JP2006219613A - Dicarboxylic acid and its salt - Google Patents
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Abstract
Description
本発明は、微生物に資化され難く、さらに耐硬水性に優れるジカルボン酸及びその塩、及び、これらのジカルボン酸及びその塩を含有する水溶性加工油剤、水溶性洗浄剤に関する。更に詳しくは、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドのそれぞれのポリマー及び組み合わせからなるポリマーと酸無水物(無水コハク酸、無水マレイン酸、ヘキサヒドロ無水フタル酸、無水フタル酸)のジアシル化反応物であるジカルボン酸及びそのアルカリ金属塩、アンモニウム塩、または、アミン塩からなるジカルボン酸塩、及び、これらのジカルボン酸及びその塩を含有することを特徴とする水溶性加工油剤、水溶性洗浄剤に関する。 The present invention relates to dicarboxylic acids and salts thereof that are hardly assimilated by microorganisms and have excellent hard water resistance, and to water-soluble processing oils and water-soluble cleaning agents containing these dicarboxylic acids and salts thereof. More specifically, it is a diacylation reaction product of a polymer and an acid anhydride (succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, phthalic anhydride) comprising a polymer and a combination of ethylene oxide, propylene oxide, and butylene oxide. The present invention relates to a dicarboxylic acid salt composed of dicarboxylic acid and its alkali metal salt, ammonium salt or amine salt, and a water-soluble processing oil agent and water-soluble cleaning agent characterized by containing these dicarboxylic acid and its salt.
脂肪酸のアルカリ金属塩、アンモニウム塩、または、アミン塩は、防錆剤、界面活性剤として、使用される。水溶性加工油剤や水溶性洗浄剤には、脂肪酸のアルカリ金属塩、アンモニウム塩、または、アミン塩が主要な成分として含有されていることが多い。また、脂肪酸は、防腐、防錆効果を発揮するために添加されるアルカリ金属、アンモニウム、または、アミンの中和にも利用でき、pH調整にも重要な役割を果たしている。 Alkali metal salts, ammonium salts, or amine salts of fatty acids are used as rust inhibitors and surfactants. Water-soluble processing oils and water-soluble detergents often contain fatty acid alkali metal salts, ammonium salts, or amine salts as main components. Fatty acids can also be used to neutralize alkali metals, ammonium, or amines added to exert antiseptic and rust preventive effects, and play an important role in pH adjustment.
脂肪酸は、親油基(炭化水素部位)と親水基(カルボキシル基)を有し、界面活性を示す。脂肪酸は種類により、親油基の炭素長が違うが、炭素長を選択することにより界面活性の性質を変化させることができる。 The fatty acid has a lipophilic group (hydrocarbon moiety) and a hydrophilic group (carboxyl group), and exhibits surface activity. Fatty acid has different lipophilic group carbon length depending on the type, but the surface active property can be changed by selecting the carbon length.
しかしながら、主鎖の炭素数が9以上の脂肪酸のアルカリ金属塩、アンモニウム塩、または、アミン塩は水溶液中にカルシウムイオンが存在すると不溶解性のカルシウム塩を生じ、界面活性剤としての効力を失う。また、主鎖の炭素数が9以上の脂肪酸が水溶性加工油剤や水溶性洗浄剤に含有されている場合、不溶解性のカルシウム塩により、被削材や機械周りへの付着、フィルター詰まり等の問題を引き起こす可能性がある。 However, an alkali metal salt, ammonium salt or amine salt of a fatty acid having 9 or more carbon atoms in the main chain produces an insoluble calcium salt in the presence of calcium ions in an aqueous solution and loses its effectiveness as a surfactant. . In addition, when fatty acids with 9 or more carbon atoms in the main chain are contained in water-soluble processing oils or water-soluble cleaning agents, the insoluble calcium salt causes adhesion to the work material or machine, filter clogging, etc. Can cause problems.
工業原料として代表的な脂肪酸にトール油脂肪酸やリシノレイン酸などを挙げることができるが、これらの脂肪酸は植物油脂の誘導体であり、微生物により資化され易く、水溶性加工油剤などに含有した場合、腐敗などを引き起こす要因となる。 Typical industrial fatty acids include tall oil fatty acid and ricinoleic acid, but these fatty acids are vegetable fats and oils, are easily assimilated by microorganisms, and contained in water-soluble processing oils, It becomes a factor causing corruption.
一方、優れた防食性、耐腐敗性、及び耐微生物劣化性を有している金属腐食防止剤として、ポリエーテル化合物に、不飽和カルボン酸系単量体を必須成分として含有するモノエチレン性不飽和単量体をグラフト重合してなる水溶性グラフト重合体が知られている。(特許文献1) On the other hand, as a metal corrosion inhibitor having excellent anti-corrosion, anti-corrosion, and anti-microbial degradation, a monoethylenic acid containing an unsaturated carboxylic acid monomer as an essential component in a polyether compound. A water-soluble graft polymer obtained by graft polymerization of a saturated monomer is known. (Patent Document 1)
本発明は、微生物に資化され難く、さらに耐硬水性に優れるジカルボン酸及びその塩、及び、これらのジカルボン酸及びその塩を含有することを特徴とする水溶性加工油剤、水溶性洗浄剤を提供することを目的とする。 The present invention relates to a dicarboxylic acid and a salt thereof that are not easily assimilated by microorganisms and have excellent hard water resistance, and a water-soluble processing oil agent and a water-soluble cleaning agent characterized by containing these dicarboxylic acid and a salt thereof. The purpose is to provide.
本発明者は、上記課題を解決する為に鋭意研究を重ねた結果、微生物に資化され難く、耐硬水性に優れる界面活性剤(特に、防錆剤且つ洗浄剤)として有用なジカルボン酸及びその塩を見出し、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 inventor has dicarboxylic acids useful as surfactants (especially rust preventives and cleaning agents) that are not easily assimilated by microorganisms and have excellent hard water resistance. The salt was found and the present invention was completed.
即ち、本発明は、以下を提供する。
1.エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドのそれぞれのポリマー及び組み合わせからなるポリマーと酸無水物(無水コハク酸、無水マレイン酸、ヘキサヒドロ無水フタル酸、無水フタル酸)のジアシル化反応物であるジカルボン酸及びそのアルカリ金属塩、アンモニウム塩、または、アミン塩からなるジカルボン酸塩。
2.上記項1に記載のジカルボン酸及びその塩を含有することを特徴とする水溶性加工油剤。
3.上記項1に記載のジカルボン酸及びその塩を含有することを特徴とする水溶性洗浄剤。
That is, the present invention provides the following.
1. Dicarboxylic acid which is a diacylation reaction product of a polymer and an acid anhydride (succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, phthalic anhydride) composed of a polymer and a combination of ethylene oxide, propylene oxide and butylene oxide and its Dicarboxylates comprising alkali metal salts, ammonium salts, or amine salts.
2. A water-soluble processing oil comprising the dicarboxylic acid according to item 1 and a salt thereof.
3. A water-soluble cleaning agent comprising the dicarboxylic acid according to item 1 and a salt thereof.
本発明によるジカルボン酸及びその塩は、微生物に資化され難く、さらに希釈水中にカルシウムイオンが存在しても不溶解性の塩を生じず、界面活性剤としての効力を長期間維持できる。また、水溶性加工油剤や水溶性洗浄剤への調合においても、良好な溶解性を示し、安定に配合できる。 The dicarboxylic acid and its salt according to the present invention are not easily assimilated by microorganisms, and even when calcium ions are present in the diluted water, an insoluble salt is not generated, and the efficacy as a surfactant can be maintained for a long period of time. Moreover, also in the preparation to a water-soluble processing oil agent or a water-soluble detergent, it exhibits good solubility and can be blended stably.
本発明に用いるエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド(以降、アルキレンオキサイドという)のそれぞれのポリマー及び組み合わせからなるポリマーとは、それぞれのアルキレンオキサイドのホモポリマー及び各種アルキレンオキサイド2種以上の組み合わせによるコポリマー(ランダムまたはブロックポリマーでもよい)である。ポリマーの分子量は、一般的に300〜10000が好ましい。より好ましくは、分子量500〜5000である。特に好ましくは、分子量500〜3000である。ポリマーの分子量が300よりも小さいと十分な界面活性を示さず、また、10000よりも大きいとアミンの中和やpH調整の面で十分な効果が得られない。 The polymer composed of each of ethylene oxide, propylene oxide, butylene oxide (hereinafter referred to as alkylene oxide) and a combination thereof used in the present invention is a copolymer of each alkylene oxide homopolymer and a combination of two or more of various alkylene oxides ( Random or block polymers). The molecular weight of the polymer is generally preferably from 300 to 10,000. More preferably, the molecular weight is 500 to 5000. Particularly preferably, the molecular weight is 500 to 3000. When the molecular weight of the polymer is smaller than 300, sufficient surface activity is not exhibited, and when it is larger than 10,000, sufficient effects cannot be obtained in terms of amine neutralization and pH adjustment.
酸無水物と水酸基のアシル化反応は、通常、無触媒、常圧、反応温度100〜150℃程度で進行する。ただし、触媒(p−トルエンスルホン酸等)の使用、あるいは過激な温度条件では、アシル化反応後に、開環し生成したカルボキシル基と水酸基とのエステル化反応が進行するため好ましくない。 The acylation reaction between an acid anhydride and a hydroxyl group usually proceeds without catalyst, at normal pressure, and at a reaction temperature of about 100 to 150 ° C. However, the use of a catalyst (p-toluenesulfonic acid or the like) or extreme temperature conditions is not preferable because an esterification reaction between a carboxyl group and a hydroxyl group formed by ring opening after the acylation reaction proceeds.
本発明の使用するアルキレンオキサイドと酸無水物との反応比率は、通常、アルキレンオキサイドのポリマー1当量に対して、酸無水物2.2当量から3当量の過剰使用する。 The reaction ratio between the alkylene oxide and the acid anhydride used in the present invention is usually an excess of 2.2 to 3 equivalents of acid anhydride relative to 1 equivalent of the polymer of alkylene oxide.
上記のジアシル化反応物は、定法の方法でアルカリ金属、アンモニアまたはアミンで中和すればよい。 The above diacylated reaction product may be neutralized with an alkali metal, ammonia or an amine by a conventional method.
アルカリ金属としてはナトリウムおよびカリウムが、特に好ましく、また、これらは所望により適宜併用してもよい。 Sodium and potassium are particularly preferred as the alkali metal, and these may be used in combination as desired.
アミンとしては、炭素原子数1〜5のアルキルアミン(例えば、エチルアミン、プロピルアミン等)、炭素原子数2〜10のアルカノールアミン(例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、シクロヘキシルジエタノールアミン等)、モルホリン、炭素原子数5〜20のシクロアルキルアミン(例えば、ジシクロヘキシルアミン等)、3,3−ジメチルプロパンジアミン等から調製される上記二塩基酸のアミン塩が例示されるが、特に好ましくは、炭素原子数2〜10のアルカノールアミンである。これらのアミン塩は所望により2種以上適宜併用してもよい。 Examples of the amine include alkylamines having 1 to 5 carbon atoms (for example, ethylamine, propylamine, etc.), alkanolamines having 2 to 10 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, dioxygen). Amines of the above dibasic acids prepared from isopropanolamine, triisopropanolamine, cyclohexyldiethanolamine, etc.), morpholine, cycloalkylamines having 5 to 20 carbon atoms (for example, dicyclohexylamine etc.), 3,3-dimethylpropanediamine, etc. Examples of the salt include alkanolamines having 2 to 10 carbon atoms. Two or more of these amine salts may be used in combination as desired.
アルカリ金属塩、アンモニウム塩またはアミン塩は混合して使用してもよい。 Alkali metal salts, ammonium salts or amine salts may be used in combination.
一般的な本発明のジアシル化反応物の合成法を示す。
合成法
アルキレンオキサイドのポリマーと酸無水物のジアシル化反応は、無触媒、無溶媒、常圧下で120〜150℃に5〜12時間加熱して行う。反応終了後、過剰分は昇華除去あるいは留去させて除去してもよく、あるいは、クロマトグラフィー等で精製してもよい。あるいは、そのまま後の中和工程で中和してもよい。
The synthesis method of the general diacylation reaction product of this invention is shown.
Synthesis Method The diacylation reaction between an alkylene oxide polymer and an acid anhydride is carried out by heating at 120 to 150 ° C. for 5 to 12 hours under no catalyst, no solvent, and normal pressure. After completion of the reaction, the excess may be removed by sublimation or distillation, or may be purified by chromatography or the like. Or you may neutralize as it is in the subsequent neutralization process.
反応の終点は、FT−IRを用いアシル化反応により酸無水物に由来するの2つの吸収ピーク(1779cm−1,1848cm−1)が消滅(反応が進行することによって強いエステル基由来の吸収(1728cm−1)が現れる)する時点をもって反応の終点とした。 The end point of the reaction is the disappearance of the two absorption peaks (1779 cm −1 , 1848 cm −1 ) derived from the acid anhydride by the acylation reaction using FT-IR (absorption due to strong ester groups as the reaction proceeds ( The time when 1728 cm −1 ) appears) was taken as the end point of the reaction.
本発明のジカルボン酸を水溶性加工油剤や水溶性洗浄剤に使用する場合のジカルボン酸とアルカリ金属、アンモニア又はアミンとの比率(重量モル比)は、好ましくは1:2〜1:20、特に好ましくは1:5〜1:10である。重量モル比が1:2よりも大きくなると可溶化が困難となって十分な界面活性が発揮されず、また、該重量モル比が1:20よりも小さくなると、界面活性が低下するだけでなく、作業衛生上の問題(例えば、呼吸器系等の刺激や肌荒れ等)が出てくる。 When the dicarboxylic acid of the present invention is used in a water-soluble processing oil or water-soluble detergent, the ratio (weight molar ratio) of the dicarboxylic acid to the alkali metal, ammonia or amine is preferably 1: 2 to 1:20, particularly Preferably it is 1: 5 to 1:10. When the molar ratio is larger than 1: 2, solubilization is difficult and sufficient surface activity is not exhibited. When the molar ratio is smaller than 1:20, not only the surface activity is lowered, but also Occupational hygiene problems (for example, irritation of the respiratory system, rough skin, etc.) appear.
水溶性加工油剤或いは水溶性洗浄剤に配合するときは、ジカルボン塩として通常全体の1〜80重量%、好ましくは2〜50重量%である。尚、水溶性加工油剤には、所望により鉱物油(例えば、マシン油、スピンドル油)、動植物油(例えば、ナタネ油、パーム油、牛脂、ヒマシ油)、油性向上剤(例えば、脂肪酸、脂肪酸エステル)、極圧添加剤(例えば、塩素化パラフィン、硫化油脂)、防錆剤(例えば、アルカノールアミン)、界面活性剤(例えば、アニオン、ノニオン、カチオン系界面活性剤)、防腐剤(例えば、1,2−ベンゾイソチアゾリン−3−オン)、消泡剤(例えば、シリコーン系)、防食剤(例えば、ベンゾトリアゾール)等の添加剤を適宜配合することができる。また、水溶性洗浄剤には、所望により脂肪酸(例えば、イソノナン酸、カプリル酸)、防錆剤(例えば、アルカノールアミン)、界面活性剤(例えば、アニオン、ノニオン、カチオン系界面活性剤)、防腐剤(例えば、1,2−ベンゾイソチアゾリン−3−オン)、消泡剤(例えば、シリコーン系)、防食剤(例えば、ベンゾトリアゾール)等の添加剤を適宜配合することができる。 When blended with a water-soluble processing oil or water-soluble cleaning agent, it is generally 1 to 80% by weight, preferably 2 to 50% by weight as a dicarboxylic salt. The water-soluble processing oils include mineral oils (for example, machine oil, spindle oil), animal and vegetable oils (for example, rapeseed oil, palm oil, beef tallow, castor oil), and oiliness improvers (for example, fatty acids, fatty acid esters). ), Extreme pressure additives (for example, chlorinated paraffins, sulfurized fats and oils), rust inhibitors (for example, alkanolamines), surfactants (for example, anions, nonions, cationic surfactants), preservatives (for example, 1 , 2-benzoisothiazolin-3-one), an antifoaming agent (for example, silicone-based), an anticorrosive agent (for example, benzotriazole) and the like can be appropriately blended. Further, water-soluble detergents include fatty acids (for example, isononanoic acid and caprylic acid), rust inhibitors (for example, alkanolamines), surfactants (for example, anions, nonions, and cationic surfactants), antiseptics, if desired. Additives such as an agent (for example, 1,2-benzisothiazolin-3-one), an antifoaming agent (for example, silicone), and an anticorrosive agent (for example, benzotriazole) can be appropriately blended.
尚、通常これら水溶性加工油剤或いは水溶性洗浄剤は、水に希釈して使用される。希釈倍率は、一般には、5〜100倍に希釈して使用されるが、使用用途に応じて適宜選定すればよいが、希釈時の本発明のジカルボン酸塩の濃度は、0.01〜16重量%(好ましくは0.02〜10重量%)である。濃度が0.01重量%より低いと十分な界面活性を示さない。また、16重量%を超えると界面活性は増大せず経済的に好ましくない。 Normally, these water-soluble processing oils or water-soluble cleaning agents are used after diluted in water. The dilution factor is generally used after diluting 5 to 100 times, but may be appropriately selected according to the intended use, but the concentration of the dicarboxylate of the present invention at the time of dilution is 0.01 to 16 % By weight (preferably 0.02 to 10% by weight). When the concentration is lower than 0.01% by weight, sufficient surface activity is not exhibited. On the other hand, if it exceeds 16% by weight, the surface activity does not increase, which is not economical.
以下に本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。実施例に用いた本発明のジアシル化反応物(合成No.1〜23)を表1、表2に示す。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Tables 1 and 2 show the diacylated reactants (Synthesis Nos. 1 to 23) of the present invention used in the examples.
表3には表1、表2と同じように比較例に用いた脂肪酸を示す。 Table 3 shows the fatty acids used in the comparative examples as in Tables 1 and 2.
[実施例1〜24]
表4〜5に示した配合組成の試験液を調製し、以下に示す評価方法により、カルシウムイオンに対する液の安定性(不溶解性カルシウム塩の析出状態)を評価した。
[Examples 1 to 24]
Test liquids having the blending compositions shown in Tables 4 to 5 were prepared, and the stability of the liquid against calcium ions (deposition state of insoluble calcium salt) was evaluated by the following evaluation method.
[評価方法]
表4〜5に示した試験液のカルシウムイオン濃度を100ppmに調整し、30℃の恒温槽中に、24時間静置した後、析出物の発生状態を目視にて観察した。結果を表4〜5に示した。
判定基準
◎:析出物の発生なし。
○:析出物が微量発生。
△:析出物が少量発生。
×:析出物が多量発生。
[Evaluation methods]
The calcium ion concentration of the test solutions shown in Tables 4 to 5 was adjusted to 100 ppm and allowed to stand in a thermostatic bath at 30 ° C. for 24 hours, and then the occurrence of precipitates was visually observed. The results are shown in Tables 4-5.
Judgment criteria A: No precipitate is generated.
○: A small amount of precipitate was generated.
Δ: A small amount of precipitate is generated.
X: A large amount of precipitates are generated.
[比較例1〜12]
表6に示した配合組成の試験液を調製し、上記に示した評価方法により、カルシウムイオンに対する液の安定性(不溶解性カルシウム塩の析出状態)を評価した。結果を同様に表6に示した。
[Comparative Examples 1 to 12]
Test liquids having the composition shown in Table 6 were prepared, and the stability of the liquid against calcium ions (deposition state of insoluble calcium salt) was evaluated by the evaluation method described above. The results are also shown in Table 6.
[実施例25〜34]
表7に示した配合組成のソルブルタイプの加工油剤を調製し、上記の実施例と同様に評価試験を行った。結果を表7に示した。
[Examples 25 to 34]
A solve type processing oil having the composition shown in Table 7 was prepared, and an evaluation test was conducted in the same manner as in the above examples. The results are shown in Table 7.
[比較例13〜22]
表8に示した配合組成のソルブルタイプの加工油剤を調製し、上記の実施例と同様に評価試験を行った。結果を表7に示した。
[Comparative Examples 13 to 22]
A solve type processing oil having the composition shown in Table 8 was prepared, and an evaluation test was conducted in the same manner as in the above-described Examples. The results are shown in Table 7.
[実施例35]
表1、表2に示したジアシル化反応物と表3中のトール油脂肪酸の微生物による分解性を評価した。
[Example 35]
Degradability by microorganisms of the diacylated reaction products shown in Tables 1 and 2 and tall oil fatty acids in Table 3 was evaluated.
[評価方法]
表1の合成No.3、12、表2の合成No.13と表3のNo.6(トール油脂肪酸)をpH9.0に調整したDavisの培地(リン酸緩衝液,硫酸アンモニウム,硫酸マグネシウム,炭素源)中に500ppmと腐敗液100ppmを添加し、液温25℃で撹拌し、1週間後のBODを測定した後、分解度[BOD/ThOD×100(%)]を算出した。結果を表9に示した。BODは生物化学的酸素要求量(測定値、単位はmg)で、ThODは理論的酸素要求量(計算値、単位はmg)である。
[Evaluation methods]
Synthesis No. 1 in Table 1 3, 12, Table 2, Synthesis No. 13 and No. 3 in Table 3. 500 ppm and 100 ppm septic solution were added to a Davis medium (phosphate buffer, ammonium sulfate, magnesium sulfate, carbon source) in which 6 (tall oil fatty acid) was adjusted to pH 9.0, and the mixture was stirred at a liquid temperature of 25 ° C. After measuring BOD after a week, the degree of decomposition [BOD / ThOD × 100 (%)] was calculated. The results are shown in Table 9. BOD is the biochemical oxygen demand (measured value, unit is mg), and ThOD is the theoretical oxygen demand (calculated value, unit is mg).
本発明は、微生物に資化され難く、さらに耐硬水性に優れるジカルボン酸及びその塩として有効である。 INDUSTRIAL APPLICABILITY The present invention is effective as a dicarboxylic acid and a salt thereof that are not easily assimilated by microorganisms and have excellent hard water resistance.
Claims (3)
A water-soluble cleaning agent comprising the dicarboxylic acid according to claim 1 and a salt thereof.
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JP2016014146A (en) * | 2015-08-19 | 2016-01-28 | 出光興産株式会社 | Aqueous detergent |
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JPS56167724A (en) * | 1980-04-25 | 1981-12-23 | Siemens Ag | Manufacture of transparent injection molding resin |
JPS59225146A (en) * | 1983-06-03 | 1984-12-18 | New Japan Chem Co Ltd | Novel compound and its preparation |
JPH03294399A (en) * | 1990-04-12 | 1991-12-25 | Asahi Denka Kogyo Kk | Metal working oil |
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JPS56167724A (en) * | 1980-04-25 | 1981-12-23 | Siemens Ag | Manufacture of transparent injection molding resin |
JPS59225146A (en) * | 1983-06-03 | 1984-12-18 | New Japan Chem Co Ltd | Novel compound and its preparation |
JPH03294399A (en) * | 1990-04-12 | 1991-12-25 | Asahi Denka Kogyo Kk | Metal working oil |
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