JP2015189170A - Water-repellent treated substrate and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a water-repellent treated substrate that does not impair the quality texture of the substrate even while possessing the high water-repellency as well as that can realize the water-repellency with a small amount of water-repellent; and a production method thereof.SOLUTION: Provided is a water-repellent treated substrate production method including a step for forming an interlayer onto a substrate, and a step of forming a water-repellent layer onto said interlayer, and which is characterized in that the interlayer is composed of organosilicon-based material and the water-repellent layer is composed of fluorine-based compound. The substrate obtained by said production method has a water contact angle of 130° or more.

Description

  The present invention relates to a water repellent substrate and a method for producing the same.

  Conventionally, as a method for imparting water repellency to a substrate, a method of applying a water repellent to the substrate or immersing the substrate in the water repellent is generally used. However, when trying to impart water repellency to highly hydrophilic substrates such as paper, the substrate absorbs the water repellant, making it difficult to hold the water repellant on the surface of the substrate. Thus, sufficient water repellency could not be obtained.

  In order to solve the above problems, there has been proposed a processing method for imparting water repellency to a substrate by spraying and drying a water repellent dissolved or dispersed in an aqueous alcohol solution on the surface of the substrate ( Patent Document 1).

JP 2005-188016 A

  However, even if the above processing method is used, if the base material is highly hydrophilic, the base material soaks in the water repellent, and the base material feels worse. There was a problem that an agent was required.

  Therefore, an object of the present invention is to provide a water-repellent treated substrate that retains the texture of the substrate while having high water repellency, and that can exhibit water repellency with a small amount of water repellent, and its An object is to provide a manufacturing method.

  The method for producing a water repellent substrate according to the present invention comprises a step of forming an intermediate layer on the base material, and a step of forming a water repellent layer on the intermediate layer. The water-repellent layer is made of a fluorine-based compound.

  According to such a configuration, since the intermediate layer made of the organic silicon-based material is formed before the water repellent layer is formed on the base material, the water repellent layer can be prevented from soaking into the base material. As a result, the texture of the substrate can be prevented from being damaged, and water repellency can be expressed with a small amount of water repellent.

  Further, since the adhesion between the intermediate layer made of an organic silicon material and the water repellent layer made of a fluorine compound is good, a water repellent layer having excellent durability can be formed.

  The intermediate layer may be formed by a CVD method.

  According to such a configuration, an intermediate layer having a uniform thickness can be formed.

  The CVD method may be a plasma CVD method.

  According to such a configuration, since the film can be formed at a lower temperature than other CVD methods, an intermediate layer can be formed even with a low heat resistant substrate.

  The film thickness of the intermediate layer may be 50 to 1000 nm.

  According to such a structure, the intermediate | middle layer which is excellent in adhesiveness with a board | substrate and does not impair the texture of a base material can be formed.

  The water repellent layer may be formed by a wet process.

  According to such a configuration, a water repellent layer having a uniform thickness can be formed.

  The wet process may be a dip method.

  According to such a configuration, a water repellent layer having a more uniform film thickness can be formed.

  The film thickness of the water repellent layer may be 5 to 1200 nm.

  According to such a configuration, it is possible to form a water-repellent layer that has excellent adhesion to the substrate and does not impair the texture of the substrate.

  As described above, according to the base material subjected to the water-repellent treatment according to the present invention, the intermediate layer made of the organosilicon material is formed before the water-repellent layer is formed on the base material. It is possible to prevent the water repellent from permeating the base material. Thereby, it is possible to prevent the texture of the base material from being damaged and to exhibit water repellency with a small amount of water repellent. Furthermore, since the adhesiveness between the intermediate layer made of an organosilicon material and the water repellent layer made of a fluorine compound is good, the durability of the water repellent layer is improved.

It is a figure which shows typically the manufacturing method of the base material in which the water-repellent process concerning this embodiment was made | formed. It is sectional drawing of the fibrous base material in which the water repellent process was made. In Comparative example 2 and Experimental example 1, it is a microscope picture at the time of dripping a water droplet on the surface.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, all of these embodiments are illustrative and do not give a limited interpretation of the present invention. In the drawings, the same or corresponding parts are denoted by the same reference numerals.

  FIG. 1 is a diagram schematically illustrating a method for manufacturing a base material 10 that has been subjected to water repellent treatment according to the present embodiment. As shown in FIG. 1C, the base material 10 subjected to the water repellent treatment according to this embodiment has an intermediate layer 12 and a water repellent layer 13 formed on the base material 11. Hereinafter, the manufacturing method will be described.

(1) Substrate First, a substrate 11 is prepared as shown in FIG. Examples of the substrate 11 include a plastic film, paper, and cloth. Although FIG. 1 illustrates the case where a planar material such as a plastic film is used as a base material, the base material is not limited to a planar material, and as shown in FIG. The manufacturing method according to this embodiment can also be applied to the base material. In addition, the production method according to the present embodiment is suitable because it can impart water repellency without impairing the texture of the substrate even when the substrate is highly hydrophilic. In addition, when using paper as a base material, it is preferable that the basis weight is 60 g / m ² or less from the viewpoint of transparency and air permeability, and in consideration of air permeability, the basis weight is 10 g / m ² or less. Is preferred.

(2) Intermediate Layer Forming Step Next, as shown in FIG. 1 (b), an intermediate layer 12 made of an organosilicon material is formed on the base material 11. By forming the intermediate layer 12 made of an organosilicon material before forming the water repellent layer 13 on the base material 11, it is possible to prevent the water repellent layer 13 from penetrating into the base material. Thereby, it can prevent that the texture of the base material 11 is impaired, and can express water repellency with a small amount of water repellent.

  The intermediate layer 12 is preferably formed by a CVD method. Thereby, the intermediate | middle layer 12 of a uniform film thickness can be formed, and the adhesiveness of the intermediate | middle layer 12 and the water-repellent layer 13 becomes more favorable. In addition, since the CVD method has a high film formation speed and a large area on which film formation can be performed at one time, mass production is possible and manufacturing at low cost is possible.

  Among the CVD methods, it is particularly preferable to use a plasma CVD (PECVD) method. The plasma CVD method is a CVD method using plasma as the activation energy of the pre-reaction gas, and has a feature that a film can be formed at a lower temperature than other CVD methods. Therefore, even a low heat resistant substrate can impart water repellency.

  Generally, when the film thickness of the intermediate layer 12 is small, adhesion to the substrate 11 cannot be obtained, and when the film thickness is large, the texture of the substrate 11 tends to be impaired. For this reason, the thickness of the intermediate layer 12 is preferably in the range of 50 to 1000 nm.

(3) Water-repellent layer forming step Next, as shown in FIG. 1 (c), a water-repellent layer 13 made of a fluorine-based compound is formed on the surface of the substrate 11 on which the intermediate layer 12 is formed. Since the water-repellent layer 13 is made of a fluorine-based compound, it has a water-repellent effect as well as good adhesion to the intermediate layer 12 made of an organic silicon-based material. An aqueous layer 13 can be formed.

  The water repellent layer 13 is preferably formed by a wet process. Thereby, the water repellent layer 13 having a uniform film thickness can be formed.

  Examples of the wet process include a dip method, a spin coat method, a spray method, and the like, but it is particularly preferable that the wet process is formed by a dip method. Thereby, the water repellent layer 13 having a more uniform film thickness can be formed. Moreover, it can be produced in large quantities at a low cost.

  Generally, when the film thickness of the water repellent layer 13 is small, adhesion to the intermediate layer 12 cannot be obtained, and when the film thickness is large, the texture of the substrate 11 tends to be impaired. For this reason, the thickness of the water repellent layer 13 is preferably in the range of 5 to 1200 nm.

Examples of the organic silicon material of the intermediate layer 12 include alkoxysilanes such as methylmethoxysilane, tetraethyl orthosilicate (TEOS), disiloxanes such as hexamethyldisiloxane (HMDSO), and disilazanes such as hexamethyldisilazane. In particular, hexamethyldisiloxane (HMDSO) is preferable. Moreover, as a fluorine-type compound of the water repellent layer 13, a polytetrafluoroethylene derivative is preferable and the polytetrafluoroethylene derivative which has Si group at the terminal is especially preferable. As can be seen from the fact that polytetrafluoroethylene derivatives having an Si group at the terminal are used as the outermost antifouling film for smartphones and the like, the water repellent effect of the material itself is very high. Further, since the adhesion between the SiO ₂ in the intermediate layer 12 made of HMDSO and the Si group in the water-repellent layer 13 made of a polytetrafluoroethylene derivative having a Si group at the terminal is very good, the durability is further improved. An excellent water repellent layer 13 can be formed.

  In this embodiment, the intermediate layer 12 and the water repellent layer 13 are formed only on one side of the base material 11, but these may be formed on both sides. In this case, the water repellency is provided on both sides of the base material 11. Can be granted.

  As described above, according to the base material 10 subjected to the water repellent treatment according to the present embodiment, the intermediate layer 12 made of an organosilicon material is formed before the water repellent layer 13 is formed on the base material 11. Therefore, it is possible to prevent the water repellent from permeating the base material 11. Thereby, it is possible to prevent the texture of the base material 11 from being damaged, and to exhibit water repellency with a small amount of water repellent. Furthermore, since the adhesiveness between the intermediate layer 12 made of an organic silicon material and the water repellent layer 13 made of a fluorine compound is good, the durability of the water repellent layer 13 is improved.

(Experimental example)
In order to verify the effect of the water repellent treated substrate manufactured by the manufacturing method according to this embodiment, the following three types of samples were used to compare water repellency and texture.
Experimental example 1: Paper base material + intermediate layer + water repellent layer Comparative example 1: Paper base material + water repellent layer Comparative example 2: Paper base material

As the paper base material in Experimental Example 1 and each Comparative Example, Japanese paper (basis weight 6 g / m ² ) manufactured by Daifuku Paper Co., Ltd. was used.

For the formation of the intermediate layer in Experimental Example 1, a plasma CVD method is used, and the HMDSO flow rate is 5 sccm (8.45 × 10 ⁻³ Pa · m ³ / sec), the O ₂ flow rate is 350 sccm (5.92 × 10 ⁻¹ Pa ·). m ³ / sec) and a film forming pressure of 1.5 Pa, an intermediate layer made of HDMSO having a film thickness of 300 nm was formed on the paper substrate.

  In the formation of the water repellent layer in Experimental Example 1 and Comparative Example 1, a fluorine-containing resin “Top CleanSafe (WAF)” (registered trademark) (CEKO Co.) was used, and a water repellent was applied to the substrate by the dipping method. Then, drying and effect treatment were performed for 30 minutes at a temperature of 150 ° C. to form a water repellent layer having a thickness of 20 nm.

The above comparison results are shown in Table 1. The symbols in the table indicate that the characteristics are excellent in the order of ◎, ○, Δ, and ×, and the water contact angle was measured by the droplet method.

  The following was found by the above comparative test.

(1) Regarding water repellency-In Experimental Example 1, the water repellent was retained on the intermediate layer formed on the base material, and thus exhibited high water repellency.
In Comparative Example 1, although some water repellency was exhibited, the water repellant soaked into the base material and not all of the base material was covered with the water repellent layer. It was inferior.
In Comparative Example 2, water soaked into the base material.

  FIG. 3 is a photomicrograph when water droplets are dropped on the surface in Comparative Example 2 and Experimental Example 1. As shown in FIG. 3A, it can be seen that in Comparative Example 2 where the water repellent treatment is not performed, the paper base material sucks water. On the other hand, as shown in FIG. 3B, it can be seen that the paper substrate subjected to the water repellent treatment according to the present embodiment exhibits high water repellency and water droplets are held on the substrate surface.

(2) Regarding the texture of the base material-In Experimental Example 1, the intermediate layer prevented the penetration of the water repellent into the base material, and the texture close to that of the paper base material alone (Comparative Example 2) was maintained.
In Comparative Example 1, the water repellent soaked into the base material, so the texture of the base material was impaired.

Further, the base material subjected to the water repellent treatment according to the present embodiment has an advantage over Comparative Example 1 in terms of manufacturing cost. In Comparative Example 1, the water repellent soaks into the substrate, and a large amount of water repellent is required for the expression of water repellency. However, in Experimental Example 1, the water repellent is retained on the surface of the intermediate layer. The use efficiency of the liquid agent is good, and a high water repellent effect can be obtained with a small amount of the water repellent.

DESCRIPTION OF SYMBOLS 10 Base material 11 which was water-repellent-treated 11 Base material 12 Intermediate layer 13 Water-repellent layer 20 Base material 21 which was water-repellent-treated Fibrous base material 22 Intermediate layer 23 Water-repellent layer

Claims (13)

Forming an intermediate layer on the substrate;
Forming a water repellent layer on the intermediate layer;
A method for producing a water repellent base material comprising:
The intermediate layer is made of an organosilicon material,
The said water-repellent layer is a manufacturing method of the base material in which the water-repellent process which consists of a fluorine-type compound was made | formed. The organosilicon material is hexamethyldisiloxane (HMDSO),
The method for producing a water repellent substrate according to claim 1, wherein the fluorine-based compound is a polytetrafluoroethylene derivative having a Si group at a terminal. The said intermediate | middle layer is a manufacturing method of the base material with which the water repellent process was made | formed of Claim 1 or 2 formed by CVD method. The method of manufacturing a substrate subjected to water repellent treatment according to claim 3, wherein the CVD method is a plasma CVD method. The method for producing a base material subjected to water repellent treatment according to any one of claims 1 to 4, wherein the intermediate layer has a thickness of 50 to 1000 nm. The said water-repellent layer is a manufacturing method of the base material with which the water-repellent process of any one of Claims 1-5 made | formed by the wet process. The method for manufacturing a substrate subjected to water repellent treatment according to claim 6, wherein the wet process is a dip method. The film thickness of the said water repellent layer is 5-1200 nm, The manufacturing method of the base material with which the water repellent process of any one of Claims 1-7 was made | formed. The water contact angle is 130 ° or more,
The manufacturing method of the base material in which the water repellent process of any one of Claims 1-8 was made | formed. A substrate;
An intermediate layer made of hexamethyldisiloxane (HMDSO) formed on the substrate;
A water repellent layer made of a polytetrafluoroethylene derivative having a Si group at the end formed on the intermediate layer;
A water repellent base material having The water-repellent-treated substrate according to claim 10, wherein the intermediate layer is formed by a plasma CVD method. The base material subjected to the water repellent treatment according to claim 10 or 11, wherein the water repellent layer is formed by a dip method. The water contact angle is 130 ° or more, The substrate subjected to the water repellent treatment according to any one of claims 10 to 12.

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