JPH02180984A - Water-and oil-repellent material - Google Patents

Abstract

PURPOSE:To obtain the title material which can exhibit excellent water- and oil-repellent properties without detriment to the hue, etc., inherent in an object by treating the surface of the object with a water- and oil-repelling agent comprising a specified fluorosilane compound or adding this agent thereto. CONSTITUTION:The surface of, for example, a metal, a resin, a paper or a glass is treated with a fluorosilane compound of the formula (wherein R<1> is a 1-5C alkyl; and X is CO, Br, OCH3 or OC2H5), or this agent is added to, for example, a resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to water and oil repellent products treated with a water and oil repellent comprising a fluorine-containing silane compound.

[Conventional technology and problems]

General metal materials inherently have poor resistance to moisture, and moisture adhering to or adsorbing on the surface oxidizes the surface layer, which causes corrosion, and the surface is easily stained because it has poor water and oil repellency. . To prevent this, treatments such as plating the metal surface or coating it with a suitable resin have been used. However, in the plating process, a new metal layer is deposited on the base metal, and the problem of surface oxidation of the metal still remains, and the combinations of the base, metal, and coating layer are inevitably limited.

When a resin is applied to the surface of the metal scrap, the above-mentioned problem in 1st plating is improved, but since the adhesion between the resin and the metal is often insufficient, corrosion occurs at the interface between the two. Furthermore, metallic luster is lost in both plating and resin application.

In general, resins are hydrocarbon-based polymer compounds and are often relatively water resistant, but their application to fields where even small amounts of moisture can be affected, such as semiconductor encapsulants, has yet to be applied. There is a problem that water resistance is not sufficient. Furthermore, although water stains are relatively easy to remove from resins, oil stains are generally difficult to remove and resins also have the disadvantage of poor oil repellency.

In order to solve these problems, silicone-based resins or fluororesins are being considered, but although silicone-based resins have excellent water resistance, their oil repellency is not yet sufficient, and fluororesin has excellent water and oil repellency, but is generally difficult to process and difficult to create into complex shapes.

In the past, attempts have been made to add fluorine-based surfactants to resins or to treat the surface, but in order to obtain the desired effect with the addition method, it is generally necessary to add several tens of weight percent. , it just becomes more expensive (
In some cases, the surfactant may be eluted from the surface, causing a problem in durability, and surface treatment methods also have a general problem in that the surfactant is difficult to adhere to the resin surface.

Paper is inherently highly absorbent and is suitable for office use,
When used for packaging, etc., it is easy to tear if it gets wet. This is an even bigger problem with cardboard for transporting packages.

Furthermore, papers used for food packaging etc. have problems such as oozing of the contents, so paper with oil repellency is required for this purpose. To address these issues, adding or coating hydrocarbon-based organic compounds to paper to make it more water resistant has been considered, but the water resistance is not necessarily sufficient and the oil resistance is extremely poor. .

In recent years, attempts have been made to use phosphoric acid esters having perfluoroalkyl groups in order to improve the water and oil repellency of paper (Japanese Patent Publication No. 48-4770, Japanese Patent Publication No. 40-6
No. 857, JP-A No. 49-124031), the adhesion between the compound and the paper substrate is not necessarily sufficient and still needs improvement.

[Knowledge related to problem solving]

In order to solve the above-mentioned problems, the present inventors conducted extensive research on a method for more effectively imparting water and oil repellency to these various materials, and as a result, the general formula C, F, , 5o2NR"
Adding a fluorine-containing silane compound represented by CH, CH2CH25iX, (wherein R'', X is as described above) to the materials, or treating the surfaces of the materials with a solution containing the compound. We found that the first goal could be achieved by

[Structure of the invention]

According to the present invention, the general formula % formula % () (wherein 81 is c, +5 alkyl group, X is CQ, Br,
A material is provided which has been surface-treated with a water- and oil-repellent agent made of a fluorine-containing silane compound represented by 0C11, QC21+, or which has been subjected to water- and oil-repellent treatment by adding the water- and oil-repellent agent.

In the fluorine-containing silane compound of the present invention, its trihalosilyl group and trialkoxysilyl group react with water to form a trihydroxysilyl group, which is used to produce metals, resins,
It forms dehydration condensation or hydrogen bonds with the polar groups present on the surface of paper and colored tiles, or strongly adsorbs to these materials that do not have hydroxyl groups on the surface. The group imparts water and oil repellency.

In the present invention, 81 in the fluorine-containing silane compound represented by the general formula (1) is an alkyl group of cl-5.

Also, X is CQ, Br or -0CI4. , -0C2Hs
It is.

The fluorine-containing silane compound has excellent water and oil repellency and also has good adhesion to metals, resins, and the like.

The metal materials to which the present invention is applied are not particularly limited, but specific examples include copper, aluminum, iron, lead, zinc, tin, titanium, cobalt, and nickel.

In addition to alloys such as chromium, stainless steel, SUS, Hastelloy, Inconel, and Stellite, Sm-Co, Nd
It can also be applied to -Fe-B alloy magnets. The metal material may have any shape such as a plate, a sphere, or a ribbon, and the present invention is not affected by the shape or size of the metal material.

The type of resin to which the present invention is applied is not limited.

Phenol resin, furan resin, xylene/formaldehyde resin, ketone/formaldehyde resin, urea resin,
Melamine resin, aniline resin, alkyd resin, polyester resin, epoxy resin, polyvinyl acetate resin, polyacrylate resin, polymethacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylonitrile resin, polyvinyl ether resin, polycarbonate resin, polyamide Resin, polyurethane resin, etc. can be applied to most hydrocarbon resins. Note that the adhesion to silicone resins and fluororesins is lower than that to hydrocarbon resins. The present invention is in the form of resin.

It is completely unaffected by size and can be applied to plate-like, membrane-like, and fibrous objects.

The paper to which the present invention is applied is not particularly limited, and specific examples include Japanese paper, Western paper, and thick paper such as cardboard. The present invention is completely unaffected by the shape and size of paper.

The present invention can also be applied to various types of glasses.

In the present invention, when a material is surface-treated with a solution of a fluorine-containing silane compound represented by the above-mentioned formula, the concentration varies depending on the type of material and its surface area, but for metals, paper, and glass, it is 0.01 A range of 20% by weight is preferred. If it is less than 0.01% by weight, there will be no effect on water and oil repellency, and if it is more than 20% by weight, there will be no significant change in the water- and oil-repellent effect compared to when it is less than 20% by weight. On the other hand, when added to the resin, the range of o, i to 20% by weight is suitable. If it is less than 0.1% by weight, there is no effect on water and oil repellency, and if it is less than 20% by weight, there is no significant change in water and oil repellency compared to when it is less than 20% by weight.

Next, a method for imparting water and oil repellency to metals, resins, paper and glass using the fluorine-containing silane compound of the present invention will be described.

In the above treatment method, the fluorine-containing silane compound of the present invention is added to a solvent, and this solution is applied to the surface of a material to be treated, such as metal, resin, or glass. Alternatively, the solution is added to a resin or the like. The coating method is a dipping method, a spray method, a brushing operation, or any other conventional coating method. The solvent for preparing the fluorine-containing silane compound is preferably an organic solvent such as a halogenated hydrocarbon, alcohol, or ether, and an anhydrous solvent or one to which a small amount of an aqueous solution of an amine or acid is added as necessary is used. Ru. The amine used here may be any of primary amines, secondary amines and tertiary amines, but -class amines are particularly effective. The acids used include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, formic acid,
Organic acids such as acetic acid, oxalic acid, and toluenesulfonic acid can be used.

In an aqueous solution of these amines or acids, the trihalogenosilyl group or trialkoxysilyl group of the fluorine-containing silane compound is hydrolyzed to form a trihydroxysilyl group, and this trihydroxysilyl group is used as a material to be treated. It dehydrates and condenses with hydroxyl groups on the surface, or has the effect of strongly adsorbing to treated materials that do not have hydroxyl groups on the surface.

Furthermore, the acid and amine serve as catalysts that promote this hydrolysis, dehydration, and condensation. The concentration of these amines or acids is 15% by weight of the total amount of the processing solution.
Hereinafter, preferably 0.05 to 5% by weight is suitable.

When treating materials such as metals, resins, and glass with these fluorine-containing silane compounds, the treatment temperature varies depending on the solvent, but the treatment is carried out in a temperature range from room temperature to the boiling point of the solvent. When using anhydrous solvents in the treatment of metal materials,
Alternatively, if processing at room temperature, 60 to 15
Dry the treated material at 0°C, preferably 80-130°C.

These treatments are necessary to more firmly bond the fluorine-containing silane compound to the metal material.

In addition to the above-mentioned surface treatment, methods for treating the resin include a method in which the fluorine-containing silane compound of the present invention is added to the resin before molding.

The addition method is carried out by adding the fluorine-containing silane compound of the present invention to a resin stock solution before curing and molding. In addition, the surface treatment method for resin is completely cured resin or
This is carried out by immersing each pre-cured resin in a solution of the fluorine-containing silane compound of the present invention, impregnating it with the fluorine-containing silane compound, and drying the resin before completely curing it.

As mentioned above, in the fluorine-containing silane compound of the present invention, the trihalogenosilyl group or trialkoxysilyl group is hydrolyzed to form a trihydroxysilyl group, and the polar groups present in the resin (for example, carboxyl group, It has the effect of dehydration condensation or strong adsorption with hydroxyl groups, amino groups, etc.).

As a method for treating paper with the fluorine-containing silane compound of the present invention, both an internal addition method and an external addition method can be applied.

In the internal addition method, paper is made by adding the fluorine-containing silane compound of the present invention into a pulp stock solution before paper making.

The external addition method is carried out by immersing paper, which is a base material, in a solution of the fluorine-containing silane compound of the present invention, impregnating it with the fluorine-containing silane compound, and drying it. When treating paper materials with these fluorine-containing silane compounds by external addition method,
Although the treatment temperature varies depending on each solvent, the treatment is carried out in a temperature range from room temperature to the boiling point of the solvent. After processing, it is usually room temperature ~ 1
It is dried at 20°C, preferably 60-80°C.

These treatments are necessary to more firmly bond the fluorine-containing silane compound to the paper material that is the substrate.

The method for treating glass with the fluorine-containing silane compound of the present invention is carried out by applying the same solution of the fluorine-containing silane compound to the glass surface as in the metal treatment described above and drying it.

〔Effect of the invention〕

The metal according to the present invention to which the fluorine-containing silane compound of the present invention is attached or bonded has almost no difference in visible light reflectance compared to the original metal, and does not lose its luster. Further, even in resin 1 paper and glass, there is no change in color tone before and after surface treatment with the fluorine-containing silane compound of the present invention, and therefore it is possible to impart water and oil repellency without impairing the original beauty of the substrate.

[Examples and comparative examples]

Example 1 Aluminum plate (100m x 50+IIm x 1
mm).

C, F□, SO□N (C, II,) (CH2), S! (
A 0.5% solution of QC, H5) II in acetone (containing 0.5% by weight of 10% acetic acid) was applied to the surface of the aluminum plate. As a result of infrared spectroscopic analysis of this aluminum plate using a high-sensitivity reflection method, a C--F bond was confirmed at 1300 to 1400 cm+-1.

The contact angle of this aluminum plate to water and liquid paraffin was measured to evaluate water and oil repellency.

The results are shown in Table 1.

Comparative Example 1.2 Using the same aluminum plate as in Example 1, acrylic resin (manufactured by Tokyo Paint, self-curing type) was used instead of fluorine-containing silane to obtain an aluminum plate to which the acrylic resin was attached. Further, copper plating was applied to the same aluminum plate as in Example 1 to obtain a copper-plated aluminum plate.

Example 1 The water repellency and oil repellency test results of this aluminum plate
The results are shown in Table 1.

Table 1 Example 2 Copper plate (50mm x 100mm x III+n+)
To.

C,FSO□N (C,H,) (C)1. )3
A 5% by weight acetone solution of Si (OCR,)3 (10
% dilute aqueous hydrochloric acid solution) was applied to obtain a copper plate to which the fluorine-containing silane compound was attached.

After coating, this copper plate was dried at 80°C for 1 hour, and the infrared absorption spectrum of this copper plate was measured using a reflection method.
Absorption based on CF bonds was observed at 1100 to 1300 cm-'', and it was confirmed that a fluorine-containing silane compound was present on the surface.

As a corrosion resistance test, this copper plate was immersed in a 5% saline solution, and the weight change due to corrosion was measured.

Comparative Example 3 The results of a corrosion resistance test similar to that of Example 2 using an untreated copper plate are shown in Table 2 together with the results of Example 2.

Table 2 Weight reduction rate Confirmed that something exists.

As a stain resistance test, this iron plate was exposed outdoors and the surface was observed with the naked eye.

Comparative Example 4 The same antifouling test as in Example 3 was conducted using an untreated iron plate, and the results are shown in Table 3 together with the results of Example 3.

Table 3 Example 3 Iron plate (100m++ x 50n+a+ x 1mm)
, Cs Fx 7 SOa N (C2Is) (
CH2)3Si(OC2H5)) in 5% by weight ethanol solution (10% = 0.5% low propylamine aqueous solution)
% by weight) to obtain an iron plate to which the fluorine-containing silane compound was attached.

After drying this iron plate at 120°C for 1 hour, the infrared absorption spectrum of this iron plate was measured using a reflection method.
Absorption based on CF bonds is observed at 100 to 1300 cm-1, and fluorine-containing silane compound Δ is present on the surface of the iron plate. Condition X: Dirt is present in several places on the surface. (Tokyo Paint Ring, melamine hardening type) 1
00g as a fluorine-containing silane compound, Cl1F,,So
, add 5g of N(CH,)(CH2)3Si(OCH3), 50+un+X 100mm+X Jam
A bonded copper plate (manufactured by Nippon Test Panel) with a thickness of 0.
It was applied to a thickness of 11III+ and cured at 120°C for 20 minutes. As a water and oil repellency test, the contact angle between water and liquid paraffin was measured.

Comparative Example S An epoxy resin (manufactured by Tokyo Paint, melamine curing type) to which no fluorine-containing silane compound was added was cured at 120°C for 20 minutes, and the same water and oil repellency tests as in Example 4 were conducted. The results are shown in Table 4 together with the results of Example 4.

Table 4 Example 5 Epoxy resin (Tokyo Paint Kan, melamine hardening type) was bonded to a steel plate (manufactured by Nippon Test Panel, 50 ma x 100
a+ieX1mm) at a thickness of 0.1mm and heated at 80℃
It was precured for 30 minutes.

This treated steel sheet was treated with fluorine-containing silane compounds C, F SO
□N (CH,)3si 10% by weight of (OCH,)3
, Freon ■ C, H7 113 solution for 10 seconds and then cured at 120° C. for 20 minutes. When we took a part of the sample after curing and performed infrared spectroscopic analysis using multiple reflection method, we found that it was 1100-1300c.
C--F bond absorption was observed in "m-", and adhesion of the fluorine-containing silane compound was confirmed.Water repellency and oil repellency were evaluated in the same manner as in Example 4.

Comparative Example 6 The same treatment as in Example 5 was performed except that fluorine-based surfactants C, F17SO, and Na were used instead of the fluorine-containing silane compound. Evaluation of water repellency and oil repellency was performed in the same manner as in Example 4.

The results are shown in Table 5 together with the results of Example 5.

Table 5 Example 6 Acrylic resin (Tokyo Paint Ring, self-curing type) was bonded to a bonded steel plate (manufactured by Nippon Test Panel, 50 m1 x 10
0mm x lam) with a thickness of 0.1mm,
Cured for 20 minutes at 0°C.

This treated steel sheet is used as a fluorine-containing silane compound.

Table 6 After being immersed in the solution for 30 seconds, it was dried at room temperature.

When a part of the dried sample was taken and subjected to infrared spectroscopic analysis using the multiple reflection method, it was found that C
-F bond absorption was observed, and attachment of the fluorine-containing silane compound was confirmed.

Comparative Example 7 In place of the fluorine-containing silane compound, a fluorine-based surfactant C7F1. The same treatment as in Example 10 was performed except that Co and K were used.

No C--F bond could be confirmed by infrared spectroscopy.

Evaluation of water repellency and oil repellency was performed in the same manner as in Example 4.

The results are shown in Table 6 together with the results of Example 6.

Example 7 A commercially available A4 type report paper (manufactured by KOKUYO Co., Ltd.) was immersed in the liquid for 5 minutes and dried at room temperature for 2 hours.

When a part of this was taken and the infrared absorption spectrum was measured using the multiple reflection method, absorption based on C-F bonds was observed at 11.00 to 1300 cm-'', indicating that a fluorine-containing silane compound was present on the surface. This was confirmed.

As a water and oil repellency test, water droplets and liquid paraffin droplets were dropped onto this report paper, and the absorption rate was evaluated visually.

Comparative Example 8 The same water and oil repellency tests as in Example 7 were conducted using untreated report paper, and the results are shown in Table 7 together with the results of Example 7.

Table 7 Example 8 Comparative Example 9 Using a Fluorine-containing Silane Compound Paper was made without using a fluorine-containing silane, and the same tests as in Example 7 were conducted.The results are shown in Example 8. Table 8 shows the results of Example 9. 2% by weight of the pulp based on the weight of the pulp was added and paper was made.

After drying, a part of the sample was taken, and absorption believed to be a C--F bond was confirmed at 1100 to 1300 cm<-1> by infrared absorption multiple reflection method.

As in Example 7, water and oil repellency were evaluated based on the absorption rate of water and liquid paraffin.

Example 9 As a fluorine-containing silane compound, The same treatment as in Example 8 was performed.

Example 10 Commercially available packaging cardboard (manufactured by Aiya Shiki Kogyo Co., Ltd.) was immersed in a liquid containing a fluorine-containing silane compound for 3 minutes, and dried at 50° C. for 1 hour.

When we took a part of this and measured its infrared absorption spectrum using the multiple reflection method, we found that C at 1100"1300cm-1
Absorption based on -F bonds was observed, confirming the presence of a fluorine-containing silane compound on the surface.

Water repellency and oil repellency tests were conducted in the same manner as in Example 7.

Comparative example 10 Instead of fluorine-containing silane compounds, The same treatment as in 10 was performed.

The results of the same test as in Example 7 are shown in Example 7. It is shown in Table 9 together with the results of 10.

table

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1 is an alkyl group of C_1_-_5, X is Cl
, Br, OCH_3, OC_2H_5) is surface-treated with a water and oil repellent consisting of a fluorine-containing silane compound,
Or a material treated to be water and oil repellent by adding the water and oil repellent. 2. A water- and oil-repellent metal, resin, paper, or glass whose surface is treated with the water- and oil-repellent agent according to claim 1, or to which the water- and oil-repellent agent is added. 3. A water- and oil-repellent metal, resin, paper or glass, which is treated with a solution of the water- and oil-repellent agent according to claim 1 having a concentration of 0.01 to 20% by weight. 4. A water- and oil-repellent resin, characterized in that 0.1 to 20% by weight of the water- and oil-repellent agent according to claim 1 is added.