JPH04117481A - Antifreeze - Google Patents
AntifreezeInfo
- Publication number
- JPH04117481A JPH04117481A JP2269049A JP26904990A JPH04117481A JP H04117481 A JPH04117481 A JP H04117481A JP 2269049 A JP2269049 A JP 2269049A JP 26904990 A JP26904990 A JP 26904990A JP H04117481 A JPH04117481 A JP H04117481A
- Authority
- JP
- Japan
- Prior art keywords
- antifreeze
- alkali metal
- acid
- sebacic acid
- corrosion
- 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.)
- Granted
Links
- 230000002528 anti-freeze Effects 0.000 title claims abstract description 30
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 52
- -1 amine salt Chemical class 0.000 claims abstract description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 25
- 150000003852 triazoles Chemical class 0.000 claims abstract description 7
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 6
- 150000002826 nitrites Chemical class 0.000 claims description 6
- 150000004760 silicates Chemical class 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 40
- 239000008233 hard water Substances 0.000 abstract description 27
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract description 9
- 230000000711 cancerogenic effect Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 abstract 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 231100000357 carcinogen Toxicity 0.000 abstract 1
- 239000003183 carcinogenic agent Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 238000005536 corrosion prevention Methods 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 239000012964 benzotriazole Substances 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 235000011118 potassium hydroxide Nutrition 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 231100000315 carcinogenic Toxicity 0.000 description 4
- 150000004005 nitrosamines Chemical class 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000192700 Cyanobacteria Species 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 3
- 235000010234 sodium benzoate Nutrition 0.000 description 3
- 239000004299 sodium benzoate Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- SMNNDVUKAKPGDD-UHFFFAOYSA-N 2-butylbenzoic acid Chemical compound CCCCC1=CC=CC=C1C(O)=O SMNNDVUKAKPGDD-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- NCXUIEDQTCQZRK-UHFFFAOYSA-L disodium;decanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCCCC([O-])=O NCXUIEDQTCQZRK-UHFFFAOYSA-L 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- VLDHWMAJBNWALQ-UHFFFAOYSA-N sodium;3h-1,3-benzothiazole-2-thione Chemical compound [Na+].C1=CC=C2SC(S)=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000511343 Chondrostoma nasus Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、主に内燃機間の冷却液に使用される不凍液に
関し、詳細には冷却系統の金属の腐食防止機能に優れ、
かつ硬度の高い硬水に対しても極めて安定な不凍液に関
する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antifreeze liquid mainly used as a coolant between internal combustion engines.
The present invention also relates to an antifreeze solution that is extremely stable even in highly hard water.
（従来の技術）
従来より、主に内燃機間の冷却液に使用される不凍液は
、グリコール類を主成分とし、これに前記冷却系統の金
属の腐食防止機能を有する種々の腐食防止剤が混合され
て成るものであった。(Prior Art) Conventionally, antifreeze fluid, which is mainly used as a coolant between internal combustion engines, has glycols as its main component, and various corrosion inhibitors that have the function of preventing corrosion of metals in the cooling system are mixed with this. It consisted of
その代表的な不凍液としては、英国規格Ｂ５３１５０が
挙げられ、これはエチレングリコールを主成分とし、こ
れに腐食防止剤としてリン酸アミン塩及びメルカプトベ
ンゾチアゾールのナトリウム塩を含有するというもので
あった。A typical antifreeze solution is British Standard B53150, which contains ethylene glycol as a main component and contains phosphoric acid amine salt and mercaptobenzothiazole sodium salt as corrosion inhibitors.
ところがこの場合、腐食防止剤として採用されているア
ミン塩は、亜硝酸塩と反応して発ガン性物質であるニト
ロソアミンを生成し易いという欠点があった。However, in this case, the amine salt employed as a corrosion inhibitor has the disadvantage that it easily reacts with nitrite to produce nitrosamines, which are carcinogenic substances.
上記の欠点に鑑み、アミン塩以外の腐食防止剤として、
リン酸塩、ケイ酸塩、ホウ酸塩、亜硝酸塩が採用された
が、これらを採用した従来のものは、発ガン性物質であ
るニトロソアミンを生成するという欠点は解消するもの
の、以下の欠点があった。In view of the above drawbacks, as a corrosion inhibitor other than amine salts,
Phosphates, silicates, borates, and nitrites have been adopted, but although conventional methods that use these eliminate the disadvantage of producing nitrosamines, which are carcinogenic substances, they have the following disadvantages: there were.
まずリン酸塩は、
■河川等に流入すると、富栄養化により、藻類の繁殖を
促進し、アオコや赤潮の発生等公害の原因となる。First, when phosphates flow into rivers, etc., they cause eutrophication, which promotes the growth of algae and causes pollution such as blue-green algae and red tide.
■冷却液中等に含まれる硬水成分と反応し、沈澱物を生
成する。従って腐食防止機能が低下するばかりでなく、
この沈澱物の堆積により、冷却系統の循環路等が閉塞し
てトラブルが発生する。■Reacts with hard water components contained in coolant, etc., and forms precipitates. Therefore, not only the corrosion prevention function is reduced, but also
The accumulation of this sediment clogs the circulation path of the cooling system, causing trouble.
次にケイ酸塩は、液中での安定性に劣り、熱やｐＨが変
化した場合、或いは他の塩類が共存すると容易にゲル化
し易く、これにより腐食防止機能が低下する。Next, silicates have poor stability in liquids and are easily gelled when heat or pH changes, or when other salts coexist, thereby reducing their corrosion prevention function.
次にホウ酸塩は、特にアルミニウム又はその合金を腐食
させる傾向にある。Borate salts, in turn, are particularly prone to corrode aluminum or its alloys.
そして亜硝酸塩は、消耗が速いので、その分腐食防止機
能も速く低下する。Since nitrite is rapidly consumed, its anti-corrosion function also deteriorates rapidly.
また、上記従来の欠点の中で、特に■に挙げである硬水
に対して安定性に欠けるという問題は、図に示す如く、
世界的に硬度（ｐｐｍ）の高い硬水を不凍液の希釈水と
して使用する国が多いという現状においては重大であっ
た。In addition, among the above-mentioned conventional drawbacks, especially the problem of lack of stability against hard water, which is listed in (①), is as shown in the figure.
This was a serious problem in the current situation where many countries around the world use hard water with high hardness (ppm) as dilution water for antifreeze.
そこで、硬水に対する安定性を向上させるものとして、
炭素数が７〜１４の２種のジカルボン酸を含むという特
開平２−１８２７８２号公報記載の「腐食防止剤として
ジカルボン酸混合物を含む熱媒液」が提案されている。Therefore, to improve stability against hard water,
``Heating medium liquid containing a dicarboxylic acid mixture as a corrosion inhibitor'' described in JP-A-2-182782 has been proposed, which contains two types of dicarboxylic acids having 7 to 14 carbon atoms.
（発明が解決しようとする課題）
しかしながら、上記特開平２−１８２７８２号公報記載
の「腐食防止剤としてジカルボン酸混合物を含む熱媒液
」は、ある程度は硬水に対する安定性を向上させるもの
の、硬度の高い硬水に対しては不十分であった。(Problems to be Solved by the Invention) However, although the "thermal fluid containing a dicarboxylic acid mixture as a corrosion inhibitor" described in JP-A-2-182782 improves the stability against hard water to some extent, It was insufficient for highly hard water.
そこで案出されたのが本発明であり、その目的とすると
ころは、従来のリン酸塩、アミン塩、ケイ酸塩、ホウ酸
塩、及び亜硝酸塩から成る腐食防止剤を採用せず、主に
冷却系統の金属の腐食防止機能に優れ、かつ硬度の高い
硬水に対しても極めて安定な不凍液を提供することにあ
る。Therefore, the present invention was devised, and its purpose is to eliminate the use of conventional corrosion inhibitors consisting of phosphates, amine salts, silicates, borates, and nitrites, and to The purpose of the present invention is to provide an antifreeze solution that has an excellent function of preventing corrosion of metals in cooling systems and is extremely stable even in highly hard water.
（課題を解決するための手段）
上記の目的を達成するために本発明の採った手段につい
て、以下に説明する。(Means for Solving the Problems) The means taken by the present invention to achieve the above object will be explained below.
すなわち、本発明に係る不凍液の構成は、「グリコール
類を主成分とし、成分中にリン酸塩、アミン塩、ケイ酸
塩、ホウ酸塩及び亜硝酸塩を含有しない不凍液であって
、
セバシン酸又はそのアルカリ金属塩のうち少なくとも１
を０．５〜４． ０ｗｔ％、ｐ−ｔｅｒｔブチル安息香
酸又はそのアルカリ金属塩のうち少なくとも１ｅ０．
５〜３． ０ｗｔ％、トリアゾール類を０．０５〜１−
０ｗｔ％の範囲で含有していることを特徴とする不凍
液」
を内容とする。In other words, the composition of the antifreeze solution according to the present invention is "an antifreeze solution that contains glycols as a main component and does not contain phosphates, amine salts, silicates, borates, or nitrites, and contains sebacic acid or At least one of its alkali metal salts
0.5 to 4. 0 wt%, at least 1e0 of p-tertbutylbenzoic acid or its alkali metal salt.
5-3. 0 wt%, triazoles 0.05-1-
"An antifreeze containing 0wt%."
（発明の作用）
上記手段により、本発明に係る不凍液については、
まず、主成分のグリコール類は、冷却液等の凝固点を降
下させる。(Action of the Invention) According to the above-mentioned means, in the antifreeze according to the present invention, first, the glycols as the main components lower the freezing point of the cooling liquid, etc.
次に、セバシン酸又はそのアルカリ金属塩は、冷却系統
の金属、特に鉄又はアルミニウムを成分とする金属の腐
食を防止する。さらには冷却液中等に含まれる硬水成分
を溶解させるので、この硬水成分と不凍液に含有する成
分とによる沈澱物の生成を抑制する。Second, sebacic acid or its alkali metal salts prevent corrosion of metals in the cooling system, especially metals containing iron or aluminum. Furthermore, since the hard water component contained in the coolant and the like is dissolved, the formation of precipitates due to the hard water component and the components contained in the antifreeze solution is suppressed.
前記セバシン酸又はそのアルカリ金属塩のうち少なくと
も１の含有量を、０．５〜４． ０ｗｔ％の範囲に限定
しているのは以下の理由による。The content of at least one of the sebacic acid or its alkali metal salt is 0.5 to 4. The reason why the content is limited to 0 wt% is as follows.
つまり、０− ５ｗｔ％未満では十分な腐食防止機能が
得られず、また４、 ０ｗｔ％を越えて含有していて
も腐食防止機能はあまり向上しないばかりか、かえって
硬水に対する安定性に悪影響を及ぼす可能性があるから
である。In other words, if the content is less than 0-5 wt%, sufficient corrosion prevention function cannot be obtained, and if the content exceeds 4.0 wt%, the corrosion prevention function will not improve much, and on the contrary, it will have a negative effect on the stability against hard water. This is because there is a possibility.
次に、ｐ−ｔｅｒｔブチル安息香酸又はそのアルカリ金
属塩は、セバシン酸又はそのアルカリ金属塩と少量だけ
共存させることにより、セバシン酸又はそのアルカリ金
属塩を単独で使用した場合に比へて著しく腐食防止機能
を向上させると共に、硬水成分との沈澱物の生成を極め
て有効に抑制する。Next, when p-tert-butylbenzoic acid or its alkali metal salt coexists with sebacic acid or its alkali metal salt in a small amount, the corrosion is significantly greater than when sebacic acid or its alkali metal salt is used alone. It improves the prevention function and extremely effectively suppresses the formation of precipitates with hard water components.
前記ｐ−ｔｅｒｔブチル安息香酸又はそのアルカリ金属
塩のうち少なくとも１の含有量を、０．５〜３． ０ｗ
ｔ％の範囲に限定しているのは以下の理由による。The content of at least one of the p-tertbutylbenzoic acid or its alkali metal salt is 0.5 to 3. 0w
The reason why the range is limited to t% is as follows.
つまり、０． ５ｗｔ％未満では共存するセバシン酸又
はそのアルカリ金属塩の含有量を、あまり減少させるこ
とができず、従って、硬水に対する安定性の面から不都
合である。また共存するセバシン酸又はそのアルカリ金
属塩の腐食防止機能に有効な含有量は、上記のように決
まっているので、ｐ−ｔｅｒｔブチル安息香酸又はその
アルカリ金属塩の含有量が３． ０ｗｔ％を越えて含有
していても、セバシン酸又はそのアルカリ金属塩の含有
量をそれ以下にすることができないばかりか経済的にも
無駄だからである。In other words, 0. If it is less than 5 wt%, the content of coexisting sebacic acid or its alkali metal salt cannot be significantly reduced, which is disadvantageous in terms of stability against hard water. Furthermore, since the effective content of coexisting sebacic acid or its alkali metal salt for corrosion prevention function is determined as described above, the content of p-tertbutylbenzoic acid or its alkali metal salt is 3. This is because even if the content exceeds 0 wt%, it is not only impossible to reduce the content of sebacic acid or its alkali metal salt to less than that, but it is also economically wasteful.
なお、セバシン酸、ｐ−ｔｅｒｔブチル安息香酸は、各
々単独でも金属の腐食防止機能を有するが、これらのア
ルカリ金属塩にもその機能がある。従って予め不凍液成
分中に、セバシン酸、ｐ−ｔｅｒｔブチル安息香酸の各
々のアルカリ金属塩を含有させておいても良い。或いは
、セバシン酸、ｐ−ｔｅｒｔブチル安息香酸は、Ｎａ。Incidentally, sebacic acid and p-tert-butylbenzoic acid each have a function of preventing corrosion of metals by themselves, but their alkali metal salts also have this function. Therefore, each of the alkali metal salts of sebacic acid and p-tert-butylbenzoic acid may be included in the antifreeze component in advance. Alternatively, sebacic acid and p-tertbutylbenzoic acid are Na.
Ｋ、Ｌｉ等のアルカリ金属成分の存在下において、各々
のアルカリ金属塩を生成することは当然に予測されるこ
とであり、前記アルカリ金属成分の存在下に、セバシン
酸、ｐ−ｔｅｒｔブチル安息香酸を含有させても良い。It is naturally expected that in the presence of alkali metal components such as K and Li, respective alkali metal salts will be produced. may be included.
そして、トリアゾール類は、冷却系統の金属、特に銅及
びアルミニウムを成分とする金属の腐食を防止する。Triazoles also prevent corrosion of metals in the cooling system, particularly metals containing copper and aluminum.
前記トリアゾール類の含有量を、０．０５〜１、 ０ｗ
ｔ％の範囲に限定しであるのは、以下の理由による。The content of the triazoles is 0.05 to 1,0w
The reason why the range is limited to t% is as follows.
つまり０． ０５ｗｔ％５ｗｔ％未満な腐食防止機能が
発現できず、また１、０冒ｔ％を越えて含有していても
腐食防止機能はあまり向上せず、経済的にも無駄だから
である。In other words, 0. This is because if the content is less than 1.0 wt%, the corrosion prevention function cannot be achieved, and if the content exceeds 1.0 wt%, the corrosion prevention function will not improve much and it is economically wasteful.
またミ 本発明に係る不凍液は、
アミン塩及び亜硝酸塩を含有していないので、発ガン性
物質であるニトロソアミンを生成しない。Furthermore, since the antifreeze solution according to the present invention does not contain amine salts or nitrites, it does not produce nitrosamines, which are carcinogenic substances.
次に、リン酸塩を含有していないので、河川等に流人し
てもアオコや赤潮の発生による公害の心配がなく、また
冷却液中等に含まれる硬水成分とによる沈澱物を生成し
ない。Secondly, since it does not contain phosphates, there is no concern about pollution caused by blue-green algae or red tide even if people are carried away into rivers, etc., and it does not form precipitates due to hard water components contained in coolant and the like.
次に、ケイ酸塩を含有していないので、他の塩類が共存
してもゲル化しない。Secondly, since it does not contain silicate, it will not gel even if other salts coexist.
そして、ホウ酸塩を含有していないので、冷却系統のア
ルミニウム成分を腐食させない。And since it does not contain borate, it will not corrode the aluminum components of the cooling system.
（実施例）
以下表１．３．５及び７について本実施例を詳細に説明
するが、これは代表的なものを示したものであり、本実
施例によって本発明が限定されるものではない。(Example) This example will be explained in detail with reference to Tables 1.3.5 and 7 below, but these are representative examples and the present invention is not limited to this example. .
まず、本発明に係る実施例は１〜６とし、その構成を表
１に示す。First, Examples 1 to 6 according to the present invention are shown in Table 1.
前記表１中の実施例１及び２は、エチレングリコール、
セバシン酸、ｐ−ｔｅｒｔブチル安息香酸、ベンゾトリ
アゾール、苛性カリ、水より構成しである。次に実施例
３は、エチレングリコール、セバシン酸、ｐ−ｔｅｒｔ
ブチル安患香酸、安息香酸ナトリウムＪベンゾトリアゾ
ール、苛性カリ、水より構成しである。次に実施例４は
、エチレングリコール、セバシン酸、ｐ−ｔｅｒｔブチ
ル安患香酸、トリルトリアゾール、苛性カリ、水より構
成しである。次に実施例５は、エチレングリコール、セ
バシン酸、ｐ−ｔｅｒｔブチル安息香酸、ベンゾトリア
ゾール、硝酸ナトリウム、苛性カリ、水より構成しであ
る。そして実施例６は、エチレングリコール、セバシン
酸、ｐ−ｔｅｒｔブチル安息香酸、安息香酸ナトリウム
、ベンゾトリアゾール、硝酸ナトリウム、モリブデン酸
ナトリウム、苛性カリ、水より構成しである。Examples 1 and 2 in Table 1 above contain ethylene glycol,
It is composed of sebacic acid, p-tert-butylbenzoic acid, benzotriazole, caustic potash, and water. Next, in Example 3, ethylene glycol, sebacic acid, p-tert
It consists of butyl benzoic acid, sodium benzoate, J-benzotriazole, caustic potash, and water. Next, Example 4 was composed of ethylene glycol, sebacic acid, p-tert-butyl benzoic acid, tolyltriazole, caustic potash, and water. Next, Example 5 was composed of ethylene glycol, sebacic acid, p-tert-butylbenzoic acid, benzotriazole, sodium nitrate, caustic potassium, and water. Example 6 is composed of ethylene glycol, sebacic acid, p-tert-butylbenzoic acid, sodium benzoate, benzotriazole, sodium nitrate, sodium molybdate, caustic potassium, and water.
なお、本発明に係る不凍液は、前記の成分以外に消泡剤
、着色剤等を含有していても良いし、他の従来公知の腐
食防止剤であるタングステン酸塩、硫酸塩等を併用して
も良い。In addition, the antifreeze according to the present invention may contain antifoaming agents, colorants, etc. in addition to the above-mentioned components, and may also contain other conventionally known corrosion inhibitors such as tungstates and sulfates. It's okay.
次に比較例は７〜９、従来例は１０〜１３とし、その構
成を表２に示す。Next, comparative examples are numbered 7 to 9, and conventional examples are numbered 10 to 13, and their configurations are shown in Table 2.
この比較例７及び８は、エチレングリコール、セバシン
酸、ｐ−ｔｅｒｔブチル安息香酸、ベンゾトリアゾール
、苛性カリ、水より構成しである。Comparative Examples 7 and 8 were composed of ethylene glycol, sebacic acid, p-tert-butylbenzoic acid, benzotriazole, caustic potash, and water.
そして比較例９は、エチレングリコール、セバシン酸ナ
トリウム、ｐ−ｔｅｒｔブチル安息香酸、ヘンシトリア
ゾール、苛性カリ、水より構成しである。Comparative Example 9 was composed of ethylene glycol, sodium sebacate, p-tert-butylbenzoic acid, hensitriazole, caustic potash, and water.
また、従来例１０は、エチレングリコール、セバシン酸
、ドデカンニ酸、ベンゾトリアゾール、苛性カリ、水よ
り構成されている。次に従来例１１は、エチレングリコ
ール、セバシン酸ナトリウム、ベンゾトリアゾール、水
より構成されている。次に従来例１２は、エチレングリ
コール、硝酸ナトリウム、トリエタノールアミン、オル
トリン酸、メルカプトベンゾチアゾールナトリウム塩、
水より構成されている。そして従来例１３は、エチレン
グリコール、安息香酸ナトリウム、トリルトリアゾール
、硝酸ナトリウム１、メタケイ酸ナトリウム（９水塩）
、亜硝酸ナトリウム、ホウ砂（１０水塩）、水より構成
されている。Furthermore, Conventional Example 10 is composed of ethylene glycol, sebacic acid, dodecanoic acid, benzotriazole, caustic potash, and water. Next, Conventional Example 11 was composed of ethylene glycol, sodium sebacate, benzotriazole, and water. Next, Conventional Example 12 contains ethylene glycol, sodium nitrate, triethanolamine, orthophosphoric acid, mercaptobenzothiazole sodium salt,
It is composed of water. Conventional Example 13 contains ethylene glycol, sodium benzoate, tolyltriazole, sodium nitrate 1, and sodium metasilicate (nase hydrate).
, sodium nitrite, borax (decahydrate), and water.
このようにして得られた、実施例１〜６、比較例７〜９
及び従来例１０〜１３について、以下の試験Ａ−Ｃを行
ったところ、試験Ａについては表３及び表４、試験Ｂに
ついては表５及び表６、そして試験Ｃについては表７及
び表８の結果が各々得られた。Examples 1 to 6 and Comparative Examples 7 to 9 thus obtained
The following tests A-C were conducted for Conventional Examples 10 to 13, and the results were as follows: Tables 3 and 4 for test A, Tables 5 and 6 for test B, and Tables 7 and 8 for test C. Results were obtained for each.
但し、この試験については、以下の方法を採用した。However, for this test, the following method was adopted.
まず試験Ａについては、硬水に対する安定性を確認する
ための試験であって、この試験に供する各不凍液は、イ
オン交換水にＣａ２′″が４００ｐｐ−となるようにＣ
ａＣｌ２２ を添加した硬水（ＣａＣＯ３として全硬度
１０１０００ｐｐにより５０ｖｏ１％に希釈した。First, test A is a test to confirm stability against hard water, and each antifreeze solution used in this test was prepared by adding carbon to the ion-exchanged water so that Ca2'" was 400 pp-.
Diluted to 50vol% with hard water (total hardness 101000pp as CaCO3) supplemented with aCl22.
そしてこの希釈液を室温で暗所に２４ｈｒ放置し、沈澱
量ｖｏｌ ％を測定した。Then, this diluted solution was allowed to stand in a dark place at room temperature for 24 hours, and the amount of precipitate (vol%) was measured.
次に試験Ｂについては、アルミニウムに対する腐食防止
機能の確認試験であって、ＡＳＴＭ Ｄ４３４０−８
４ （Ｃｏｒｒｏｓｉｏｎ ｏｆ Ｃａ５ｔ Ａｌｕｍ
ｉｎｕｍＡｌｌｏｙｓ ｉｎ Ｅｎ３ｉｎｅ Ｃ
ｏｏｌａｎｔｓ Ｕｎｄｅｒ Ｈｅａｔ−Ｒｅｊｅ
ｃｔ−ｎ３ Ｃｏｎｄｉｔｉｏｎｓ）に規定されている
アルミニウム合金熱交換面腐食試験により行った。また
この試験Ｂには、表９の試験条件を採用した。Next, Test B is a confirmation test for corrosion prevention function against aluminum, and is based on ASTM D4340-8.
4 (Corrosion of Ca5t Alum
inumAlloys in En3ine C
oolants Under Heat-Reje
The test was carried out using an aluminum alloy heat exchange surface corrosion test specified in ct-n3 Conditions). Further, for this test B, the test conditions shown in Table 9 were adopted.
次に試験Ｃについては、Ｊ ｌ５Ｋ２２３４−１９８７
（不凍液）の７・４項に規定されている金属に対する腐
食防止機能の確認試験であって、試験に供する不凍液は
、調合水（ＩＮの水にＮａ２Ｓ Ｏａを１４８ｍｇ、Ｎ
ａＣ３ｉを１６５ｍｇ、ＮａＨＣＯ３を１３８ｅｎｇ各
々溶解したもの）にて３０ｖｏ１％に希釈したものを採
用し、試験に供する金属には、アルミニウム鋳物、鋳鉄
、鋼、黄銅、はんだ、銅の試験片を各々採用した。Next, for test C, J l5K2234-1987
(Antifreeze) This is a confirmation test for the corrosion prevention function for metals specified in Section 7.4, and the antifreeze used for the test is mixed water (IN water with 148 mg of Na2S Oa, N
165 mg of aC3i and 138 eng of NaHCO3 were diluted to 30 vol 1% with 165 mg of aC3i and 138 eng of NaHCO3, respectively, and test pieces of aluminum casting, cast iron, steel, brass, solder, and copper were used as the metals to be tested. .
（以下余白）
表
上記表３より明らかなように、実施例１〜６は、硬度の
高い硬水に対する安定性に極めて優れ、かつ表７より明
らかなように、アルミニウム鋳物、鋳鉄、鋼、黄銅、は
んだ、鋼のいずれの金属に対しても腐食防止機能に優れ
、さらには表５より明らかなように腐食速度が遅く、ア
ルミニウムに対する腐食防止機能に優れることがわかる
。(Leaving space below) Table As is clear from Table 3 above, Examples 1 to 6 have excellent stability against highly hard water, and as is clear from Table 7, aluminum casting, cast iron, steel, brass, It has an excellent corrosion prevention function against both metals, solder and steel, and furthermore, as is clear from Table 5, the corrosion rate is slow, indicating that it has an excellent corrosion prevention function against aluminum.
これに比へ比較例７は、表４より明らかなように硬水に
対する安定性には優れるものの、表６及び表８より明ら
かなように腐食防止機能に劣り、特にアルミニウム鋳物
については、試験片の外観において一部腐食が確認され
ると共に質量変化も顕著である。これは、比較例７はセ
バシン酸の含有量が少ないことに起因すると考えられる
。次に比較例８は、表４より明らかなように硬水に対す
る安定性には優れるものの、表６及び表８より明らかな
ように腐食防止機能に劣り、特に黄銅、はんだ及び銅の
試験片の質量変化が顕著である。これは、比較例８は、
ヘンシトリアゾールの含有量が少ないことに起因すると
考えられる
次に比較例９は表６及び表８より明らかなように腐食防
止機能にはある程度優れるものの、表４より明らかなよ
うに硬水に対する安定性に劣ることがわかる。これは、
比較例９はセバシン酸の含有量が多く、ｐ−ｔｅｒｔブ
チル安息香酸の含有量が少ないことに起因すると考えら
れる。In contrast, although Comparative Example 7 has excellent stability against hard water as shown in Table 4, it is inferior in corrosion prevention function as shown in Tables 6 and 8. Corrosion is confirmed in some parts of the exterior, and the change in mass is also significant. This is considered to be due to the fact that Comparative Example 7 had a low content of sebacic acid. Next, Comparative Example 8 has excellent stability against hard water as shown in Table 4, but as shown in Tables 6 and 8, it has poor corrosion prevention function, especially the weight of brass, solder, and copper test pieces. The change is noticeable. This means that Comparative Example 8 is
This is thought to be due to the low content of hensitriazole.Although Comparative Example 9 has a certain degree of excellent corrosion prevention function as shown in Tables 6 and 8, it has poor stability against hard water as shown in Table 4. I know it's inferior. this is,
This is thought to be due to the fact that Comparative Example 9 had a high content of sebacic acid and a low content of p-tert-butylbenzoic acid.
次に従来例１０は、表６及び表８より明らかなように腐
食防止機能には優れるものの、表４より明らかなように
硬水に対する安定性が不十分である。次に従来例１１及
び１２については、表６及び表８より明らかなように腐
食防止機能には優れるものの、表４より明らかなように
硬水に対する安定性に著しく劣っている。そして、従来
例１３は、表４より明らかなように硬水に対する安定性
には優れるものの、表６より明らかなように腐食防止機
能に劣っている。Next, Conventional Example 10 has an excellent corrosion prevention function as shown in Tables 6 and 8, but as shown in Table 4, its stability against hard water is insufficient. Next, as for Conventional Examples 11 and 12, as is clear from Tables 6 and 8, they are excellent in corrosion prevention function, but as is clear from Table 4, they are significantly inferior in stability against hard water. As shown in Table 4, Conventional Example 13 has excellent stability against hard water, but as shown in Table 6, it is inferior in corrosion prevention function.
（発明の効果）
以上説明した通り本発明に係る不凍液を採用すると、以
下の効果を奏する。(Effects of the Invention) As explained above, when the antifreeze solution according to the present invention is employed, the following effects are achieved.
つまり本発明に係る不凍液は、
「セバシン酸又はそのアルカリ金属塩のうち少なくとも
１を０．５〜４． ０ｗｔ％、ｐ−ｔｅｒｔブチル安息
香酸又はそのアルカリ金属塩のうち少なくともｌを０．
５〜３． Ｏｕｔ％、トリアゾール類を０．０５〜
１． ０ｗｔ％の範囲で含有する不凍液」により構成さ
れるので、
■金属の腐食防止機能に優れ、かつ硬度の高い硬水に対
して極めて安定である。従って、硬度の高い硬水を不凍
液の希釈水として使用しなければならない国等において
は特に有効と成る。In other words, the antifreeze according to the present invention contains 0.5 to 4.0 wt% of at least one of sebacic acid or an alkali metal salt thereof, and 0.5 to 4.0 wt% of at least one of p-tertbutylbenzoic acid or an alkali metal salt thereof.
5-3. Out%, triazoles from 0.05
1. Since it is composed of "antifreeze containing in the range of 0wt%," it has excellent corrosion prevention function for metals and is extremely stable against highly hard water. Therefore, it is particularly effective in countries where hard water with high hardness must be used as dilution water for antifreeze.
■セバシン酸又はそのアルカリ金属塩に、ｐ−ｔｅｒｔ
ブチル安息香酸又はそのアルカリ金属塩のうち少なくと
もｌを少量だけ共存させることにより、高価なセバシン
酸又はそのアルカリ金属塩の含有量を少量にすることが
でき、従って安価に提供できる。■P-tert in sebacic acid or its alkali metal salt
By allowing at least a small amount of butylbenzoic acid or its alkali metal salt to coexist, the content of expensive sebacic acid or its alkali metal salt can be reduced to a small amount, and therefore it can be provided at low cost.
また本発明に係る不凍液は、
成分中にリン酸塩、アミン塩、ケイ酸塩、ホウ酸塩及び
亜硝酸塩を含有しないので、
■発ガン性物質であるニトロソアミンを生成する心配が
ない。Furthermore, since the antifreeze solution according to the present invention does not contain phosphates, amine salts, silicates, borates, or nitrites, there is no need to worry about the formation of nitrosamines, which are carcinogenic substances.
■不凍液成分が河川等に流入しても、アオコや赤潮の発
生による公害の心配が少なく、また硬水成分と沈澱物を
生成せず、従って冷却系統に使用した場合に循環路等が
閉塞するようなトラブルを起こす心配がない。■Even if antifreeze components flow into rivers, etc., there is little concern about pollution due to blue-green algae or red tide, and they do not generate hard water components and sediments, so when used in cooling systems, they do not block circulation channels, etc. There is no need to worry about causing any trouble.
■他の塩類が共存してもゲル化せず、このゲル化による
腐食防止機能の低下の心配がない。■It does not gel even if other salts coexist, so there is no need to worry about a decline in corrosion prevention function due to gelation.
■アルミニウム又はその合金を腐食させない。■Do not corrode aluminum or its alloys.
図は北米、ヨーロッパ、オーストラリア、中近東、アジ
ア諸国、日本における水の全硬度を示すグラフである。
以
上The figure is a graph showing the total hardness of water in North America, Europe, Australia, the Middle East, Asian countries, and Japan. that's all
Claims (1)
塩、ケイ酸塩、ホウ酸塩及び亜硝酸塩を含有しない不凍
液であって、 セバシン酸又はそのアルカリ金属塩のうち少なくとも１
を０．５〜４．０ｗｔ％、ｐ−ｔｅｒｔブチル安息香酸
又はそのアルカリ金属塩のうち少なくとも１を０．５〜
３．０ｗｔ％、トリアゾール類を０．０５〜１．０ｗｔ
％の範囲で含有していることを特徴とする不凍液。[Scope of Claims] An antifreeze solution containing glycols as a main component and containing no phosphates, amine salts, silicates, borates, or nitrites, the antifreeze solution containing sebacic acid or its alkali metal salts. at least 1
0.5 to 4.0 wt%, and 0.5 to 4.0 wt% of at least one of p-tertbutylbenzoic acid or an alkali metal salt thereof.
3.0wt%, triazoles 0.05-1.0wt
An antifreeze solution characterized by containing within a range of %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269049A JP2772578B2 (en) | 1990-06-29 | 1990-10-05 | antifreeze |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17420290 | 1990-06-29 | ||
| JP2-174202 | 1990-06-29 | ||
| JP2269049A JP2772578B2 (en) | 1990-06-29 | 1990-10-05 | antifreeze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04117481A true JPH04117481A (en) | 1992-04-17 |
| JP2772578B2 JP2772578B2 (en) | 1998-07-02 |
Family
ID=26495901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2269049A Expired - Lifetime JP2772578B2 (en) | 1990-06-29 | 1990-10-05 | antifreeze |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2772578B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387360A (en) * | 1992-10-07 | 1995-02-07 | Ethylene Chemical Co., Ltd. | Engine antifreeze coolant composition |
| US5489391A (en) * | 1991-10-18 | 1996-02-06 | C C I Co. Ltd. | Coolant compositions with p-tert-butylbenzoic acid or salt |
| US5643493A (en) * | 1996-03-13 | 1997-07-01 | The Dow Chemical Company | Coolant inhibitor concentrate |
| EP0827996A1 (en) * | 1996-09-04 | 1998-03-11 | CCI Co. Limited | Cavitation damage inhibitive antifreeze/coolant composition |
| KR100241279B1 (en) * | 1997-08-30 | 2000-02-01 | 정몽규 | Hard water-resistant composition of antifreezing solution |
| WO2000022189A1 (en) * | 1998-10-14 | 2000-04-20 | Texaco Development Corporation | Corrosion inhibitors and synergistic inhibitor combinations for the protection of light metals in heat-transfer fluids and engine coolants |
| US7540974B2 (en) | 2004-10-25 | 2009-06-02 | Honda R&D Co, Ltd. | Antifreeze/coolant composition |
| US8187763B2 (en) | 2003-07-11 | 2012-05-29 | Honda Motor Co., Ltd. | Cooling liquid composition for fuel cell |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5044544B2 (en) * | 2006-03-31 | 2012-10-10 | シーシーアイ株式会社 | Coolant composition |
-
1990
- 1990-10-05 JP JP2269049A patent/JP2772578B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489391A (en) * | 1991-10-18 | 1996-02-06 | C C I Co. Ltd. | Coolant compositions with p-tert-butylbenzoic acid or salt |
| US5387360A (en) * | 1992-10-07 | 1995-02-07 | Ethylene Chemical Co., Ltd. | Engine antifreeze coolant composition |
| US5643493A (en) * | 1996-03-13 | 1997-07-01 | The Dow Chemical Company | Coolant inhibitor concentrate |
| EP0827996A1 (en) * | 1996-09-04 | 1998-03-11 | CCI Co. Limited | Cavitation damage inhibitive antifreeze/coolant composition |
| KR100241279B1 (en) * | 1997-08-30 | 2000-02-01 | 정몽규 | Hard water-resistant composition of antifreezing solution |
| WO2000022189A1 (en) * | 1998-10-14 | 2000-04-20 | Texaco Development Corporation | Corrosion inhibitors and synergistic inhibitor combinations for the protection of light metals in heat-transfer fluids and engine coolants |
| EP0995785A1 (en) * | 1998-10-14 | 2000-04-26 | Texaco Development Corporation | Corrosion inhibitors and synergistic inhibitor combinations for the protection of light metals in heat-transfer fluids and engine coolants |
| CZ301124B6 (en) * | 1998-10-14 | 2009-11-11 | Texaco Development Corporation | Corrosion inhibitors and synergistic combinations of inhibitors for protection of light metals in heat-exchange fluids and engine coolants |
| US8187763B2 (en) | 2003-07-11 | 2012-05-29 | Honda Motor Co., Ltd. | Cooling liquid composition for fuel cell |
| US7540974B2 (en) | 2004-10-25 | 2009-06-02 | Honda R&D Co, Ltd. | Antifreeze/coolant composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2772578B2 (en) | 1998-07-02 |
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