JPH0525304A - Modification of solid surface - Google Patents

Abstract

PURPOSE:To modify the solid surface at a low cost by carrying out a gas phase treatment of the surface of a material having exposed hydroxyl groups with a perfluoro group-containing silane-based compound, chemically bonding the compound to the surface and giving durable water repellency thereto. CONSTITUTION:A material (e.g. borosilicate glass base plate) having exposed hydroxyl groups on the surface to be treated is subjected to a gas phase treatment with a perfluoro group-containing silane-based compound (e.g. 1H,1H,2H,2 H-perfluorodecyltrichlorosilane) represented by the formula [Rf-X is perfluoro group-containing group; Y and Z are Rf-X, Cl, R (H, CH3 or C2H5) or OR; X is A-B-C (A is alkylene, oxyalkylene, polyoxyethylene, etc.; B is SO2, CO, NH, SO2NH, etc.; C is O, S, SO2 CO, CH=CH, N=N, etc.)] to chemically bond the perfluoro group-containing silane-based compound to the hydroxyl groups on the surface of the material to be treated. Thereby, the solid surface can be modified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for surface modification of a solid in which a fluorine-containing compound is chemically bonded to the surface of an object to be treated having hydroxyl groups on the surface.

[0002]

2. Description of the Related Art Generally, as a method of imparting water repellency to a solid surface, a method of adsorbing, dipping, coating or spraying a fluorine-based or silane-based compound imparting water repellency, or plasma using a fluorocarbon-based gas There are treatment methods such as fluorination by treatment, formation of a polymer film, and heat vapor deposition. For example, heating vapor deposition using carbon fluoride on the surface of an electric heating tube (Japanese Patent Laid-Open No. 50-75178), water-repellent treatment method of solid surface using plasma sputtering (Japanese Patent Laid-Open No. 60-75178).
-13065), a surface treatment method for glass molded articles using a silane compound (Japanese Patent Publication No. 60-21936), and a fluorine-containing functionalization method in which a fluorine compound is bonded to a polymer surface in a gas phase (JP-A-2-
279735) etc.

[0003]

However, in the method of adsorbing the water repellent, the life of the adsorbing film is extremely short, and
Water repellent effect diminishes after about 80 hours. Also, in the method of dipping, coating or spraying, since the surface and the compound that imparts water repellency are not chemically bound, peeling of the coating, abrasion, deterioration of performance such as deterioration is likely to occur, and it does not last for a long time. There are drawbacks. If the thickness of the coating is increased in order to eliminate this drawback, the transparency is impaired. Moreover, since these methods use a large amount of solvent, there are problems such as operational safety and environmental damage. In addition, the method of processing in vacuum such as plasma processing or heating vapor deposition or the method of processing at high temperature requires a special apparatus, and the processing apparatus is very expensive. Moreover, depending on the type of the treated substrate, it may be difficult to draw a vacuum, or heat may be applied to the treated substrate, so that a substrate having no heat resistance may be difficult to treat. Further, these methods also have a problem that uniform treatment cannot be performed when the surface of the object to be treated has a complicated shape, or is spherical, powdery, capillary, or the like.

[0004]

It is an object of the present invention to chemically bond a fluorine-containing compound to the surface of an object to be treated having a hydroxyl group on the surface so that it does not deteriorate its function even when used for a long period of time and is in a gas phase. It is intended to provide a solid surface modification method capable of uniformly treating a surface having a complicated shape by the treatment.

[0005]

The method for modifying the surface of a solid according to the present invention comprises subjecting an object having a hydroxyl group on the surface to a gas phase treatment with a silane compound having a perfluoro group, and subjecting the surface of the object to a perm treatment. This is to chemically bond a silane compound having a fluoro group. The surface modification method for a solid according to the present invention uses a silane compound having a perfluoro group represented by Formula 1.

[0006]

[Chemical 5]

In the solid surface modification method according to the present invention, Rf of the group Rf-X- having a perfluoro group is a perfluoroalkyl group Rf ₁ represented by the formula 2 and a perfluoroalkenyl group represented by the formula 3. A silane compound selected from at least one group selected from the group consisting of the group Rf ₂ and the perfluoroaryl group Rf ₃ represented by the formula 4.

[0008]

[Chemical 6]

[0009]

[Chemical 7]

[Chemical 8]

Next, the present invention will be described in detail. The object to be treated by the present invention may be one having a hydroxyl group on the surface, for example, cotton, hemp, paper, rayon, acetate,
Treatment of cellulose products such as pulp and wood, polyvinyl alcohol, polyvinyl butyral, phenol resin, epoxy resin, phenoxy resin, melamine resin, alkyd resin, modified acrylic resin, modified methacrylic resin, modified polyurethane resin, and other synthetic resins Those that have hydroxyl groups themselves, glass products such as quartz glass, soda lime glass, aluminosilicate glass, borosilicate glass, and Al, Zn, Sn, Ti, Ni, Cu, C
o, W, Mo, Mg, Fe, Al ₂ O ₃ , Fe ₂ O ₃ , Fe
Examples include metals, alloys and metal oxides such as ₃ O ₄ ... In which natural oxides are formed.

Furthermore, even a protein product such as leather, silk, wool, and fur, which has no hydroxyl group on the surface, or a solid such as ceramics, has good adhesion to the solid to be treated and has a hydroxyl group, for example, If a hydroxyl group is generated on the surface by a physical / chemical method such as coating with a synthetic resin, corona treatment, plasma treatment, ozonization, etc., the treatment can be performed by the method of the present invention.

As the silane compound having a perfluoro group, a compound represented by the formula 1 containing a group having a hydroxyl group on the surface and having reactivity with the surface of the object to be treated can be used.

[0013]

[Chemical 9]

Specific examples of the silane compound having a perfluoro group are listed below. _{RFCH 2 CH 2 SiCl 3 RFCH 2} CH 2 Si (CH 3) Cl 2 RFCH 2 CH 2 Si (CH 3) 2 Cl (RFCH 2 CH 2) 2 SiCl 2 (RFCH 2 CH 2) 3 SiCl RFCONHCH 2 CH 2 NH _{(CH 2) 3 SiCl 3 RFCH} 2 CH 2 OCONH (CH 2) 3 SiCl 3 RFCH 2 CH 2 NH (CH 2) 2 SiCl 3 RFSi (CH 3) 2 Cl ( provided _{that, RF = Rf 1, Rf 2} , Rf ₃ ) It is possible to dilute a silane compound having a perfluoro group with a solvent. In this case, the amount of the solvent is smaller than that of dipping, coating or spraying, so that it does not affect the human body. There is much less danger than before and environmental damage. Examples of the diluting solvent include n-hexane,
Alkanes such as n-heptane and n-hexadecane, aromatic hydrocarbons such as benzene and toluene, acetone,
Ketones such as methyl ethyl ketone, alicyclic hydrocarbons such as cyclopentadiene and cyclopentane, ethers such as ethyl ether, isopropyl ether and dioxane, esters such as ethyl acetate and butyl acetate, and silane compounds having a perfluoro group It is possible to use a solvent which is dissolved or uniformly dispersed and which is a single solvent or a mixture of two or more solvents having no reactivity with the silane compound having a perfluoro group. It is preferable that the diluent solvent does not contain a compound having a hydroxyl group such as water and alcohol, and even if it is dissolved at a concentration of 2.0 × 10 ^{−3 to} 5.0 × 10 ⁻² mol / l, the effect is obtained. You can get enough. Also,
The vapor of the silane-based compound having a perfluoro group may be saturated vapor or sublimation vapor, but it is more preferable to perform it in an atmosphere of an inert gas such as N ₂ or He because the effect of moisture in the atmosphere is less. preferable.

The heating temperature is appropriately selected depending on the silane compound having a perfluoro group. Further, generally, the higher the temperature is, the higher the vapor pressure becomes, and the processing time is shortened because the vapor amount of the silane compound having a perfluoro group is large. However, if the temperature is too high, the silane compound having a perfluoro group is decomposed or Be careful as there is a risk of solvent evaporation and boiling.

The treatment time varies depending on the type of silane compound having a perfluoro group, the treatment temperature and the flow rate of the inert gas, but it is generally several minutes to several hours. A silane compound having a perfluoro group, for example, RFCH ₂
It is possible that CH ₂ SiCl ₃ and -OH on the surface of the object to be treated will undergo a dehydrochlorination reaction.

[0017]

[Chemical 10]

Since such a bond is formed to chemically bond with the surface of the object to be treated, the effect can be maintained even if it is used for a long period of time. Further, since the treatment is carried out in the gas phase, the surface of the object to be treated has a very small amount of unreacted silane compound having a perfluoro group. Therefore, there is almost no need for post-treatment, and the workability is improved. Moreover, even a coating film such as paint having no solvent resistance can be treated without causing performance deterioration. Also, since it is not processed at high temperature,
It is industrially very effective because even plastics and other materials with low heat resistance can be processed without causing changes in physical properties or appearance.

[0019]

According to the present invention, since the surface of the object to be treated is similar to the state in which fluorine atoms are arranged on the surface, water repellency / oil repellency, antifouling property, adhesion property, low friction property, wear resistance Shows excellent effects such as chemical resistance and chemical resistance. Moreover, since the surface of the object to be treated and the silane compound having a perfluoro group are chemically bonded, the effect can be maintained even after long-term use. it can.

[0020]

【Example】

Example 1 As shown in the figure, at the bottom of a separable flask equipped with a thermometer 2 and having an inner diameter of 85 mm and an inner volume of 500 cm ³ , the following structural formula CF _3- (CF ₂ ) ₇ was used as a silane compound having a perfluoro group. A solution prepared by dissolving 0.03980 g of 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane represented by — (CH ₂ ) ₂ —SiCl ₃ in 18.00 g of n-hexadecane was added. The borosilicate glass substrate 4 was attached to the substrate holder 3, and the sample solution 1 was treated at 40 ° C. for 3 minutes while stirring.

Table 1 shows the results of measuring the contact angles of various liquids using a goniometer-type contact angle measuring instrument (manufactured by Elma Co .; GI-1000 type) for the obtained samples. This sample was washed several times with a commercially available detergent, and the contact angle of distilled water was measured again. As a result, it was found that the effect was 112 ° and the effect continued. Example 2 The following structure as a silane compound having a perfluoroalkyl group formula _{CF 3 - (CF 2) 5} - (CH 2) 1H represented by _{2 -SiCl 3, 1H, 2H,} 2H- perfluorooctyl trichlorosilane Table 1 shows the results obtained by dissolving 0.04232 g in 18.00 g of n-hexadecane and subjecting to gas phase treatment at 35 ° C. for 3 minutes, and similarly measuring the contact angle with various liquids.

After washing this sample several times with a commercially available detergent, the contact angle of distilled water was measured again, and it was found that it was 105 ° and the effect continued. Comparative Example 1 Table 1 shows the results of measuring the contact angles of various liquids on a glass substrate that had not been treated in the same manner as in Example 1.

[0023]

[Table 1]

As is clear from Table 1, both Examples 1 and 2 were confirmed to have high water repellency and oil repellency against various liquids. Example 3 For an Al substrate, 1H, 1H, 2H, and 2H-perfluorodecyltrichlorosilane (0.07781 g) were dissolved in n-hexadecane (25.09 g), and the same procedure as in Example 1 was performed.
Table 2 shows the results of measuring the contact angle with various liquids after gas phase treatment at 0 ° C. for 5 minutes.

This sample was dipped in a 10% HCl aqueous solution at 40 ° C. for 5 minutes, rinsed with distilled water, and then the contact angle was measured again with distilled water. It was Example 4 With respect to an Al substrate, 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (0.04733 g) was n-typed.
Table 2 shows the results obtained by dissolving 20.49 g of hexadecane and subjecting it to gas phase treatment at 35 ° C. for 5 minutes to measure the contact angle with various liquids as in Example 1.

This sample was dipped in a 10% HCl aqueous solution at 40 ° C. for 5 minutes, rinsed with distilled water, and then the contact angle was measured again with distilled water. The contact angle was 123 °, showing that the effect persisted. It was Comparative Example 2 Table 2 shows the results of measuring the contact angles of various liquids with respect to the Al substrate which was not subjected to any treatment in the same manner as in Example 1.

This sample was immersed in a 10% HCl aqueous solution at 40 ° C. for 5 minutes, rinsed with distilled water, and then the contact angle was measured again with distilled water. The contact angle was 65 °, and the surface was attacked by the HCl aqueous solution. I found out.

[0028]

[Table 2]

As is clear from Table 2, in Examples 3 and 4, high water repellency and oil repellency against various liquids were confirmed. Example 5 With respect to a Cu substrate, 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (0.01741 g) was dissolved in 23.30 g of n-hexadecane, and gas phase treatment was performed for 5 minutes under the same conditions as in Example 1 Table 3 shows the results of measuring the contact angle with various liquids in the same manner as in.

This sample was immersed in a 10% HCl aqueous solution at 40 ° C. for 5 minutes, rinsed with distilled water, and then the contact angle was measured again with distilled water. The contact angle was 116 °, and it was found that the effect continued. It was Example 6 For Cu substrates, 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (0.05350 g) was added to n-.
Table 3 shows the results of dissolving in 15.45 g of hexadecane, treating at 35 ° C. for 5 minutes, and measuring contact angles with various liquids in the same manner as in Example 1.

This sample was immersed in a 10% HCl aqueous solution at 40 ° C. for 5 minutes, rinsed with distilled water, and then the contact angle was measured again with distilled water. The contact angle was 112 °, and it was found that the effect continued. It was Comparative Example 3 Table 3 shows the results of measuring the contact angles of various liquids in the same manner as in Example 1 with respect to a Cu substrate that had not been treated.

[0032]

[Table 3]

As is clear from Table 3, in both Examples 5 and 6, high water repellency and oil repellency were confirmed for various liquids. Example 7 As a resin having a hydroxyl group on the surface, a polyvinyl alcohol resin (Gohsenol NH-26, manufactured by Nippon Synthetic Chemical Industry) and a phenolic resin (PSK-2323, manufactured by Gunei Chemical Co., Ltd.) were formed into films, 1H, 1H, 2H, 2H, perfluorodecyltrichlorosilane 0.03550 g n
-Dissolved in 15.45 g of hexadecane, subjected to gas phase treatment at 40 ° C for 1 hour, and measuring the contact angle of distilled water.
Shown in.

Using CFC 113, these samples were
The results of measuring the contact angle of distilled water again after ultrasonic cleaning for 0 minutes and drying are shown in Table 4. Comparative Example 4 As a resin having no hydroxyl group on the surface, a polyester resin (polyethylene terephthalate film, Lumirror T-
60, made by Toray) and nylon resin (Ultramid 1)
Table 4 shows the results of measuring the contact angle of distilled water by treating the film-shaped C., manufactured by BASF) under the same conditions as in Example 7.

Using CFC 113, these samples were
The results of measuring the contact angle of distilled water again after ultrasonic cleaning for 0 minutes and drying are shown in Table 4.

[0036]

[Table 4]

As is clear from Table 4, those having no hydroxyl group on the surface are not chemically bonded and are washed away by chlorofluorocarbon cleaning, and those having a hydroxyl group on the surface are chemically bonded. Therefore, it was found that the effect did not disappear even if the fluorocarbon cleaning was performed, and the effect continued.

[0038]

EFFECTS OF THE INVENTION According to the present invention, since the surface of the object to be treated having hydroxyl groups on the surface is chemically bonded to the silane compound having a perfluoro group, the durability does not deteriorate even when used for a long period of time. A highly water-repellent surface is obtained, and since the silane-based compound having a perfluoro group is vapor-phase treated, the entire surface of the object to be treated is treated thoroughly even if the shape of the object is complicated. It Moreover, since the amount of the diluting solvent is smaller than that of the method of dipping, coating or spraying, there are less problems such as danger of work and environmental damage than before. Further, since the device required for the present invention is simple and inexpensive, the manufacturing cost can be reduced.

[Brief description of drawings]

FIG. 1 is a view showing an example of a vapor phase contact device for carrying out the present invention.

[Explanation of symbols]

1 …… Sample solution 2 ... Thermometer 3 ... Board holder 4 ... Object to be processed

Claims (3)

[Claims] 1. An object to be treated having a hydroxyl group on the surface is subjected to a gas phase treatment with a silane compound having a perfluoro group, and the hydroxyl group on the surface of the object to be treated and the silane compound having the perfluoro group are chemically treated. A method for modifying the surface of a solid, which comprises bonding to 2. The method for modifying the surface of a solid according to claim 1, wherein the silane compound having a perfluoro group is represented by Formula 1. [Chemical 1] 3. A group Rf-X- having the perfluoro group.
Rf of R is a perfluoroalkyl group R represented by the formula 2.
The above silane-based compound selected from at least one of the group consisting of f ₁ , a perfluoroalkenyl group Rf ₂ represented by formula 3 and a perfluoroaryl group Rf ₃ represented by formula 4 is used. The method for modifying the surface of a solid according to claim 2. [Chemical 2] [Chemical 3] [Chemical 4]