JP4038763B2 - Gelling agent for organic solvents or oils and fats - Google Patents
Gelling agent for organic solvents or oils and fats Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明は有機溶媒または油脂類のゲル化剤に関する。さらに詳しくは有機溶媒、動植物油、鉱物油などに添加することにより該有機溶媒、油などをゲル化させるためのゲル化剤に関する。
【0002】
【従来の技術】
ゲル化剤は種々の用途、すなわち油回収剤、化粧品、医薬部外品、インキなどの粘度調節剤、農薬、香料などの徐放剤、プラスチック、ゴムの加工助剤などに広く用いられている。近年、低分子の有機ゲル化剤が注目されており、その機能が種々研究されている。公知の低分子有機ゲル化剤としては、ソルビトールジアセタール、12−ヒドロキシステアリン酸、コレステロール系アミド化合物、糖誘導体などがあげられる(例えば、(株)エヌティーエス刊、ゲルハンドブック
312ページ参照)。
【0003】
しかしながら、低分子有機ゲル化剤はいまだその数が少なく、またその機能も限られているため、新規な機能を有する低分子ゲル化剤が求められている。また、前記のような公知の低分子有機ゲル化剤は、一般的に高添加量で使用しなければ所望のゲル強度を発現できないため、低添加量でゲル強度の強いゲルを形成させることができる低分子有機ゲル化剤が求められている。
【0004】
また、これらの有機ゲル化剤の殆どのものは、ゲル化対象物に添加し、一旦加熱して溶解させ、その後冷却してゲル化させる必要があり、操作が煩雑でその用途が非常に制限されている。さらに、ゲル化剤を用いてゲル化させたゲルを再び加熱すると、ゲル強度が低下したり、ゲルが溶解するという致命的な欠点があった。
【0005】
【発明が解決しようとする課題】
本発明は、低添加量でゲル強度の強いゲルを形成させることができ、かつ加温、冷却することなく、室温でゲル化対象物に添加するだけで容易にゲル化でき、さらにはゲル化剤を用いてゲル化させたゲルを加熱してもゲル強度が低下したり、ゲルが溶解することのない新規な有機溶媒もしくは油脂類のゲル化剤を提供することを目的とする。
【0006】
【課題を解決するための手段】
かかる目的を達成するために、本発明者は鋭意検討した結果、樹脂酸類のアルカリ土類金属塩を用いることにより当該目的を達成しうることを見出した。
【0007】
すなわち、本発明は、樹脂酸類のアルカリ土類金属塩を有効成分とすることを特徴とする有機溶媒もしくは油脂類のゲル化剤に関する。
【0008】
【発明の実施の形態】
本発明のゲル化剤における有効成分である樹脂酸類のアルカリ土類金属塩は、通常二つの樹脂酸残基とアルカリ土類金属から構成される化合物である。
【0009】
樹脂酸類のアルカリ土類金属塩は樹脂酸類とアルカリ土類金属化合物とを反応させることにより得られる。
【0010】
樹脂酸類としては、例えば、アビエチン酸、レボピマル酸、ネオアビエチン酸、パラストリン酸、ピマル酸、イソピマル酸、サンダラコピマル酸、デヒドロアビエチン酸、ジヒドロアビエチン酸類、テトラヒドロアビエチン酸類をあげることができる。また、前記樹脂酸の混合物であるガムロジン、ウッドロジン、トール油ロジン、不均化ロジン、水素化ロジン、脱水素化ロジンなども挙げられる。
【0011】
アルカリ土類金属化合物としては、樹脂酸類と反応して塩を形成するアルカリ土類金属化合物であれば特に制限されず、使用することができる。具体的には、カルシウム化合物、ストロンチウム化合物、バリウム化合物、マグネシウム化合物などが挙げられる。これらのうちでは、コスト等の面からカルシウム化合物を用いたものが好ましい。これらのうちでは、樹脂酸類との反応性の点から、アルカリ土類金属の酸化物またはアルカリ土類金属の水酸化物、具体的には水酸化マグネシウム、酸化マグネシウム、水酸化カルシウム、酸化カルシウム、水酸化ストロンチウム、酸化ストロンチウム、水酸化バリウム、酸化バリウムなどを用いることが好ましい。
【0012】
本発明に用いられる樹脂酸類のアルカリ土類金属塩の合成方法としては、例えば、樹脂酸類を適当な溶媒中で反応させる方法が挙げられる。溶媒としては、樹脂酸類およびアルカリ土類金属化合物と反応せず、樹脂酸類を溶解するものであれば、特に制限されず、公知のものを用いることができる。具体的には、例えば、メタノール、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、2−メトキシエタノールなどのアルコール類、アセトン、2−ブタノン等のケトン類、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドンなどのアミド類、ジメチルスルホキシド、スルホランなどの含イオウ溶媒、ニトロメタン、ニトロプロパン等の含窒素溶媒、ジエチルエーテル、メチルt−ブチルエーテル、ジt−ブチルエーテル、ジメトキシエタノール、ジメトキシエチレングリコール、テトラヒドロフラン、ジオキサンなどのエーテル結合を少なくとも一つ有するエーテル系溶媒などが挙げられる。これらのうち、エーテル系溶媒を反応溶媒に用いた場合には、反応後の樹脂酸類のアルカリ土類金属塩はこれらの溶媒に溶解した状態で得られ、このものはそのままゲル化剤として使用できるため、これらエーテル系溶媒を使うことが好ましい。尚、溶媒中に少量の水を存在させることにより、樹脂酸類とアルカリ土類金属化合物の反応速度を速くすることができるため特に好ましい。
【0013】
樹脂酸類とアルカリ土類金属化合物とを反応させる際の樹脂酸類とアルカリ土類金属化合物のモル比は、特に制限されないが、一般的にエーテル系溶媒を用いた場合には、樹脂酸1モルに対し、アルカリ土類金属化合物を0.2モル以上使用することが好ましい。樹脂酸類1モルに対し、アルカリ土類金属化合物を0.2モル未満となる場合には、未反応の樹脂酸類が多く残存してしまいゲル化性能を十分に発揮できない場合もある。また、樹脂酸類1モルに対し、アルカリ土類金属化合物を0.5モルを超えて使用する場合には、未反応のアルカリ土類金属化合物が残存するが、ゲル化性能には問題はない。必要であれば、ろ過や遠心分離により未反応のアルカリ土類金属化合物を除去できる。また、エーテル系溶媒以外の溶媒を用いる場合には、通常、樹脂酸1モルに対し、アルカリ土類金属化合物を0.2モル以上使用することが好ましい。なお、樹脂酸類1モルに対し、アルカリ土類金属化合物を0.5モルを超えて使用する場合には、未反応のアルカリ土類金属化合物が残存するが、ゲル化性能には問題はない。
【0014】
反応温度は、特に制限されないが、通常、特殊な装置を要することのない室温から反応に用いる溶媒の沸点の範囲が好適である。
【0015】
反応時間は、反応温度により異なるが、通常5分から24時間程度である。5分に満たない場合には反応が十分に進行しない場合があり、24時間以上反応を行なっても特に有利な点はない。
【0016】
エーテル系溶媒以外の溶媒を用いた場合には、通常、反応終了後、樹脂酸類のアルカリ土類金属塩は反応溶媒中に粉末となって分散しており、ろ過あるいは遠心分離により反応溶媒と分離でき、必要に応じて、樹脂酸類のアルカリ土類金属塩を溶解しない溶媒で洗浄できる。得られた樹脂酸類のアルカリ土類金属塩は、例えば、ジエチルエーテル、メチルt−ブチルエーテル、ジt−ブチルエーテル、ジメトキシエタノール、ジメトキシエチレングリコール、テトラヒドロフラン、ジオキサンなどのエーテル結合を含む溶媒や樹脂酸類のアルカリ土類金属塩を溶解する溶媒に溶解して本発明に使用できる。
【0017】
なお、前記の方法で樹脂酸類のアルカリ土類金属塩の合成が困難な場合、一般的に複分解法と呼ばれる方法も採用できる。複分解法とは樹脂酸類を一旦、アルカリ金属水酸化物と反応させ樹脂酸類のアルカリ金属塩とした後、アルカリ土類金属化合物と反応させる方法である。
【0018】
複分解法では、樹脂酸類のアルカリ金属塩を反応させるアルカリ土類金属化合物としては、通常、水溶性の有機アルカリ土類金属塩類、無機アルカリ土類金属塩類を用いれば良い。具体的にはアルカリ土類金属の酢酸塩、硫酸塩、硝酸塩、塩化物およびこれらの水和物などが挙げられる。
【0019】
複分解法による場合には、反応終了後、生成物は反応溶媒である水に分散した状態で存在するため、ろ過あるいは遠心分離により容易に水と分離できる。また、生成物の水による洗浄も可能である。
【0020】
複分解法により得られた樹脂酸類のアルカリ土類金属塩は前記エーテル系溶媒や樹脂酸類のアルカリ土類金属塩を溶解する溶媒に溶解して本発明に使用できる。
【0021】
このようにして得られた、樹脂酸類のアルカリ土類金属塩は、各種のゲル化対象物に適用できる。例えば、ヘキサン、ヘプタン、シクロヘキサン、ベンゼン、トルエン、キシレンなどの非極性〜中極性の溶媒(具体的には、誘電率が3.0以下程度の溶媒)、ガソリン、灯油、軽油、重油、原油、流動パラフィンなどの鉱油類、また大豆油、菜種油、サラダ油などの一般的な動植物油に対して優れたゲル化能を発現しうる。
【0022】
本発明のゲル化剤は、通常、当該ゲル化剤を溶解し得る溶媒に溶解して使用される。当該ゲル化剤を溶解する溶媒としては、例えば、前記エーテル系溶剤が挙げられるが、これらに限定されるものではない。
【0023】
アルカリ土類金属塩の溶液の濃度は一般に溶媒に対し2重量%以上とすることが好ましく、できるだけ高濃度とするのが好ましい。2重量%に満たない場合には、ゲル化能力を十分に発揮できない場合がある。通常は、10重量%以上が特に好ましい。
【0024】
得られたアルカリ土類金属塩の溶液は各種溶媒、鉱物油、動植物油等のゲル化対象物に添加することにより、ゲル化対象物を速やかにゲル化させることができる。
【0025】
当該アルカリ土類金属塩溶液の使用量は、ゲル化の対象物の種類および有機ゲル化剤中の有効成分の種類に応じて適宜に決定される。通常はゲル化対象物に対してアルカリ土類金属塩の含有量が0.05〜30重量%程度、好ましくは0.1〜10重量%となるようにする。
【0026】
【発明の効果】
本発明のゲル化剤は、各種のゲル化対象物、例えば、ヘキサン、ヘプタン、シクロヘキサン、ベンゼン、トルエン、キシレンなどの非極性〜中極性の溶媒、ガソリン、灯油、軽油、重油、原油、流動パラフィンなどの鉱油類、また大豆油、菜種油、サラダ油などの一般的な動植物油などの芳香族溶媒に対し低添加率で優れたゲル化効果を発現する。得られたゲルは従来の低分子有機ゲル化剤と異なり加熱しても強度が低下したり、溶解することが無いというなもので従来に無いものである。そのため、本発明の有機ゲル化剤の作用効果を活かして、油回収剤、化粧品、医薬部外品、インキなどの粘度調節剤、農薬、香料などの徐放剤、プラスチック、ゴムの加工助剤などに広く適用できる。
【0027】
【実施例】
以下に実施例をあげて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【0028】
実施例1
デヒドロアビエチン酸3.00g(10mモル)をテトラヒドロフラン14.5g、水0.5gよりなる混合溶媒に溶解し、これに水酸化カルシウム0.37g(5mモル)を加え室温で攪拌し反応させた。反応後不溶物をろ過しデヒドロアビエチン酸カルシウム塩の溶液を得た。このものの一部をとり105℃、2時間乾燥しその乾燥減量から固形分を求め、乾燥した固形物のIRスペクトルを測定した。
固形分:17.2重量%
IR:1521cm−1、1415cm−1
固形分より計算しテトラヒドロフランを加え15重量%溶液とした。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフランの15重量%溶液を加えゲル形成の有無を観察した。結果を表1に示す。
【0029】
【表1】
G:ゲル化 P:一部ゲル化 N:ゲル化せず
【0030】
実施例2
実施例1のデヒドロアビエチン酸3.00g(10mモル)に代えて13ベータ−デルタ8−ジヒドロアビエチン酸3.04g(10mモル)を用いたほかは同様な操作を行い13ベータ−デルタ8−ジヒドロアビエチン酸カルシウム塩の溶液を得た。
固形分:17.4重量%
IR:1523cm−1、1416cm−1
得られた溶液は固形分より計算しテトラヒドロフランを加え15重量%とした。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフランの15重量%溶液を加えゲル形成の有無を観察した。結果を表2に示す。
【0031】
【表2】
G:ゲル化 P:一部ゲル化 N:ゲル化せず
【0032】
実施例3
実施例1のデヒドロアビエチン酸3.00g(10mモル)に代えて不均化ロジン(商品名:ロンヂスR、荒川化学工業(株)製、酸価158)3.54gを用いたほかは同様な操作を行い不均化ロジンカルシウム塩の溶液を得た。
固形分:19.3重量%
IR:1525cm−1、1418cm−1
得られた溶液は固形分より計算しテトラヒドロフランを加え15重量%とした。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフランの15重量%溶液を加えゲル形成の有無を観察した。結果を表3に示す。
【0033】
【表3】
G:ゲル化 P:一部ゲル化 N:ゲル化せず
【0034】
実施例4
実施例1のデヒドロアビエチン酸3.00g(10mモル)に代えてトール油ロジン(商品名:TOR35−240、アリゾナケミカル社製、酸価171)3.27gを用いたほかは同様な操作を行いトール油ロジンカルシウム塩の溶液を得た。
固形分:18.6重量%
IR:1524cm−1、1417cm−1
得られた溶液は固形分より計算しテトラヒドロフラン溶液を加え15重量%とした。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフランの15重量%溶液を加えゲル形成の有無を観察した。結果を表4に示す。
【0035】
【表4】
G:ゲル化 P:一部ゲル化 N:ゲル化せず
【0036】
実施例5
実施例1の水酸化カルシウム0.37g(5mモル)に代えて水酸化ストロンチウム・8水和物1.33g(5mモル)用いたほかは同様な操作を行いデヒドロアビエチン酸ストロンチウム塩の溶液を得た。
固形分:17.6重量%
IR:1525cm−1、1405cm−1
得られた溶液は固形分より計算しテトラヒドロフラン溶液を加え15重量%とした。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフランの15重量%溶液を加えゲル形成の有無を観察した。結果を表5に示す。
【0037】
【表5】
G:ゲル化 P:一部ゲル化 N:ゲル化せず
【0038】
実施例6
イソプロパノール(88重量%)、水(12重量%)からなる混合物(以下、88%IPAと略す)200gに水酸化カルシウム3.7g(0.05モル)を加え攪拌し分散させた後、精製不均化ロジン(商品名:KR−614、荒川化学工業(株)製、酸価173)33gを88%IPA 200gに溶解した溶液を還流下で30分かけて滴下した。さらに還流下で4時間攪拌し冷却後、ろ過し、88%IPA100gにて洗浄した。得られたろ過物を取り出し、80℃で4時間減圧乾燥し、28.8gの白色粉末を得た。
融点:300℃まで溶融せず
IR:1521cm−1、1414cm−1
このものをテトラヒドロフランに溶解し15重量%溶液を調製した。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフラン溶液の15重量%溶液を加えゲル形成の有無を観察した。結果を表6に示す。
【0039】
【表6】
G:ゲル化 P:一部ゲル化 N:ゲル化せず
【0040】
実施例7
実施例6の水酸化カルシウムに代えて水酸化バリウム・8水和物を13.3g(0.05モル)に変えた以外は同様の操作を行い25.1gの白色粉末を得た。
融点:300℃まで溶融せず
IR:1536cm−1、1396cm−1
このものにテトラヒドロフランを加え15重量%分散液を調製した。
ゲル化対象物10gを試験管に取り、室温で攪拌しながら、表1に示した重量のテトラヒドロフラン溶液の15重量%分散液を加えゲル形成の有無を観察した。
結果を表7に示す。
【0041】
【表7】
G:ゲル化 P:一部ゲル化 N:ゲル化せず[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic solvent or an oil or fat gelling agent. More specifically, the present invention relates to a gelling agent for adding an organic solvent, animal or vegetable oil, mineral oil or the like to gel the organic solvent or oil.
[0002]
[Prior art]
Gelling agents are widely used in various applications, such as oil recovery agents, cosmetics, quasi-drugs, viscosity regulators such as inks, sustained release agents such as agricultural chemicals and fragrances, plastics and rubber processing aids. . In recent years, low molecular weight organic gelling agents have attracted attention, and their functions have been studied in various ways. Known low-molecular organic gelling agents include sorbitol diacetal, 12-hydroxystearic acid, cholesterol-based amide compounds, sugar derivatives, and the like (for example, refer to page 312 of Gel Handbook, Inc.).
[0003]
However, since the number of low-molecular organic gelling agents is still small and their functions are limited, low-molecular gelling agents having a novel function are required. In addition, since the known low molecular organic gelling agents as described above generally cannot exhibit a desired gel strength unless used in a high addition amount, a gel having a high gel strength can be formed with a low addition amount. There is a need for low molecular weight organic gelling agents that can be produced.
[0004]
In addition, most of these organic gelling agents need to be added to the object to be gelled, once heated and dissolved, and then cooled to be gelled. Has been. Furthermore, when the gel gelled with the gelling agent is heated again, there are fatal drawbacks that the gel strength is reduced and the gel is dissolved.
[0005]
[Problems to be solved by the invention]
The present invention can form a gel with high gel strength with a low addition amount, and can be easily gelled by adding to a gelation object at room temperature without heating and cooling, and further gelation. It is an object of the present invention to provide a novel organic solvent or oil and fat gelling agent in which gel strength does not decrease even when a gel gelled with an agent is heated or the gel does not dissolve.
[0006]
[Means for Solving the Problems]
In order to achieve this object, the present inventor has intensively studied and found that the object can be achieved by using an alkaline earth metal salt of a resin acid.
[0007]
That is, the present invention relates to a gelling agent for organic solvents or oils and fats, characterized by comprising an alkaline earth metal salt of a resin acid as an active ingredient.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The alkaline earth metal salt of a resin acid, which is an active ingredient in the gelling agent of the present invention, is usually a compound composed of two resin acid residues and an alkaline earth metal.
[0009]
Alkaline earth metal salts of resin acids can be obtained by reacting resin acids with alkaline earth metal compounds.
[0010]
Examples of the resin acids include abietic acid, levopimaric acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimalic acid, dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid. Also included are gum rosin, wood rosin, tall oil rosin, disproportionated rosin, hydrogenated rosin, dehydrogenated rosin and the like, which are a mixture of the resin acids.
[0011]
The alkaline earth metal compound is not particularly limited as long as it is an alkaline earth metal compound that reacts with resin acids to form a salt, and can be used. Specific examples include calcium compounds, strontium compounds, barium compounds, magnesium compounds, and the like. Among these, those using a calcium compound are preferable from the viewpoint of cost and the like. Among these, from the viewpoint of reactivity with resin acids, alkaline earth metal oxides or alkaline earth metal hydroxides, specifically magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium oxide, It is preferable to use strontium hydroxide, strontium oxide, barium hydroxide, barium oxide, or the like.
[0012]
Examples of the method for synthesizing the alkaline earth metal salt of the resin acid used in the present invention include a method of reacting the resin acid in an appropriate solvent. The solvent is not particularly limited as long as it does not react with the resin acid and the alkaline earth metal compound and dissolves the resin acid, and a known solvent can be used. Specifically, for example, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2-methoxyethanol, acetone, 2-butanone, etc. Ketones, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, nitrogen-containing solvents such as nitromethane and nitropropane, diethyl ether, methyl t-butyl ether, di-t- Examples thereof include ether solvents having at least one ether bond such as butyl ether, dimethoxyethanol, dimethoxyethylene glycol, tetrahydrofuran, and dioxane. Among these, when an ether solvent is used as the reaction solvent, the alkaline earth metal salt of the resin acid after the reaction is obtained in a state dissolved in these solvents, and this can be used as a gelling agent as it is. Therefore, it is preferable to use these ether solvents. The presence of a small amount of water in the solvent is particularly preferable because the reaction rate between the resin acid and the alkaline earth metal compound can be increased.
[0013]
The molar ratio of the resin acid to the alkaline earth metal compound when the resin acid and the alkaline earth metal compound are reacted is not particularly limited. Generally, when an ether solvent is used, 1 mole of the resin acid is used. On the other hand, it is preferable to use 0.2 mol or more of alkaline earth metal compound. When the amount of the alkaline earth metal compound is less than 0.2 mol with respect to 1 mol of the resin acids, a large amount of unreacted resin acids may remain and the gelling performance may not be sufficiently exhibited. In addition, when the alkaline earth metal compound is used in an amount exceeding 0.5 mol with respect to 1 mol of the resin acid, unreacted alkaline earth metal compound remains, but there is no problem in gelling performance. If necessary, unreacted alkaline earth metal compound can be removed by filtration or centrifugation. In addition, when a solvent other than the ether solvent is used, it is usually preferable to use 0.2 mol or more of the alkaline earth metal compound with respect to 1 mol of the resin acid. In addition, when the alkaline earth metal compound is used in an amount exceeding 0.5 mol with respect to 1 mol of the resin acid, an unreacted alkaline earth metal compound remains, but there is no problem in gelling performance.
[0014]
The reaction temperature is not particularly limited, but usually the range of room temperature without requiring a special apparatus to the boiling point of the solvent used for the reaction is suitable.
[0015]
The reaction time varies depending on the reaction temperature, but is usually about 5 minutes to 24 hours. If it is less than 5 minutes, the reaction may not proceed sufficiently, and there is no particular advantage even if the reaction is carried out for 24 hours or longer.
[0016]
When a solvent other than an ether solvent is used, the alkaline earth metal salt of the resin acid is usually dispersed as a powder in the reaction solvent after completion of the reaction, and separated from the reaction solvent by filtration or centrifugation. If necessary, it can be washed with a solvent that does not dissolve the alkaline earth metal salt of the resin acid. The alkaline earth metal salt of the obtained resin acid is, for example, a solvent containing an ether bond such as diethyl ether, methyl t-butyl ether, di-t-butyl ether, dimethoxyethanol, dimethoxyethylene glycol, tetrahydrofuran, dioxane, or an alkali of a resin acid. It can be used in the present invention after being dissolved in a solvent that dissolves the earth metal salt.
[0017]
If it is difficult to synthesize an alkaline earth metal salt of a resin acid by the above method, a method generally called a metathesis method can also be adopted. The metathesis method is a method in which a resin acid is once reacted with an alkali metal hydroxide to obtain an alkali metal salt of the resin acid and then reacted with an alkaline earth metal compound.
[0018]
In the metathesis method, water-soluble organic alkaline earth metal salts and inorganic alkaline earth metal salts are usually used as the alkaline earth metal compound with which the alkali metal salt of the resin acid is reacted. Specific examples include alkaline earth metal acetates, sulfates, nitrates, chlorides and hydrates thereof.
[0019]
In the case of the metathesis method, after completion of the reaction, the product exists in a dispersed state in water as a reaction solvent, and therefore can be easily separated from water by filtration or centrifugation. It is also possible to wash the product with water.
[0020]
The alkaline earth metal salt of a resin acid obtained by the metathesis method can be used in the present invention after being dissolved in the ether solvent or a solvent capable of dissolving the alkaline earth metal salt of a resin acid.
[0021]
The alkaline earth metal salt of the resin acid thus obtained can be applied to various gelation objects. For example, nonpolar to medium polar solvents such as hexane, heptane, cyclohexane, benzene, toluene, xylene (specifically, solvents having a dielectric constant of about 3.0 or less), gasoline, kerosene, light oil, heavy oil, crude oil, Excellent gelling ability can be expressed against mineral oils such as liquid paraffin, and general animal and vegetable oils such as soybean oil, rapeseed oil and salad oil.
[0022]
The gelling agent of the present invention is usually used after being dissolved in a solvent capable of dissolving the gelling agent. Examples of the solvent that dissolves the gelling agent include the ether solvents, but are not limited thereto.
[0023]
In general, the concentration of the alkaline earth metal salt solution is preferably 2% by weight or more with respect to the solvent, and is preferably as high as possible. If it is less than 2% by weight, the gelation ability may not be fully exhibited. Usually, 10% by weight or more is particularly preferable.
[0024]
By adding the obtained alkaline earth metal salt solution to gelled objects such as various solvents, mineral oil, animal and vegetable oils, the gelled object can be rapidly gelled.
[0025]
The amount of the alkaline earth metal salt solution used is appropriately determined according to the type of the gelation target and the type of the active ingredient in the organic gelling agent. Usually, the content of the alkaline earth metal salt is about 0.05 to 30% by weight, preferably 0.1 to 10% by weight with respect to the object to be gelled.
[0026]
【The invention's effect】
The gelling agent of the present invention includes various gelling objects, for example, nonpolar to medium polar solvents such as hexane, heptane, cyclohexane, benzene, toluene, xylene, gasoline, kerosene, light oil, heavy oil, crude oil, liquid paraffin. It exhibits an excellent gelling effect at a low addition rate with respect to aromatic solvents such as mineral oils such as soybean oil, rapeseed oil, and general animal and vegetable oils such as salad oil. Unlike the conventional low molecular weight organic gelling agent, the obtained gel does not decrease in strength or dissolve even when heated. Therefore, taking advantage of the effects of the organic gelling agent of the present invention, oil recovery agents, cosmetics, quasi drugs, viscosity regulators such as inks, sustained release agents such as agricultural chemicals and fragrances, plastics, rubber processing aids It can be applied widely.
[0027]
【Example】
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
[0028]
Example 1
3.00 g (10 mmol) of dehydroabietic acid was dissolved in a mixed solvent consisting of 14.5 g of tetrahydrofuran and 0.5 g of water, 0.37 g (5 mmol) of calcium hydroxide was added thereto, and the mixture was stirred and reacted at room temperature. After the reaction, insolubles were filtered to obtain a solution of calcium dehydroabietic acid. A portion of this was taken and dried at 105 ° C. for 2 hours, the solid content was determined from the loss on drying, and the IR spectrum of the dried solid was measured.
Solid content: 17.2% by weight
IR: 1521 cm −1 , 1415 cm −1
Calculated from the solid content, tetrahydrofuran was added to make a 15 wt% solution.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 1.
[0029]
[Table 1]
G: Gelled P: Partially gelled N: Not gelled [0030]
Example 2
The same procedure was performed except that 3.04 g (10 mmol) of 13 beta-delta 8-dihydroabietic acid was used instead of 3.00 g (10 mmol) of dehydroabietic acid of Example 1, and 13 beta-delta 8-dihydro was used. A solution of calcium abietic acid salt was obtained.
Solid content: 17.4% by weight
IR: 1523 cm −1 , 1416 cm −1
The obtained solution was calculated from the solid content, and tetrahydrofuran was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 2.
[0031]
[Table 2]
G: Gelled P: Partially gelled N: Not gelled [0032]
Example 3
The same procedure except that 3.54 g of disproportionated rosin (trade name: Longis R, manufactured by Arakawa Chemical Industries, Ltd., acid value 158) was used instead of 3.00 g (10 mmol) of dehydroabietic acid of Example 1. Operation was performed to obtain a solution of disproportionated rosin calcium salt.
Solid content: 19.3% by weight
IR: 1525 cm −1 , 1418 cm −1
The obtained solution was calculated from the solid content, and tetrahydrofuran was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 3.
[0033]
[Table 3]
G: Gelled P: Partially gelled N: Not gelled [0034]
Example 4
The same operation was performed except that 3.27 g of tall oil rosin (trade name: TOR35-240, manufactured by Arizona Chemical Co., acid value 171) was used instead of 3.00 g (10 mmol) of dehydroabietic acid of Example 1. A solution of tall oil rosin calcium salt was obtained.
Solid content: 18.6% by weight
IR: 1524 cm −1 , 1417 cm −1
The obtained solution was calculated from the solid content, and the tetrahydrofuran solution was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 4.
[0035]
[Table 4]
G: Gelled P: Partially gelled N: Not gelled [0036]
Example 5
A solution of strontium dehydroabietic acid salt was obtained in the same manner as in Example 1 except that 1.33 g (5 mmol) of strontium hydroxide octahydrate was used instead of 0.37 g (5 mmol) of calcium hydroxide. It was.
Solid content: 17.6% by weight
IR: 1525 cm −1 , 1405 cm −1
The obtained solution was calculated from the solid content, and the tetrahydrofuran solution was added to make 15% by weight.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% solution of tetrahydrofuran having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 5.
[0037]
[Table 5]
G: Gelled P: Partially gelled N: Not gelled [0038]
Example 6
After adding 3.7 g (0.05 mol) of calcium hydroxide to 200 g of a mixture of isopropanol (88 wt%) and water (12 wt%) (hereinafter abbreviated as 88% IPA) and stirring and dispersing, A solution prepared by dissolving 33 g of averaged rosin (trade name: KR-614, manufactured by Arakawa Chemical Industries, Ltd., acid value 173) in 200 g of 88% IPA was added dropwise over 30 minutes under reflux. The mixture was further stirred for 4 hours under reflux, cooled, filtered, and washed with 100 g of 88% IPA. The obtained filtrate was taken out and dried under reduced pressure at 80 ° C. for 4 hours to obtain 28.8 g of white powder.
Melting point: not melted to 300 ° C. IR: 1521 cm −1 , 1414 cm −1
This was dissolved in tetrahydrofuran to prepare a 15% by weight solution.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15% by weight solution of a tetrahydrofuran solution having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed. The results are shown in Table 6.
[0039]
[Table 6]
G: Gelled P: Partially gelled N: Not gelled [0040]
Example 7
The same operation was carried out except that barium hydroxide octahydrate was changed to 13.3 g (0.05 mol) instead of calcium hydroxide in Example 6 to obtain 25.1 g of white powder.
Melting point: not melted to 300 ° C. IR: 1536 cm −1 , 1396 cm −1
Tetrahydrofuran was added to this to prepare a 15 wt% dispersion.
10 g of the object to be gelled was placed in a test tube, and while stirring at room temperature, a 15 wt% dispersion of a tetrahydrofuran solution having the weight shown in Table 1 was added, and the presence or absence of gel formation was observed.
The results are shown in Table 7.
[0041]
[Table 7]
G: Gelled P: Partially gelled N: Not gelled
Claims (4)
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