JP2001254073A - Water repellency-imparting material - Google Patents
Water repellency-imparting materialInfo
- Publication number
- JP2001254073A JP2001254073A JP2000068791A JP2000068791A JP2001254073A JP 2001254073 A JP2001254073 A JP 2001254073A JP 2000068791 A JP2000068791 A JP 2000068791A JP 2000068791 A JP2000068791 A JP 2000068791A JP 2001254073 A JP2001254073 A JP 2001254073A
- Authority
- JP
- Japan
- Prior art keywords
- water repellency
- water
- imparting
- imparting material
- manufactured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- Application Of Or Painting With Fluid Materials (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、撥水性付与組成
物、該撥水性付与組成物を含む撥水性付与材およびその
製造方法に関する。TECHNICAL FIELD The present invention relates to a water repellency-imparting composition, a water repellency-imparting material containing the water-repellency-imparting composition, and a method for producing the same.
【０００２】[0002]
【従来の技術】これまで、自動車の塗装面上に撥水機能
を与える目的で数々の自動車用撥水剤が市販されてい
る。自動車のワックス掛けによる撥水処理は一般的に作
業性が悪く大きな労力が必要なため、これを改善する提
案がされている。例えば作業性を高めるため、撥水剤を
水と界面活性剤等の乳化剤により液体状にしたものが特
開平１０−２９８６００公報や特開平７−５３９２１公
報に、また、簡便性を高めるため、布帛に複数のシリコ
ーンオイル化合物を撥水剤としてあらかじめ担持して使
用するものが特開平１１−１５２４６２公報に記載され
ている。しかしながら、撥水剤と水を乳化すると乳化剤
による即時撥水性能と耐候性の低下がおこるという問題
があり、また布帛に担持して使用する場合では、撥水剤
が布帛に吸着してしまい、十分な即時撥水性と耐候性を
塗装面に付与出来ないという問題があった。さらに、高
価なシリコーンオイル化合物を多種類かつ多量に使用し
ているため価格が高くなるという問題があった。2. Description of the Related Art A number of automotive water repellents have hitherto been marketed for the purpose of imparting a water repellent function to a painted surface of an automobile. Since water repellency treatment by waxing automobiles generally has poor workability and requires large labor, proposals have been made to improve this. For example, in order to improve workability, a water-repellent agent made into a liquid state with water and an emulsifier such as a surfactant is disclosed in JP-A-10-298600 and JP-A-7-53921. Japanese Patent Application Laid-Open No. H11-152462 discloses a method in which a plurality of silicone oil compounds are previously supported as water repellents and used. However, when the water repellent and water are emulsified, there is a problem that the instant water repellency and the weather resistance are reduced by the emulsifier, and when used by being carried on a fabric, the water repellent is adsorbed on the fabric, There was a problem that sufficient instant water repellency and weather resistance could not be imparted to the painted surface. Further, there is a problem that the price is increased due to the use of a large number and kinds of expensive silicone oil compounds.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記従来の
技術の欠点に鑑み、撥水材に実質的に乳化剤や界面活性
剤を使用することなく、作業性が高く、かつ撥水機能の
高く、担体に担持した場合に、塗装面を拭くことによ
り、水分を吸収し、自動車塗装面に対し効率的に移行
し、即時撥水性と耐候性（特に撥水持続性能とし、以下
撥水持続性と表記する）を車体塗装面に同時に与え、し
かも簡便で安価な撥水性付与組成物、該撥水性付与組成
物を用いた撥水性付与材およびその製造方法を提供する
ことを課題とする。SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, the present invention provides high workability and water repellency without using an emulsifier or a surfactant for the water repellent material. When carried on a carrier, it absorbs moisture by wiping the painted surface when it is carried on a carrier, transfers efficiently to the painted surface of automobiles, and has immediate water repellency and weather resistance (especially water repellency sustainability; The object of the present invention is to provide a simple and inexpensive water-repellent composition, a water-repellent material using the water-repellent composition, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記課題を
解決するために鋭意研究を重ねた結果、アミノ変性シリ
コーンオイルと、安価で入手しやすい炭化水素化合物を
撥水性付与組成物とし、これと親水性不織布を含む撥水
性付与材が、洗車後の水分を吸収すると共に、拭くだけ
で簡便に即時撥水性と撥水持続性を車体塗装面に同時に
与えることを見いだし、この知見に基づいて本発明をな
すに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that an amino-modified silicone oil and an inexpensive and easily available hydrocarbon compound are used as a water-repellent composition, Based on this finding, we found that this and the water repellency-imparting material containing hydrophilic non-woven fabric, while absorbing water after car washing, can simultaneously give water repellency and water repellency to the painted surface simply and simply by wiping. This has led to the present invention.
【０００５】すなわち、本発明の第１は、アミノ変性シ
リコーンオイルと炭化水素化合物を含有することを特徴
とする撥水性付与組成物である。発明の第２は、溶媒を
含むことを特徴とする発明の第１記載の撥水性付与組成
物である。発明の第３は、アミノ変性シリコーンオイル
のアミン当量が３００〜１００００ｇ／ｍｏｌであるこ
とを特徴とする発明の第１又は２記載の撥水性付与組成
物である。That is, a first aspect of the present invention is a water repellency-imparting composition comprising an amino-modified silicone oil and a hydrocarbon compound. A second aspect of the present invention is the water-repellent composition according to the first aspect of the present invention, which comprises a solvent. A third aspect of the present invention is the water-repellent composition according to the first or second aspect of the invention, wherein the amine equivalent of the amino-modified silicone oil is 300 to 10,000 g / mol.
【０００６】発明の第４は、炭化水素化合物の炭素数が
４〜４０であることを特徴とする発明の第１から３いず
れかに記載の撥水性付与組成物である。発明の第５は、
発明の第１から４いずれかに記載の撥水性付与組成物と
親水性布帛を含む撥水性付与材である。発明の第６は、
発明の第１から４いずれかに記載の撥水性付与組成物を
発明の第５記載の親水性布帛に含浸する事を特徴とする
撥水性付与材の製造方法である。A fourth aspect of the present invention is the water repellent composition according to any one of the first to third aspects, wherein the hydrocarbon compound has 4 to 40 carbon atoms. The fifth aspect of the invention is that
A water repellency-imparting material comprising the water repellency-imparting composition according to any one of the first to fourth aspects of the invention and a hydrophilic cloth. The sixth aspect of the invention is as follows.
A method for producing a water repellency-imparting material, characterized by impregnating the water-repellent imparting composition according to any one of the first to fourth aspects of the invention with the hydrophilic cloth according to the fifth aspect of the invention.
【０００７】[0007]
【発明の実施の形態】以下、本願発明について具体的に
説明する。本発明の撥水性付与組成物は主として有機又
は無機繊維、塗料、無機質硬性物質表面に塗布等により
撥水性を付与するために用いることができる。さらに、
本発明の撥水性付与組成物は親水性布帛等の担体と共に
用いて撥水性付与材として用いることもできる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The water repellency-imparting composition of the present invention can be used mainly for imparting water repellency to the surface of organic or inorganic fibers, paints, inorganic hard materials by coating or the like. further,
The water repellency-imparting composition of the present invention can be used as a water repellency-imparting material when used together with a carrier such as a hydrophilic cloth.
【０００８】本発明の撥水性付与組成物においては、撥
水持続性を付与するための撥水剤として、アミノ変性シ
リコーンオイルを含有していることが必須である。本発
明で言うアミノ変性シリコーンオイルとは、オルガノポ
リシロキサンにアミノ基が結合した化合物である。特に
アミン当量が、３００〜１００００ｇ／ｍｏｌのものを
使用することが好ましく、より好ましくは、３００〜５
０００ｇ／ｍｏｌのものである。アミノ変性シリコーン
オイルの動粘度は２５℃で１０〜３０００ｃＳｔ、好ま
しくは１０〜１０００ｃＳｔのものがよい。この様なア
ミノ変性シリコーンオイルの例として、Ｘ−２２−１６
１Ａ、Ｘ−２２−１６１Ｂ（信越化学工業（株）社
製）、ＴＳＦ４７０２、ＴＳＦ４７０３、ＴＳＦ４７０
０、ＴＳＦ４７０１（東芝シリコーン（株）社製）、Ｌ
６５４、Ｌ６５５、Ｌ６５６（旭化成ワッカーシリコー
ン（株）社製）を挙げることが出来る。これらアミノ変
性シリコーンオイルは単独でも２種類以上の混合物とし
ても使用することが出来る。The water repellency-imparting composition of the present invention must contain an amino-modified silicone oil as a water repellent for imparting water repellency. The amino-modified silicone oil referred to in the present invention is a compound in which an amino group is bonded to an organopolysiloxane. In particular, it is preferable to use one having an amine equivalent of 300 to 10000 g / mol, more preferably 300 to 5 g / mol.
000 g / mol. The kinematic viscosity of the amino-modified silicone oil at 25 ° C is 10 to 3000 cSt, preferably 10 to 1000 cSt. Examples of such an amino-modified silicone oil include X-22-16
1A, X-22-161B (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4702, TSF4703, TSF470
0, TSF4701 (manufactured by Toshiba Silicone Co., Ltd.), L
654, L655 and L656 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.). These amino-modified silicone oils can be used alone or as a mixture of two or more.
【０００９】本発明の撥水性付与組成物においては、即
時撥水性を付与するための撥水剤として、炭化水素化合
物を含有していることが必須である。本発明で使用する
炭化水素化合物は、アミノ変性シリコーンオイルと親和
性により吸着することが出来、塗装面上を覆うことによ
り撥水性を与えるものであれば特に限定される物ではな
く、例えばパラフィン系炭化水素、ナフテン系炭化水
素、オレフィン系炭化水素、芳香族炭化水素等が挙げら
れる。これらの中で撥水性付与時の作業性から室温で液
状のものが好ましいことと、低分子量では塗布後すぐに
揮発してしまい十分な撥水効果が出ないことから、炭素
数４〜４０のものを使用することが好ましい。このよう
な炭化水素化合物の例として、オクタン、ノナン、デカ
ン、ドデカン等のパラフィン系炭化水素やデカリン等の
ナフテン系炭化水素、またベンゼンやナフタリン等の芳
香族炭化水素、石油から分離精製されたスピンドル油、
ケロシン油、流動パラフィンが挙げられる。中でも流動
パラフィンは、安全性、安定性、価格面から特に好まし
い。これら炭化水素化合物は単体又は２種類以上の混合
物として使用することが出来る。It is essential that the water repellency-imparting composition of the present invention contains a hydrocarbon compound as a water repellent for imparting immediate water repellency. The hydrocarbon compound used in the present invention is not particularly limited as long as it can be adsorbed with affinity to amino-modified silicone oil and imparts water repellency by covering the painted surface. Examples include hydrocarbons, naphthenic hydrocarbons, olefinic hydrocarbons, and aromatic hydrocarbons. Among them, those which are liquid at room temperature are preferred from the viewpoint of workability at the time of imparting water repellency, and those having a low molecular weight volatilize immediately after coating and do not have a sufficient water repellent effect. Preferably, one is used. Examples of such hydrocarbon compounds include paraffinic hydrocarbons such as octane, nonane, decane and dodecane, naphthenic hydrocarbons such as decalin, aromatic hydrocarbons such as benzene and naphthalene, and spindles separated and refined from petroleum. oil,
Kerosene oil and liquid paraffin. Among them, liquid paraffin is particularly preferable in terms of safety, stability, and price. These hydrocarbon compounds can be used alone or as a mixture of two or more.
【００１０】本発明の撥水性付与組成物は即時撥水性と
撥水持続性のバランスを考慮して、アミノ変性シリコー
ンオイルと炭化水素化合物の混合比が重量比で６：４〜
２：８であることが好ましく、５：５であることが特に
好ましい。本発明の撥水性付与組成物は、均一に撥水性
を塗装面等に付与するため、あるいは均一に担体に担持
するために、溶媒を含むことが好ましい。本発明の撥水
性付与組成物に含まれる溶媒は、疎水性及び／又は揮発
性で、かつ撥水性付与組成物中のアミノ変性シリコーン
オイル及び炭化水素化合物と相溶するものが好ましく、
これら溶媒は単品としても２種類以上の混合物としても
使用することが出来る。溶媒を含む撥水性付与組成物を
塗装面等に付与後、あるいは担体に担持後、溶媒を乾燥
により除去する場合、乾燥工程で、沸点の低いものの方
が揮発しやすく、価格面で有利であるため、低沸点のア
ルコール溶媒や炭化水素溶媒を使用することが好まし
い。The composition for imparting water repellency of the present invention has a mixing ratio of the amino-modified silicone oil to the hydrocarbon compound of 6: 4 by weight in consideration of the balance between immediate water repellency and water repellency.
The ratio is preferably 2: 8, and particularly preferably 5: 5. The water repellency-imparting composition of the present invention preferably contains a solvent in order to uniformly impart water repellency to a painted surface or the like or to uniformly support the carrier. The solvent contained in the water repellency-imparting composition of the present invention is preferably hydrophobic and / or volatile and compatible with the amino-modified silicone oil and the hydrocarbon compound in the water-repellency-imparting composition,
These solvents can be used either individually or as a mixture of two or more. After applying the water repellency-imparting composition containing a solvent to a painted surface or the like, or after being carried on a carrier, when the solvent is removed by drying, those having a lower boiling point are more likely to volatilize in the drying step, which is advantageous in terms of price. Therefore, it is preferable to use a low-boiling alcohol solvent or hydrocarbon solvent.
【００１１】本発明で使用する親水性布帛とは、水に対
する親和性が高く吸水性に優れるものであれば特に限定
されるものではないが、例えばセルロース繊維である
綿、綿リンター、パルプ、ビスコース法レーヨン、銅ア
ンモニア法レーヨン及びそれらを改質した繊維を使用し
た布帛を挙げることが出来る。これらの繊維は単体又は
混合物として使用することが出来る。親水性布帛と本発
明の撥水性付与組成物を含む本発明の撥水性付与材は、
水分の吸収能力が高いため洗車後の水分を吸い取ること
が出来るという性質と共に、親水性の布帛が疎水性の撥
水剤を該撥水性付与材から塗装面に積極的に移行させる
事が出来、優れた撥水性を効率的に塗装面等に付与する
ことが出来る。親水性布帛は、例えばポリエチレン、ポ
リプロピレン、ポリエステル、アクリル、ナイロン繊維
等の疎水性繊維を混紡したものも使用することができる
が、撥水性付与組成物が疎水性繊維に吸着すると撥水性
付与材としての性能低下が起こるため、疎水性繊維の混
紡量は５０重量％以下、さらに４０重量％以下であるこ
とが好ましい。また、親水性布帛の目付量は薄すぎると
水の吸収能が低下すると共に、担持出来る撥水性付与組
成物量も減るため、１５〜１２０ｇ／ｍ2 で使用するこ
とが好ましい。The hydrophilic fabric used in the present invention is not particularly limited as long as it has a high affinity for water and is excellent in water absorption. Examples thereof include cellulose fibers such as cotton, cotton linter, pulp, and bis. Coarse rayon, cuprammonium rayon and fabrics using modified fibers thereof can be mentioned. These fibers can be used alone or as a mixture. The water repellency-imparting material of the present invention containing the hydrophilic fabric and the water-repellent imparting composition of the present invention is:
Along with the property of being able to absorb water after car washing because of its high water absorption capacity, the hydrophilic fabric can positively transfer the hydrophobic water repellent from the water repellency-imparting material to the painted surface, Excellent water repellency can be efficiently imparted to painted surfaces and the like. As the hydrophilic cloth, for example, polyethylene, polypropylene, polyester, acrylic, and a mixture of hydrophobic fibers such as nylon fibers can be used. However, when the water repellency-imparting composition is adsorbed on the hydrophobic fibers, the hydrophilic fabric is used as a water-repellency-imparting material. Therefore, the blended amount of the hydrophobic fiber is preferably 50% by weight or less, more preferably 40% by weight or less. If the basis weight of the hydrophilic fabric is too small, the water absorption capacity is reduced and the amount of the water repellency-imparting composition that can be supported is also reduced. Therefore, it is preferable to use the hydrophilic fabric at 15 to 120 g / m 2 .
【００１２】親水性布帛の中でも特に親水性不織布を使
用することが、寸法や目付量等の製造安定性が高いこ
と、コストの面で優れることから好ましい。この様な親
水性布帛の例として、 綿布、亜麻、***、ラミー、マ
ニラ麻、羊毛、山羊毛、家蚕絹、野蚕絹、Ｃ７０５０
Ｋ、ＪＦ６０１、ＧＮ２５２、ＲＰ７０９（旭化成工業
（株）社製不織布）、ＬＩ−６０（大和紡績（株）社製
不織布）、ＣＯ４０Ｎ／Ａ０２（ユニチカ（株）社製不
織布）、が挙げられる。[0012] Among the hydrophilic fabrics, it is particularly preferable to use a hydrophilic nonwoven fabric because the production stability such as dimensions and basis weight is high and the cost is excellent. Examples of such hydrophilic fabrics include cotton cloth, flax, hemp, ramie, Manila hemp, wool, goat wool, silkworm silk, wild silkworm silk, C7050
K, JF601, GN252, RP709 (non-woven fabric manufactured by Asahi Kasei Corporation), LI-60 (non-woven fabric manufactured by Daiwa Spinning Co., Ltd.), CO40N / A02 (non-woven fabric manufactured by Unitika Ltd.).
【００１３】本発明の撥水性付与材は、撥水性付与組成
物を親水性布帛に含浸して製造される。含浸方法として
は一般的に使用されている、ディップコート法、キッシ
ングコート法、グラビヤコート法、バーコート法、ワイ
ヤーバーコート法、ロールコート法、ナイフコート法等
で含浸する事が出来る。溶媒の揮発方法としては一般的
には乾燥機を使用し、例えば横型塗布乾燥機や縦型乾燥
機、ドライヤー型乾燥機等を使用することが出来る。The water repellency-imparting material of the present invention is produced by impregnating a water-repellent composition with a hydrophilic cloth. As the impregnation method, dip coating, kissing coating, gravure coating, bar coating, wire bar coating, roll coating, knife coating and the like can be used. As a method for evaporating the solvent, a drier is generally used, and for example, a horizontal coating drier, a vertical drier, a dryer drier, or the like can be used.
【００１４】撥水性付与材中のアミノ変性シリコーンオ
イルおよび炭化水素化合物が布帛重量に対して少なすぎ
ると、撥水効果を発揮するほど撥水性付与組成物を塗装
面に付与することが出来ず、また塗装面を覆う膜形成量
以上では、過剰のためコスト高になるので、撥水性付与
材中のアミノ変性シリコーンオイルと炭化水素化合物の
総量が、布帛重量に対して０．５〜５０重量％含浸され
ていることが好ましく、１〜１０重量％含浸されている
ことが特に好ましい。本発明の撥水性付与材は乾いた塗
装面であっても拭き上げることにより、撥水性を与える
ことが出来るため、自動車の塗装面の他に家具やテキス
タイル、タイル等の撥水性付与材として使用することが
出来る。If the amino-modified silicone oil and the hydrocarbon compound in the water repellency-imparting material are too small relative to the weight of the fabric, the water-repellency-imparting composition cannot be applied to the coated surface so as to exert a water-repellent effect. In addition, if the amount of film forming the coating surface is greater than the amount, the total cost of the amino-modified silicone oil and the hydrocarbon compound in the water repellency-imparting material is 0.5 to 50% by weight based on the weight of the fabric. It is preferably impregnated, particularly preferably 1 to 10% by weight. Since the water repellency-imparting material of the present invention can impart water repellency by wiping even a dry painted surface, it is used as a water repellency-imparting material for furniture, textiles, tiles, etc. in addition to painted surfaces of automobiles. You can do it.
【００１５】[0015]
【発明の実施の態様】以下に、本発明の実施例を詳細に
説明する、また例中の「％」は「重量％」を示す。ま
た、実施例中で行う撥水性付与材の評価方法は以下の通
りである。 ＜撥水持続性評価方法＞カチオン電着塗装片面メラミン
焼き付け塗装板（ＪＩＳ Ｇ３１４１（ＳＰｃｃ Ｓ
Ｄ）６ｍｍ×５０ｍｍ×１５０ｍｍ 初期接触角；７３
〜７７°）を試験片とし、表面を５ｍｌ容のピペットマ
ンを使用し、水（約１０ｍｌ）で濡らしたものを撥水性
付与材（１２０ｍｍ×１２０ｍｍ）で１０往復拭き、撥
水剤を付与する。この時、撥水性付与材の水の吸収性を
目視観察し、以下の基準で判定する。直ちに、この試験
片の接触角（°）を接触角計（ＣＡ−Ｄ型、協和界面化
学（株）製、測定条件；室温）にて測定し、即時撥水性
とする。撥水剤を付与した試験片を約１２時間放置し、
同様の方法で接触角を測定し、経時後撥水性とする。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples of the present invention will be described in detail. In the examples, “%” indicates “% by weight”. The method for evaluating the water repellency-imparting material performed in the examples is as follows. <Method for evaluating water repellency persistence> Cathodic electrodeposition coated single-sided melamine baked coated plate (JIS G3141 (SPcc S
D) 6 mm x 50 mm x 150 mm Initial contact angle; 73
７７77 °) as a test piece, the surface of which was wetted with water (about 10 ml) was wiped 10 times with a water repellency-imparting material (120 mm × 120 mm) using a 5 ml pipetteman, and a water repellent was applied. At this time, the water absorbency of the water repellency-imparting material is visually observed and determined based on the following criteria. Immediately, the contact angle (°) of the test piece is measured with a contact angle meter (CA-D type, manufactured by Kyowa Interface Chemical Co., Ltd., measurement conditions: room temperature), and the water repellency is determined immediately. The test piece provided with the water repellent was left for about 12 hours,
The contact angle is measured in the same manner, and the water repellency is determined after a lapse of time.
【００１６】この試験片にラボラトリーウォッシャー
（モデル−ＡＷ−６２ ヤマト化学（株））を使用して
１０分間シャワーをあてる。試験片が乾燥した後、接触
角を測定する。接触角測定後すぐに、同一の試料にてこ
の操作を４回繰り返し、その都度接触角を測定し、撥水
持続性を調べる。評価基準は以下の通りである。 ・水の吸収性：拭いた直後の水滴の残量を目視で判定。 ○ 塗装面上に水滴が事実上残らない。 △ 塗装面上に微かに水滴が残る。 × 水が吸収されず塗装面上に水滴が残る。 ・撥水性 ○ 接触角が９３°以上 △ 接触角が９０°以上９３°未満 × 接触角が９０°未満The test piece is showered for 10 minutes using a laboratory washer (Model-AW-62 Yamato Chemical Co., Ltd.). After the specimen has dried, the contact angle is measured. Immediately after the measurement of the contact angle, this operation is repeated four times with the same sample. Each time, the contact angle is measured to check the water repellency persistence. The evaluation criteria are as follows. -Water absorbency: The remaining amount of water droplets immediately after wiping is visually determined. ○ Virtually no water droplets remain on painted surfaces. △ Water droplets are slightly left on the painted surface. × Water is not absorbed and water droplets remain on the painted surface.・ Water repellency ○ Contact angle is 93 ° or more △ Contact angle is 90 ° or more and less than 93 ° × Contact angle is less than 90 °
【００１７】[0017]
【実施例１】アミノ変性シリコーンオイル（商品名：Ｘ
２２−１６１Ａ アミン当量８４０動粘度２９ｃＳｔ
信越化学工業（株）社製）１．０ｇとドデカン（和光純
薬工業（株）社製）１．０ｇをイソプロピルアルコール
（和光純薬工業（株）社製）９８．０ｇに溶解して均一
で透明な溶液とし、これを親水性不織布（商品名：ＧＮ
２５２ コットンリンター１００％ 目付２５ｇ／ｍ2
旭化成工業（株）社製）に不織布重量の２倍量含浸さ
せ、その後イソプロピルアルコールを揮発させ、本発明
の撥水性付与材を得た（表１）。得られた撥水性付与材
を用いて撥水持続性評価方法に従い評価を行った。評価
結果を表３に示す。Example 1 Amino-modified silicone oil (trade name: X
22-161A Amine equivalent 840 Kinematic viscosity 29 cSt
Dissolve 1.0 g of Dodecane (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of dodecane in 98.0 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and uniformly dissolve them. And a transparent solution, which is made of a hydrophilic nonwoven fabric (trade name: GN
252 100% Cotton Linter 25g / m 2
Asahi Kasei Kogyo Co., Ltd.) was impregnated with twice the weight of the nonwoven fabric, and then isopropyl alcohol was volatilized to obtain the water repellency-imparting material of the present invention (Table 1). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００１８】[0018]
【実施例２】アミノ変性シリコーンオイル（商品名：Ｌ
６５６ アミン当量８００ 動粘度２５ｃＳｔ 旭化成
ワッカーシリコーン（株）社製）１．０ｇとドデカン
１．０ｇ（和光純薬工業（株）社製）をノルマルヘキサ
ン（和光純薬工業（株）社製）９８．０ｇに溶解し、こ
れを親水性不織布（商品名：Ｃ７０５０Ｋ コットンリ
ンター７０％ アクリル繊維３０％ 目付５０ｇ／ｍ2
旭化成工業（株）社製）に不織布重量の２倍量含浸さ
せ、その後ノルマルヘキサンを揮発させ、本発明の撥水
性付与材を得た（表１）。得られた撥水性付与材を用い
て撥水持続性評価方法に従い評価を行った。評価結果を
表３に示す。Example 2 Amino-modified silicone oil (trade name: L
656 Amine equivalent 800 Kinematic viscosity 25 cSt 1.0 g of dodecane (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of dodecane (manufactured by Wako Pure Chemical Industries, Ltd.) 98 were dissolved in normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.) 98 2.0 g, and then dissolved in a hydrophilic non-woven fabric (trade name: C7050K, cotton linter 70%, acrylic fiber 30%, basis weight 50 g / m 2).
Asahi Kasei Kogyo Co., Ltd.) was impregnated with twice the weight of the nonwoven fabric, and then normal hexane was volatilized to obtain the water repellency-imparting material of the present invention (Table 1). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００１９】[0019]
【実施例３】アミノ変性シリコーンオイル（商品名：Ｔ
ＳＦ４７０１ アミン当量２５００動粘度４５ｃＳｔ
東芝シリコーン（株）社製）１．０ｇと流動パラフィン
（和光純薬工業（株）社製）１．０ｇをイソプロピルア
ルコール（和光純薬工業（株）社製）９８．０ｇに溶解
し、これを親水性不織布（商品名：ＲＰ７０９ コット
ンリンター７８％ ポリプロピレン繊維２２％ 目付７
０ｇ／ｍ2 旭化成工業（株）社製）に不織布重量の２倍
量含浸させ、その後イソプロピルアルコールを揮発さ
せ、本発明の撥水性付与材を得た（表１）。得られた撥
水性付与材を用いて撥水持続性評価方法に従い評価を行
った。評価結果を表３に示す。Example 3 Amino-modified silicone oil (trade name: T
SF4701 amine equivalent 2500 kinematic viscosity 45cSt
1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of liquid paraffin are dissolved in 98.0 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.). Is a hydrophilic non-woven fabric (trade name: RP709, cotton linter 78%, polypropylene fiber 22%, basis weight 7)
0 g / m 2 (manufactured by Asahi Kasei Corporation) was impregnated with twice the weight of the nonwoven fabric, and then isopropyl alcohol was volatilized to obtain the water repellency-imparting material of the present invention (Table 1). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２０】[0020]
【実施例４】アミノ変性シリコーンオイル（商品名：Ｌ
６５６）１．０ｇと流動パラフィン（和光純薬工業
（株）社製）１．０ｇをイソプロピルアルコール（和光
純薬工業（株）社製）９８．０ｇに溶解し、これを親水
性不織布（商品名：ＬＩ−６０レーヨン繊維７０％ ポ
リプロピレン繊維３０％ 目付６０ｇ／ｍ2 大和紡績
（株）社製）に不織布重量の２倍量含浸させ、その後イ
ソプロピルアルコールを揮発させ、本発明の撥水性付与
材を得た（表１）。得られた撥水性付与材を用いて撥水
持続性評価方法に従い評価を行った。評価結果を表３に
示す。Example 4 Amino-modified silicone oil (trade name: L
656) and 1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 98.0 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and this is dissolved in a hydrophilic nonwoven fabric (product). Name: LI-60 rayon fiber 70%, polypropylene fiber 30%, basis weight 60 g / m 2 (manufactured by Daiwa Spinning Co., Ltd.) is impregnated with twice the weight of the nonwoven fabric, and then isopropyl alcohol is volatilized to give the water repellency-imparting material of the present invention. (Table 1). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２１】[0021]
【実施例５】アミノ変性シリコーンオイル（商品名：Ｌ
６５６）１．０ｇと流動パラフィン（和光純薬工業
（株）社製）１．０ｇをイソプロピルアルコール（和光
純薬工業（株）社製）９８．０ｇに溶解し、これを親水
性不織布（商品名：ＣＯ４０Ｎ／Ａ０２ コットン繊維
５０％ ポリエステル繊維２５％ ナイロン繊維２５％
目付４０ｇ／ｍ2 ユニチカ（株）社製）に不織布重量
の２倍量含浸させ、その後イソプロピルアルコールを揮
発させ、本発明の撥水性付与材を得た（表１）。得られ
た撥水性付与材を用いて撥水持続性評価方法に従い評価
を行った。評価結果を表３に示す。Example 5 Amino-modified silicone oil (trade name: L
656) and 1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 98.0 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and this is dissolved in a hydrophilic nonwoven fabric (product). Name: CO40N / A02 Cotton fiber 50% Polyester fiber 25% Nylon fiber 25%
Basis weight 40 g / m 2 by Unitika Co., Ltd.) was impregnated twice the amount of the nonwoven weight, then isopropyl alcohol was volatilized to obtain a water repellency imparting agent of the present invention (Table 1). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２２】[0022]
【実施例６】アミノ変性シリコーンオイル（商品名：Ｌ
６５６）１．０ｇと流動パラフィン（和光純薬工業
（株）社製）１．０ｇをイソプロピルアルコール（和光
純薬工業（株）社製）９８．０ｇに溶解し、これを綿布
（綿１００％ 目付１４４ｇ／ｍ 2）に不織布重量の２
倍量含浸させ、その後イソプロピルアルコールを揮発さ
せ、本発明の撥水性付与材を得た（表１）。得られた撥
水性付与材を用いて撥水持続性評価方法に従い評価を行
った。評価結果を表３に示す。Example 6 Amino-modified silicone oil (trade name: L
656) 1.0 g with liquid paraffin (Wako Pure Chemical Industries, Ltd.)
1.0 g of isopropyl alcohol (Wako)
Dissolved in 98.0 g of a cotton cloth.
(100% cotton, basis weight 144g / m Two2) Non-woven fabric weight 2
Twice the volume, then volatilize the isopropyl alcohol.
Thus, a water repellency-imparting material of the present invention was obtained (Table 1). Obtained repellency
The water-repellent material was evaluated according to the water repellency durability evaluation method
Was. Table 3 shows the evaluation results.
【００２３】[0023]
【比較例１】アミノ変性シリコーンオイル（商品名：Ｌ
６５６）１．０ｇをイソプロピルアルコール（和光純薬
工業（株）社製）９９．０ｇに溶解し、これを親水性不
織布（商品名：ＧＮ２５２）に不織布重量の２倍量含浸
させ、その後イソプロピルアルコールを揮発させ、撥水
性付与材を得た（表２）。得られた撥水性付与材を用い
て撥水持続性評価方法に従い評価を行った。評価結果を
表３に示す。Comparative Example 1 Amino-modified silicone oil (trade name: L
656) 1.0 g was dissolved in 99.0 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and this was impregnated into a hydrophilic nonwoven fabric (trade name: GN252) twice as much as the weight of the nonwoven fabric, and then isopropyl alcohol was dissolved. Was volatilized to obtain a water repellency-imparting material (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２４】[0024]
【比較例２】シリコーンオイル（商品名：ＴＳＦ４５１
−１００ 動粘度１００ｃＳｔ 東芝シリコーン（株）
社製）１．０ｇと流動パラフィン（和光純薬工業（株）
社製）１．０ｇをノルマルヘキサン（和光純薬工業
（株）社製）９８．０ｇに溶解し、これを親水性不織布
（商品名：ＧＮ２５２）に不織布重量の２倍量含浸さ
せ、その後ノルマルヘキサンを揮発させ、撥水性付与材
を得た（表２）。得られた撥水性付与材を用いて撥水持
続性評価方法に従い評価を行った。評価結果を表３に示
す。[Comparative Example 2] Silicone oil (trade name: TSF451)
-100 Kinematic viscosity 100cSt Toshiba Silicone Co., Ltd.
1.0g and liquid paraffin (Wako Pure Chemical Industries, Ltd.)
1.0 g was dissolved in 98.0 g of normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and this was impregnated into a hydrophilic nonwoven fabric (trade name: GN252) in an amount twice the weight of the nonwoven fabric. Hexane was volatilized to obtain a water repellent material (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２５】[0025]
【比較例３】シリコーンオイル（商品名：ＴＳＦ４５１
−１００）１．０ｇとドデカン（和光純薬工業（株）社
製）１．０ｇとデカグリセリンモノラウレート（商品
名：Ｄｅｃａｇｌｙｎ １−Ｌ ＨＬＢ：１５．５ 日
光ケミカルズ（株）社製）１．０ｇをノルマルヘキサン
（和光純薬工業（株）社製）９７．０ｇに溶解し、これ
を親水性不織布（商品名：ＧＮ２５２）に不織布重量の
２倍量含浸させ、その後ノルマルヘキサンを揮発させ、
撥水性付与材を得た（表２）。得られた撥水性付与材を
用いて撥水持続性評価方法に従い評価を行った。評価結
果を表３に示す。Comparative Example 3 Silicone oil (trade name: TSF451)
-100) 1.0 g and dodecane (manufactured by Wako Pure Chemical Industries, Ltd.) 1.0 g and decaglycerin monolaurate (trade name: Decaglyn 1-L HLB: 15.5 manufactured by Nikko Chemicals Co., Ltd.) 1 Was dissolved in 97.0 g of normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and this was impregnated into a hydrophilic nonwoven fabric (trade name: GN252) twice as much as the weight of the nonwoven fabric, and then normal hexane was volatilized. ,
Water repellency-imparting materials were obtained (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２６】[0026]
【比較例４】シリコーンオイル（商品名：ＴＳＦ４５１
−１００）１．０ｇと流動パラフィン（和光純薬工業
（株）社製）１．０ｇとソルビタンセスキオレエート
（商品名：ＳＯ−１５ ＨＬＢ３．７ 日光ケミカルズ
（株）社製）１．０ｇをノルマルヘキサン（和光純薬工
業（株）社製）９７．０ｇに溶解し、これを不織布（商
品名：Ｃ１０４０ アクリル繊維９０％ ポリエステル
繊維１０％ 目付４０ｇ／ｍ2 旭化成工業（株）社製）
に不織布重量の２倍量含浸させ、その後ノルマルヘキサ
ンを揮発させ、撥水性付与材を得た（表２）。得られた
撥水性付与材を用いて撥水持続性評価方法に従い評価を
行った。評価結果を表３に示す。[Comparative Example 4] Silicone oil (trade name: TSF451)
-100), 1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of sorbitan sesquioleate (trade name: SO-15 HLB 3.7, manufactured by Nikko Chemicals Co., Ltd.) Normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 97.0 g, and this is nonwoven fabric (trade name: C1040, acrylic fiber 90%, polyester fiber 10%, basis weight 40 g / m 2 manufactured by Asahi Kasei Corporation)
Was impregnated with twice the weight of the nonwoven fabric, and then normal hexane was volatilized to obtain a water repellent material (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２７】[0027]
【比較例５】シリコーンレジンとジメチルシロキサンの
４０％水溶性エマルション溶液（商品名：Ｒ２７０１
動粘度２０００ｃＳｔ 旭化成ワッカーシリコーン
（株）社製）２．５ｇをイソプロピルアルコール（和光
純薬工業（株）社製）９７．５ｇに溶解し、これを不織
布（商品名：Ｃ１０４０ アクリル繊維９０％ ポリエ
ステル繊維１０％ 目付４０ｇ／ｍ2 旭化成工業（株）
社製）に不織布重量の２倍量含浸させ、その後イソプロ
ピルアルコールを揮発させ、撥水性付与材を得た（表
２）。得られた撥水性付与材を用いて撥水持続性評価方
法に従い評価を行った。評価結果を表３に示す。Comparative Example 5 A 40% aqueous emulsion solution of silicone resin and dimethylsiloxane (trade name: R2701)
Kinematic viscosity: 2000 cSt 2.5 g of Asahi Kasei Wacker Silicone Co., Ltd.) was dissolved in 97.5 g of isopropyl alcohol (Wako Pure Chemical Industries, Ltd.), and this was dissolved in a nonwoven fabric (trade name: C1040 acrylic fiber 90% polyester fiber) 10% basis weight 40 g / m 2 Asahi Kasei Industry Co., Ltd.
Was impregnated with twice the weight of the nonwoven fabric, and then isopropyl alcohol was volatilized to obtain a water repellent material (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２８】[0028]
【比較例６】アミノ変性シリコーンオイル（商品名：Ｌ
６５６）１．０ｇと流動パラフィン（和光純薬工業
（株）社製）１．０ｇとソルビタンセスキオレエート
（商品名：ＳＯ−１５ ＨＬＢ３．７ 日光ケミカルズ
（株）社製）１．０ｇをイソプロピルアルコール（和光
純薬工業（株）社製）９７．０ｇに溶解し、これを親水
性不織布（商品名：ＣＯ４０Ｎ／Ａ０２）に不織布重量
の２倍量含浸させ、その後イソプロピルアルコールを揮
発させ、撥水性付与材を得た（表２）。得られた撥水性
付与材を用いて撥水持続性評価方法に従い評価を行っ
た。評価結果を表３に示す。Comparative Example 6 Amino-modified silicone oil (trade name: L
656), 1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of sorbitan sesquioleate (trade name: SO-15 HLB 3.7, manufactured by Nikko Chemicals Co., Ltd.) This was dissolved in 97.0 g of alcohol (manufactured by Wako Pure Chemical Industries, Ltd.), and impregnated with a hydrophilic nonwoven fabric (trade name: CO40N / A02) in an amount twice the weight of the nonwoven fabric. Water-based materials were obtained (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００２９】[0029]
【比較例７】アミノ変性シリコーンオイル（商品名：Ｌ
６５４ アミン当量３５００ 動粘度１３０ｃＳｔ 旭
化成ワッカーシリコーン（株）社製）１．０ｇと流動パ
ラフィン（和光純薬工業（株）社製）１．０ｇとジオク
チルメチルアンモニウムクロライド（商品名：ＣＡ−３
０８０ 日光ケミカルズ（株）社製）１．０ｇをイソプ
ロピルアルコール（和光純薬工業（株）社製）９７．０
ｇに溶解し、これを親水性不織布（商品名：ＣＯ４０Ｎ
／Ａ０２）に不織布重量の２倍量含浸させ、その後イソ
プロピルアルコールを揮発させ、撥水性付与材を得た
（表２）。得られた撥水性付与材を用いて撥水持続性評
価方法に従い評価を行った。評価結果を表３に示す。Comparative Example 7 Amino-modified silicone oil (trade name: L
654 Amine equivalent 3500 Kinematic viscosity 130 cSt 1.0 g of Asahi Kasei Wacker Silicone Co., Ltd., 1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.), and dioctylmethylammonium chloride (trade name: CA-3)
080 Nikko Chemicals Co., Ltd. (1.0 g) is isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) 97.0
g of a hydrophilic nonwoven fabric (trade name: CO40N)
/ A02) was impregnated with twice the weight of the nonwoven fabric, and then isopropyl alcohol was volatilized to obtain a water repellency-imparting material (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００３０】[0030]
【比較例８】アミノ変性シリコーンオイル（商品名：Ｌ
６５６）１．０ｇと流動パラフィン（和光純薬工業
（株）社製）１．０ｇをノルマルヘキサン（和光純薬工
業（株）社製）９８．０ｇに溶解し、これを不織布（商
品名：Ｅ３０４０ ポリエステル１００％ 目付４０ｇ
／ｍ2 旭化成工業（株）社製）に不織布重量の２倍量
含浸させ、その後ノルマルヘキサンを揮発させ、撥水性
付与材を得た（表２）。得られた撥水性付与材を用いて
撥水持続性評価方法に従い評価を行った。評価結果を表
３に示す。Comparative Example 8 Amino-modified silicone oil (trade name: L
656) and 1.0 g of liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 98.0 g of normal hexane (manufactured by Wako Pure Chemical Industries, Ltd.), and this is dissolved in a nonwoven fabric (trade name: E3040 100% polyester 40g weight
/ M 2 (manufactured by Asahi Chemical Industry Co., Ltd.) was impregnated with twice the weight of the nonwoven fabric, and then normal hexane was volatilized to obtain a water repellency-imparting material (Table 2). Using the obtained water repellency-imparting material, evaluation was performed according to the method for evaluating water repellency persistence. Table 3 shows the evaluation results.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【発明の効果】本発明の、撥水性付与組成物と親水性不
織布を含んだ撥水性付与材により、自動車塗装面に対し
て洗車後の水を吸収すると同時に、即時撥水性と撥水持
続性を付与することが出来る。According to the present invention, the water repellency-imparting material containing the water repellency-imparting composition and the hydrophilic nonwoven fabric absorbs water after car washing on the painted surface of the automobile, and at the same time, has immediate water repellency and water repellency persistence. Can be given.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｂ０５Ｄ 5/00 Ｂ０５Ｄ 5/00 Ｚ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // B05D 5/00 B05D 5/00 Z
Claims (6)
化合物を含有することを特徴とする撥水性付与組成物。1. A water-repellent composition containing an amino-modified silicone oil and a hydrocarbon compound.
載の撥水性付与組成物。2. The water repellent composition according to claim 1, further comprising a solvent.
量が３００〜１００００ｇ／ｍｏｌであることを特徴と
する請求項１又は２記載の撥水性付与組成物。3. The water-repellent composition according to claim 1, wherein the amino-modified silicone oil has an amine equivalent of 300 to 10,000 g / mol.
ることを特徴とする請求項１から３いずれかに記載の撥
水性付与組成物。4. The water repellent composition according to claim 1, wherein the hydrocarbon compound has 4 to 40 carbon atoms.
付与組成物と親水性布帛を含む撥水性付与材。5. A water repellency-imparting material comprising the water repellency-imparting composition according to claim 1 and a hydrophilic cloth.
付与組成物を請求項５記載の親水性布帛に含浸する事を
特徴とする撥水性付与材の製造方法。6. A method for producing a water repellency-imparting material, comprising impregnating the hydrophilic fabric according to claim 5 with the water-repellency-imparting composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000068791A JP2001254073A (en) | 2000-03-13 | 2000-03-13 | Water repellency-imparting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000068791A JP2001254073A (en) | 2000-03-13 | 2000-03-13 | Water repellency-imparting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001254073A true JP2001254073A (en) | 2001-09-18 |
Family
ID=18587796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000068791A Pending JP2001254073A (en) | 2000-03-13 | 2000-03-13 | Water repellency-imparting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001254073A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005218980A (en) * | 2004-02-06 | 2005-08-18 | Car Mate Mfg Co Ltd | Method for applying coating composition, and body with coating composition impregnated thereinto |
| JP2017186703A (en) * | 2016-04-07 | 2017-10-12 | 明成化学工業株式会社 | Composition for fiber treatment and fiber product treated with the composition |
-
2000
- 2000-03-13 JP JP2000068791A patent/JP2001254073A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005218980A (en) * | 2004-02-06 | 2005-08-18 | Car Mate Mfg Co Ltd | Method for applying coating composition, and body with coating composition impregnated thereinto |
| JP2017186703A (en) * | 2016-04-07 | 2017-10-12 | 明成化学工業株式会社 | Composition for fiber treatment and fiber product treated with the composition |
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