JP2008307814A - Waterproof fabric and method for producing the same - Google Patents
Waterproof fabric and method for producing the same Download PDFInfo
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- JP2008307814A JP2008307814A JP2007158710A JP2007158710A JP2008307814A JP 2008307814 A JP2008307814 A JP 2008307814A JP 2007158710 A JP2007158710 A JP 2007158710A JP 2007158710 A JP2007158710 A JP 2007158710A JP 2008307814 A JP2008307814 A JP 2008307814A
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- 239000010419 fine particle Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 37
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 11
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
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- 239000010410 layer Substances 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 230000008961 swelling Effects 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
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- 239000005871 repellent Substances 0.000 description 8
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- 230000002378 acidificating effect Effects 0.000 description 6
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- 150000002148 esters Chemical class 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 239000012463 white pigment Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
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- 230000001877 deodorizing effect Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
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- 229920000728 polyester Polymers 0.000 description 3
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- 210000004243 sweat Anatomy 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 229920000747 poly(lactic acid) Polymers 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000009991 scouring Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract
【課題】透湿性防水布帛を含めた防水布帛において、衣服の内側の湿度および結露を低減することで優れた透湿性を示し、かつ湿潤時に人の肌に優しいｐＨ４．０〜７．０を維持する防水布帛およびその製造方法を目的とする。
【解決手段】繊維布帛の少なくとも片面に、無孔質膜を有する樹脂層が形成された防水布帛であって、前記無孔質膜に、ウレタン樹脂と、両性金属の酸化物および／または二酸化ケイ素の微粒子とが含まれ、湿潤時にｐＨ４．０〜７．０を示すことを特徴とする防水布帛。離型紙上に、両性金属の酸化物および／または二酸化ケイ素の微粒子を含むウレタン樹脂溶液を塗布した後、ウレタン系接着剤を塗布し、この上に繊維布帛を貼り合わせることを特徴とする防水布帛の製造方法。
【選択図】なし[PROBLEMS] To provide a waterproof fabric including a moisture permeable waterproof fabric, which exhibits excellent moisture permeability by reducing moisture and dew condensation on the inner side of clothes and maintains a pH of 4.0 to 7.0 that is gentle to human skin when wet. A waterproof fabric and a method for manufacturing the waterproof fabric.
A waterproof fabric in which a resin layer having a nonporous membrane is formed on at least one surface of a fiber fabric, wherein the nonporous membrane is formed of a urethane resin, an amphoteric metal oxide and / or silicon dioxide. A waterproof fabric characterized by having a pH of 4.0 to 7.0 when wet. A waterproof fabric characterized in that a urethane resin solution containing amphoteric metal oxide and / or silicon dioxide fine particles is applied onto a release paper, and then a urethane adhesive is applied, and a fiber fabric is bonded thereto. Manufacturing method.
[Selection figure] None
Description
本発明は、防水布帛およびその製造方法に関する。 The present invention relates to a waterproof fabric and a manufacturing method thereof.
透湿性防水布帛は、湿気を通過させるが、雨等の水の浸入を防止する素材として、合羽、スキーウエアー、ウインドブレーカーをはじめ、テント、靴材等といった身の回りの様々な物品に使用されている。
透湿性防水布帛としては、例えば、繊維布帛の片面に無孔質のウレタン樹脂皮膜を貼り合わせて得られた防水布帛（特許文献１参照）等が知られている。
Moisture permeable waterproof fabric allows moisture to pass through, but is used in a variety of personal items such as hems, ski wear, windbreakers, tents, and shoe materials as a material that prevents rain and other water from entering. .
As a moisture-permeable waterproof fabric, for example, a waterproof fabric (see Patent Document 1) obtained by bonding a nonporous urethane resin film to one side of a fiber fabric is known.
ところで、透湿性防水布帛を用いた衣服を着用する場合、激しい運動条件下では、透湿性防水布帛の内側（身体側）の無孔質膜面上に、汗または汗からの蒸気による結露水等の水分が付着し、この水分が着用者の肌に転着して、快適さが損なわれることがある。特にこの現象は、透湿性がほとんどない防水布帛を用いた衣服において顕著に見受けられる。 By the way, when wearing clothes using a moisture permeable waterproof fabric, under intense exercise conditions, dew condensation water due to sweat or vapor from sweat on the inside (body side) of the moisture permeable waterproof fabric, etc. The moisture may adhere to the skin of the wearer and the comfort may be impaired. In particular, this phenomenon is remarkably observed in clothes using a waterproof fabric having little moisture permeability.
透湿性防水布帛の透湿性の度合いは、透湿度で表すことができる。透湿度の測定には、主に酢酸カリウム法（ＪＩＳ Ｌ１０９９−１９９３Ｂ−１法）が用いられる。一般に、酢酸カリウム法で測定された透湿度が高いほど、衣服の内側の結露を低減する効果に優れる。
このような結露を低減する効果に優れた透湿性防水布帛としては、水膨潤性の無孔質膜を有する透湿性防水布帛が知られており、幅広く実用化されている。
As such a moisture-permeable waterproof fabric excellent in the effect of reducing condensation, a moisture-permeable waterproof fabric having a water-swellable nonporous membrane is known and widely used.
ところで、人間の肌の表面は弱酸性に維持されている。肌の表面が弱酸性に維持されることにより、細菌の増殖の抑制効果、皮膚の蛋白質をひきしめる効果等があるとされている。ゆえに、人の肌にｐＨ４．０未満の酸性あるいはｐＨ７．０を超えるアルカリ性の水分が付着すると、肌の酸性度のバランスが崩れ、肌ストレスや肌荒れの原因となる恐れがある。 By the way, the surface of human skin is kept weakly acidic. It is said that maintaining the surface of the skin weakly acidic has an effect of suppressing the growth of bacteria, an effect of attracting skin proteins, and the like. Therefore, when acidic water having a pH of less than 4.0 or alkaline water having a pH of more than 7.0 is attached to human skin, the balance of the acidity of the skin is lost, which may cause skin stress or rough skin.
同時に、このような透湿性防水布帛には、激しい運動によって生じる衣服内の湿気を衣服の外部に速やかに放出し、かつ、衣服の内側に結露した水分を速やかに吸収して衣服の外部に放出する高い透湿性を備えていることが望まれる。
本発明は、前記事情に鑑みてなされたものであって、透湿性防水布帛を含めた防水布帛において、衣服の内側の湿度および結露を低減することで優れた透湿性を示し、かつ湿潤時に人の肌に優しいｐＨ４．０〜７．０を維持する防水布帛およびその製造方法を目的とする。
At the same time, such a moisture-permeable waterproof fabric quickly releases moisture in the clothes caused by intense exercise to the outside of the clothes, and quickly absorbs moisture condensed on the inside of the clothes and releases it to the outside of the clothes. It is desirable to have high moisture permeability.
The present invention has been made in view of the above circumstances, and in a waterproof fabric including a moisture permeable waterproof fabric, it shows excellent moisture permeability by reducing the humidity and dew condensation inside the garment, and when wet, It aims at the waterproof fabric which maintains pH 4.0-7.0 gentle to skin of the skin, and its manufacturing method.
前記の課題を達成するために、本発明は以下の構成を採用した。
（１）繊維布帛の少なくとも片面に、無孔質膜を有する樹脂層が形成された防水布帛であって、前記無孔質膜に、ウレタン樹脂と、両性金属の酸化物および／または二酸化ケイ素の微粒子とが含まれ、湿潤時にｐＨ４．０〜７．０を示すことを特徴とする防水布帛。
（２）前記無孔質膜を形成するウレタン樹脂１００質量部に対し、前記微粒子が０．５〜５０質量部含まれることを特徴とする（１）に記載の防水布帛。
（３）前記微粒子の平均粒子径が、０．０５〜５μｍであることを特徴とする（１）または（２）に記載の防水布帛。
（４）酢酸カリウム法による透湿度が１５０００ｇ／ｍ２・２４ｈｒｓ以上であることを特徴とする（１）〜（３）のいずれかに記載の防水布帛。
In order to achieve the above object, the present invention adopts the following configuration.
(1) A waterproof fabric in which a resin layer having a nonporous membrane is formed on at least one surface of a fiber fabric, wherein the nonporous membrane is made of urethane resin, an amphoteric metal oxide and / or silicon dioxide. A waterproof fabric comprising fine particles and having a pH of 4.0 to 7.0 when wet.
(2) The waterproof fabric according to (1), wherein the fine particles are contained in an amount of 0.5 to 50 parts by mass with respect to 100 parts by mass of the urethane resin forming the nonporous membrane.
(3) The waterproof fabric according to (1) or (2), wherein an average particle diameter of the fine particles is 0.05 to 5 μm.
(4) The waterproof fabric according to any one of (1) to (3), wherein the moisture permeability measured by the potassium acetate method is 15000 g / m 2 · 24 hrs or more.
（５）耐水圧が１００ｋＰａ以上であることを特徴とする（１）〜（４）のいずれかに記載の防水布帛。
（６）前記樹脂層が、前記無孔質膜と、前記微粒子を含まない樹脂皮膜との多層構造であることを特徴とする（１）〜（５）のいずれかに記載の防水布帛。
（７）離型紙上に、両性金属の酸化物および／または二酸化ケイ素の微粒子を含むウレタン樹脂溶液を塗布した後、ウレタン系接着剤を塗布し、この上に繊維布帛を貼り合わせることを特徴とする防水布帛の製造方法。
(5) The waterproof fabric according to any one of (1) to (4), wherein the water pressure resistance is 100 kPa or more.
(6) The waterproof fabric according to any one of (1) to (5), wherein the resin layer has a multilayer structure of the nonporous film and a resin film not containing the fine particles.
(7) It is characterized by applying a urethane resin solution containing amphoteric metal oxide and / or silicon dioxide fine particles on a release paper, then applying a urethane adhesive, and bonding a fiber fabric thereon. A method for producing a waterproof fabric.
本発明の防水布帛によると、湿潤時に人の肌に優しいｐＨ４．０〜７．０を維持できる。また、無孔質膜が水膨潤性を有するウレタン樹脂である場合には、優れた透湿性も発揮する。
本発明の防水布帛の製造方法によると、湿潤時に人の肌に優しいｐＨ４．０〜７．０を維持できる防水布帛を製造できる。
According to the waterproof fabric of the present invention, it is possible to maintain pH 4.0 to 7.0 that is gentle to human skin when wet. In addition, when the nonporous film is a urethane resin having water swellability, excellent moisture permeability is also exhibited.
According to the method for producing a waterproof fabric of the present invention, it is possible to produce a waterproof fabric that can maintain pH 4.0 to 7.0 that is gentle to human skin when wet.
本発明の防水布帛は、繊維布帛の少なくとも片面に、無孔質膜を有する樹脂層が形成された防水布帛であって、前記無孔質膜に、ウレタン樹脂と、両性金属の酸化物および／または二酸化ケイ素の微粒子とが含まれ、湿潤時にｐＨ４．０〜７．０を示すことを特徴とする。 The waterproof fabric of the present invention is a waterproof fabric in which a resin layer having a nonporous membrane is formed on at least one side of a fiber fabric, and the nonporous membrane is coated with a urethane resin, an amphoteric metal oxide, and / or Or fine particles of silicon dioxide, and has a pH of 4.0 to 7.0 when wet.
繊維布帛の素材としては、ポリエステル、ナイロン、アクリル、ポリウレタン、アセテート、レーヨン、ポリ乳酸等の化学繊維、または、綿、麻、絹、羊毛等の天然繊維やこれらの混繊、混紡、交織品等が挙げられるが、特に限定されるものではない。また、繊維布帛は織物、編物、不織布等、いかなる形態であってもよい。さらに、繊維布帛には、染色、捺染をはじめ、制電加工、撥水加工、抗菌防臭加工、制菌加工、紫外線遮蔽加工等を施してあってもよい。 The material of the fiber fabric includes chemical fibers such as polyester, nylon, acrylic, polyurethane, acetate, rayon, polylactic acid, or natural fibers such as cotton, hemp, silk, wool, etc. However, it is not particularly limited. Further, the fiber fabric may be in any form such as a woven fabric, a knitted fabric, or a non-woven fabric. Furthermore, the textile fabric may be subjected to dyeing and printing, antistatic processing, water repellent processing, antibacterial and deodorizing processing, antibacterial processing, ultraviolet shielding processing, and the like.
樹脂層を形成する無孔質膜の厚みは、１〜５０μｍ程度が好ましく、３〜３０μｍがより好ましい。無孔質膜の厚みが１μｍ未満であると、防水性が低下する。５０μｍを超えると、得られる防水布帛の風合が硬くなる。 About 1-50 micrometers is preferable and, as for the thickness of the nonporous film | membrane which forms a resin layer, 3-30 micrometers is more preferable. When the thickness of the nonporous membrane is less than 1 μm, the waterproof property is lowered. When the thickness exceeds 50 μm, the texture of the resulting waterproof fabric becomes hard.
無孔質膜はウレタン樹脂を主体に形成されている。ウレタン樹脂は、エーテル系、エステル系、エーテル・エステル系いずれであってもよいが、エーテル系、エーテル・エステル系が好ましい。
エーテル系、エーテル・エステル系のウレタン樹脂は、水膨潤性を有するウレタン樹脂である。水膨潤性を有するウレタン樹脂は、着用時に衣服内に生じた汗などの水滴を吸収し易いことから、湿潤時にｐＨ４．０〜７．０を安定して示しやすく、かつ優れた透湿性を有している。
水膨潤性を有するウレタン樹脂は、ウレタン樹脂を構成するポリオール成分がポリエチレンエーテルグリコール基を含むことから親水性を示し、水と接触すると、樹脂中に水を吸収して膨潤する性質を有する。したがって、水膨潤性を有するウレタン樹脂を用いた防水布帛は、結露した水分が無孔質膜の中に吸収されるため、結露が生じにくくなる。
なお、無孔質膜を有する樹脂層を繊維布帛の少なくとも片面に形成させる際に、樹脂層と、繊維布帛とを接着剤を用いて貼り合せる場合には、その接着剤についても、親水基を有するエーテル系、エーテル・エステル系のウレタン系接着剤を用いるのが好ましい。このような水膨潤性のウレタン樹脂および、ウレタン系接着剤は市販品を入手することができる。
The non-porous film is formed mainly of urethane resin. The urethane resin may be any of ether type, ester type and ether / ester type, but ether type and ether / ester type are preferable.
Ether-based and ether-ester-based urethane resins are water-swellable urethane resins. Urethane resin with water swellability is easy to absorb water droplets such as sweat generated in clothes when worn, so it is easy to stably show pH 4.0 to 7.0 when wet and has excellent moisture permeability. is doing.
The urethane resin having water swellability is hydrophilic because the polyol component constituting the urethane resin contains a polyethylene ether glycol group, and has a property of absorbing water into the resin and swelling when contacted with water. Therefore, in the waterproof fabric using the urethane resin having water swellability, the condensed moisture is absorbed in the non-porous film, so that the condensation is less likely to occur.
When the resin layer having a nonporous film is formed on at least one side of the fiber fabric, when the resin layer and the fiber fabric are bonded using an adhesive, the adhesive also has a hydrophilic group. It is preferable to use an ether-based or ether-ester-based urethane adhesive. Such water-swellable urethane resins and urethane adhesives are commercially available.
両性金属の酸化物および／または前記二酸化ケイ素の微粒子の平均粒子径は、０．０５〜５μｍであることが好ましい。微粒子の平均粒子径が前記範囲を下回ると、微粒子の製造が困難であり、平均粒子径が前記範囲を超えると、耐水圧が低下する原因となる。ここで、両性金属とは、酸にもアルカリにも反応する金属のことをいい、アルミニウム、亜鉛、スズ、鉛が挙げられる。
両性金属の酸化物の微粒子としては、酸化亜鉛や酸化アルミニウムが市販されている。酸化亜鉛は湿潤時に弱酸性を示しにくいため、酸性を示す酸化アルミニウム（Ａｌ２Ｏ３）の微粒子が好ましい。
The average particle diameter of the amphoteric metal oxide and / or the silicon dioxide fine particles is preferably 0.05 to 5 μm. When the average particle diameter of the fine particles is below the above range, it is difficult to produce the fine particles, and when the average particle diameter exceeds the above range, the water pressure resistance is reduced. Here, the amphoteric metal refers to a metal that reacts with both acid and alkali, and includes aluminum, zinc, tin, and lead.
Zinc oxide and aluminum oxide are commercially available as amphoteric metal oxide fine particles. Since zinc oxide hardly exhibits weak acidity when wet, fine particles of aluminum oxide (Al 2 O 3 ) exhibiting acidity are preferable.
酸化アルミニウムの微粒子は、１μｍ以下の平均粒子径を有する市販品があり、本発明ではそれら市販品を用いてもよい。酸化アルミニウムの微粒子には、湿式法、乾式法で製造されたものがあるが、本発明ではどちらを用いてもよい。なお、酸化アルミニウムの微粒子は凝集していることが多いため、無孔質膜に均一に分散させるために、ジメチルホルムアミド溶剤、ビヒクルとしてのウレタン樹脂、分散剤等を配合し、ディパーサー等でプレミックスし、さらに、サンドミル、三本ロールミル、ビーズビル等で粉砕し、平均粒子径を０．０５〜５μｍに調製したものを使用するのが好ましい。 The aluminum oxide fine particles include commercially available products having an average particle diameter of 1 μm or less, and these commercially available products may be used in the present invention. The aluminum oxide fine particles are produced by a wet method or a dry method, and either one may be used in the present invention. Since aluminum oxide fine particles are often aggregated, a dimethylformamide solvent, a urethane resin as a vehicle, a dispersing agent, etc. are blended in order to disperse uniformly in a non-porous film, and pre-mixed with a deparser or the like. It is preferable to use a mixture that has been mixed and further pulverized with a sand mill, a three-roll mill, a bead bill, or the like to have an average particle diameter of 0.05 to 5 μm.
二酸化ケイ素の微粒子は市販されており、本発明ではそれら市販品を用いてもよい。二酸化ケイ素の微粒子には、湿式法、乾式法で製造されたものがあるが、本発明ではどちらを用いてもよい。
また、二酸化ケイ素の微粒子には、無孔質系と多孔質系が存在するが、本発明では無孔質系が好ましく用いられる。
また、二酸化ケイ素の微粒子の表面は親水性であってもよく、メチル基、トリメチルシリル基、ジメチルシリコーン基等で疎水化処理されていてもよい。
なお、二酸化ケイ素の微粒子は凝集していることが多いため、無孔質膜に均一に分散させるために、酸化アルミニウムの微粒子の調製と同様に、二酸化ケイ素の微粒子をジメチルホルムアミド溶剤等に分散したものを使用するのが好ましい。
Silicon dioxide fine particles are commercially available, and those commercially available products may be used in the present invention. Some silicon dioxide fine particles are produced by a wet method or a dry method, and either one may be used in the present invention.
The silicon dioxide fine particles include a nonporous system and a porous system. In the present invention, a nonporous system is preferably used.
The surface of the silicon dioxide fine particles may be hydrophilic, and may be hydrophobized with a methyl group, a trimethylsilyl group, a dimethylsilicone group or the like.
Since the silicon dioxide fine particles are often aggregated, the silicon dioxide fine particles were dispersed in a dimethylformamide solvent or the like in the same manner as the preparation of the aluminum oxide fine particles in order to uniformly disperse the nonporous film. It is preferable to use one.
人の肌にｐＨ４．０未満の酸性あるいはｐＨ７．０を超えるアルカリ性の液体が付着すると、肌の酸性度のバランスが崩れ、肌ストレスや肌荒れの原因となる恐れがあるが、本発明の防水布帛は、無孔質膜に前記微粒子を含んでいるため、無孔質膜の表面が、湿潤時に人の肌に優しいｐＨ４．０〜７．０を示すことができる。これは、前記微粒子が湿潤状態で弱酸性の性質を有するためと考えられる。 If an acidic liquid having a pH of less than 4.0 or an alkaline liquid having a pH of more than 7.0 adheres to human skin, the balance of the acidity of the skin may be lost, which may cause skin stress or rough skin, but the waterproof fabric of the present invention. Since the non-porous film contains the fine particles, the surface of the non-porous film can exhibit a pH of 4.0 to 7.0 that is gentle to human skin when wet. This is presumably because the fine particles have a weakly acidic property in a wet state.
前記微粒子の含有量は、無孔質膜を形成するウレタン樹脂１００質量部に対し、質量比で０．５〜５０質量部が好ましい。より好ましくは、１〜５０質量部である。前記範囲内であれば、防水布帛に付着した水分がｐＨ４．０〜７．０を示しやすい。 The content of the fine particles is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the urethane resin forming the nonporous film. More preferably, it is 1-50 mass parts. If it is in the said range, the water | moisture content adhering to the waterproof fabric will show pH 4.0-7.0 easily.
樹脂層は、無孔質膜のみを有していてもよいが、前記微粒子を含まない樹脂皮膜との多層構造であってもよい。なお、多層構造の樹脂層が形成された防水布帛の場合、無孔質膜と、前記微粒子を含まない樹脂皮膜のどちらが表層であってもよいが、樹脂層の表面をｐＨ４．０〜７．０に維持する観点からは、無孔質膜が表層であるのが好ましい。
前記微粒子を含まない樹脂皮膜としては、ウレタン樹脂皮膜、ポリテトラフルオロエチレン樹脂皮膜、ポリエステル樹脂皮膜、ポリアミド樹脂皮膜を挙げることができる。中でも、得られる防水布帛の透湿性、湿潤時にｐＨ４．０〜７．０を示しやすいことから、水膨潤性を有したウレタン樹脂皮膜が好ましい。なお、前記微粒子を含まない樹脂皮膜は、無孔質であってもよく、多孔質であってもよい。
無孔質膜のみを有した樹脂層が形成された防水布帛において、耐水圧が１００ｋＰａ程度で不十分である場合、微粒子を含まない水膨潤性のウレタン樹脂皮膜をさらに積層することによって、例えば、２００ｋＰａ以上の十分な耐水圧を得ることができる。
The resin layer may have only a nonporous film, but may have a multilayer structure with the resin film not containing the fine particles. In the case of a waterproof fabric in which a resin layer having a multilayer structure is formed, either the nonporous film or the resin film not containing the fine particles may be a surface layer, but the surface of the resin layer has a pH of 4.0 to 7. From the viewpoint of maintaining 0, it is preferable that the nonporous membrane is a surface layer.
Examples of the resin film not containing fine particles include a urethane resin film, a polytetrafluoroethylene resin film, a polyester resin film, and a polyamide resin film. Among them, a urethane resin film having water swellability is preferable because the waterproof fabric obtained has a moisture permeability and a pH of 4.0 to 7.0 when wet. The resin film not containing the fine particles may be nonporous or porous.
In a waterproof fabric formed with a resin layer having only a nonporous membrane, when the water pressure resistance is insufficient at about 100 kPa, by further laminating a water-swellable urethane resin film that does not contain fine particles, for example, A sufficient water pressure resistance of 200 kPa or more can be obtained.
樹脂層の表面には、意匠性の価値の向上、滑り性の向上等を目的として、グラビア柄模様、スリット模様等の模様を有していてもよい。模様は、樹脂層の全面に設けられていてもよいが、意匠性や滑り性が必要な箇所等に対して、点状、線状、局所的に設けられていてもよい。 The surface of the resin layer may have a pattern such as a gravure pattern or a slit pattern for the purpose of improving the value of design and improving the slipperiness. The pattern may be provided on the entire surface of the resin layer, but may be provided in a dot shape, a linear shape, or locally with respect to a place where designability and slipperiness are required.
本発明の防水布帛は、透湿性も有する透湿性防水布帛であるとよく、酢酸カリウム法による透湿度が１５０００ｇ／ｍ２・２４ｈｒｓ以上であるとよい。透湿度が１５０００ｇ／ｍ２・２４ｈｒｓ以上であると、衣服として用いた場合にムレを抑制するとともに、万が一、繊維布帛が湿潤した場合においても、ｐＨ４．０〜７．０に安定して保つことができる。なお、本発明の防水布帛の酢酸カリウム法による透湿度の上限は、用いる繊維布帛の種類、樹脂層の構成によっても異なるが、５００００ｇ／ｍ２・２４ｈｒｓ程度である。ここで、酢酸カリウム法による透湿度とは、ＪＩＳ Ｌ１０９９−１９９３Ｂ−１法にて測定した値を２４時間当りの透湿量に換算したものをいう。 The waterproof fabric of the present invention is preferably a moisture-permeable waterproof fabric having moisture permeability, and the moisture permeability by the potassium acetate method is preferably 15000 g / m 2 · 24 hrs or more. When the moisture permeability is 15000 g / m 2 · 24 hrs or more, it suppresses stuffiness when used as clothes, and should maintain a stable pH of 4.0 to 7.0 even when the fiber fabric is wet. Can do. In addition, although the upper limit of the water vapor transmission rate by the potassium acetate method of the waterproof fabric of this invention changes also with the kind of fiber fabric to be used, and the structure of a resin layer, it is about 50000 g / m < 2 > * 24hrs. Here, the moisture permeability by the potassium acetate method means a value obtained by converting a value measured by the JIS L1099-1993B-1 method into a moisture permeability per 24 hours.
また、本発明の防水布帛は、防水性の指標となる耐水圧が１００ｋＰａ以上であるとよい。また、本発明の防水布帛の耐水圧の上限は、繊維布帛の種類、樹脂層の構成等によって異なるが、４００ｋＰａ程度が目安である。なお、耐水圧はＪＩＳ Ｌ１０９２−１９９８耐水度試験（静水圧法）Ｂ法（高水圧法）に準じて測定することができる。水圧をかけることにより試験片が伸びる場合には、試験片の上にナイロンタフタ（２．５４ｃｍ当りのたて糸とよこ糸の密度の合計が２１０本程度のもの）を重ねて、試験機に取り付けて測定を行う。 In addition, the waterproof fabric of the present invention preferably has a water pressure resistance of 100 kPa or more, which is an index of waterproofness. The upper limit of the water pressure resistance of the waterproof fabric of the present invention varies depending on the type of fiber fabric, the configuration of the resin layer, etc., but is about 400 kPa. The water pressure resistance can be measured according to JIS L1092-1998 water resistance test (hydrostatic pressure method) B method (high water pressure method). When the test piece is stretched by applying water pressure, the nylon taffeta (with a total of about 210 warp and weft density per 2.54 cm) is stacked on the test piece and attached to the tester. I do.
次に、本発明の防水布帛の製造方法を説明する。
透湿性防水布帛を含めた本発明の防水布帛の製造方法は、離型紙上に、両性金属の酸化物および／または二酸化ケイ素の微粒子を含むウレタン樹脂溶液を塗布した後、ウレタン系接着剤を塗布し、この上に繊維布帛を貼り合わせることを特徴とする。
Next, the manufacturing method of the waterproof fabric of this invention is demonstrated.
The method for producing the waterproof fabric of the present invention including the moisture-permeable waterproof fabric is such that a urethane resin solution containing amphoteric metal oxides and / or silicon dioxide fine particles is applied on a release paper, and then a urethane adhesive is applied. In addition, a fiber fabric is bonded onto this.
本発明の防水布帛の製造方法として、さらに詳しくは、ドライラミネート法と、ウエットラミネート法が例示できる。
ドライラミネート法は、まず、両性金属の酸化物および／または二酸化ケイ素の微粒子を含むウレタン樹脂溶液を離型紙上に塗布し、乾燥させて、無孔質膜を形成する。次いで、得られた無孔質膜上に、ウレタン系接着剤を塗布し、乾燥させる。さらに、繊維布帛と貼り合わせ、熱圧着することで、繊維布帛の表面に樹脂層を有した防水布帛を製造する。
ウエットラミネート法は、ウレタン系接着剤を乾燥せずに繊維布帛を貼り合わせる方法である。すなわち、両性金属の酸化物および／または二酸化ケイ素の微粒子を含むウレタン樹脂溶液を離型紙上に塗布し、乾燥させ、無孔質膜を形成する。次いで、得られた無孔質膜上に、ウレタン系接着剤を塗布し、該接着剤が乾燥しないうちに、繊維布帛と貼り合わせることで、繊維布帛の表面に樹脂層を有した防水布帛を製造する。
More specifically, examples of the method for producing the waterproof fabric of the present invention include a dry laminating method and a wet laminating method.
In the dry laminating method, first, a urethane resin solution containing amphoteric metal oxides and / or silicon dioxide fine particles is applied onto release paper and dried to form a nonporous film. Next, a urethane-based adhesive is applied on the obtained nonporous film and dried. Further, a waterproof fabric having a resin layer on the surface of the fiber fabric is manufactured by bonding with the fiber fabric and thermocompression bonding.
The wet laminating method is a method in which the fiber fabric is bonded without drying the urethane-based adhesive. That is, a urethane resin solution containing amphoteric metal oxide and / or silicon dioxide fine particles is applied onto a release paper and dried to form a nonporous film. Subsequently, a waterproof adhesive having a resin layer on the surface of the fiber cloth is obtained by applying a urethane adhesive on the obtained nonporous film and bonding the fiber adhesive to the fiber cloth before the adhesive is dried. To manufacture.
繊維布帛に塗布するウレタン樹脂溶液は、ウレタン樹脂と、両性金属の酸化物および／または二酸化ケイ素の微粒子とが含まれる溶液である。ウレタン樹脂は、好ましくは水膨潤性のウレタン樹脂が用いられる。さらに、材料の分散性をよくするために、ジメチルホルムアミド（ＤＭＦ）、トルエン、メチルエチルケトン等を主体とした有機溶媒が好ましく用いられる。有機溶媒は１種で用いてもよく、２種以上を用いてもよい。また、前記微粒子は、両性金属の酸化物の微粒子または二酸化ケイ素の微粒子を単独で用いてもよく、両方を混合して用いてもよい。
さらに、ウレタン樹脂溶液中には、顔料等の着色剤、ポリイソシアネート系架橋剤、触媒、酸化防止剤、紫外線吸収剤等を添加してもよい。
また、ウレタン系接着剤には、好ましくは水膨潤性のウレタン系接着剤が用いられる。
The urethane resin solution applied to the fiber fabric is a solution containing urethane resin and amphoteric metal oxide and / or silicon dioxide fine particles. As the urethane resin, a water-swellable urethane resin is preferably used. Furthermore, in order to improve the dispersibility of the material, an organic solvent mainly composed of dimethylformamide (DMF), toluene, methyl ethyl ketone or the like is preferably used. One organic solvent may be used, or two or more organic solvents may be used. As the fine particles, amphoteric metal oxide fine particles or silicon dioxide fine particles may be used alone, or a mixture of both may be used.
Furthermore, a colorant such as a pigment, a polyisocyanate crosslinking agent, a catalyst, an antioxidant, an ultraviolet absorber, and the like may be added to the urethane resin solution.
The urethane adhesive is preferably a water-swellable urethane adhesive.
繊維布帛には、必要に応じて、精練、染色、捺染、制電加工、撥水加工、抗菌防臭加工、制菌加工、紫外線遮蔽加工、カレンダー加工等を施してもよい。
ウレタン樹脂溶液を離型紙上に塗布するには、ナイフコータ、バーコータ、コンマコータ等を用いればよい。
樹脂層は、無孔質膜のみであってもよいが、必要に応じて、さらに微粒子を含まない樹脂皮膜を積層して多層構造の樹脂層を形成してもよい。無孔質膜への微粒子を含まない樹脂皮膜の積層は、例えば、無孔質膜上に該樹脂皮膜の樹脂溶液を塗布して、乾燥させることにより形成できる。
樹脂層上への接着剤の塗布には、ナイフコータ、バーコータ、コンマコータ、グラビアコータ等を用いることができる。
また、樹脂層と繊維布帛とを貼り合わせた後に、必要に応じて、撥水加工、制電加工、撥水加工、抗菌防臭加工、制菌加工、紫外線遮蔽加工、カレンダー加工を行ってもよい。
The fiber fabric may be subjected to scouring, dyeing, textile printing, antistatic processing, water repellent processing, antibacterial and deodorizing processing, antibacterial processing, ultraviolet shielding processing, calendar processing, and the like as necessary.
In order to apply the urethane resin solution onto the release paper, a knife coater, a bar coater, a comma coater or the like may be used.
The resin layer may be only a non-porous film, but a resin film having a multilayer structure may be formed by further laminating a resin film not containing fine particles as necessary. The lamination of the resin film not containing fine particles on the nonporous film can be formed, for example, by applying a resin solution of the resin film on the nonporous film and drying it.
A knife coater, a bar coater, a comma coater, a gravure coater, or the like can be used for applying the adhesive onto the resin layer.
Moreover, after bonding a resin layer and a fiber fabric, you may perform a water-repellent process, an antistatic process, a water-repellent process, an antibacterial deodorizing process, an antibacterial process, an ultraviolet shielding process, and a calendar process as needed. .
樹脂層の表面に、意匠性や滑り性向上のためグラビア柄模様、スリット模様等の模様を形成する場合には、樹脂層上にグラビアコータやスクリーン捺染機を用いて、点状、線状、菱形等、所望の模様となるようにウレタン樹脂溶液等を塗布して、乾燥させればよい。 When forming a gravure pattern, slit pattern, etc. on the surface of the resin layer to improve design and slipperiness, use a gravure coater or screen printing machine on the resin layer, What is necessary is just to apply | coat a urethane resin solution etc. so that it may become a desired pattern, such as a rhombus, and to make it dry.
このようにして製造される本発明の防水布帛は、防水布帛の樹脂層表面が結露等により湿潤した場合でも、樹脂層表面に付着した水分がｐＨ４．０〜７．０を示す。したがって、この水分が人の肌に転着しても、肌荒れを生じさせる心配がなく、人の肌に優しい。
また、本発明の防水布帛は、優れた防水性に加えて、衣服の内側の湿度および結露を低減する優れた透湿性を有している。
よって、本発明の防水布帛をウインドブレーカー、コート、ジャケット、スキーウエアー、スノーボードウエアー、テント等に用いれば、使用者に快適な環境を提供することができる。
In the waterproof fabric of the present invention produced in this way, even when the resin layer surface of the waterproof fabric is wetted by condensation or the like, the moisture attached to the resin layer surface has a pH of 4.0 to 7.0. Therefore, even if this moisture is transferred to a person's skin, there is no worry of causing rough skin, and it is gentle on the person's skin.
Moreover, the waterproof fabric of this invention has the outstanding moisture permeability which reduces the humidity and dew condensation inside clothes in addition to the outstanding waterproofness.
Therefore, if the waterproof fabric of this invention is used for a windbreaker, a coat, a jacket, ski wear, snowboard wear, a tent, etc., a comfortable environment can be provided to the user.
以下、実施例により本発明をさらに説明するが、本発明はこれらの実施例によりなんら限定されるものではない。なお、例中の「部」は質量部である。
以下の実施例における評価は、次の方法で行った。
（防水布帛のｐＨ）
ＪＩＳ Ｌ１０９６ ８．４０．１−１９９９により測定した。
（透湿度）
酢酸カリウム法：ＪＩＳ Ｌ１０９９−１９９３Ｂ−１にて測定した。
なお、２４時間当りの透湿量に換算した。
（耐水圧）
ＪＩＳ Ｌ１０９２−１９９８耐水度試験（静水圧法）Ｂ法（高水圧法）に準じた方法で測定した。水圧をかけることにより試験片が伸びて測定しにくい場合には、試験片の上にナイロンタフタ（２．５４ｃｍ当りのたて糸とよこ糸の密度の合計が２１０本程度のもの。）を重ねて、試験機に取り付けて測定を行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited at all by these Examples. In addition, "part" in an example is a mass part.
Evaluation in the following examples was performed by the following method.
(PH of waterproof fabric)
It was measured according to JIS L1096 8.40.1-1999.
(Moisture permeability)
Potassium acetate method: Measured in accordance with JIS L1099-1993B-1.
In addition, it converted into the moisture permeation amount per 24 hours.
(Water pressure resistance)
It measured by the method according to JIS L1092-1998 water resistance test (hydrostatic pressure method) B method (high water pressure method). If it is difficult to measure the test piece by applying water pressure, the test piece is overlaid with nylon taffeta (the total density of warp and weft yarns is about 210 per 2.54 cm). It was attached to the machine and measured.
また、各実施例で用いたウレタン樹脂の水膨潤度は、次の方法で求められた。
（水膨潤度）
離型紙の上にウレタン樹脂溶液を０．０８ｍｍの厚みで塗布し、１２０℃で３分間乾燥し、１８時間経過後、得られた無孔質膜を離型紙から剥離し、５×５ｃｍの大きさに切り取って試験片とし、その質量を測定した。次いで、ウレタン樹脂の試験片を、水道水に５分間浸漬した後、取り出して、再度、質量を測定した。そして、水道水に浸漬する前と後における質量の増加率を求めて、水膨潤度とした。ウレタン系接着剤の水膨潤度も同様にして測定した。
Moreover, the water swelling degree of the urethane resin used in each Example was calculated | required with the following method.
(Water swelling)
A urethane resin solution is applied to a release paper with a thickness of 0.08 mm, dried at 120 ° C. for 3 minutes, and after 18 hours, the obtained nonporous film is peeled off from the release paper and has a size of 5 × 5 cm. The sample was cut out into test pieces and the mass was measured. Next, the test piece of urethane resin was immersed in tap water for 5 minutes, then taken out, and the mass was measured again. And the increase rate of the mass before and after being immersed in tap water was calculated | required, and it was set as the water swelling degree. The degree of water swelling of the urethane adhesive was also measured in the same manner.
＜実施例１＞
ナイロンタフタ（繊維太さ：たて糸８３デシテックス／７２フィラメント、よこ糸８３デシテックス／７２フィラメント。繊維密度：たて糸１１４本／２．５４ｃｍ、よこ糸９２本／２．５４ｃｍ。）を酸性染料で黒色に染色した。次いで、このナイロンタフタに、フッ素系撥水剤アサヒガ−ドＡＧ７１０（旭硝子（株）製）を用いて撥水加工を施し、繊維布帛とした。
<Example 1>
Nylon taffeta (fiber thickness: warp 83 dtex / 72 filament, weft 83 dtex / 72 filament, fiber density: 114 warp / 2.54 cm, warp 92 / 2.54 cm) was dyed black with an acid dye. Next, this nylon taffeta was subjected to water repellent treatment using a fluorine-based water repellent Asahi Guard AG710 (manufactured by Asahi Glass Co., Ltd.) to obtain a fiber fabric.
次いで、離型紙上に、下記原料を混合した樹脂溶液を、コンマコ−タを用いてスリット０．１ｍｍで塗布し、１２０℃にて乾燥して、厚さ７μｍの無孔質膜を得た。
［樹脂溶液の原料（無孔質膜用）］
エ−テル系ポリウレタン樹脂（固形分３０％、水膨潤度８５％） １００部
酸化アルミニウム分散品 ２０部
（平均一次粒子径１３ｎｍ、分散後平均粒子径０．４μｍ、固形分１５％）
メチルエチルケトン ３０部
白色顔料 ８部
Next, on the release paper, a resin solution in which the following raw materials were mixed was applied with a slit 0.1 mm using a comma coater and dried at 120 ° C. to obtain a 7 μm thick nonporous film.
[Raw material of resin solution (for nonporous membrane)]
Ether polyurethane resin (solid content 30%, water swelling degree 85%) 100 parts Aluminum oxide dispersion 20 parts (average primary particle size 13 nm, average particle size after dispersion 0.4 μm, solid content 15%)
Methyl ethyl ketone 30 parts White pigment 8 parts
次いで、無孔質膜上に、下記原料を混合した樹脂溶液（ウレタン系接着剤）を、コンマコ−タを用いてスリット０．０８ｍｍで塗布し、１２０℃で２分間乾燥した。
［樹脂溶液の原料（ウレタン系接着剤用）］
エ−テル・エステル系ポリウレタン樹脂（固形分４５％、水膨潤度３０％）
１００部
トルエン ３０部
イソシアネ−ト系架橋剤 ９部
有機錫系触媒 １部
Next, a resin solution (urethane adhesive) in which the following raw materials were mixed was applied on the nonporous film with a slit of 0.08 mm using a comma coater and dried at 120 ° C. for 2 minutes.
[Raw material of resin solution (for urethane adhesive)]
Ether ester polyurethane resin (solid content 45%, water swelling 30%)
100 parts Toluene 30 parts Isocyanate-based crosslinking agent 9 parts Organotin-based catalyst 1 part
次いで、このウレタン系接着剤の塗布面に繊維布帛を重ね合わせてから、熱圧着により貼り合わせ、その後、６０℃にて７２時間エ−ジングを行った（ドライラミネート法）。
次いで、離型紙を剥離し、無孔質膜を有する樹脂層が形成された実施例１の防水布帛を得た。この防水布帛の透湿度、耐水圧を測定した結果を表１に示す。
Next, a fiber fabric was superposed on the application surface of the urethane adhesive, and then bonded by thermocompression bonding, and then aged at 60 ° C. for 72 hours (dry laminating method).
Next, the release paper was peeled off to obtain a waterproof fabric of Example 1 in which a resin layer having a nonporous film was formed. Table 1 shows the results of measuring the moisture permeability and water pressure resistance of this waterproof fabric.
＜実施例２＞
実施例１で用いた無孔質膜用の樹脂溶液の代わりに、下記の原料を混合した無孔質膜用の樹脂溶液を用いたこと以外は実施例１と同様にして、実施例２の防水布帛を得た。この防水布帛の透湿度、耐水圧を測定した結果を表１に示す。
［樹脂溶液の原料（無孔質膜用）］
エ−テル系ポリウレタン樹脂（固形分３０％、水膨潤度８５％） １００部
二酸化ケイ素分散品 １５部
（平均一次粒子径１６ｎｍ、分散後平均粒子径０．３μｍ、固形分１４％）
メチルエチルケトン ３０部
白色顔料 ８部
<Example 2>
In place of the resin solution for nonporous membrane used in Example 1, a resin solution for nonporous membrane mixed with the following raw materials was used in the same manner as in Example 1 except that A waterproof fabric was obtained. Table 1 shows the results of measuring the moisture permeability and water pressure resistance of this waterproof fabric.
[Raw material of resin solution (for nonporous membrane)]
Ether polyurethane resin (solid content 30%, water swelling degree 85%) 100 parts Silicon dioxide dispersion 15 parts (average primary particle size 16 nm, average particle size after dispersion 0.3 μm, solid content 14%)
Methyl ethyl ketone 30 parts White pigment 8 parts
＜実施例３＞
ポリエステルタフタ（繊維太さ：たて糸８３デシテックス／７２フィラメント、よこ糸８３デシテックス／７２フィラメント。繊維密度：たて糸１１４本／２．５４ｃｍ、よこ糸９２本／２．５４ｃｍ。）を分散染料で青色に染色した。次いで、このポリエステルタフタに、フッ素系撥水剤アサヒガ−ドＡＧ７１０（旭硝子（株）製）を用いて撥水加工を施し、繊維布帛とした。
<Example 3>
Polyester taffeta (fiber thickness: warp 83 dtex / 72 filament, weft 83 dtex / 72 filament, fiber density: 114 warp / 2.54 cm, weft 92 / 2.54 cm) was dyed blue with disperse dye. Next, the polyester taffeta was subjected to water repellent treatment using a fluorine-based water repellent Asahi Guard AG710 (manufactured by Asahi Glass Co., Ltd.) to obtain a fiber fabric.
次に、離型紙上に、下記原料を混合した樹脂溶液を、コンマコ−タを用いてスリット０．０８ｍｍで塗布し、１２０℃にて乾燥して、酸化アルミニウムの微粒子を含む厚さ７μｍの無孔質膜を形成した。
［樹脂溶液の原料（無孔質膜用）］
エ−テル系ポリウレタン樹脂（固形分３０％、水膨潤度８５％） １００部
酸化アルミニウム分散品 ２５部
（平均一次粒子径１３ｎｍ、分散後平均粒子径０．４μｍ、固形分１５％）
メチルエチルケトン ３０部
白色顔料 ８部
Next, on the release paper, a resin solution in which the following raw materials are mixed is applied with a slit of 0.08 mm using a comma coater, dried at 120 ° C., and 7 μm thick containing aluminum oxide fine particles. A porous membrane was formed.
[Raw material of resin solution (for nonporous membrane)]
Ether polyurethane resin (solid content 30%, water swelling degree 85%) 100 parts Aluminum oxide dispersion 25 parts (average primary particle size 13 nm, average particle size after dispersion 0.4 μm, solid content 15%)
Methyl ethyl ketone 30 parts White pigment 8 parts
次いで、無孔質膜上に、酸化アルミニウムの微粒子を含まない下記の原料を混合した樹脂溶液を０．０７ｍｍのスリットで塗布して、乾燥させて樹脂皮膜を形成した。
［樹脂溶液の原料（樹脂皮膜用）］
エ−テル系ポリウレタン樹脂（固形分３０％、水膨潤度７０％） １００部
メチルエチルケトン ３０部
白色顔料 ８部
Next, a resin solution in which the following raw materials not containing aluminum oxide fine particles were mixed was applied on a nonporous film with a 0.07 mm slit and dried to form a resin film.
[Raw material for resin solution (for resin film)]
Ether polyurethane resin (solid content 30%, water swelling 70%) 100 parts methyl ethyl ketone 30 parts white pigment 8 parts
次いで、ウレタン系接着剤用の下記原料を混合した樹脂溶液を、コンマコ−タを用いて樹脂皮膜上にスリット０．０７ｍｍで塗布し、１２０℃で２分間乾燥した。
［樹脂溶液の原料（ウレタン系接着剤用）］
エ−テル・エステル系ポリウレタン樹脂 １００部
（固形分４５％、水膨潤度３０％）
トルエン ３０部
イソシアネ−ト系架橋剤 ９部
有機錫系触媒 １部
Subsequently, the resin solution which mixed the following raw material for urethane type adhesives was apply | coated with the slit 0.07mm on the resin film using the comma coater, and it dried for 2 minutes at 120 degreeC.
[Raw material of resin solution (for urethane adhesive)]
Ether ester polyurethane resin 100 parts (45% solid content, 30% water swelling)
Toluene 30 parts Isocyanate-based crosslinking agent 9 parts Organotin-based catalyst 1 part
このウレタン系接着剤の塗布面に、前記繊維布帛を重ね合わせてから、熱圧着により貼り合わせ、その後、６０℃にて７２時間のエ−ジングを行った。
次に、離型紙を剥離して、前記無孔質膜と、前記樹脂皮膜との多層構造の樹脂層が形成された実施例３の防水布帛を得た。なお、この防水布帛は、無孔質膜が樹脂層の表層側となる。この防水布帛の透湿度、耐水圧を測定した結果を表１に示す。
The fiber fabric was overlaid on the surface of the urethane adhesive, and bonded by thermocompression bonding. Thereafter, aging was performed at 60 ° C. for 72 hours.
Next, the release paper was peeled off to obtain a waterproof fabric of Example 3 in which a resin layer having a multilayer structure of the nonporous film and the resin film was formed. In this waterproof fabric, the nonporous membrane is on the surface layer side of the resin layer. Table 1 shows the results of measuring the moisture permeability and water pressure resistance of this waterproof fabric.
＜実施例４＞
無孔質膜およびウレタン系接着剤に用いるウレタン樹脂として、下記の水膨潤性のないウレタン樹脂を配合した樹脂溶液を用いたこと以外は、実施例１と同様にして実施例４の防水布帛を得た。この防水布帛の透湿度、耐水圧を測定した結果を表１に示す。
［樹脂溶液の原料（無孔質膜用）］
エステル系ポリウレタン樹脂（固形分３０％） １００部
酸化アルミニウム分散品 ２０部
（平均一次粒子径１３ｎｍ、分散後平均粒子径０．４μｍ、固形分１５％）
メチルエチルケトン ３０部
［樹脂溶液の原料（ウレタン系接着剤用）］
エステル系ポリウレタン樹脂（固形分４５％） １００部
ジメチルホルムアミド ３０部
トルエン ３０部
イソシアネ−ト系架橋剤 １２部
有機錫系触媒 ２部
<Example 4>
The waterproof fabric of Example 4 was used in the same manner as in Example 1 except that a resin solution containing a urethane resin having no water swellability described below was used as the urethane resin used for the nonporous membrane and the urethane-based adhesive. Obtained. Table 1 shows the results of measuring the moisture permeability and water pressure resistance of this waterproof fabric.
[Raw material of resin solution (for nonporous membrane)]
Ester-based polyurethane resin (solid content 30%) 100 parts Aluminum oxide dispersion 20 parts (average primary particle size 13 nm, average particle size after dispersion 0.4 μm, solid content 15%)
30 parts of methyl ethyl ketone [raw material of resin solution (for urethane adhesive)]
Ester-based polyurethane resin (solid content 45%) 100 parts Dimethylformamide 30 parts Toluene 30 parts Isocyanate-based crosslinking agent 12 parts Organotin-based catalyst 2 parts
＜比較例１＞
実施例１で用いた無孔質膜用の樹脂溶液の代わりに、前記微粒子を含まない下記の原料を混合した無孔質膜用の樹脂溶液に変更した以外は実施例１と同様にして、比較例１の防水布帛を得た。この防水布帛の透湿度、耐水圧を測定した結果を表１に示す。
［樹脂溶液の原料（無孔質膜用）］
エーテル系ポリウレタン樹脂（固形分３０％、水膨潤度８５％） １００部
メチルエチルケトン ３０部
白色顔料 ８部
<Comparative Example 1>
Instead of the resin solution for nonporous membrane used in Example 1, the same as in Example 1 except that the resin solution for nonporous membrane mixed with the following raw materials not containing the fine particles was changed, A waterproof fabric of Comparative Example 1 was obtained. Table 1 shows the results of measuring the moisture permeability and water pressure resistance of this waterproof fabric.
[Raw material of resin solution (for nonporous membrane)]
Ether type polyurethane resin (solid content 30%, water swelling degree 85%) 100 parts Methyl ethyl ketone 30 parts White pigment 8 parts
（評価）
比較例１の防水布帛は、表面に付着した水分がｐＨ７．１を示した。一方、実施例１〜４の防水布帛は、その表面に付着した水分がいずれも弱酸性を示した。これにより、無孔質膜中に両性金属の酸化物および／または二酸化ケイ素の微粒子を含むことで、人の肌に優しい防水布帛が得られることが確認された。特に、二酸化ケイ素を含んだ実施例２はｐＨ６．０を示し、樹脂層が多層構造を有し、酸化アルミニウムの微粒子を含んだ実施例３の防水布帛はｐＨ５．８を示したことから、これらの防水布帛を用いれば、湿潤時に弱酸性となる特に優れた防水布帛が得られることが示唆された。
また、耐水圧においては、各実施例ともに良好であったが、特に、多層構造を有した実施例３の防水布帛は優れた耐水圧を示した。これにより、本発明の防水布帛は優れた防水性を有することが確認され、さらに、高い耐水圧（優れた防水性）を必要とする場合には、樹脂層を多層構造とすることで、特に優れた耐水圧を有した防水布帛を得られることが確認された。
(Evaluation)
In the waterproof fabric of Comparative Example 1, the moisture adhering to the surface showed pH 7.1. On the other hand, as for the waterproof fabric of Examples 1-4, all the water | moisture content adhering to the surface showed weak acidity. Thus, it was confirmed that a waterproof fabric gentle to human skin can be obtained by including amphoteric metal oxide and / or silicon dioxide fine particles in the nonporous film. In particular, since Example 2 containing silicon dioxide showed pH 6.0, the resin layer had a multilayer structure, and the waterproof fabric of Example 3 containing fine particles of aluminum oxide showed pH 5.8. It was suggested that a particularly excellent waterproof fabric that is weakly acidic when wet can be obtained by using the waterproof fabric.
In each example, the water pressure resistance was good. In particular, the waterproof fabric of Example 3 having a multilayer structure showed an excellent water pressure resistance. Thereby, it is confirmed that the waterproof fabric of the present invention has an excellent waterproof property. Further, when a high water pressure resistance (excellent waterproof property) is required, the resin layer has a multilayer structure, It was confirmed that a waterproof fabric having excellent water pressure resistance can be obtained.
Claims (7)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101539034B1 (en) * | 2013-05-16 | 2015-07-30 | 한국생산기술연구원 | Method of Manufacturing the Permeable and Waterproofing Textiles Using Polyurethane Resin and Method of Manufacturing of the Permeable and Waterproofing Gloves |
| JP2016044261A (en) * | 2014-08-25 | 2016-04-04 | ユニチカトレーディング株式会社 | Moisture permeable waterproof membrane and moisture permeable waterproof fabric |
| JP2021030683A (en) * | 2019-08-29 | 2021-03-01 | 王子ホールディングス株式会社 | Synthetic leather manufacturing process Release sheet and synthetic leather manufacturing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101539034B1 (en) * | 2013-05-16 | 2015-07-30 | 한국생산기술연구원 | Method of Manufacturing the Permeable and Waterproofing Textiles Using Polyurethane Resin and Method of Manufacturing of the Permeable and Waterproofing Gloves |
| JP2016044261A (en) * | 2014-08-25 | 2016-04-04 | ユニチカトレーディング株式会社 | Moisture permeable waterproof membrane and moisture permeable waterproof fabric |
| JP2021030683A (en) * | 2019-08-29 | 2021-03-01 | 王子ホールディングス株式会社 | Synthetic leather manufacturing process Release sheet and synthetic leather manufacturing method |
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