JP2769566B2 - Water repellent treatment method using phosphazene compound - Google Patents
Water repellent treatment method using phosphazene compoundInfo
- Publication number
- JP2769566B2 JP2769566B2 JP62180619A JP18061987A JP2769566B2 JP 2769566 B2 JP2769566 B2 JP 2769566B2 JP 62180619 A JP62180619 A JP 62180619A JP 18061987 A JP18061987 A JP 18061987A JP 2769566 B2 JP2769566 B2 JP 2769566B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- phosphazene compound
- water repellency
- compound
- phosphazene
- 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.)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、布地等の繊維構成物に、一般式（NPR2）ｎ
（ｎ≧３）で示されるホスファゼン化合物（燐−窒素化
合物）の溶液を含浸させたのち、乾燥熱処理し、布地等
の繊維構成物（以下単に布地等と略記する）に、ホスフ
ァゼン化合物を付着あるいは反応架橋させ布地等に撥水
性を付与する方法に関するものである。
［従来技術およびその問題点］
今日、撥水剤としてポリシロキサン系、アクリル酸フ
ルオロアルキルエステル系、脂肪族系等が広く利用され
ている。しかしながら、これらの撥水剤を使用して撥水
処理を行なうと、処理された布地等が、帯電しやすいと
か、目ずれを起こすとか、油焼け現象を呈するとか、離
形性が強すぎるとかの種々の問題点をかかえており、そ
れぞれの系としての機能の広がりにも自づから限界がみ
られた。
本発明の目的は、上記問題点を解消し得て、実用性に
優れた撥水処理方法を提供することにある。
［問題点を解決するための手段］
本発明は、布地等の繊維構成物に、一般式（NPR2）ｎ
で示されるホスファゼン化合物の溶液を含浸させた後に
乾燥し、更に熱処理するものである。上式（NPR2）ｎに
おいて、ｎは３以上であり、Ｒについては広範な選択が
可能である。
この系に属する化合物は、撥水性以外にも、種々変化
に富む機能を併有している。
例えば難燃性があり、耐油性があり、とか耐寒性にす
ぐれるとか、帯電しにくいとか種々の機能を併有してい
る。
これらの化合物は一般式（NPCl2）ｎ（ｎ≧３）とし
て示される二塩化窒化燐の塩素のＲ置換誘導体である。
一般式（NPR2）ｎ中、Ｒはアルコキシ基、アリルオキ
シ基、アルキルチオ基、アリルチオ基、フルオロアルコ
キシ基、パーフルオロオキシ基あるいはアミノ基等であ
り、Ｒのすべてが同一であるか、あるいは異種基を含ん
でもよい。例えば、Ｒの一部をアミノ基としておき、布
等の構成繊維との架橋性をよくする事もできる。
一般に、これらホスファゼン化合物の合成方法あるい
は構造等は報告されている。
例えば、［NP（OCH2CF3）2］3（Ｉ）はＲtz［R.F.
W.Rtz and C.J.Grundman,U.S.Pat.2876247:R.F.W.R
tz and M.Hess,Chem.Ber.84889（1951）］、［NP（OC6
Ｈ5）2］3（II）はShaw［D.Dell,B.W.Fitzsimmon and
R.A.Shaw,J.Chem.Soc.,4070（1965）］およびＮ3Ｐ3（N
H2）2（OCH2CF3）4（III）はLeuton［M.V.Leuton and
B.Lewis,J.Chem.Soc.,655（1966）］により報告されて
いる。
本発明は、一般式（NPR2）ｎ（ｎ≧３）で示されるホ
スファゼン化合物で、布地等に適当な処理を施せば、布
地等に撥水性を付与できる事を見出して完成されたもの
である。
すなわち、本発明では布地等にホスファゼン化合物の
溶液（必要ならばイソシアナート等の架橋剤を添加）を
含浸させ、そのままか、又はマングル等で絞液したの
ち、乾燥し、更に一層の熱処理を行なう事により該布地
等に撥水性を付与するものであり、環状を保ったＲ置換
体であっても開環させた直鎖状ホスファゼンでも、いず
れも撥水効果が得られる事を確認した。
化合物の種類により撥水性に程度差がみられるが、そ
れとともに、併有する他の機能、例えば柔軟性、撥油
性、変色の程度等にも種々の変化がみられる。
これらの変化は置換基Ｒの変化によるところが大き
い。
これらの環状化合物の一部を例示すると、［NP（OC6
Ｈ5）2］3、Ｎ3Ｐ3（NH2）2（ｎ−PrO）4、［NP（OC6Ｈ
4NH2）2］3、［NP（OC6Ｈ4Ｏ）2］3、［NP（OCH2C
F3）2］3、Ｎ3Ｐ3（NH2）2（OCH2CF3）4、［NP（NH2Ｃ6
Ｈ5）2］3、［NP（OC6Ｈ5）2］3が挙げられる。
直鎖状化合物は、環状化合物の同一式のｎ倍で示すこ
とができる。
なお、直鎖状ホスファゼン化合物の製造方法として
は、例えば特公昭62-20124号公報および特公昭62-20125
号公報に開示された方法がある。
本発明でいう布地等としては、天然繊維、半合成繊
維、合成繊維等の繊維で構成される織物、編物、不織布
等だけでなく、その加工品であるコーテッドファブリッ
ク、合成皮革等も含まれる。又、その形状如何の制約を
うけるものではない。
布地等にホスファゼン溶液を含浸させるには、パッデ
ィング法、スプレー法又はコーティング法を布地等の素
材、形状、組織等、溶液の粘性、粘度等を勘案し適宜選
択使用する。
熱処理効果は一様でなく、個々の化合物でさまざまで
あるが、アミノ基等の官能基を含むものにははっきりと
その効果がみられ、構成繊維との間に架橋反応が生じて
いると思われる。
イソシアネート等を架橋剤として使用すると、その効
果は顕著にあらわれ、繰り返し洗濯等によってもその撥
水度の低下が殆どみられず、熱処理のみではその効果の
すくないホスファゼン化合物であっても、イソシアネー
ト等の架橋剤を併用することにより、その撥水効果の耐
久性を改善できる。
［発明の効果］
本発明の撥水処理方法によれば、布地等に優れた撥水
性を付与することができるだけでなく、従来の方法のよ
うに、処理された布地等が、帯電しやすいとか、目ずれ
を起こすとか、油焼け現象を呈するとか、離形性が強す
ぎるとかという欠点がない。
［実施例］
以下に実施例を示すが、撥水性の評価はJISL-1092ス
プレー法により、撥油性の評価はAATCC118-1966により
行なった。
撥水効果の耐久性を評価するための洗濯は、JISL0217
-103により、また、乾燥はタンブラーで行なった。
実施例１
環状ホスファゼン［NP（OC6Ｈ5）2］3の粉末をトリク
レン溶媒に溶かし、５％溶液を調製した。
この溶液に、ナイロンタフタを、室温で20秒間浸漬含
浸させたのち、マングル絞液し、次いでこのタフタを10
0℃で３分間乾燥し、更に160℃で30秒間の加熱処理を行
なった。
得られたタフタの撥水度は80で、風合は柔軟であっ
た。これは、撥水度があまり大きくなく、かつ柔軟であ
り、コーティングの前処理として好適である。
実施例２
環状ホスファゼン［NP（OCH2CF3）2］3の粉末をメチ
ルエチルケトンに溶かし、５％溶液を調製した。
以下実施例１と同じ方法で、布地を処理した。
得られたタフタの撥水度は85であり、３回洗濯後50に
低下した。風合は柔軟で、変色もすくなかった。
実施例３
環状ホスファゼンＮ3Ｐ3（NH2）2（OCH2CF3）4の泥状
物をTHF溶媒に溶かし、５％溶液を調製した。以下実施
例１と同じ方法で布地を処理した。
得られた布地の撥水度は80であり、３回洗濯後70に低
下した。
実施例４
実施例３の溶液にイソシアネート（商品名コロネート
HL:日本ポリウレタン社製）0.2％を加えた浴を調整し
た。
以下実施例３と同様とした。
得られた布地の撥水度は90であり、３回洗濯後も90を
保った。撥油度は２級であった。
実施例５
直鎖状ホスファゼンポリマー［NP（OCH2CF3）2］ｎ
（ｎ＝6600）をDMFに溶解し、３％溶液を調製した。
以下実施例２と同様に処理をすすめた。
得られたタフタの撥水度は90であり、３回洗濯後も90
を保った。撥油度は４級であり、変色はすくなかった。
また、難燃性を示した。
実施例６
直鎖状ホスファゼンポリマー［NP（OC6Ｈ5）2］ｎ
（ｎ＝4500）をDMF溶媒に溶かし、３％溶液を調整し
た。
以下実施例１と同様に処理をすすめた。
得られたタフタの撥水度は80であり、３回洗濯後も80
を保った。撥油度は２級であった。
実施例７
直鎖状ホスファゼンポリマー［NP（OCH2CF3）2］ｎ
（ｎ＝6600）をTHF:DMF＝50:50の混合溶媒に溶解し、30
％溶液を調整した。
この溶液を、コーティング布（テトロンツィール）の
生地面側に流涎させながら、ナイフオーバーロール方式
で塗布含浸させ、100℃で３分間乾燥させ、更に150℃で
３分間熱処理した。
生地面の撥水度は90であり、３回洗濯後も90を保っ
た。撥油度は４級であった。なお、処理前後における色
差は4.5級以上で良好であった。
実施例８
実施例７に使用した［NP（OCH2CF3）2］ｎ（ｎ＝660
0）のDMF40％溶液をテトロンツイール裏面に塗布し、水
中に静かに浸漬すると不透明な凝固膜を形成した。
この処理布をマングル絞液し、乾燥、熱処理をした。
得られた凝固膜はすぐれた撥水性を示すとともに多孔
性で透湿性もあり、この処理布は防水布として役立つ。
この膜形成の過程から、この化合物の濃厚溶液を適当
な紡糸口金から押出し、水等の凝固浴に導くことにより
撥水性とともに撥油性があり、かつ、難燃性に富む繊維
をつくり得た。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fiber composition such as a fabric, which has the general formula (NPR 2 ) n
After impregnating with a solution of a phosphazene compound (phosphorus-nitrogen compound) represented by (n ≧ 3), drying and heat-treating, the phosphazene compound is adhered to a fiber component such as fabric (hereinafter simply referred to as fabric or the like). The present invention relates to a method for imparting water repellency to a fabric or the like by reaction crosslinking. [Prior art and its problems] Polysiloxanes, fluoroalkyl acrylates, aliphatics, and the like are widely used today as water repellents. However, when a water-repellent treatment is performed using these water-repellent agents, the treated fabric or the like tends to be easily charged, causes misalignment, exhibits an oil burning phenomenon, or has excessively strong releasability. However, there were some limitations on the spread of functions of each system. An object of the present invention is to provide a water repellent treatment method which can solve the above problems and is excellent in practicality. [Means for Solving the Problems] The present invention relates to a method for preparing a fiber composition such as a fabric by the general formula (NPR 2 ) n
Is impregnated with a solution of a phosphazene compound represented by the formula (2), dried, and further heat-treated. In the above formula (NPR 2 ) n, n is 3 or more, and R can be selected from a wide range. The compounds belonging to this system have various functions in addition to water repellency. For example, it has various functions, such as being flame-retardant, oil-resistant, having excellent cold resistance, and being difficult to be charged. These compounds are R-substituted derivatives of phosphorus dichloride nitride represented by the general formula (NPCl 2 ) n (n ≧ 3). In the general formula (NPR 2 ) n, R represents an alkoxy group, an allyloxy group, an alkylthio group, an allylthio group, a fluoroalkoxy group, a perfluorooxy group, an amino group, or the like, and all of R are the same or different groups. May be included. For example, a part of R may be an amino group to improve crosslinkability with constituent fibers such as cloth. In general, methods for synthesizing these phosphazene compounds and structures have been reported. For example, [NP (OCH 2 CF 3 ) 2 ] 3 (I) is Rtz [RF
W. Rtz and CJGrundman, US Pat. 2876247: RFWR
tz and M. Hess, Chem. Ber. 84889 (1951)], [NP (OC 6
H 5 ) 2 ] 3 (II) is based on Shaw [D. Dell, BWFitzsimmon and
RAShaw, J. Chem. Soc., 4070 (1965)] and N 3 P 3 (N
H 2 ) 2 (OCH 2 CF 3 ) 4 (III) is from Leuton [MVLeuton and
B. Lewis, J. Chem. Soc., 655 (1966)]. The present invention is a phosphazene compound represented by the general formula (NPR 2 ) n (n ≧ 3), which has been completed by finding that water repellency can be imparted to a fabric or the like by appropriately treating the fabric or the like. is there. That is, in the present invention, a cloth or the like is impregnated with a solution of a phosphazene compound (a cross-linking agent such as an isocyanate is added if necessary), squeezed as it is, or squeezed with a mangle or the like, dried, and further heat-treated. This imparts water repellency to the fabric or the like, and it was confirmed that both the R-substituted product maintaining the ring shape and the opened linear phosphazene can provide a water repellent effect. Although the degree of water repellency varies depending on the type of compound, various changes are also observed in other functions such as flexibility, oil repellency, degree of discoloration, and the like. These changes are largely due to changes in the substituent R. Examples of some of these cyclic compounds include [NP (OC 6
H 5) 2] 3, N 3 P 3 (NH 2) 2 (n-PrO) 4, [NP (OC 6 H
4 NH 2 ) 2 ] 3 , [NP (OC 6 H 4 O) 2 ] 3 , [NP (OCH 2 C
F 3) 2] 3, N 3 P 3 (NH 2) 2 (OCH 2 CF 3) 4, [NP (NH 2 C 6
H 5) 2] 3, it includes [NP (OC 6 H 5) 2] 3. A linear compound can be represented by n times the same formula as a cyclic compound. As a method for producing a linear phosphazene compound, for example, JP-B-62-20124 and JP-B-62-20125
There is a method disclosed in Japanese Patent Publication No. The fabrics and the like in the present invention include not only woven fabrics, knitted fabrics, and nonwoven fabrics made of fibers such as natural fibers, semi-synthetic fibers, and synthetic fibers, but also processed products such as coated fabrics and synthetic leathers. Also, there is no restriction on the shape. In order to impregnate a phosphazene solution into a cloth or the like, a padding method, a spray method or a coating method is appropriately selected and used in consideration of the material, shape, texture, etc. of the cloth and the viscosity and viscosity of the solution. The effect of heat treatment is not uniform and varies depending on the individual compound, but those containing functional groups such as amino groups have a clear effect, and a cross-linking reaction with the constituent fibers seems to occur. It is. When an isocyanate or the like is used as a cross-linking agent, its effect is remarkably exhibited, and its water repellency is hardly reduced even by repeated washing and the like. By using a crosslinking agent together, the durability of the water repellent effect can be improved. [Effects of the Invention] According to the water repellent treatment method of the present invention, not only can excellent water repellency be imparted to a fabric or the like, but also a treated fabric or the like is easily charged as in a conventional method. There are no drawbacks such as misalignment, oil burning, and excessive releasability. [Examples] Examples are shown below. The water repellency was evaluated by the JISL-1092 spray method, and the oil repellency was evaluated by AATCC118-1966. Washing to evaluate the durability of the water repellent effect is JISL0217
According to -103, drying was performed in a tumbler. Example 1 A powder of cyclic phosphazene [NP (OC 6 H 5 ) 2 ] 3 was dissolved in a trichlene solvent to prepare a 5% solution. This solution was immersed and impregnated with nylon taffeta at room temperature for 20 seconds, squeezed into a mangle, and then immersed in this taffeta for 10 seconds.
After drying at 0 ° C. for 3 minutes, a heat treatment was further performed at 160 ° C. for 30 seconds. The water repellency of the obtained taffeta was 80, and the hand was soft. This is not so large in water repellency and flexible, and is suitable as a pretreatment for coating. Example 2 A powder of cyclic phosphazene [NP (OCH 2 CF 3 ) 2 ] 3 was dissolved in methyl ethyl ketone to prepare a 5% solution. Thereafter, the fabric was treated in the same manner as in Example 1. The water repellency of the obtained taffeta was 85, and decreased to 50 after washing three times. The hand was soft and did not discolor. Example 3 A mud of cyclic phosphazene N 3 P 3 (NH 2 ) 2 (OCH 2 CF 3 ) 4 was dissolved in a THF solvent to prepare a 5% solution. Thereafter, the fabric was treated in the same manner as in Example 1. The water repellency of the obtained fabric was 80, and decreased to 70 after washing three times. Example 4 An isocyanate (trade name: Coronate) was added to the solution of Example 3
HL: manufactured by Nippon Polyurethane Co., Ltd.). Hereinafter, the same as Example 3 was performed. The water repellency of the obtained fabric was 90, and kept 90 even after washing three times. Oil repellency was second grade. Example 5 Linear phosphazene polymer [NP (OCH 2 CF 3 ) 2 ] n
(N = 6600) was dissolved in DMF to prepare a 3% solution. Thereafter, the same processing as in Example 2 was performed. The water repellency of the obtained taffeta is 90, even after washing three times.
Kept. The oil repellency was grade 4, and the discoloration was not so small.
It also exhibited flame retardancy. Example 6 Linear phosphazene polymer [NP (OC 6 H 5 ) 2 ] n
(N = 4500) was dissolved in DMF solvent to prepare a 3% solution. Thereafter, the same processing as in Example 1 was performed. The water repellency of the obtained taffeta is 80, even after washing three times.
Kept. Oil repellency was second grade. Example 7 Linear phosphazene polymer [NP (OCH 2 CF 3 ) 2 ] n
(N = 6600) was dissolved in a mixed solvent of THF: DMF = 50: 50, and 30
% Solution was prepared. This solution was applied and impregnated by a knife-over-roll method while dripping on the cloth surface side of the coated cloth (Tetronzil), dried at 100 ° C. for 3 minutes, and further heat-treated at 150 ° C. for 3 minutes. The water repellency of the fabric surface was 90, and was maintained at 90 after washing three times. Oil repellency was grade 4. The color difference before and after the treatment was good at 4.5 class or more. Example 8 [NP (OCH 2 CF 3 ) 2 ] n (n = 660 used in Example 7)
A 40% solution of DMF in 0) was applied to the back of the tetron tweel and immersed gently in water to form an opaque coagulated film. This treated cloth was mangled, dried and heat-treated. The obtained coagulated membrane has excellent water repellency and is porous and moisture-permeable, and this treated cloth serves as a waterproof cloth. During the process of film formation, a concentrated solution of this compound was extruded from a suitable spinneret and introduced into a coagulation bath such as water, whereby fibers having both water repellency, oil repellency and flame retardancy could be produced.
フロントページの続き (72)発明者 梶原 鳴雪 愛知県名古屋市名東区西山台117番地 (72)発明者 坂間 隆 大阪府大阪市東区瓦町２丁目５番地 中 外貿易株式会社大阪支店内 (72)発明者 住友 俊夫 京都府京都市南区吉祥院落合町15番地 第一レース株式会社京都工場内 (56)参考文献 特開 昭61−266669（ＪＰ，Ａ) 特開 昭62−78271（ＪＰ，Ａ) 特開 昭51−70728（ＪＰ，Ａ)Continuation of front page (72) Inventor Naruki Kajiwara 117 Nishiyamadai, Meito-ku, Nagoya City, Aichi Prefecture (72) Inventor Takashi Sakuma 2-5, Kawaramachi, Higashi-ku, Osaka-shi, Osaka Outside Trading Co., Ltd. Osaka Branch (72) Inventor Toshio Sumitomo 15 Ochiaicho, Kichijoin, Minami-ku, Kyoto, Kyoto Prefecture Daiichi Race Co., Ltd. Kyoto Factory (56) References JP-A-61-266669 (JP, A) JP-A-62-78271 (JP, A) JP-A-51-70728 (JP, A)
Claims (1)
ｎは３以上であり、Ｒはアルコキシ基、アリルオキシ
基、アルキルチオ基、アリルチオ基、フルオロアルコキ
シ基、パーフルオロオキシ基あるいはアミノ基からなる
群から選ばれた少なくとも一種を意味する）で示される
ホスファゼン化合物が前記繊維構成物に所望の程度の撥
水性を付与するのに必要な量溶解された溶液を含浸さ
せ、次に該繊維構成物を乾燥し、更に熱処理する事を特
徴とするホスファゼン化合物による撥水処理方法。 ２．前記ホスファゼン化合物がｎ＝３の環状化合物であ
ることを特徴とする特許請求の範囲第１項記載のホスフ
ァゼン化合物による撥水処理方法。 ３．前記ホスファゼン化合物がｎ≧３の直鎖状化合物で
あることを特徴とする特許請求の範囲第１項記載のホス
ファゼン化合物による撥水処理方法。 ４．架橋剤としてイソシアネートを併用することを特徴
とする特許請求の範囲第１項記載のホスファゼン化合物
による撥水処理方法。(57) [Claims] General formula (NPR 2 ) n (wherein,
n is 3 or more, and R represents at least one selected from the group consisting of an alkoxy group, an allyloxy group, an alkylthio group, an allylthio group, a fluoroalkoxy group, a perfluorooxy group, and an amino group). Is impregnated with a dissolved solution in an amount necessary to impart a desired degree of water repellency to the fiber composition, and then the fiber composition is dried and further heat-treated. Water treatment method. 2. 2. The method according to claim 1, wherein the phosphazene compound is a cyclic compound having n = 3. 3. 2. The method according to claim 1, wherein the phosphazene compound is a linear compound having n ≧ 3. 4. 2. The method for treating water repellency with a phosphazene compound according to claim 1, wherein an isocyanate is used in combination as a crosslinking agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62180619A JP2769566B2 (en) | 1987-07-20 | 1987-07-20 | Water repellent treatment method using phosphazene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62180619A JP2769566B2 (en) | 1987-07-20 | 1987-07-20 | Water repellent treatment method using phosphazene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6426785A JPS6426785A (en) | 1989-01-30 |
| JP2769566B2 true JP2769566B2 (en) | 1998-06-25 |
Family
ID=16086384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62180619A Expired - Fee Related JP2769566B2 (en) | 1987-07-20 | 1987-07-20 | Water repellent treatment method using phosphazene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2769566B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5170728A (en) * | 1974-12-12 | 1976-06-18 | Ethyl Corp | HOSUFUAZEN CHENSEISEISEIBUTSUOYOBI SONOSEIZOHO |
| JPS61266669A (en) * | 1985-05-15 | 1986-11-26 | 日東紡績株式会社 | Novel flame-proof processing method |
| JPS6278271A (en) * | 1985-10-02 | 1987-04-10 | 日東紡績株式会社 | Flame-proof processing of woven/knitted fabric containing cellulose fiber |
-
1987
- 1987-07-20 JP JP62180619A patent/JP2769566B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6426785A (en) | 1989-01-30 |
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