JP2007270374A - Water repellent and oil repellent cloth and method for producing the same - Google Patents
Water repellent and oil repellent cloth and method for producing the same Download PDFInfo
- Publication number
- JP2007270374A JP2007270374A JP2006096610A JP2006096610A JP2007270374A JP 2007270374 A JP2007270374 A JP 2007270374A JP 2006096610 A JP2006096610 A JP 2006096610A JP 2006096610 A JP2006096610 A JP 2006096610A JP 2007270374 A JP2007270374 A JP 2007270374A
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- crosslinking agent
- repellent
- repellent fabric
- 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.)
- Pending
Links
Abstract
Description
本発明は、撥水撥油性布帛およびその製造方法に関する。 The present invention relates to a water / oil repellent fabric and a method for producing the same.
繊維布帛の撥水撥油加工方法として、フッ素系撥水剤と架橋剤とを併用して繊維布帛を処理する方法は、従来から広範囲に行われている（特許文献１）。
近年、特に繊維製品の人体への安全性や製造時の環境負荷への対応が注目され、繊維布帛への撥水撥油加工に対しても、上記のような安全性や環境負荷への対応が求められている。
例えば、環境負荷への対応としては、アルキルフェノール誘導体や有機スズ系化合物を含まない薬剤が、薬剤メーカーにより開発され、繊維布帛の撥水撥油加工に用いられている。
As a water / oil / oil repellent processing method for fiber fabrics, a method for treating fiber fabrics using a fluorine-based water repellent and a crosslinking agent in combination has been widely performed (Patent Document 1).
In recent years, attention has been paid especially to the safety of textile products to the human body and the environmental impact during production, and the above-mentioned safety and environmental impacts are also applied to water and oil repellent finishing on textile fabrics. Is required.
For example, in response to environmental impact, a drug that does not contain an alkylphenol derivative or an organotin compound has been developed by a drug manufacturer and is used for water / oil repellent finishing of fiber fabrics.
また、最近では、界面活性剤等に使用されるパーフルオロオクタンスルホン酸：Ｃ８Ｆ１７ＳＯ３Ｈ（以下、「ＰＦＯＳ」ということもある）の人体への有害性が問題視され、ＰＦＯＳおよびその関連物質の製造を自主的に廃止するメーカーが多い。
一方、ＰＦＯＳと類似構造を持つパーフルオロオクタン酸：Ｃ７Ｆ１５ＣＯＯＨ（以下、「ＰＦＯＡ」ということもある）に関しては、その毒性等についての調査、研究が実施されている。
一般に、ＰＦＯＡは、従来のフッ素系撥水剤の製造過程において、微量の不純物として撥水剤中に混入してくる。そのためＰＦＯＡを含有しないフッ素系撥水剤の開発が求められていた。
In recent years, the harmfulness of perfluorooctane sulfonic acid: C 8 F 17 SO 3 H (hereinafter sometimes referred to as “PFOS”) used in surfactants to the human body is regarded as a problem, and PFOS and Many manufacturers voluntarily abolish the production of related substances.
On the other hand, perfluorooctanoic acid: C 7 F 15 COOH (hereinafter sometimes referred to as “PFOA”) having a structure similar to that of PFOS has been investigated and researched on its toxicity.
In general, PFOA is mixed in the water repellent as a trace amount of impurities in the process of manufacturing a conventional fluorine water repellent. Therefore, development of a fluorine-based water repellent that does not contain PFOA has been demanded.
そこで、撥水剤メーカーはＰＦＯＡを含有しないフッ素系撥水剤の開発を行ったが、この撥水剤を繊維布帛に付与した場合に、十分な耐久撥水性能を得ることができなかった。
本発明は、上記の如き従来技術の問題点を解消し、撥水撥油性の耐久性に優れ、かつ、撥水撥油性布帛の製造工程でのＰＦＯＡの環境（排水）への放出や撥水撥油性布帛からのＰＦＯＡの発生を抑えることのできる、撥水撥油性布帛およびその製造方法を提供することを課題とする。 The present invention solves the problems of the prior art as described above, is excellent in durability of water and oil repellency, and releases PFOA to the environment (drainage) and water repellency in the manufacturing process of the water and oil repellency fabric. It is an object of the present invention to provide a water / oil repellent fabric capable of suppressing generation of PFOA from the oil repellent fabric and a method for producing the same.
本発明者らは、上記課題を解決するため鋭意検討した結果、ＰＦＯＡを含まないフッ素系撥水剤を特定の架橋剤を用いて繊維布帛に付与することにより上記課題を解決することできることを見出し、本発明を完成するに至ったものである。
すなわち、本発明は、下記の構成（１）〜（１７）からなる。
（１）繊維布帛にパーフルオロオクタン酸非含有フッ素系撥水剤と架橋剤を付与してなり、前記架橋剤がイソシアネート系架橋剤、メラミン系架橋剤、カルボジイミド系架橋剤およびオキサゾリン系架橋剤からなる群から選ばれる少なくとも１種であることを特徴とする撥水撥油性布帛。
（２）前記パーフルオロオクタン酸非含有フッ素系撥水剤の、高速液体クロマトグラフィー質量分析にて測定したパーフルオロオクタン酸の濃度が、定性限界値未満である、上記（１）に記載の撥水撥油性布帛。
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by applying a fluorine-based water repellent containing no PFOA to a fiber fabric using a specific crosslinking agent. The present invention has been completed.
That is, the present invention comprises the following configurations (1) to (17).
(1) A perfluorooctanoic acid-free fluorine-based water repellent and a crosslinking agent are added to a fiber fabric, and the crosslinking agent is composed of an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent. A water / oil repellent fabric, which is at least one selected from the group consisting of:
(2) The concentration of perfluorooctanoic acid measured by high performance liquid chromatography / mass spectrometry of the fluorine-containing water repellent containing no perfluorooctanoic acid is less than a qualitative limit value. Water / oil repellent fabric.
（３）前記架橋剤が、非ブロックタイプの水分散型ポリイソシアネート系架橋剤から選ばれる少なくとも１種である、上記（１）または（２）に記載の撥水撥油性布帛。
（４）前記非ブロックタイプの水分散型ポリイソシアネート系架橋剤が、脂肪族系イソシアネート化合物からなる、上記（１）〜（３）のいずれかに記載の撥水撥油性布帛。
（５）前記非ブロックタイプの水分散型ポリイソシアネート系架橋剤が、親水性成分を含有する化合物である、上記（１）〜（４）のいずれかに記載の撥水撥油性布帛。
（６）前記非ブロックタイプの水分散型ポリイソシアネート系架橋剤に含有される親水性成分が、ポリエーテル系化合物の単位を含む、上記（５）に記載の撥水撥油性布帛。
（７）前記ポリエーテル系化合物の単位が、ポリエチレングリコール基および／またはポリプロピレングリコール基である、上記（６）に記載の撥水撥油性布帛。
(3) The water / oil repellent fabric according to (1) or (2), wherein the cross-linking agent is at least one selected from non-blocking water-dispersed polyisocyanate cross-linking agents.
(4) The water / oil repellent fabric according to any one of the above (1) to (3), wherein the non-block type water-dispersed polyisocyanate-based crosslinking agent comprises an aliphatic isocyanate compound.
(5) The water / oil repellent fabric according to any one of the above (1) to (4), wherein the non-blocking water-dispersed polyisocyanate crosslinking agent is a compound containing a hydrophilic component.
(6) The water / oil repellent fabric according to (5) above, wherein the hydrophilic component contained in the non-blocking type water-dispersed polyisocyanate crosslinking agent contains a unit of a polyether compound.
(7) The water / oil repellent fabric according to (6), wherein the unit of the polyether compound is a polyethylene glycol group and / or a polypropylene glycol group.
（８）前記パーフルオロオクタン酸非含有フッ素系撥水剤が、Ｎ−メチロール基を含有しないモノマーのみから構成された重合体である、上記（１）〜（７）のいずれかに記載の撥水撥油性布帛。
（９）ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトンＡ法に準じて測定した遊離ホルムアルデヒド量が、吸光度の差（Ａ−Ａ０）として０．０５以下である、上記（１）〜（８）のいずれかに記載の撥水撥油性布帛。
（１０）ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトンＡ法における布帛質量の１０倍の質量の試験布を用い、ＪＩＳ Ｌ１０４１Ｂ法に準じて測定した遊離ホルムアルデヒド量が、１．６ｐｐｍ以下である、上記（１）〜（９）のいずれかに記載の撥水撥油性布帛。
(8) The perfluorooctanoic acid-free fluorine-based water repellent is a polymer composed only of a monomer that does not contain an N-methylol group, and is described in any one of (1) to (7) above. Water / oil repellent fabric.
(9) JIS L1041 Free formaldehyde test The amount of free formaldehyde measured according to the acetylacetone A method is 0.05 or less as the difference in absorbance (A-A 0 ), and any one of the above (1) to (8) The water- and oil-repellent fabric described.
(10) JIS L1041 free formaldehyde test The amount of free formaldehyde measured according to the JIS L1041B method using a test cloth having a mass 10 times the mass of the fabric in the acetylacetone A method is 1.6 ppm or less. (9) The water / oil repellent fabric according to any one of the above.
（１１）ＪＩＳ Ｌ０８５５（強試験）に従う窒素酸化物に対する染色堅牢度が、４級以上である、上記（１）〜（１０）いずれかに記載の撥水撥油性布帛。
（１２）ＪＩＳ Ｌ０２１７ １０３に従う洗濯２０回後のＪＩＳ Ｌ１０９２（スプレー試験）による撥水度が３級以上である、上記（１）〜（１１）のいずれかに記載の撥水撥油性布帛。
（１３）ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８−１９９７による撥油性が２級以上である、上記（１）〜（１２）のいずれかに記載の撥水撥油性布帛。
（１４）湿磨耗後のＪＩＳ Ｌ１０９２（スプレー試験）による撥水度が３級以上である、上記（１）〜（１３）のいずれかに記載の撥水撥油性布帛。
(11) The water- and oil-repellent fabric according to any one of (1) to (10) above, wherein the dyeing fastness to nitrogen oxides according to JIS L0855 (strong test) is quaternary or higher.
(12) The water / oil repellent fabric according to any one of (1) to (11) above, wherein the water repellency according to JIS L1092 (spray test) after 20 washings according to JIS L0217 103 is grade 3 or higher.
(13) The water / oil repellent fabric according to any one of the above (1) to (12), wherein the oil repellency according to AATCC Test Method 118-1997 is second or higher.
(14) The water / oil repellent fabric according to any one of the above (1) to (13), wherein the water repellency according to JIS L1092 (spray test) after wet wear is 3 or more.
（１５）繊維布帛に、パーフルオロオクタン酸非含有フッ素系撥水剤と、イソシアネート系架橋剤、メラミン系架橋剤、カルボジイミド系架橋剤およびオキサゾリン系架橋剤からなる群から選ばれる少なくとも１種の架橋剤とを含む処理液を付与した後、熱処理を行うことを特徴とする撥水撥油性布帛の製造方法。
（１６）前記架橋剤が、非ブロックタイプの水分散型ポリイソシアネート系架橋剤から選ばれる少なくとも１種である、上記（１５）に記載の撥水撥油性布帛の製造方法。
（１７）前記熱処理が、６０〜２００℃の温度で行われる、上記（１５）または（１６）に記載の撥水撥油性布帛の製造方法。
(15) At least one type of crosslinking selected from the group consisting of a perfluorooctanoic acid-free fluorine-based water repellent, an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent. A method for producing a water- and oil-repellent fabric, comprising applying a treatment liquid containing an agent and then performing a heat treatment.
(16) The method for producing a water / oil repellent fabric according to (15), wherein the cross-linking agent is at least one selected from non-block type water-dispersed polyisocyanate cross-linking agents.
(17) The method for producing a water / oil repellent fabric according to (15) or (16), wherein the heat treatment is performed at a temperature of 60 to 200 ° C.
本発明によれば、撥水撥油性の耐久性に優れ、かつ、撥水撥油性布帛の製造工程でのＰＦＯＡの環境（排水）への放出や撥水撥油性布帛からのＰＦＯＡの発生を抑えることのできる、撥水撥油性布帛が提供される。
特に、本発明の好ましい態様においては、洗濯を行っても優れた撥水撥油性を維持し、布帛を湿った状態にて磨耗した湿磨耗後も優れた撥水撥油性を維持することができ、また窒素酸化物に対する耐黄変性にも優れ、さらに遊離ホルムアルデヒドの発生を抑えることもできる、撥水撥油性布帛を得ることができる。
なお、本発明の撥水撥油性布帛は、ウインドブレーカー、スキーウエアーなどのスポーツウエアーやフィッシングウエアー、作業服、エプロン、防水シーツ、テーブルクロス、靴、鞄などの用途へ展開することにより、安全で利便性に優れた衣服やシーツ等を提供することができる。
According to the present invention, the durability of water and oil repellency is excellent, and the release of PFOA to the environment (drainage) and the generation of PFOA from the water and oil repellency fabric in the manufacturing process of the water and oil repellency fabric are suppressed. A water- and oil-repellent fabric that can be provided is provided.
In particular, in a preferred embodiment of the present invention, excellent water and oil repellency can be maintained even after washing, and excellent water and oil repellency can be maintained even after wet wear when the fabric is worn in a wet state. In addition, a water- and oil-repellent fabric that is excellent in yellowing resistance to nitrogen oxides and that can also suppress the generation of free formaldehyde can be obtained.
The water- and oil-repellent fabrics of the present invention can be used safely for sports wear such as windbreakers and ski wear, fishing wear, work clothes, aprons, waterproof sheets, tablecloths, shoes and bags. It is possible to provide clothes and sheets that are highly convenient.
以下に本発明の好ましい実施の態様について具体的に説明するが、本発明はこれらの態様のみに限定されるものではなく、その精神および実施の範囲内において多くの変形が可能であることを理解されたい。
本発明に用いられる繊維布帛は、ポリエステル、ナイロン、アクリル、ポリウレタン等の合成繊維、レーヨン、バンブー繊維、大豆蛋白繊維などの再生繊維、アセテートなどの半合成繊維、綿、麻、絹、毛などの天然繊維などのいずれの繊維からなるものであってもよく、またこれらの繊維の混繊、混紡、交織、交編などの複数の繊維を組み合わせたものであってもよく、特に限定されるものではない。
また、その形態は、織物、編物、不織布等のいかなるものであってもよく、特に限定されるものではない。
Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to these embodiments, and it is understood that many variations can be made within the spirit and scope of practice. I want to be.
The fiber fabric used in the present invention includes synthetic fibers such as polyester, nylon, acrylic, and polyurethane, regenerated fibers such as rayon, bamboo fiber, and soy protein fiber, semi-synthetic fibers such as acetate, cotton, hemp, silk, and hair. It may be composed of any fiber such as natural fiber, and may be a combination of a plurality of fibers such as mixed fiber, mixed spinning, union, knitting, and the like, which are particularly limited. is not.
Moreover, the form may be anything such as a woven fabric, a knitted fabric, and a non-woven fabric, and is not particularly limited.
本発明において、パーフルオロオクタン酸非含有フッ素系撥水剤とは、ＰＦＯＡや炭素数９以上のパーフルオロノナン酸、パーフルオロデカン酸などのＰＦＯＡ類縁物質およびそれらの前駆体（分解してＰＦＯＡやＰＦＯＡ類縁物質となりうる物質）を含有しない撥水剤である。
また、ＰＦＯＡ非含有とは、現在の最高精度の分析機器である高速液体クロマトグラフィー質量分析により測定したパーフルオロオクタン酸の濃度が、定性限界値未満であることをいう。現在の定性限界値は、２〜４ｐｐｂである。
In the present invention, a fluorine-based water repellent containing no perfluorooctanoic acid is PFOA, perfluorononanoic acid having 9 or more carbon atoms, PFOA-related substances such as perfluorodecanoic acid and their precursors (decomposed to PFOA and It is a water repellent that does not contain a substance that can be a PFOA related substance.
Moreover, PFOA non-containment means that the density | concentration of the perfluoro octanoic acid measured by the high performance liquid chromatography mass spectrometry which is the present highest precision analytical instrument is less than a qualitative limit value. The current qualitative limit is 2-4 ppb.
また、パ−フルオロオクタン酸非含有フッ素系撥水剤は、ホルムアルデヒドの発生を抑制する観点からは、Ｎ−メチロール基を含有しないモノマーのみから構成された重合体であることが好ましく、より好ましくはＮ−メチロール基を含有しないモノマーのみから構成されたパーフルオロアルキルアクリレート共重合体である。
このような撥水剤としては、旭硝子（株）のアサヒガードＡＧ−Ｅ０６０、ＡＧ−Ｅ０６１が市販されている。
Further, the perfluorooctanoic acid-free fluorine-based water repellent is preferably a polymer composed only of a monomer not containing an N-methylol group, more preferably from the viewpoint of suppressing the generation of formaldehyde. It is a perfluoroalkyl acrylate copolymer composed only of a monomer not containing an N-methylol group.
As such a water repellent, Asahi Guard AG-E060 and AG-E061 manufactured by Asahi Glass Co., Ltd. are commercially available.
また、本発明に用いる架橋剤は、イソシアネート系架橋剤、メラミン系架橋剤、カルボジイミド系架橋剤およびオキサゾリン系架橋剤からなる群から選ばれる少なくとも１種からなる。
これらの架橋剤を用いることにより、得られる撥水撥油性布帛の、撥水撥油性の洗濯や湿磨耗に対する耐久性を向上させることができる。
特に、耐久性の観点からは、芳香族ブロックイソシアネート系架橋剤が好ましい。
また、窒素酸化物に対する黄変の防止の観点からは、脂肪族ブロックイソシアネート系架橋剤、脂肪族カルボジイミド系架橋剤およびオキサゾリン系架橋剤が好ましい。
耐久性と窒素酸化物に対する黄変の防止の観点からは、非ブロックタイプの水分散型ポリイソシアネ−ト系架橋剤が好ましい。
Moreover, the crosslinking agent used for this invention consists of at least 1 sort (s) chosen from the group which consists of an isocyanate type crosslinking agent, a melamine type crosslinking agent, a carbodiimide type crosslinking agent, and an oxazoline type crosslinking agent.
By using these cross-linking agents, it is possible to improve the durability of the resulting water / oil repellent fabric against water / oil repellent washing and wet wear.
In particular, an aromatic blocked isocyanate crosslinking agent is preferable from the viewpoint of durability.
From the viewpoint of preventing yellowing of nitrogen oxides, an aliphatic blocked isocyanate crosslinking agent, an aliphatic carbodiimide crosslinking agent and an oxazoline crosslinking agent are preferred.
From the viewpoint of durability and prevention of yellowing against nitrogen oxides, non-block type water-dispersed polyisocyanate crosslinking agents are preferred.
また、本発明において、非ブロックタイプの水分散型ポリイソシアネート系架橋剤は脂肪族系イソシアネート化合物からなるのが好ましく、この脂肪族系イソシアネート化合物は親水性成分を含む化合物であるのが好ましい。ここで、非ブロックタイプの水分散型ポリイソシアネート系架橋剤に含有される親水性成分は、ポリエーテル系化合物の単位を主として含むのが好ましく、このポリエーテル系化合物の単位はポリエチレングリコール基および／またはポリプロピレングリコール基であるのが好ましい。
非ブロックタイプとは、イソシアネート基をオキシム類、フェノール類、エノール類等の活性水素化合物と反応させて、常温では不活性にしたブロックイソシアネートではないものをいう。すなわち、非ブロックタイプとは、末端のイソシアネート基がブロックされていないタイプのものである。
In the present invention, the non-block type water-dispersed polyisocyanate crosslinking agent is preferably composed of an aliphatic isocyanate compound, and the aliphatic isocyanate compound is preferably a compound containing a hydrophilic component. Here, the hydrophilic component contained in the non-blocking type water-dispersed polyisocyanate crosslinking agent preferably contains mainly a polyether compound unit, and the polyether compound unit comprises a polyethylene glycol group and / or Or it is preferably a polypropylene glycol group.
The non-block type refers to a non-blocked isocyanate that is inactivated at room temperature by reacting an isocyanate group with an active hydrogen compound such as oximes, phenols, enols and the like. That is, the non-blocking type is a type in which the terminal isocyanate group is not blocked.
非ブロックタイプの水分散型ポリイソシアネート系架橋剤としては、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水添ジフェニルメタンジイソシアネート等の脂肪族系ジイソシアネートまたはジフェニルメタンジイソシアネート、トルイレンジイソシアネート、キシリレンジイソシアネート等の芳香族系ジイソシアネートを変性してイソシアヌレート体、アダクト体、ビュウレット体等を含むポリイソシアネート体とし、親水性成分を一部反応させた化合物が挙げられる。
本発明に用いる非ブロックタイプの水分散型ポリイソシアネート系架橋剤は、窒素酸化物に対する黄変を防止する観点から、脂肪族系化合物であるのが好ましい。
Non-blocking water-dispersed polyisocyanate crosslinking agents include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, or aromatic diisocyanates such as diphenylmethane diisocyanate, toluylene diisocyanate and xylylene diisocyanate. A compound obtained by modifying a polyisocyanate body containing an isocyanurate body, an adduct body, a burette body, etc., and partially reacting a hydrophilic component.
The non-blocking water-dispersed polyisocyanate crosslinking agent used in the present invention is preferably an aliphatic compound from the viewpoint of preventing yellowing of nitrogen oxides.
前述したように、本発明に用いる非ブロックタイプの水分散型ポリイソシアネート系架橋剤は、親水性成分を含有する化合物であるのが好ましい。一般に、撥水加工において親水性成分を含有する化合物を撥水剤と併用することは、撥水性の低下が予想され、特に撥水性能の洗濯耐久性の低下が懸念されるものである。ところが、本発明では、このような当業者の常識に反して、親水性成分を含有する非ブロックタイプの水分散型ポリイソシアネート系架橋剤を用いたにもかかわらず、優れた撥水性能だけではなく、撥水性能の優れた洗濯耐久性をも有する撥水撥油性布帛が得られることが見出されたのである。 As described above, the non-blocking water-dispersed polyisocyanate crosslinking agent used in the present invention is preferably a compound containing a hydrophilic component. In general, when a compound containing a hydrophilic component is used in combination with a water repellent in a water repellent process, a decrease in water repellency is expected, and in particular, a decrease in washing durability due to water repellency is a concern. However, in the present invention, contrary to the common knowledge of those skilled in the art, in spite of using a non-blocking type water-dispersed polyisocyanate-based crosslinking agent containing a hydrophilic component, only excellent water repellency performance can be obtained. In addition, it has been found that a water / oil repellent fabric having excellent water repellency and washing durability can be obtained.
本発明に有用なかかる架橋剤の具体的な商品名としては、タケネートＷＤ７２０、ＷＤ７２５（武田薬品工業（株）製）、ＮＫアシストＩＳ−８０Ｄ、ＩＳ―１００Ｎ（日華化学（株）製）、バイヒジュールＶＰＬＳ２３１９、ＶＰＬＳ２３３６（住化バイエルウレタン（株）製）、アクアネート１００、２００（日本ポリウレタン工業（株）製）などが挙げられる。 Specific product names of such crosslinking agents useful in the present invention include Takenate WD720, WD725 (manufactured by Takeda Pharmaceutical Co., Ltd.), NK Assist IS-80D, IS-100N (manufactured by Nikka Chemical Co., Ltd.), Examples include Bihijoule VPLS2319, VPLS2336 (manufactured by Sumika Bayer Urethane Co., Ltd.), Aquanate 100, 200 (manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like.
これらの非ブロックタイプの水分散型ポリイソシアネート系架橋剤は、当初、水系ウレタン樹脂等に対する架橋剤として開発されたが、これらを撥水加工に用いることには撥水性能やその耐久性の問題や加工液安定性、ポットライフ等の問題があるため、撥水加工用の架橋剤としては使用されてはいなかった。
しかしながら、本発明においては、非ブロックタイプの水分散型ポリイソシアネート架橋剤を撥水加工に用いることにより、撥水撥油性布帛からのホルムアルデヒドの発生を抑え、窒素酸化物による黄変を防止し、洗濯、湿磨耗に対する耐久性に優れた撥水撥油性布帛を得ることが可能になったのである。
These non-blocking water-dispersed polyisocyanate crosslinking agents were originally developed as crosslinking agents for water-based urethane resins, etc., but using them for water-repellent finishing has problems with water repellency and durability. However, it has not been used as a cross-linking agent for water-repellent processing because of problems such as stability of processing liquid and pot life.
However, in the present invention, by using a non-blocking type water-dispersed polyisocyanate crosslinking agent for water-repellent processing, generation of formaldehyde from the water- and oil-repellent fabric is suppressed, and yellowing due to nitrogen oxides is prevented. It has become possible to obtain a water- and oil-repellent fabric excellent in durability against washing and wet wear.
本発明において、フッ素系撥水剤の繊維布帛への付着量は、繊維布帛の質量に対して０．１〜２．５質量％が好ましく、０．４〜１．５質量％がより好ましい。付着量が０．１％未満では耐久性が得られにくくなることがあり、また２．５％を超えると得られる布帛の風合いが粗硬になることがある。
また、非ブロックタイプの水分散型ポリイソシアネート系架橋剤の繊維布帛への付着量は、繊維布帛の質量に対して０．０５〜１．０質量％が好ましく、０．１０〜０．４５質量％が特に好ましい。付着量が０．０５％未満では耐久性が得られにくくなることがあり、付着量が１．０％を超えると風合いが粗硬となることがある。
In this invention, 0.1-2.5 mass% is preferable with respect to the mass of a fiber fabric, and, as for the adhesion amount to the fiber fabric of a fluorine-type water repellent, 0.4-1.5 mass% is more preferable. If the adhesion amount is less than 0.1%, durability may be difficult to obtain, and if it exceeds 2.5%, the texture of the resulting fabric may become coarse.
Further, the amount of non-block type water-dispersed polyisocyanate crosslinking agent attached to the fiber fabric is preferably 0.05 to 1.0% by mass, and preferably 0.10 to 0.45% by mass with respect to the mass of the fiber fabric. % Is particularly preferred. If the adhesion amount is less than 0.05%, it may be difficult to obtain durability, and if the adhesion amount exceeds 1.0%, the texture may become rough.
また、本発明の撥水撥油性布帛からの遊離ホルムアルデヒド量は、ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトン法Ａ法に準じて測定した吸光度の差（Ａ−Ａ０）として０．０５以下であるのがよい。
ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトン法Ａ法に準じて測定した吸光度の差（Ａ−Ａ０）が０．０５以下であれば、「有害物質を含有する家庭用品の規制に関する法律」（法律第１１２号）の生後２４ヶ月以下の乳幼児用の繊維製品の規制をクリアすることができる。
Further, the amount of free formaldehyde from the water / oil repellent fabric of the present invention should be 0.05 or less as the difference in absorbance (A-A 0 ) measured according to JIS L1041 Free Formaldehyde Test Acetylacetone Method A Method. .
If the difference in absorbance measured according to JIS L1041 free formaldehyde test acetylacetone method A method (A-A 0 ) is 0.05 or less, the “Act on the Regulation of Household Products Containing Hazardous Substances” (Act No. 112) ) Of the textile products for infants under 24 months of age can be cleared.
また、さらに好ましくは、遊離ホルムアルデヒド量が、ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトン法Ａ法における布帛質量の１０倍の質量の試験布を用い、ＪＩＳ Ｌ１０４１Ｂ法に準じて測定して、１．６ｐｐｍ以下（試験布１ｇ当り）であるのがよい。
この方法は、試験布の量をＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトン法Ａ法に規定されている質量の１０倍の２５ｇの布帛を用い、その以外はＢ法に準じる方法により遊離ホルムアルデヒド濃度の測定を行うものである。このＪＩＳ Ｌ１０４２Ａ法は、「有害物質を含有する家庭用品の規制に関する法律」のなかで、２４ヶ月以下の乳幼児以外の肌着等の繊維製品からのホルムアルデヒドの遊離量を測定する際に用いられる方法であり、Ｂ法に比べて試験布の質量を２．５倍にして吸光度の差を求めるものがＡ法であるが、さらに、本発明では、Ａ法の試験布の１０倍の質量の布帛を用いて遊離ホルムアルデヒド量の測定を行っている。したがって、この方法により行った試験では、ホルムアルデヒド濃度の検出限界値である吸光度差０．０５に対応するホルムアルデヒド濃度は１．６ｐｐｍ（試験布１ｇ当り）となる。
More preferably, the amount of free formaldehyde is 1.6 ppm or less as measured according to JIS L1041B method using a test cloth having a mass 10 times the mass of fabric in acetylacetone method A of JIS L1041 free formaldehyde test A method. (Per gram of cloth).
In this method, the amount of the test cloth is 10 g of the mass specified in JIS L1041 free formaldehyde test acetylacetone method A, and 25 g of the cloth is used. Is. This JIS L1042A method is a method used to measure the amount of formaldehyde released from textile products such as underwear other than infants under 24 months in the “Law Concerning Regulations on Household Products Containing Hazardous Substances”. Yes, the method of obtaining the difference in absorbance by increasing the mass of the test cloth by 2.5 times compared to the method B is the A method. In the present invention, a fabric having a mass 10 times that of the test cloth of the A method is used. Used to measure the amount of free formaldehyde. Therefore, in the test conducted by this method, the formaldehyde concentration corresponding to the absorbance difference 0.05 which is the detection limit value of the formaldehyde concentration is 1.6 ppm (per 1 g of the test cloth).
また、本発明の撥水撥油性布帛においては、窒素酸化物による耐黄変性能は、ＪＩＳ Ｌ０８５５（強試験）に従う窒素酸化物に対する染色堅牢度試験にて評価を行い、染色堅牢度が４級以上であるのがよい。
また、ＪＩＳ Ｌ０２１７ １０３法に従う洗濯２０回後のＪＩＳ Ｌ１０９２（スプレー試験）での撥水度が３級以上であり、かつ、ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８−１９９７での撥油性が２級以上であるのがよい。
また、湿磨耗後のＪＩＳ Ｌ１０９２（スプレー試験）での撥水度が３級以上であるのがよい。
湿磨耗は、ＪＩＳ Ｌ１０７６に記載のアピアランス・リテンション形試験機を用い、試料ホルダと支持台に同一の試験片を表面同士が磨耗されるように取り付け、支持台の中央部に水を滴下し、２枚の試料の間に水が介在する状態にて、７５０ｇの荷重で３５０回磨耗する。その後、室温にて乾燥し、ＪＩＳ Ｌ１０９２（スプレー試験）での撥水試験を行うことにより評価する。
In the water / oil repellent fabric of the present invention, the yellowing resistance by nitrogen oxides is evaluated by a dyeing fastness test for nitrogen oxides according to JIS L0855 (strong test). That is good.
Further, the water repellency in JIS L1092 (spray test) after 20 washings according to JIS L0217 103 method is grade 3 or higher, and the oil repellency in AATCC Test Method 118-1997 is grade 2 or higher. Good.
Further, the water repellency in JIS L1092 (spray test) after wet wear should be 3 or more.
For wet wear, using the appearance and retention type tester described in JIS L1076, attach the same specimen to the sample holder and the support base so that the surfaces are worn, and drop water on the center of the support base. It wears 350 times with a load of 750 g with water intervening between the two samples. Then, it dries at room temperature and evaluates by performing the water-repellency test by JISL1092 (spray test).
次に、本発明の撥水撥油性布帛の好ましい製造方法について説明する。
前述した如き繊維布帛に対して、パーフルオロオクタン酸非含有フッ素系撥水剤と、イソシアネート系架橋剤、メラミン系架橋剤、カルボジイミド系架橋剤およびオキサゾリン系架橋剤からなる群から選ばれる少なくとも１種の架橋剤を含む処理液を付与した後、好ましくは６０〜２００℃の温度において、熱処理を行うことにより本発明の撥水撥油性布帛を得ることができる。
ここで、繊維布帛は、精練、染色、捺染等の加工が施されたものであってもよく、また帯電防止加工や柔軟加工、抗菌加工、消臭加工を施したもの、ウレタン樹脂やアクリル樹脂から得られる多孔質膜、無孔質膜やポリテトラフルオロエチレン膜またはそれらを組み合わせた透湿性防水膜を付与した防水加工布帛などであってもよい。
Next, a preferred method for producing the water / oil repellent fabric of the present invention will be described.
At least one selected from the group consisting of a perfluorooctanoic acid-free fluorine-based water repellent, an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent for the fiber fabric as described above. The water / oil repellent fabric of the present invention can be obtained by performing a heat treatment, preferably at a temperature of 60 to 200 ° C., after applying the treatment liquid containing the crosslinking agent.
Here, the fiber fabric may be subjected to processing such as scouring, dyeing, and printing, and may be subjected to antistatic processing, soft processing, antibacterial processing, deodorization processing, urethane resin, acrylic resin, etc. It may be a waterproof film provided with a porous film, a nonporous film, a polytetrafluoroethylene film, or a moisture-permeable waterproof film obtained by combining them.
また、繊維布帛に、パーフルオロオクタン酸非含有フッ素系撥水剤とイソシアネート系架橋剤、メラミン系架橋剤、カルボジイミド系架橋剤およびオキサゾリン系架橋剤からなる群から選ばれる少なくとも１種の架橋剤を含む処理液は、水溶液や水分散液などの水系処理液であってもターペンやイソプロピルアルコール、トルエン、メチルエチルケトン、エタノールなどを用いた溶剤系処理液であってもよい。環境面、耐久性、黄変防止等の観点からは、架橋剤として非ブロックタイプの水分散型ポリイソシアネート系架橋剤を用いた水系処理液が好ましい。
これらの処理液においては、ＰＦＯＡ非含有フッ素系撥水剤や、上記の架橋剤以外の、ＰＦＯＡを含まず、ホルムアルデヒドが発生しにくく、窒素酸化物による黄変がしにくい薬剤を任意に併用してもよいことは勿論である。例えば、そのようなフッ素系撥油ＳＲ剤を併用することにより、洗濯耐久性のある撥水撥油ＳＲ加工が可能である。一般には、フッ素系撥油ＳＲ剤は、親水性成分量が多いため、撥水性能をほとんど有さないが、本発明に用いることにより優れた撥水撥油性能を有し、ホルムアルデヒドの発生を抑え、窒素酸化物による黄変を抑えた撥水撥油ＳＲ布帛が得られる。
また、制電性を付与するための帯電防止剤、風合い調整のための柔軟剤、紫外線遮蔽加工のための紫外線吸収剤、処理液安定性の向上のための界面活性剤、抗菌性付与のための抗菌剤、架橋用の触媒等の併用も可能である。
Further, the fiber fabric is provided with at least one crosslinking agent selected from the group consisting of a perfluorooctanoic acid-free fluorine-based water repellent and an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent. The treatment liquid to be contained may be an aqueous treatment liquid such as an aqueous solution or an aqueous dispersion, or a solvent-based treatment liquid using terpene, isopropyl alcohol, toluene, methyl ethyl ketone, ethanol, or the like. From the viewpoints of environmental aspect, durability, yellowing prevention and the like, an aqueous treatment liquid using a non-blocking water-dispersed polyisocyanate-based crosslinking agent as a crosslinking agent is preferable.
In these treatment liquids, a PFOA-free fluorine-based water repellent and a PFOA-free chemical other than the above-mentioned cross-linking agents are used in combination with an agent that hardly generates formaldehyde and hardly yellows due to nitrogen oxides. Of course, it may be. For example, by using such a fluorine-based oil repellent SR agent in combination, water- and oil-repellent SR processing having washing durability is possible. In general, the fluorine-based oil repellent SR agent has little water repellency because it has a large amount of hydrophilic components, but it has excellent water repellency and oil repellency when used in the present invention, and generates formaldehyde. A water- and oil-repellent SR fabric that suppresses yellowing due to nitrogen oxides is obtained.
Antistatic agent for imparting antistatic properties, softener for adjusting texture, UV absorber for UV shielding processing, surfactant for improving processing solution stability, for imparting antibacterial properties These antibacterial agents and cross-linking catalysts can be used in combination.
これらの処理液の付与方法としては、特に限定されるものではなく、パッド・ドライ法、パッド・スチーム法、パッド・ドライ・スチーム法、グラビアコーテイング法、スプレー法などの種々の方法を用いることができる。
また、処理液を付与した後、好ましくは６０〜２００℃の温度で、熱処理を行うのであるが、熱処理はホットシリンダーを用いるか、またはスチーマー、ノンタッチ型乾燥機、ネットドライヤー、ピンテンターなどの公知の熱処理装置を用いて行うことができる。また、熱処理は複数回行ってもよい。
熱処理温度が６０℃より低いと撥水撥油性能が不充分になることがあり、２００℃を超えると熱分解により、布帛の黄変が生じることがある。
The method for applying these treatment liquids is not particularly limited, and various methods such as a pad / dry method, a pad / steam method, a pad / dry / steam method, a gravure coating method, and a spray method may be used. it can.
Further, after the treatment liquid is applied, the heat treatment is preferably performed at a temperature of 60 to 200 ° C., but the heat treatment is performed using a hot cylinder or a known method such as a steamer, a non-touch dryer, a net dryer, or a pin tenter. It can be performed using a heat treatment apparatus. Moreover, you may perform heat processing in multiple times.
If the heat treatment temperature is lower than 60 ° C, the water and oil repellency may be insufficient, and if it exceeds 200 ° C, the fabric may be yellowed due to thermal decomposition.
熱処理を行った後、さらに、帯電防止加工や柔軟加工、抗菌加工、消臭加工、ウレタン樹脂やアクリル樹脂から得られる多孔質膜、無孔質膜やポリテトラフルオロエチレン膜またこれらを組み合わせた透湿性防水膜を付与する防水加工などを施してもよい。 After heat treatment, antistatic processing, soft processing, antibacterial processing, deodorization processing, porous film obtained from urethane resin and acrylic resin, nonporous film, polytetrafluoroethylene film, or a combination of these You may give the waterproof process etc. which provide a damp waterproof film.
以下、実施例により本発明をさらに説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、実施例では、窒素酸化物による黄変を分かりやすくするために、繊維布帛として染色されていない白生地を用いているが、本発明の撥水撥油性布帛には染色された繊維布帛を用いてもよいことはあらためて述べるまでもないことである。
例中の「％」は質量％であり、また例中の撥水性評価方法、撥油性評価方法、洗濯、湿磨耗、遊離ホルムアルデヒド濃度測定方法、窒素酸化物による黄変試験、透湿度測定および耐水度測定は、以下の操作により行った。
（１）撥水性評価方法：ＪＩＳ Ｌ１０９２（スプレー試験）に準じて行った。
（２）撥油性評価方法：ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８−１９９７に準じて行った。
（３）洗濯：ＪＩＳ Ｌ０２１７ １０３に準じて行い、乾燥にはつり干しを行い、その後のドライアイロン仕上げは行っていない。
（４）湿磨耗：ＪＩＳ Ｌ１０７６に記載のアピアランス・リテンション形試験機を用い、試料ホルダ（底面積約１３ｃｍ２）と支持台に同一の試験片を表面同士が磨耗されるように取り付け、支持台の中央部に水を滴下し、２枚の試料の間に水が介在する状態にて、７５０ｇ荷重で３５０回磨耗する。その後、室温にて乾燥し、ＪＩＳ Ｌ１０９２（スプレー試験）での撥水試験を行う。
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited at all by these Examples. In the examples, in order to make it easy to understand yellowing due to nitrogen oxides, a white fabric that is not dyed is used as the fiber fabric. However, the water- and oil-repellent fabric of the present invention includes a dyed fiber fabric. It is needless to say that what may be used.
“%” In the examples is% by mass, and the water repellency evaluation method, oil repellency evaluation method, laundry, wet wear, free formaldehyde concentration measurement method, nitrogen oxide yellowing test, moisture permeability measurement and water resistance in the examples The degree was measured by the following operation.
(1) Water repellency evaluation method: Executed according to JIS L1092 (spray test).
(2) Oil repellency evaluation method: It was performed according to AATCC Test Method 118-1997.
(3) Laundry: Performed in accordance with JIS L0217 103, dried for hanging, and subsequent dry ironing was not performed.
(4) Wet wear: Using the appearance and retention type tester described in JIS L1076, attach the same test piece to the sample holder (bottom area of about 13 cm 2 ) and the support base so that the surfaces are worn away. Water is dripped at the center of the sample, and wears 350 times with a load of 750 g in a state where water is interposed between the two samples. Then, it dries at room temperature and performs the water repellency test by JISL1092 (spray test).
（５）ホルムアルデヒド濃度測定方法１：ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトン法Ａ法により行った。
（６）ホルムアルデヒド濃度測定方法２：ＪＩＳ Ｌ１０４１遊離ホルムアルデヒド試験アセチルアセトン法に規定の試験布をＡ法に規定されている質量の１０倍の２５ｇの量で用い、他はＢ法に準じて、遊離ホルムアルデヒド濃度の測定を行った。
この測定方法において、吸光度差の検出限界は０．０５であり、０．０５に対応するホルムアルデヒド濃度は１．６ｐｐｍとなる。したがって、１．６ｐｐｍ（試験布１ｇ当り）が検出限界となる。
（７）窒素酸化物による黄変試験：ＪＩＳ Ｌ０８５５（強試験）に準じて行った。
（８）透湿度測定：ＪＩＳ Ｌ１０９９（Ａ−１）法に準じて行った。ただし、単位は２４時間当りに換算した。
（９）耐水度測定：ＪＩＳ Ｌ１０９２ 静水圧法 Ａ法に準じて行った。
なお、以下の実施例で使用したアサヒガードＡＧ−Ｅ０６１（旭硝子（株）製）は、ＰＦＯＡ非含有フッ素系撥水剤であり、高速液体クロマトグラフィー質量分析にて測定したパーフルオロオクタン酸の濃度が定性限界値未満であった。
(5) Formaldehyde concentration measurement method 1: JIS L1041 free formaldehyde test The acetylacetone method A was used.
(6) Formaldehyde concentration measurement method 2: JIS L1041 free formaldehyde test Using the test cloth specified in the acetylacetone method in an amount of 25 g which is 10 times the mass specified in the A method, and otherwise, according to the B method, free formaldehyde The concentration was measured.
In this measurement method, the detection limit of the absorbance difference is 0.05, and the formaldehyde concentration corresponding to 0.05 is 1.6 ppm. Accordingly, the detection limit is 1.6 ppm (per 1 g of test cloth).
(7) Yellowing test using nitrogen oxides: Performed according to JIS L0855 (strong test).
(8) Moisture permeability measurement: Measured according to JIS L1099 (A-1) method. However, the unit was converted per 24 hours.
(9) Water resistance measurement: JIS L1092 hydrostatic pressure method It was performed according to the method A.
In addition, Asahi Guard AG-E061 (Asahi Glass Co., Ltd.) used in the following Examples is a PFOA-free fluorine-based water repellent, and the concentration of perfluorooctanoic acid measured by high performance liquid chromatography mass spectrometry Was less than the qualitative limit.
実施例１
ポリエステルポンジ（タテ密度７８本／２．５４ｃｍ、ヨコ密度７２本／２．５４ｃｍ、目付け１０４ｇ／ｍ２）を精練加工した後の白生地を繊維布帛として用い、繊維布帛を下記処理液に浸漬した後、マングルにて絞り、熱風オーブンにて１２０℃で熱処理後、さらに１７０℃で１分間熱処理を行い、撥水撥油性布帛を得た。
処理液
アサヒガードＡＧ−Ｅ０６１ ５％
（ＰＦＯＡ非含有フッ素系撥水剤：旭硝子（株）製、固形分２０％）
（モノマーとしてＮ−メチロール基を含有しないモノマーのみから構成）
アクアネート１００ ０．２％
（日本ポリウレタン工業（株）製、固形分１００％）
（非ブロックタイプの水分散型ポリイソシアネート系架橋剤、脂肪族系、ポリエチレングリコール基含有）
水 ９４．８％
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛の質量に対して、０．７５％、非ブロックタイプの水分散型ポリイソシアネート系架橋剤の付着量は０．１５％であった。
得られた撥水撥油性布帛の性能を表１に示す。
Example 1
A white fabric after scouring polyester polyester (vertical density 78 / 2.54 cm, horizontal density 72 / 2.54 cm, basis weight 104 g / m 2 ) was used as a fiber fabric, and the fiber fabric was immersed in the following treatment liquid. After that, it was squeezed with a mangle, heat-treated at 120 ° C. in a hot air oven, and further heat-treated at 170 ° C. for 1 minute to obtain a water- and oil-repellent fabric.
Treatment liquid Asahi Guard AG-E061 5%
(PFOA-free fluorine-based water repellent: manufactured by Asahi Glass Co., Ltd., solid content 20%)
(Consisting only of monomers that do not contain N-methylol groups as monomers)
Aquanate 100 0.2%
(Nippon Polyurethane Industry Co., Ltd., solid content 100%)
(Non-block type water-dispersed polyisocyanate crosslinking agent, aliphatic, polyethylene glycol group-containing)
94.8% water
The amount of PFOA-free fluorine-based water repellent attached to the obtained water- and oil-repellent fabric was 0.75% with respect to the mass of the fiber fabric, and the non-block type water-dispersed polyisocyanate-based cross-linking agent was attached. The amount was 0.15%.
The performance of the obtained water / oil repellent fabric is shown in Table 1.
実施例２
処理液として下記を用いた以外は実施例１と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛の性能を表１に示す。
処理液
アサヒガードＡＧ−Ｅ０６１ ５％
ベッカミンＭ３ ０．３％
（メラミン系架橋剤：大日本インキ化学工業（株）製、固形分８０％）
キャタリストＡＣＸ ０．１％
（反応触媒：大日本インキ化学工業（株）製）
水 ９４．６％
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛の質量に対して、０．７５％、メラミン系架橋剤の付着量は０．１８％であった。
Example 2
A water / oil repellent fabric was obtained in the same manner as in Example 1 except that the following treatment liquid was used.
The performance of the obtained water / oil repellent fabric is shown in Table 1.
Treatment liquid Asahi Guard AG-E061 5%
Becamine M3 0.3%
(Melamine-based crosslinking agent: manufactured by Dainippon Ink & Chemicals, Inc., solid content 80%)
Catalyst ACX 0.1%
(Reaction catalyst: manufactured by Dainippon Ink & Chemicals, Inc.)
94.6% water
The amount of PFOA-free fluorine-based water repellent adhered to the obtained water / oil-repellent fabric was 0.75% with respect to the mass of the fiber fabric, and the amount of melamine-based crosslinking agent adhered was 0.18%. It was.
表１の結果から、実施例１の撥水撥油性布帛は、撥水撥油性の洗濯耐久性および耐湿磨耗性能が良好で、遊離ホルムアルデヒドが検出限界以下であり、窒素酸化物に対する耐黄変性も良好である。また、実施例２の撥水撥油性布帛は、窒素酸化物に対する耐黄変性が良好ではあるが、洗濯や湿磨耗に対する撥水撥油性の低下が見られる。 From the results of Table 1, the water / oil repellent fabric of Example 1 has good water and oil repellency washing durability and wet wear resistance, free formaldehyde is below the detection limit, and yellowing resistance to nitrogen oxides is also good. It is good. Further, the water / oil repellent fabric of Example 2 has good yellowing resistance to nitrogen oxides, but shows a decrease in water / oil repellency against washing and wet wear.
実施例３
ナイロンツイル（タテ密度２１０本／２．５４ｃｍ、ヨコ密度１５４本／２．５４ｃｍ、目付け８６ｇ／ｍ２）を精練した白生地を繊維布帛として用い、この布帛を下記処理液に浸漬した後、マングルにて絞り、熱風オーブンにて１２０℃で乾燥後、さらに１６０℃で１分間熱処理を行い、撥水撥油性布帛を得た。
Example 3
A white fabric scoured with nylon twill (vertical density 210 / 2.54 cm, horizontal density 154 / 2.54 cm, basis weight 86 g / m 2 ) was used as a fiber fabric. After squeezing and drying at 120 ° C. in a hot air oven, heat treatment was further performed at 160 ° C. for 1 minute to obtain a water / oil repellent fabric.
処理液
アサヒガードＡＧ−Ｅ０６１ ５％
ＮＫアシストＩＳ８０Ｄ ０．４％
（大日本インキ化学工業（株）製、固形分８０％）
（非ブロックタイプの水分散型ポリイソシアネート系架橋剤、脂肪族系、ポリエチレングリコール基含有）
水 ９４．６％
Treatment liquid Asahi Guard AG-E061 5%
NK Assist IS80D 0.4%
(Dainippon Ink Chemical Co., Ltd., solid content 80%)
(Non-block type water-dispersed polyisocyanate crosslinking agent, aliphatic, polyethylene glycol group-containing)
94.6% water
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛質量に対して、０．７５％、非ブロックタイプの水分散型ポリイソシアネート系架橋剤の付着量は０．２４％であった。
上記撥水撥油性布帛の裏面に、下記処方のウレタン樹脂溶液をフローティングナイフ方式により塗布後、水中で凝固させ、脱溶媒を行い、熱風オーブンにて１２０℃で乾燥後、１６０℃で１分間熱処理を行って、微多孔質のウレタン樹脂膜を付与し、透湿防水性能を持つ撥水撥油性布帛を得た。
得られた撥水撥油性布帛の性能を表２に示す。
The amount of PFOA-free fluorine-based water repellent attached to the obtained water / oil-repellent fabric was 0.75% with respect to the mass of the fiber fabric, and the amount of non-block type water-dispersed polyisocyanate-based cross-linking agent attached Was 0.24%.
A urethane resin solution having the following formulation is applied to the back surface of the water and oil repellent fabric by a floating knife method, solidified in water, desolvated, dried at 120 ° C. in a hot air oven, and heat treated at 160 ° C. for 1 minute. Then, a microporous urethane resin film was applied to obtain a water / oil repellent fabric having moisture permeability and waterproof performance.
The performance of the obtained water / oil repellent fabric is shown in Table 2.
ウレタン樹脂溶液
クリスボン８００６ １００質量部
（ウレタン樹脂：大日本インキ化学工業（株）製）
Ｎ，Ｎ−ジメチルホルムアミド ４０質量部
バーノックＢＬ５０ ５質量部
（脂肪族ブロックイソシアネート系架橋剤：大日本インキ化学工業（株）製）
Urethane resin solution Crisbon 8006 100 parts by mass (urethane resin: manufactured by Dainippon Ink & Chemicals, Inc.)
N, N-dimethylformamide 40 parts by mass Barnock BL50 5 parts by mass (aliphatic blocked isocyanate crosslinking agent: manufactured by Dainippon Ink & Chemicals, Inc.)
実施例４
処理液として下記を用いた以外は実施例３と同様にして、撥水撥油性布帛を得た。
得られた透湿防水性を持つ撥水撥油性布帛の性能を表２に示す。
処理液
アサヒガードＡＧ−Ｅ０６１ ５％
エラストロンＢＮ６９ ０．６％
（芳香族ブロックイソシアネート系架橋剤：第一工業製薬（株）製、固形分４０％）
水 ９４．４％
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛質量に対して、０．７５％、芳香族ブロックイソシアネート系架橋剤の付着量は０．１８％であった。
Example 4
A water / oil repellent fabric was obtained in the same manner as in Example 3 except that the following treatment liquid was used.
Table 2 shows the performance of the obtained water- and oil-repellent fabric having moisture permeability and waterproofness.
Treatment liquid Asahi Guard AG-E061 5%
Elastron BN69 0.6%
(Aromatic blocked isocyanate crosslinking agent: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content 40%)
94.4% water
The amount of PFOA-free fluorine-based water repellent attached to the obtained water / oil repellent fabric was 0.75% with respect to the mass of the fiber fabric, and the amount of the aromatic blocked isocyanate-based cross-linking agent was 0.18%. Met.
表２の結果から、実施例３の撥水撥油性布帛は、撥水撥油性能の洗濯耐久性、湿磨耗耐久性が良好であり、遊離ホルムアルデヒドが検出限界以下であり、窒素酸化物に対する耐黄変性も良好である。
実施例４の撥水撥油性布帛は、撥水撥油性の洗濯耐久性、湿磨耗耐久性が良好であり、遊離ホルムアルデヒドが検出限界以下である。ただし、窒素酸化物に対する黄変が見られる。
From the results in Table 2, the water / oil repellent fabric of Example 3 has good water and oil repellency washing durability and wet wear durability, free formaldehyde is below the detection limit, and resistance to nitrogen oxides. Yellowing is also good.
The water / oil repellent fabric of Example 4 has good water / oil repellent washing durability and wet wear durability, and free formaldehyde is below the detection limit. However, yellowing with respect to nitrogen oxide is seen.
実施例５
綿ツイル（タテ密度１００本／２．５４ｃｍ、ヨコ密度９４本／２．５４ｃｍ、目付け１６０ｇ／ｍ２）を精練加工した後の白生地を繊維布帛として用い、繊維布帛を下記処理液に浸漬した後、マングルにて絞り、熱風オーブンにて１２０℃で乾燥後、さらに１７０℃で１分間熱処理を行い、撥水撥油性布帛を得た。
Example 5
A white fabric after scouring cotton twill (vertical density 100 / 2.54 cm, horizontal density 94 / 2.54 cm, basis weight 160 g / m 2 ) was used as a fiber fabric, and the fiber fabric was immersed in the following treatment liquid. After that, it was squeezed with a mangle, dried at 120 ° C. in a hot air oven, and further heat treated at 170 ° C. for 1 minute to obtain a water / oil repellent fabric.
処理液
アサヒガードＡＧ−Ｅ０６１ ８％
バイビジュアルＶＰＬＳ２３１９ ０．４％
（住化バイエルウレタン（株）製、固形分１００％）
（非ブロックタイプの水分散型ポリイソシアネート系架橋剤、脂肪族系、ポリエチレングリコール基含有）
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛質量に対して、１．２％、非ブロックタイプの水分散型ポリイソシアネート系架橋剤の付着量は０．３％であった。
得られた撥水撥油性布帛の性能を表３に示す。
Treatment liquid Asahi Guard AG-E061 8%
Bivisual VPLS2319 0.4%
(Sumika Bayer Urethane Co., Ltd., 100% solid content)
(Non-block type water-dispersed polyisocyanate crosslinking agent, aliphatic, polyethylene glycol group-containing)
The amount of PFOA-free fluorine-based water repellent attached to the obtained water / oil-repellent fabric was 1.2% with respect to the mass of the fiber fabric, and the amount of non-block type water-dispersed polyisocyanate cross-linking agent attached Was 0.3%.
The performance of the obtained water / oil repellent fabric is shown in Table 3.
実施例６
処理液として下記を用いた以外は実施例１と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛質量に対して、１．２％、脂肪族ブロックイソシアネート系架橋剤の付着量は０．１５％であった。
Example 6
A water / oil repellent fabric was obtained in the same manner as in Example 1 except that the following treatment liquid was used.
The amount of the PFOA-free fluorine-based water repellent attached to the obtained water / oil repellent fabric was 1.2% with respect to the mass of the fiber fabric, and the amount of the aliphatic blocked isocyanate cross-linking agent was 0.15%. Met.
処理液
アサヒガードＡＧ−Ｅ０６１ ８％
エラストロンＢＮ１１ ０．６％
（脂肪族ブロックイソシアネート系架橋剤：第一工業製薬（株）製、固形分３４％）
水 ９１．４％
Treatment liquid Asahi Guard AG-E061 8%
Elastron BN11 0.6%
(Aliphatic blocked isocyanate crosslinking agent: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content: 34%)
Water 91.4%
表３の結果より、実施例５の撥水撥油性布帛は、撥水撥油性能の洗濯耐久性および耐磨耗性が良好で、遊離ホルムアルデヒドが検出限界以下であり、窒素酸化物に対する耐黄変性も良好である。
実施例６の撥水撥油性布帛は、遊離ホルムアルデヒドが検出限界以下であり、窒素酸化物に対する耐黄変性も良好であるが、洗濯後や湿磨耗後に撥水撥油性の低下が見られる。
From the results shown in Table 3, the water- and oil-repellent fabric of Example 5 has good water- and oil-repellent washing durability and abrasion resistance, free formaldehyde is below the detection limit, and yellow resistance against nitrogen oxides. Denaturation is also good.
In the water / oil repellent fabric of Example 6, free formaldehyde is below the detection limit and yellowing resistance to nitrogen oxides is good, but a decrease in water and oil repellency is observed after washing and after wet wear.
実施例７
処理液として下記を用いた以外は実施例１と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛質量に対して、０．７５％、カルボジイミド系架橋剤の付着量は０．１５％であった。
得られた撥水撥油性布帛の性能を表４に示す。
処理液
アサヒガードＡＧ−Ｅ０６１ ５％
カルボジライトＶ０２ ０．５％
（カルボジイミド系架橋剤：日清紡績（株）製、固形分４０％）
水 ９４．５％
Example 7
A water / oil repellent fabric was obtained in the same manner as in Example 1 except that the following treatment liquid was used.
The amount of PFOA-free fluorine-based water repellent attached to the obtained water / oil repellent fabric was 0.75% with respect to the mass of the fiber fabric, and the amount of carbodiimide-based cross-linking agent attached was 0.15%. .
The performance of the obtained water / oil repellent fabric is shown in Table 4.
Treatment liquid Asahi Guard AG-E061 5%
Carbodilite V02 0.5%
(Carbodiimide type cross-linking agent: Nisshinbo Co., Ltd., solid content 40%)
Water 94.5%
実施例８
処理液として下記を用いた以外は実施例１と同様にして、撥水撥油性布帛を得た。
得られた撥水撥油性布帛へのＰＦＯＡ非含有フッ素系撥水剤の付着量は、繊維布帛質量に対して、０．７５％、オキサゾリン系架橋剤の付着量は０．１５％であった。
得られた撥水撥油性布帛の性能を表４に示す。
処理液
アサヒガードＡＧ−Ｅ０６１ ５％
エポクロスＷＳ５００ ０．５％
（オキサゾリン系架橋剤：日本触媒化学工業（株）製、固形分４０％）
水 ９４．５％
Example 8
A water / oil repellent fabric was obtained in the same manner as in Example 1 except that the following treatment liquid was used.
The amount of PFOA-free fluorine-based water repellent attached to the obtained water / oil repellent fabric was 0.75% with respect to the mass of the fiber fabric, and the amount of oxazoline-based cross-linking agent attached was 0.15%. .
The performance of the obtained water / oil repellent fabric is shown in Table 4.
Treatment liquid Asahi Guard AG-E061 5%
Epochros WS500 0.5%
(Oxazoline-based crosslinking agent: Nippon Shokubai Chemical Industry Co., Ltd., solid content 40%)
Water 94.5%
実施例７の撥水撥油性布帛は、遊離ホルムアルデヒドが検出限界以下であり、窒素酸化物に対する耐黄変性も良好であるが、洗濯後や湿磨耗後に撥水撥油性の低下が見られる。
また、実施例８の撥水撥油性布帛は、遊離ホルムアルデヒドが検出限界以下であり、窒素酸化物に対する耐黄変性も良好であるが、洗濯後や湿磨耗後に撥水撥油性の低下が見られる。
In the water- and oil-repellent fabric of Example 7, free formaldehyde is below the detection limit and yellowing resistance to nitrogen oxides is good, but a decrease in water- and oil-repellency is observed after washing and after wet wear.
In addition, the water / oil repellent fabric of Example 8 has free formaldehyde below the detection limit and good yellowing resistance to nitrogen oxides, but a decrease in water and oil repellency after washing and after wet wear is observed. .
本発明の撥水撥油性布帛は、ウインドブレーカー、スキーウエアーなどのスポーツウエアーやフィッシングウエアー、作業服、エプロン、防水シーツ、テーブルクロス、靴、鞄などの用途へ展開することにより、安全で利便性に優れた衣服やシーツ等を提供することができ、産業上有用である。 The water- and oil-repellent fabric of the present invention is safe and convenient by being used in sportswear and fishing wear such as windbreakers and skiwear, workwear, aprons, waterproof sheets, tablecloths, shoes and bags. It is possible to provide clothes, sheets and the like excellent in the industrial use, which is industrially useful.
Claims (17)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006096610A JP2007270374A (en) | 2006-03-31 | 2006-03-31 | Water repellent and oil repellent cloth and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006096610A JP2007270374A (en) | 2006-03-31 | 2006-03-31 | Water repellent and oil repellent cloth and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011161111A Division JP2011214216A (en) | 2011-07-22 | 2011-07-22 | Water and oil repellent fabric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007270374A true JP2007270374A (en) | 2007-10-18 |
| JP2007270374A5 JP2007270374A5 (en) | 2009-03-05 |
Family
ID=38673463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006096610A Pending JP2007270374A (en) | 2006-03-31 | 2006-03-31 | Water repellent and oil repellent cloth and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007270374A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010196196A (en) * | 2009-02-25 | 2010-09-09 | Tokushu Paper Mfg Co Ltd | Sheet-like material |
| JP2011214216A (en) * | 2011-07-22 | 2011-10-27 | Komatsu Seiren Co Ltd | Water and oil repellent fabric |
| WO2012160711A1 (en) * | 2011-05-26 | 2012-11-29 | 株式会社 きものブレイン | Method for processing silk fiber |
| JP2013036136A (en) * | 2011-08-08 | 2013-02-21 | Komatsu Seiren Co Ltd | Water and oil repellent fabric with stain release property |
| WO2013061954A1 (en) * | 2011-10-25 | 2013-05-02 | 旭化成ケミカルズ株式会社 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| WO2013187360A1 (en) | 2012-06-11 | 2013-12-19 | セーレン株式会社 | Stretchable coated fabric and process for producing same |
| JP2014062348A (en) * | 2012-09-24 | 2014-04-10 | Teijin Frontier Co Ltd | Water repellent fabric |
| JPWO2012147582A1 (en) * | 2011-04-25 | 2014-07-28 | 帝人フロンティア株式会社 | Fabrics and textile products |
| JP2014148775A (en) * | 2013-02-04 | 2014-08-21 | Asahi Kasei Fibers Corp | Durable and water repellent polyester fiber cloth and its manufacturing method |
| JP2014152401A (en) * | 2013-02-04 | 2014-08-25 | Asahi Kasei Fibers Corp | Durable antistatic water-repellent polyester fiber cloth and method for producing the same |
| JP2014194098A (en) * | 2013-03-29 | 2014-10-09 | Toray Ind Inc | Fiber structure |
| JP2014198913A (en) * | 2013-03-29 | 2014-10-23 | 一村産業株式会社 | Water-repellent cloth and production method thereof |
| JP2015086489A (en) * | 2013-10-31 | 2015-05-07 | 帝人フロンティア株式会社 | Stain suppressing fabric and textile product |
| CN106215881A (en) * | 2016-09-07 | 2016-12-14 | 济南大学 | A kind of preparation method of cyanurotriamide modified porous magnetic dextran microspheres |
| JP2017071888A (en) * | 2011-08-04 | 2017-04-13 | 旭化成株式会社 | Durable water-repellent polyamide fiber fabric and method for producing the same |
| WO2017205328A1 (en) | 2016-05-23 | 2017-11-30 | Microban Products Company | Odor adsorbent composition and method for use in polymers |
| WO2020203432A1 (en) | 2019-04-01 | 2020-10-08 | 美津濃株式会社 | Swim suit |
| WO2020203434A1 (en) | 2019-04-01 | 2020-10-08 | 東レ株式会社 | Fibrous structure containing elastic polyurethane yarn |
| US10834922B2 (en) | 2014-11-26 | 2020-11-17 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US10842147B2 (en) | 2014-11-26 | 2020-11-24 | Microban Products Company | Surface disinfectant with residual biocidal property |
| CN112323497A (en) * | 2020-11-24 | 2021-02-05 | 京准化工技术(上海)有限公司 | Six-carbon fluorine washing-resistant waterproof moisture-proof agent and preparation method and application thereof |
| US10925281B2 (en) | 2014-11-26 | 2021-02-23 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11033023B2 (en) | 2014-11-26 | 2021-06-15 | Microban Products Company | Surface disinfectant with residual biocidal property |
| CN113338031A (en) * | 2021-06-15 | 2021-09-03 | 上海荟姿新材料科技有限公司 | Fabric finishing agent and application thereof in fabric |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6140340A (en) * | 1984-07-31 | 1986-02-26 | Dainippon Ink & Chem Inc | Stabilizer for polyurethane |
| JPS63154720A (en) * | 1986-12-19 | 1988-06-28 | Dainippon Ink & Chem Inc | Production of urethane resin excellent in light resistance and nitrogen oxide resistance |
| JPH10212404A (en) * | 1997-01-29 | 1998-08-11 | Dainippon Ink & Chem Inc | Antifouling coating agent comprising aqueous resin composition having excellent durability and releasable coating agent |
| JP2001262472A (en) * | 2000-03-14 | 2001-09-26 | Nicca Chemical Co Ltd | Method for processing fibrous material |
| JP2003171880A (en) * | 2001-12-07 | 2003-06-20 | Nicca Chemical Co Ltd | Method for producing water and oil repellent fibrous product |
| JP2004300630A (en) * | 2003-03-31 | 2004-10-28 | Nicca Chemical Co Ltd | Method for producing fiber product having water and oil repellency and water and oil repellent |
| JP2007247089A (en) * | 2006-03-15 | 2007-09-27 | Toray Ind Inc | Fiber structure |
-
2006
- 2006-03-31 JP JP2006096610A patent/JP2007270374A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6140340A (en) * | 1984-07-31 | 1986-02-26 | Dainippon Ink & Chem Inc | Stabilizer for polyurethane |
| JPS63154720A (en) * | 1986-12-19 | 1988-06-28 | Dainippon Ink & Chem Inc | Production of urethane resin excellent in light resistance and nitrogen oxide resistance |
| JPH10212404A (en) * | 1997-01-29 | 1998-08-11 | Dainippon Ink & Chem Inc | Antifouling coating agent comprising aqueous resin composition having excellent durability and releasable coating agent |
| JP2001262472A (en) * | 2000-03-14 | 2001-09-26 | Nicca Chemical Co Ltd | Method for processing fibrous material |
| JP2003171880A (en) * | 2001-12-07 | 2003-06-20 | Nicca Chemical Co Ltd | Method for producing water and oil repellent fibrous product |
| JP2004300630A (en) * | 2003-03-31 | 2004-10-28 | Nicca Chemical Co Ltd | Method for producing fiber product having water and oil repellency and water and oil repellent |
| JP2007247089A (en) * | 2006-03-15 | 2007-09-27 | Toray Ind Inc | Fiber structure |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010196196A (en) * | 2009-02-25 | 2010-09-09 | Tokushu Paper Mfg Co Ltd | Sheet-like material |
| JPWO2012147582A1 (en) * | 2011-04-25 | 2014-07-28 | 帝人フロンティア株式会社 | Fabrics and textile products |
| US9725847B2 (en) | 2011-04-25 | 2017-08-08 | Teijin Frontier Co., Ltd. | Cloth containing an organic fiber and having a fluorine compound attached to the cloth, and textile product comprising the cloth |
| JP5890400B2 (en) * | 2011-04-25 | 2016-03-22 | 帝人フロンティア株式会社 | Fabrics and textile products |
| WO2012160711A1 (en) * | 2011-05-26 | 2012-11-29 | 株式会社 きものブレイン | Method for processing silk fiber |
| JP2012246580A (en) * | 2011-05-26 | 2012-12-13 | Kimono Brain:Kk | Method for processing silk fiber |
| JP2011214216A (en) * | 2011-07-22 | 2011-10-27 | Komatsu Seiren Co Ltd | Water and oil repellent fabric |
| JP2017071888A (en) * | 2011-08-04 | 2017-04-13 | 旭化成株式会社 | Durable water-repellent polyamide fiber fabric and method for producing the same |
| JP2013036136A (en) * | 2011-08-08 | 2013-02-21 | Komatsu Seiren Co Ltd | Water and oil repellent fabric with stain release property |
| CN106008904A (en) * | 2011-10-25 | 2016-10-12 | 旭化成株式会社 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| KR20140040276A (en) * | 2011-10-25 | 2014-04-02 | 아사히 가세이 케미칼즈 가부시키가이샤 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| CN103890034A (en) * | 2011-10-25 | 2014-06-25 | 旭化成化学株式会社 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| WO2013061954A1 (en) * | 2011-10-25 | 2013-05-02 | 旭化成ケミカルズ株式会社 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| KR101593855B1 (en) | 2011-10-25 | 2016-02-12 | 아사히 가세이 케미칼즈 가부시키가이샤 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| JPWO2013061954A1 (en) * | 2011-10-25 | 2015-04-02 | 旭化成ケミカルズ株式会社 | Aqueous dispersion of block polyisocyanate, fiber treatment agent composition, and fabric |
| WO2013187360A1 (en) | 2012-06-11 | 2013-12-19 | セーレン株式会社 | Stretchable coated fabric and process for producing same |
| US20150140884A1 (en) * | 2012-06-11 | 2015-05-21 | Seiren Co., Ltd. | Stretchable coated fabric and process for producing same |
| JP2014062348A (en) * | 2012-09-24 | 2014-04-10 | Teijin Frontier Co Ltd | Water repellent fabric |
| JP2014148775A (en) * | 2013-02-04 | 2014-08-21 | Asahi Kasei Fibers Corp | Durable and water repellent polyester fiber cloth and its manufacturing method |
| JP2014152401A (en) * | 2013-02-04 | 2014-08-25 | Asahi Kasei Fibers Corp | Durable antistatic water-repellent polyester fiber cloth and method for producing the same |
| JP2014194098A (en) * | 2013-03-29 | 2014-10-09 | Toray Ind Inc | Fiber structure |
| JP2014198913A (en) * | 2013-03-29 | 2014-10-23 | 一村産業株式会社 | Water-repellent cloth and production method thereof |
| JP2015086489A (en) * | 2013-10-31 | 2015-05-07 | 帝人フロンティア株式会社 | Stain suppressing fabric and textile product |
| US11134674B2 (en) | 2014-11-26 | 2021-10-05 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US10842147B2 (en) | 2014-11-26 | 2020-11-24 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11134678B2 (en) | 2014-11-26 | 2021-10-05 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11033023B2 (en) | 2014-11-26 | 2021-06-15 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US11026418B2 (en) | 2014-11-26 | 2021-06-08 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US10925281B2 (en) | 2014-11-26 | 2021-02-23 | Microban Products Company | Surface disinfectant with residual biocidal property |
| US10834922B2 (en) | 2014-11-26 | 2020-11-17 | Microban Products Company | Surface disinfectant with residual biocidal property |
| WO2017205328A1 (en) | 2016-05-23 | 2017-11-30 | Microban Products Company | Odor adsorbent composition and method for use in polymers |
| EP3462874A4 (en) * | 2016-05-23 | 2020-01-15 | Microban Products Company | Odor adsorbent composition and method for use in polymers |
| CN109219350A (en) * | 2016-05-23 | 2019-01-15 | 美可帮产品公司 | For the odor adsorption agent composition and method in polymer |
| CN109219350B (en) * | 2016-05-23 | 2023-02-21 | 美可帮产品公司 | Odor adsorbent compositions and methods for use in polymers |
| CN106215881A (en) * | 2016-09-07 | 2016-12-14 | 济南大学 | A kind of preparation method of cyanurotriamide modified porous magnetic dextran microspheres |
| WO2020203434A1 (en) | 2019-04-01 | 2020-10-08 | 東レ株式会社 | Fibrous structure containing elastic polyurethane yarn |
| WO2020203432A1 (en) | 2019-04-01 | 2020-10-08 | 美津濃株式会社 | Swim suit |
| CN113710838A (en) * | 2019-04-01 | 2021-11-26 | 美津浓株式会社 | Swimming suit |
| KR20210144691A (en) | 2019-04-01 | 2021-11-30 | 미즈노 가부시키가이샤 | swimsuit |
| CN112323497A (en) * | 2020-11-24 | 2021-02-05 | 京准化工技术(上海)有限公司 | Six-carbon fluorine washing-resistant waterproof moisture-proof agent and preparation method and application thereof |
| CN113338031A (en) * | 2021-06-15 | 2021-09-03 | 上海荟姿新材料科技有限公司 | Fabric finishing agent and application thereof in fabric |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007270374A (en) | Water repellent and oil repellent cloth and method for producing the same | |
| JP2013036136A (en) | Water and oil repellent fabric with stain release property | |
| JP5509342B2 (en) | Permanent and durable water-repellent finishing method for fiber structures | |
| KR20080059111A (en) | Fabric treated with durable stain repel and stain release finish and method of industrial laundering to maintain durability of finish | |
| US20090233507A1 (en) | Fabric treatment process | |
| Sayed et al. | Finishing of textiles with fluorocarbons | |
| JP2010150693A (en) | Fibrous structural material and method for producing the same | |
| WO2014061182A1 (en) | Moisture-permeable waterproof sheet and method for manufacturing same | |
| JP6263853B2 (en) | Fiber structure | |
| JPWO2017126358A1 (en) | Fiber structure | |
| JP5958016B2 (en) | Fiber structure | |
| JP2011214216A (en) | Water and oil repellent fabric | |
| JP6632798B2 (en) | Antifouling polyester fabric | |
| JP5114946B2 (en) | Fiber structure | |
| JP2007247089A (en) | Fiber structure | |
| JP4298662B2 (en) | Composition having reversibly adaptable surface energy properties, treated substrate and method of making the same | |
| JPWO2005085517A1 (en) | Hydrophobicizing method for fiber structure | |
| JP2006207060A (en) | Water repellent and oil repellent cloth and method for producing the same | |
| KR20170049004A (en) | A fabric coating method for improving soil repellent and water emission and flame resistacne function, and a fabric product coated for improving soil repellent and water emission and flame resistacne function | |
| US20100192272A1 (en) | Fiber structure | |
| JP6214945B2 (en) | Water repellent pollen prevention fabric | |
| JP2016069767A (en) | Water and oil repellent fabric | |
| KR101926189B1 (en) | Coating agent of the antistatic and antifouling fabric, carseat fabric and method of it | |
| JP2008303511A (en) | Fibrous structure | |
| WO2019073898A1 (en) | Stainproof fiber structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Effective date: 20090119 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090119 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110512 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110524 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110722 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20120131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120321 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20120329 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Effective date: 20120511 Free format text: JAPANESE INTERMEDIATE CODE: A912 |