JP2024055162A - Hydrophilic and oil-repellent film composition, hydrophilic and oil-repellent nonwoven fabric, film-forming liquid composition, method for producing film-forming liquid composition, and method for producing hydrophilic and oil-repellent nonwoven fabric - Google Patents
Hydrophilic and oil-repellent film composition, hydrophilic and oil-repellent nonwoven fabric, film-forming liquid composition, method for producing film-forming liquid composition, and method for producing hydrophilic and oil-repellent nonwoven fabric Download PDFInfo
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- JP2024055162A JP2024055162A JP2022161868A JP2022161868A JP2024055162A JP 2024055162 A JP2024055162 A JP 2024055162A JP 2022161868 A JP2022161868 A JP 2022161868A JP 2022161868 A JP2022161868 A JP 2022161868A JP 2024055162 A JP2024055162 A JP 2024055162A
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- hydrophilic
- oil
- film
- fluorine
- nonwoven fabric
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- D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
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Abstract
【課題】親水撥油性、水に対する耐久性及び擦り耐性などの特性に優れ、不織布などの布製品の繊維表面に付着させることによって、その布製品が有する風合いを過度に低下させずに上記の特性を向上させることができる親水撥油性膜組成物を提供する。【解決手段】親水撥油性膜組成物は、フッ素系化合物（Ａ）と、バインダ（Ｂ）と、増粘剤（Ｃ）とを含み、前記フッ素系化合物（Ａ）は、一般式（１）又は一般式（２）で表される化合物であって、前記バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、前記フッ素系化合物（Ａ）、前記バインダ（Ｂ）及び前記増粘剤（Ｃ）の合計量に対して、前記フッ素系化合物（Ａ）の含有率が２～２０質量％の範囲内、前記バインダ（Ｂ）の含有率が６０～９７質量％の範囲内、前記増粘剤（Ｃ）の含有率が１～２０質量％の範囲内にある親水撥油性膜組成物。【選択図】図１[Problem] To provide a hydrophilic and oil-repellent film composition which is excellent in properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance, and which, when attached to the fiber surface of a cloth product such as a nonwoven fabric, can improve the above properties without excessively deteriorating the texture of the cloth product. [Solution] The hydrophilic and oil-repellent film composition comprises a fluorine-based compound (A), a binder (B), and a thickener (C), the fluorine-based compound (A) is a compound represented by general formula (1) or general formula (2), the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and the content of the fluorine-based compound (A) is within the range of 2 to 20 mass%, the content of the binder (B) is within the range of 60 to 97 mass%, and the content of the thickener (C) is within the range of 1 to 20 mass% relative to the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C). [Selected Figure] Figure 1
Description
本発明は、親水撥油性膜組成物、親水撥油性不織布、膜形成用液組成物、膜形成用液組成物の製造方法及び親水撥油性不織布の製造方法に関する。 The present invention relates to a hydrophilic and oil-repellent film composition, a hydrophilic and oil-repellent nonwoven fabric, a film-forming liquid composition, a method for producing the film-forming liquid composition, and a method for producing the hydrophilic and oil-repellent nonwoven fabric.
不織布の繊維表面に親水撥油性膜組成物を付着させた親水撥油性不織布は、防汚機能を備えていて、油分による汚れが生じにくい。このため、親水撥油性不織布は、例えば、機械油を使用する工場、油が飛散する厨房、油蒸気が立ちこめるレンジフード、換気扇等において、油汚れを防止する分野並びに油水分離機能が求められる分野に用いられる。親水撥油性不織布の製造方法としては、親水撥油性膜形成用の液組成物に不織布をディッピングし、不織布の繊維表面に付着させた液組成物を乾燥する方法が用いられる。 A hydrophilic/oil-repellent nonwoven fabric having a hydrophilic/oil-repellent film composition applied to the fiber surface of the nonwoven fabric has a stain-resistant function and is less susceptible to stains due to oil. For this reason, hydrophilic/oil-repellent nonwoven fabrics are used in fields where prevention of oil stains and oil/water separation functions are required, for example, in factories that use machine oil, kitchens where oil is scattered, range hoods and ventilation fans where oil vapor is present, etc. A method of manufacturing hydrophilic/oil-repellent nonwoven fabrics is used in which a nonwoven fabric is dipped in a liquid composition for forming a hydrophilic/oil-repellent film and the liquid composition applied to the fiber surface of the nonwoven fabric is dried.
親水撥油性膜形成用の液組成物としては、親水撥油剤と、バインダ（造膜剤）と、溶媒とを含む液組成物が用いられる。親水撥油性膜形成用の液組成物としては、親水撥油剤として、ベタイン構造である親水性基を有するフッ素系化合物を用い、バインダとして、ポリアクリル酸を用いた液組成物が知られている（特許文献１）。また、親水撥油剤として、ベタイン構造である親水性基を有するフッ素系化合物を用い、バインダとして、自己反応型のカルボキシル基含有物及び／又はアセチル基含有物を用いた液組成物も知られている（特許文献２）。 As a liquid composition for forming a hydrophilic and oil-repellent film, a liquid composition containing a hydrophilic and oil-repellent agent, a binder (film-forming agent), and a solvent is used. As a liquid composition for forming a hydrophilic and oil-repellent film, a liquid composition is known that uses a fluorine-based compound having a hydrophilic group with a betaine structure as the hydrophilic and oil-repellent agent, and polyacrylic acid as the binder (Patent Document 1). In addition, a liquid composition is also known that uses a fluorine-based compound having a hydrophilic group with a betaine structure as the hydrophilic and oil-repellent agent, and a self-reactive carboxyl group-containing material and/or acetyl group-containing material as the binder (Patent Document 2).
油汚れを防止する分野並びに油水分離機能が求められる分野で利用する親水撥油性不織布は、長期間にわたって安定して親水撥油性を有することが好ましい。
しかしながら、特許文献１に記載されている親水撥油性膜成形用の液組成物において、バインダとして用いられているポリアクリル酸は水溶性である。このため、特許文献１に記載されている親水撥油性不織布は、水に対する耐久性が低く、擦り耐性が不十分となる場合があった。水に対する耐久性や擦り耐性を向上させるために、不織布の繊維表面への親水撥油性膜組成物の付着量を多くして、親水撥油性膜組成物の厚さを厚くすることが考えられる。しかしながら、親水撥油性膜組成物の付着量を多くしすぎると親水撥油性不織布の風合いが、不織布の風合いと比較して低下して、成形加工が難しくなることがある。
It is preferable that hydrophilic and oil-repellent nonwoven fabrics used in fields where prevention of oil stains and oil-water separation function are required have hydrophilic and oil-repellent properties that remain stable for a long period of time.
However, in the liquid composition for forming the hydrophilic and oil-repellent film described in Patent Document 1, the polyacrylic acid used as a binder is water-soluble. Therefore, the hydrophilic and oil-repellent nonwoven fabric described in Patent Document 1 may have low water durability and insufficient abrasion resistance. In order to improve water durability and abrasion resistance, it is considered to increase the amount of the hydrophilic and oil-repellent film composition attached to the fiber surface of the nonwoven fabric to increase the thickness of the hydrophilic and oil-repellent film composition. However, if the amount of the hydrophilic and oil-repellent film composition attached is too large, the texture of the hydrophilic and oil-repellent nonwoven fabric may be lower than that of the nonwoven fabric, making it difficult to mold the fabric.
また、特許文献２に記載されている親水撥油性膜成形用の液組成物において、バインダとして用いられている自己反応型のカルボキシル基及びアセチル基含有物は難水溶性である。しかしながら、カルボキシル基含有物及びアセチル基含有物は、不織布などの布製品に対する付着性が弱い。このため、バインダとして自己反応型のカルボキシル基含有物やアセチル基含有物を用いた膜形成用液組成物において膜成分の濃度を高めて、不織布の繊維表面に親水撥油性膜組成物を形成する必要があった。しかしながら、膜形成用液組成物の膜成分濃度を高くすると、親水撥油性膜組成物の付着量が多くなりすぎて、親水撥油性不織布の風合いが、不織布の風合いと比較して低下するおそれがある。 In addition, in the liquid composition for forming a hydrophilic and oil-repellent film described in Patent Document 2, the self-reactive carboxyl group- and acetyl group-containing substances used as binders are poorly water-soluble. However, the carboxyl group-containing substances and acetyl group-containing substances have poor adhesion to fabric products such as nonwoven fabrics. For this reason, it was necessary to increase the concentration of the film components in the film-forming liquid composition using the self-reactive carboxyl group-containing substance or acetyl group-containing substance as a binder to form a hydrophilic and oil-repellent film composition on the fiber surface of the nonwoven fabric. However, if the film component concentration of the film-forming liquid composition is increased, the amount of the hydrophilic and oil-repellent film composition attached becomes too large, and the texture of the hydrophilic and oil-repellent nonwoven fabric may be deteriorated compared to the texture of the nonwoven fabric.
本発明は、前述した事情に鑑みてなされたものであって、その目的は、親水撥油性、水に対する耐久性及び擦り耐性などの特性に優れ、不織布などの布製品の繊維表面に付着させることによって、その布製品が有する風合いを過度に低下させずに上記の特性を向上させることができる親水撥油性膜組成物、並びにその親水撥油性膜組成物の製造に用いることができる膜形成用液組成物とその製造方法、さらに親水撥油性、水に対する耐久性及び擦り耐性などの特性が優れ、かつ風合いが良好な親水撥油性不織布とその製造方法を提供することにある。 The present invention has been made in consideration of the above-mentioned circumstances, and its purpose is to provide a hydrophilic and oil-repellent film composition that has excellent properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance, and that can improve the above properties without excessively reducing the texture of a fabric product such as a nonwoven fabric by adhering it to the fiber surface of the fabric product, as well as a film-forming liquid composition that can be used to produce the hydrophilic and oil-repellent film composition and its manufacturing method, and further a hydrophilic and oil-repellent nonwoven fabric that has excellent properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance, and has a good texture, and a manufacturing method thereof.
上記課題を解決するために、本発明の態様１の親水撥油性膜組成物は、フッ素系化合物（Ａ）と、バインダ（Ｂ）と、増粘剤（Ｃ）とを含み、前記フッ素系化合物（Ａ）は、下記の一般式（１）又は一般式（２）で表される化合物であって、前記バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、前記フッ素系化合物（Ａ）、前記バインダ（Ｂ）及び前記増粘剤（Ｃ）の合計量に対して、前記フッ素系化合物（Ａ）の含有率が２質量％以上２０質量％以下の範囲内、前記バインダ（Ｂ）の含有率が６０質量％以上９７質量％以下の範囲内、前記増粘剤（Ｃ）の含有率が１質量％以上２０質量％以下の範囲内にある構成とされている。 In order to solve the above problems, the hydrophilic and oil-repellent film composition of aspect 1 of the present invention comprises a fluorine-based compound (A), a binder (B), and a thickener (C), the fluorine-based compound (A) being a compound represented by the following general formula (1) or (2), the binder (B) being a polymer containing at least one of a carboxyl group and an acetyl group, and the content of the fluorine-based compound (A) is within the range of 2% by mass to 20% by mass, the content of the binder (B) is within the range of 60% by mass to 97% by mass, and the content of the thickener (C) is within the range of 1% by mass to 20% by mass, relative to the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C).
上記一般式（１）及び（２）中、ｐ、ｑ及びｒは、それぞれ同一又は互いに異なる１～６の整数を表し、Ｘは、エーテル結合、エステル結合、ＣＯ－ＮＲ結合、Ｏ－ＣＯ－ＮＲ結合及びＳＯ２－ＮＲ結合から選択される１種以上の結合を含んでいてもよい炭素数が１～１０の炭化水素（Ｒは、水素原子または１価の炭化水素基を表す）を表し、Ｙは、ベタイン構造である親水性基を表す。 In the above general formulas (1) and (2), p, q and r each represent an integer of 1 to 6, which may be the same or different, X represents a hydrocarbon having 1 to 10 carbon atoms (R represents a hydrogen atom or a monovalent hydrocarbon group) which may contain one or more bonds selected from an ether bond, an ester bond, a CO—NR bond, an O—CO—NR bond and an SO 2 —NR bond, and Y represents a hydrophilic group which is a betaine structure.
本発明の態様１の親水撥油性膜組成物によれば、フッ素系化合物（Ａ）として、上記の一般式（１）又は一般式（２）で表される化合物を上記の含有率で含むので、親水撥油性に優れたものとなる。また、バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、その含有率が上記の範囲内にあるので、水に溶解しにくく、かつ擦り特性が向上する。さらに増粘剤（Ｃ）を上記の含有率で含むので、不織布などの布製品の繊維表面に対する付着性が向上する。このため、態様１の親水撥油性膜組成物によれば、基材が不織布などの布製品である場合は、その布製品が有する風合いを過度に低下させない程度の付着量で、その布製品の親水撥油性、水に対する耐久性及び擦り耐性などの特性を向上させることができる。 According to the hydrophilic and oil-repellent film composition of the present invention, the fluorine-based compound (A) contains the compound represented by the above general formula (1) or (2) at the above content, so that the composition has excellent hydrophilic and oil-repellent properties. In addition, the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and the content of the binder (B) is within the above range, so that the composition is less likely to dissolve in water and has improved scrubbing properties. Furthermore, the binder (B) contains the above content of the thickener (C), so that the adhesiveness to the fiber surface of a cloth product such as a nonwoven fabric is improved. Therefore, according to the hydrophilic and oil-repellent film composition of the present invention, when the substrate is a cloth product such as a nonwoven fabric, the hydrophilic and oil-repellent properties, durability against water, and scrubbing resistance of the cloth product can be improved with an amount of adhesion that does not excessively reduce the texture of the cloth product.
本発明の態様２は、態様１の親水撥油性膜組成物において、前記バインダ（Ｂ）は、カルボキシル基を有するポリオレフィン、エチレン－酢酸ビニル共重合体、エチレン－酢酸ビニル－アクリル酸共重合体又はアクリル樹脂である構成とされている。
この場合、バインダ（Ｂ）が、カルボキシル基を有するポリオレフィン、エチレン－酢酸ビニル共重合体、エチレン－酢酸ビニル－アクリル酸共重合体又はアクリル樹脂とされているので、親水撥油性膜組成物は水により溶解しにくくなり、水に対する耐久性がより向上する。
A second aspect of the present invention is the hydrophilic and oil-repellent film composition of the first aspect, wherein the binder (B) is a polyolefin having a carboxyl group, an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate-acrylic acid copolymer, or an acrylic resin.
In this case, since the binder (B) is a polyolefin having a carboxyl group, an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate-acrylic acid copolymer, or an acrylic resin, the hydrophilic and oil-repellent film composition is less likely to dissolve in water, and its durability against water is further improved.
本発明の態様３は、態様１または態様２の親水撥油性膜組成物において、前記増粘剤（Ｃ）は、層状無機化合物又は増粘多糖類である構成とされている。
この場合、増粘剤（Ｃ）が層状無機化合物又は増粘多糖類であり、フッ素系化合物（Ａ）に対して不活性である。このため、フッ素系化合物（Ａ）の性状を変えずに不織布などの布製品の繊維表面に対する付着性をより高くすることができる。
A third aspect of the present invention is the hydrophilic/oil-repellent film composition according to the first or second aspect, wherein the thickener (C) is a layered inorganic compound or a thickening polysaccharide.
In this case, the thickener (C) is a layered inorganic compound or a thickening polysaccharide, and is inactive to the fluorine-based compound (A), so that the adhesion of the fluorine-based compound (A) to the fiber surface of a fabric product such as a nonwoven fabric can be increased without changing the properties of the fluorine-based compound (A).
本発明の態様４の親水撥油性不織布は、不織布と、前記不織布の繊維表面に付着させた態様１から３のいずれか１つに記載の親水撥油性膜組成物とを含み、前記親水撥油性膜組成物の付着量が０．０２ｇ／ｍ２以上０．５ｇ／ｍ２以下の範囲内にある構成とされている。 The hydrophilic and oil-repellent nonwoven fabric of aspect 4 of the present invention comprises a nonwoven fabric and the hydrophilic and oil-repellent film composition according to any one of aspects 1 to 3 adhered to the fiber surface of the nonwoven fabric, and the amount of the hydrophilic and oil-repellent film composition adhered is in the range of 0.02 g/ m2 or more and 0.5 g/ m2 or less.
本発明の態様４の親水撥油性不織布によれば、不織布の繊維表面に上述の親水撥油性膜組成物を付着させているので、親水撥油性、水に対する耐久性及び擦り耐性などの特性が向上する。また、親水撥油性膜組成物の付着量が上記の範囲内にあるので、基材となった不織布が有する風合いが損なわれない。 According to the hydrophilic and oil-repellent nonwoven fabric of aspect 4 of the present invention, the above-mentioned hydrophilic and oil-repellent film composition is adhered to the fiber surface of the nonwoven fabric, so that the properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance are improved. In addition, since the amount of the hydrophilic and oil-repellent film composition adhered is within the above-mentioned range, the texture of the nonwoven fabric used as the base material is not impaired.
本発明の態様５は、態様４の親水撥油性不織布において、前記繊維表面に前記親水撥油性膜組成物を付着させる前の不織布の曲げ応力に対する曲げ応力の変動率が７５％以内である構成とされている。
この場合、親水撥油性膜組成物が付着した親水撥油性不織布は、基材である不織布の曲げ応力に対する曲げ応力の変動率が低いので基材となった不織布が有する風合いがより損なわれない。
A fifth aspect of the present invention is configured such that, in the hydrophilic and oil-repellent nonwoven fabric of the fourth aspect, the variation rate of bending stress relative to the bending stress of the nonwoven fabric before the hydrophilic and oil-repellent film composition is applied to the fiber surface is within 75%.
In this case, the hydrophilic/oil-repellent nonwoven fabric to which the hydrophilic/oil-repellent film composition is applied has a low rate of variation in bending stress relative to the bending stress of the nonwoven fabric substrate, so that the texture of the nonwoven fabric substrate is not impaired.
本発明の態様６の膜形成用液組成物は、フッ素系化合物（Ａ）と、バインダ（Ｂ）と、増粘剤（Ｃ）と、溶媒（Ｄ）とを含み、前記フッ素系化合物（Ａ）は、上記の一般式（１）又は一般式（２）で表される化合物であって、前記バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、前記溶媒（Ｄ）は、炭素数が１～３の範囲内にある１種又は２種以上のアルコールと、水とを含み、前記フッ素系化合物（Ａ）、前記バインダ（Ｂ）及び前記増粘剤（Ｃ）の合計量に対して、前記フッ素系化合物（Ａ）の含有率が２質量％以上２０質量％以下の範囲内、前記バインダ（Ｂ）の含有率が６０質量％以上９７質量％以下の範囲内、前記増粘剤（Ｃ）の含有率が１質量％以上２０質量％以下の範囲内にある構成とされている。 The film-forming liquid composition of the sixth aspect of the present invention includes a fluorine-based compound (A), a binder (B), a thickener (C), and a solvent (D), the fluorine-based compound (A) is a compound represented by the above general formula (1) or (2), the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and the solvent (D) includes one or more alcohols having a carbon number in the range of 1 to 3 and water, and the content of the fluorine-based compound (A) is in the range of 2% by mass to 20% by mass, the content of the binder (B) is in the range of 60% by mass to 97% by mass, and the content of the thickener (C) is in the range of 1% by mass to 20% by mass, based on the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C).
本発明の態様６の膜形成用液組成物によれば、フッ素系化合物（Ａ）として、上記の一般式（１）又は一般式（２）で表される化合物を上記の含有率で含むので、この膜形成用液組成物を用いて形成した膜組成物は、親水撥油性に優れたものとなる。また、バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、その含有率が上記の範囲内とされているので、この膜形成用液組成物を用いて形成した膜組成物は、水に溶解しにくく、かつ擦り特性が向上する。 According to the film-forming liquid composition of aspect 6 of the present invention, the fluorine-based compound (A) contains the compound represented by the above general formula (1) or general formula (2) at the above content, so that the film composition formed using this film-forming liquid composition has excellent hydrophilic and oil-repellent properties. In addition, the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and the content thereof is within the above range, so that the film composition formed using this film-forming liquid composition is less likely to dissolve in water and has improved rubbing properties.
また、増粘剤（Ｃ）を上記の含有率で含むので、膜形成用液組成物の粘度が高くなり、不織布などの布製品への膜形成用液組成物の付着性が向上する。さらに、溶媒（Ｄ）として炭素数が１～３の範囲内にあるアルコールと水とを含むので、フッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）を均一に分散させることができる。このため、本発明の膜形成用液組成物を用いることによって、布製品の繊維表面に付着させる膜組成物の量を少なくしても、厚さが薄く、且つ均一な親水撥油性膜組成物を形成することができる。よって、本実施形態の膜形成用液組成物を用いることによって、親水撥油性、水に対する耐久性及び擦り耐性などの特性が優れ、かつ風合いが良好な親水撥油性不織布を得ることができる。 In addition, since the thickener (C) is contained in the above content, the viscosity of the film-forming liquid composition is increased, and the adhesion of the film-forming liquid composition to fabric products such as nonwoven fabrics is improved. Furthermore, since the solvent (D) contains an alcohol having a carbon number of 1 to 3 and water, the fluorine-based compound (A), the binder (B) and the thickener (C) can be uniformly dispersed. Therefore, by using the film-forming liquid composition of the present invention, even if the amount of the film composition to be attached to the fiber surface of the fabric product is reduced, a thin and uniform hydrophilic and oil-repellent film composition can be formed. Therefore, by using the film-forming liquid composition of this embodiment, a hydrophilic and oil-repellent nonwoven fabric having excellent properties such as hydrophilic and oil-repellency, durability against water, and abrasion resistance, and having a good texture can be obtained.
本発明の態様７の膜形成用液組成物の製造方法は、分散剤（Ｅ）を含む水に、フッ素系化合物（Ａ）を分散させてフッ素系化合物（Ａ）水性分散液を得るフッ素系化合物分散液作製工程と、前記フッ素系化合物（Ａ）水性分散液と、バインダ（Ｂ）を含有するバインダ含有水性組成物と、増粘剤（Ｃ）を含有する増粘剤（Ｃ）含有水性組成物と、溶媒（Ｄ）とを混合する混合工程とを有し、前記分散剤（Ｅ）は、ジカルボン酸、トリカルボン酸及びヒドロキシカルボン酸からなる群より選ばれる少なくとも一種のカルボキシル基含有化合物であって、前記フッ素系化合物（Ａ）水性分散液の前記フッ素系化合物（Ａ）に対する前記分散剤（Ｅ）の含有率０．２質量％以上１０質量％以下の範囲内である構成とされている。 The method for producing a film-forming liquid composition according to the seventh aspect of the present invention includes a fluorine-based compound dispersion preparation step of dispersing a fluorine-based compound (A) in water containing a dispersant (E) to obtain an aqueous dispersion of a fluorine-based compound (A), and a mixing step of mixing the aqueous dispersion of the fluorine-based compound (A), a binder-containing aqueous composition containing a binder (B), a thickener (C)-containing aqueous composition containing a thickener (C), and a solvent (D), in which the dispersant (E) is at least one carboxyl group-containing compound selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and hydroxycarboxylic acids, and the content of the dispersant (E) relative to the fluorine-based compound (A) in the aqueous dispersion of the fluorine-based compound (A) is within a range of 0.2% by mass to 10% by mass.
本発明の態様７の膜形成用液組成物の製造方法によれば、分散剤（Ｅ）を含む水に、フッ素系化合物（Ａ）を分散させてフッ素系化合物（Ａ）水性分散液を得るフッ素系化合物（Ａ）水性分散液作製工程を含み、分散剤（Ｅ）は、ジカルボン酸、トリカルボン酸及びヒドロキシカルボン酸からなる群より選ばれる少なくとも一種のカルボキシル基含有化合物であって、フッ素系化合物分散液は分散剤（Ｅ）を上記の含有率で含むので、フッ素系化合物（Ａ）が均一に分散された膜形成用液組成物を製造することができる。 According to the method for producing a film-forming liquid composition of aspect 7 of the present invention, the method includes a fluorine-based compound (A) aqueous dispersion preparation step of dispersing a fluorine-based compound (A) in water containing a dispersant (E) to obtain an aqueous dispersion of a fluorine-based compound (A), and the dispersant (E) is at least one carboxyl group-containing compound selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and hydroxycarboxylic acids. The fluorine-based compound dispersion contains the dispersant (E) in the above content, so that a film-forming liquid composition in which the fluorine-based compound (A) is uniformly dispersed can be produced.
本発明の態様８の親水撥油性不織布の製造方法は、本発明の態様５に記載の膜形成用液組成物に、不織布をディッピングして膜形成用液組成物含有不織布を得る含浸工程と、乾燥後の膜組成物の付着量が０．０２ｇ／ｍ２以上０．５ｇ／ｍ２以下の範囲内となるように前記膜形成用液組成物含有不織布中の前記膜形成用液組成物を脱液する脱液工程と、脱液後の前記膜形成用液組成物含有不織布を乾燥する乾燥工程とを有する構成とされている。 The method for producing a hydrophilic and oil-repellent nonwoven fabric according to aspect 8 of the present invention comprises an impregnation step of dipping a nonwoven fabric into the film-forming liquid composition according to aspect 5 of the present invention to obtain a film-forming liquid composition-containing nonwoven fabric, a draining step of draining the film-forming liquid composition from the film-forming liquid composition-containing nonwoven fabric so that the amount of film composition adhered after drying is within the range of 0.02 g/ m2 or more and 0.5 g/m2 or less, and a drying step of drying the film-forming liquid composition-containing nonwoven fabric after draining.
本発明の態様８の親水撥油性不織布の製造方法によれば、含浸工程において、膜形成用液組成物に不織布をディッピングするので、不織布の繊維表面に均一に上述の親水撥油性膜組成物を付着させることができ、親水撥油性、水に対する耐久性及び擦り耐性などの特性に優れた親水撥油性不織布を安定して製造することができる。また、脱液工程において、乾燥後の膜形成用液組成物の付着量が０．０２ｇ／ｍ２以上０．５ｇ／ｍ２以下の範囲内となるように膜形成用液組成物含有不織布中の膜形成用液組成物を脱液するので、風合いが良好な親水撥油性不織布を安定して製造することができる。 According to the method for producing a hydrophilic and oil-repellent nonwoven fabric of the eighth aspect of the present invention, in the impregnation step, the nonwoven fabric is dipped into the film-forming liquid composition, so that the above-mentioned hydrophilic and oil-repellent film composition can be uniformly attached to the fiber surface of the nonwoven fabric, and a hydrophilic and oil-repellent nonwoven fabric having excellent properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance can be stably produced. In addition, in the liquid removal step, the liquid composition for film formation is removed from the nonwoven fabric containing the film-forming liquid composition so that the amount of the film-forming liquid composition attached after drying is within the range of 0.02 g/m2 or more and 0.5 g/ m2 or less, so that a hydrophilic and oil-repellent nonwoven fabric having a good texture can be stably produced.
本発明によれば、親水撥油性、水に対する耐久性及び擦り耐性などの特性が優れ、不織布などの布製品の繊維表面に付着させることによって、その布製品が有する風合いを過度に低下させずに上記の特性を向上させることができる親水撥油性膜組成物、並びにその親水撥油性膜組成物の製造に用いることができる膜形成用液組成物とその製造方法、さらに親水撥油性、水に対する耐久性及び擦り耐性などの特性に優れ、かつ風合いが良好な親水撥油性不織布とその製造方法を提供することが可能となる。 According to the present invention, it is possible to provide a hydrophilic and oil-repellent film composition that has excellent properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance, and that can improve the above properties without excessively reducing the texture of a fabric product such as a nonwoven fabric by adhering it to the fiber surface of the fabric product, as well as a film-forming liquid composition that can be used to produce the hydrophilic and oil-repellent film composition and a method for producing the same, and further a hydrophilic and oil-repellent nonwoven fabric that has excellent properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance, and has a good texture, and a method for producing the same.
次に、本発明の一実施形態に係る実施形態について説明する。 Next, we will explain one embodiment of the present invention.
［膜形成用液組成物］
本実施形態の膜形成用液組成物は、フッ素系化合物（Ａ）と、バインダ（Ｂ）と、増粘剤（Ｃ）と、溶媒（Ｄ）とを含む。膜形成用液組成物は、さらに、分散剤（Ｅ）を含んでいてもよい。本実施形態の膜形成用液組成物は、親水撥油性膜組成物の原料として用いられる。本実施形態の膜形成用液組成物を不織布などの布製品に塗布して、布製品を構成する繊維表面に親水撥油性膜組成物を付着させることによって、布製品の親水撥油性、水に対する耐久性及び擦り耐性などの特性を向上させることができる。
[Film-forming liquid composition]
The film-forming liquid composition of this embodiment includes a fluorine-based compound (A), a binder (B), a thickener (C), and a solvent (D). The film-forming liquid composition may further include a dispersant (E). The film-forming liquid composition of this embodiment is used as a raw material for a hydrophilic and oil-repellent film composition. The film-forming liquid composition of this embodiment is applied to a fabric product such as a nonwoven fabric, and the hydrophilic and oil-repellent film composition is attached to the fiber surface constituting the fabric product, thereby improving the properties of the fabric product, such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance.
フッ素系化合物（Ａ）は、下記の一般式（１）又は一般式（２）で表される化合物とされている。 The fluorine-based compound (A) is a compound represented by the following general formula (1) or general formula (2).
上記一般式（１）及び（２）中、ｐ、ｑ及びｒは、それぞれ同一又は互いに異なる１～６の整数を表し、Ｘは、エーテル結合、エステル結合、ＣＯ－ＮＲ結合、Ｏ－ＣＯ－ＮＲ結合及びＳＯ２－ＮＲ結合から選択される１種以上の結合を含んでいてもよい炭素数が１～１０の炭化水素（Ｒは、水素原子または１価の炭化水素基を表す）を表し、Ｙは、ベタイン構造である親水性基を表す。 In the above general formulas (1) and (2), p, q and r each represent an integer of 1 to 6, which may be the same or different, X represents a hydrocarbon having 1 to 10 carbon atoms (R represents a hydrogen atom or a monovalent hydrocarbon group) which may contain one or more bonds selected from an ether bond, an ester bond, a CO—NR bond, an O—CO—NR bond and an SO 2 —NR bond, and Y represents a hydrophilic group which is a betaine structure.
一般式（１）で表されるフッ素系化合物（Ａ）のペルフルオロエーテル基（ＣｐＦ２Ｐ＋１－Ｏ－ＣｑＦ２ｑ－Ｏ－ＣｒＦ２ｒ－）の例としては、下記式（３）～（７）で示される基を挙げることができる。 Examples of the perfluoroether group (C p F 2P+1 -O-C q F 2q -O-C r F 2r -) of the fluorine-based compound (A) represented by general formula (1) include groups represented by the following formulas (3) to (7).
一般式（２）で表されるフッ素系化合物（Ａ）のペルフルオロエーテル基（ＣｐＦ２Ｐ＋１－Ｏ－ＣｑＦ２ｑ）の例としては、下記式（８）～（１１）で示される基を挙げることができる。 Examples of the perfluoroether group (C p F 2P+1 —O—C q F 2q ) of the fluorine-based compound (A) represented by general formula (2) include groups represented by the following formulas (8) to (11).
上記一般式（１）又は一般式（２）中のＸとしては、下記式（１２）～（１６）で示される２価の基を挙げることができる。なお、下記式（１２）はエーテル結合、下記式（１３）はエステル結合、下記式（１４）はＣＯ－ＮＲ結合、下記式（１５）はＯ－ＣＯ－ＮＲ結合、下記式（１６）はＳＯ２－ＮＲ結合を含む２価の基を示している。 Examples of X in the above general formula (1) or (2) include divalent groups represented by the following formulae (12) to (16): Formula (12) represents an ether bond, Formula (13) represents an ester bond, Formula (14) represents a CO-NR bond, Formula (15) represents an O-CO-NR bond, and Formula (16) represents a divalent group containing an SO 2 -NR bond.
上記式（１２）～（１６）中、Ｒ２及びＲ３は、一方が単結合で他方が２価の炭化水素基もしくは両方がそれぞれ独立して２価の炭化水素基を表す。Ｒ２は、ペルフルオロエーテル基と接続され、Ｒ３は、親水性基と接続される。２価の炭化水素基は、特に限定されないが、炭素数が１～１０の範囲内にあることが好ましい。２価の炭化水素基は、鎖状炭化水素基であってもよいし、環状炭化水素基であってもよいし、鎖状炭化水素基と環状炭化水素基とを組み合わせた基であってもよい。また、２価の炭化水素基は、飽和炭化水素基であってもよいし、不飽和炭化水素基であってもよい。２価の炭化水素基の例としては、アルキレン基、フェニレン基、アルキレン基とフェニレン基とを組み合わせた基を挙げることができる。アルキレン基の例としては、メチレン基、エチレン基、トリメチレン基、プロピレン基を挙げることができる。Ｒ２及びＲ３の一方が単結合で他方が２価の炭化水素基である場合、Ｒ２が単結合であってもよい。 In the above formulas (12) to (16), R 2 and R 3 each independently represent a divalent hydrocarbon group, one of which is a single bond and the other of which is a divalent hydrocarbon group. R 2 is connected to a perfluoroether group, and R 3 is connected to a hydrophilic group. The divalent hydrocarbon group is not particularly limited, but preferably has a carbon number in the range of 1 to 10. The divalent hydrocarbon group may be a chain-like hydrocarbon group, a cyclic hydrocarbon group, or a group in which a chain-like hydrocarbon group and a cyclic hydrocarbon group are combined. The divalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group, a phenylene group, and a group in which an alkylene group and a phenylene group are combined. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. When one of R 2 and R 3 is a single bond and the other is a divalent hydrocarbon group, R 2 may be a single bond.
式（１４）～（１６）中、Ｒは、水素原子または１価の炭化水素基を表す。１価の炭化水素基は、特に限定されないが、炭素数が１～６の範囲内にあることが好ましい。１価の炭化水素基は、鎖状炭化水素基であってもよいし、環状炭化水素基であってもよいし、鎖状炭化水素基と環状炭化水素基とを組み合わせた基であってもよい。また、２価の炭化水素基は、飽和炭化水素基であってもよいし、不飽和炭化水素基であってもよい。１価の炭化水素基の例としては、メチル基、エチル基等のアルキル基、フェニル基、ビニル基等を挙げることができる。 In formulas (14) to (16), R represents a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group is not particularly limited, but preferably has a carbon number in the range of 1 to 6. The monovalent hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group, or a group that combines a chain hydrocarbon group and a cyclic hydrocarbon group. The divalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl and ethyl groups, phenyl groups, and vinyl groups.
上記一般式（１）又は一般式（２）中のＹで表される親水性基のベタイン構造は、特に制限はない。ベタイン構造の例としては、カルボキシベタイン型、スルホベタイン型、アミンオキシド型、フォスフォベタイン型等を挙げることができる。 The betaine structure of the hydrophilic group represented by Y in the above general formula (1) or general formula (2) is not particularly limited. Examples of the betaine structure include a carboxybetaine type, a sulfobetaine type, an amine oxide type, and a phosphobetaine type.
バインダ（Ｂ）は、例えば、親水撥油性膜組成物を形成する際に、フッ素系化合物（Ａ）同士を結び付けると共に、親水撥油性膜組成物を不織布などの基材に接着させる機能を有する。バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーとされていて、水と任意に混和させることができるものである。バインダ（Ｂ）の平均粒子径は、限定されるものでないが１μｍ以下であることが好ましい。バインダ（Ｂ）としては、例えば、カルボキシル基を有するポリオレフィン、エチレン－酢酸ビニル共重合体、エチレン－酢酸ビニル－アクリル酸共重合体、アクリル樹脂を用いることができる。アクリル樹脂を水に分散させた分散液は、ｐＨが８．０～９．０の弱アルカリ性を示してもよい。 The binder (B) has the function of binding the fluorine-based compounds (A) together when forming the hydrophilic and oil-repellent film composition, for example, and adhering the hydrophilic and oil-repellent film composition to a substrate such as a nonwoven fabric. The binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and can be mixed with water as desired. The average particle size of the binder (B) is not limited, but is preferably 1 μm or less. For example, polyolefins having carboxyl groups, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate-acrylic acid copolymers, and acrylic resins can be used as the binder (B). The dispersion liquid in which the acrylic resin is dispersed in water may be weakly alkaline, with a pH of 8.0 to 9.0.
増粘剤（Ｃ）は、例えば、膜形成用液組成物の粘度を調整する機能を有する。増粘剤（Ｃ）としては、増粘多糖類及び難水溶性の層状無機化合物を用いることができる。水溶性の増粘多糖類の例としては、キサンタンガム、ヒドロキシエチルセルロース、ヒドロキシメチルセルロース、カルボキシメチルセルロース、デンプン、デキストリン、カラギーナン、グァーガム、ペクチン等を挙げることができる。キサンタンガムとしては、キサンタンＧ（三晶株式会社製）が例示される。難水溶性の層状無機化合物の例としては、ベントナイト（商品名：モイストナイトＳ、クニミネ工業社製）、スメクトナイト（商品名：スメクトンＳＡ、クニミネ工業社製）、ヘクトライト（商品名：ラポナイトＲＤＳ、ロックウッド社製）等を挙げることができる。これらの層状無機化合物は粒子状であって、好ましくは０．１μｍ～１０μｍの平均粒子径を有する。平均粒子径が０．１μｍ未満又は１０μｍを超えると、水分散液になりにくい。膜形成用液組成物の粘度は、特に限定されないが、２５℃で０．５ｍＰａ・ｓ以上、２０ｍＰａ・ｓ以下の範囲内であることが好ましく、１ｍＰａ・ｓ以上、１０ｍＰａ・ｓ以下の範囲内にあることがより好ましい。 The thickener (C) has a function of adjusting the viscosity of the film-forming liquid composition, for example. As the thickener (C), thickening polysaccharides and poorly water-soluble layered inorganic compounds can be used. Examples of water-soluble thickening polysaccharides include xanthan gum, hydroxyethyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, starch, dextrin, carrageenan, guar gum, and pectin. An example of xanthan gum is Xanthan G (manufactured by Sansho Co., Ltd.). Examples of poorly water-soluble layered inorganic compounds include bentonite (trade name: Moistonite S, manufactured by Kunimine Kogyo Co., Ltd.), smectonite (trade name: Sumecton SA, manufactured by Kunimine Kogyo Co., Ltd.), and hectorite (trade name: Laponite RDS, manufactured by Rockwood Co., Ltd.). These layered inorganic compounds are particulate and preferably have an average particle size of 0.1 μm to 10 μm. If the average particle size is less than 0.1 μm or more than 10 μm, it is difficult to form an aqueous dispersion. The viscosity of the film-forming liquid composition is not particularly limited, but is preferably in the range of 0.5 mPa·s or more and 20 mPa·s or less at 25°C, and more preferably in the range of 1 mPa·s or more and 10 mPa·s or less.
溶媒（Ｄ）は、炭素数が１～３の範囲内にある１種又は２種以上のアルコールと、水とを含む混合溶媒である。アルコールと水との割合は、例えば、質量比で０．４５：９９．５５～０．６０：９９．４０の範囲内にある。溶媒（Ｄ）は、アルコール及び水以外の他の溶媒を含んでいてもよい。他の溶媒としては、炭素数が４以上のアルコール、グリコール、ケトン等を挙げることができる。他の溶媒の含有量は、例えば、溶媒の全体量に対して１０質量％以下であってもよい。 Solvent (D) is a mixed solvent containing one or more alcohols having a carbon number in the range of 1 to 3 and water. The ratio of alcohol to water is, for example, in the range of 0.45:99.55 to 0.60:99.40 by mass. Solvent (D) may contain other solvents in addition to alcohol and water. Examples of other solvents include alcohols, glycols, ketones, etc. having a carbon number of 4 or more. The content of other solvents may be, for example, 10 mass% or less of the total amount of the solvent.
分散剤（Ｅ）は、例えば、フッ素系化合物（Ａ）の溶媒（Ｄ）に対する分散性を向上させる機能を有する。分散剤（Ｅ）としては、カルボキシル基を２つ以上有するカルボン酸、カルボキシル基と水酸基とを有するヒドロキシカルボン酸を用いることができる。カルボキシル基を２つ以上有するカルボン酸は、ジカルボン酸またはトリカルボン酸であってもよい。ジカルボン酸の例としては、コハク酸、マレイン酸を挙げることができる。トリカルボン酸の例としてはクエン酸を挙げることができる。ヒドロキシカルボン酸の例としては、グルコン酸を挙げることができる。分散剤（Ｅ）は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 The dispersant (E) has a function of improving the dispersibility of the fluorine-based compound (A) in the solvent (D), for example. As the dispersant (E), a carboxylic acid having two or more carboxyl groups, or a hydroxycarboxylic acid having a carboxyl group and a hydroxyl group can be used. The carboxylic acid having two or more carboxyl groups may be a dicarboxylic acid or a tricarboxylic acid. Examples of the dicarboxylic acid include succinic acid and maleic acid. Examples of the tricarboxylic acid include citric acid. Examples of the hydroxycarboxylic acid include gluconic acid. The dispersant (E) may be used alone or in combination of two or more.
膜形成用液組成物中のフッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）の合計濃度（以下、膜成分濃度ともいう）は、例えば、０．０２質量％以上０．５０質量％以下の範囲内にある。膜成分濃度が低くなりすぎると、不織布などの布製品の繊維表面に塗布したときに親水撥油性が発現しないおそれがある。膜成分濃度が高くなりすぎると、布製品の繊維表面に塗布する際に、膜成分の付着量が多くなりやすく、不織布の風合いを損なわずに、膜厚が薄く、且つ均一な膜組成物を形成するのが困難となるおそれがある。膜成分濃度は、特に限定されないが、０．０３質量％以上０．４５質量％以下の範囲内にあることが好ましく、０．０４質量％以上０．４０質量％以下の範囲内にあることがより好ましい。 The total concentration of the fluorine-based compound (A), binder (B) and thickener (C) in the film-forming liquid composition (hereinafter also referred to as the film component concentration) is, for example, in the range of 0.02% by mass or more and 0.50% by mass or less. If the film component concentration is too low, hydrophilic and oil-repellent properties may not be exhibited when applied to the fiber surface of a fabric product such as a nonwoven fabric. If the film component concentration is too high, the amount of film component attached is likely to be large when applied to the fiber surface of a fabric product, and it may be difficult to form a thin and uniform film composition without impairing the texture of the nonwoven fabric. The film component concentration is not particularly limited, but is preferably in the range of 0.03% by mass or more and 0.45% by mass or less, and more preferably in the range of 0.04% by mass or more and 0.40% by mass or less.
膜形成用液組成物中のフッ素系化合物（Ａ）の含有率は、フッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）の合計量に対して、２質量％以上２０質量％以下の範囲内とされている。フッ素系化合物（Ａ）の含有率が少なくなりすぎると、膜組成物としたときの親水撥油性が低下するおそれがある。フッ素系化合物（Ａ）の含有率が多くなりすぎると、膜組成物としたときにフッ素系化合物（Ａ）が膜組成物から脱落しやすくなるおそれがある。フッ素系化合物（Ａ）の含有率は、特に限定されないが、２．５質量％以上１９．５質量％以下の範囲内にあることが好ましく、３．０質量％以上１９．０質量％以下の範囲内にあることがより好ましい。 The content of the fluorine-based compound (A) in the film-forming liquid composition is in the range of 2% by mass to 20% by mass based on the total amount of the fluorine-based compound (A), the binder (B) and the thickener (C). If the content of the fluorine-based compound (A) is too low, the hydrophilic and oil-repellent properties of the film composition may be reduced. If the content of the fluorine-based compound (A) is too high, the fluorine-based compound (A) may easily fall off from the film composition when the film composition is formed. The content of the fluorine-based compound (A) is not particularly limited, but is preferably in the range of 2.5% by mass to 19.5% by mass, and more preferably in the range of 3.0% by mass to 19.0% by mass.
膜形成用液組成物中のバインダ（Ｂ）の含有率は、フッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）の合計量に対して、６０質量％以上９７質量％以下の範囲内とされている。バインダ（Ｂ）の含有率は、特に限定されないが、６２．０質量％以上９６．５質量％以下の範囲内にあることが好ましく、６５．０質量％以上９６．０質量％以下の範囲内にあることがより好ましい。 The content of the binder (B) in the film-forming liquid composition is within the range of 60% by mass to 97% by mass based on the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C). The content of the binder (B) is not particularly limited, but is preferably within the range of 62.0% by mass to 96.5% by mass, and more preferably within the range of 65.0% by mass to 96.0% by mass.
膜形成用液組成物中の増粘剤（Ｃ）の含有率は、フッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）の合計量に対して、１質量％以上２０質量％以下の範囲内とされている。増粘剤（Ｃ）の含有率は、特に限定されないが、１．１質量％以上１９．０質量％以下の範囲内にあることが好ましく、１．２質量％以上１８．０質量％以下の範囲内にあることがより好ましい。 The content of the thickener (C) in the film-forming liquid composition is within the range of 1% by mass to 20% by mass based on the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C). The content of the thickener (C) is not particularly limited, but is preferably within the range of 1.1% by mass to 19.0% by mass, and more preferably within the range of 1.2% by mass to 18.0% by mass.
膜形成用液組成物中の溶媒（Ｄ）の含有率は、例えば、８０．０質量％以上９９．５質量％以下の範囲内にある。溶媒（Ｄ）の含有率は、特に限定されないが、８２．５質量％以上９９．０質量％以下の範囲内にあることが好ましく、８５．０質量％以上９８．５質量％以下の範囲内にあることがより好ましい。 The content of the solvent (D) in the film-forming liquid composition is, for example, in the range of 80.0% by mass to 99.5% by mass. The content of the solvent (D) is not particularly limited, but is preferably in the range of 82.5% by mass to 99.0% by mass, and more preferably in the range of 85.0% by mass to 98.5% by mass.
分散剤（Ｅ）の含有率は、例えば、フッ素系化合物（Ａ）の含有量に対して０．２質量％以上１０質量％以下の範囲内にある。分散剤（Ｅ）の含有率が少なくなりすぎると、フッ素系化合物（Ａ）の分散性が不十分となるおそれがある。一方、分散剤（Ｅ）の含有率が多くなりすぎると、フッ素系化合物（Ａ）の分散性が不安定となるおそれがある。分散剤（Ｅ）の含有率は、特に限定されないが、０．３質量％以上９．０質量％以下の範囲内にあることが好ましく、０．５質量％以上８．５質量％以下の範囲内にあることがより好ましい。 The content of the dispersant (E) is, for example, in the range of 0.2% by mass to 10% by mass relative to the content of the fluorine-based compound (A). If the content of the dispersant (E) is too low, the dispersibility of the fluorine-based compound (A) may be insufficient. On the other hand, if the content of the dispersant (E) is too high, the dispersibility of the fluorine-based compound (A) may be unstable. The content of the dispersant (E) is not particularly limited, but is preferably in the range of 0.3% by mass to 9.0% by mass, and more preferably in the range of 0.5% by mass to 8.5% by mass.
次に、本実施形態の膜形成用液組成物の製造方法について説明する。
図１は、本発明の一実施形態に係る膜形成用液組成物を製造する方法を示すフロー図である。
Next, a method for producing the film-forming liquid composition of the present embodiment will be described.
FIG. 1 is a flow diagram showing a method for producing a film-forming liquid composition according to one embodiment of the present invention.
図１に示す膜形成用液組成物１００の製造方法は、フッ素系化合物（Ａ）水性分散液１０を作製するフッ素系化合物（Ａ）水性分散液作製工程と、バインダ（Ｂ）を含有するバインダ（Ｂ）含有水性組成物２０を用意する工程と、増粘剤（Ｃ）を含有する増粘剤（Ｃ）含有水性組成物３０を作製する増粘剤（Ｃ）含有水性組成物作製工程と、溶媒（Ｄ）４０を用意する工程と、フッ素系化合物（Ａ）水性分散液１０、バインダ（Ｂ）含有水性組成物２０、増粘剤（Ｃ）含有水性組成物３０及び溶媒（Ｄ）４０を混合する混合工程とを有する。
The method for producing the film-forming
フッ素系化合物（Ａ）水性分散液作製工程では、分散剤（Ｅ）１１と水１２とを混合して、分散剤（Ｅ）水溶液１３を作製する。また、フッ素系化合物（Ａ）１４とアルコール１５とを混合して、フッ素化合物（Ａ）のアルコール溶液１６を作製する。次いで、分散剤（Ｅ）水溶液１３とフッ素化合物（Ａ）のアルコール溶液１６とを混合して、フッ素化合物（Ａ）を析出させて、フッ素系化合物（Ａ）水性分散液１０を得る。分散剤（Ｅ）１１は、ジカルボン酸、トリカルボン酸及びヒドロキシカルボン酸からなる群より選ばれる少なくとも一種のカルボキシル基含有化合物であってもよい。フッ素系化合物（Ａ）水性分散液１０の分散剤（Ｅ）１１の含有率は、フッ素系化合物（Ａ）１４の含有量に対して０．２質量％以上１０質量％以下の範囲内にあってもよい。分散剤（Ｅ）水溶液１３とフッ素化合物（Ａ）のアルコール溶液１６との混合方法には、特に制限はなく、例えば、分散剤（Ｅ）水溶液１３を攪拌しながら、その分散剤（Ｅ）水溶液１３にフッ素系化合物（Ａ）のアルコール溶液１６を滴下する方法を用いることができる。
In the fluorine-based compound (A) aqueous dispersion preparation process, dispersant (E) 11 and
バインダ（Ｂ）含有水性組成物２０は、例えば、バインダ（Ｂ）の水分散液（エマルジョン）もしくは乳化液であってもよい。バインダ（Ｂ）含有水性組成物２０としては、カルボキシル基を有するポリオレフィン系水分散液、エチレン－酢酸ビニル共重合体の自己乳化液、又はエチレン－酢酸ビニル－アクリル酸共重合体の自己乳化液、アクリルエマルジョンを用いることができる。カルボキシル基を有するポリオレフィン系水分散液としては、ザイクセンＡ、ザイクセンＬ、ザイクセンＮ（いずれも住友精化株式会社製）を用いることができる。エチレン－酢酸ビニル共重合体の自己乳化液としては、エチレン－酢酸ビニル共重合樹脂エマルジョン（スミカフレックス３５５ＨＱ、スミカフレックス４０１Ｑ、いずれも住友化学株式会社製）エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂エマルジョン（スミカフレックス９５０ＨＱ、住友化学株式会社製）、エチレン－酢酸ビニル－塩化ビニル共重合樹脂エマルジョン（スミカフレックス８３０、住友化学株式会社製）を用いることができる。エチレン－酢酸ビニル－アクリル酸共重合体の自己乳化液としては、スミカフレックスＳ－９００ＨＬ（住友化学社製）を用いることができる。アクリルエマルジョンとしては、ＴＯＣＲＹＬ ＢＣＸ－１１６０Ｒ－２（トーヨーケム株式会社製）を用いることができる。
The binder (B)-containing
増粘剤（Ｃ）含有水性組成物３０は、例えば、増粘剤（Ｃ）の水溶液もしくは水分散液であってもよい。増粘剤（Ｃ）含有水性組成物作製工程では、増粘剤（Ｃ）３１と水３２とを混合して、増粘剤（Ｃ）含有水性組成物３０を作製する。
The thickener (C)-containing
混合工程において、フッ素系化合物（Ａ）水性分散液１０、バインダ（Ｂ）含有水性組成物２０、増粘剤（Ｃ）含有水性組成物３０及び溶媒（Ｄ）４０を混合する方法には、特に制限はない。例えば、バインダ（Ｂ）含有水性組成物２０と溶媒（Ｄ）との混合物に、フッ素系化合物（Ａ）水性分散液１０に加えて混合し、次いで、増粘剤（Ｃ）含有水性組成物３０を加えて混合する方法を用いてもよい。
以上のようにして得られた膜形成用液組成物１００は、さらに、必要に応じて溶媒（Ｄ）を添加して、膜成分濃度を調整してもよい。
In the mixing step, there is no particular limitation on the method for mixing the fluorine-based compound (A)
The film forming
以上のような構成とされた本実施形態の膜形成用液組成物によれば、フッ素系化合物（Ａ）として、上記の一般式（１）又は一般式（２）で表される化合物を上記の含有率で含むので、この膜形成用液組成物を用いて形成した膜組成物は、親水撥油性に優れたものとなる。また、バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、バインダ（Ｂ）を上記の含有率で含むので、この膜形成用液組成物を用いて形成した膜組成物は、水に溶解しにくくなり、擦り特性が向上する。また、増粘剤（Ｃ）を上記の含有率で含むので、膜形成用液組成物の粘度が高くなり、不織布などの布製品への膜形成用液組成物の付着性が向上する。さらに、溶媒（Ｄ）として炭素数が１～３の範囲内にあるアルコールと水とを含むので、フッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）を均一に分散させることができる。このため、本実施形態の膜形成用液組成物を用いることによって、布製品の繊維表面に付着させる膜組成物の量を少なくしても、不織布の風合いを損なわずに、厚さが薄く、且つ均一な親水撥油性膜組成物を形成することができる。よって、本実施形態の膜形成用液組成物を用いることによって、親水撥油性、水に対する耐久性及び擦り耐性などの特性が優れ、かつ風合いが良好な親水撥油性不織布を得ることができる。 According to the film-forming liquid composition of the present embodiment configured as described above, since the fluorine-based compound (A) contains the compound represented by the above general formula (1) or general formula (2) at the above content, the film composition formed using this film-forming liquid composition has excellent hydrophilic and oil-repellent properties. In addition, the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and since the binder (B) is contained at the above content, the film composition formed using this film-forming liquid composition is less likely to dissolve in water and has improved rubbing properties. In addition, since the thickener (C) is contained at the above content, the viscosity of the film-forming liquid composition is increased, and the adhesion of the film-forming liquid composition to fabric products such as nonwoven fabrics is improved. Furthermore, since the solvent (D) contains an alcohol having a carbon number in the range of 1 to 3 and water, the fluorine-based compound (A), the binder (B) and the thickener (C) can be uniformly dispersed. Therefore, by using the film-forming liquid composition of this embodiment, even if the amount of the film composition applied to the fiber surface of the cloth product is reduced, a thin and uniform hydrophilic and oil-repellent film composition can be formed without impairing the texture of the nonwoven fabric. Therefore, by using the film-forming liquid composition of this embodiment, a hydrophilic and oil-repellent nonwoven fabric having excellent properties such as hydrophilic and oil-repellency, durability against water, and abrasion resistance, and having a good texture can be obtained.
本実施形態の膜形成用液組成物において、バインダ（Ｂ）が、カルボキシル基を有するポリオレフィン、エチレン－酢酸ビニル共重合体、又はエチレン－酢酸ビニル－アクリル酸共重合体である場合は、この膜形成用液組成物を用いて形成した膜組成物は、水により溶解しにくくなるので、水に対する耐久性がより向上する。また、本実施形態の膜形成用液組成物において、増粘剤（Ｃ）が層状無機化合物又は増粘多糖類である場合は、フッ素系化合物（Ａ）に対して不活性であるので、フッ素系化合物（Ａ）の性状を変えずに、膜形成用液組成物の粘度を調整することができる。 In the film-forming liquid composition of this embodiment, when the binder (B) is a polyolefin having a carboxyl group, an ethylene-vinyl acetate copolymer, or an ethylene-vinyl acetate-acrylic acid copolymer, the film composition formed using this film-forming liquid composition is less likely to dissolve in water, and therefore has improved durability against water. In addition, in the film-forming liquid composition of this embodiment, when the thickener (C) is a layered inorganic compound or a thickening polysaccharide, it is inactive against the fluorine-based compound (A), and therefore the viscosity of the film-forming liquid composition can be adjusted without changing the properties of the fluorine-based compound (A).
本実施形態の膜形成用液組成物の製造方法によれば、分散剤（Ｅ）水溶液１３とフッ素化合物（Ａ）のアルコール溶液１６とを混合して、フッ素化合物（Ａ）を析出させて、フッ素系化合物（Ａ）水性分散液１０を得るフッ素系化合物（Ａ）分散液作製工程を含むので、フッ素化合物（Ａ）が均一に分散した膜形成用液組成物１００を製造することができる。なお、図１に示す膜形成用液組成物の製造方法においては、増粘剤（Ｃ）３１と水３２とを混合して、増粘剤（Ｃ）含有水性組成物３０を作製しているが、市販の増粘剤（Ｃ）含有水性組成物を用いてもよい。
According to the method for producing a film-forming liquid composition of this embodiment, the method includes a fluorine-based compound (A) dispersion production step of mixing an aqueous solution of a dispersant (E) 13 with an alcohol solution of a fluorine compound (A) 16 to precipitate the fluorine compound (A) and obtain an aqueous dispersion of a fluorine-based compound (A) 10, so that a film-forming
［親水撥油性膜組成物］
本実施形態の親水撥油性膜組成物は、フッ素系化合物（Ａ）と、バインダ（Ｂ）と、増粘剤（Ｃ）と、溶媒（Ｄ）とを含む膜形成用液組成物の硬化物である。親水撥油性膜組成物は、例えば、膜形成用液組成物の溶媒（Ｄ）を除去することによって形成された硬化物であってもよい。溶媒（Ｄ）を除去する方法として、例えば、常圧加熱、減圧加熱などを用いることができる。
[Hydrophilic and oil-repellent film composition]
The hydrophilic and oil-repellent film composition of this embodiment is a cured product of a film-forming liquid composition containing a fluorine-based compound (A), a binder (B), a thickener (C), and a solvent (D). The hydrophilic and oil-repellent film composition may be, for example, a cured product formed by removing the solvent (D) from the film-forming liquid composition. As a method for removing the solvent (D), for example, normal pressure heating, reduced pressure heating, etc. can be used.
本実施形態の親水撥油性膜組成物は、マトリックス成分と、マトリックス成分に分散されているフッ素系化合物（Ａ）とを含む構成とされていてもよい。マトリックス成分はバインダ（Ｂ）と増粘剤（Ｃ）を含有する。マトリックス成分は、分散剤（Ｅ）を含有していてもよい。 The hydrophilic/oil-repellent film composition of this embodiment may be configured to include a matrix component and a fluorine-based compound (A) dispersed in the matrix component. The matrix component contains a binder (B) and a thickener (C). The matrix component may contain a dispersant (E).
親水撥油性膜組成物は、例えば、基材の表面に、上述の膜形成用液組成物を塗布し、膜形成用液組成物の溶媒（Ｄ）を除去することによって製造することができる。膜組成物用液組成物の塗布方法としては、例えば、ディッピング法、スクリーン印刷法、バーコート法、ダイコート法、ドクターブレード法、スピン法、刷毛塗り法等を用いることができる。 The hydrophilic and oil-repellent film composition can be produced, for example, by applying the above-mentioned film-forming liquid composition to the surface of a substrate and removing the solvent (D) of the film-forming liquid composition. Examples of methods that can be used to apply the film-forming liquid composition include dipping, screen printing, bar coating, die coating, doctor blade, spin coating, and brush coating.
以上のような構成とされた本実施形態の親水撥油性膜組成物によれば、フッ素系化合物（Ａ）として、上記の一般式（１）又は一般式（２）で表される化合物を上記の含有率で含むので、親水撥油性に優れたものとなる。また、バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、その含有率が上記の範囲内にあるので、水に溶解しにくく、かつ擦り特性が向上する。さらに増粘剤（Ｃ）を上記の含有率で含むので、不織布などの布製品の繊維表面に対する付着性が向上する。このため、本実施形態の親水撥油性膜組成物によれば、基材が布製品である場合は、その布製品が有する風合いを過度に低下させない程度の付着量で、その布製品の親水撥油性、水に対する耐久性及び擦り耐性などの特性を向上させることができる。 According to the hydrophilic and oil-repellent film composition of the present embodiment configured as described above, since the fluorine-based compound (A) contains the compound represented by the above general formula (1) or general formula (2) at the above content, the composition has excellent hydrophilic and oil-repellent properties. In addition, the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group, and since the content is within the above range, it is difficult to dissolve in water and has improved scrubbing properties. Furthermore, since the thickener (C) is contained at the above content, the adhesion to the fiber surface of a cloth product such as a nonwoven fabric is improved. Therefore, according to the hydrophilic and oil-repellent film composition of the present embodiment, when the substrate is a cloth product, the hydrophilic and oil-repellent properties of the cloth product, such as the hydrophilic and oil-repellent properties, durability against water, and scrubbing resistance, can be improved with an adhesion amount that does not excessively reduce the texture of the cloth product.
本実施形態の親水撥油性膜組成物において、バインダ（Ｂ）が、カルボキシル基を有するポリオレフィン、エチレン－酢酸ビニル共重合体、エチレン－酢酸ビニル－アクリル酸共重合体又はアクリル樹脂である場合は、水により溶解しにくくなるので、水に対する耐久性がより向上する。また、本実施形態の親水撥油性膜組成物において、増粘剤（Ｃ）が層状無機化合物又は増粘多糖類である場合は、フッ素系化合物（Ａ）に対して不活性であるので、フッ素系化合物（Ａ）の性状を変えずに不織布などの布製品の繊維表面に対する付着性をより高くすることができる。 In the hydrophilic and oil-repellent film composition of this embodiment, if the binder (B) is a polyolefin having a carboxyl group, an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate-acrylic acid copolymer, or an acrylic resin, it becomes less soluble in water, and therefore the durability against water is improved. In addition, in the hydrophilic and oil-repellent film composition of this embodiment, if the thickener (C) is a layered inorganic compound or a thickening polysaccharide, it is inactive against the fluorine-based compound (A), and therefore the adhesion to the fiber surface of a cloth product such as a nonwoven fabric can be improved without changing the properties of the fluorine-based compound (A).
［親水撥油性不織布］
本実施形態の親水撥油性不織布は、不織布と、不織布の繊維表面に形成された上述の親水撥油性膜組成物とを含む。親水撥油性不織布の親水撥油性膜組成物の付着量は、０．０２ｇ／ｍ２以上０．５０ｇ／ｍ２以下の範囲内とされている。親水撥油性膜組成物の付着量が少なくなりすぎると、親水撥油性が低下するおそれがある。一方、親水撥油性膜組成物の付着量が多くなりすぎると、風合いが低下するおそれがある。親水撥油性膜組成物の付着量は、０．０３ｇ／ｍ２以上０．４５ｇ／ｍ２以下の範囲内にあることが好ましく、０．０５ｇ／ｍ２以上０．４０ｇ／ｍ２以下の範囲内にあることがより好ましい。
[Hydrophilic and oil-repellent nonwoven fabric]
The hydrophilic and oil-repellent nonwoven fabric of the present embodiment includes a nonwoven fabric and the above-mentioned hydrophilic and oil-repellent film composition formed on the fiber surface of the nonwoven fabric. The amount of the hydrophilic and oil-repellent film composition attached to the hydrophilic and oil-repellent nonwoven fabric is in the range of 0.02 g/m 2 or more and 0.50 g/m 2 or less. If the amount of the hydrophilic and oil-repellent film composition attached is too small, the hydrophilic and oil-repellent properties may be reduced. On the other hand, if the amount of the hydrophilic and oil-repellent film composition attached is too large, the texture may be reduced. The amount of the hydrophilic and oil-repellent film composition attached is preferably in the range of 0.03 g/m 2 or more and 0.45 g/m 2 or less, and more preferably in the range of 0.05 g/m 2 or more and 0.40 g/m 2 or less.
親水撥油性不織布は、繊維表面に親水撥油性膜組成物を付着させる前の基材となった不織布の曲げ応力に対する曲げ応力の変動率は７５％以内であってもよい。曲げ応力の変動率は、下記の式より算出した値である。変動率は、特に制限はないが、７０％以内であることが好ましく、６５％以内であることがより好ましい。
変動率（％）＝（Ｙ－Ｘ）／Ｘ×１００
（Ｘは、繊維表面に膜組成物を付着させる前の不織布の曲げ応力を表し、Ｙは、繊維表面に膜組成物を付着させる不織布の曲げ応力を表す。）
The hydrophilic and oil-repellent nonwoven fabric may have a bending stress variation rate of 75% or less relative to the bending stress of the nonwoven fabric that has become the substrate before the hydrophilic and oil-repellent film composition is applied to the fiber surface. The bending stress variation rate is a value calculated by the following formula. The variation rate is not particularly limited, but is preferably 70% or less, and more preferably 65% or less.
Fluctuation rate (%) = (Y-X)/
(X represents the bending stress of the nonwoven fabric before the membrane composition is applied to the fiber surface, and Y represents the bending stress of the nonwoven fabric after the membrane composition is applied to the fiber surface.)
親水撥油性不織布は、例えば、含浸工程と、脱液工程と、乾燥工程とを有する方法によって製造することができる。
含浸工程は、上述の膜形成用液組成物に、不織布をディッピングして膜形成用液組成物含有不織布を得る工程である。
The hydrophilic and oil-repellent nonwoven fabric can be produced, for example, by a method including an impregnation step, a dewatering step, and a drying step.
The impregnation step is a step of dipping a nonwoven fabric into the above-mentioned film-forming liquid composition to obtain a nonwoven fabric containing the film-forming liquid composition.
脱液工程は、膜形成用液組成物含有不織布を脱液して、乾燥後の膜形成組成物の付着量が０．０２ｇ／ｍ２以上０．５ｇ／ｍ２以下の範囲内となるように調整する工程である。ディッピングした不織布を脱液する方法としては、例えば不織布を絞る、ローラーを用いて脱液する方法がある。 The deliquification step is a step of deliquifying the nonwoven fabric containing the film-forming liquid composition and adjusting the amount of the film-forming composition adhered after drying to within a range of 0.02 g/ m2 to 0.5 g/ m2 . Methods for deliquifying the dipped nonwoven fabric include, for example, squeezing the nonwoven fabric or using a roller to deliquify.
乾燥工程は、膜形成用液組成物含有不織布を乾燥する工程である。膜形成用液組成物含有不織布の乾燥方法としては、例えば、常圧加熱、減圧加熱などを用いることができる。 The drying process is a process for drying the nonwoven fabric containing the film-forming liquid composition. For example, normal pressure heating, reduced pressure heating, etc. can be used as a method for drying the nonwoven fabric containing the film-forming liquid composition.
以上のような構成とされた本実施形態の親水撥油性不織布によれば、不織布の繊維表面に上述の親水撥油性膜組成物を付着させているので、親水撥油性、水に対する耐久性及び擦り耐性などの特性が向上する。また、本実施形態の親水撥油性不織布は、親水撥油性膜組成物の付着量が上記の範囲内にあるので、基材となった不織布が有する風合いが損なわれない。また、本実施形態の親水撥油性不織布において、繊維表面に親水撥油性膜組成物が形成される前の基材となった不織布の曲げ応力に対する曲げ応力の変動率が上記の範囲にある場合は、曲げ応力の変動率が低く、基材となった不織布が有する風合いがより損なわれない。 According to the hydrophilic and oil-repellent nonwoven fabric of the present embodiment configured as described above, the hydrophilic and oil-repellent film composition is adhered to the fiber surface of the nonwoven fabric, so that the properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance are improved. In addition, since the amount of the hydrophilic and oil-repellent film composition adhered to the hydrophilic and oil-repellent nonwoven fabric of the present embodiment is within the above range, the texture of the nonwoven fabric used as the substrate is not impaired. In addition, in the hydrophilic and oil-repellent nonwoven fabric of the present embodiment, when the rate of variation of bending stress relative to the bending stress of the nonwoven fabric used as the substrate before the hydrophilic and oil-repellent film composition is formed on the fiber surface is within the above range, the rate of variation of bending stress is low, and the texture of the nonwoven fabric used as the substrate is not impaired.
本実施形態の親水撥油性不織布の製造方法によれば、含浸工程において、膜形成用液組成物に不織布をディッピングするので、不織布の繊維表面に均一に上述の親水撥油性膜組成物を付着させることができ、親水撥油性、水に対する耐久性及び擦り耐性などの特性に優れた親水撥油性不織布を安定して製造することができる。また、乾燥後の膜組成物の付着量を調整する工程である脱液工程において、膜形成用液組成物の付着量が０．０２ｇ／ｍ２以上０．５ｇ／ｍ２以下の範囲内となるように膜形成用液組成物含有不織布中の膜形成用液組成物を脱液するので、風合いが良好な親水撥油性不織布を安定して製造することができる。 According to the method for producing a hydrophilic and oil-repellent nonwoven fabric of the present embodiment, in the impregnation step, the nonwoven fabric is dipped into the film-forming liquid composition, so that the above-mentioned hydrophilic and oil-repellent film composition can be uniformly attached to the fiber surface of the nonwoven fabric, and a hydrophilic and oil-repellent nonwoven fabric having excellent properties such as hydrophilic and oil-repellent properties, durability against water, and abrasion resistance can be stably produced. In addition, in the draining step, which is a step of adjusting the adhesion amount of the film composition after drying, the film-forming liquid composition is drained from the nonwoven fabric containing the film-forming liquid composition so that the adhesion amount of the film-forming liquid composition is within the range of 0.02 g/ m2 or more and 0.5 g/ m2 or less, so that a hydrophilic and oil-repellent nonwoven fabric having a good texture can be stably produced.
以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的思想を逸脱しない範囲で適宜変更可能である。 The above describes an embodiment of the present invention, but the present invention is not limited to this and can be modified as appropriate without departing from the technical concept of the invention.
［本発明例１］
（１）フッ素系化合物分散液の作製
フッ素系化合物（Ａ）として、上記の式（１７）のフッ素系ベタイン化合物を用意した。このフッ素系ベタイン化合物をエタノールに溶解して、濃度５０質量％のフッ素系化合物エタノール溶液を作製した。
[Example 1]
(1) Preparation of Fluorine-Based Compound Dispersion The fluorine-based betaine compound of the above formula (17) was prepared as the fluorine-based compound (A). This fluorine-based betaine compound was dissolved in ethanol to prepare a fluorine-based compound ethanol solution having a concentration of 50 mass%.
５００ｍＬビーカーに、水１６３．６ｇと、分散剤（Ｅ）としてマレイン酸１．４ｇとを入れて、攪拌機で攪拌混合してマレイン酸水溶液とした。このマレイン酸水溶液を攪拌しながら、マレイン酸水溶液に、上記のフッ素系化合物エタノール溶液を５５．０ｇ添加し、フッ素系化合物を析出させた。フッ素系化合物エタノール溶液の添加後、さらに３０分間撹拌を続けて、フッ素系化合物分散液を作製した。フッ素系化合物分散液中のフッ素系化合物に対するマレイン酸の添加量は５質量％である。 163.6 g of water and 1.4 g of maleic acid as a dispersant (E) were placed in a 500 mL beaker and stirred and mixed with a stirrer to prepare an aqueous maleic acid solution. While stirring this aqueous maleic acid solution, 55.0 g of the above ethanol solution of the fluorine-based compound was added to the aqueous maleic acid solution to precipitate the fluorine-based compound. After the addition of the ethanol solution of the fluorine-based compound, stirring was continued for an additional 30 minutes to prepare a fluorine-based compound dispersion. The amount of maleic acid added relative to the fluorine-based compound in the fluorine-based compound dispersion was 5% by mass.
（２）膜形成用液組成物の作製
増粘剤（Ｃ）して、ベントナイト（モイストナイトＳ、クニミネ工業株式会社製）を用意した。このベントナイトを水に分散させて、濃度０．５質量％のベントナイト水分散液（増粘剤含有水性組成物）を作製した。
(2) Preparation of film-forming liquid composition Bentonite (Moistonite S, manufactured by Kunimine Kogyo Co., Ltd.) was prepared as a thickener (C). This bentonite was dispersed in water to prepare a bentonite aqueous dispersion (aqueous composition containing a thickener) having a concentration of 0.5% by mass.
５００ｍＬビーカーに、水９１．３８ｇと、バインダ含有水性組成物としてエチレン－酢酸ビニル共重合樹脂エマルジョン（スミカフレックス３５５ＨＱ、不揮発分５５％、住友化学株式会社製）０．３２ｇと、上記（１）で作製したフッ素系化合物分散液０．３０ｇを入れて、攪拌機で攪拌混合した。次いで、得られた混合液を攪拌しながら、混合液に、上記のベントナイト水分散液７．５０ｇと工業アルコール（ＡＰ－７、日本アルコール産業株式会社製）０．５ｇとを添加して、膜形成用液組成物を得た。 91.38 g of water, 0.32 g of ethylene-vinyl acetate copolymer resin emulsion (Sumikaflex 355HQ, non-volatile content 55%, manufactured by Sumitomo Chemical Co., Ltd.) as a binder-containing aqueous composition, and 0.30 g of the fluorine-based compound dispersion liquid prepared in (1) above were placed in a 500 mL beaker and stirred and mixed with a stirrer. Next, while stirring the resulting mixture, 7.50 g of the bentonite aqueous dispersion liquid and 0.5 g of industrial alcohol (AP-7, manufactured by Nippon Alcohol Industry Co., Ltd.) were added to the mixture to obtain a film-forming liquid composition.
［本発明例２～７、比較例１～５］
（１）フッ素系化合物分散液の作製において、フッ素系化合物（Ａ）の種類、分散剤（Ｅ）の種類と添加量、水の添加量を、下記の表１に記載したように変えたこと以外は、本発明例１と同様にしてフッ素系化合物分散液を作製した。
次いで、（２）膜形成用液組成物の作製において、バインダ含有水性組成物及び増粘剤（Ｃ）の種類を、下記の表２に記載したものに変えたこと以外は、本発明例１と同様にして膜形成用液組成物を作製した。
[Inventive Examples 2 to 7, Comparative Examples 1 to 5]
(1) In the preparation of a fluorine-based compound dispersion, a fluorine-based compound dispersion was prepared in the same manner as in Invention Example 1, except that the type of the fluorine-based compound (A), the type and added amount of the dispersant (E), and the added amount of water were changed as shown in Table 1 below.
Next, in the preparation of the film-forming liquid composition (2), a film-forming liquid composition was prepared in the same manner as in Example 1 of the present invention, except that the types of the binder-containing aqueous composition and the thickener (C) were changed to those shown in Table 2 below.
表２中、エチレン－酢酸ビニル共重合樹脂エマルジョンＡは、スミカフレックス３５５ＨＱ（住友化学株式会社製、平均粒子径：０．７μｍ）であり、エチレン－酢酸ビニル共重合樹脂エマルジョンＢは、スミカフレックス４０１ＨＱ（住友化学株式会社製、平均粒子径：０．８μｍ）であり、エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂エマルジョンは、スミカフレックス９５０ＨＱ（住友化学株式会社製、平均粒子径：０．６μｍ）であり、アクリルエマルジョンは、ＴＯＣＲＹＬ ＢＣＸ－１１６０Ｒ－２（トーヨーケム株式会社製）であり、エチレン－酢酸ビニル－塩化ビニル共重合樹脂エマルジョンは、スミカフレックス８３０（住友化学株式会社製、平均粒子径：０．５μｍ）であり、ポリオレフィン系水性ディスパージョンＡは、ザイクセンＮ（住友精化株式会社製、平均粒子径：０．２μｍ以下）であり、ポリオレフィン系水性ディスパージョンＢは、ザイクセンＬ（住友精化株式会社製、平均粒子径：０．２μｍ以下）である。また、ベントナイトは、モイストナイトＳ（クニミネ工業株式会社製）であり、キサンタンガムは、キサンタンＧ（三晶株式会社製）であり、セルロース誘導体は、メトローズＳＭ－１５（信越化学工業株式会社製）であり、スメクトンは、スメクトンＳＡ（クニミネ工業株式会社製）であり、合成ヘクトライトは、ラポナイトＲＤＳ（ＢＹＫ社製）である。 In Table 2, ethylene-vinyl acetate copolymer resin emulsion A is Sumikaflex 355HQ (manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.7 μm), ethylene-vinyl acetate copolymer resin emulsion B is Sumikaflex 401HQ (manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.8 μm), ethylene-vinyl acetate-vinyl versatate copolymer resin emulsion is Sumikaflex 950HQ (manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.6 μm), and acrylic emulsion is TOCRYL. The emulsion is BCX-1160R-2 (manufactured by Toyochem Co., Ltd.), the ethylene-vinyl acetate-vinyl chloride copolymer resin emulsion is Sumikaflex 830 (manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.5 μm), the polyolefin-based aqueous dispersion A is ZAIKSE N (manufactured by Sumitomo Seika Chemical Co., Ltd., average particle size: 0.2 μm or less), and the polyolefin-based aqueous dispersion B is ZAIKSE L (manufactured by Sumitomo Seika Chemical Co., Ltd., average particle size: 0.2 μm or less). The bentonite is Moistonite S (manufactured by Kunimine Kogyo Co., Ltd.), the xanthan gum is Xanthan G (manufactured by Sansho Co., Ltd.), the cellulose derivative is Metrose SM-15 (manufactured by Shin-Etsu Chemical Co., Ltd.), the Sumecton is Sumecton SA (manufactured by Kunimine Kogyo Co., Ltd.), and the synthetic hectorite is Laponite RDS (manufactured by BYK).
［評価］
本発明例１～７及び比較例１～５で用いたフッ素系化合物（Ａ）分散液と、バインダ（Ｂ）含有水性組成物、増粘剤（Ｃ）及び溶媒（Ｄ）の合計量を１００質量部とした各材料の配合量と、得られた膜形成用液組成物の組成を、表３に示す。
また、本発明例１～７及び比較例１～５で得られた膜形成用液組成物を用いて、下記の方法により、不織布の繊維表面に膜組成物を形成して、膜組成物付き不織布を作製した。そして、得られた膜組成物付き不織布について、下記の評価を行った。
[evaluation]
Table 3 shows the blending amounts of each material per 100 parts by mass of the total amount of the fluorine-based compound (A) dispersion, the binder (B)-containing aqueous composition, the thickener (C) and the solvent (D) used in Examples 1 to 7 of the present invention and Comparative Examples 1 to 5, and the compositions of the obtained film-forming liquid compositions.
In addition, a nonwoven fabric with a film composition was produced by forming a film composition on the fiber surface of a nonwoven fabric by the following method using the film-forming liquid compositions obtained in Examples 1 to 7 of the present invention and Comparative Examples 1 to 5. The nonwoven fabric with the film composition obtained was then evaluated as follows.
（膜組成物付きの不織布の作製方法）
ポリエチレンテレフタレート（ＰＥＴ）繊維とガラス繊維とからなる不織布（商品名：３３６、安積濾紙株式会社製）を用意した。この不織布（５０ｍｍ×８０ｍｍ、厚み０．４ｍｍ）を、本発明例１～７及び比較例１～５で得られた膜形成用液組成物のそれぞれにディッピングして、膜形成用液組成物含有不織布を得た。次いで、膜形成用液組成物から取り出した不織布を、ローラーで液切りして、過剰の膜形成用液組成物を脱液した後、室温（２５±３℃）で２４時間乾燥して、膜組成物付きの不織布を作製した。得られた膜組成物付き不織布の膜組成物の付着量を表４に示す。なお、付着量は、膜組成物付きの不織布の重量からディッピングする前の不織布の重量を差し引いた値である。
(Method of Making Nonwoven Fabric with Film Composition)
A nonwoven fabric (product name: 336, manufactured by Azumi Filter Paper Co., Ltd.) made of polyethylene terephthalate (PET) fibers and glass fibers was prepared. This nonwoven fabric (50 mm x 80 mm, thickness 0.4 mm) was dipped into each of the film-forming liquid compositions obtained in Examples 1 to 7 of the present invention and Comparative Examples 1 to 5 to obtain a nonwoven fabric containing the film-forming liquid composition. Next, the nonwoven fabric removed from the film-forming liquid composition was drained with a roller to remove excess film-forming liquid composition, and then dried at room temperature (25±3°C) for 24 hours to produce a nonwoven fabric with a film composition. The amount of the film composition attached to the obtained nonwoven fabric with the film composition is shown in Table 4. The amount of attachment is the weight of the nonwoven fabric with the film composition minus the weight of the nonwoven fabric before dipping.
（濡れ性）
膜組成物付きの不織布の水に対する濡れ性とｎ-ヘキサデカン（油）に対する濡れ性を、次のようにして評価した。その結果を表４に示す。
水の濡れ性は、膜組成物付きの不織布に水を２００μＬ滴下し、水の浸透性を観察することによって測定した。水を滴下してから１分以内に、水が浸透したものを良好とし、水が浸透しなかったものを不良とした。
ｎ－ヘキサデカンの濡れ性は、膜組成物付きの不織布にｎ－ヘキサデカンを２００μＬ滴下し、ｎ－ヘキサデカンの浸透性を観察することによって測定した。ｎ－ヘキサデカンを滴下してから１分以内に、ｎ－ヘキサデカンが浸透しなかったものを良好とし、ｎ－ヘキサデカンが浸透したものを不良とした。
(Wettability)
The wettability of the nonwoven fabric with the film composition to water and to n-hexadecane (oil) was evaluated as follows. The results are shown in Table 4.
The wettability of water was measured by dropping 200 μL of water onto the nonwoven fabric with the membrane composition and observing the water permeability. If the water permeated within 1 minute after dropping, it was rated as good, and if the water did not permeate, it was rated as poor.
The wettability of n-hexadecane was measured by dropping 200 μL of n-hexadecane onto the nonwoven fabric with the membrane composition and observing the permeability of n-hexadecane. Within 1 minute after dropping the n-hexadecane, the sample in which n-hexadecane did not permeate was rated as good, and the sample in which n-hexadecane permeated was rated as poor.
（曲げ応力）
ディッピングする前の不織布（不織布単体）と膜組成物付き不織布とについて、３点曲げ試験を行って曲げ応力を測定した。測定装置は、東洋精機社製の万能材料試験機ストログラフＶＧ２０Ｆを用い、直線形曲げ治具Ｆ－０（圧子及び支点の半径Ｒ５ｍｍ）を支点間距離１５ｍｍで取り付けた。２つに分かれた支持台の中央に試験片（不織布）を設置し、上方から速度５ｍｍ／分で圧子を降下させた際の試験片の曲げ応力を測定した。測定環境は、温度２３℃、相対湿度：５０％とした。その結果を表４に示す。
(Bending Stress)
A three-point bending test was performed on the nonwoven fabric (nonwoven fabric alone) before dipping and the nonwoven fabric with the membrane composition to measure bending stress. The measurement device used was a universal material testing machine Strograph VG20F manufactured by Toyo Seiki Co., Ltd., and a linear bending jig F-0 (indenter and fulcrum radius R 5 mm) was attached with a support distance of 15 mm. A test piece (nonwoven fabric) was placed in the center of the two divided support tables, and the bending stress of the test piece was measured when the indenter was lowered from above at a speed of 5 mm/min. The measurement environment was a temperature of 23°C and a relative humidity of 50%. The results are shown in Table 4.
（風合い）
不織布単体の曲げ応力に対する不織布の膜組成物付き不織布の曲げ応力の変動率が７５％以下のものを良好とし、７５％を超えたものを不良とした。その結果を表４に示す。
(Texture)
The variation rate of the bending stress of the nonwoven fabric with the film composition relative to the bending stress of the nonwoven fabric alone was 75% or less, which was rated as good, and that of more than 75% was rated as poor. The results are shown in Table 4.
表４に示す評価結果から明らかなように、フッ素系化合物（Ａ）、バインダ（Ｂ）及び増粘剤（Ｃ）の含有率が本発明の範囲内にある膜形成用液組成物を用いて製造し、且つ膜組成物の付着量が本発明の範囲内にある本発明例１～７の膜組成物付きの不織布は、親水撥油性を有し、且つ風合いが良好であることが確認された。これに対して、フッ素系化合物（Ａ）及び増粘剤（Ｃ）の含有率が本発明の範囲よりも少なく、バインダ（Ｂ）の含有率が本発明の範囲を超える膜形成用液組成物を用いて製造した比較例１の膜組成物付きの不織布は、親水撥油性が発現しなかった。また、フッ素系化合物（Ａ）及び増粘剤（Ｃ）の含有率が本発明の範囲を超え、バインダ（Ｂ）の含有率が本発明の範囲よりも少ない膜形成用液組成物を用いて製造した比較例２の膜組成物付きの不織布は、撥油性が発現せず、且つ風合いが不良となった。また、膜組成物の付着量が本発明の範囲を超える比較例３の膜組成物付きの不織布は、風合いが不良となった。また、膜組成物の付着量が本発明の範囲よりも少ない比較例４の膜組成物付きの不織布は、親水撥油性が発現しなかった。さらに、フッ素系化合物（Ａ）及びバインダ（Ｂ）の含有率が本発明の範囲内にあり、増粘剤（Ｃ）を含まない膜形成用液組成物を用いて製造した比較例５の膜組成物付きの不織布は、親水撥油性が発現しなかった。これは、膜組成物の付着量が本発明の範囲より少なくなったためである。 As is clear from the evaluation results shown in Table 4, the nonwoven fabrics with the film composition of Examples 1 to 7 of the present invention, which were manufactured using a film-forming liquid composition in which the contents of the fluorine-based compound (A), binder (B) and thickener (C) were within the range of the present invention, and the amount of the film composition attached was within the range of the present invention, were confirmed to have hydrophilic and oil-repellent properties and good texture. In contrast, the nonwoven fabric with the film composition of Comparative Example 1, which was manufactured using a film-forming liquid composition in which the contents of the fluorine-based compound (A) and thickener (C) were less than the range of the present invention and the content of the binder (B) exceeded the range of the present invention, did not exhibit hydrophilic and oil-repellent properties. In addition, the nonwoven fabric with the film composition of Comparative Example 2, which was manufactured using a film-forming liquid composition in which the contents of the fluorine-based compound (A) and thickener (C) exceeded the range of the present invention and the content of the binder (B) was less than the range of the present invention, did not exhibit oil-repellent properties and had a poor texture. In addition, the nonwoven fabric with the film composition of Comparative Example 3, in which the amount of the film composition attached exceeded the range of the present invention, had a poor texture. In addition, the nonwoven fabric with the film composition of Comparative Example 4, in which the amount of the film composition attached was less than the range of the present invention, did not exhibit hydrophilic and oil-repellent properties. Furthermore, the nonwoven fabric with the film composition of Comparative Example 5, which was produced using a film-forming liquid composition in which the content of the fluorine-based compound (A) and the binder (B) was within the range of the present invention and did not contain a thickener (C), did not exhibit hydrophilic and oil-repellent properties. This is because the amount of the film composition attached was less than the range of the present invention.
Claims (8)
前記フッ素系化合物（Ａ）は、下記の一般式（１）又は一般式（２）で表される化合物であって、前記バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、
前記フッ素系化合物（Ａ）、前記バインダ（Ｂ）及び前記増粘剤（Ｃ）の合計量に対して、前記フッ素系化合物（Ａ）の含有率が２質量％以上２０質量％以下の範囲内、前記バインダ（Ｂ）の含有率が６０質量％以上９７質量％以下の範囲内、前記増粘剤（Ｃ）の含有率が１質量％以上２０質量％以下の範囲内にある親水撥油性膜組成物。
The fluorine-based compound (A) is a compound represented by the following general formula (1) or general formula (2), and the binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group,
A hydrophilic and oil-repellent film composition, in which the content of the fluorine-based compound (A) is within the range of 2 mass% or more and 20 mass% or less, the content of the binder (B) is within the range of 60 mass% or more and 97 mass% or less, and the content of the thickener (C) is within the range of 1 mass% or more and 20 mass% or less, based on the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C).
前記フッ素系化合物（Ａ）は、下記の一般式（１）又は一般式（２）で表される化合物であって、
前記バインダ（Ｂ）は、カルボキシル基及びアセチル基の少なくとも一方を含有するポリマーであり、
前記溶媒（Ｄ）は、炭素数が１～３の範囲内にある１種又は２種以上のアルコールと、水とを含み、
前記フッ素系化合物（Ａ）、前記バインダ（Ｂ）及び前記増粘剤（Ｃ）の合計量に対して、前記フッ素系化合物（Ａ）の含有率が２質量％以上２０質量％以下の範囲内、前記バインダ（Ｂ）の含有率が６０質量％以上９７質量％以下の範囲内、前記増粘剤（Ｃ）の含有率が１質量％以上２０質量％以下の範囲内にある膜形成用液組成物。
The fluorine-based compound (A) is a compound represented by the following general formula (1) or general formula (2):
The binder (B) is a polymer containing at least one of a carboxyl group and an acetyl group,
The solvent (D) contains one or more alcohols having a carbon number of 1 to 3 and water,
The film-forming liquid composition has a content of the fluorine-based compound (A) in the range of 2 mass% or more and 20 mass% or less, a content of the binder (B) in the range of 60 mass% or more and 97 mass% or less, and a content of the thickener (C) in the range of 1 mass% or more and 20 mass% or less, based on the total amount of the fluorine-based compound (A), the binder (B), and the thickener (C).
前記フッ素系化合物（Ａ）水性分散液と、バインダ（Ｂ）を含有するバインダ（Ｂ）含有水性組成物と、増粘剤（Ｃ）を含有する増粘剤（Ｃ）含有水性組成物と、溶媒（Ｄ）とを混合する混合工程とを有し、
前記分散剤（Ｅ）は、ジカルボン酸、トリカルボン酸及びヒドロキシカルボン酸からな－る群より選ばれる少なくとも一種のカルボキシル基含有化合物であって、
前記フッ素系化合物（Ａ）水性分散液の前記フッ素系化合物（Ａ）に対する前記分散剤（Ｅ）の含有率が０．２質量％以上１０質量％以下の範囲内である膜形成用液組成物の製造方法。 a fluorine-based compound aqueous dispersion preparation step of dispersing a fluorine-based compound (A) in water containing a dispersant (E) to obtain an aqueous dispersion of the fluorine-based compound (A);
a mixing step of mixing the aqueous dispersion of the fluorine-based compound (A), a binder (B)-containing aqueous composition containing the binder (B), a thickener (C)-containing aqueous composition containing the thickener (C), and a solvent (D),
The dispersant (E) is at least one carboxyl group-containing compound selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and hydroxycarboxylic acids,
The method for producing a film-forming liquid composition, wherein the content of the dispersant (E) relative to the fluorine-based compound (A) in the aqueous dispersion of the fluorine-based compound (A) is within a range of 0.2 mass % or more and 10 mass % or less.
前記ディッピングした不織布を脱液して、乾燥後の前記膜形成用液組成物の付着量が、０．０２ｇ／ｍ２以上０．５ｇ／ｍ２以下の範囲内にある膜形成用液組成物含有不織布を得る脱液工程と、
前記膜形成用液組成物含有不織布を乾燥する乾燥工程と、
を有する親水撥油性不織布の製造方法。 An impregnation step of dipping a nonwoven fabric into the film forming liquid composition according to claim 5;
a draining step of draining the dipped nonwoven fabric to obtain a film-forming liquid composition-containing nonwoven fabric having an adhesion amount of the film-forming liquid composition in the range of 0.02 g/ m2 or more and 0.5 g/ m2 or less after drying;
a drying step of drying the nonwoven fabric containing the film forming liquid composition;
A method for producing a hydrophilic and oil-repellent nonwoven fabric having the above structure.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05279546A (en) * | 1992-03-31 | 1993-10-26 | Japan Synthetic Rubber Co Ltd | Aqueous fluororesin composition |
| JP6420655B2 (en) * | 2014-12-15 | 2018-11-07 | ユニチカトレーディング株式会社 | Fabric and method for producing the fabric |
| JP6563041B2 (en) * | 2016-02-01 | 2019-08-21 | 三菱マテリアル株式会社 | Hydrophilic oil repellent and production method thereof, surface coating material, coating film, resin composition, oil-water separation filter medium, porous body |
| JP2018012770A (en) * | 2016-07-20 | 2018-01-25 | 三菱マテリアル電子化成株式会社 | Hydrophilic oil repellent copolymer, surface coating material, coated film and manufacturing method of coated film |
| JP7417424B2 (en) * | 2019-02-20 | 2024-01-18 | 三菱マテリアル電子化成株式会社 | Liquid composition for forming antifouling film |
| JP2021065859A (en) * | 2019-10-25 | 2021-04-30 | 三菱マテリアル電子化成株式会社 | Oil-water separation filter medium, and oil-water separation device |
| JP2022179956A (en) * | 2021-05-24 | 2022-12-06 | 三菱マテリアル電子化成株式会社 | Liquid composition for forming hydrophilic and oleophobic film and method for producing the same, hydrophilic and oleophobic film and hydrophilic and oleophobic nonwoven fabric |
-
2022
- 2022-10-06 JP JP2022161868A patent/JP2024055162A/en active Pending
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2023
- 2023-10-04 WO PCT/JP2023/036220 patent/WO2024075779A1/en unknown
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| WO2024075779A1 (en) | 2024-04-11 |
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