JPS6361061A - Composition for preventing color change and corrosion of copper metal - Google Patents
Composition for preventing color change and corrosion of copper metalInfo
- Publication number
- JPS6361061A JPS6361061A JP20627386A JP20627386A JPS6361061A JP S6361061 A JPS6361061 A JP S6361061A JP 20627386 A JP20627386 A JP 20627386A JP 20627386 A JP20627386 A JP 20627386A JP S6361061 A JPS6361061 A JP S6361061A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- polyvinyl chloride
- chloride resin
- group
- periodic table
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 title claims abstract description 20
- 238000005260 corrosion Methods 0.000 title claims abstract description 15
- 230000007797 corrosion Effects 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 20
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 20
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 230000000737 periodic effect Effects 0.000 claims abstract description 13
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 12
- 238000002845 discoloration Methods 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000008054 sulfonate salts Chemical class 0.000 claims 1
- 239000012964 benzotriazole Substances 0.000 abstract description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- -1 carbonated Chemical compound 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000004649 discoloration prevention Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- IQZGIUOEBQVRRY-UHFFFAOYSA-N 4-dodecyl-2h-benzotriazole Chemical compound CCCCCCCCCCCCC1=CC=CC2=NNN=C12 IQZGIUOEBQVRRY-UHFFFAOYSA-N 0.000 description 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 159000000004 beryllium salts Chemical class 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 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
- 229910001629 magnesium chloride 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ポリ塩化ビニル樹脂に混練してなる銅系金属
の変色腐食防止組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for preventing discoloration and corrosion of copper-based metals, which is kneaded with polyvinyl chloride resin.
更に詳しくは、式；
（式中；Ｒ１−Ｒ４は各々水素−Ｃ１〜Ｃ１，のアルキ
ル基、ハロゲン原子、あるいはカルボキシル基を示す、
）で表されるベンゾトリアゾール類の周期律表第２族（
カルシウム及びカドミウムを除く）の金属から選ばれた
１種ないし２種以上の金属塩もしくは該ベンゾトリアゾ
ール類と周期律表第２族（カルシウム及びカドミウムを
除く）の金属を含む化合物（酸化物、水酸化物、硫酸塩
、炭藤塩、硝酸塩、塩化物、カルボン酸塩、あるいはス
ルホン酸塩）の１種ないし２種以上からなる有効成分を
ポリ塩化ビニル樹脂に混練してなる銅系金属の変色腐食
防止組成物に関する。More specifically, the formula;
) Group 2 of the periodic table of benzotriazoles (
One or more metal salts selected from metals (excluding calcium and cadmium), or compounds (oxides, water, Discoloration of copper-based metals made by kneading one or more active ingredients of oxides, sulfates, carbonate salts, nitrates, chlorides, carboxylates, or sulfonates into polyvinyl chloride resin. TECHNICAL FIELD The present invention relates to corrosion-inhibiting compositions.
近年、ポリ塩化ビニルで被覆した電線において施設中に
雨水の浸入や、腐食ガスの浸入あるいは酸素による銅線
の腐食劣化を防止する目的で、予め、銅の変色腐食防止
剤を混練しておき、しかる後に被覆加工し、変色腐食の
起こりにくい電線の要求が強くなってきている。該目的
を達成させるために、従来からの銅の防食剤であるベン
ゾトリアゾールを適用した場合、塩化ビニル自体の脱塩
酸による分解を促進する致命的な欠点が有り、この改善
が強く望まれていた。In recent years, in order to prevent the intrusion of rainwater into facilities, the infiltration of corrosive gases, and the corrosion and deterioration of copper wires due to oxygen, electric wires coated with polyvinyl chloride are mixed with a copper discoloration inhibitor in advance. There is an increasing demand for electric wires that are coated and are less susceptible to discoloration and corrosion. In order to achieve this objective, when benzotriazole, a conventional copper corrosion inhibitor, is applied, it has the fatal disadvantage of accelerating the decomposition of vinyl chloride itself by dehydrochlorination, and there is a strong desire to improve this. .
本発明者らは１種々研究を行ないベンゾトリアゾール類
の周期律表第２族の金属塩類並びにベンゾトリアゾール
類と周期律表第２族の金属化合物とを混合したものが銅
の変色腐食を防止すると共に、ポリ塩化ビニル樹脂の劣
化も起こさないなど優れた性質を有することを見出し、
本発明を完成した。The present inventors conducted various studies and found that metal salts of benzotriazoles belonging to Group 2 of the periodic table and mixtures of benzotriazoles and metal compounds of group 2 of the periodic table prevent discoloration and corrosion of copper. We also discovered that it has excellent properties such as not causing the deterioration of polyvinyl chloride resin.
The invention has been completed.
近年、ポリ塩化ビニル樹脂で被覆した電線を長年にわた
って屋外使用する場合その接続部分より雨水や腐食性ガ
スが電線内に侵入し、内部の銅線を腐食劣化させ、遂に
は、切断にいたる事故が発生し、その解決が強く望まれ
ている。この解決方法として、銅の防食剤として最も優
れており広く工業的に用いられているベンゾトリアゾー
ルを混練したポリ塩化ビニル樹脂で銅線を被覆加工し腐
食し雅い電線を製造することが提案されている。In recent years, when electric wires coated with polyvinyl chloride resin are used outdoors for many years, rainwater and corrosive gases can enter the wires through the connections, corrode and deteriorate the internal copper wires, and eventually cause accidents that can lead to disconnection. has occurred, and its resolution is strongly desired. As a solution to this problem, it has been proposed to coat copper wires with polyvinyl chloride resin mixed with benzotriazole, which is the most excellent anti-corrosion agent for copper and is widely used industrially, to prevent corrosion and produce elegant electric wires. ing.
しかしながら、この方法は樹脂を加工する再ベンゾトリ
アゾールがポリ塩化ビニル樹脂の脱塩酸反応を著しく促
進するので樹脂が分解着色し、その結果電気絶縁性が低
下する致命的欠点がありこの改善が強く望まれていた。However, this method has the fatal drawback that the re-benzotriazole used to process the resin significantly accelerates the dehydrochloric acid reaction of polyvinyl chloride resin, causing the resin to decompose and become colored, resulting in a decrease in electrical insulation properties, and improvement of this method is strongly desired. It was rare.
ポリ塩化ビニル樹脂の脱塩酸反応を防止するための安定
剤として、従来より、鉛系、カドミウム系、有機スズ糸
導１種々の化合物が広く使用されているが、ベンゾトリ
アゾールを使用した場合、いずれの安定剤も有効でない
。Conventionally, various lead-based, cadmium-based, and organic tin compounds have been widely used as stabilizers to prevent the dehydrochloric acid reaction of polyvinyl chloride resin, but when benzotriazole is used, stabilizers are also not effective.
本発明者等は種々研究の結果、ベンゾトリアゾール類の
周期律表第２族の金属塩（カルシウム及びカドミウムを
除く）類、並びにベンゾトリアゾール類と該周期律表第
２族の金属化合物とを混合したものがポリ塩化ビニル樹
脂の劣化も起こさず銅の変色腐食を防止する優れた性質
を有することを見出し本発明を完成した。As a result of various studies, the present inventors have discovered that benzotriazoles are mixed with metal salts of group 2 of the periodic table (excluding calcium and cadmium), and benzotriazoles are mixed with metal compounds of group 2 of the periodic table. The present invention was completed by discovering that the obtained product has excellent properties of preventing discoloration and corrosion of copper without causing deterioration of polyvinyl chloride resin.
ベンゾトリアゾール類はポリ塩化ビニル樹脂と混合した
とき、そ、れ自体が脱塩酸反応の触媒的な作用をするも
のと考えられ、脱塩酸した残りの部分はアリル基の活性
塩素となって次々と脱塩酸反応を起こし、いわゆるジッ
パ−反応に近い機構で分解が進むものと思われる。周期
律表第２族の金属塩（カルシウム及びカドミウムを除く
）類は、このベンゾトリアゾール類による脱塩酸反応を
阻止する効果が優れ、しかも銅に対する変色防止効果を
阻害しない特色を有するものである。When benzotriazole is mixed with polyvinyl chloride resin, it is thought that it itself acts as a catalyst for the dehydrochlorination reaction, and the remaining portion after dehydrochlorination becomes the active chlorine of the allyl group and is converted one after another. It is thought that a dehydrochloric acid reaction occurs and the decomposition proceeds through a mechanism similar to the so-called zipper reaction. Metal salts of Group 2 of the periodic table (excluding calcium and cadmium) have an excellent effect of inhibiting the dehydrochlorination reaction caused by benzotriazoles, and have the characteristic that they do not inhibit the discoloration prevention effect on copper.
本発明において周期律表第２族の金属のうちカルシウム
とカドミウムを除いているが、これらの塩類は既にポリ
塩化ビニル樹脂の安定剤として使用されているものであ
り、また増量剤として使用されているものであって、ベ
ンゾトリアゾール類による脱塩酸反応を阻止する効果を
見出すことができなかった。これらの２元素が脱塩酸反
応の阻止に有効でない理由を理論的に説明することは困
這である。が、ベンゾトリアゾール単独とほぼ同じ程度
の脱塩酸反応が進行するのである。In the present invention, calcium and cadmium are excluded from the metals in Group 2 of the periodic table, but these salts have already been used as stabilizers for polyvinyl chloride resin, and have not been used as fillers. However, no effect of inhibiting the dehydrochlorination reaction by benzotriazoles could be found. It is difficult to theoretically explain why these two elements are not effective in inhibiting the dehydrochlorination reaction. However, the dehydrochlorination reaction proceeds to approximately the same extent as with benzotriazole alone.
本発明において使用しうるベンゾトリアゾール類として
は、ベンゾトリアゾール、メチルベンゾトリアゾール、
エチルベンゾトリアゾール、ドデシルベンゾトリアゾー
ル、クロルベンゾトリアゾール、カルボキシベンゾトリ
アゾールなどを挙げることができる。ベンゾトリアゾー
ル類の周期律表第２族の金属塩類としては、該ベンゾト
リアゾール類のマグネシウム塩、亜鉛塩、バリウム塩。Examples of benzotriazoles that can be used in the present invention include benzotriazole, methylbenzotriazole,
Examples include ethylbenzotriazole, dodecylbenzotriazole, chlorbenzotriazole, carboxybenzotriazole, and the like. Examples of metal salts of Group 2 of the periodic table of benzotriazoles include magnesium salts, zinc salts, and barium salts of the benzotriazoles.
ベリリウム塩、ストロンチウム塩、などが挙げられる０
周期律表第２族の金属を含む化合物としては、酸化ベリ
リウム、酸化マグネシウム、酸化亜鉛、酸化ストロンチ
ウム、酸化バリウム、水酸化マグネシウム、水酸化亜鉛
、水酸化バリウム、塩基性炭酸マグネシウム、炭酸亜鉛
、炭酸ストロンチウム、炭酸バリウム、塩化マグネシウ
ム、塩化亜鉛、塩化ストロンチウム、塩化バリウム、硫
酸マグネシウム、硫酸亜鉛、硫酸ストロンチウム。Beryllium salts, strontium salts, etc.0
Compounds containing metals from Group 2 of the periodic table include beryllium oxide, magnesium oxide, zinc oxide, strontium oxide, barium oxide, magnesium hydroxide, zinc hydroxide, barium hydroxide, basic magnesium carbonate, zinc carbonate, and carbonic acid. Strontium, barium carbonate, magnesium chloride, zinc chloride, strontium chloride, barium chloride, magnesium sulfate, zinc sulfate, strontium sulfate.
硫酸バリウム、ステアリン酸マグネシウム、ステアリン
酸亜鉛、ステアリン酸バリウムなどを挙げることができ
る。Examples include barium sulfate, magnesium stearate, zinc stearate, barium stearate, and the like.
本発明の銅系金属の変色腐食防止組成物はポリ塩化ビニ
ル樹脂用として使用されている鉛系安定剤、有機スズ系
安定剤、カドミウム系安定剤等と併用して使用した場合
特に効果が著しいが、樹脂と混練する場合、可塑剤、添
加剤、フィラー、安定剤等と別に添加しても、また、予
めこれらの内の１種または２種以上のものと混合して加
えても良い。The composition for preventing discoloration and corrosion of copper-based metals of the present invention is particularly effective when used in combination with lead-based stabilizers, organotin-based stabilizers, cadmium-based stabilizers, etc. used for polyvinyl chloride resins. However, when kneading with a resin, it may be added separately from plasticizers, additives, fillers, stabilizers, etc., or it may be added in advance by mixing with one or more of these.
以下実施例をもって本発明を具体的に説明するがこれに
よって本発明が限定されるものではない。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.
実施例１゜
三井東圧■製のポリ塩化ビニル樹脂ビニクロン４０００
Ｍ３ （重合度１３００）１００部、ジオクチシフタレ
−６９０部、焼成りシー５部、沈降性炭酸カルシウム４
５部、三塩基性硫酸鉛５部。Example 1 Polyvinyl chloride resin Vinicron 4000 manufactured by Mitsui Toatsu ■
100 parts of M3 (degree of polymerization 1300), 690 parts of diocticephthalate, 5 parts of calcined sea, 4 parts of precipitated calcium carbonate
5 parts tribasic lead sulfate.
及び本発明に係る銅系金属の変色腐食防止組成物の所定
量を乳鉢で充分混合し、１６０〜１７０’Ｃに加熱した
２本ロールで１０分間混練して、厚さ２ＩＩＩＩｌのシ
ートとした。該軟質ポリ塩化ビニル樹脂シートを５Ｉ角
に切断して、１８０部２℃のオイルバスの中に浸漬した
ガラス製試験管内にいれ、ｐＨ試験紙で試験管上部より
塩酸ガスが発生するまでの時間を測定し、分解開始時間
とした。また、ＩＮ塩酸に６０秒浸漬した後水洗し、メ
タノールで洗浄して乾燥した銅板試験片に該軟質ポリ塩
化ビニル樹脂シートを圧着し、７０部２℃に設定した乾
燥器内で１時間加熱後、該樹脂シートを剥離した。該銅
板試験片を２５部１℃でｌｏｐｐｍの硫化水素を含む雰
囲気中及びｌ１０ＰＰのアンモニアガスを含む雰囲気中
に２４時間放置し、各々の変色度合を観察した結果を表
１に示す、尚１表１の数値は、ＪＩＳ Ｋ ２５１
３の銅板腐食分類表によった。A predetermined amount of the composition for preventing discoloration and corrosion of copper-based metals according to the present invention was thoroughly mixed in a mortar and kneaded for 10 minutes using two rolls heated to 160 to 170'C to form a sheet with a thickness of 2IIIl. Cut the soft polyvinyl chloride resin sheet into 5I square pieces, place 180 parts in a glass test tube immersed in an oil bath at 2°C, and measure the time until hydrochloric acid gas is generated from the top of the test tube using pH test paper. was measured and taken as the decomposition start time. In addition, the soft polyvinyl chloride resin sheet was crimped onto a copper plate test piece that had been immersed in IN hydrochloric acid for 60 seconds, washed with water, washed with methanol and dried, and heated in a dryer set at 2°C for 1 hour. , the resin sheet was peeled off. 25 parts of the copper plate test piece were left for 24 hours at 1°C in an atmosphere containing loppm of hydrogen sulfide and an atmosphere containing 110PP of ammonia gas, and the degree of discoloration of each was observed. The results are shown in Table 1. The value of 1 is JIS K 251
According to the copper plate corrosion classification table 3.
実施例（１）から（１３）で明らかなごとく、本発明品
を添加することにより安定でしかも銅系金属に対し優れ
た変色腐食防止性を持つポリ塩化ビニル樹脂が得られる
ことが判明した。As is clear from Examples (1) to (13), it was found that by adding the product of the present invention, a polyvinyl chloride resin that is stable and has excellent discoloration and corrosion prevention properties against copper-based metals can be obtained.
Claims (1)
８のアルキル基、ハロゲン原子、あるいはカルボキシル
基を示す、）で表されるベンゾトリアゾール類の周期律
表第２族（カルシウム及びカドミウムを除く）の金属か
ら選ばれた１種ないし２種以上の金属塩もしくは該ベン
ゾトリアゾール類と周期律表第２族（カルシウム及びカ
ドミウムを除く）の金属を含む化合物（酸化物、水酸化
物、硫酸塩、炭酸塩、硝酸塩、塩化物、カルボン酸塩、
あるいはスルホン酸塩）の１種ないし２種以上とをポリ
塩化ビニル樹脂に混練してなる銅系金属の変色腐食防止
組成物。[Claims] [1] Formula; R_1 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula; R_1 to R_4 are each hydrogen, C_1 to C_1_
One or more metals selected from Group 2 metals of the periodic table (excluding calcium and cadmium) of benzotriazoles represented by 8 alkyl groups, halogen atoms, or carboxyl groups Salts or compounds containing the benzotriazoles and metals of Group 2 of the periodic table (excluding calcium and cadmium) (oxides, hydroxides, sulfates, carbonates, nitrates, chlorides, carboxylates,
A composition for preventing discoloration and corrosion of copper-based metals, which is prepared by kneading one or more types of sulfonate or sulfonate salts into a polyvinyl chloride resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20627386A JPS6361061A (en) | 1986-09-01 | 1986-09-01 | Composition for preventing color change and corrosion of copper metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20627386A JPS6361061A (en) | 1986-09-01 | 1986-09-01 | Composition for preventing color change and corrosion of copper metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6361061A true JPS6361061A (en) | 1988-03-17 |
Family
ID=16520593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20627386A Pending JPS6361061A (en) | 1986-09-01 | 1986-09-01 | Composition for preventing color change and corrosion of copper metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6361061A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007037045A1 (en) * | 2005-09-28 | 2007-04-05 | Chubu Chelest Co., Ltd. | Metal rust preventive compound powder, process for producing the same, composition for metal rust prevention and film for metal rust prevention |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56147839A (en) * | 1980-04-18 | 1981-11-17 | Adeka Argus Chem Co Ltd | Flexible polyvinyl chloride resin composition |
-
1986
- 1986-09-01 JP JP20627386A patent/JPS6361061A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56147839A (en) * | 1980-04-18 | 1981-11-17 | Adeka Argus Chem Co Ltd | Flexible polyvinyl chloride resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007037045A1 (en) * | 2005-09-28 | 2007-04-05 | Chubu Chelest Co., Ltd. | Metal rust preventive compound powder, process for producing the same, composition for metal rust prevention and film for metal rust prevention |
| JP5124738B2 (en) * | 2005-09-28 | 2013-01-23 | 中部キレスト株式会社 | Metal rust preventive compound powder and its production method, metal rust preventive composition and metal rust preventive film |
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