JP2005015748A - Fiber treating agent and its treating method - Google Patents
Fiber treating agent and its treating method Download PDFInfo
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Abstract
Description
【０００１】
【産業上の利用分野】
本発明は、繊維の加工剤として使用されるシロキサン重合体に効率良くラジカル重合可能な二重結合を有するビニル基含有モノマーを導入することで、他のビニルモノマーとの共重合体を容易に得ることができ、繊維に対して耐久性を有するシロキサン重合体を得ることができる。また、アミノ基を有するシロキサン重合体に用いた場合は、アミノ基を効率よく封鎖し、熱による着色防止性に優れるシロキサン重合体を得ることができる。
【０００２】
【従来の技術】
従来、繊維加工の分野において、シロキサン重合体が、柔軟性および伸縮性に優れることから繊維の柔軟剤として多岐にわたり使用されている。シロキサン重合体の繊維に対する耐久性を発現させる方法として、一般的にはシロキサン重合体とバインダー樹脂を併用加工する方法やシロキサン重合体とバインダー樹脂の共重合体を繊維に処理することで耐久性を発現する方法がある。しかし、シロキサン重合体とバインダー樹脂の併用加工は、シロキサン重合体と樹脂の加工比率の調整が困難である。例えば、シロキサン重合体とバインダー樹脂の比率において、シロキサン重合体の比率が高い場合は、耐久性に乏しくまた逆に低い場合は重合体の風合が十分に発現せず、風合が粗硬になる。さらに、加工液の併用安定性がしばしば問題になる。
シロキサン重合体とバインダー樹脂との共重合体を得る場合は、シロキサンモノマーにラジカル重合可能な二重結合を有するビニル基含有モノマーを導入し、高分子化後ビニルモノマーを共重合していくのが一般的であるが、反応が多岐に渡り、汎用性に欠けるため工業的には非常に不利である。
また、アミノ基を含有するシロキサン重合体（以下と表記アミノ変性シリコーン）は、アミノ基が熱によって変化しやすいために白物では黄変、色物では変色といったトラブルをもつ欠点を有する。そのため、一般的にはアミノ基を封鎖する方法が取られている。
例えば、酸無水物、カルボキシル基含有化合物、エポキシキ含有化合物などが挙げられるが、反応性に乏しく、また反応に高熱を必要とし工業的には有利ではない。
【０００３】
【発明が解決しようとする課題】
本発明は、活性水素を有するシロキサン重合体に重合性不飽和基含有イソシアネート化合物を反応させることで、効率良くラジカル重合可能な二重結合を有するビニル基含有モノマーを導入し、他のビニルモノマーとの共重合体を容易に得ることができ、かつ繊維材料に加工した時、耐久性のある柔軟性を付与することができる。また、アミノ変性シリコーンに用いた場合は、アミノ基を効率よく封鎖し、熱による着色防止性および柔軟性に優れるアミノ変性シリコーンを得ることができる。
従って、本発明は上記のような従来技術の問題点を解決し、工業的に簡易かつ安価に、また、環境汚染を生じることなくシリコーン骨格にラジカル重合可能な二重結合を有するビニル基含有モノマーを導入でき、他のビニルモノマーの共重合体を提供する。また、アミノ基を有するシリコーンのアミノ基を効率よく封鎖し、熱による着色防止性および柔軟性に優れるアミノ変性シリコーンを提供する。
【０００４】
【課題を解決するための手段】
前述の課題を達成するために、シロキサン重合体とビニルモノマーの共重合体およびアミノ変性シリコーンのアミノ基封鎖方法を鋭意検討した結果、活性水素を有するシロキサン重合体に重合性不飽和基含有イソシアネート化合物を反応させて得られる反応性シロキサン重合体が他のビニルモノマーと容易に共重合が可能であることを見出し、本発明に到達した。
また、アミノ変性シリコーンに重合性不飽和基含有イソシアネート化合物を反応させることで、容易にアミノ基が封鎖されたアミノ変性シリコーンが得られることを見出し、本発明に到達した。
すなわち、本発明は活性水素を有するシロキサン重合体に重合性不飽和基含有イソシアネート化合物を反応させて得られる反応性シロキサン重合体である。
【０００５】
本発明では繊維材料を加工の対象として用いる。繊維材料としてはポリアラミド系繊維、ポリエステル系繊維、アクリル繊維、ポリオレフィン系繊維、ウレタン系繊維、レーヨン、綿、獣毛繊維などを挙げることができる。
これらの単独であっても複合されていても良い。用いる繊維の形態としては糸状、綿状、織編物、立毛布、不織布等が挙げられる。
【０００６】
本発明の活性水素を有するシロキサン重合体とは、アミノ変性シリコーン、シラノール基変性シリコーン、カルボキシル基変性シリコーン、ハイドロジェンポリシロキサンなどを挙げる事ができる。活性水素の位置はシロキサン重合体の側鎖あるいは末端のいずれか分子骨格中にひとつ以上存在すれば良い。さらに、２種類以上の活性水素が同一シロキサン重合体の骨格に存在していても良い。本発明ではこのようなシロキサン重合体をそれぞれの単独で、または２種類以上を併用して、使用することができる。さらに本発明のこのようなシロキサン重合体の、活性水素数、分子量、粘度については特に限定しない。
【０００７】
本発明の重合性不飽和基含有イソシアネート化合物としては化１に示したものが好ましく、例えば２−メタクリロイルオキシエチレンイソシネートおよびメタクリロイルイソシアネートを挙げる事ができる。
【０００８】
本発明の反応性シロキサン重合体（Ａ）は、活性水素好ましくはアミノ基を有するシロキサン重合体と重合性不飽和含有イソシアネート化合物を、常温で反応させることにより得られる。例えば、アミノ変性シリコーンを例に挙げると、温度計還流冷却機及び攪拌機を備えた、容量１リットルの反応機中にアミノ変性シリコーンを常温で撹拌しながら、２−メタクリロイルオキシエチレンイソシアネート（或いはメタクリロイルイソシアネート）を添加する事で、重合性不飽和基が化学結合した反応性シロキサン重合体を得ることができる。
アミノ変性シリコーンに重合性不飽和基含有イソシアネート化合物を反応させる量は、任意の割合でよいが、本発明の目的である耐久性向上には、重合性不飽和基含有イソシアネート化合物はシリコーンの活性水素に対して飽和量が好ましい。過飽和量以上では、目的である反応以外の反応が起こる可能性があり、好ましくなく、アミノ基の封鎖量が５％以下では、目的とするラジカル重合可能なビニル基含有モノマーの導入が十分ではなく、他のビニルモノマーとの共重合性あるいは耐久性に十分な効果を与えない。また、着色防止性を考慮した場合は、アミノ基の封鎖率は８０％以上必要である。
本発明において、反応性シロキサン重合体とビニル基含有モノマーの共重合体（Ｃ）の合成は、溶液重合法で開始剤を用いてラジカルを発生させることで合成することができる。具体的には、温度計還流冷却機及び攪拌機を備えた、容量１リットルの反応機中に反応性シロキサン重合体とビニル含有モノマーを溶解させ、開始剤添加後反応させることで得ることができる。また、反応性シロキサン重合体とビニル基含有モノマーの比は任意の割合で良いが、好ましくは反応性シロキサン重合体に対して１０％以上が良い。ビニル基含有モノマーが１０％未満だと十分なグラフト化が期待できない。
また、ビニル基含有モノマー（Ｂ）は、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、エチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、１．６ヘキサンジオールジアクリレート、２−ヒドロキシメタクリレート、２−ヒドロキシアクリレート、グリセリンジメタクリレート、グリセリントリメタクリレート、グリセリンジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールプロパンジアクリレート、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、アクリル酸イソブチル、アクリル酸メトキシエチル、アクリル酸イソオクチル、アクリル酸ｎ−オクチル、アクリル酸イソノニル、アクリル酸ジメチルアミノエチル、アクリル酸亜鉛、アクリル酸２−ヒドロキシプロピル、メタクリル酸、メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸ターシャリーブチル、メタクリル酸シクロヘキシル、メタクリル酸２−ヒドロキシプロピル、アクリロニトリル、アクリルアミド、スチレンが挙げられる。
これらのビニル基含有モノマーは１種類単独でも２種類以上混合しても使用することができる。
【０００９】
本発明の重合開始剤としては、過硫酸カリウム、過硫酸アンモン、過酸化水素、過酸化ベンゾイルなどの過酸化物、硫酸第二セリウムアンモニウム、硝酸第二セリウムアンモニウムなどのセリウムアンモニウム塩、α、α−アゾビスイソブチロニトリル、２，２−′アゾビス（２−アミノジノプロパン）・２塩酸塩などが挙げられ、これらの開始剤は１種類単独でも２種類以上混合しても使用することができる。
【００１０】
本発明の繊維加工方法としては、従来の公知の方法でよく具体的にはスプレー法、バッド法、吸尽法、コーティング法等が挙げられる。一般にパッド法の場合、繊維材料を請求項に示される繊維処理液を浸漬し、マングル絞った後、約１００℃前後で乾燥し、１１０℃〜１７０℃で１〜２分間キュアリングすれば良い。
【００１１】
【実施例】
以下、本発明の実施例を示し、本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
本発明で評価した加工工程、耐洗濯耐久性、黄変性、風合は次の通りである。実施例中の部及び％は、それぞれ重量部、重量％を示し、耐洗濯耐久性、黄変性、風合は、以下の方法で測定した。綿ブロード４０Ｓでの評価結果を表１に示した。
洗濯耐久性
ＪＩＳ１０３法に従い、洗濯１０回を繰り返した後、風合を確認した。
黄変性
黄変度（ΔＹＩ） ；水処理の加工上りを基準として、分光色彩計にて測色ＣＬＲ−７１００Ｆ（島津製作所製）。＋数値が高い程黄変性大。
風合
専門検査員１０名の触感観察により判断した。その基準は次の通りである。
○：ドライ感がある、△：若干ドライ感がある、×：ヌメリ感がある。
加工条件
（加工条件） 試 験 布：綿ブロード４０Ｓ
パディング：２回浸漬 ２回絞り、絞り率 ８３％
乾 燥：１００℃ × ３分
キュアリング：１７０℃ × １分
【００１２】
実施合成例 １
温度計還流冷却機及び攪拌機を備えた容量３リットルの反応機中に、アミノ変性シリコーン（２５℃の粘度：１５２０ｍＰａ・Ｓ、アミン価：３１）３００部、２−メタクリロイルオキシエチレンイソシネート２１部添加し、常温で１時間反応後アミン価が３．２になったことを確認し、乳化剤１００部（ポリオキシエチレンアルキルエーテル 炭素数：１２〜１４、エチレンオキサイド付加モル数：７モル）を投入し、十分撹拌を行ったあと、乳化水６００部投入し、４０％のシリコンエマルジョン水分散体を得た。
実施合成例 ２
温度計還流冷却機及び攪拌機を備えた容量３リットルの反応機中に、アミノ変性シリコーン（２５℃の粘度：２１００ｍＰａ・Ｓ、アミノ価：３３）３００部、２−メタクリロイルオキシエチレンイソシネート２１ｇ添加し、常温で１時間反応後アミン価が３．７になったことを確認し、乳化剤１００部（ポリオキシエチレンアルキルエーテル 炭素数：１２〜１４、エチレンオキサイド付加モル数：７モル）を投入し、十分撹拌を行ったあと、乳化水６００部投入し、４０％のシリコンエマルジョン水分散体を得た。
実施合成例 ３
温度計還流冷却機及び攪拌機を備えた容量３リットルの反応機中に、過酸化ベンゾイル０．５部、軟水５１０部を投入し、８０℃で保持した反応機に、実施合成例 ２で得られたシリコンエマルジョン１００部、アクリル酸ブチル１００部、乳化剤７．０部（ポリオキシエチレンアルキルエーテル 炭素数：１２〜１４、エチレンオキサイド付加モル数：７モル）、を１０時間かけて滴下重合を行い、２０％アクリル−シリコンエマルジョン水分散体を得た。
比較合成例 １
温度計還流冷却機及び攪拌機を備えた容量３リットルの反応機中に、アミノ変性シリコーン（２５℃の粘度：１５２０ｍ・Ｐａ、アミノ価３１）３００部、乳化剤１００部（ポリオキシエチレンアルキルエーテル 炭素数：１２〜１４、エチレンオキサイド付加モル数：７モル）を投入し、十分撹拌を行ったあと、乳化水６００部投入し、４０％のシリコンエマルジョン水分散体を得た。
比較合成例 ２
温度計還流冷却機及び攪拌機を備えた容量３リットルの反応機中に、アミノ変性シリコーン（２５℃の粘度：２１００ｍＰａ・Ｓ、アミノ価：３３）３００部、乳化剤１００部（アルキルエーテル 炭素数：１２〜１４、エチレンオキサイド：７）を投入し、十分撹拌を行ったあと、乳化水６００部投入し、４０％のシリコンエマルジョン水分散体を得た。
【００１３】
実施加工例を示した。重量％は純分換算比で示した。
【表１】
以上の結果、本発明によれば、工業的に簡易的で安価に、また環境汚染を生じることなくシリコーン骨格にラジカル重合可能な官能基を導入でき、他のビニルモノマーの共重合体を提供する。また、繊維に処理した場合、耐久性のある柔軟性を付与できる。さらに、アミノ基を有するシリコーンのアミノ基を効率よく封鎖し、熱による着色防止性に優れるアミノ変性シリコーンを提供できる。
【００１６】
【本発明の効果】
本発明によればシリコーン骨格にラジカル重合可能な官能基を導入でき、他のビニルモノマーの共重合体を提供する。また、アミノ基を有するシリコーンのアミノ基を効率よく封鎖し、熱による着色防止性に優れるアミノ変性シリコーンを提供できる。[0001]
[Industrial application fields]
The present invention easily obtains a copolymer with another vinyl monomer by introducing a vinyl group-containing monomer having a double bond capable of efficient radical polymerization into a siloxane polymer used as a fiber processing agent. And a siloxane polymer having durability against fibers can be obtained. Moreover, when it uses for the siloxane polymer which has an amino group, an amino group can be blocked efficiently and the siloxane polymer which is excellent in the coloring prevention property by a heat | fever can be obtained.
[0002]
[Prior art]
Conventionally, in the field of fiber processing, siloxane polymers are widely used as fiber softeners because of their excellent flexibility and stretchability. As a method of developing durability of siloxane polymer fibers, generally, a method of processing a siloxane polymer and a binder resin together, or a fiber treatment with a copolymer of a siloxane polymer and a binder resin, the durability is improved. There are ways to express. However, in the combined processing of the siloxane polymer and the binder resin, it is difficult to adjust the processing ratio of the siloxane polymer and the resin. For example, when the ratio of the siloxane polymer to the binder resin is high, if the ratio of the siloxane polymer is high, the durability is poor, and conversely, if the ratio is low, the texture of the polymer is not sufficiently expressed, and the texture is coarse. Become. Furthermore, the combined stability of the processing fluid often becomes a problem.
When obtaining a copolymer of a siloxane polymer and a binder resin, a vinyl group-containing monomer having a radically polymerizable double bond is introduced into the siloxane monomer, and the vinyl monomer is copolymerized after polymerization. Although it is general, it is very disadvantageous industrially because of the wide variety of reactions and lack of versatility.
In addition, siloxane polymers containing amino groups (hereinafter referred to as amino-modified silicones) have the drawback of having troubles such as yellowing of white materials and discoloration of colored materials because the amino groups are easily changed by heat. Therefore, generally, a method of blocking an amino group is taken.
For example, acid anhydrides, carboxyl group-containing compounds, epoxy-containing compounds and the like can be mentioned, but they are poor in reactivity and require high heat for the reaction, which is not industrially advantageous.
[0003]
[Problems to be solved by the invention]
The present invention introduces a vinyl group-containing monomer having a double bond capable of efficient radical polymerization by reacting a polymerizable unsaturated group-containing isocyanate compound with a siloxane polymer having active hydrogen, and another vinyl monomer. This copolymer can be easily obtained, and when it is processed into a fiber material, durable flexibility can be imparted. Moreover, when it uses for an amino modified silicone, an amino group can be efficiently blocked and the amino modified silicone excellent in the coloring prevention property by heat | fever and a softness | flexibility can be obtained.
Accordingly, the present invention solves the problems of the prior art as described above, is industrially simple and inexpensive, and contains a vinyl group-containing monomer having a double bond capable of radical polymerization on the silicone skeleton without causing environmental pollution. To provide a copolymer of other vinyl monomers. Moreover, the amino group of silicone which has an amino group is efficiently blocked, and the amino modification silicone which is excellent in the anti-coloration property by heat and a softness | flexibility is provided.
[0004]
[Means for Solving the Problems]
In order to achieve the above-mentioned problems, as a result of intensive studies on a copolymer of a siloxane polymer and a vinyl monomer and an amino group blocking method of an amino-modified silicone, a siloxane polymer having active hydrogen is added to a polymerizable unsaturated group-containing isocyanate compound. The present inventors have found that a reactive siloxane polymer obtained by reacting can be easily copolymerized with other vinyl monomers, and reached the present invention.
Further, the present inventors have found that an amino-modified silicone having an amino group blocked easily can be obtained by reacting an amino-modified silicone with a polymerizable unsaturated group-containing isocyanate compound.
That is, the present invention is a reactive siloxane polymer obtained by reacting a polymerizable unsaturated group-containing isocyanate compound with a siloxane polymer having active hydrogen.
[0005]
In the present invention, a fiber material is used as an object to be processed. Examples of the fiber material include polyaramid fiber, polyester fiber, acrylic fiber, polyolefin fiber, urethane fiber, rayon, cotton, and animal hair fiber.
These may be used alone or in combination. Examples of the form of fibers used include yarn, cotton, woven and knitted fabric, napped cloth, and nonwoven fabric.
[0006]
Examples of the siloxane polymer having active hydrogen of the present invention include amino-modified silicone, silanol group-modified silicone, carboxyl group-modified silicone, and hydrogen polysiloxane. One or more active hydrogens may be present in the molecular skeleton at either the side chain or the terminal of the siloxane polymer. Further, two or more types of active hydrogen may be present in the same siloxane polymer skeleton. In the present invention, such siloxane polymers can be used alone or in combination of two or more. Furthermore, the number of active hydrogens, molecular weight, and viscosity of such a siloxane polymer of the present invention are not particularly limited.
[0007]
As the polymerizable unsaturated group-containing isocyanate compound of the present invention, those shown in Chemical Formula 1 are preferred, and examples thereof include 2-methacryloyloxyethylene isocyanate and methacryloyl isocyanate.
[0008]
The reactive siloxane polymer (A) of the present invention is obtained by reacting a siloxane polymer having active hydrogen, preferably an amino group, with a polymerizable unsaturated-containing isocyanate compound at room temperature. For example, when amino-modified silicone is taken as an example, 2-methacryloyloxyethylene isocyanate (or methacryloyl isocyanate) is stirred at room temperature in a 1 liter reactor equipped with a thermometer reflux condenser and a stirrer. ) Can be added to obtain a reactive siloxane polymer in which polymerizable unsaturated groups are chemically bonded.
The amount of the amino-modified silicone reacted with the polymerizable unsaturated group-containing isocyanate compound may be any ratio. For the purpose of improving durability, which is the object of the present invention, the polymerizable unsaturated group-containing isocyanate compound is an active hydrogen of silicone. The amount of saturation is preferred. Above the supersaturation amount, a reaction other than the target reaction may occur, which is not preferable. When the amino group blocking amount is 5% or less, introduction of the target radical polymerizable vinyl group-containing monomer is not sufficient. It does not give a sufficient effect to the copolymerization or durability with other vinyl monomers. Moreover, when the anti-coloring property is taken into consideration, the amino group blocking ratio needs to be 80% or more.
In the present invention, the copolymer (C) of a reactive siloxane polymer and a vinyl group-containing monomer can be synthesized by generating radicals using an initiator in a solution polymerization method. Specifically, it can be obtained by dissolving the reactive siloxane polymer and the vinyl-containing monomer in a 1 liter reactor equipped with a thermometer reflux condenser and a stirrer, and reacting after adding the initiator. The ratio of the reactive siloxane polymer to the vinyl group-containing monomer may be any ratio, but preferably 10% or more with respect to the reactive siloxane polymer. If the vinyl group-containing monomer is less than 10%, sufficient grafting cannot be expected.
The vinyl group-containing monomer (B) is ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, 1.6 hexanediol diacrylate, 2-hydroxy methacrylate, 2-hydroxy acrylate, glycerin. Dimethacrylate, glycerin trimethacrylate, glycerin diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, methoxyethyl acrylate Isooctyl acrylate, n-octyl acrylate, isononyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 2-hydroxypropyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary methacrylate Examples include butyl, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, acrylonitrile, acrylamide, and styrene.
These vinyl group-containing monomers can be used alone or in combination of two or more.
[0009]
Examples of the polymerization initiator of the present invention include potassium persulfate, ammonium persulfate, hydrogen peroxide, peroxides such as benzoyl peroxide, cerium ammonium salts such as ceric ammonium sulfate and ceric ammonium nitrate, α, α -Azobisisobutyronitrile, 2,2-'azobis (2-aminodinopropane) dihydrochloride, etc., and these initiators may be used alone or in combination of two or more. it can.
[0010]
The fiber processing method of the present invention may be a conventionally known method, and specifically includes a spray method, a bad method, an exhaust method, a coating method, and the like. In general, in the case of the pad method, the fiber material is dipped in the fiber treatment solution indicated in the claims, mangled, dried at about 100 ° C., and cured at 110 ° C. to 170 ° C. for 1 to 2 minutes.
[0011]
【Example】
EXAMPLES Hereinafter, although the Example of this invention is shown and this invention is demonstrated further in detail, this invention is not limited to these Examples.
The processing steps evaluated in the present invention, the durability against washing, yellowing, and the texture are as follows. Parts and% in the examples represent parts by weight and% by weight, respectively, and washing durability, yellowing, and texture were measured by the following methods. The evaluation results with cotton broad 40S are shown in Table 1.
Washing durability According to JIS103 method, after washing 10 times, the texture was confirmed.
Yellowing degree yellowness (ΔYI): Color measurement CLR-7100F (manufactured by Shimadzu Corporation) with a spectrocolorimeter on the basis of processing up of water treatment. + The higher the value, the greater the yellowing.
Judgment was made by tactile sensation observations by 10 inspectors. The standard is as follows.
○: dry feeling, Δ: slightly dry feeling, x: slimy feeling
Processing conditions (processing conditions) Test Cloth: Cotton Broad 40S
Padding: 2 times immersion 2 times drawing, drawing rate 83%
Drying: 100 ° C. × 3 minutes Curing: 170 ° C. × 1 minute
Implementation synthesis example 1
In a reactor having a capacity of 3 liters equipped with a thermometer reflux condenser and a stirrer, 300 parts of amino-modified silicone (viscosity at 25 ° C .: 1520 mPa · S, amine value: 31), 21 parts of 2-methacryloyloxyethylene isocyanate After adding and confirming that the amine value was 3.2 after reacting at room temperature for 1 hour, 100 parts of an emulsifier (polyoxyethylene alkyl ether carbon number: 12 to 14, ethylene oxide addition mole number: 7 moles) was added. After sufficiently stirring, 600 parts of emulsified water was added to obtain a 40% silicon emulsion aqueous dispersion.
Implementation synthesis example 2
Addition of 300 parts of amino-modified silicone (viscosity at 25 ° C .: 2100 mPa · S, amino value: 33) and 21 g of 2-methacryloyloxyethylene isocyanate in a reactor of 3 liters equipped with a thermometer reflux condenser and a stirrer After the reaction at room temperature for 1 hour, it was confirmed that the amine value was 3.7, and 100 parts of emulsifier (polyoxyethylene alkyl ether carbon number: 12 to 14, ethylene oxide addition mole number: 7 moles) was added. After sufficiently stirring, 600 parts of emulsified water was added to obtain a 40% silicon emulsion aqueous dispersion.
Implementation synthesis example 3
In a reactor having a capacity of 3 liters equipped with a thermometer reflux condenser and a stirrer, 0.5 part of benzoyl peroxide and 510 parts of soft water were put into a reactor maintained at 80 ° C. 100 parts of a silicone emulsion, 100 parts of butyl acrylate, 7.0 parts of an emulsifier (polyoxyethylene alkyl ether carbon number: 12-14, ethylene oxide addition mole number: 7 moles), drop polymerization is performed over 10 hours, A 20% acrylic-silicone emulsion aqueous dispersion was obtained.
Comparative synthesis example 1
In a 3 liter reactor equipped with a thermometer reflux condenser and a stirrer, 300 parts of amino-modified silicone (viscosity at 25 ° C .: 1520 m · Pa, amino value 31), 100 parts of emulsifier (polyoxyethylene alkyl ether carbon number) 12 to 14 and the number of moles of ethylene oxide added: 7 moles), and after sufficient stirring, 600 parts of emulsified water was added to obtain a 40% silicon emulsion aqueous dispersion.
Comparative Synthesis Example 2
In a reactor having a capacity of 3 liters equipped with a thermometer reflux condenser and a stirrer, 300 parts of amino-modified silicone (viscosity at 25 ° C .: 2100 mPa · S, amino value: 33), 100 parts of emulsifier (alkyl ether carbon number: 12) -14, ethylene oxide: 7) was added, and after sufficient stirring, 600 parts of emulsified water was added to obtain a 40% silicon emulsion aqueous dispersion.
[0013]
An example of processing was shown. % By weight is expressed as a pure conversion ratio.
[Table 1]
As a result of the above, according to the present invention, a functional group capable of radical polymerization can be introduced into the silicone skeleton in an industrially simple and inexpensive manner without causing environmental pollution, and a copolymer of another vinyl monomer is provided. . Moreover, when processed to a fiber, durable softness | flexibility can be provided. Furthermore, an amino-modified silicone that is capable of efficiently blocking amino groups of silicone having amino groups and having excellent anti-coloration properties due to heat can be provided.
[0016]
[Effect of the present invention]
According to the present invention, a functional group capable of radical polymerization can be introduced into the silicone skeleton, and a copolymer of another vinyl monomer is provided. Moreover, the amino group of silicone which has an amino group can be efficiently blocked, and the amino modified silicone which is excellent in the coloring prevention property by heat | fever can be provided.
Claims (6)
ＣＨ２＝Ｃ（Ｒ）ＣＯＯ−Ａ−ＮＣＯ （化１）
但し、Ｒは水素原子、メチル基、エチル基、Ａは炭素数２〜１２のアルキレン基The reactive siloxane polymer according to claim 1, wherein the unsaturated group-containing isocyanate compound is represented by the following chemical formula (1).
CH 2 = C (R) COO -A-NCO ( Formula 1)
However, R is a hydrogen atom, a methyl group, an ethyl group, and A is an alkylene group having 2 to 12 carbon atoms.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010248424A (en) * | 2009-04-17 | 2010-11-04 | Kansai Paint Co Ltd | Silsesquioxane compound bearing polymerizable functional group |
| JP2010270230A (en) * | 2009-05-22 | 2010-12-02 | Kansai Paint Co Ltd | Silsesquioxane compound having polymerizable functional group and ultraviolet-absorbing group |
| WO2022186137A1 (en) * | 2021-03-05 | 2022-09-09 | ダウ・東レ株式会社 | Co-modified organopolysiloxane and curable organopolysiloxane composition including same |
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| JPS60259680A (en) * | 1984-06-06 | 1985-12-21 | 信越化学工業株式会社 | Fiber treating agent |
| JPH02154076A (en) * | 1988-12-06 | 1990-06-13 | Shin Etsu Chem Co Ltd | Textile treating agent |
| JPH02252721A (en) * | 1989-03-28 | 1990-10-11 | Showa Highpolymer Co Ltd | Curable resin composition |
| JPH06184257A (en) * | 1992-12-16 | 1994-07-05 | Three Bond Co Ltd | Optically curable silicone composition |
| JPH0733987A (en) * | 1993-07-20 | 1995-02-03 | Three Bond Co Ltd | Anaerobically curable and photocurable silicone composition |
| JPH09132621A (en) * | 1996-11-01 | 1997-05-20 | Kureha Chem Ind Co Ltd | Contact lens material |
| JPH11158779A (en) * | 1997-11-25 | 1999-06-15 | Toshiba Silicone Co Ltd | Fiber processing agent |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60259680A (en) * | 1984-06-06 | 1985-12-21 | 信越化学工業株式会社 | Fiber treating agent |
| JPH02154076A (en) * | 1988-12-06 | 1990-06-13 | Shin Etsu Chem Co Ltd | Textile treating agent |
| JPH02252721A (en) * | 1989-03-28 | 1990-10-11 | Showa Highpolymer Co Ltd | Curable resin composition |
| JPH06184257A (en) * | 1992-12-16 | 1994-07-05 | Three Bond Co Ltd | Optically curable silicone composition |
| JPH0733987A (en) * | 1993-07-20 | 1995-02-03 | Three Bond Co Ltd | Anaerobically curable and photocurable silicone composition |
| JPH09132621A (en) * | 1996-11-01 | 1997-05-20 | Kureha Chem Ind Co Ltd | Contact lens material |
| JPH11158779A (en) * | 1997-11-25 | 1999-06-15 | Toshiba Silicone Co Ltd | Fiber processing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010248424A (en) * | 2009-04-17 | 2010-11-04 | Kansai Paint Co Ltd | Silsesquioxane compound bearing polymerizable functional group |
| JP2010270230A (en) * | 2009-05-22 | 2010-12-02 | Kansai Paint Co Ltd | Silsesquioxane compound having polymerizable functional group and ultraviolet-absorbing group |
| WO2022186137A1 (en) * | 2021-03-05 | 2022-09-09 | ダウ・東レ株式会社 | Co-modified organopolysiloxane and curable organopolysiloxane composition including same |
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| JP4749659B2 (en) | 2011-08-17 |
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