JP2006002285A - Water repellent for textile product - Google Patents
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本発明は、繊維製品の表面に噴霧して、繊維製品に撥水性を与えるための繊維製品用撥水剤に関するものである。 The present invention relates to a water repellent for a textile product for spraying the surface of the textile product to impart water repellency to the textile product.
従来より、繊維製品用撥水剤として、シリコーン系樹脂やフッ素系樹脂等が用いられている。具体的には、シリコーン系樹脂等を含有する液体を、スプレー等の手段で繊維製品表面に噴霧し、シリコーン系樹脂皮膜等を形成することによって、繊維製品に撥水性を与えることが行われている。現在、このような撥水剤は広く用いられている。 Conventionally, silicone resins, fluorine resins, and the like have been used as water repellents for textile products. Specifically, a liquid containing a silicone resin or the like is sprayed on the surface of the fiber product by means such as spraying to form a silicone resin film or the like, thereby imparting water repellency to the fiber product. Yes. Currently, such water repellents are widely used.
一方、繊維製品用ではなく、自動車等のミラー用の撥水剤として、一次平均粒径が１０ｎｍ未満の疎水性シリカ微粒子と、シランカップリング剤と、酸と、溶剤と、望ましくは樹脂とを含有するものが知られている（特許文献１）。しかしながら、このような撥水剤は、シランカップリング剤，酸，樹脂等を使用しているため、繊維製品用としては使用することができない。なぜなら、シランカップリング剤，酸，樹脂等は、繊維と反応する恐れや、繊維に半永久的に付着する恐れがあり、繊維製品を変質させる恐れがあるからである。 On the other hand, as a water repellent agent for mirrors of automobiles and the like, not for textiles, hydrophobic silica fine particles having a primary average particle size of less than 10 nm, a silane coupling agent, an acid, a solvent, and preferably a resin. What is contained is known (patent document 1). However, since such a water repellent agent uses a silane coupling agent, acid, resin, etc., it cannot be used for textile products. This is because silane coupling agents, acids, resins, and the like may react with the fibers, may adhere to the fibers semi-permanently, and may change the quality of the fiber product.
本発明者は、上記のような技術状況下において、疎水性シリカ微粒子のみによって、繊維製品に撥水性を与えられないかを検討した。しかしながら、繊維製品に疎水性シリカ微粒子のみを付着させようとしても、その微粒子のみでは、繊維表面を被覆しにくく、繊維製品に撥水性は与えられないと考えられた。また、繊維表面を覆い尽くすほど、大量に疎水性シリカ微粒子を付着させると、繊維製品表面が白化し、使用できないと考えられた。すなわち、疎水性シリカ微粒子のみでは、繊維製品に十分な撥水性（従来の撥水剤と同等の撥水性）を付与することができないか、又は繊維製品表面が白化するため、使用することができないと考えられた。 The present inventor examined whether water repellent property could be imparted to a textile product only by hydrophobic silica fine particles under the above technical situation. However, even if only the hydrophobic silica fine particles are allowed to adhere to the fiber product, it is considered that the fiber surface is difficult to cover with only the fine particles, and the water repellent property is not given to the fiber product. Further, it was thought that the surface of the fiber product was whitened and could not be used if the hydrophobic silica fine particles were adhered in a large amount so as to cover the fiber surface. That is, the hydrophobic silica fine particles alone cannot provide sufficient water repellency (water repellency equivalent to that of conventional water repellents) to the fiber product, or the fiber product surface is whitened and cannot be used. It was considered.
それでもなお、本発明者は研究を続けていたところ、驚くべきことに、特定の分散剤を用いて疎水性シリカ微粒子を分散させておき、これを繊維製品表面に付与した後、直ちにこの特定の分散剤を揮発させると、繊維製品表面を白化させることがなく、しかも、従来の撥水剤と同等か又はそれ以上の撥水性を与えられることが判明した。本発明は、このような知見に基づいてなされたものである。 Nevertheless, as the present inventors continued research, surprisingly, after the hydrophobic silica fine particles were dispersed using a specific dispersant and applied to the fiber product surface, the specific product was immediately used. It has been found that when the dispersant is volatilized, the surface of the textile product is not whitened, and water repellency equivalent to or higher than that of a conventional water repellent can be provided. The present invention has been made based on such knowledge.
すなわち、本発明は、実質的に、（ａ）疎水性シリカ微粒子と、（ｂ）該疎水性シリカ微粒子を均一に分散させるためのビニルトリメトキシシラン等の常温揮発性分散剤と、（ｃ）該疎水性シリカ微粒子を分散させるためのイソプロパノール等の分散媒体とからなる繊維製品用撥水剤に関するものである。なお、本発明において、繊維製品とは繊維からなる製品の全てを含むものであって、編織物や不織布はもとより、これを構成している糸及び単繊維をも含み、編織物や不織布等を用いた衣料、カーテンや絨毯、傘等の最終製品をも含むものである。 That is, the present invention substantially includes (a) hydrophobic silica fine particles, (b) a room temperature volatile dispersant such as vinyltrimethoxysilane for uniformly dispersing the hydrophobic silica fine particles, and (c) The present invention relates to a water repellent for textile products comprising a dispersion medium such as isopropanol for dispersing the hydrophobic silica fine particles. In the present invention, the fiber product includes all the products made of fibers, and includes not only the knitted fabric and non-woven fabric, but also the yarns and single fibers constituting the knitted fabric and non-woven fabric. Including used products, final products such as curtains, carpets and umbrellas.
本発明で用いる（ａ）疎水性シリカ微粒子とは、無水二酸化珪素微粒子の表面を、ヘキサメチルジシラザン処理、ジメチルジクロロシラン処理又はジメチルシリコーンオイル処理等の疎水処理を施したものである。表面に何らの処理も施さない親水性シリカ微粒子は、十分な撥水性を与えるものではないので、好ましくない。 The (a) hydrophobic silica fine particles used in the present invention are those obtained by subjecting the surfaces of anhydrous silicon dioxide fine particles to a hydrophobic treatment such as hexamethyldisilazane treatment, dimethyldichlorosilane treatment, or dimethylsilicone oil treatment. Hydrophilic silica fine particles that are not subjected to any treatment on the surface are not preferable because they do not give sufficient water repellency.
また、本発明において微粒子とは、本発明に係る撥水剤を繊維製品に付着させたときに、繊維製品を白化させないような大きさの粒子のことを意味している。一般的には、平均一次粒径が３０ｎｍ未満のものが用いられる。平均一次粒径が３０ｎｍ以上になると、繊維製品に付着させたときに、凝集して粗大なシリカ粒子を生じやすくなり、繊維製品表面が白化する恐れがある。ここで、平均一次粒径は、電子顕微鏡上で観察される実際の画像から、コンピュターノギスにより、一次粒子３０００個の粒径を実測し、その平均値を算出して得たものである。 In the present invention, the fine particles mean particles having a size that does not whiten the fiber product when the water repellent according to the present invention is adhered to the fiber product. Generally, those having an average primary particle size of less than 30 nm are used. When the average primary particle size is 30 nm or more, when adhered to the fiber product, it tends to agglomerate and produce coarse silica particles, and the fiber product surface may be whitened. Here, the average primary particle size is obtained by actually measuring the particle size of 3000 primary particles from an actual image observed on an electron microscope using a computer vernier caliper, and calculating the average value.
本発明で用いる疎水性シリカ微粒子の具体例としては、アエロジルＲ８１２，アエロジルＲ９７４，アエロジルＲＹ２００，アエロジルＲ９７２，アエロジルＮＸ９０，アエロジルＲＹ２００Ｓ，アエロジルＲ２０２，アエロジルＲＸ２００，アエロジルＲ８０５，アエロジルＲＡ２００Ｈ，アエロジルＲＡ２００ＨＳ，アエロジルＲ９７６，アエロジルＲ９７６Ｓ，アエロジルＲＹ３００，アエロジルＲＸ３００，アエロジルＲ８１２Ｓ（以上、日本アエロジル社製）等が挙げられる。 Specific examples of the hydrophobic silica fine particles used in the present invention include Aerosil R812, Aerosil R974, Aerosil RY200, Aerosil R972, Aerosil NX90, Aerosil RY200S, Aerosil R202, Aerosil RX200, Aerosil R805, Aerosil RA200H, Aerosil RA200HS, Aerosil R976, Aerosil R976S, Aerosil RY300, Aerosil RX300, Aerosil R812S (manufactured by Nippon Aerosil Co., Ltd.) and the like.
本発明で用いる（ｂ）常温揮発性分散剤とは、疎水性シリカ微粒子を均一に分散させうるものである。具体的には、疎水性シリカ微粒子の多くを、ナノメートルオーダーの粒径に分散させうるものである。すなわち、この分散剤によって、疎水性シリカ微粒子は、完全に一次粒子に分散してしまうものではないが、ミクロンメートルオーダーに凝集した疎水シリカ粒子の存在を極力少なくしうるものである。 The (b) normal temperature volatile dispersant used in the present invention is one that can uniformly disperse hydrophobic silica fine particles. Specifically, many of the hydrophobic silica fine particles can be dispersed in a particle size of nanometer order. That is, with this dispersant, the hydrophobic silica fine particles are not completely dispersed in the primary particles, but the presence of the hydrophobic silica particles agglomerated on the order of micrometers can be minimized.
また、本発明で用いる分散剤は、液状のものであって、常温揮発性のものである。常温揮発性とは、以下のように定義されるものである。すなわち、恒温恒湿室（２３℃、５０％ＲＨ、無風状態）内で、直径８５ｍｍで深さ１８ｍｍの円形ガラス製のシャーレを、水平な上皿天秤上で囲いが無い状態に置き、このシャーレに分散剤を３０ｇ入れる。そして、蓋をしない状態で、２４時間放置しておいたときに、分散剤の常温揮発量が５ｇ以上であるものを、常温揮発性であると定義した。本発明において、常温揮発性ではない分散剤を用いたときには、十分な撥水性を繊維製品に与えることができないので、好ましくない。撥水性が不十分となる理由は、定かではないが、以下のように推定している。すなわち、疎水性シリカ微粒子が撥水機能を発揮するためには、シリカ微粒子表面が露出した状態で繊維製品表面に存在していることが必要であると考えている。疎水性シリカ微粒子は、繊維製品表面に付与される前、分散媒中で、分散剤によって、あたかもその周囲を囲まれるような形態で良好に分散している。したがって、分散剤として常温揮発性ではないものを用いると、シリカ微粒子を繊維製品表面に付与した後、分散剤がシリカ微粒子表面に残留しやすくなる。その結果、シリカ微粒子表面が露出した状態となりにくく、分散剤で被覆された状態となりやすく、十分な撥水性を繊維製品に与えないのではないかと推定している。 The dispersant used in the present invention is liquid and volatile at room temperature. The room temperature volatility is defined as follows. That is, in a constant temperature and humidity chamber (23 ° C., 50% RH, no wind), a circular glass petri dish having a diameter of 85 mm and a depth of 18 mm is placed on a horizontal pan balance without any enclosure. 30 g of dispersant is put into And when it was left to stand for 24 hours without a cover, what the normal temperature volatilization amount of the dispersing agent was 5 g or more was defined as being normal temperature volatile. In the present invention, when a dispersant that is not volatile at room temperature is used, it is not preferable because sufficient water repellency cannot be imparted to the fiber product. The reason for insufficient water repellency is not clear, but is estimated as follows. That is, in order for the hydrophobic silica fine particles to exhibit the water repellent function, it is considered necessary that the silica fine particle surfaces be present on the fiber product surface in an exposed state. Hydrophobic silica fine particles are well dispersed in a dispersion medium as if surrounded by the dispersing agent in the dispersion medium before being applied to the fiber product surface. Therefore, if a dispersant that is not volatile at room temperature is used, the dispersant tends to remain on the surface of the silica fine particles after the silica fine particles are applied to the surface of the fiber product. As a result, it is estimated that the surface of the silica fine particles is unlikely to be exposed and is likely to be covered with a dispersant, and sufficient water repellency may not be imparted to the fiber product.
常温揮発性で、疎水性シリカ微粒子を良好に分散させる分散剤としては、具体的には、ビニルトリメトキシシラン，ジメチルジメトキシシラン，トリメチルメトキシシラン，ジメチルジメトキシシラン，メチルトリメトキシシラン又はテトラエトキシシラン等が用いられる。 Specific examples of dispersants that are volatile at room temperature and that favorably disperse hydrophobic silica fine particles include vinyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, and tetraethoxysilane. Is used.
本発明において、疎水性シリカ微粒子は、分散媒体を母体としてこの中で、分散剤の分散機能により均一に分散される。繊維製品に噴霧又は塗布するための撥水剤は液状で取り扱われるから、この分散媒体も液状のものが用いられる。分散媒体も特に限定されるものではないが、具体的には、炭素数１〜４のモノアルコールや水等、又はこれらの混合物を用いるのが好ましい。特に、本発明においては、揮発性の良好なイソプロパノールやエタノールを用いるのが好ましい。 In the present invention, the hydrophobic silica fine particles are uniformly dispersed by the dispersing function of the dispersant in the dispersion medium as a base material. Since the water repellent for spraying or applying to textiles is handled in liquid form, this dispersion medium is also in liquid form. Although the dispersion medium is not particularly limited, specifically, it is preferable to use a monoalcohol having 1 to 4 carbon atoms, water, or a mixture thereof. In particular, in the present invention, it is preferable to use isopropanol or ethanol having good volatility.
本発明において、撥水剤中の疎水性シリカ微粒子の配合割合は、特に限定されるものではない。要するに、所定量の疎水性シリカ微粒子を繊維製品の表面に付与すればよいのであるから、撥水剤中の疎水性シリカ微粒子の配合割合が少ない場合は、繊維製品表面に対する撥水剤の噴霧量又は塗布量を多くすればよい。また、逆に配合割合が多い場合は、繊維製品表面に対する撥水剤の噴霧量又は塗布量を少なくすればよい。また、常温揮発性分散剤についても、疎水性シリカ微粒子が良好に分散しうる量を配合すればよいのであるから、特に限定されない。一般的には、疎水性シリカ微粒子は０．１〜１０質量％程度で、常温揮発性分散剤も０．１〜１０質量％程度である。また、疎水性シリカ微粒子と常温揮発性分散剤との配合比は、等質量％であるか、又は常温揮発性分散剤が過剰であるのが好ましい。 In the present invention, the blending ratio of the hydrophobic silica fine particles in the water repellent is not particularly limited. In short, it is only necessary to apply a predetermined amount of hydrophobic silica fine particles to the surface of the fiber product. Therefore, when the blending ratio of the hydrophobic silica fine particles in the water repellent is small, the spray amount of the water repellent on the surface of the fiber product Or what is necessary is just to increase the application quantity. On the other hand, when the blending ratio is large, the spray amount or the coating amount of the water repellent on the surface of the fiber product may be reduced. Also, the room temperature volatile dispersant is not particularly limited because it is sufficient to add an amount capable of satisfactorily dispersing the hydrophobic silica fine particles. Generally, the hydrophobic silica fine particles are about 0.1 to 10% by mass, and the room temperature volatile dispersant is about 0.1 to 10% by mass. In addition, the blending ratio of the hydrophobic silica fine particles and the room temperature volatile dispersant is preferably equal mass% or the room temperature volatile dispersant is excessive.
本発明に係る撥水剤は、実質的に、上記した（ａ）疎水性シリカ微粒子、（ｂ）常温揮発性分散剤及び（ｃ）分散媒体のみからなる。ここで、実質的にという意味は、（ａ）〜（ｃ）成分以外のその他の第三成分を全く含有しないという意味ではなく、本発明に係る撥水剤の撥水機能を阻害しない程度に、第三成分を含有する場合も含まれるという意味である。例えば、撥水剤の商品価値を高めるために、香料や染顔料等が含有されている場合も含まれる。また、撥水剤の付与による繊維製品の風合いの低下を防止するため、或いは疎水性シリカ微粒子の分散性を更に向上させるために、柔軟剤等の界面活性剤等が含有されている場合も含まれる。さらに、疎水性シリカ微粒子と繊維製品表面との密着性を向上させるために、樹脂等が含有されている場合も含まれる。また、撥水剤をスプレー缶から噴射するための噴射ガス等や、撥水剤の混合及び分散のためのガラス球を混入しておいてもよい。すなわち、撥水剤が、実質的に、（ａ）疎水性シリカ微粒子、（ｂ）常温揮発性分散剤及び（ｃ）分散媒体のみからなるものであればよく、撥水機能に直接関連しない各種の補助物質が混合又は混入していても差し支えないということである。しかしながら、これらの第三成分が疎水性シリカ微粒子に付着して、その撥水機能を大幅に低下させたり、常温揮発性分散剤の分散機能を大幅に低下させたりするようなときは、このような第三成分は含まれるべきではない。 The water repellent according to the present invention substantially consists of (a) hydrophobic silica fine particles, (b) a room temperature volatile dispersant, and (c) a dispersion medium. Here, the meaning of “substantially” does not mean that no other third component other than the components (a) to (c) is contained, and does not inhibit the water repellent function of the water repellent according to the present invention. It also means that a case of containing a third component is also included. For example, in order to increase the commercial value of the water repellent, a case where a fragrance, a dye or pigment is contained is also included. Also included are cases where a surfactant such as a softener is contained in order to prevent a decrease in the texture of the fiber product due to the application of a water repellent or to further improve the dispersibility of the hydrophobic silica fine particles. It is. Furthermore, a case where a resin or the like is contained in order to improve the adhesion between the hydrophobic silica fine particles and the fiber product surface is also included. Moreover, you may mix the spraying gas etc. for injecting a water repellent from a spray can, and the glass bulb | ball for mixing and dispersion | distribution of a water repellent. That is, the water repellent may be substantially composed only of (a) hydrophobic silica fine particles, (b) a room temperature volatile dispersant, and (c) a dispersion medium, and various types not directly related to the water repellent function. This means that the auxiliary substances may be mixed or mixed. However, when these third components adhere to the hydrophobic silica fine particles, the water repellency function is greatly reduced, or the dispersion function of the room temperature volatile dispersant is greatly reduced. No third component should be included.
本発明に係る撥水剤は、家庭用として使用するときは、主にスプレー缶やトリガー式の噴霧器等の各種噴霧器に充填され、繊維製品に噴霧して使用される。業務用として使用するときは、液体を噴霧する従来周知の噴霧装置を用いて、本発明に係る撥水剤を噴霧すればよい。また、家庭用として使用するときは、周知のスプレー缶に本発明に係る撥水剤を充填して防水スプレーとし、繊維製品に噴霧すればよい。撥水剤をスプレー缶に充填する場合には、ジメチルエーテル、液化石油ガス（ＬＰＧ）、炭酸ガス、窒素ガス等の噴射ガスと共に、充填される。撥水剤と噴射ガスとの質量比は、従来公知の任意の比でよい。具体的には、撥水剤：噴射ガス＝１：２〜５：１である。また、スプレー缶に充填したときは、同時にガラス球等の混合助材もスプレー缶に収納するとよい。使用時にスプレー缶を振ることによって、撥水剤をよく混合しうるからである。なお、上記では、繊維製品に撥水剤を付与する方法として噴霧の例を挙げたが、噴霧に限られることはなく、浸漬や塗布等の手段で繊維製品に撥水剤を付与してもよい。 When the water repellent according to the present invention is used for household use, it is mainly filled in various sprayers such as spray cans and trigger sprayers and used by spraying on textiles. When used for business purposes, the water repellent according to the present invention may be sprayed using a conventionally known spraying device for spraying a liquid. In addition, when used for home use, a well-known spray can may be filled with the water repellent according to the present invention to form a waterproof spray and sprayed onto a textile product. When filling the spray can with the water repellent, it is filled together with an injection gas such as dimethyl ether, liquefied petroleum gas (LPG), carbon dioxide gas or nitrogen gas. The mass ratio between the water repellent and the jet gas may be any conventionally known ratio. Specifically, the ratio of water repellent: propellant gas = 1: 2 to 5: 1. Moreover, when filling a spray can, mixing aids, such as a glass bulb | ball, should also be accommodated in a spray can simultaneously. This is because the water repellent can be mixed well by shaking the spray can during use. In the above, an example of spraying is given as a method of applying a water repellent to a textile product, but it is not limited to spraying, and a water repellent agent may be applied to a textile product by means such as immersion or coating. Good.
繊維製品に撥水剤を噴霧すると、噴射ガスは噴霧時に大気中に蒸散し、撥水剤が繊維製品表面に付与される。すなわち、（ａ）疎水性シリカ微粒子、（ｂ）常温揮発性分散剤及び（ｃ）分散媒体が、繊維製品表面に付与される。そして、常温揮発性分散剤は、直ちに（数分乃至数十分程度）で大気中に揮発する。また、分散媒体についても、イソプロパノールやエタノール等のアルコール類を使用した場合は、概ね、数分乃至数時間内には大気中に揮発する。最終的には、繊維製品表面に、疎水性シリカ微粒子のみが残存し、繊維製品を被覆した状態となっている。疎水性シリカ微粒子は、一次粒子及び二次粒子の形態で、繊維製品表面を被覆しているが、その粒径は、大きくても数百ｎｍ以下のものが多くなっている。したがって、目視しても、疎水性シリカ微粒子の二次粒子を確認することは困難で、繊維製品表面が白化していることは認められない。 When the water repellent is sprayed on the textile, the propellant gas evaporates into the atmosphere at the time of spraying, and the water repellent is applied to the textile surface. That is, (a) hydrophobic silica fine particles, (b) a room temperature volatile dispersant, and (c) a dispersion medium are applied to the fiber product surface. The normal temperature volatile dispersant volatilizes in the atmosphere immediately (several minutes to several tens of minutes). As for the dispersion medium, when alcohols such as isopropanol and ethanol are used, they are generally volatilized in the atmosphere within several minutes to several hours. Ultimately, only the hydrophobic silica fine particles remain on the surface of the fiber product, and the fiber product is covered. Hydrophobic silica fine particles cover the surface of the fiber product in the form of primary particles and secondary particles, but the particle size is increased to several hundred nm or less at most. Therefore, it is difficult to confirm secondary particles of the hydrophobic silica fine particles by visual observation, and it is not recognized that the surface of the fiber product is whitened.
以上説明したように、本発明に係る撥水剤を用いて、繊維製品を撥水処理すれば、疎水性シリカ微粒子のみで撥水性を付与しうると共に、その表面の白化を防止しうるという効果を奏する。そして、疎水性シリカ微粒子のみによる撥水性は、後述の実施例からも実証されうるように、従来の撥水処理による撥水性に比べて、格段に優れた性能を持つものである。したがって、本発明に係る撥水剤は、従来のものに比べて、格別顕著な作用効果を奏するものである。 As described above, when the fiber product is subjected to water repellency treatment using the water repellent according to the present invention, it is possible to impart water repellency with only hydrophobic silica fine particles and to prevent whitening of the surface. Play. And the water repellency only by the hydrophobic silica fine particles has remarkably superior performance as compared with the water repellency by the conventional water repellency treatment, as can be demonstrated from the examples described later. Therefore, the water repellent according to the present invention has a particularly remarkable effect as compared with the conventional one.
以下、本発明を実施例に基づいて説明するが、本発明は、実施例に限定されるものではない。本発明は、（ａ）〜（ｃ）成分のみからなる撥水剤が、従来のものに比べて、格別顕著な撥水性を付与しうるとの知見に基づくものとして、解釈されるべきである。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example. The present invention should be construed as being based on the knowledge that a water repellent comprising only the components (a) to (c) can impart exceptional water repellency compared to conventional ones. .
実施例１
容器に、常温揮発性分散剤（信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上）１０ｇと、分散媒体（安藤パラケミー社製、イソプロピルアルコール）３０ｇを入れて、攪拌機（日本精機社製、ホモジナイザー「ＡＭ−７」）を用い、毎分５０００回転で攪拌しながら、疎水性シリカ微粒子（日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ）１０ｇを徐々に添加し、均一に分散させて、半透明の粘稠液を得た。この粘稠液に、上記の分散媒体２００ｇを添加して、疎水性シリカ微粒子の濃度が４質量％の撥水剤を得た。
Example 1
In a container, 10 g of a room temperature volatile dispersant (manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane “KBM1003”, room temperature volatility of 5 g or more) and 30 g of a dispersion medium (manufactured by Ando Parachemy, isopropyl alcohol) are added. While using a homogenizer “AM-7” manufactured by Nippon Seiki Co., Ltd. and stirring at 5000 revolutions per minute, hydrophobic silica fine particles (“Aerosil R812” manufactured by Nippon Aerosil Co., Ltd.), the surface of the silica fine particles treated with hexamethyldisilazane, 10 g (average primary particle size 7 nm) was gradually added and dispersed uniformly to obtain a translucent viscous liquid. To this viscous liquid, 200 g of the above dispersion medium was added to obtain a water repellent having a hydrophobic silica fine particle concentration of 4 mass%.
実施例２
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『信越化学工業社製、ジメチルジメトキシシラン「ＫＢＭ２２」、常温揮発量５ｇ以上』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 2
Instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, room temperature volatilization amount 5 g or more”, “Shin-Etsu Chemical Co., Ltd., dimethyldimethoxysilane“ KBM22 ”, room temperature volatilization amount 5 g. Other than using the above, a water repellent was obtained in the same manner as in Example 1.
実施例３
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『東芝シリコーン社製、トリメチルメトキシシラン「ＴＳＬ８１１１」、常温揮発量５ｇ以上』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 3
Instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, room temperature volatilization amount 5 g or more”, “Toshiba Silicone Corp., trimethylmethoxysilane“ TSL8111 ”, room temperature volatilization amount 5 g or more. A water repellent was obtained in the same manner as in Example 1, except that
実施例４
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『東芝シリコーン社製、ジメチルジメトキシシラン「ＴＳＬ８１１２」、常温揮発量５ｇ以上』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 4
Instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, room temperature volatility of 5 g or more”, “Toshiba Silicone Corp., dimethyldimethoxysilane“ TSL8112 ”, room temperature volatility of 5 g or more. A water repellent was obtained in the same manner as in Example 1, except that
実施例５
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『東芝シリコーン社製、メチルトリメトキシシラン「ＴＳＬ８１１３」、常温揮発量５ｇ以上』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 5
Instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, room temperature volatilization amount 5 g or more” as a room temperature volatile dispersant, “Toshiba Silicone Co., Ltd., methyltrimethoxysilane“ TSL8113 ”, room temperature volatilization amount 5 g Other than using the above, a water repellent was obtained in the same manner as in Example 1.
実施例６
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『東芝シリコーン社製、テトラエトキシシラン「ＴＳＬ８１２４」、常温揮発量５ｇ以上』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 6
Instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, normal temperature volatilization amount 5 g or more”, “Toshiba Silicone Corp., tetraethoxysilane“ TSL8124 ”, normal temperature volatility 5 g or more A water repellent was obtained in the same manner as in Example 1, except that
実施例７
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ９７４」、シリカ微粒子表面をジメチルジクロロシラン処理したもの、平均一次粒径１２ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 7
As hydrophobic silica fine particles, “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., instead of the surface of silica fine particles treated with hexamethyldisilazane, average primary particle size of 7 nm, “Aerosil R974” manufactured by Nippon Aerosil Co., Ltd., silica fine particles A water repellent was obtained in the same manner as in Example 1 except that the surface was treated with dimethyldichlorosilane and the average primary particle size was 12 nm.
実施例８
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ＲＹ２００」、シリカ微粒子表面をジメチルシリコーンオイル処理したもの、平均一次粒径１２ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 8
Instead of “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., the surface of the silica fine particle treated with hexamethyldisilazane, average primary particle size of 7 nm as the hydrophobic silica fine particles, “Aerosil RY200” manufactured by Nippon Aerosil Co., Ltd., silica fine particles A water repellent was obtained in the same manner as in Example 1 except that the surface was treated with dimethyl silicone oil and the average primary particle size was 12 nm.
実施例９
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ９７２」、シリカ微粒子表面をジメチルジクロロシラン処理したもの、平均一次粒径１６ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 9
As the hydrophobic silica fine particles, “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., instead of the surface of the silica fine particles treated with hexamethyldisilazane, average primary particle size of 7 nm, “Aerosil R972” manufactured by Nippon Aerosil Co., Ltd., silica fine particles A water repellent was obtained in the same manner as in Example 1 except that the surface was treated with dimethyldichlorosilane and the average primary particle size was 16 nm.
実施例１０
分散媒体として、『安藤パラケミー社製、イソプロピルアルコール』に代えて、『コニシ社製、エタノール』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Example 10
A water repellent was obtained in the same manner as in Example 1 except that “ethanol produced by Konishi Co., Ltd.” was used instead of “isopropyl alcohol produced by Ando Parachemie Co., Ltd.” as the dispersion medium.
比較例１
常温揮発性分散剤（信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上）を使用しない他は、実施例１と同一の方法で撥水剤を得た。この場合、分散媒体の総質量を２４０ｇとし、撥水剤質量が２５０ｇとなるようにした。
Comparative Example 1
A water repellent was obtained in the same manner as in Example 1 except that a normal temperature volatile dispersant (manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane “KBM1003”, normal temperature volatility of 5 g or more) was not used. In this case, the total mass of the dispersion medium was 240 g, and the water repellent mass was 250 g.
比較例２
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『信越化学工業社製、グリシドキシプロピルトリメトキシシラン「ＫＢＭ４０３」、常温揮発量５ｇ未満』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 2
As a room temperature volatile dispersant, instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, room temperature volatility of 5 g or more”, “Shin-Etsu Chemical Co., Ltd., glycidoxypropyltrimethoxysilane“ KBM403 ” A water repellent was obtained in the same manner as in Example 1 except that “room temperature volatilization amount of less than 5 g” was used.
比較例３
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『信越化学工業社製、メタクリロキシプロピルトリメトキシシラン「ＫＢＭ５０３」、常温揮発量５ｇ未満』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 3
As a room temperature volatile dispersant, instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, room temperature volatility of 5 g or more”, “Shin-Etsu Chemical Co., Ltd., methacryloxypropyltrimethoxysilane“ KBM503 ”, room temperature A water repellent was obtained in the same manner as in Example 1 except that the volatilization amount was less than 5 g.
比較例４
常温揮発性分散剤として、『信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上』に代えて、『信越化学工業社製、アミノエチルアミノプロピルトリメトキシシラン「ＫＢＭ６０３」、常温揮発量５ｇ未満』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 4
As a room temperature volatile dispersant, instead of “Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane“ KBM1003 ”, normal temperature volatility of 5 g or more”, “Shin-Etsu Chemical Co., Ltd., aminoethylaminopropyltrimethoxysilane“ KBM603 ” A water repellent was obtained in the same manner as in Example 1 except that “room temperature volatilization amount of less than 5 g” was used.
比較例５
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ＮＹ５０」、シリカ粒子表面をジメチルシリコーンオイル処理したもの、平均一次粒径３０ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 5
Instead of “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., the surface of silica fine particles treated with hexamethyldisilazane, average primary particle size of 7 nm as hydrophobic silica fine particles, “Aerosil NY50” manufactured by Nippon Aerosil Co., Ltd., silica particles A water repellent was obtained in the same manner as in Example 1 except that the surface was treated with dimethylsilicone oil and the average primary particle size was 30 nm.
比較例６
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ＮＡＸ５０」、シリカ粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径３０ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 6
Instead of “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., the surface of the silica fine particle treated with hexamethyldisilazane, average primary particle size of 7 nm as hydrophobic silica fine particles, “Aerosil NAX50” manufactured by Nippon Aerosil Co., Ltd., silica particles A water repellent was obtained in the same manner as in Example 1, except that the surface was treated with hexamethyldisilazane and the average primary particle size was 30 nm.
比較例７
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ＲＹ５０」、シリカ粒子表面をジメチルシリコーンオイル処理したもの、平均一次粒径４０ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 7
As the hydrophobic silica fine particles, “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., instead of the surface of the silica fine particles treated with hexamethyldisilazane, average primary particle size of 7 nm, “Aerosil RY50” manufactured by Nippon Aerosil Co., Ltd., silica particles A water repellent was obtained in the same manner as in Example 1 except that the surface was treated with dimethyl silicone oil and the average primary particle size was 40 nm.
比較例８
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ＲＸ５０」、シリカ粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径４０ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 8
As hydrophobic silica fine particles, “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., instead of the surface of silica fine particles treated with hexamethyldisilazane, average primary particle size of 7 nm, “Aerosil RX50” manufactured by Nippon Aerosil Co., Ltd., silica particles A water repellent was obtained in the same manner as in Example 1, except that the surface was treated with hexamethyldisilazane and the average primary particle size was 40 nm.
比較例９
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ２００」、シリカ微粒子表面の処理無しの親水性シリカ微粒子、平均一次粒径１２ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 9
As the hydrophobic silica fine particles, “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., instead of the surface of silica fine particles treated with hexamethyldisilazane, average primary particle size 7 nm, “Aerosil 200” manufactured by Nippon Aerosil Co., Ltd., silica fine particles A water repellent was obtained in the same manner as in Example 1 except that hydrophilic silica fine particles having no surface treatment and an average primary particle size of 12 nm were used.
比較例１０
常温揮発性分散剤（信越化学工業社製、ビニルトリメトキシシラン「ＫＢＭ１００３」、常温揮発量５ｇ以上）を使用しない他は、比較例９と同一の方法で撥水剤を得た。この場合、分散媒体の総質量を２４０ｇとし、撥水剤質量が２５０ｇとなるようにした。
Comparative Example 10
A water repellent was obtained in the same manner as in Comparative Example 9 except that a normal temperature volatile dispersant (manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane “KBM1003”, normal temperature volatility of 5 g or more) was not used. In this case, the total mass of the dispersion medium was 240 g, and the water repellent mass was 250 g.
比較例１１
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『日本アエロジル社製「Ａｅｒｏｓｉｌ ３００」、シリカ微粒子表面の処理無しの親水性シリカ微粒子、平均一次粒径７ｎｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 11
As hydrophobic silica fine particles, “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., instead of the surface of silica fine particles treated with hexamethyldisilazane, average primary particle size of 7 nm, “Aerosil 300” manufactured by Nippon Aerosil Co., Ltd., silica fine particles A water repellent was obtained in the same manner as in Example 1 except that hydrophilic silica fine particles having no surface treatment and an average primary particle size of 7 nm were used.
比較例１２
疎水性シリカ微粒子として、『日本アエロジル社製「Ａｅｒｏｓｉｌ Ｒ８１２」、シリカ微粒子表面をヘキサメチルジシラザン処理したもの、平均一次粒径７ｎｍ』に代えて、『富士シリシア化学社製「サイロホービック ２００」、シリカ粒子表面を有機ケイ素化合物処理したもの、平均一次粒径１．８μｍ』を使用した他は、実施例１と同一の方法で撥水剤を得た。
Comparative Example 12
Instead of “Aerosil R812” manufactured by Nippon Aerosil Co., Ltd., and the silica particle surface treated with hexamethyldisilazane, average primary particle size of 7 nm as hydrophobic silica fine particles, “Silo Hovic 200 manufactured by Fuji Silysia Chemical Ltd.” A water repellent was obtained in the same manner as in Example 1 except that the surface of the silica particles was treated with an organosilicon compound and the average primary particle size was 1.8 μm.
比較例１３
市販品であるコニシ社製の防水スプレー（シリコーン樹脂系撥水剤を用いた防水スプレー）を準備した。
Comparative Example 13
A commercially available waterproof spray manufactured by Konishi (waterproof spray using a silicone resin water repellent) was prepared.
比較例１４
市販品であるコロンブス社製のプロテクティブスプレー（フッ素樹脂系撥水剤を用いた防水スプレー）を準備した。
Comparative Example 14
A commercially available protective spray manufactured by Columbus (waterproof spray using a fluororesin water repellent) was prepared.
実施例１〜１０及び比較例１〜１２に係る各撥水剤の分散安定性を、以下の二つの方法で評価した。この結果を表１に示した。
［沈降堆積物量］
各撥水剤を、試験管（直径約１．２ｃｍ）に約３０ｍｌ入れて密栓し、室温で７日間放置する。そして、試験管の底に堆積した堆積物の厚さ（ｍｍ）を測定し、この厚さを沈降堆積物量（ｍｍ）とした。沈降堆積物量（ｍｍ）の値は小さいほど、疎水性シリカ微粒子が良好に分散媒体中に分散していることを意味する。
［再分散性］
沈降堆積物量の測定後、試験管を１分間振って、底に堆積した堆積物を再分散させた。再分散の状態を、以下の基準で評価した。
○：均一な分散液に再び戻り、底には堆積物が残らない状態となった。
△：分散はするが堆積物が細かく分散せず、しばらくすると試験管の底に再び堆積物が 発生する状態であった。
×：あまり分散せず、堆積物が荒く砕けるだけで、そのまま沈降する状態であった。
The dispersion stability of each water repellent according to Examples 1 to 10 and Comparative Examples 1 to 12 was evaluated by the following two methods. The results are shown in Table 1.
[Amount of sedimentation sediment]
About 30 ml of each water repellent is put in a test tube (diameter: about 1.2 cm), sealed, and left at room temperature for 7 days. And the thickness (mm) of the deposit deposited on the bottom of the test tube was measured, and this thickness was defined as the amount of sediment (mm). It means that the smaller the value of the sediment amount (mm), the better the hydrophobic silica fine particles are dispersed in the dispersion medium.
[Redispersibility]
After measuring the amount of sediment, the test tube was shaken for 1 minute to redisperse the sediment deposited on the bottom. The state of redispersion was evaluated according to the following criteria.
○: Returned to the uniform dispersion again, and no deposits remained on the bottom.
Δ: Dispersed, but the deposit was not finely dispersed. After a while, the deposit was generated again at the bottom of the test tube.
X: It did not disperse | distribute so much, and it was in the state which settled as it was, only by depositing coarsely.
［表１］
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
沈降堆積物量（ｍｍ） 再分散性
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ０．５ ○
実施例２ ０．５ ○
実施例３ ０．５ ○
実施例４ ０．５ ○
実施例５ ０．５ ○
実施例６ ０．５ ○
実施例７ ０．５ ○
実施例８ ０．５ ○
実施例９ ０．５ ○
実施例１０ ０．５ ○
比較例１ ５．０ △
比較例２ ０．５ ○
比較例３ １．５ ○
比較例４ １．５ ○
比較例５ ８．０ △
比較例６ ４．０ △
比較例７ １．０ ○
比較例８ ３．０ △
比較例９ １．０ ○
比較例１０ ３．０ △
比較例１１ １．０ ○
比較例１２ ３．０ △
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Amount of sediment (mm) Redispersibility ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 0.5 ○
Example 2 0.5 ○
Example 3 0.5 ○
Example 4 0.5 ○
Example 5 0.5 ○
Example 6 0.5 ○
Example 7 0.5 ○
Example 8 0.5 ○
Example 9 0.5 ○
Example 10 0.5 ○
Comparative Example 1 5.0
Comparative Example 2 0.5 ○
Comparative Example 3 1.5 ○
Comparative Example 4 1.5
Comparative Example 5 8.0
Comparative Example 6 4.0
Comparative Example 7 1.0
Comparative Example 8 3.0
Comparative Example 9 1.0
Comparative Example 10 3.0
Comparative Example 11 1.0
Comparative Example 12 3.0
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１〜１０及び比較例１〜１２に係る各撥水剤７５質量部と、噴射ガスであるジメチルエーテル２５質量部とを、スプレー缶に充填し、よく振ってから１時間程度放置して、２２個の防水スプレーを得た。これらの防水スプレー、及び比較例１３、１４に係る防水スプレーについて、白化及び撥水性を評価するため、以下の試験体１及び２を準備した。
［試験体１］
東レ社製テトロン「セラミカタフタ ♯２１０」（ポリエステル１００％織物よりなる布帛）を、直径８．５ｃｍのリング枠に張設したもの。
［試験体２］
清原社製「シーチング ♯６２００」（綿１００％織物よりなる布帛）を、直径８．５ｃｍのリング枠に張設したもの。
Fill each spray can with 75 parts by mass of each of the water repellents according to Examples 1 to 10 and Comparative Examples 1 to 12 and 25 parts by mass of dimethyl ether, which is a propelled gas, and leave it for about 1 hour after shaking well. 22 waterproof sprays were obtained. In order to evaluate whitening and water repellency of these waterproof sprays and the waterproof sprays according to Comparative Examples 13 and 14, the following test bodies 1 and 2 were prepared.
[Test body 1]
Tetoron “Cerami Katafata # 210” (fabric made of 100% polyester fabric) made by Toray Co., Ltd. stretched on a ring frame with a diameter of 8.5 cm.
[Specimen 2]
Kiyohara's “Sheeting # 6200” (a fabric made of 100% cotton) is stretched over a 8.5 cm diameter ring frame.
［白化試験］
試験体１及び２の各張設布帛部の約半分の区域に、各防水スプレーにて撥水剤を噴霧した。撥水剤の噴霧量は約２ｇとし、噴霧後３０分以上乾燥・養生した。そして、噴霧区域と非噴霧区域の色の差を目視にて比較し、以下の基準で白化状態を評価した。
○：両区域の色の差が見られない。
△：両区域の色の差は殆ど見られないが、噴霧区域の方が少し白く見える。
×：噴霧区域の方が明らかに白くなっている。
[Whitening test]
The water-repellent agent was sprayed with each waterproof spray on a half area of each stretched fabric part of the test bodies 1 and 2. The spray amount of the water repellent was about 2 g, and it was dried and cured for 30 minutes or more after spraying. Then, the difference in color between the spray area and the non-spray area was visually compared, and the whitening state was evaluated according to the following criteria.
○: There is no color difference between the two areas.
Δ: Almost no difference in color between the two areas is seen, but the sprayed area looks a little whiter.
X: The spray area is clearly whiter.
試験体１及び２の各張設布帛全体に、各防水スプレーにて撥水剤約２ｇを噴霧して付与し、噴霧後３０分以上乾燥・養生して、各張設布帛を撥水処理した。そして、以下の試験を行い、撥水性を評価した。
［降雨試験］
ＪＩＳ Ｌ １０９２ ５．２記載の撥水度試験（スプレー試験）に準拠した方法で撥水度を判定した。すなわち、撥水処理した試験体１及び２を、撥水度試験装置にセットし、４５°傾斜した状態で、上から雨状に水（２５０ｍｌ）を落とし、水をはじく状態（撥水度）を０〜１００の範囲で判定した。０〜１００の範囲は、次のように区分されており、撥水度１００が最も良好な撥水性を示すものであり、撥水度８０以上が実用範囲である。
０：張設布帛の表面及び裏面が全体に湿潤を示すもの。
２０：張設布帛の表面全体に湿潤を示し、裏面の半分に湿潤を示すもの。
５０：張設布帛の表面全体に湿潤を示すもの。
７０：張設布帛の表面の半分に湿潤を示し、小さな個々の湿潤が張設布帛を浸透する 状態を示すもの。
８０：張設布帛の表面に小さな個々の水滴状の湿潤を示すもの。
９０：張設布帛の表面に湿潤を示さないが、小さな水滴の付着を示すもの。
１００：張設布帛の表面に湿潤や水滴の付着がないもの。
About 2 g of the water repellent was sprayed and applied to each of the stretched fabrics of the test bodies 1 and 2 with each waterproof spray, dried and cured for 30 minutes or more after spraying, and each stretched fabric was subjected to a water repellent treatment. . And the following tests were done and water repellency was evaluated.
[Rainfall test]
The water repellency was determined by a method based on the water repellency test (spray test) described in JIS L 1092 5.2. That is, the test bodies 1 and 2 subjected to water repellency treatment are set in a water repellency test apparatus, and in a state inclined by 45 °, water (250 ml) is dropped from the top in a rainy state and water is repelled (water repellency). Was determined in the range of 0-100. The range of 0 to 100 is divided as follows, and the water repellency of 100 indicates the best water repellency, and the water repellency of 80 or more is the practical range.
0: The surface of the stretched fabric and the back surface are all wet.
20: The entire surface of the stretched fabric shows wetness, and the back half shows wetness.
50: The surface of the stretched fabric shows wetness.
70: The half of the surface of the tension fabric shows wetness, and a small individual wetness penetrates the tension fabric.
80: The surface of the stretched fabric exhibits small individual water droplets.
90: The surface of the stretched fabric does not show wetness but shows adhesion of small water droplets.
100: The surface of the stretched fabric is free from moisture and water droplets.
［撥水耐久性試験］
降雨試験を終えた試験体１及び２に、そのまま連続３０分間の連続降雨試験を行い、その後の撥水度を、上記した０〜１００の範囲で判定した。
[Water repellent durability test]
The test bodies 1 and 2 which finished the rain test were subjected to a continuous rain test for 30 minutes as they were, and the subsequent water repellency was determined in the range of 0 to 100 described above.
［降雨乾燥後試験］
撥水耐久性試験を終えた試験体１及び２を乾燥し、その後、何らの撥水処理を行うことなく、上記した降雨試験を行い、その撥水度を上記した０〜１００の範囲で判定した。
[Test after rain and drying]
The test specimens 1 and 2 that have finished the water-repellent durability test are dried, and then the above-described rain test is performed without performing any water-repellent treatment, and the water-repellent degree is determined in the range of 0 to 100 described above. did.
以上の各試験の結果を、表２及び表３に示した。表２は試験体１の結果であり、表３は試験体２の結果である。
The results of the above tests are shown in Tables 2 and 3. Table 2 shows the results of the test body 1, and Table 3 shows the results of the test body 2.
［表２］
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験体１ 白化試験 降雨試験 撥水耐久性試験 降雨乾燥後試験
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ○ １００ ９０ １００
実施例２ ○ １００ ９０ １００
実施例３ ○ １００ ９０ １００
実施例４ ○ １００ ９０ １００
実施例５ ○ １００ ９０ １００
実施例６ ○ １００ ９０ １００
実施例７ ○ １００ ９０ １００
実施例８ ○ １００ ９０ １００
実施例９ ○ １００ ９０ １００
実施例１０ ○ １００ ９０ １００
比較例１ × １００ ９０ １００
比較例２ ○ ７０ ２０ ２０
比較例３ ○ ７０ ２０ ２０
比較例４ △ ８０ ２０ ２０
比較例５ × １００ ８０ ９０
比較例６ × １００ ８０ ９０
比較例７ × ９０ ６０ ６０
比較例８ × ９０ ６０ ６０
比較例９ ○ ９０ ６０ ６０
比較例１０ × ９０ ６０ ６０
比較例１１ ○ ９０ ６０ ６０
比較例１２ × ５０ ０ ０
比較例１３ ○ １００ ９０ ９０
比較例１４ ○ １００ １００ １００
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 2]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Specimen 1 Whitening test Rain test Water repellent durability test After rain dry test ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━
Example 1 ○ 100 90 100
Example 2 ○ 100 90 100
Example 3 ○ 100 90 100
Example 4 ○ 100 90 100
Example 5 ○ 100 90 100
Example 6 ○ 100 90 100
Example 7 ○ 100 90 100
Example 8 ○ 100 90 100
Example 9 ○ 100 90 100
Example 10 ○ 100 90 100
Comparative Example 1 × 100 90 100
Comparative Example 2 ○ 70 20 20
Comparative Example 3 ○ 70 20 20
Comparative Example 4 △ 80 20 20
Comparative Example 5 × 100 80 90
Comparative Example 6 × 100 80 90
Comparative Example 7 × 90 60 60
Comparative Example 8 × 90 60 60
Comparative Example 9 ○ 90 60 60
Comparative Example 10 × 90 60 60
Comparative Example 11 ○ 90 60 60
Comparative Example 12 × 50 0 0
Comparative Example 13 ○ 100 90 90
Comparative Example 14 ○ 100 100 100
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
［表３］
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
試験体２ 白化試験 降雨試験 撥水耐久性試験 降雨乾燥後試験
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ ○ １００ ８０ １００
実施例２ ○ １００ ８０ １００
実施例３ ○ １００ ８０ １００
実施例４ ○ １００ ８０ １００
実施例５ ○ １００ ８０ １００
実施例６ ○ １００ ８０ １００
実施例７ ○ １００ ８０ １００
実施例８ ○ １００ ８０ １００
実施例９ ○ １００ ８０ １００
実施例１０ ○ １００ ８０ １００
比較例１ △ １００ ８０ １００
比較例２ ○ ０ ０ ０
比較例３ ○ ５０ ０ ０
比較例４ △ ６０ ０ ０
比較例５ × ９０ ８０ ９０
比較例６ × ９０ ８０ ９０
比較例７ △ ８０ ５０ ５０
比較例８ △ ９０ ５０ ５０
比較例９ ○ ８０ ５０ ５０
比較例１０ △ ８０ ５０ ５０
比較例１１ ○ ８０ ５０ ５０
比較例１２ × ０ ０ ０
比較例１３ ○ ９０ ０ ０
比較例１４ ○ １００ ６０ ６０
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 3]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Specimen 2 Whitening test Rain test Water repellent durability test Test after rain drying ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━
Example 1 ○ 100 80 100
Example 2 ○ 100 80 100
Example 3 ○ 100 80 100
Example 4 ○ 100 80 100
Example 5 ○ 100 80 100
Example 6 ○ 100 80 100
Example 7 ○ 100 80 100
Example 8 ○ 100 80 100
Example 9 ○ 100 80 100
Example 10 ○ 100 80 100
Comparative Example 1 △ 100 80 100
Comparative Example 2 ○ 0 0 0
Comparative Example 3 ○ 50 0 0
Comparative Example 4 △ 60 0 0
Comparative Example 5 × 90 80 90
Comparative Example 6 × 90 80 90
Comparative Example 7 △ 80 50 50
Comparative Example 8 △ 90 50 50
Comparative Example 9 ○ 80 50 50
Comparative Example 10 △ 80 50 50
Comparative Example 11 ○ 80 50 50
Comparative Example 12 × 0 0 0
Comparative Example 13 ○ 90 0 0
Comparative Example 14 ○ 100 60 60
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
表２及び表３の結果から、以下の事実が確認できる。実施例に係る各撥水剤と従来の撥水剤である比較例１３及び１４とを対比すると、実施例に係る各撥水剤は、従来のものよりも綿布に対する撥水性に優れていることが分かる（表３）。常温揮発性分散剤を配合しない比較例１に係る撥水剤と対比すると、その撥水性は同等であるが、実施例に係る各撥水剤は布帛に白化が見られないという利点がある。これによって、常温揮発性分散剤は、布帛の白化を防止するという性能を与えていることが分かる。また、常温揮発性でない分散剤を配合した比較例２〜４に係る撥水剤と対比すると、実施例に係る各撥水剤の方が撥水性に優れているという利点がある。これによって、常温揮発性分散剤は良好な撥水性能を与えるのに必要な成分であることが分かる。平均一次粒径の大きい疎水性シリカ粒子を配合した比較例５〜８及び１２に係る撥水剤と対比すると、白化の点でも撥水性の点でも、実施例に係る各撥水剤の方が優れているという利点がある。これによって、疎水性シリカ微粒子が白化の防止及び良好な撥水性に寄与していることが分かる。親水性シリカ微粒子を配合した比較例９〜１１に係る各撥水剤と対比すると、実施例に係る各撥水剤の方が撥水性に優れているという利点がある。したがって、撥水性を与えるには親水性のものではなく疎水性のものを用いる必要のあることが分かる。 From the results in Tables 2 and 3, the following facts can be confirmed. When comparing each of the water repellents according to Examples with Comparative Examples 13 and 14 that are conventional water repellents, each of the water repellents according to Examples is superior in water repellency to cotton cloth than the conventional ones. (Table 3). When compared with the water repellent according to Comparative Example 1 that does not contain a room temperature volatile dispersant, the water repellency is the same, but each water repellent according to the example has the advantage that no whitening is observed in the fabric. Thus, it can be seen that the room temperature volatile dispersant has a performance of preventing whitening of the fabric. Further, when compared with the water repellents according to Comparative Examples 2 to 4 in which a dispersant that is not volatile at normal temperature is used, each water repellent according to the example has an advantage that it is superior in water repellency. Thus, it can be seen that the room temperature volatile dispersant is a component necessary for providing good water repellency. When compared with the water repellents according to Comparative Examples 5 to 8 and 12 in which hydrophobic silica particles having a large average primary particle size were blended, each of the water repellents according to the examples was whitening and water repellent. There is an advantage of being excellent. This shows that the hydrophobic silica fine particles contribute to prevention of whitening and good water repellency. When compared with the water repellents according to Comparative Examples 9 to 11 in which hydrophilic silica fine particles are blended, each water repellent according to the example has an advantage that the water repellency is superior. Therefore, it can be seen that it is necessary to use a hydrophobic material rather than a hydrophilic material to impart water repellency.
Claims (7)
（ａ）疎水性シリカ微粒子
（ｂ）該疎水性シリカ微粒子を均一に分散させるためのビニルトリメトキシシラン等の常温揮発性分散剤
（ｃ）該疎水性シリカ微粒子を分散させるためのイソプロパノール等の分散媒体 A water repellent for textiles, which substantially comprises only the following components (a), (b) and (c).
(A) Hydrophobic silica fine particles (b) A room temperature volatile dispersant such as vinyltrimethoxysilane for uniformly dispersing the hydrophobic silica fine particles (c) Dispersion of isopropanol or the like for dispersing the hydrophobic silica fine particles Medium
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007099909A1 (en) * | 2006-02-28 | 2007-09-07 | Konishi Co., Ltd. | Water repellent for textile |
| DE102006053326A1 (en) * | 2006-11-10 | 2008-05-15 | Bühler PARTEC GmbH | Equipment of substrates |
| KR100861984B1 (en) | 2008-01-22 | 2008-10-07 | (주)정상 엔지니어링 | A waterproof agent of concrete and manufacturing method thereof |
| JP2010095832A (en) * | 2008-10-20 | 2010-04-30 | Teijin Techno Products Ltd | Para-type wholly aromatic copolyamide fiber and method for producing the same |
| US20130309282A1 (en) * | 2011-01-31 | 2013-11-21 | Kikuboshi Corporation | Hairstyling agent composition |
| JP2018104866A (en) * | 2016-12-28 | 2018-07-05 | 日華化学株式会社 | Water-repellent composition, water-repellent fiber product and method for producing water-repellent fiber product |
-
2004
- 2004-06-17 JP JP2004179598A patent/JP4148922B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007099909A1 (en) * | 2006-02-28 | 2007-09-07 | Konishi Co., Ltd. | Water repellent for textile |
| DE102006053326A1 (en) * | 2006-11-10 | 2008-05-15 | Bühler PARTEC GmbH | Equipment of substrates |
| KR100861984B1 (en) | 2008-01-22 | 2008-10-07 | (주)정상 엔지니어링 | A waterproof agent of concrete and manufacturing method thereof |
| JP2010095832A (en) * | 2008-10-20 | 2010-04-30 | Teijin Techno Products Ltd | Para-type wholly aromatic copolyamide fiber and method for producing the same |
| US20130309282A1 (en) * | 2011-01-31 | 2013-11-21 | Kikuboshi Corporation | Hairstyling agent composition |
| JP2018104866A (en) * | 2016-12-28 | 2018-07-05 | 日華化学株式会社 | Water-repellent composition, water-repellent fiber product and method for producing water-repellent fiber product |
| JP6995477B2 (en) | 2016-12-28 | 2022-01-14 | 日華化学株式会社 | Method for manufacturing water repellent composition, water repellent fiber product and water repellent fiber product |
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