつ３時間炭酸ガスを吹き込んだ。沈殿物を濾過し、炭酸ガス雰囲気下５０℃以下にて乾燥し、炭酸カルシウムー炭酸マグネシウム複塩（合成ドロマイト）１５２．３部を得た。得られた複塩のカルシウムとマグネシウムの比率は、ＣａＯとＭｇＯ換算で５４：４６であった。
[Production Example 1]
58.3 parts of magnesium hydroxide (parts are parts by weight; the same applies hereinafter) and 74.1 parts of calcium hydroxide are suspended and dissolved in 2000 parts of water, and carbon dioxide gas is blown in for 3 hours while stirring at 10 ° C. It is. The precipitate was filtered and dried under a carbon dioxide atmosphere at 50 ° C. or lower to obtain 152.3 parts of calcium carbonate-magnesium carbonate double salt (synthetic dolomite). The ratio of calcium and magnesium of the obtained double salt was 54:46 in terms of CaO and MgO.
［製造例２］
製造例１にて得られた炭酸カルシウムー炭酸マグネシウム複塩（合成ドロマイト）を１０００℃にて１時間焼成し、軽焼合成ドロマイトを得た。
[Production Example 2]
The calcium carbonate-magnesium carbonate double salt (synthetic dolomite) obtained in Production Example 1 was fired at 1000 ° C. for 1 hour to obtain a lightly burned synthetic dolomite.
［製造例３］
透輝石（ＣａＭｇ（ＳｉＯ3）2）を１０００℃にて１時間焼成し、軽焼透輝石を得た。
[Production Example 3]
Diopside (CaMg (SiO 3) 2) was fired at 1000 ° C. for 1 hour to obtain a light burned diopside.
［製造例４］
ペンタエリスリトール１３６部にアジピン酸７３部、ステアリン酸２８４．５部を加え、２３０℃にて２時間撹拌、エステル化反応を行い、ペンタエリスリトールのアジピン酸・ステアリン酸混合部分エステル(エステル化率４５〜５５％)を得た。
[Production Example 4]
Add 73 parts of adipic acid and 284.5 parts of stearic acid to 136 parts of pentaerythritol, stir at 230 ° C. for 2 hours to carry out an esterification reaction. 55%).
［実施例３〜５、７〜１４、参考例１、２、６、比較例１〜５］
表１に示す配合のハロゲン含有樹脂組成物を熱ロールを用い１５５℃にて５分間混練し、次いで熱プレスを用い１５５℃にて５分間プレスし、厚さ３ｍｍのシートを作成した。得られたシートを用い、ギアオーブンを用いた１８０℃における熱着色試験（静的熱安定性試験）、ラボプラストミルを用いた２００℃における動的熱安定性試験、１８０℃におけるコンゴーレッド試験を行った。熱着色試験は、シートが茶褐色化もしくは部分黒化するまでの時間、動的熱安定性試験は樹脂が分解し混練トルクが上昇開始する間での時間を測定した。これらの試験結果を表１に示す。なお、表中の記号は以下の透りである。
＊１：新第一塩ビ（株）製「１０００Ｚ」（重合度１０５０）を使用した。
＊２：いずれも田源石灰工業（株）を使用した。
＊３：「プレンライザーＳＴ−２１０」（商品名；味の素ファインテクノ(株)製、ジペンタエリスリトールのアジピン酸エステルを主成分とする化合物、ＯＨ価９００）
＊４：「プレンライザーＳＴ−２２０」（商品名；味の素ファインテクノ(株)製、ペンタタエリスリトールのアジピン酸エステル誘導体を主成分とする化合物、ＯＨ価９００）
[Examples 3-5, 7-14, Reference Examples 1, 2, 6, Comparative Examples 1-5]
The halogen-containing resin composition having the composition shown in Table 1 was kneaded at 155 ° C. for 5 minutes using a hot roll, and then pressed at 155 ° C. for 5 minutes using a hot press to prepare a sheet having a thickness of 3 mm. Using the obtained sheet, a thermal coloring test at 180 ° C. using a gear oven (static thermal stability test), a dynamic thermal stability test at 200 ° C. using a lab plast mill, and a Congo red test at 180 ° C. went. In the thermal coloring test, the time until the sheet browned or partially blackened, and in the dynamic thermal stability test, the time until the resin was decomposed and the kneading torque started to increase was measured. These test results are shown in Table 1. In addition, the symbol in a table | surface is the following transparency.
* 1: “1000Z” (degree of polymerization 1050) manufactured by Shin Daiichi Vinyl Co., Ltd. was used.
* 2: All used Tagen Lime Industry Co., Ltd.
* 3: “Planelizer ST-210” (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd., a compound mainly composed of adipic acid ester of dipentaerythritol, OH number 900)
* 4: “Planelizer ST-220” (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd., a compound mainly composed of an adipate ester derivative of pentataerythritol, OH number 900)
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2006251710A JP2006328428A (en) | 1998-03-26 | 2006-09-15 | Thermal stabilizer for halogen-including resin |
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| Application Number | Priority Date | Filing Date | Title |
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| JP7940498 | 1998-03-26 | ||
| JP2006251710A JP2006328428A (en) | 1998-03-26 | 2006-09-15 | Thermal stabilizer for halogen-including resin |
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| Application Number | Title | Priority Date | Filing Date |
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| JP6801199A Division JPH11335502A (en) | 1998-03-26 | 1999-03-15 | Thermal stabilizer and thermally stabilized resin composition containing halogen |
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| JP2006328428A true JP2006328428A (en) | 2006-12-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256783A (en) * | 2019-07-11 | 2019-09-20 | 临安市锦新塑料化工有限公司 | A kind of PVC calcium zinc stabilizer and its preparation process |
| CN115449127A (en) * | 2022-09-02 | 2022-12-09 | 浙江工业大学 | Dianion type zinc salt heat stabilizer for transparent PVC and preparation method and application thereof |
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2006
- 2006-09-15 JP JP2006251710A patent/JP2006328428A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256783A (en) * | 2019-07-11 | 2019-09-20 | 临安市锦新塑料化工有限公司 | A kind of PVC calcium zinc stabilizer and its preparation process |
| CN115449127A (en) * | 2022-09-02 | 2022-12-09 | 浙江工业大学 | Dianion type zinc salt heat stabilizer for transparent PVC and preparation method and application thereof |
| CN115449127B (en) * | 2022-09-02 | 2024-01-12 | 浙江工业大学 | Double-anion zinc salt heat stabilizer for transparent PVC, and preparation method and application thereof |
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