JP5062580B2 - Environment-friendly water-soluble rust additive composition - Google Patents
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Description
本発明は、地球環境に優しく、人類に対しより安全で、金属防錆性に優れた水溶性防錆（添加）剤に関する。 The present invention relates to a water-soluble rust preventive (additive) agent that is friendly to the global environment, safer for human beings, and excellent in metal rust preventive properties.
現在主流の水溶性防錆剤組成物は、有機アミン化合物（有機カルボン酸塩含む），有機硼素化合物（有機酸二量体と有機アミンと硼酸の反応生成物、アルカノールアミンと硼酸の反応生成物等），有機チオカルボン酸化合物（有機チオカルボン酸のアルカノールアミン塩等），有機スルホン酸化合物（有機スルホン酸のアルカリ金属塩及び有機アミン塩等），ホスホン酸化合物（ピロリン酸のアルカリ金属塩、リン酸塩等）と、たとえば下記の文献に示す様な、窒素（Ｎ），リン（Ｐ）及び硫黄（Ｓ）の少なくとも１つを含有する化合物で構成されている。更に詳しく説明すると以下の通りである。 Currently, the mainstream water-soluble rust preventive compositions are organic amine compounds (including organic carboxylates), organic boron compounds (reaction products of organic acid dimer, organic amine and boric acid, reaction products of alkanolamine and boric acid. ), Organic thiocarboxylic acid compounds (such as alkanolamine salts of organic thiocarboxylic acids), organic sulfonic acid compounds (such as alkali metal salts and organic amine salts of organic sulfonic acids), phosphonic acid compounds (alkali metal salts of pyrophosphoric acid, phosphoric acid, etc.) Salt) and a compound containing at least one of nitrogen (N), phosphorus (P) and sulfur (S) as shown in the following literature, for example. More detailed description is as follows.
アルカノールアミンと硼酸との脱水縮合物、及び水溶性有機酸とを含有する水溶性防錆剤が特許文献１に記載されている。またヒドロキシー２−ナフトエ酸からなる塩を含有する水溶性金属防錆剤が特許文献２に開示されている。特許文献３には、界面活性剤とカルボン酸塩又はスルホン酸塩とから成る水溶性防錆剤が、また特許文献４には、カルボン酸塩，高級アルキルアミン及び溶剤から成る水溶性防錆剤が記載されている。 Patent Document 1 discloses a water-soluble rust preventive containing a dehydration condensate of alkanolamine and boric acid and a water-soluble organic acid. Further, Patent Document 2 discloses a water-soluble metal rust preventive containing a salt composed of hydroxy-2-naphthoic acid. Patent Document 3 discloses a water-soluble rust inhibitor composed of a surfactant and a carboxylate or sulfonate, and Patent Document 4 discloses a water-soluble rust inhibitor composed of a carboxylate, a higher alkylamine and a solvent. Is described.
特許文献５には、カルボン酸塩とＮ−アシルアミノ酸又はその塩との併用による水溶性防錆剤が、特許文献６には変性ビスフェノールＡエポキシ樹脂又はその誘導体を含有する水性防錆剤が開示されている。 Patent Document 5 discloses a water-soluble rust inhibitor using a combination of a carboxylate and an N-acylamino acid or a salt thereof, and Patent Document 6 discloses an aqueous rust inhibitor containing a modified bisphenol A epoxy resin or a derivative thereof. Has been.
また、ベンゾチアゾリルチオカルボン酸化合物，アルカノールアミン及びモリブデン酸又はその塩から成る防錆剤が特許文献７に、アルキレンジアミン誘導体から成る防錆剤が特許文献８に、酸化α−オレフィン，ワックス類，有機スルホン酸ナトリウム塩，アミン及びグリコールエーテルから成る水溶性防錆剤が特許文献９に開示されている。
従来の様な窒素（Ｎ），リン（P），硫黄（S），ハロゲン（F、Ｃl、Ｂr）の少なくとも１種を含む化合物を配合した水溶性防錆（添加）剤組成物の使用は、地球環境に悪影響を及ぼし、環境破壊の一因を成している。即ち、
（イ） これらの組成物から成る防錆剤は金属の防錆に使用された後、廃水処理されて廃棄される。しかし、これらの廃液中には、まだ窒素，リン，硫黄，ハロゲンを含む化合物が含まれている。このため、これらが廃水系又は水域に廃棄されると、河川，湖沼，海等に於いて、富栄養化現象が起こり、藻やプランクトン等の異常発生により、水質汚濁や赤潮などの環境破壊を引き起こす。
Use of a water-soluble rust preventive (additive) composition containing a compound containing at least one of nitrogen (N), phosphorus (P), sulfur (S) and halogen (F, Cl, Br) as in the past , Adversely affecting the global environment and contributing to environmental destruction. That is,
(A) Rust preventives composed of these compositions are used for metal rust prevention, then treated with waste water and discarded. However, these waste liquids still contain compounds containing nitrogen, phosphorus, sulfur and halogen. For this reason, when these are disposed of in wastewater systems or water bodies, eutrophication phenomena occur in rivers, lakes, seas, etc., and environmental destruction such as water pollution and red tide is caused by abnormal occurrence of algae and plankton. cause.
（ロ） これらの廃液を焼却処理する場合は、組成物中の含窒素化合物がNOxの形態に変化し、含硫黄化合物がSOxの形態に成り、これらも酸性雨の一原因に成る。 (B) When these waste liquids are incinerated, the nitrogen-containing compound in the composition changes to the form of NOx, and the sulfur-containing compound becomes the form of SOx, which also causes acid rain.
（ハ） またハロゲンは各種公害を引き起こす。 (C) Halogen also causes various pollution.
本発明は、従来の防錆剤の上記問題点を解決せんとするものであり、その廃液は従来品に比し、より地球環境に優しく、人類に対しより安全で、且つ、金属防錆性に優れた水溶性防錆（添加）剤組成物を提供する事を目的とする。なおパラーターシャリーブチル安息香酸（ｐ−ｔ−Ｂｕ安息香酸）のK塩又はNa塩の融点は２２０〜２３０℃付近であり、熱に対して比較的安定であり、毒性もラットに対しLD５０:約８００ｇ／ｋｇと安全性の高い物質である。 The present invention is intended to solve the above problems of conventional rust preventives, and its waste liquid is more environmentally friendly than conventional products, safer for human beings, and has a metal rust preventive property. An object of the present invention is to provide a water-soluble rust preventive (additive) composition excellent in water. The melting point of K salt or Na salt of para-tertiary butyl benzoic acid (pt-Bu benzoic acid) is around 220-230 ° C., is relatively stable to heat, and toxicity is also LD50 for rats: It is a highly safe substance of about 800 g / kg.
本発明者は、ｐ−ｔ−Ｂｕ安息香酸アルカリ金属塩固有の諸特性（π−電子雲の面学吸着，立体反発効果，ＨＬＢ効果，塩溶効果等）とホルミル安息香酸（以下ＨＢＡという）のアルカリ金属塩の固有性の持つ特性（アニオン・キャプチャー効果）を適正複合する事により、優れた防錆性能が得られると言う知見を得て、本発明を完成するに至った。 The present inventor has found that various characteristics peculiar to alkali metal salts of pt-Bu benzoic acid (planar adsorption of π-electron cloud, steric repulsion effect, HLB effect, salt solubility effect, etc.) and formylbenzoic acid (hereinafter referred to as HBA). The present invention has been completed by obtaining the knowledge that an excellent rust prevention performance can be obtained by appropriately combining the unique properties (anion-capture effect) of the alkali metal salt.
即ち、ｐ−ｔ−Ｂｕ安息香酸のアルカリ金属塩（たとえばカリウム塩、ナトリウム塩等）と、ＨＢＡのアルカリ金属塩（たとえばカリウム塩、ナトリウム塩等）の複合体から構成される。 That is, it is composed of a complex of an alkali metal salt of pt-Bubenzoic acid (eg, potassium salt, sodium salt, etc.) and an alkali metal salt of HBA (eg, potassium salt, sodium salt, etc.).
さらに、当該水溶性防錆添加剤の組成物を１００重量部とする場合、上記ｐ−ｔ−Ｂｕ安息香酸塩が８０〜９５重量部、上記ＨＢＡ塩が５〜２０重量部とし、上記組成物を２０重量％以下の水溶液に調整して水溶性防錆剤としている。２０重量％以下の水溶液に調整するのは、防錆剤として使用するに際して、安全性（高アルカリや水に溶かした時の発熱軽減のため）、経済性、作業性等を考慮したためである。 Furthermore, when the composition of the water-soluble anticorrosive additive is 100 parts by weight, the pt-Bu benzoate is 80 to 95 parts by weight, the HBA salt is 5 to 20 parts by weight, and the composition Is adjusted to an aqueous solution of 20% by weight or less to form a water-soluble rust inhibitor. The reason why the aqueous solution is adjusted to 20% by weight or less is that when used as a rust inhibitor, safety (for reducing heat generation when dissolved in high alkali or water), economy, workability, and the like are taken into consideration.
そして上記水溶性防錆添加剤の組成物の水溶液（防錆剤）中には、窒素（Ｎ），リン（Ｐ），硫黄（Ｓ），ハロゲン（Ｆ、ＣＬ、Ｂｒ）等を含む化合物を本質的に含有せず、環境配慮型になっている。 And in the aqueous solution (antirust agent) of the composition of the water-soluble antirust additive, a compound containing nitrogen (N), phosphorus (P), sulfur (S), halogen (F, CL, Br), etc. It is essentially environmentally friendly.
本発明に於いて使用される複合体とは、単なる混合物ではなく、お互いの相乗効果を発揮する混合物を言う。従って個々の単独体よりも優れた効果を発揮するものであり、これを換言すれば、たとえば個々の単独体の効果を単に加えた場合に比し、更に優れた効果を（相乗効果）を発揮するものである。 The composite used in the present invention is not a simple mixture but a mixture that exhibits a synergistic effect with each other. Therefore, it exhibits an effect superior to that of each individual body. In other words, for example, an effect superior to that obtained by simply adding the effect of an individual body alone (synergistic effect) is exhibited. To do.
本発明の複合体としては、ｐ−ｔ−Ｂｕ安息香酸塩とＨＢＡ塩とを混合後アルカリ塩としても良いし、また予め塩の形にした後に混合しても良い。 As the composite of the present invention, pt-Bu benzoate and HBA salt may be mixed to form an alkali salt, or may be mixed after previously forming a salt form.
これ等本発明複合塩の塩の種類としては同じ金属塩でも良いし、また異なった金属塩でも良い。たとえば一方がＫ塩で他の一方がＮａ塩でも良い。これ等の複合体の製法としては、その代表的な方法を以下に例示するが、これに限定されず複合体とすることが出来る限り、限定されるものではない。 The types of salts of the composite salt of the present invention may be the same metal salt or different metal salts. For example, one may be K salt and the other may be Na salt. Typical methods for producing these composites are illustrated below, but are not limited thereto as long as the composites are not limited thereto.
Ａ液 （１）ｐ−ｔ−Ｂｕ安息香酸を所定秤量する。
（２）１０％ＫＯＨ（又はＮａＯＨ）水溶液を注ぎ込み、４０℃〜６０℃で３０分〜１時間、適正速度（泡を抱かない、飛び散らない層流）で撹拌をして「完全中和」（透明クリア液）する。
Ｂ液 （３）別の容器にＨＢＡ安息香酸を所定秤量する。
（４）１０％ＫＯＨ（又はＮａＯＨ）水溶液を注ぎ込み、４０℃〜６０℃で３０分〜１時間、適正速度で撹拌をして「完全中和」する。
（５）Ａ液（所定秤量）→Ｂ液（所定秤量）→水（所定秤量）の順に仕込み、均一混合系にするために約３０分適正速度で撹拌をする。そして最後に１５０〜２００メッシュでろ過をする。
Liquid A (1) A predetermined amount of pt-Bubenzoic acid is weighed.
(2) A 10% KOH (or NaOH) aqueous solution is poured and stirred at 40 to 60 ° C. for 30 minutes to 1 hour at an appropriate speed (non-foamed, non-spraying laminar flow). Clear liquid).
Liquid B (3) A predetermined amount of HBA benzoic acid is weighed into another container.
(4) Pour a 10% KOH (or NaOH) aqueous solution, and stir at an appropriate speed for 30 minutes to 1 hour at 40 ° C. to 60 ° C. to “completely neutralize”.
(5) Charge A liquid (predetermined weighing) → B liquid (predetermined weighing) → water (predetermined weighing) in this order, and stir at an appropriate speed for about 30 minutes to obtain a homogeneous mixing system. Finally, filtration is performed with 150 to 200 mesh.
本発明に於いて、複合体の製造に用いられるアルカリ金属塩のアルカリ金属としは、リチウム，カリウム，ナトリウムが代表例として例示出来、このなかでカリウム及びナトリウムが好ましい。 In the present invention, the alkali metal of the alkali metal salt used in the production of the composite can be exemplified by lithium, potassium and sodium, and potassium and sodium are preferred.
これ等複合体に於けるｐ−ｔ−Ｂｕ安息香酸塩とＨＢＡ塩との配合割合は、前者が８０〜９５重量部、好ましくは９０〜９５重量部、後者が５〜２０重量部、好ましくは５〜１０重量部（両者の混合物を１００重量部とした時）である。この際、両者の割合が上記所定の範囲外になると、著しく防錆力が低下する。 The compounding ratio of pt-Bu benzoate and HBA salt in these composites is 80 to 95 parts by weight of the former, preferably 90 to 95 parts by weight, and 5 to 20 parts by weight of the latter, preferably 5 to 10 parts by weight (when the mixture of both is 100 parts by weight). At this time, if the ratio between the two is out of the predetermined range, the rust prevention power is remarkably reduced.
本発明は、ｐ−ｔ−Ｂｕ安息香酸塩とＨＢＡ塩との複合体を主成分とするものである為、その廃液は従来品に比し、安全であり、詳しくはより地球環境に優しく、人類に対しより安全であるという大きな利点を有し、しかもその防錆性は従来のものに比し、優るとも劣らないものであり、その産業上の効果は極めて大きい。 Since the present invention is mainly composed of a complex of pt-Bu benzoate and HBA salt, its waste liquid is safer than conventional products, and more specifically, it is more friendly to the global environment. It has the great advantage of being safer for human beings, and its rust prevention property is not inferior to that of the conventional one, and its industrial effect is extremely large.
＜防錆効果の測定＞
防錆効果は、鋳物切り屑（ＦＣ−２０；約０．５ｍｍ直径；２〜３ｍｍ長）による浸漬試験法で評価した。具体的には、試料液１０ｍｌ中に鋳物切り屑（ＦＣ−２０）７．５ｇを浸漬し、１分間撹拌し、鋳物（ＦＣ−２０）ブロック及び濾紙上に盛り、２４時間の室温静置後に錆発生度合いを次の基準で評価した。
○：錆の発生なし（良好）
△：わずかに錆発生（５％程度）
×：錆発生（５０％以上）
上記の評価のうち良好（○印）なものは、１ヶ月の室温静置後も良好な結果を示した。この事から、長期に渡って防錆効果が維持できるものと考えらる。
<Measurement of rust prevention effect>
The antirust effect was evaluated by an immersion test method using cast chips (FC-20; about 0.5 mm diameter; 2-3 mm length). Specifically, 7.5 g of casting chips (FC-20) is immersed in 10 ml of the sample solution, stirred for 1 minute, placed on the casting (FC-20) block and filter paper, and allowed to stand at room temperature for 24 hours. The degree of rust generation was evaluated according to the following criteria.
○: No occurrence of rust (good)
Δ: Slightly rusted (about 5%)
×: Rust generation (50% or more)
Among the above evaluations, those with good (circles) showed good results even after standing at room temperature for 1 month. From this, it is considered that the antirust effect can be maintained over a long period of time.
以下に本発明の好ましい実施例について説明する。 In the following, preferred embodiments of the present invention will be described.
濃度１．０重量％及び１．５重量％水溶液において、本発明品３種と、比較のための各種脂肪族カルボン酸のカリウム塩との防錆効果の比較試験を上記の方法で実施した。 The comparative test of the antirust effect of three kinds of products of the present invention and potassium salts of various aliphatic carboxylic acids for comparison was carried out by the above method in aqueous solutions having a concentration of 1.0% by weight and 1.5% by weight.
選択した脂肪族有機酸として、（１）グリコール酸・（２）グルコン酸・（３）１２−ヒドロキシステアリン酸・（４）セバシン酸・（５）シクロヘキサンカルボン酸・（６）クマリン酸・（７）コハク酸・（８）マレイン酸・（９）Ｌ−アスコルビン酸・（１０）イタコン酸・（１１）ソルビン酸・（１２）フロイック酸・（１３）ジグリコール酸・（１４）1，２−シクロヘキサンジカルボン酸である。結果を表１に示す。 The selected aliphatic organic acids are (1) glycolic acid, (2) gluconic acid, (3) 12-hydroxystearic acid, (4) sebacic acid, (5) cyclohexanecarboxylic acid, (6) coumaric acid, (7 ) Succinic acid, (8) Maleic acid, (9) L-Ascorbic acid, (10) Itaconic acid, (11) Sorbic acid, (12) Fleuc acid, (13) Diglycolic acid, (14) 1, 2- Cyclohexanedicarboxylic acid. The results are shown in Table 1.
濃度０．５重量％及び１．０重量％水溶液において、同様に各種芳香族カルボン酸アルカリ金属塩との防錆効果の比較試験を上記の方法で実施した。 Similarly, the comparative test of the rust prevention effect with various aromatic carboxylic acid alkali metal salts was carried out by the above-mentioned method in aqueous solutions having a concentration of 0.5% by weight and 1.0% by weight.
選択した芳香族カルボン酸として、（１）安息香酸・（２）ｐ−トルイル酸・（３）１−ナフトエ酸・（４）１−ヒドロキシー２ナフトエ酸・（５）２−ヒドロキシー３ナフトエ酸・（６）ベンジル酸・（７）アニス酸・（８）ピロメリット酸・（９）ジフェニル酢酸・（１０）トランスーけい皮酸・（１１）フタル酸・（１２）イソフタル酸・（１３）１，８−ナフタレンジカルボン酸・（１４）２，３−ジヒドロキシナフタレン・（１５）２，６−ナフタレンジカルボン酸・（１６）２，７−ジヒドロキシナフタレン・（１７）１，４，５，8，−ナフタレンテトラカルボン酸である。結果を表２に示す。 As the selected aromatic carboxylic acid, (1) benzoic acid, (2) p-toluic acid, (3) 1-naphthoic acid, (4) 1-hydroxy-2 naphthoic acid, (5) 2-hydroxy-3 naphthoic acid, (6) benzylic acid, (7) anisic acid, (8) pyromellitic acid, (9) diphenylacetic acid, (10) transcinnamic acid, (11) phthalic acid, (12) isophthalic acid, (13) 1, 8-Naphthalenedicarboxylic acid, (14) 2,3-dihydroxynaphthalene, (15) 2,6-naphthalenedicarboxylic acid, (16) 2,7-dihydroxynaphthalene, (17) 1,4,5,8, -naphthalene Tetracarboxylic acid. The results are shown in Table 2.
従来型水溶性防錆（添加）剤との防錆効果の位置付け試験を上記の方法で、濃度０．３重量％，０．５重量％及び１．０重量％水溶液で実施した。 The positioning test of the antirust effect with the conventional water-soluble anticorrosive (additive) agent was carried out by the above method with a concentration of 0.3 wt%, 0.5 wt% and 1.0 wt% aqueous solution.
選択した代表的なものとして、（１）ｐ−ｔＢｕ安息香酸アルカリ金属塩，（２）有機硼素化合物（有機酸二量体と有機アミンと硼素の反応生成物），（３）脂肪族有機酸アルカノールアミン塩，（４）芳香族有機酸アルカノールアミン塩である。結果を表３に示す。 Representative selected ones are: (1) p-tBu benzoic acid alkali metal salt, (2) organic boron compound (reaction product of organic acid dimer, organic amine and boron), (3) aliphatic organic acid Alkanolamine salt, (4) Aromatic organic acid alkanolamine salt. The results are shown in Table 3.
本実施例において、本発明品−１，本発明品−２及び本発明品−３は、ｐ−ｔ−Ｂｕ安息香酸カリウム塩とＨＢＡカリウム塩の本発明範囲内での規定に合致する配合比のものである。 In this example, the present product-1, the present product-2, and the present product-3 are blending ratios that meet the provisions of pt-Bu benzoic acid potassium salt and HBA potassium salt within the scope of the present invention. belongs to.
本発明品−１：ｐ−ｔ−Ｂｕ安息香酸カリウム塩／ＨＢＡカリウム塩＝９５／５
本発明品−２：ｐ−ｔ−Ｂｕ安息香酸カリウム塩／ＨＢＡカリウム塩＝９０／１０
本発明品−３：ｐ−ｔ−Ｂｕ安息香酸カリウム塩／ＨＢＡカリウム塩＝８０／２０
但し上記各種本発明品は上記所定の成分を、所定の配合比で使用して、複合体としたものである。また配合比率はいづれも重量を示す。
Invention product-1: pt-Bu benzoic acid potassium salt / HBA potassium salt = 95/5
Invention product-2: pt-Bu benzoic acid potassium salt / HBA potassium salt = 90/10
Invention product-3: pt-Bu benzoic acid potassium salt / HBA potassium salt = 80/20
However, the above-mentioned various products of the present invention are composites using the above-mentioned predetermined components at a predetermined blending ratio. The blending ratios all indicate weight.
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| JP5062580B2 true JP5062580B2 (en) | 2012-10-31 |
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| GB8727323D0 (en) * | 1987-11-21 | 1987-12-23 | Ciba Geigy Ag | Corrosion inhibitor |
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| JP4124719B2 (en) * | 2003-11-27 | 2008-07-23 | 日産自動車株式会社 | Manufacturing method of gear part having lubricating film |
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