JP2011006581A - Water soluble thickener having temperature sensitivity - Google Patents
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本発明は、感温性を有する水溶性増粘剤に関する。さらに詳しくは、Ｎ−置換アクリルアミド構成単位として含む水溶性ポリマーと金属塩と水性媒体とからなり、広いｐＨ範囲と高濃度塩水中で優れた増粘効果を有し、しかも金属イオンの組成と濃度のコントロールで感温点ＬＣＳＴ（下限臨界溶解温度）を測定可能の範囲において自由に調整できることを特徴とした水性増粘剤に関する。
The present invention relates to a water-soluble thickener having temperature sensitivity. More specifically, it is composed of a water-soluble polymer, a metal salt, and an aqueous medium contained as an N-substituted acrylamide structural unit, and has an excellent thickening effect in a wide pH range and high-concentration salt water, and the composition and concentration of metal ions It is related with the aqueous | water-based thickener characterized by the temperature-sensitive point LCST (lower limit critical solution temperature) being freely adjustable in the range which can be measured by control of this.
水溶性増粘剤が石油掘削用添加剤、コンクリート軽量化添加剤、潤滑剤用添加剤、凝集剤、水性分散剤、化粧料、衛生材料、医薬品など広範な分野で使用され、天然系およびその誘導体として多糖類、澱粉、寒天、セルロースなど、合成系としてポリアミド系化合物、ポリビニルアルコール系化合物、ポリアルキレンオキサイド系化合物、ポリアクリル酸系化合物及びこれらの組み合わせた化合物がよく知られている。中にポリアクリルアミド、ポリアクリル酸、ポリアクリル酸ナトリウムなどが安価で増粘効果が高いため、水溶性増粘剤として多く用いられている。また、ポリアクリルアミド系化合物はその水溶液において、ある温度（下限臨界溶解温度：ＬＣＳＴ）以下では溶解した均一な溶液状態となり、ある温度以上では凝集を起こす特性を有することで感温性増粘剤として注目されてきた。（特許文献１〜３）。 Water-soluble thickeners are used in a wide range of fields such as oil drilling additives, concrete lightening additives, lubricant additives, flocculants, aqueous dispersants, cosmetics, hygiene materials, and pharmaceuticals. Polysaccharides, starch, agar, cellulose and the like are well known as derivatives, and polyamide compounds, polyvinyl alcohol compounds, polyalkylene oxide compounds, polyacrylic acid compounds and combinations thereof are well known as synthetic systems. Among them, polyacrylamide, polyacrylic acid, sodium polyacrylate and the like are inexpensive and have a high thickening effect, and are therefore often used as water-soluble thickeners. In addition, polyacrylamide compounds are dissolved in a solution at a certain temperature (lower critical solution temperature: LCST) or lower in an aqueous solution, and have a property of causing aggregation above a certain temperature. Has attracted attention. (Patent Documents 1 to 3).
このような水溶性増粘剤が多様化ニーズに応じえるため、耐熱性、耐酸性、耐アルカリ性、耐塩水性などの機能性に優れたものが求められている。
しかしながら、ポリアクリル酸はｐＨ５以下の酸性下、又は塩の存在下でカルボキシル基が解離し難くなり、溶液の粘度が急激に低下し、酸性や塩共存の条件に対応できない状況であった。
Since such water-soluble thickeners can meet diversification needs, those having excellent functionality such as heat resistance, acid resistance, alkali resistance, and salt water resistance are required.
However, polyacrylic acid is in a situation where it is difficult to dissociate carboxyl groups in the presence of acid at a pH of 5 or lower, or in the presence of a salt, the viscosity of the solution is drastically reduced, and the conditions of acidity and salt coexistence cannot be met.
この問題を解決するために、化粧料に配合する増粘剤として２−アクリルアミド−２−メチルプロパンスルホン酸などアクリルアミドアルキルスルホン酸の使用が提案された（ホモポリマーは特許文献４、アクリル酸との共重合体は特許文献５、アルキル基含有不飽和単量体との共重合体は特許文献６に報告された）。該アクリルアミドアルキルスルホン酸は耐酸性骨格を有するため、酸性条件での使用は可能となったが、塩水中、特にカルシウムなど多価金属塩の存在による溶液粘度低下が改善できず、増粘剤として満足できる使用性に至っているとは言えない。 In order to solve this problem, it has been proposed to use acrylamide alkyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid as a thickener to be blended in cosmetics (the homopolymer is disclosed in Patent Document 4, Patent Document 4). The copolymer was reported in Patent Document 5, and the copolymer with an alkyl group-containing unsaturated monomer was reported in Patent Document 6). Since the acrylamide alkyl sulfonic acid has an acid-resistant skeleton, it can be used under acidic conditions. However, the decrease in solution viscosity due to the presence of a polyvalent metal salt such as calcium in salt water cannot be improved. It cannot be said that the usability is satisfactory.
一方、アクリル酸ナトリウムのホモポリマーとコポリマーは高分子電解質であり、ポリマー鎖が同種電荷の静電反発作用によって伸ばされ、溶液中で拡張した容積を取り、高い溶液粘度を達成し、大きな増粘効果を与えることができる。しかし、水溶性無機塩の添加によるポリマー鎖の拡張は崩壊され、溶液粘度が極端に低下し、極めて深刻的な欠点である。 On the other hand, sodium acrylate homopolymers and copolymers are polyelectrolytes, where the polymer chain is stretched by electrostatic repulsion of the same charge, taking up an expanded volume in solution, achieving high solution viscosity, and large thickening Can give an effect. However, the expansion of the polymer chain due to the addition of water-soluble inorganic salts is disrupted and the solution viscosity is extremely lowered, which is a very serious drawback.
ポリアクリルアミド系増粘剤は、非イオン性であるため、塩類の存在下又は広いｐＨ範囲において、溶液粘度が安定に維持できるという特徴がある。特に、Ｎ−イソプロピルアクリルアミドなどＮ−置換型（メタ）アクリルアミド系ポリマーが、一定温度以上に加熱することで増粘し、冷却すると元の粘度に戻るという熱可逆性の増粘特性を付与できるので、その温度応答性を利用した医薬、農薬、工業など多方面で幅広く応用されている（特許文献７〜１０）。 Since the polyacrylamide thickener is nonionic, it has a feature that the solution viscosity can be stably maintained in the presence of salts or in a wide pH range. In particular, N-substituted (meth) acrylamide polymers such as N-isopropylacrylamide can be given a thermoreversible thickening property that increases in viscosity when heated above a certain temperature and returns to its original viscosity when cooled. It is widely applied in various fields such as pharmaceuticals, agricultural chemicals, and industries using the temperature responsiveness (Patent Documents 7 to 10).
これらのＮ−置換型アクリルアミド系感温性ポリマーが、構成するモノマーの構造改良、親水性又は疎水性ビニルモノマーとの共重合によって、感温点ＬＣＳＴを２０〜１００℃まで変動させることは可能であるが、水溶性無機塩によりＬＣＳＴが低下するという問題点が残されている。例えば、Ｎ−イソプロピルアクリルアミドホモポリマーにおいて、水溶液中のＬＣＳＴが３２℃であるが、塩化カルシウムを５重量％添加するとＬＣＳＴが２６℃となり、塩化カルシウムを２０重量％添加すると、ＬＣＳＴが５℃まで低下してしまい、高塩濃度における一定温度以上の安定な増粘効果が得られない。 These N-substituted acrylamide-based temperature-sensitive polymers can change the temperature-sensitive LCST from 20 to 100 ° C. by improving the structure of the constituent monomers and copolymerizing with hydrophilic or hydrophobic vinyl monomers. However, there remains a problem that the LCST is lowered by the water-soluble inorganic salt. For example, in an N-isopropylacrylamide homopolymer, the LCST in an aqueous solution is 32 ° C., but when 5% by weight of calcium chloride is added, the LCST becomes 26 ° C., and when 20% by weight of calcium chloride is added, the LCST decreases to 5 ° C. Therefore, a stable thickening effect over a certain temperature at a high salt concentration cannot be obtained.
以上のことにより、様々の用途において、高塩濃度含有系、強酸性又は強アルカリ性に求められている感温性増粘剤は未だに見当たらない。 As described above, a thermosensitive thickener required for a high salt concentration-containing system, strong acidity or strong alkalinity has not yet been found in various applications.
本発明の課題は、高塩濃度、広いｐＨ範囲において、感温点ＬＣＳＴをコントロールでき、高耐塩水性、高耐酸性と高耐アルカリ性を併せ持つ感温性を有し、安定な増粘効果を有する水溶性増粘剤を提供することである。 The object of the present invention is to control the temperature sensing point LCST in a high salt concentration and a wide pH range, have a high salt water resistance, a temperature sensitivity having both high acid resistance and high alkali resistance, and a stable thickening effect. It is to provide a water-soluble thickener.
本発明者らは、かかる課題を解決するために鋭意検討を重ねた結果、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミド、ビニルピロリドンを構成単位として含む水溶性ポリマーと、ルイス酸である金属陽イオンを有する金属塩を水性媒体に配合することで上記課題を解決し、さらに、得られる感温性増粘剤が含有する金属イオンの組成と濃度をコントロールすることで感温点を観察可能の範囲において自由に調整する方法を見出し、本発明を完成するに至った。つまり、
（１）Ｎ−置換アクリルアミド構成単位として含む水溶性ポリマーと、金属塩と、水性媒体からなることを特徴とする感温性を有する水溶性増粘剤、
（２）水溶性ポリマーの構成単位であるＮ−置換アクリルアミドは、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミド、ビニルピロリドンからなる群より選ばれる化合物であり、それらの単独重合体、又は共重合体、及びそれらとその他の共重合可能なビニル系単量体との共重合体である（１）記載の感温性を有する水溶性増粘剤、
（３）前述の金属塩が水溶性の無機塩、有機塩、又は錯体、混合塩からなる群より選ばれ、当該金属塩には、少なくとも１種以上のルイス酸である金属陽イオンを含む（１）又は（２）の感温性を有する水溶性増粘剤、
（４）金属塩を１重量％から水性媒体と水溶性ポリマーから構成される水溶液に対する飽和濃度の重量％までを含有する（１）〜（４）の感温性を有する水溶性増粘剤、
（５）Ｎ−置換アクリルアミドを構成単位として含む水溶性ポリマーとルイス酸性金属陽イオンからなる金属塩を水性媒体に溶解したことを特徴とする（１）〜（４）の水性増粘剤（６）感温点（下限臨界溶解温度）を０〜１５０℃に調整できる（１）〜（５）の水溶性増粘剤、
（７）感温点（下限臨界溶解温度）を０〜１５０℃に調整できる（１）〜（６）の水溶性増粘剤の製造方法、
を提供するものである。
As a result of intensive studies to solve such problems, the present inventors have obtained a water-soluble polymer containing acryloylmorpholine, N, N-dimethylacrylamide, and vinylpyrrolidone as constituent units, and a metal cation that is a Lewis acid. In the range in which the temperature sensitive point can be observed by controlling the composition and concentration of the metal ions contained in the resulting temperature-sensitive thickener, by adding the metal salt to the aqueous medium. The inventors have found a method for adjusting freely and have completed the present invention. That means
(1) A water-soluble thickener having temperature sensitivity, characterized by comprising a water-soluble polymer contained as an N-substituted acrylamide structural unit, a metal salt, and an aqueous medium,
(2) N-substituted acrylamide which is a structural unit of the water-soluble polymer is a compound selected from the group consisting of acryloylmorpholine, N, N-dimethylacrylamide and vinylpyrrolidone, and homopolymers or copolymers thereof. And a water-soluble thickener having temperature sensitivity according to (1), which is a copolymer of these and other copolymerizable vinyl monomers,
(3) The metal salt is selected from the group consisting of a water-soluble inorganic salt, organic salt, complex, or mixed salt, and the metal salt contains at least one metal cation that is a Lewis acid ( 1) or (2) a water-soluble thickener having temperature sensitivity;
(4) A water-soluble thickening agent having a temperature sensitivity of (1) to (4), containing a metal salt from 1% by weight to a saturated concentration by weight with respect to an aqueous solution composed of an aqueous medium and a water-soluble polymer.
(5) An aqueous thickener (6) characterized in that a water-soluble polymer containing N-substituted acrylamide as a structural unit and a metal salt composed of a Lewis acidic metal cation are dissolved in an aqueous medium (6) ) (1) to (5) water-soluble thickener capable of adjusting the temperature sensitive point (lower critical solution temperature) to 0 to 150 ° C.,
(7) The method for producing the water-soluble thickener according to (1) to (6), wherein the temperature sensitive point (lower critical solution temperature) can be adjusted to 0 to 150 ° C.
Is to provide.
本発明により、高耐塩水性、高耐酸性と高耐アルカリ性を併せ持つ感温性を有する水溶性増粘剤を提供できる。詳細には、Ｎ−置換アクリルアミド構成単位として含む水溶性ポリマーと金属塩を水性媒体に配合することで高塩濃度、広いｐＨ範囲において、安定的に優れる増粘効果を有する水溶性増粘剤が得られる。
さらに、水溶性ポリマーの構成モノマー品種と比例、増粘剤に配合される金属イオンの組成と濃度のコントロールすることで感温点ＬＣＳＴを自由に調整する方法を提供できる。
INDUSTRIAL APPLICABILITY According to the present invention, a water-soluble thickener having high salt water resistance, high acid resistance, and high temperature sensitivity having high alkali resistance can be provided. Specifically, a water-soluble thickener having a stable and excellent thickening effect in a high salt concentration and a wide pH range by blending a water-soluble polymer containing a N-substituted acrylamide structural unit and a metal salt in an aqueous medium. can get.
Furthermore, it is possible to provide a method for freely adjusting the temperature sensitive point LCST by controlling the composition and concentration of metal ions blended in the thickener in proportion to the constituent monomers of the water-soluble polymer.
以下、本発明について詳細に説明する。
本発明における水溶性ポリマーの構成単位Ｎ−置換アクリルアミドは、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミド、ビニルピロリドンからなる群より選ばれる１種又は２種以上のモノマーである。これらのモノマーの単独重合体、又は共重合体、及びこれらのモノマーとその他の共重合可能なビニル系単量体との共重合体である。
Hereinafter, the present invention will be described in detail.
The structural unit N-substituted acrylamide of the water-soluble polymer in the present invention is one or more monomers selected from the group consisting of acryloylmorpholine, N, N-dimethylacrylamide, and vinylpyrrolidone. These are homopolymers or copolymers of these monomers, and copolymers of these monomers with other copolymerizable vinyl monomers.
その他の共重合可能なビニル系単量体において、得られるポリマーの水溶性を損なわない範囲で特に限定されるものではない。例えば、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−ヒドロキシエチル（メタ）アクリルアミド、Ｎ−ヒドロキシプロピル（メタ）アクリルアミド、Ｎ−ヒドロキシブチル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−ヒドロキシエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジヒドロキシエチル（メタ）アクリルアミドなどの非置換、低級アルキル置換、低級ヒドロキシアルキル置換アクリルアミド類、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチルアクリレートなどのアミノ系モノマー、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどのヒドロキシ低級アルキル（メタ）アクリレート類、アクリロニトリル、(メタ)アクリル酸、アクリル酸メチル、アクリル酸エチルなどのアクリル酸低級アルキルエステル、N-ビニルラクトン、無水マレイン酸などが挙げられる。また、これらの中の１種ないし２種以上のモノマーを混合して使用することができる。 Other copolymerizable vinyl monomers are not particularly limited as long as the water solubility of the resulting polymer is not impaired. For example, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-hydroxymethyl ( (Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-methyl-N-hydroxyethyl (meth) acrylamide, N, N-dihydroxyethyl Non-substituted, lower alkyl-substituted, lower hydroxyalkyl-substituted acrylamides such as (meth) acrylamide, amino-based mono, such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate -Hydroxy lower alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, acrylonitrile, (meth) acrylic acid, methyl acrylate, ethyl acrylate, etc. Acrylic acid lower alkyl ester, N-vinyl lactone, maleic anhydride and the like. One or more of these monomers can be mixed and used.
共重合体は、構成単位であるＮ−置換アクリルアミドの使用割合としては１０〜１００重量％、また、十分な感温増粘効果を確保する観点から、好ましくは、２０〜１００重量％、より好ましくは、３０〜１００重量％程度である。Ｎ−置換アクリルアミドの使用量が１０％以下では、高塩濃度、強酸性又は強アルカリ性領域において、共重合モノマーの品種と組配合比にもよるが、十分な増粘効果を付与できない可能性があり、好ましくない。 The copolymer is preferably used in an amount of 10 to 100% by weight of the N-substituted acrylamide as a structural unit, and preferably 20 to 100% by weight, more preferably from the viewpoint of securing a sufficient temperature-sensitive thickening effect. Is about 30 to 100% by weight. If the amount of N-substituted acrylamide used is 10% or less, there is a possibility that a sufficient thickening effect cannot be imparted in a high salt concentration, strongly acidic or strongly alkaline region, depending on the copolymer monomer type and combination ratio. Yes, not preferred.
重合方法としては、特に限定されるものではなく、公知のラジカル重合開始剤、連鎖移動剤などを使用してラジカル重合法により実施可能である。例えば溶液重合、塊状重合、乳化重合、懸濁重合などの熱重合法や、紫外線による光重合法があり、本発明においては、水溶性増粘剤として提供されるため、特に水溶液重合が好ましい。 The polymerization method is not particularly limited, and can be carried out by a radical polymerization method using a known radical polymerization initiator, chain transfer agent or the like. For example, there are thermal polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization, and photopolymerization using ultraviolet rays. In the present invention, aqueous polymerization is particularly preferable because it is provided as a water-soluble thickener.
重合は通常ラジカル重合開始剤の存在下、所定温度に保つことにより行う。重合中、同一温度に保つ必要はなく、重合の進行にともない適宜変えてよく、必要に応じて加熱あるいは除熱しながら行う。重合温度は使用するモノマーの種類や重合開始剤の種類などにより異なり、単一開始剤の場合には概ね３０〜１００℃の範囲であり、レドックス系重合開始剤の場合にはより低く、一括で重合を行う場合には概ね−５〜６０℃であり、逐次添加する場合には概ね−５〜１００℃である。重合器内の雰囲気は特に限定はないが、重合を速やかに行わせるには窒素ガスのような不活性ガスで置換した方がよい。重合時間は特に限定はないが、概ね１〜４０時間である。 The polymerization is usually carried out by maintaining a predetermined temperature in the presence of a radical polymerization initiator. During the polymerization, it is not necessary to maintain the same temperature, and it may be changed as the polymerization proceeds, and is performed while heating or removing heat as necessary. The polymerization temperature varies depending on the type of monomer used and the type of polymerization initiator, and is generally in the range of 30 to 100 ° C. in the case of a single initiator, lower in the case of a redox polymerization initiator, and collectively. When the polymerization is carried out, it is generally -5 to 60 ° C, and when it is successively added, it is generally -5 to 100 ° C. The atmosphere in the polymerization vessel is not particularly limited, but it is better to substitute with an inert gas such as nitrogen gas in order to perform the polymerization quickly. The polymerization time is not particularly limited, but is generally 1 to 40 hours.
ラジカル重合開始剤としては一般の重合開始剤が使用でき、また、水を溶媒とする場合の重合開始剤としては水溶性のものであれば特に制限はない。具体的には過酸化物系では、例えば、過硫酸アンモニウム、過硫酸カリウム、過酸化水素、ｔｅｒｔ−ブチルパーオキサイドなどが挙げられる。この場合、単独でも使用できるが、還元剤と組み合わせてレドックス系重合開始剤としても使える。還元剤としては、例えば亜硫酸塩、亜硫酸水素塩、次亜リン酸、次亜リン酸塩、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラメチルエチレンジアミンなどを挙げることができる。また、アゾ化合物としては、２，２'− アゾビス−２−アミジノプロパン塩酸塩、２，２'− アゾビス−２，４−ジメチルバレロニトリル、４，４'−アゾビス−４− シアノバレイン酸及びその塩などを使用することができる。更に上記した重合開始剤を２種以上併用してもよい。 A general polymerization initiator can be used as the radical polymerization initiator, and the water-soluble polymerization initiator is not particularly limited as long as it is water-soluble. Specific examples of peroxides include ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl peroxide. In this case, it can be used alone, but it can also be used as a redox polymerization initiator in combination with a reducing agent. Examples of the reducing agent include sulfite, bisulfite, hypophosphorous acid, hypophosphite, N, N, N ′, N′-tetramethylethylenediamine, and the like. Examples of the azo compound include 2,2′-azobis-2-amidinopropane hydrochloride, 2,2′-azobis-2,4-dimethylvaleronitrile, 4,4′-azobis-4-cyanovaleric acid and salts thereof. Etc. can be used. Furthermore, two or more kinds of the above polymerization initiators may be used in combination.
ラジカル重合開始剤の使用量は、モノマーの総計量１００重量％に対して、好ましくは０．０１〜１０重量％、特に好ましくは０．１〜５重量％である。 The amount of the radical polymerization initiator used is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on 100% by weight of the total amount of monomers.
連鎖移動剤は、特に限定されず公知のものを用いることができる。また、水を溶媒とする場合の連鎖移動剤としては水溶性のものであればよい。具体的には、例えば、メルカプトエタノール、チオグリコール酸、α−チオグリセリン、２−メルカプトエチルアミン塩酸塩、１，２−ジメチルカプトエタンなどが挙げられる。連鎖移動剤の使用量としては、重合体を構成するモノマーの総計量１００重量部に対して０．００１〜１０重量部程度使用される。 A chain transfer agent is not specifically limited, A well-known thing can be used. The chain transfer agent in the case of using water as a solvent may be water-soluble. Specific examples include mercaptoethanol, thioglycolic acid, α-thioglycerin, 2-mercaptoethylamine hydrochloride, 1,2-dimethylcaptoethane, and the like. The amount of the chain transfer agent used is about 0.001 to 10 parts by weight with respect to 100 parts by weight of the total monomer constituting the polymer.
重合に供するモノマー類、ラジカル重合開始剤連鎖移動剤などのほかに、必要に応じてｐＨ調整剤などを併用し、重合を開始する時点で一度に反応容器に仕込んでもよいが、重合の進行に応じて、１種あるいはそれ以上の成分を、単独あるいは溶媒などに混合したものを逐次添加してもよい。重合時のモノマー（総計量）は水あるいは有機溶媒に対して５〜８５重量％、好ましく５〜５０重量％である。水溶液中のラジカル重合で得られたポリマーは水溶液のまま使用できるが、有機溶媒中の重合された場合は公知の方法、例えば、溶媒除去、貧溶媒での沈殿、乾燥など方法でポリマーを分離、精製してから使用すると良い。 In addition to monomers to be used for polymerization, radical polymerization initiator chain transfer agent, etc., if necessary, a pH adjuster or the like may be used together and charged into the reaction vessel at the time of starting the polymerization. Depending on the type, one or more components may be added singly or mixed in a solvent or the like. The monomer (total amount) at the time of polymerization is 5 to 85% by weight, preferably 5 to 50% by weight, based on water or an organic solvent. The polymer obtained by radical polymerization in an aqueous solution can be used as an aqueous solution, but when polymerized in an organic solvent, the polymer is separated by a known method such as solvent removal, precipitation in a poor solvent, drying, It is recommended to use after purification.
このようにして得られるポリマーの重量平均分子量はポリエチレンオキサイド換算で、特に制限はないが、通常、１，０００〜２０，０００，０００、好ましくは１０，０００〜５，０００，０００、さらに好ましくは１００，０００〜２，０００，０００である。共重合体の分子量が１，０００以下では、感温点を示さず、増粘剤として好ましくない。一方、分子量が２０，０００，０００を超えると、製造した増粘剤を水に溶かした場合、水に溶解し難くなり、共重合体の組成によって不溶成分が発生する可能性があり、好ましくない。 The weight average molecular weight of the polymer thus obtained is not particularly limited in terms of polyethylene oxide, but is usually 1,000 to 20,000,000, preferably 10,000 to 5,000,000, more preferably 100,000 to 2,000,000. When the molecular weight of the copolymer is 1,000 or less, the temperature sensitive point is not exhibited, which is not preferable as a thickener. On the other hand, when the molecular weight exceeds 20,000,000, when the produced thickener is dissolved in water, it becomes difficult to dissolve in water, and an insoluble component may be generated depending on the composition of the copolymer, which is not preferable. .
本発明の金属塩は水溶性の無機塩、有機塩、又は錯体、混合塩である。例えば、塩酸、硫酸、硝酸、リン酸、炭酸、酢酸、乳酸、クエン酸などの金属塩が挙げられ、特に水性媒体に対する溶解性の高い無機塩が好ましい。 The metal salt of the present invention is a water-soluble inorganic salt, organic salt, complex or mixed salt. Examples thereof include metal salts such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, acetic acid, lactic acid, and citric acid, and inorganic salts that are particularly highly soluble in an aqueous medium are preferable.
金属塩の金属イオンとしては、リチウムイオン、ナトリウムイオン、カリウムイオンなどのアルカリ金属イオン、マグネシウムイオン、カルシウムイオンなどのアルカリ土類金属イオン、アルミニウムイオン、ガリウムイオンなどのアルミニウム族金属イオン、スズイオン、鉛イオンなどの炭素族金属イオン、チタンイオン、クロムイオン、マンガンイオン、鉄イオン、コバルトイオン、ニッケルイオン銅イオン、亜鉛イオンなどの遷移金属イオンが挙げられる。これらの金属イオンからなる群より選択される１種又は２種以上を用いることができる。 Metal ions of the metal salt include alkali metal ions such as lithium ion, sodium ion and potassium ion, alkaline earth metal ions such as magnesium ion and calcium ion, aluminum group metal ions such as aluminum ion and gallium ion, tin ion and lead Examples include carbon group metal ions such as ions, transition metal ions such as titanium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, and zinc ions. One or more selected from the group consisting of these metal ions can be used.
前記の金属塩は少なくとも１種以上はルイス酸である金属陽イオンから構成される。具体的には、１価のリチウムイオン、銀イオン、２価のマグネシウムイオン、カルシウムイオン、銅イオン、亜鉛イオン、鉄イオン、ニッケルイオン、３価のアルミニウムイオン、鉄イオン、クロムイオン、コパルトイオンなどが挙げられる。 At least one of the metal salts is composed of a metal cation that is a Lewis acid. Specifically, monovalent lithium ion, silver ion, divalent magnesium ion, calcium ion, copper ion, zinc ion, iron ion, nickel ion, trivalent aluminum ion, iron ion, chromium ion, cobalt ion, etc. Can be mentioned.
金属塩の使用量は水性媒体と水溶性ポリマーから構成される水溶液に対して、１重量％から飽和濃度の重量％まで、好ましくは２重量％以上から飽和濃度の重量％まで、特に好ましくは３重量％以上から飽和濃度の重量％まで、である。本発明の水溶性ポリマーの構成単位Ｎ−置換アクリルアミドは、ポリマー分子内、分子間、又はポリマーと水性媒体の間に水素結合を形成するため、ポリマー濃度にも関連するが、金属塩の添加量は１重量％未満の場合、水素結合を十分に破壊できず、ルイス酸性金属イオンによる十分な感温増粘効果が得られないことがある。 The amount of the metal salt used is from 1% by weight to a saturated concentration by weight, preferably from 2% by weight to a saturated concentration by weight, particularly preferably 3%, based on an aqueous solution composed of an aqueous medium and a water-soluble polymer. From more than% by weight to% by weight of saturation concentration. The structural unit N-substituted acrylamide of the water-soluble polymer of the present invention forms a hydrogen bond within the polymer molecule, between the molecules, or between the polymer and the aqueous medium. If it is less than 1% by weight, hydrogen bonds cannot be sufficiently broken, and a sufficient temperature-sensitive thickening effect by Lewis acidic metal ions may not be obtained.
本発明の水性媒体とは、水を主成分として含む液媒体である。例えば、水、水と混和性を有する有機溶媒との混合液が用いられる。また、水については、特に限定なく使用可能である。純水やイオン交換水などの上質の水を使用することもできるが、水道水、工業用水、河川水、海水、地下水など入手の容易な水も利用することができる。 The aqueous medium of the present invention is a liquid medium containing water as a main component. For example, a mixed solution of water or an organic solvent miscible with water is used. Moreover, about water, it can be used without limitation. High-quality water such as pure water or ion exchange water can be used, but easily available water such as tap water, industrial water, river water, seawater, and groundwater can also be used.
本発明の水溶性増粘剤は、Ｎ−置換アクリルアミドを構成単位として含む水溶性ポリマーとルイス酸性金属陽イオンからなる金属塩を水性媒体に溶解することで得られる。溶解方法は公知の方法が用いられ、例えばポリマーと金属塩を別々に水性媒体に溶解してから混合する方法、ポリマーを溶解した水性媒体に金属塩を添加して、溶解させる方法、又は金属塩を溶解した水性媒体に精製したポリマーを添加して溶解させる方法、水性媒体に精製したポリマーと金属塩を溶解させる方法が挙がられる。またポリマーと金属塩の添加順序については特に限定しない。 The water-soluble thickener of the present invention can be obtained by dissolving a water-soluble polymer containing N-substituted acrylamide as a structural unit and a metal salt composed of a Lewis acidic metal cation in an aqueous medium. A known method is used as the dissolution method, for example, a method in which a polymer and a metal salt are separately dissolved in an aqueous medium and then mixed, a method in which a metal salt is added to an aqueous medium in which a polymer is dissolved, and a metal salt is dissolved. There are a method in which a purified polymer is added and dissolved in an aqueous medium in which is dissolved, and a method in which the purified polymer and a metal salt are dissolved in an aqueous medium. Further, the order of adding the polymer and the metal salt is not particularly limited.
本発明の水溶性増粘剤において、水溶性ポリマーは、水性媒体に対して０．１〜５０重量％含有する。好ましくは、０．１〜３０重量％、さらに好ましくは、０．２〜１０重量％である。これ以外の含有量であると、高塩濃度、広いｐＨ範囲において、安定的に優れる増粘効果を有する水溶性増粘剤が得られない。 In the water-soluble thickener of the present invention, the water-soluble polymer is contained in an amount of 0.1 to 50% by weight based on the aqueous medium. Preferably, it is 0.1 to 30% by weight, and more preferably 0.2 to 10% by weight. If the content is other than this, a water-soluble thickener having a thickening effect that is stably excellent in a high salt concentration and a wide pH range cannot be obtained.
本発明の感温点を有する水性増粘剤の感温点ＬＣＳＴ（下限臨界溶解温度）を０〜１５０℃自由に調整することができる。感温点の調整方法としては、公知の親水性モノマーとの共重合で感温点を向上させ、疎水性モノマーの共重合で感温点を低下させる方法、本発明の金属塩添加による感温点調整の方法、またはそれらの方法を併用することができる。 The temperature sensitive point LCST (lower critical solution temperature) of the aqueous thickener having the temperature sensitive point of the present invention can be freely adjusted from 0 to 150 ° C. As a method for adjusting the temperature sensitive point, a method of improving the temperature sensitive point by copolymerization with a known hydrophilic monomer and a method of lowering the temperature sensitive point by copolymerization of a hydrophobic monomer, the temperature sensitive effect by adding the metal salt of the present invention. A point adjustment method or a combination of these methods can be used.
本発明の金属塩添加による感温点調整の方法はルイス酸性金属イオンの配合で感温点を向上、ルイス酸性以外の金属イオンの配合で感温点を低下させる方法である。また、金属塩の含有量が多いほど、感温点の向上又は低下する幅が大きい。 The method of adjusting the temperature point by adding a metal salt of the present invention is a method of improving the temperature point by blending Lewis acidic metal ions and decreasing the temperature point by blending metal ions other than Lewis acid. Moreover, the greater the content of the metal salt, the greater the range in which the temperature sensitive point is improved or decreased.
本発明の感温性を有する水溶性増粘剤が温度により溶液の粘度変化が起きるため、種々の用途に使用することが可能である。例えば、耐高濃度塩水感温性ゲル化剤、金属イオン吸着剤、水処理剤、紙加工剤、土壌改質剤、繊維改質剤と加工剤、石油掘削剤、天然ガス抽出でのガス水和物生成の抑制剤、感温性凝集剤、コンクリート混合剤、化粧料、ヘアセッティング又はヘアスプレー添加剤、入浴剤、衛生用品、薬物徐放性の媒体、印刷インク、感温遮光シート、湿度センサー、土壌保水材、保護コーティング剤、感温性分離材料、保冷剤、水性塗料等の用途として使用可能である。 Since the temperature-sensitive water-soluble thickener of the present invention changes the viscosity of the solution depending on the temperature, it can be used for various applications. For example, high-concentration salt water temperature-sensitive gelling agent, metal ion adsorbent, water treatment agent, paper processing agent, soil modifier, fiber modifier and processing agent, petroleum drilling agent, gas water in natural gas extraction Inhibitor of Japanese product formation, temperature-sensitive flocculant, concrete admixture, cosmetics, hair setting or hair spray additive, bath agent, hygiene product, drug sustained-release medium, printing ink, temperature-sensitive light-shielding sheet, humidity It can be used for applications such as sensors, soil water retention materials, protective coating agents, temperature sensitive separation materials, cold insulation agents, and water-based paints.
本発明の感温性を有する水溶性増粘剤の感温増粘特性を阻害しない範囲で、顔料、染料、酸化防止剤、紫外線吸収剤、防腐防かび剤、消臭剤、香料などの他の任意成分を併用してもよい。 Other than pigments, dyes, antioxidants, ultraviolet absorbers, antiseptics, antiseptics, fragrances, etc., as long as the temperature-sensitive thickening properties of the temperature-sensitive water-soluble thickener of the present invention are not impaired. These optional components may be used in combination.
以下、実施例によって本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例中、％および部は、特に断わらない限り重量基準である。また、実施例における各種物性の測定又は評価は以下の方法で行った。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the examples,% and parts are based on weight unless otherwise specified. In addition, various physical properties in the examples were measured or evaluated by the following methods.
重量平均分子量測定：重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって分析した結果を、ポリエチレンオキサイドを標準サンプルとして作成した検量線を用いて換算したものである。ここで、ＧＰＣの測定条件は、下記の通りである。
ＧＰＣ：（株）島津製作所製 ＬＣ−１０Ａ
カラム：Ｗａｔｅｒ製のＵｌｔｒａｈｙｄｒｏｇｅｌ Ｌｉｎｅｒ（７．８ｍｍ×３００ｍｍ）
検出器：示差屈折計ＲＩＤ−１０Ａ
溶離液：０．５ｍｏｌ／Ｌ 硝酸ナトリウム水溶液
流速：０．５ｍＬ／分
温度：３０℃
サンプル濃度：０．１％
サンプル注入量：２０μＬ
Weight average molecular weight measurement: The weight average molecular weight is obtained by converting the result of analysis by gel permeation chromatography (GPC) using a calibration curve prepared using polyethylene oxide as a standard sample. Here, the measurement conditions of GPC are as follows.
GPC: LC-10A manufactured by Shimadzu Corporation
Column: Ultrahydrogel Liner (7.8 mm x 300 mm) manufactured by Water
Detector: differential refractometer RID-10A
Eluent: 0.5 mol / L Sodium nitrate aqueous solution Flow rate: 0.5 mL / min Temperature: 30 ° C
Sample concentration: 0.1%
Sample injection volume: 20 μL
粘度測定：（株）東京計器製のＢ型粘度計（測定温度２５℃〜８０℃の時に使用した）；
東機産業（株）製コーンプレート型RE550型粘度計（測定温度１００℃以上の時に使用した）
Viscosity measurement: B-type viscometer manufactured by Tokyo Keiki Co., Ltd. (used when the measurement temperature is 25 ° C. to 80 ° C.);
Cone plate type RE550 viscometer manufactured by Toki Sangyo Co., Ltd. (used when measuring temperature is 100 ° C or higher)
合成例１
攪拌機，温度計，還流冷却管及び窒素ガス導入管を備えた１Ｌの反応容器に脱イオン水２５０部、アクリロイルモルホリン（ＡＣＭＯ）４５部を仕込み、希硫酸にてｐＨを６．５に調節し、窒素ガスを通じて反応系内の酸素を除去した。系内を２５℃とし、開始剤として５％過硫酸アンモニウム水溶液２．９１部および２％亜硫酸水素ナトリウム水溶液３．６５部を投入した。窒素ガスを吹き込みながら、２５℃で１０ｈ攪拌を行った。その後脱イオン水１５０部を加え、固形分１０％、粘度３３０ｃｐｓ、重量平均分子量７３万のアクリロイルモルホリンホモポリマー水溶液を得た。
Synthesis example 1
A 1 L reaction vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 250 parts of deionized water and 45 parts of acryloylmorpholine (ACMO), and the pH was adjusted to 6.5 with dilute sulfuric acid. Oxygen in the reaction system was removed through nitrogen gas. The temperature inside the system was 25 ° C., and 2.91 parts of 5% aqueous ammonium persulfate solution and 3.65 parts of 2% aqueous sodium hydrogen sulfite solution were added as initiators. The mixture was stirred at 25 ° C. for 10 hours while blowing nitrogen gas. Thereafter, 150 parts of deionized water was added to obtain an aqueous acryloylmorpholine homopolymer solution having a solid content of 10%, a viscosity of 330 cps, and a weight average molecular weight of 730,000.
合成例２
攪拌機，温度計，還流冷却管及び窒素ガス導入管を備えた１Ｌの反応容器に脱イオン水４００部、アクリロイルモルホリン（ＡＣＭＯ）４５部を仕込み、窒素ガスを通じて反応系内の酸素を除去した。系内を５０℃とし、水溶性アゾ系開始剤ＶＡ−０４４（和光純薬製）の１０％水溶液２．０６部を投入した。窒素ガスを吹き込みながら、５０℃で１０ｈ攪拌し、固形分１０％、粘度２３００ｃｐｓ、重量平均分子量２４２万のアクリロイルモルホリンホモポリマー水溶液を得た。
Synthesis example 2
400 parts of deionized water and 45 parts of acryloylmorpholine (ACMO) were charged into a 1 L reaction vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, and oxygen in the reaction system was removed through nitrogen gas. The system was set to 50 ° C., and 2.06 parts of a 10% aqueous solution of a water-soluble azo initiator VA-044 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. While blowing nitrogen gas, the mixture was stirred at 50 ° C. for 10 hours to obtain an aqueous acryloylmorpholine homopolymer solution having a solid content of 10%, a viscosity of 2300 cps, and a weight average molecular weight of 220,000.
合成例３〜８
合成例１又は合成例２において、構成モノマー成分の種類またはそれらの配合比を表１のように変えたほか、合成例１又は合成例２と同様の操作を行い、各種のホモポリマーとコポリマー水溶液を得た。各合成例の仕込み比、得られた各ポリマー水溶液の組成及び性状値を表１に示す。
Synthesis Examples 3-8
In Synthetic Example 1 or Synthetic Example 2, the types of constituent monomer components or their blending ratios were changed as shown in Table 1, and the same operations as in Synthetic Example 1 or Synthetic Example 2 were performed. Got. Table 1 shows the charging ratio of each synthesis example, the composition and property values of each polymer aqueous solution obtained.
実施例１〜１１
合成例１で製造した固形分１０％、粘度３３０ｃｐｓのアクリロイルモルホリンホモポリマー水溶液９０ｇを量り取って、脱イオン水３６０ｇと表２に示す所定量の塩化カルシウム（ＣａＣｌ２）、塩化マグネシウム（ＭｇＣｌ２）、塩化アルミニウム（ＡｌＣｌ３）を加え、室温で攪拌しながら無機塩を溶解させ、さらに２４ｈ静置し、目的の水溶性増粘剤を得た。
Examples 1-11
90 g of an acryloylmorpholine homopolymer aqueous solution having a solid content of 10% and a viscosity of 330 cps produced in Synthesis Example 1 was weighed, and 360 g of deionized water and predetermined amounts of calcium chloride (CaCl 2), magnesium chloride (MgCl 2), and chloride shown in Table 2 were obtained. Aluminum (AlCl3) was added, the inorganic salt was dissolved while stirring at room temperature, and the mixture was further allowed to stand for 24 hours to obtain the desired water-soluble thickener.
製造した水溶性増粘剤を測定試料として毛細管に入れて封管し、オイルバスの温度センサー付近に取り付けた。オイルバス中のオイルを攪拌しながら加熱し、測定試料が濁った時の温度を下限臨界溶解温度（ＬＣＳＴ）とする。表２に各水溶性増粘剤のＬＳＣＴ、図１にＬＣＳＴと無機塩品種、濃度の相関を示す。 The produced water-soluble thickener was put in a capillary tube as a measurement sample, sealed, and attached near the temperature sensor of the oil bath. The oil in the oil bath is heated with stirring, and the temperature when the measurement sample becomes cloudy is defined as the lower critical solution temperature (LCST). Table 2 shows the LSCT of each water-soluble thickener, and FIG. 1 shows the correlation between LCST, inorganic salt variety, and concentration.
実施例１２〜１８
合成例で製造したポリマー水溶液、脱イオン水、塩化カルシウム（ＣａＣｌ２）を表３に示す所定量を量り取って、室温で混合させ、さらに２４ｈ静置し、目的の水溶性増粘剤を得た。実施例１と同様にＬＣＳＴを測定し、表３に示す。
Examples 12-18
A predetermined amount of the polymer aqueous solution, deionized water, and calcium chloride (CaCl2) produced in the synthesis example were weighed out and mixed at room temperature, and allowed to stand for 24 hours to obtain the target water-soluble thickener. . LCST was measured in the same manner as in Example 1, and is shown in Table 3.
比較例１〜１６
合成例で製造したポリマー水溶液、脱イオン水、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）硫酸ナトリウム（Ｎａ２ＳＯ４）を表４に示す所定量を量り取って、室温で混合させ、さらに２４ｈ静置し、比較の水溶性増粘剤を得た。実施例１と同様にＬＣＳＴを測定し、表４と図２に示す。
Comparative Examples 1-16
A predetermined amount of the polymer aqueous solution, deionized water, sodium chloride (NaCl), and potassium chloride (KCl) sodium sulfate (Na2SO4) prepared in the synthesis example were weighed out at room temperature and allowed to stand for 24 hours. A comparative water-soluble thickener was obtained. LCST was measured in the same manner as in Example 1, and is shown in Table 4 and FIG.
実施例１９〜４２
合成例で製造したポリマー水溶液、脱イオン水、塩化ナトリウム（ＮａＣｌ）、硫酸ナトリウム（Ｎａ２ＳＯ４）、塩化カルシウム（ＣａＣｌ２）を表５に示す所定量を量り取って、室温で混合させ、さらに２４ｈ静置し、目的の水溶性増粘剤を得た。実施例１と同様にＬＣＳＴを測定し、表５、図４、と図５に示す。
Examples 19-42
A predetermined amount of the polymer aqueous solution, deionized water, sodium chloride (NaCl), sodium sulfate (Na 2 SO 4), and calcium chloride (CaCl 2) prepared in the synthesis example are weighed out at room temperature and mixed for 24 hours. The desired water-soluble thickener was obtained. LCST was measured in the same manner as in Example 1, and is shown in Table 5, FIG. 4, and FIG.
試験例：増粘効果
ポリマー濃度１０ｗｔ％の実施例１２〜１５と比較例１〜４で製造された水溶性増粘剤を毎分２℃の温度勾配で昇温して、粘度を測定した。その結果を表６に示す。
Test Example: Thickening Effect Water-soluble thickeners produced in Examples 12 to 15 and Comparative Examples 1 to 4 having a polymer concentration of 10 wt% were heated at a temperature gradient of 2 ° C. per minute, and the viscosity was measured. The results are shown in Table 6.
試験例：耐酸性、耐塩基性評価
実施例１〜１１で製造された水溶性増粘剤のｐＨを１０ｍｏｌ／Ｌの塩酸で１、また水酸化ナトリウム水溶液で１４に調製し、実施例１と同様にＬＣＳＴを測定した。結果は、ｐＨ１と１４は共に表２と図１に示すＬＣＳＴが観察され、本発明の感温性を有する水溶性増粘剤の感温点が水溶液のｐＨに左右されなかった。
Test example: Acid resistance and base resistance evaluation
The pH of the water-soluble thickener produced in Examples 1 to 11 was adjusted to 1 with 10 mol / L hydrochloric acid and 14 with an aqueous sodium hydroxide solution, and LCST was measured in the same manner as in Example 1. As a result, the LCSTs shown in Table 2 and FIG. 1 were observed for both pH 1 and 14, and the temperature sensitive point of the water-soluble thickener having the temperature sensitivity of the present invention was not affected by the pH of the aqueous solution.
以上の結果から、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミド、ビニルピロリドンを構成単位として含む水溶性ポリマーは感温性を有し、感温点以下の温度範囲では温度の上昇と共に水溶液粘度が徐々に低下し、感温点以上の温度ではポリマーの凝集が起こり、水溶液からポリマーが析出、沈降するため、水溶液粘度が急激に低下し、増粘剤の効果が失ってしまう。通常の無機塩添加による水溶液粘度が少々向上できるが、反面に塩濃度の向上と共に感温点（ＬＣＳＴ）が低下し、高温領域での使用は不可能であった。しかし、これらのポリマー水溶液にルイス酸性金属陽イオンを配合することによって、ＬＣＳＴ以上の温度でポリマー水溶液の粘度が急激に増加し、優れる増粘効果を得ることができた。それは、ポリマーとルイス酸性金属陽イオンの間に錯体を形成し、ポリマーが水溶液から析出せず、均一且つ高粘度を維持することができるようになったと本発明者らが推察している。 From the above results, the water-soluble polymer containing acryloylmorpholine, N, N-dimethylacrylamide, and vinylpyrrolidone as a structural unit has temperature sensitivity, and the viscosity of the aqueous solution gradually increases with increasing temperature in the temperature range below the temperature sensitive point. When the temperature is higher than the temperature sensitive point, the polymer aggregates and the polymer precipitates and settles out of the aqueous solution, so that the viscosity of the aqueous solution is drastically lowered and the effect of the thickener is lost. Although the viscosity of the aqueous solution can be slightly improved by adding an ordinary inorganic salt, the temperature sensitive point (LCST) is lowered as the salt concentration is increased, and the use in a high temperature region is impossible. However, by adding a Lewis acidic metal cation to these polymer aqueous solutions, the viscosity of the polymer aqueous solution rapidly increased at a temperature of LCST or higher, and an excellent thickening effect could be obtained. The inventors speculate that a complex is formed between the polymer and the Lewis acid metal cation so that the polymer does not precipitate from the aqueous solution and can maintain a uniform and high viscosity.
さらに本発明の水溶性増粘剤において、配合する無機塩の品種と濃度の組み合わせによってＬＣＳＴが測定可能の温度範囲内で任意に調整することができ、強酸性から強アルカリ性まで全ｐＨ領域においても増粘特性を維持できた。即ち、本発明で製造した水溶性増粘剤が十分な耐熱性、耐加水分解性を有し、高温、高濃度塩水下、広範なｐＨ領域においても優れた増粘効果を有する水溶性増粘剤を提供できることが明らかであった。 Furthermore, in the water-soluble thickener of the present invention, it can be arbitrarily adjusted within the temperature range in which LCST can be measured by the combination of the variety and concentration of the inorganic salt to be blended, and even in the entire pH range from strong acidity to strong alkalinity. The thickening property could be maintained. That is, the water-soluble thickener produced in the present invention has sufficient heat resistance and hydrolysis resistance, and has an excellent thickening effect even in a wide pH range under high temperature and high concentration salt water. It was clear that an agent could be provided.
以上説明してきたように、本発明の水溶性増粘剤は、Ｎ−置換アクリルアミド構成単位として含む水溶性ポリマーと金属塩を水性媒体に配合することで高塩濃度、広いｐＨ範囲、温度範囲において、感温点ＬＣＳＴは任意に調整でき、安定的に優れる増粘効果を有し、石油掘削用添加剤、コンクリート軽量化添加剤、潤滑剤用添加剤、凝集剤、水性分散剤、化粧料、衛生材料、医薬品など広範な分野で使用できる。特に、高耐塩水性、高耐酸性と高耐アルカリ性を有するため、高塩濃度含有系、強酸性又は強アルカリなど過酷の環境に好適に用いることができる。 As described above, the water-soluble thickener of the present invention can be used in a high salt concentration, a wide pH range, and a temperature range by blending a water-soluble polymer containing a N-substituted acrylamide structural unit and a metal salt in an aqueous medium. The temperature sensitive point LCST can be arbitrarily adjusted and has a stable and excellent thickening effect, such as oil drilling additives, concrete lightening additives, lubricant additives, flocculants, aqueous dispersions, cosmetics, It can be used in a wide range of fields such as sanitary materials and pharmaceuticals. In particular, since it has high salt water resistance, high acid resistance and high alkali resistance, it can be suitably used in harsh environments such as high salt concentration-containing systems, strong acidity or strong alkali.
Claims (7)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015086349A (en) * | 2013-11-01 | 2015-05-07 | 株式会社ダイセル | Thickener |
| JP2017036404A (en) * | 2015-08-11 | 2017-02-16 | 日本ペイントホールディングス株式会社 | Composition, manufacturing method of micro-sucker film, micro-sucker film and article |
| CN113956492A (en) * | 2021-11-22 | 2022-01-21 | 卫辉市化工有限公司 | Preparation method and application of intelligent temperature-change polymer plugging agent |
| JP7523743B2 (en) | 2019-03-29 | 2024-07-29 | 国立大学法人秋田大学 | Method for producing filler for temperature-sensitive display member |
-
2009
- 2009-06-25 JP JP2009151488A patent/JP2011006581A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015086349A (en) * | 2013-11-01 | 2015-05-07 | 株式会社ダイセル | Thickener |
| JP2017036404A (en) * | 2015-08-11 | 2017-02-16 | 日本ペイントホールディングス株式会社 | Composition, manufacturing method of micro-sucker film, micro-sucker film and article |
| JP7523743B2 (en) | 2019-03-29 | 2024-07-29 | 国立大学法人秋田大学 | Method for producing filler for temperature-sensitive display member |
| CN113956492A (en) * | 2021-11-22 | 2022-01-21 | 卫辉市化工有限公司 | Preparation method and application of intelligent temperature-change polymer plugging agent |
| CN113956492B (en) * | 2021-11-22 | 2023-03-03 | 卫辉市化工有限公司 | Preparation method and application of intelligent temperature-change polymer plugging agent |
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