JPH069848A - Thermally reversible thickening agent - Google Patents
Thermally reversible thickening agentInfo
- Publication number
- JPH069848A JPH069848A JP4046142A JP4614292A JPH069848A JP H069848 A JPH069848 A JP H069848A JP 4046142 A JP4046142 A JP 4046142A JP 4614292 A JP4614292 A JP 4614292A JP H069848 A JPH069848 A JP H069848A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- polymer
- viscosity
- water
- morpholine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、増粘剤に関し、更に詳
しくは、水、水と水系溶剤の混合物、ラテックス、エマ
ルション、水系塗料、水系接着剤、水系染色剤等の水性
液の熱可逆型増粘剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thickener, and more specifically, it is a thermoreversible agent for water, a mixture of water and an aqueous solvent, a latex, an emulsion, an aqueous paint, an aqueous adhesive, an aqueous dye and the like. Mold thickener.
【０００２】[0002]
【従来の技術】従来、一定の転移温度を越えると水性液
を増粘させるような熱可逆型増粘剤としては、メチルセ
ルロース、Ｎ−アルキルアクリルアミド系重合体などが
提案されている（例えば特開平1-14276号公報）。2. Description of the Related Art Heretofore, as a thermoreversible thickener which thickens an aqueous liquid when a certain transition temperature is exceeded, methyl cellulose, N-alkyl acrylamide polymers and the like have been proposed (for example, Japanese Patent Laid-Open Publication No. Hei 10 (1999) -242242). 1-14276 publication).
【０００３】[0003]
【発明が解決しようとする課題】しかし、従来のメチル
セルロースなどは、増粘を開始する温度を調整しにく
く、転移温度以上に温度が上がっても急勾配に増粘しな
いという欠点を有しており、Ｎ−アルキルアクリルアミ
ド系重合体は、転移温度を調整するためにはその温度に
応じたアルキル基を有するＮ−アルキルアクリルアミド
の種々原料を調達のうえ合成し、重合する必要があっ
た。However, the conventional methyl cellulose and the like have a drawback that it is difficult to adjust the temperature at which thickening is started and the thickening does not occur steeply even if the temperature rises above the transition temperature. In order to adjust the transition temperature, the N-alkylacrylamide polymer needs to be prepared by synthesizing and polymerizing various raw materials of N-alkylacrylamide having an alkyl group according to the temperature.
【０００４】[0004]
【課題を解決するための手段】本発明者らはこれらの問
題点を解決すべく鋭意検討した結果、窒素含有環を有す
る活性水素化合物のアルキレンオキシド付加物のビニル
系カルボン酸エステルを用いたビニル系重合体を水性液
に添加した場合、一定の温度までは温度上昇に伴って粘
度を低下させるが、この一定の温度を越えると高い勾配
で粘度を上昇させるような転移温度を有すること；この
温度・粘度関係の変化は温度の上げ下げに伴い可逆的に
繰り返し起こること；この転移温度は、重合体を構成す
る上記エステル中のアルキレンオキシドの種類や付加モ
ル数を変化させることによって容易に、しかも連続する
任意の温度に調整できることを見いだし、本発明に到達
した。Means for Solving the Problems As a result of intensive investigations by the present inventors in order to solve these problems, as a result, a vinyl-based carboxylic acid ester of an alkylene oxide adduct of an active hydrogen compound having a nitrogen-containing ring was used. When a system polymer is added to an aqueous liquid, it has a transition temperature such that the viscosity decreases with increasing temperature up to a certain temperature, but above this certain temperature, the viscosity increases with a high gradient; The change in the temperature-viscosity relationship is reversibly repeated as the temperature is raised or lowered; this transition temperature can be easily and easily changed by changing the kind of alkylene oxide in the ester constituting the polymer or the number of added moles. They have found that the temperature can be adjusted to any continuous temperature and have reached the present invention.
【０００５】すなわち本発明は、窒素含有環を有する活
性水素化合物のアルキレンオキシド付加物のビニル系カ
ルボン酸エステル（ａ）を構成単位として５０重量％以
上含有する水溶性ビニル系重合体（Ａ）からなり、該重
合体（Ａ）が、一定の転移温度を越えると水性液を増粘
させ、且つ、温度・粘度関係の可逆性を有する重合体で
あることを特徴とする熱可逆型増粘剤である。That is, the present invention relates to a water-soluble vinyl polymer (A) containing a vinyl carboxylic acid ester (a) of an alkylene oxide adduct of an active hydrogen compound having a nitrogen-containing ring as a constituent unit in an amount of 50% by weight or more. The thermoreversible thickener, wherein the polymer (A) is a polymer that thickens an aqueous liquid when it exceeds a certain transition temperature and has reversibility in a temperature-viscosity relationship. Is.
【０００６】本発明において、窒素含有環を有する活性
水素化合物としては、窒素含有環とアルキレンオキシド
が付加するための活性水素を有する化合物であり、例え
ば、窒素含有脂環式化合物［アジリジン環を有するもの
（アジリジン、２−メチルアジリジンなど）、ピロリジ
ン環を有するもの（ピロリジン、２−メチルピロリジ
ン、２−ピロリドン、スクシンイミドなど）、ピペリジ
ン環を有するもの（ピペリジン、２−メチルピペリジ
ン、３，５−ジメチルピペリジン、２−エチルピペリジ
ン、４−ピペリジノピペリジン、４−ピロリジノピペリ
ジン、エチルピペコリネートなど）、ピペラジン環を有
するもの（１−メチルピペラジン、１−メチル−３−エ
チルピペラジンなど）、モルホリン環を有するもの（モ
ルホリン、２−メチルモルホリン、３，５−ジメチルモ
ルホリン、チオモルホリンなど）、および、ε−カプロ
ラクタムなど］、窒素含有不飽和環状化合物（３−ピロ
リン、２，５−ジメチル−３−ピロリン、２−ヒドロキ
シピリジン、４−ピリジルカルビノール、２−ヒドロキ
シピリミジンなど）などが挙げられる。In the present invention, the active hydrogen compound having a nitrogen-containing ring is a compound having active hydrogen for addition of a nitrogen-containing ring and an alkylene oxide, for example, a nitrogen-containing alicyclic compound [having an aziridine ring Those having a pyrrolidine ring (pyrrolidine, 2-methylpyrrolidine, 2-pyrrolidone, succinimide, etc.), those having a piperidine ring (piperidine, 2-methylpiperidine, 3,5-dimethyl) Piperidine, 2-ethylpiperidine, 4-piperidinopiperidine, 4-pyrrolidinopiperidine, ethylpipecolate, etc.), those having a piperazine ring (1-methylpiperazine, 1-methyl-3-ethylpiperazine, etc.), morpholine Having a ring (morpholine, 2-methyl Ruphorin, 3,5-dimethylmorpholine, thiomorpholine, etc.), and ε-caprolactam, etc.], nitrogen-containing unsaturated cyclic compounds (3-pyrroline, 2,5-dimethyl-3-pyrroline, 2-hydroxypyridine, 4- Pyridyl carbinol, 2-hydroxypyrimidine, etc.) and the like.
【０００７】これらのうち好ましいものは窒素含有脂環
式化合物であり、さらに好ましいものはピペリジン環を
有するものおよびモルホリン環を有するもの、もっとも
好ましいものはモルホリン環を有するものである。Of these, preferred are nitrogen-containing alicyclic compounds, more preferred are those having a piperidine ring and those having a morpholine ring, and most preferred are those having a morpholine ring.
【０００８】本発明において、アルキレンオキシドとし
ては、エチレンオキシド、プロピレンオキシド、ブチレ
ンオキシドなどが挙げられる。In the present invention, examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide.
【０００９】これらのうち好ましいものは、エチレンオ
キシド及び／またはプロピレンオキシドである。Preferred of these are ethylene oxide and / or propylene oxide.
【００１０】本発明の増粘剤の転移温度は、該重合体
（Ａ）を構成する該エステル（ａ）中のアルキレンオキ
シドの種類や付加モル数を変えることによって容易に調
整可能であり、エチレンオキシドの場合は、付加モル数
を多くすると転移温度は高くなり、プロピレンオキシド
やブチレンオキシドの場合は、付加モル数を多くすると
転移温度は低くなる。アルキレンオキシドの付加モル数
は、目的とする転移温度、窒素含有環を有する活性水素
化合物の種類、アルキレンオキシドの種類等によって変
化するが、通常１〜５０モル、好ましくは１〜５モルで
ある。The transition temperature of the thickener of the present invention can be easily adjusted by changing the kind of alkylene oxide in the ester (a) constituting the polymer (A) and the number of added moles of ethylene oxide. In the case of, the transition temperature becomes higher as the number of added moles increases, and in the case of propylene oxide or butylene oxide, the transition temperature becomes lower as the number of added moles increases. The number of moles of alkylene oxide added varies depending on the desired transition temperature, the type of active hydrogen compound having a nitrogen-containing ring, the type of alkylene oxide, etc., but is usually 1 to 50 moles, preferably 1 to 5 moles.
【００１１】該エステル（ａ）は、上記に例示した該ア
ルキレンオキシド付加物と、ビニル系カルボン酸類との
エステルである。The ester (a) is an ester of the above-mentioned alkylene oxide adduct and vinyl carboxylic acid.
【００１２】ビニル系カルボン酸類としては、該アルキ
レンオキシド付加物と反応してビニル系カルボン酸エス
テルを与える化合物であれば特に制限はなく、ビニル系
カルボン酸［（メタ）アクリル酸、（イソ）クロトン
酸、マレイン酸、フマル酸、イタコン酸、ビニル安息香
酸、２−カルボキシ−４−イソプロペニル−３−ピロリ
ジン酢酸など］、及びこれらビニル系カルボン酸のエス
テル形成性誘導体（無水物、酸ハロゲン化物、メチルエ
ステル等）が挙げられる。The vinyl carboxylic acid is not particularly limited as long as it is a compound which reacts with the alkylene oxide adduct to give a vinyl carboxylic acid ester, and vinyl carboxylic acid [(meth) acrylic acid, (iso) croton Acid, maleic acid, fumaric acid, itaconic acid, vinylbenzoic acid, 2-carboxy-4-isopropenyl-3-pyrrolidineacetic acid, etc.], and ester-forming derivatives of these vinylic carboxylic acids (anhydrides, acid halides, Methyl ester and the like).
【００１３】これらビニル系カルボン酸類のうち、（メ
タ）アクリル酸、マレイン酸、ビニル安息香酸、及びこ
れらのエステル形成性誘導体が好ましく、（メタ）アク
リル酸、及び（メタ）アクリル酸のエステル形成性誘導
体が特に好ましい。Of these vinyl-based carboxylic acids, (meth) acrylic acid, maleic acid, vinylbenzoic acid, and ester-forming derivatives thereof are preferable, and (meth) acrylic acid and (meth) acrylic acid ester-forming properties are preferable. Derivatives are especially preferred.
【００１４】ビニル系重合体（Ａ）は、該エステル
（ａ）一種以上の重合体でも、（ａ）一種以上と他のビ
ニル系モノマー（ｂ）との共重合体で、（ａ）一種以上
を構成単位として５０重量％以上含有するものでも良
い。The vinyl polymer (A) is a copolymer of one or more of the ester (a) or a copolymer of (a) one or more and another vinyl monomer (b), and (a) one or more. May be contained as a structural unit in an amount of 50% by weight or more.
【００１５】他のビニル系モノマー（ｂ）としては、ビ
ニル重合性モノマーであれば特に制限はないが、例え
ば、（ｂ−１）親水性のもの［（ａ）を除く］、（ｂ−
２）イオン性のもの、（ｂ−３）親油性のもの等が挙げ
られる。The other vinyl-based monomer (b) is not particularly limited as long as it is a vinyl-polymerizable monomer. For example, (b-1) a hydrophilic monomer [excluding (a)], (b-
2) ionic compounds, (b-3) lipophilic compounds and the like.
【００１６】（ｂ−１）としては、例えば、ヒドロキシ
エチル（メタ）アクリレート、ポリエチレングリコール
モノ（メタ）アクリレート、（メタ）アクリルアミド、
Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ビニル−
２−ピロリドン等が挙げられる。（ｂ−２）としては、
例えば、（メタ）アクリル酸、（無水）マレイン酸、ス
チレンスルホン酸等の酸及びこれらの塩、Ｎ，Ｎ−ジメ
チルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエ
チルアミノプロピル（メタ）アクリレート等のアミン及
びこれらの塩等が挙げられる。（ｂ−３）としては、例
えば、メチル（メタ）アクリレート、ブチル（メタ）ア
クリレート、グリシジル（メタ）アクリレート等の（メ
タ）アクリレート誘導体、Ｎ−ブチル（メタ）アクリル
アミド、Ｎ−シクロヘキシル（メタ）アクリルアミド等
のＮ−アルキル（メタ）アクリルアミド誘導体、（メ
タ）アクリロニトリル、スチレン、酢酸ビニル、塩化ビ
ニルブタジエン、イソプレン等が挙げられる。Examples of (b-1) include hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acrylamide,
N-methylol (meth) acrylamide, N-vinyl-
2-pyrrolidone and the like can be mentioned. As (b-2),
For example, acids such as (meth) acrylic acid, (anhydrous) maleic acid, styrenesulfonic acid and salts thereof, amines such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate. And salts thereof. Examples of (b-3) include (meth) acrylate derivatives such as methyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, N-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide. And N-alkyl (meth) acrylamide derivatives such as (meth) acrylonitrile, styrene, vinyl acetate, vinyl chloride butadiene, and isoprene.
【００１７】他のビニル系モノマー（ｂ）を用いる場合
は、（ｂ−１）が好ましい。When other vinyl-based monomer (b) is used, (b-1) is preferable.
【００１８】ビニル系重合体（Ａ）を構成するモノマ−
のうち、（ａ）の構成比は通常５０重量％以上、好まし
くは７０重量％以上である。（Ａ）が（ａ）単独から構
成される場合、（Ａ）を添加した水性液は、転移温度を
越えると非常に狭い温度幅で増粘しゲル化に至るが、
（ａ）の構成比が低いと、広い温度幅にわたって温度の
上昇とともに増粘するので、使用目的に応じてその増粘
特性の制御が可能である。Monomer constituting vinyl polymer (A)
Among them, the constituent ratio of (a) is usually 50% by weight or more, preferably 70% by weight or more. When (A) is composed of (a) alone, the aqueous liquid to which (A) is added thickens and gels in a very narrow temperature range when it exceeds the transition temperature.
When the composition ratio of (a) is low, the viscosity increases as the temperature rises over a wide temperature range, so that the viscosity increasing property can be controlled according to the purpose of use.
【００１９】ビニル系重合体（Ａ）の重量平均分子量は
通常１，０００〜５，０００，０００、好ましくは、１
０，０００〜２，０００，０００、特に好ましくは１０
０，０００〜１，０００，０００である。The weight average molecular weight of the vinyl polymer (A) is usually 1,000 to 5,000,000, preferably 1
20,000 to 2,000,000, particularly preferably 10
It is from 10,000 to 1,000,000.
【００２０】ビニル系重合体（Ａ）は、（Ａ）を構成す
るモノマー成分（ａ）および必要により（ｂ）を用い、
ラジカル重合して得られる。重合方法には特に制限がな
く、通常の方法（溶液重合法、塊状重合法、乳化重合
法、懸濁重合法など）が使用でき、モノマー成分を、ラ
ジカル重合開始剤の存在下、加熱あるいは光増感剤の存
在下に光照射するか、放射線を照射するなどして重合を
開始させることにより、ビニル系重合体（Ａ）が得られ
る。The vinyl polymer (A) uses the monomer component (a) constituting (A) and, if necessary, (b),
Obtained by radical polymerization. The polymerization method is not particularly limited, and a usual method (solution polymerization method, bulk polymerization method, emulsion polymerization method, suspension polymerization method, etc.) can be used, and the monomer component is heated or exposed to light in the presence of a radical polymerization initiator. The vinyl polymer (A) is obtained by initiating the polymerization by irradiation with light or irradiation with radiation in the presence of a sensitizer.
【００２１】反応温度は通常２０〜３５０℃、好ましく
は５０〜１５０℃、反応圧力は通常０〜２０気圧、好ま
しくは０〜１０気圧、反応時間は、通常１〜６００分、
好ましくは５〜２４０分である。The reaction temperature is usually 20 to 350 ° C., preferably 50 to 150 ° C., the reaction pressure is usually 0 to 20 atmospheres, preferably 0 to 10 atmospheres, and the reaction time is usually 1 to 600 minutes.
It is preferably 5 to 240 minutes.
【００２２】使用されるラジカル重合開始剤も特に制限
はなく、アゾ系開始剤［2,2'-アゾビス（ジメチルバレ
ロニトリル）、2,2'-アゾビス（イソブチロニトリ
ル）、4,4'-アゾビス(4-シアノペンタン酸）、2,2'-ア
ゾビス（2-アミジノプロパン）塩酸塩等］、パーオキシ
ド系開始剤（過酸化水素、ベンゾイルパ−オキシド、ジ
クミルパーオキシド、ジ−ｔｅｒｔ−ブチルパーオキシ
ド、クメンハイドロパーオキシド等）など、通常用いら
れるものが使用できる。The radical polymerization initiator used is also not particularly limited, and azo initiators [2,2'-azobis (dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 4,4 'are used. -Azobis (4-cyanopentanoic acid), 2,2'-azobis (2-amidinopropane) hydrochloride, etc.], peroxide initiators (hydrogen peroxide, benzoylperoxide, dicumyl peroxide, di-tert-butyl) Peroxides, cumene hydroperoxide, etc.) that are commonly used can be used.
【００２３】該重合体（Ａ）の転移温度は、前記のよう
に連続的に調整することができるが、通常５〜９５℃の
範囲内にこの転移温度を有する。The transition temperature of the polymer (A) can be continuously adjusted as described above, but it usually has the transition temperature in the range of 5 to 95 ° C.
【００２４】本発明の増粘剤中には、必要により、酸化
防止剤、紫外線吸収剤、耐水化剤、香料、消泡剤、染料
等を含有していても良い。The thickener of the present invention may optionally contain an antioxidant, an ultraviolet absorber, a water resistant agent, a fragrance, an antifoaming agent, a dye and the like.
【００２５】本発明の増粘剤の形態には特に制限はな
く、（Ａ）からなる乾燥粉砕状の固体でも、（Ａ）から
なる任意の濃度の溶液状でも良い。溶液状の場合の溶剤
としては、水、アセトン、メタノール、イソプロピルア
ルコールなどが挙げられる。The form of the thickener of the present invention is not particularly limited, and may be a dry and pulverized solid of (A) or a solution of (A) having an arbitrary concentration. Examples of the solvent in the case of solution include water, acetone, methanol, isopropyl alcohol and the like.
【００２６】水性液に添加する際の本発明の増粘剤の使
用量は、水性液の種類、粘度等によって変化するが、水
性液１００重量部に対する該ビニル系重合体（Ａ）の重
量に基づいて、通常０．０００１〜３０部、好ましくは
０．００１〜２０部である。The amount of the thickener of the present invention used when added to the aqueous liquid varies depending on the type, viscosity and the like of the aqueous liquid, but is based on the weight of the vinyl polymer (A) per 100 parts by weight of the aqueous liquid. Based on this, it is usually 0.0001 to 30 parts, preferably 0.001 to 20 parts.
【００２７】本発明の増粘剤は、該増粘剤の転移温度以
下で水性液に混合溶解され、その後昇温して使用され
る。但し、転移温度は、水性液中の塩、界面活性剤、溶
剤等の成分の種類及び量によって変化するので、適用す
る水性液中での転移温度を用いる必要がある。The thickener of the present invention is mixed and dissolved in an aqueous liquid at a temperature not higher than the transition temperature of the thickener, and then heated to be used. However, since the transition temperature changes depending on the types and amounts of components such as salts, surfactants and solvents in the aqueous liquid, it is necessary to use the transition temperature in the applied aqueous liquid.
【００２８】本発明の増粘剤は、水、水と水系溶剤との
混合物、無機物あるいは有機物を含む水溶液もしくは分
散液等の水性液に適用して、増粘からゲル化に至る粘度
特性を調整するのに有用である。水性液としては、無機
塩水溶液、水溶性樹脂水溶液、水に不溶性の無機及び有
機物質の水性スラリーおよびコロイド状分散液、天然及
び合成ラテックス、各種樹脂エマルションなど、及びこ
れらの混合物などが挙げられ、具体的には、塗料、イン
キ、接着剤、捺染糊剤、化粧品、樹脂モルタル、セメン
ト等で水性のものが挙げられる。The thickener of the present invention is applied to an aqueous liquid such as water, a mixture of water and an aqueous solvent, an aqueous solution or a dispersion containing an inorganic substance or an organic substance, and adjusts the viscosity characteristic from thickening to gelation. Useful to do. Examples of the aqueous liquid include an inorganic salt aqueous solution, a water-soluble resin aqueous solution, an aqueous slurry and colloidal dispersion of water-insoluble inorganic and organic substances, natural and synthetic latex, various resin emulsions, and the like, and a mixture thereof. Specific examples thereof include water-based paints, inks, adhesives, printing pastes, cosmetics, resin mortars, cements and the like.
【００２９】また、不織布用バインダー、塗工紙用コー
ティング剤等のマイグレーション防止剤としても有用で
ある。It is also useful as a migration inhibitor such as a binder for non-woven fabrics and a coating agent for coated papers.
【００３０】[0030]
【実施例】以下、実施例により本発明をさらに説明する
が、本発明はこれに限定されるものではない。実施例中
の部は重量部である。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples are parts by weight.
【００３１】製造例１ ２−モルホリノエチルメタクリレート（モルホリンのエ
チレンオキシド１モル付加物とメタクリル酸とのエステ
ル）１００部と、2,2'-アゾビス（2,4-ジメチルバレロ
ニトリル）０．１部とをアンプルに加え、凍結脱気後密
閉し、５０℃で８時間重合させて、重合体１を得た。Production Example 1 100 parts of 2-morpholinoethylmethacrylate (ester of morpholine ethylene oxide 1 mol adduct with methacrylic acid) and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) Was added to an ampoule, frozen and deaerated, then sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 1.
【００３２】製造例２ ２−（２−モルホリノエトキシ）エチルメタクリレート
（モルホリンのエチレンオキシド２モル付加物とメタク
リル酸とのエステル）１００部と、2,2'-アゾビス（2,4
-ジメチルバレロニトリル）０．１部とをアンプルに加
え、凍結脱気後密閉し、６０℃で８時間重合させて、重
合体２を得た。Production Example 2 100 parts of 2- (2-morpholinoethoxy) ethyl methacrylate (an ester of morpholine with 2 moles of ethylene oxide and methacrylic acid) and 2,2'-azobis (2,4)
-Dimethylvaleronitrile) (0.1 part) was added to an ampoule, freeze-deaerated, sealed, and polymerized at 60 ° C for 8 hours to obtain a polymer 2.
【００３３】製造例３ ２−モルホリノプロピルメタクリレート（モルホリンの
プロピレンオキシド１モル付加物とメタクリル酸とのエ
ステル）１００部と、2,2'-アゾビス（2,4-ジメチルバ
レロニトリル）０．１部とをアンプルに加え、凍結脱気
後密閉し、５０℃で８時間重合させて、重合体３を得
た。Production Example 3 100 parts of 2-morpholinopropyl methacrylate (ester of morpholine 1 mol adduct of morpholine and methacrylic acid) and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) And were added to an ampoule, and the mixture was freeze-deaerated, sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 3.
【００３４】製造例４ モルホリンエチレンオキシド４モル付加物のメタクリル
酸エステル１００部と、2,2'-アゾビス（2,4-ジメチル
バレロニトリル）０．１部とをアンプルに加え、凍結脱
気後密閉し、５０℃で８時間重合させて、重合体４を得
た。Production Example 4 100 parts of methacrylic acid ester of 4 mol adduct of morpholine ethylene oxide and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) were added to an ampoule, freeze-deaerated and then sealed. Then, it was polymerized at 50 ° C. for 8 hours to obtain a polymer 4.
【００３５】製造例５ 3,5-ジメチルモルホリンエチレンオキシド４モル付加物
のメタクリル酸エステル８５部と、ヒドロキシエチルメ
タクリレート１５部と、2,2'-アゾビス（2,4-ジメチル
バレロニトリル）０．１部とをアンプルに加え、凍結脱
気後密閉し、５０℃で８時間重合させて、重合体５を得
た。Production Example 5 85 parts of methacrylic acid ester of 3,5-dimethylmorpholine ethylene oxide 4 mol adduct, 15 parts of hydroxyethyl methacrylate, 2,2'-azobis (2,4-dimethylvaleronitrile) 0.1 Parts were added to an ampoule, and the mixture was freeze-deaerated, sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer 5.
【００３６】実施例１ 重合体１を、２０℃で、イオン交換水９５部に対して５
部加えて均一に混合溶解した。この水溶液を毎分１℃の
割合で昇温させて、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表１に示す。次に、増粘さ
せた水溶液を、３８℃から３０℃まで、毎分１℃の割合
で温度を低下させ、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表２に示す。Example 1 Polymer 1 was added to 5 parts of deionized water at 20 ° C.
Part of the mixture was added and uniformly mixed and dissolved. This aqueous solution was heated at a rate of 1 ° C./min to measure the viscosity (B-type viscometer, ST
Use rotor). The results are shown in Table 1. Next, the viscosity of the thickened aqueous solution was lowered from 38 ° C. to 30 ° C. at a rate of 1 ° C./min, and the viscosity was measured (B-type viscometer, ST
Use rotor). The results are shown in Table 2.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】実施例２ 重合体２を、２０℃で、イオン交換水９５部に対して５
部加えて均一に混合溶解した。この水溶液を毎分１℃の
割合で昇温させて、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表３に示す。次に、増粘さ
せた水溶液を、５０℃から４２℃まで、毎分１℃の割合
で温度を低下させ、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表４に示す。Example 2 Polymer 2 was added to 5 parts of 95 parts of ion-exchanged water at 20 ° C.
Part of the mixture was added and uniformly mixed and dissolved. This aqueous solution was heated at a rate of 1 ° C./min to measure the viscosity (B-type viscometer, ST
Use rotor). The results are shown in Table 3. Next, the viscosity of the thickened aqueous solution was lowered from 50 ° C. to 42 ° C. at a rate of 1 ° C./min, and the viscosity was measured (B-type viscometer, ST
Use rotor). The results are shown in Table 4.
【００４０】[0040]
【表３】 [Table 3]
【００４１】[0041]
【表４】 [Table 4]
【００４２】実施例３ 重合体３を、１０℃で、イオン交換水９５部に対して５
部加えて均一に混合溶解した。この水溶液を毎分１℃の
割合で昇温させて、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表５に示す。次に、増粘さ
せた水溶液を、１８℃から１０℃まで、毎分１℃の割合
で温度を低下させ、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表６に示す。Example 3 Polymer 3 was added at 10 ° C. to 5 parts with 95 parts of ion-exchanged water.
Part of the mixture was added and uniformly mixed and dissolved. This aqueous solution was heated at a rate of 1 ° C./min to measure the viscosity (B-type viscometer, ST
Use rotor). The results are shown in Table 5. Next, the viscosity of the thickened aqueous solution was lowered from 18 ° C. to 10 ° C. at a rate of 1 ° C./min, and the viscosity was measured (B-type viscometer, ST
Use rotor). The results are shown in Table 6.
【００４３】[0043]
【表５】 [Table 5]
【００４４】[0044]
【表６】 [Table 6]
【００４５】実施例４ 重合体４を、２５℃で、イオン交換水９５部に対して５
部加えて均一に混合溶解した。この水溶液を毎分１℃の
割合で昇温させて、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表７に示す。次に、増粘さ
せた水溶液を、７８℃から７０℃まで、毎分１℃の割合
で温度を低下させ、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表８に示す。Example 4 Polymer 4 was added to 5 parts of deionized water at 25 ° C. with 95 parts of deionized water.
Part of the mixture was added and uniformly mixed and dissolved. This aqueous solution was heated at a rate of 1 ° C./min to measure the viscosity (B-type viscometer, ST
Use rotor). The results are shown in Table 7. Next, the viscosity of the thickened aqueous solution was lowered from 78 ° C. to 70 ° C. at a rate of 1 ° C./min, and the viscosity was measured (B-type viscometer, ST
Use rotor). The results are shown in Table 8.
【００４６】[0046]
【表７】 [Table 7]
【００４７】[0047]
【表８】 [Table 8]
【００４８】実施例５ 重合体５を、２５℃で、イオン交換水９５部に対して５
部加えて均一に混合溶解した。この水溶液を毎分１℃の
割合で昇温させて、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表９に示す。次に、増粘さ
せた水溶液を、８０℃から７０℃まで、毎分１℃の割合
で温度を低下させ、粘度を測定した（Ｂ型粘度計、ＳＴ
ローター使用）。その結果を表１０に示す。Example 5 Polymer 5 was added at 5 ° C. to 5 parts with respect to 95 parts of deionized water.
Part of the mixture was added and uniformly mixed and dissolved. This aqueous solution was heated at a rate of 1 ° C./min to measure the viscosity (B-type viscometer, ST
Use rotor). The results are shown in Table 9. Next, the viscosity of the thickened aqueous solution was lowered from 80 ° C. to 70 ° C. at a rate of 1 ° C./min, and the viscosity was measured (B-type viscometer, ST
Use rotor). The results are shown in Table 10.
【００４９】[0049]
【表９】 [Table 9]
【００５０】[0050]
【表１０】 [Table 10]
【００５１】実施例６ 製造例１で得られた重合体１を、２０℃で、ウレタン系
エマルション（三洋化成工業製、サンプレンＵＸＡ３０
０４）９９．９６部に対して０．０４部加えて均一に混
合溶解した。このエマルションを毎分１℃の割合で昇温
させて、粘度を測定した（Ｂ型粘度計、ＳＴローター使
用）。その結果を表１１に示す。次に、増粘させた水溶
液を、５０℃から４０℃まで、毎分１℃の割合で温度を
低下させ、粘度を測定した（Ｂ型粘度計、ＳＴローター
使用）。その結果を表１２に示す。Example 6 The polymer 1 obtained in Production Example 1 was treated at 20 ° C. with a urethane emulsion (Sanprene UXA30 manufactured by Sanyo Kasei Co., Ltd.).
04) To 99.96 parts, 0.04 part was added and uniformly mixed and dissolved. This emulsion was heated at a rate of 1 ° C./min to measure the viscosity (using a B-type viscometer and ST rotor). The results are shown in Table 11. Next, the viscosity of the thickened aqueous solution was lowered from 50 ° C. to 40 ° C. at a rate of 1 ° C./min, and the viscosity was measured (B-type viscometer, ST rotor used). The results are shown in Table 12.
【００５２】[0052]
【表１１】 [Table 11]
【００５３】[0053]
【表１２】 [Table 12]
【００５４】[0054]
【発明の効果】本発明の増粘剤は、水性液に適用した場
合、広い温度範囲において、転移温度までは温度上昇に
伴って粘度を低下させるが、転移温度を越えると急勾配
で粘度を上昇させ、かつ、この温度・粘度変化を可逆的
に繰り返し行わせることができるものである。また、本
発明の増粘剤中の重合体の転移温度は、この重合体を構
成する、ビニル系カルボン酸エステル中のアルキレンオ
キシドの種類，付加モル数を変化させることによって容
易に、しかも任意に調整できるという利点がある。従っ
て、本発明の増粘剤は、水、無機塩水溶液、水溶性樹脂
水溶液、水に不溶性の無機及び有機物質の水性スラリー
もしくはコロイド状分散液、天然もしくは合成ラテック
ス、各種樹脂エマルションなど、具体的には、塗料、イ
ンキ、接着剤、捺染糊剤、化粧品、樹脂モルタル、セメ
ント等で水性のものに用いた場合、粘度が、温度上昇に
よって低下せず、逆に、増粘もしくはゲル化に至らしめ
られるので、非常に有用である。また、不織布用バイン
ダー、塗工紙用コーティング剤等に用いた場合、塗工後
の乾燥工程で増粘・ゲル化させるため、塗工層中の顔料
やバインダーのマイグレーションを防止する効果を有し
ており、マイグレーション防止剤としても有用である。INDUSTRIAL APPLICABILITY The thickener of the present invention, when applied to an aqueous liquid, lowers the viscosity as the temperature rises up to the transition temperature in a wide temperature range, but when it exceeds the transition temperature, the viscosity increases steeply. It is possible to raise the temperature and make this temperature / viscosity change reversibly repeated. Further, the transition temperature of the polymer in the thickener of the present invention can be easily and optionally changed by changing the type of alkylene oxide in the vinyl carboxylic acid ester constituting the polymer and the number of added moles. It has the advantage of being adjustable. Therefore, the thickeners of the present invention include water, inorganic salt aqueous solutions, water-soluble resin aqueous solutions, aqueous slurry or colloidal dispersions of water-insoluble inorganic and organic substances, natural or synthetic latex, various resin emulsions, and the like. When used in water-based paints, inks, adhesives, printing pastes, cosmetics, resin mortar, cement, etc., the viscosity does not decrease due to temperature rise, but on the contrary, it does not lead to thickening or gelation. It is very useful because it can be tightened. When used as a binder for non-woven fabrics, a coating agent for coated paper, etc., it has the effect of preventing migration of pigments and binders in the coating layer as it thickens and gels in the drying process after coating. Therefore, it is also useful as a migration inhibitor.
Claims (3)
キレンオキシド付加物のビニル系カルボン酸エステル
（ａ）を構成単位として５０重量％以上含有する水溶性
ビニル系重合体（Ａ）からなり、該重合体（Ａ）が、一
定の転移温度を越えると水性液を増粘させ、且つ、温度
・粘度関係の可逆性を有する重合体であることを特徴と
する熱可逆型増粘剤。1. A water-soluble vinyl polymer (A) containing, as a constituent unit, 50% by weight or more of a vinyl carboxylic acid ester (a) of an alkylene oxide adduct of an active hydrogen compound having a nitrogen-containing ring. A thermoreversible thickener, wherein the polymer (A) is a polymer that thickens an aqueous liquid when it exceeds a certain transition temperature and has reversibility in a temperature-viscosity relationship.
系重合体である請求項１記載の増粘剤。2. The thickener according to claim 1, wherein (A) is a vinyl polymer having a molecular weight of 10,000 to 2,000,000.
オキシド及び／またはプロピレンオキシド１〜２０モル
付加物の（メタ）アクリル酸エステルである請求項１ま
たは２記載の増粘剤。3. The thickener according to claim 1, wherein (a) is a (meth) acrylic acid ester of 1 to 20 mol of ethylene oxide and / or propylene oxide of (substituted) morpholine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4046142A JPH0723443B2 (en) | 1992-01-31 | 1992-01-31 | Thermoreversible thickener |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4046142A JPH0723443B2 (en) | 1992-01-31 | 1992-01-31 | Thermoreversible thickener |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069848A true JPH069848A (en) | 1994-01-18 |
| JPH0723443B2 JPH0723443B2 (en) | 1995-03-15 |
Family
ID=12738725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4046142A Expired - Fee Related JPH0723443B2 (en) | 1992-01-31 | 1992-01-31 | Thermoreversible thickener |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0723443B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692506A2 (en) | 1994-07-14 | 1996-01-17 | Miyoshi Yushi Kabushiki Kaisha | Thermo-sensitive polyether polyurethane, production method thereof and thermo-sensitive composition |
| EP0704504A3 (en) * | 1994-09-29 | 1997-02-19 | Canon Kk | Water-based ink for ink-jet, and ink-jet recording method and instruments using the ink |
| WO1997000275A3 (en) * | 1995-06-16 | 1997-03-06 | Gel Sciences Inc | Responsive polymer networks and methods of their use |
| EP0761782A1 (en) * | 1995-08-31 | 1997-03-12 | Canon Kabushiki Kaisha | Water-based ink for ink-jet, and ink jet recording method and instruments using the same |
| EP0765758A2 (en) * | 1995-09-29 | 1997-04-02 | Canon Kabushiki Kaisha | Ink-jet recording process, and ink-jet recording apparatus |
| EP0798119A2 (en) * | 1996-03-27 | 1997-10-01 | Canon Kabushiki Kaisha | Ink jet recording method and recording apparatus using same |
| US5866638A (en) * | 1995-12-01 | 1999-02-02 | Canon Kabushiki Kaisha | Ink for two-part liquid system recording, and ink set, ink container, recording unit, recording process and recording apparatus using the same |
| US5943080A (en) * | 1995-07-07 | 1999-08-24 | Canon Kabushiki Kaisha | Ink-jet recording method |
| JP2001214151A (en) * | 2000-02-01 | 2001-08-07 | Toyota Central Res & Dev Lab Inc | Heat-reversible viscosity-controlling material |
| FR2815637A1 (en) * | 2000-10-20 | 2002-04-26 | Rhodia Chimie Sa | Preparation of an oil-in-water emulsion used to prepare stable aqueous emulsions for e.g. food or cosmetic applications comprises a heat-thickening polymer and an oil of viscosity not less than 1Pa.s |
| JP2005290390A (en) * | 2000-02-29 | 2005-10-20 | Sanyo Chem Ind Ltd | Additive for increasing production of crude oil |
| CN106715512A (en) * | 2014-09-15 | 2017-05-24 | 巴斯夫涂料有限公司 | Aqueous thermo-thickening resin solutions |
-
1992
- 1992-01-31 JP JP4046142A patent/JPH0723443B2/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0692506A2 (en) | 1994-07-14 | 1996-01-17 | Miyoshi Yushi Kabushiki Kaisha | Thermo-sensitive polyether polyurethane, production method thereof and thermo-sensitive composition |
| EP0704504A3 (en) * | 1994-09-29 | 1997-02-19 | Canon Kk | Water-based ink for ink-jet, and ink-jet recording method and instruments using the ink |
| US5955515A (en) * | 1994-09-29 | 1999-09-21 | Canon Kabushiki Kaisha | Water-based ink for ink-jet, and ink-jet recording method and instruments using the ink |
| WO1997000275A3 (en) * | 1995-06-16 | 1997-03-06 | Gel Sciences Inc | Responsive polymer networks and methods of their use |
| US5943080A (en) * | 1995-07-07 | 1999-08-24 | Canon Kabushiki Kaisha | Ink-jet recording method |
| EP0761782A1 (en) * | 1995-08-31 | 1997-03-12 | Canon Kabushiki Kaisha | Water-based ink for ink-jet, and ink jet recording method and instruments using the same |
| US6372818B1 (en) | 1995-08-31 | 2002-04-16 | Canon Kabushiki Kaisha | Water-based ink for ink-jet, and ink-jet recording method and instruments using the same |
| EP0765758A2 (en) * | 1995-09-29 | 1997-04-02 | Canon Kabushiki Kaisha | Ink-jet recording process, and ink-jet recording apparatus |
| EP0765758A3 (en) * | 1995-09-29 | 1998-04-15 | Canon Kabushiki Kaisha | Ink-jet recording process, and ink-jet recording apparatus |
| US5866638A (en) * | 1995-12-01 | 1999-02-02 | Canon Kabushiki Kaisha | Ink for two-part liquid system recording, and ink set, ink container, recording unit, recording process and recording apparatus using the same |
| EP0798119A3 (en) * | 1996-03-27 | 1998-07-08 | Canon Kabushiki Kaisha | Ink jet recording method and recording apparatus using same |
| EP0798119A2 (en) * | 1996-03-27 | 1997-10-01 | Canon Kabushiki Kaisha | Ink jet recording method and recording apparatus using same |
| JP2001214151A (en) * | 2000-02-01 | 2001-08-07 | Toyota Central Res & Dev Lab Inc | Heat-reversible viscosity-controlling material |
| JP2005290390A (en) * | 2000-02-29 | 2005-10-20 | Sanyo Chem Ind Ltd | Additive for increasing production of crude oil |
| FR2815637A1 (en) * | 2000-10-20 | 2002-04-26 | Rhodia Chimie Sa | Preparation of an oil-in-water emulsion used to prepare stable aqueous emulsions for e.g. food or cosmetic applications comprises a heat-thickening polymer and an oil of viscosity not less than 1Pa.s |
| WO2002032560A3 (en) * | 2000-10-20 | 2002-06-27 | Rhodia Chimie Sa | Method for preparing an emulsion with high-viscosity organic phase |
| CN106715512A (en) * | 2014-09-15 | 2017-05-24 | 巴斯夫涂料有限公司 | Aqueous thermo-thickening resin solutions |
| JP2017535663A (en) * | 2014-09-15 | 2017-11-30 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Thermally thickening resin aqueous solution |
| US10538664B2 (en) | 2014-09-15 | 2020-01-21 | Basf Coatings Gmbh | Aqueous thermo-thickening resin solutions |
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| Publication number | Publication date |
|---|---|
| JPH0723443B2 (en) | 1995-03-15 |
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