JP2010229593A - Water-and oil-repellent processing agent for fiber and paper - Google Patents
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本発明は繊維、テキスタイル、紙に対しての撥水撥油剤に関するものである。 The present invention relates to a water / oil repellent agent for fibers, textiles and paper.
従来からのフッ素系化合物を用いない撥水加工剤は環境に配慮した撥水剤で撥水性は良好であるが、撥油性がなく本発明の目的を達成できるものではない（特許文献１、２）。
また近年、フッ素系化合物の撥水撥油剤に人体への安全性、環境負荷を及ぼす可能性のある物質、例えばパーフルオロオクタン酸（以下、ＰＦＯＡ）、パーフルオロオクタスルホン酸（以下、ＰＦＯＳ）等が含有することが判明している（特許文献３）。該物質を含有しないか、あるいは出来るだけ含有量の少ないフッ素系撥水撥油剤が要望されている。該環境配慮型フッ素系化合物の撥水撥油剤として３、４種類の化合物が提案されているが、より安心および安全を配慮した撥水撥油剤は少ない。
Conventional water repellents that do not use fluorine compounds are environmentally friendly water repellents and have good water repellency, but they do not have oil repellency and cannot achieve the object of the present invention (Patent Documents 1 and 2). ).
In recent years, water- and oil-repellent fluorinated compounds have safety and environmental impacts, such as perfluorooctanoic acid (hereinafter referred to as PFOA), perfluorooctasulfonic acid (hereinafter referred to as PFOS), and the like. (Patent document 3). There is a demand for a fluorine-based water and oil repellent that does not contain the substance or has as little content as possible. Three or four kinds of water- and oil-repellent agents have been proposed as the environmentally friendly fluorine-based compound, but there are few water- and oil-repellent agents that are more secure and safe.
本発明は、かかる現状を鑑み、環境に配慮した繊維布帛への撥水剤であるフッ素系化合物を含有しない撥水剤にＰＦＯＡおよび／またはＰＦＯＳ含有量の少ない撥水撥油剤を複合化することにより、現在環境配慮型フッ素系化合物の撥水撥油剤として提案されているものよりＰＦＯＡおよび／またはＰＦＯＳ含有量をさらに少なくし、より安心および安全を配慮した洗濯耐久性のある撥水撥油剤を提供することを課題とする。 In view of the present situation, the present invention is to combine a water- and oil-repellent agent having a low content of PFOA and / or PFOS with a water-repellent agent that does not contain a fluorine-based compound that is a water-repellent agent for an environment-friendly fiber fabric. Therefore, a water- and oil-repellent agent that is more durable and safer for washing and has a lower PFOA and / or PFOS content than what is currently proposed as a water- and oil-repellent agent for environmentally friendly fluorine compounds. The issue is to provide.
前記の課題を達成するために、環境問題に配慮したフッ素系化合物を含有しない化合物（Ａ）ならびにＰＦＯＡおよび／またはＰＦＯＳ含有量が高速液体クロマトグラフィー質量分析計（ＬＣ−ＭＳ）にて測定したとき検出限界値未満であるフッ素系化合物（Ｂ）と架橋剤（Ｃ）を組み合わせて、洗濯耐久性のある良好な撥水撥油性能を付与するための加工剤、加工方法の提供、ならびにそれを用いて繊維、繊維布帛、紙を処理・加工するものである。 In order to achieve the above-mentioned problems, when the content of PFOA and / or PFOS, which does not contain a fluorine-based compound in consideration of environmental problems, is measured with a high performance liquid chromatography mass spectrometer (LC-MS) Providing a processing agent and a processing method for imparting good water / oil repellency with washing durability by combining the fluorine-based compound (B) and the crosslinking agent (C) which are less than the detection limit value, and Used to process and process fibers, fiber fabrics, and paper.
前述の解決手段を採用することにより、環境、生物に配慮した撥水撥油剤で、繊維、繊維布帛に洗濯耐久性の良好な撥水撥油性能が付与でき、衣料用途、産業資材用途等に使用できる。 By adopting the above solutions, water and oil repellents that are friendly to the environment and living organisms can impart water and oil repellent performance with good washing durability to fibers and fiber fabrics. Can be used.
本発明の効果を最大限に発揮させるための具体的な内容は、シリコン系化合物、ワックス系化合物、ワックス−ジルコニウム系化合物、アルキレン尿素系化合物、脂肪族アマイド系化合物の少なくとも１種であるフッ素系化合物を含有しない化合物（Ａ）、ＰＦＯＡおよび／またはＰＦＯＳ含有量が高速液体クロマトグラフィー質量分析計（ＬＣ−ＭＳ）にて測定したとき検出限界値未満であるフッ素系化合物（Ｂ）、ならびに架橋剤（Ｃ）を複合化（配合）した撥水撥油剤である。 Specific contents for maximizing the effects of the present invention include a fluorine compound which is at least one of a silicon compound, a wax compound, a wax-zirconium compound, an alkylene urea compound, and an aliphatic amide compound. Compound (A) not containing compound, fluorine compound (B) whose PFOA and / or PFOS content is less than the detection limit when measured with a high performance liquid chromatography mass spectrometer (LC-MS), and crosslinking agent It is a water / oil repellent obtained by combining (compounding) (C).
本発明のフッ素系化合物を含有しない化合物（Ａ）のシリコン系化合物とは、メチルハイドロジェンポリシロキサン、ジメチルシロキサン反応型（ＯＨ基）ジメチルポリシロキサンなどのシリコン系化合物の少なくとも１種を言う。また、ワックス系化合物とは、通常の蝋などのワックスを始め、合成パラフィンワックス、パラフィン蝋などの少なくとも１種を言うが、これに限定されるものではない。なお、合成パラフィンでは低融点のもの、高融点のものなど多数あるが、高融点のパラフィンワックスが好適である。またパラフィンにアクリル酸エステル系の重合物を共存させた変性物も本発明の目的を達成させるために活用できる。 The silicon compound of the compound (A) containing no fluorine compound of the present invention refers to at least one of silicon compounds such as methyl hydrogen polysiloxane and dimethylsiloxane reaction type (OH group) dimethylpolysiloxane. The wax-based compound includes at least one kind of wax such as ordinary wax, synthetic paraffin wax, and paraffin wax, but is not limited thereto. There are many synthetic paraffins having a low melting point and a high melting point, and a high melting point paraffin wax is preferred. In addition, a modified product in which an acrylate polymer is coexisted with paraffin can also be used to achieve the object of the present invention.
また、ワックスージルコニウム系化合物とは、前述のワックス系化合物をジルコニウム系化合物、具体的には酢酸ジルコニウム、塩酸ジルコニウム、硝酸ジルコニウム、水酸化カリウムなどによる塩基性ジルコニウムなどを反応させたものの少なくとも１種を言う。 The wax-zirconium-based compound is at least one kind obtained by reacting the above-mentioned wax-based compound with a zirconium-based compound, specifically, basic zirconium by zirconium acetate, zirconium hydrochloride, zirconium nitrate, potassium hydroxide, or the like. Say.
アルキレン尿素化合物とは、オクタデシルエチレン尿素、あるいは、それの変性物の少なくとも１種を言う。 The alkylene urea compound refers to at least one of octadecylethylene urea or a modified product thereof.
また、脂肪族アマイド系化合物とは、Ｎ−メチロールステアリルアマイド、あるいはそれの変性物などの高級脂肪酸アマイド誘導体の少なくとも１種を言う。 The aliphatic amide compound refers to at least one of higher fatty acid amide derivatives such as N-methylol stearyl amide or a modified product thereof.
これらのフッ素系化合物を含有しない化合物（Ａ）は、単独もしくは２種以上を併用使用して用いてもよい。また、これらのうち華氏１３０〜１５５°Ｆ融点温度のパラフィンワックスが特に本発明を達成するのに適している。 These compounds (A) not containing a fluorine compound may be used alone or in combination of two or more. Of these, paraffin wax having a melting point of 130 to 155 ° F. is particularly suitable for achieving the present invention.
本発明のフッ素系化合物（Ｂ）は、環境負荷物のＰＦＯＡおよび／またはＰＦＯＳ対策を講じたフッ素系撥水撥油剤を言うものであり、かかる化合物に含有されるＰＦＯＡおよび／またはＰＦＯＳの量は、高速液体クロマトグラフィー質量分析計（ＬＣ−ＭＳ）で測定した時に、検出限界未満のものである。現在の検出限界は、２〜５ｐｐｂである。 The fluorine-based compound (B) of the present invention refers to a fluorine-based water and oil repellent that has taken measures against PFOA and / or PFOS as an environmental load, and the amount of PFOA and / or PFOS contained in the compound is as follows. When measured with a high performance liquid chromatography mass spectrometer (LC-MS), it is less than the detection limit. The current detection limit is 2-5 ppb.
また、フッ素系化合物（Ｂ）は、環境負荷物とされているパーフルオロアルキル基のＣ８以上のフッ素アルキル基を含有せず、環境負荷のないＣ６以下にフッ素アルキル基を調整したものである。 Further, the fluorine-based compound (B) does not contain a C8 or more fluorine alkyl group of a perfluoroalkyl group, which is regarded as an environmental load, and is prepared by adjusting a fluorine alkyl group to C6 or less without environmental load.
フッ素系化合物（Ｂ）は、下記式１で表わせるフッ素鎖長限定のパーフルオロアルキル基を含有するアクリレート系化合物で、該アクリレート系化合物を１種または２種以上の化合物からなる重合体または共重合体である。また、該アクリレート系化合物は他の重合性化合物、例えばアクリル酸、メタクリル酸、スチレン、塩化ビニルなどのビニル系化合物との共重合体を含むものである。 The fluorine compound (B) is an acrylate compound containing a perfluoroalkyl group having a fluorine chain length limited represented by the following formula 1, and the acrylate compound is a polymer or a copolymer composed of one or more compounds. It is a polymer. The acrylate compound includes a copolymer with another polymerizable compound, for example, a vinyl compound such as acrylic acid, methacrylic acid, styrene, and vinyl chloride.
［−ＣＨ２−Ｃ（Ｒ１）（ＣＯＯＣＨ２ＣＨ２Ｒｆ）−］ｎ ・・・式１
式１において、Ｒ１は水素または低級アルキル基であり、ＲｆはＣｍＦ２ｍ＋１で表わされるパーフルオロアルキル基である。また、ｍは１〜６までの整数であり、ｎは１０〜２００までの整数である。
[—CH 2 —C (R 1 ) (COOCH 2 CH 2 R f ) —] n Formula 1
In Formula 1, R 1 is hydrogen or a lower alkyl group, and R f is a perfluoroalkyl group represented by C m F 2m + 1 . Moreover, m is an integer from 1 to 6, and n is an integer from 10 to 200.
本発明の架橋剤（Ｃ）とは、カルボジイミドならびにその誘導体であるカルボジイミド系化合物、尿素とグリオキザール、ホルムアルデヒドとの反応物、あるいはジメチル尿素とグリオキザールの反応物の如きグリオキザール系化合物、ヘキサメチロールメラミン、トリメチロールメラミンなどのメラミン系化合物、イソシアネート系架橋剤、トリアジン環含有化合物の少なくとも１種を言う。 The crosslinking agent (C) of the present invention includes carbodiimides and carbodiimide compounds that are derivatives thereof, urea and glyoxal, a reaction product of formaldehyde, or a glyoxal compound such as a reaction product of dimethylurea and glyoxal, hexamethylolmelamine, It refers to at least one of melamine compounds such as methylol melamine, isocyanate crosslinking agents, and triazine ring-containing compounds.
イソシアネート系架橋剤としては、トリイソシアネート系化合物、ジイソシアネート系化合物がよく、それらのポリイソシアネート化合物でもよく、これらの少なくとも１種を言い、イソシアネート末端をブロック化し、水分散させて用いる。ブロック化剤としては、メチルエチルケトオキシム、ピラゾールなどの言うが、これに限定されるものではない。
具体的なイソシアネート系化合物としては、ヘキサメチレンジイソシアネート、トリヘキサメチレンジイソシアネート、ヘキサメチレントリイソシアネート、リジンエステルトリイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタンジイソシアネートなどがあるが、特にヘキサメチレンジイソシアネートのトリスビュレット変性体などのヘキサメチレンジイソシアネートの変性物であるトリイソシアネート系化合物が好ましい。
As an isocyanate type crosslinking agent, a triisocyanate type compound and a diisocyanate type compound may be sufficient, and those polyisocyanate compounds may be used, and at least one of these is used. The isocyanate terminal is blocked and used in water dispersion. Examples of the blocking agent include, but are not limited to, methyl ethyl ketoxime and pyrazole.
Specific isocyanate compounds include hexamethylene diisocyanate, trihexamethylene diisocyanate, hexamethylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate and the like. In particular, a triisocyanate compound which is a modified product of hexamethylene diisocyanate such as a modified trisburet of hexamethylene diisocyanate is preferable.
トリアジン環含有化合物とは、トリアジン環を含有し、かつ、重合性官能基を少なくとも２個含有する化合物である。 The triazine ring-containing compound is a compound containing a triazine ring and containing at least two polymerizable functional groups.
また、エポキシ系化合物、多官能型などのアジリジン系化合物、ジアルデヒド系化合物、オキサゾリン系化合物、酢酸アルミニウム、硝酸アルミニウム、塩酸アルミニウムなどのアルミニウム系化合物、炭素数が１〜４のアルキル基を有するチタンやアルミニウムのアルコキシド化合物などの有機金属系化合物、さらには、ワックス‐ジルコニウム系化合物以外の撥水性化合物原体に対し、酢酸ジルコニウム、塩酸ジルコニウム、硝酸ジルコニウム、塩基性ジルコニウムなどのジルコニウム系化合物なども本発明に言う架橋剤を意味する。 In addition, epoxy compounds, polyfunctional type aziridine compounds, dialdehyde compounds, oxazoline compounds, aluminum compounds such as aluminum acetate, aluminum nitrate, and aluminum hydrochloride, titanium having an alkyl group having 1 to 4 carbon atoms In addition, organometallic compounds such as alkoxide compounds of aluminum and aluminum, as well as zirconium compounds such as zirconium acetate, zirconium hydrochloride, zirconium nitrate, basic zirconium, etc. for water-repellent compounds other than wax-zirconium compounds. The cross-linking agent referred to in the invention is meant.
これらの架橋剤は、単独もしくは２種以上を併用使用して用いてもよい。また、特に低温反応型架橋剤がよい。 These crosslinking agents may be used alone or in combination of two or more. In particular, a low-temperature reactive crosslinking agent is preferable.
フッ素系化合物を含有しない化合物（Ａ）に、環境配慮型のフッ素系化合物（Ｂ）と架橋剤（Ｃ）を混合することにより、環境に配慮した洗濯耐久性の良好な繊維ならびに紙用撥水撥油剤を得ることが出来る。フッ素系化合物を含有しない化合物（Ａ）の単独使用では洗濯耐久性が得られず、環境配慮型のフッ素系化合物（Ｂ）を用いなければ撥油性は得られない。また架橋剤（Ｃ）を用いなければ、洗濯耐久性を得ることが出来ない。 By mixing the environmentally friendly fluorine compound (B) and the cross-linking agent (C) with the compound (A) that does not contain a fluorine compound, the fiber and water repellent for paper have good washing durability in consideration of the environment. An oil repellent can be obtained. Washing durability cannot be obtained when the compound (A) containing no fluorine compound is used alone, and oil repellency cannot be obtained unless the environmentally friendly fluorine compound (B) is used. Moreover, if the crosslinking agent (C) is not used, the washing durability cannot be obtained.
これら（Ａ）、（Ｂ）、（Ｃ）の３成分を用いることで該問題が回避でき本発明の目的を達成することが出来る。具体的には（Ａ）成分が２５〜９５質量％、（Ｂ）成分が５〜７５質量％、（Ａ）成分および（Ｂ）成分の合計１００質量％に対して、（Ｃ）成分が１０〜１００質量％の範囲で用いることがよく、その中でも特に、（Ａ）成分が６０〜９０質量％、（Ｂ）成分が１０〜４０質量％、（Ａ）成分および（Ｂ）成分の合計１００質量％に対して、（Ｃ）成分が４０〜６５質量％の範囲が効果的である。 By using these three components (A), (B), and (C), this problem can be avoided and the object of the present invention can be achieved. Specifically, the component (A) is 25 to 95% by mass, the component (B) is 5 to 75% by mass, the component (A) and the component (B) are 100% by mass, and the component (C) is 10%. It is good to use in the range of -100 mass%, and among these, (A) component is 60-90 mass%, (B) component is 10-40 mass%, (A) component and (B) component total 100 The range of 40 to 65% by mass of component (C) is effective with respect to mass%.
この際、フッ素系化合物を含有しない化合物（Ａ）成分が９５質量％以上であれば繊維布帛に加工したときにチョークマークがきつくでてしまい、一方２５質量％以下ならば撥水性が低下、またＰＦＯＡおよび／またはＰＦＯＳ含有量のさらなる低下につながらなく本発明の目的を達成することが出来ない。環境配慮型のフッ素系化合物（Ｂ）が５質量％以下であれば繊維布帛に加工したときに撥油性が得られず、７５質量％以上であればＰＦＯＡおよび／またはＰＦＯＳ含有量のさらなる低下につながらなく本発明の目的を達成することが出来ない。また、架橋剤（Ｃ）が１０質量％以下ならば洗濯耐久性が得られず、１００質量％以上であれば１００質量％のとき以上の洗濯耐久性の効果は得られず、なおかつ繊維において実用性のない粗悪な風合になる。 At this time, if the compound (A) component not containing a fluorine-based compound is 95% by mass or more, the chalk mark is tight when processed into a fiber fabric, while if it is 25% by mass or less, the water repellency is lowered. The object of the present invention cannot be achieved without further reducing the PFOA and / or PFOS content. If the environmentally friendly fluorine-based compound (B) is 5% by mass or less, oil repellency cannot be obtained when processed into a fiber fabric, and if it is 75% by mass or more, the content of PFOA and / or PFOS is further reduced. The object of the present invention cannot be achieved. Further, if the crosslinking agent (C) is 10% by mass or less, the washing durability cannot be obtained, and if it is 100% by mass or more, the effect of the washing durability more than 100% by mass cannot be obtained, and the fiber is practically used. It becomes a rough texture without sex.
本発明において、フッ素系化合物を含有しない化合物（Ａ）と、ＰＦＯＡおよび／またはＰＦＯＳ含有量が高速液体クロマトグラフィー質量分析計（ＬＣ−ＭＳ）にて測定したとき検出限界値未満であるフッ素系化合物（Ｂ）と架橋剤（Ｃ）とを複合化（配合）して用いることにより、撥水撥油性能の洗濯耐久性を向上させるものであるが、具体的にはパラフィンワックスに酢酸ジルコニウムまた塩酸ジルコニウムと該フッ素系化合物とイソシネート系架橋剤を配合する方法、ハイドロジェンポリシロキサンと該フッ素化合物とカルボジイミドを配合する方法などがあげられる。
また、帯電防止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。
In the present invention, the compound (A) containing no fluorine compound and the fluorine compound whose PFOA and / or PFOS content is less than the detection limit when measured by a high performance liquid chromatography mass spectrometer (LC-MS) (B) and crosslinker (C) are combined (blended) to improve washing durability of water and oil repellency. Specifically, paraffin wax is mixed with zirconium acetate or hydrochloric acid. Examples thereof include a method of blending zirconium, the fluorine-based compound, and an isocyanate-based crosslinking agent, and a method of blending hydrogen polysiloxane, the fluorine compound, and carbodiimide.
Antistatic agent for imparting antistatic properties, softener for adjusting texture, ultraviolet absorber for ultraviolet shielding processing, surfactant for improving treatment liquid stability, for imparting antibacterial properties These antibacterial agents and cross-linking catalysts can be used in combination.
本発明において、前述したような方法で繊維ならびに紙用加工剤を製造するが、それらの加工剤を用いて繊維・繊維布帛・紙に加工剤を付与する方法としては次のような方法があげられる。前述の方法で製造した加工剤を浸漬法、パディング法、印捺法、コーティング法、スプレー法などで繊維・繊維布帛・紙に付与した後、自然乾燥もしくは熱乾燥させる。さらに乾燥後、１００〜１８０℃の温度で熱処理を施すとさらに繊維・繊維布帛に対して洗濯耐久性に優れた撥水撥油性能が付与できる。 In the present invention, fibers and paper processing agents are produced by the method as described above. Examples of methods for applying processing agents to fibers, fiber fabrics and paper using these processing agents include the following methods. It is done. The processing agent produced by the above-described method is applied to fibers, fiber fabrics, and papers by dipping, padding, printing, coating, spraying, etc., and then naturally dried or thermally dried. Furthermore, when heat-treated at a temperature of 100 to 180 ° C. after drying, water and oil repellency with excellent washing durability can be imparted to the fiber / fiber fabric.
なお、かかる加工品は洗濯によっても撥水撥油性能の耐久性が持続するが、より効果的には洗濯後に６０℃以上の熱を掛けるとより一層撥水撥油性能が回復して良好な性能維持が図れる。 In addition, although the durability of the water and oil repellency performance of such processed products is maintained even after washing, more effectively the water and oil repellency performance is recovered and improved by applying heat of 60 ° C. or higher after washing. Maintains performance.
本発明の加工剤を用いて加工する際に、適用素材は特に限定しないが、合成繊維ではポリエステル系合成繊維、ポリアミド合成繊維、天然素材としては、木綿、麻、絹、羊毛などの資材、ならびにそれらと合成繊維との混紡、交織物、交編物、さらにはレーヨンなどの半合成繊維ならびにそれと天然繊維との混紡、交織物、交編物が上げられる。形体としては、糸、綿の形態、織物、編物、不織布などの布帛の形態などいずれの形態でもよい。 When processing using the processing agent of the present invention, the applicable material is not particularly limited, but for synthetic fibers, polyester-based synthetic fibers, polyamide synthetic fibers, natural materials include materials such as cotton, hemp, silk, and wool, and A blend of these and a synthetic fiber, a woven fabric, a knitted fabric, a semi-synthetic fiber such as rayon, and a blend of the same with a natural fiber, a woven fabric, and a knitted fabric are raised. The form may be any form such as a form of yarn, cotton, a woven fabric, a knitted fabric, or a non-woven fabric.
本発明の加工剤を用いて加工する製品形態としては、以下のものが挙げられる。通常のコート、レインコート、スキーウエア、ゴルフパンツ、ウインドブレーカーなどのアウトドア用スポーツ衣料、一般カジュアル衣料、帽子、シューズ、ならびに各種作業衣などの衣料資材、あるいは傘、テント、農業用シートカバー、建築・土木用シートカバーなどの産業資材、さらにはハンバーガーなど食品の包装紙などに適用できる。 The following are mentioned as a product form processed using the processing agent of this invention. Outdoor sports clothing such as ordinary coats, raincoats, ski wear, golf pants, windbreakers, general casual clothing, hats, shoes, and various clothing materials such as work clothes, or umbrellas, tents, agricultural seat covers, construction -It can be applied to industrial materials such as civil engineering seat covers, and food packaging such as hamburgers.
以下、実施例によりさらに本発明について詳しく説明するが、本発明はこれらの実施例より何ら限定されるものではない。なお、本発明に言う撥水度とはＪＩＳ Ｌ−１０９２スプレー法、撥油度とはＡＡＴＣＣ １１８法に基づいて測定を行い、級判定をした。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all from these Examples. The water repellency referred to in the present invention was measured based on the JIS L-1092 spray method, and the oil repellency was measured based on the AATCC 118 method, and graded.
本発明における洗濯耐久性のデータ取りは、ＪＩＳ Ｌ−０２１７ １０３法に基づいて行った。 The data of washing durability in the present invention was obtained based on JIS L-0217 103 method.
（乳化物１）
パラフィンワックスを２５質量％、酢酸ジルコニウムを３質量％、非イオン系界面活性剤を３質量％、残りが水でトータル１００質量％としたパラフィンワックス系撥水剤を調整した。
（乳化物２）
フッ素系化合物（Ｂ）は、下記式１で表わせるフッ素鎖長ＲｆがＣＦ３からＣ６Ｆ１３のパープルオロアルキル基を含有するアクリレート系化合物の共重合体であり、該フッ素系化合物の固形分３０％に調整した。
(Emulsion 1)
A paraffin wax water repellent was prepared in which the paraffin wax was 25% by mass, the zirconium acetate was 3% by mass, the nonionic surfactant was 3% by mass, and the balance was 100% by mass with water.
(Emulsion 2)
The fluorine-based compound (B) is a copolymer of an acrylate-based compound containing a purple alkyl group having a fluorine chain length R f of CF 3 to C 6 F 13 represented by the following formula 1. The solid content was adjusted to 30%.
［−ＣＨ２−Ｃ（Ｒ１）（ＣＯＯＣＨ２ＣＨ２Ｒｆ）−］ｎ ・・・式１
（乳化物３）
ハイドロジェンシリコンを２０質量％、乳化剤を２質量％、残りが水でトータル１００質量％としたシリコン系撥水剤を調整した。
[—CH 2 —C (R 1 ) (COOCH 2 CH 2 R f ) —] n Formula 1
(Emulsion 3)
A silicon-based water repellent was prepared in which 20% by mass of hydrogen silicon, 2% by mass of an emulsifier, and the remaining water was 100% by mass in total.
架橋剤（Ｃ）としては、パラキャットＰＧＥ（大原パラヂウム化学（株）社製、ブロックイソシアネート系化合物が４０％含有した乳化物３］である。
（配合物１）
乳化物１で得られたパラフィンワックス系撥水剤を８０質量％、乳化物２で得られたフッ素系化合物を２０質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを３５質量％配合した撥水撥油剤を調整した。
（配合物２）
乳化物１で得られたパラフィンワックス系撥水剤を８０質量％、乳化物２で得られたフッ素系化合物を２０質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを１０％質量配合した撥水撥油剤を調整した。
（配合物３）
乳化物１で得られたパラフィンワックス系撥水剤を８０質量％、乳化物２で得られたフッ素系化合物を２０質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを９０質量％配合した撥水撥油剤を調整した。
（配合物４）
乳化物３で得られたシリコン系撥水剤を４０質量％、乳化物２で得られたフッ素系化合物を６０質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを３５質量％配合した撥水撥油剤を調整した。
As the crosslinking agent (C), Paracat PGE (manufactured by Ohara Palladium Chemical Co., Ltd., emulsion 3 containing 40% of a blocked isocyanate compound) is used.
(Formulation 1)
80% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 20% by mass of the fluorine-based compound obtained in Emulsion 2 are combined, and 100% by mass in total of Emulsions 1 and 2 A water and oil repellent containing 35% by mass of Paracat PGE was prepared.
(Formulation 2)
80% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 20% by mass of the fluorine-based compound obtained in Emulsion 2 are combined, and 100% by mass in total of Emulsions 1 and 2 A water / oil repellent containing 10% by mass of Paracat PGE was prepared.
(Formulation 3)
80% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 20% by mass of the fluorine-based compound obtained in Emulsion 2 are combined, and 100% by mass in total of Emulsions 1 and 2 A water and oil repellent containing 90% by mass of Paracat PGE was prepared.
(Formulation 4)
40% by mass of the silicon-based water repellent obtained in Emulsion 3 and 60% by mass of the fluorine-based compound obtained in Emulsion 2 are combined with respect to a total of 100% by mass of Emulsions 1 and 2. A water / oil repellent containing 35% by mass of Paracat PGE was prepared.
配合物１で得られた撥水撥油剤を５質量％、残りが水で１００質量％の加工液を調整した。かかる加工液にポリエステル１００％加工糸織物を浸し、マングルにて絞り率が１００％になるように絞った。ついで１１０℃で予備乾燥後、１４０℃で２分間熱処理をした。この加工布の撥水度は５級、撥油度は６級であった。なお、洗濯後、タンブルドライヤーで乾燥する作業を繰り返し２０回実施した後の撥水度は５級、撥油度は５−６級であり、撥水撥油性の洗濯耐久性が良好であることが確認できた。 A processing liquid of 5% by mass of the water / oil repellent obtained in Formulation 1 and the remaining 100% by mass of water was prepared. A 100% polyester processed yarn fabric was soaked in the processing liquid and squeezed with a mangle so that the drawing ratio was 100%. Then, after preliminary drying at 110 ° C., heat treatment was performed at 140 ° C. for 2 minutes. The water repellency of this processed fabric was grade 5, and the oil repellency was grade 6. After washing and drying with a tumble dryer 20 times repeatedly, the water repellency is grade 5, the oil repellency is grade 5-6, and the water and oil repellency washing durability is good. Was confirmed.
配合物２で得られた撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は５級、撥油度は６級であり、洗濯後の撥水度は５級、撥油度は５−６級であり、撥水撥油性の洗濯耐久性が良好であることが確認できた。 Using the water / oil repellent obtained in Formulation 2, the water / oil repellency of the processed cloth obtained in the same manner as in Example 1 was measured. Water repellency before washing is grade 5, oil repellency is grade 6, water repellency after washing is grade 5, oil repellency is grade 5-6, water and oil repellency washing durability is good It was confirmed that.
配合物２で得られた撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は５級、撥油度は６級であり、洗濯後の撥水度は５級、撥油度は５−６級であり、撥水撥油性の洗濯耐久性が良好であることが確認できた。
（比較例１）
乳化物１で得られたパラフィンワックス系撥水剤を８０質量％、乳化物２で得られたフッ素系化合物を２０質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを０質量％配合した撥水撥油剤を調整した。調整した撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は５級、撥油度は６級であり、洗濯後の撥水度は１級、撥油度は０−２級であり、洗濯耐久性が乏しいものになった。
（比較例２）
乳化物１で得られたパラフィンワックス系撥水剤を８０質量％、乳化物２で得られたフッ素系化合物を２０質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを１５０質量％配合した撥水撥油剤を調整した。調整した撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は５級、撥油度は６級であり、洗濯後の撥水度は５級、撥油度は５−６級であり、架橋剤を増加した効果は得られなかった。
（比較例３）
乳化物１で得られたパラフィンワックス系撥水剤を９９質量％、乳化物２で得られたフッ素系化合物を１質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを３５質量％配合した撥水撥油剤を調整した。調整した撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は５級、撥油度は０級であり、洗濯後の撥水度は５級、撥油度は０級であり、撥油性は得られなかった。
（比較例４）
乳化物１で得られたパラフィンワックス系撥水剤を０質量％、乳化物２で得られたフッ素系撥水撥油剤を１００質量％配合し、乳化物１および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを０質量％配合した撥水撥油剤を調整した。調整した撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は５級、撥油度は６級であり、洗濯後の撥水度は５級、撥油度は５−６級であり、実施例１〜３と効果は同等だが、ＰＦＯＡおよび／またはＰＦＯＳ含有量が多いものである。
Using the water / oil repellent obtained in Formulation 2, the water / oil repellency of the processed cloth obtained in the same manner as in Example 1 was measured. Water repellency before washing is grade 5, oil repellency is grade 6, water repellency after washing is grade 5, oil repellency is grade 5-6, water and oil repellency washing durability is good It was confirmed that.
(Comparative Example 1)
80% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 20% by mass of the fluorine-based compound obtained in Emulsion 2 are combined, and 100% by mass in total of Emulsions 1 and 2 A water and oil repellent containing 0% by mass of Paracat PGE was prepared. Using the adjusted water / oil repellent, the water / oil repellency of the processed cloth obtained by the same operation as in Example 1 was measured. The water repellency before washing was grade 5, the oil repellency was grade 6, the water repellency after washing was grade 1, and the oil repellency was grade 0-2, and the washing durability was poor.
(Comparative Example 2)
80% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 20% by mass of the fluorine-based compound obtained in Emulsion 2 are combined, and 100% by mass in total of Emulsions 1 and 2 A water and oil repellent containing 150% by mass of Paracat PGE was prepared. Using the adjusted water / oil repellent, the water / oil repellency of the processed cloth obtained by the same operation as in Example 1 was measured. The water repellency before washing is grade 5 and the oil repellency is grade 6. The water repellency after washing is grade 5 and the oil repellency is grade 5-6, and the effect of increasing the crosslinking agent is not obtained. It was.
(Comparative Example 3)
99% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 1% by mass of the fluorine-based compound obtained in Emulsion 2 are combined with respect to a total of 100% by mass of Emulsions 1 and 2 A water and oil repellent containing 35% by mass of Paracat PGE was prepared. Using the adjusted water / oil repellent, the water / oil repellency of the processed cloth obtained by the same operation as in Example 1 was measured. The water repellency before washing was grade 5 and the oil repellency was grade 0, the water repellency after washing was grade 5 and the oil repellency was grade 0, and no oil repellency was obtained.
(Comparative Example 4)
0% by mass of the paraffin wax-based water repellent obtained in Emulsion 1 and 100% by mass of the fluorine-based water / oil repellent obtained in Emulsion 2 are combined, and 100% by mass in total of Emulsions 1 and 2 On the other hand, a water / oil repellent containing 0% by mass of Paracat PGE was prepared. Using the adjusted water / oil repellent, the water / oil repellency of the processed cloth obtained by the same operation as in Example 1 was measured. The water repellency before washing is grade 5, the oil repellency is grade 6, the water repellency after washing is grade 5, and the oil repellency is grade 5-6. , PFOA and / or PFOS content is high.
配合物４で得られた撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は４−５級、撥油度は４級であり、洗濯後の撥水度は４級、撥油度は２−３級であり、撥水撥油性があることが確認できた。
（比較例５）
乳化物３で得られたシリコン系撥水剤を１００質量％、乳化物２で得られたフッ素系化合物を０質量％配合し、乳化物３および乳化物２の合計１００質量％に対して、パラキャットＰＧＥを３５質量％配合した撥水撥油剤を調整した。調整した撥水撥油剤を用いて、実施例１と同様の操作にて得られた加工布の撥水撥油を測定した。洗濯前の撥水度は４−５級、撥油度は０級であり、洗濯後の撥水度は３級、撥油度は０級であり、撥油性は得られなかった。
Using the water / oil repellent obtained in Formulation 4, the water / oil repellency of the processed fabric obtained in the same manner as in Example 1 was measured. Water repellency before washing is 4-5 grade, oil repellency is 4 grade, water repellency after washing is 4 grade, oil repellency is 2-3 grade, water and oil repellency may be It could be confirmed.
(Comparative Example 5)
100% by mass of the silicone-based water repellent obtained in Emulsion 3 and 0% by mass of the fluorine-based compound obtained in Emulsion 2, and with respect to 100% by mass in total of Emulsions 3 and 2, A water / oil repellent containing 35% by mass of Paracat PGE was prepared. Using the adjusted water / oil repellent, the water / oil repellency of the processed cloth obtained by the same operation as in Example 1 was measured. The water repellency before washing was grade 4-5 and the oil repellency was grade 0, the water repellency after washing was grade 3 and the oil repellency was grade 0, and no oil repellency was obtained.
配合物１で得られた撥水撥油剤を１０質量％、残りが水で１００質量％の加工液を調整した。かかる加工液を紙に塗布量が１００％になるようにスプレー法にて処理した。ついで１１０℃で予備乾燥後、１４０℃で２分間熱処理をした。この加工紙に植物油をのせたところ、滲み込みはなく、撥油性があることが確認できた。
A processing liquid having 10% by mass of the water / oil repellent obtained in Formulation 1 and the remaining 100% by mass of water was prepared. The processing liquid was processed by a spray method so that the amount of application was 100% on paper. Then, after preliminary drying at 110 ° C., heat treatment was performed at 140 ° C. for 2 minutes. When vegetable oil was placed on this processed paper, it was confirmed that there was no oozing and oil repellency.
Claims (2)
The compound (A) component not containing a fluorine compound is at least one of a silicon compound, a wax compound, a wax-zirconium compound, an alkylene urea compound, and an aliphatic amide compound, and a crosslinking agent (C). The component is at least a carbodiimide compound, a glyoxal compound, a melamine compound, an isocyanate compound, a triazine ring-containing compound, an epoxy compound, an azolidine compound, an aluminum compound, an organometallic compound, a dialdehyde compound, or an oxazoline compound. The fiber and water / oil repellent agent for paper according to claim 1, which is one type.
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| JP2014062348A (en) * | 2012-09-24 | 2014-04-10 | Teijin Frontier Co Ltd | Water repellent fabric |
| JP5626441B1 (en) * | 2013-07-30 | 2014-11-19 | 大日本印刷株式会社 | Method for producing water / oil repellent member and water / oil repellent member |
| EP2860308A4 (en) * | 2012-06-11 | 2016-03-16 | Seiren Co Ltd | Stretchable coated fabric and process for producing same |
| WO2017126358A1 (en) * | 2016-01-20 | 2017-07-27 | 東レ株式会社 | Fibrous structure |
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| EP2860308A4 (en) * | 2012-06-11 | 2016-03-16 | 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 |
| JP5626441B1 (en) * | 2013-07-30 | 2014-11-19 | 大日本印刷株式会社 | Method for producing water / oil repellent member and water / oil repellent member |
| WO2017126358A1 (en) * | 2016-01-20 | 2017-07-27 | 東レ株式会社 | Fibrous structure |
| JP2021065267A (en) * | 2019-10-18 | 2021-04-30 | テックワン株式会社 | Method for recovering water repellency of umbrella sheet degraded by use |
| WO2021246475A1 (en) * | 2020-06-03 | 2021-12-09 | 明成化学工業株式会社 | Water repellent composition, kit, water repellent fiber product and method for manufacturing same |
| JP7009675B1 (en) * | 2020-06-03 | 2022-01-25 | 明成化学工業株式会社 | Water repellent composition, kit, water repellent fiber product and its manufacturing method |
| CN115698221A (en) * | 2020-06-03 | 2023-02-03 | 明成化学工业株式会社 | Water repellent composition, kit, water repellent fiber product, and method for producing same |
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