JPS62178902A - Surface reforming method for inorganic coating film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to modification of the surface state of an inorganic coated film.

[Conventional technology]

Plain coat films obtained by vacuum evaporation, ion blating, sputtering, etc. are widely used as antireflection films, hard coat films, and various functional films for optical materials such as glasses and lenses.

In particular, 5iO1 films are widely used because of their adhesion to substrates, hardness, ease of handling, and the like.

[Problems to be solved by the invention] - However, inorganic coated films such as 5101 have 81. Na.

When water droplets containing impurities such as Oa, etc. are contaminated, the impurities remain on the surface of the inorganic coat film during the drying process, causing a so-called fading phenomenon.

In addition, a film formed by vapor deposition generally has a lower density than a bulk film, and it is thought that water molecules can easily move within the film. Therefore, water molecules form a plate layer on the surface of the membrane, and then reach the interface between the membrane and the substrate due to Buddhism, adversely affecting the adhesion of the membrane.
This resulted in a decrease in durability.

The present invention is intended to solve these problems, and its purpose is to modify the surface condition of the inorganic coating film so that the surface has a function that can solve the above-mentioned problems. There is a particular thing.

[Means for solving problems]

That is, the present invention provides an inorganic coating film containing a reactive compound having a fluorine substituting group ≦ or hydrogen fluoride and/or
Alternatively, it is characterized by reacting with a metal fluoride.

The reactive organic compound having a fluorine substituent in the present invention has a functional group capable of reacting with the 10H group on the surface of the inorganic coating film, and further reduces surface energy by the fluorine substituent. There are many compounds having a functional group that can react with the -01 group on the surface of the inorganic coating film, but there are no particular limitations. , X represents all []・logen), Rf R8' NeYe (R represents an alkyl group having 1 to 3 carbon atoms, Ye represents a halogen ion, a sulfate ion, a carboxylate ion, etc.) (representing an anion), incyanate ester represented by Rf-N=C=O or Rf-N=C=8
The thioin cyanate ester shown by is a typical example of 3, and is thought to be bonded to the surface of the coating film through the following reaction. S10! If we take the membrane t13'lJ,
1. Carboxylic acid halides.

An Rf group is introduced through an ester bond with dehydrohalogenation reaction as shown in FIG.

Just in case, what is the reaction with ammonium salt?

It becomes an ionic bond.

Incyanate ester and thioincyanate ester have similar reactions.

Rf base force 3 is introduced by diurethane reaction.

The Rf group used here is an organic group containing fluorine, and examples thereof include those represented by the following general formula.

(A+CF'!)ni? '-a-b 10J (A is a fluorine or hydrogen atom, n is an integer from 1 to 18, a is 1 or 2, b is 0 or 1, c is 0 to 2
) l 0Fs (OFI )mSO,N (OH,)d- (where m is an integer from 0 to 17, d is an integer from 0 to 5 R1
represents an alkyl group having 1 to 5 carbon atoms) (However, t represents an integer from 0 to 5) To react a reactive organic compound having a fluorine substituent with an inorganic coating film, use 11 of the stock solution or an organic solvent. ni f? Then, a method of coating by a dipping method, a spinner method, a spray method, etc., or a method of reacting with a reactive organic compound gas having a fluorine group in a vacuum atmosphere or air can be used. It is also effective to add % to promote the reaction, and it is desirable to apply heat to an extent that does not affect the properties of the inorganic coat film during coating or after coating.

As another method, it is also possible to bond fluorine atoms directly to the surface of the inorganic coat film, and for this purpose, hydrogen fluoride and/or metal fluoride are used. In this case, the combined use of concentrated sulfuric acid is more effective, and the reaction is thought to proceed according to the following formula.

Straddle (However, M represents metal 't-) The metal fluoride in the present invention is 1iaF.

NaHF I Oa 'E'2 e A! F@e Z
nF! *S1)N3*, 81)N5
mCrF'2, 0rFB, KF, CoF,
, co'? , , Mg? , , TIF.

TjF's, FaFl, FeF'3, N1F1
, BaF, etc. are examples.

To react hydrogen fluoride to an inorganic coated film.

A method of directly reacting with hydrogen fluoride gas in a vacuum or air, or a method of immersing it in hydrofluoric acid or a mixture of hydrofluoric acid and concentrated sulfuric acid is used. In addition, when reacting a metal fluoride, the pulverized metal fluoride is used as a
A method is used in which a base material coated with an inorganic coating is immersed in ll acid and in this solution. However, since hydrogen fluoride or metal fluoride is very reactive and may etch the coated film and deteriorate its properties, it is preferable to carry out the reaction in a short time.

Also, to increase the reactivity of the inorganic coated film.

It is more effective to perform cleaning, chemical treatment, plasma treatment, etc. on the surface of the inorganic coat film as a pretreatment.

After the reaction is completed, the excess reaction solution is washed away with water or an organic solvent to obtain an inorganic coated film whose appearance, including antireflection properties, remains the same as before treatment.

The above has been described using slo and g as representative examples, but the present invention is
SiO* u, o, e ZrO, @TeL10@
, Ce01, etc. can be applied to the surface of any inorganic coating film.

[Effect]

Inorganic coat I! , for example, S10. In membranes, highly polar 10H groups are exposed on the surface, and this makes it easy for impurities contained in water to form a layer.

This can be explained by the fact that it causes discoloration. Therefore, by converting the surface of the inorganic coating film with a less polar or hydrophobic group, it is possible to improve the adhesion and durability of marks by preventing fading and water penetration.

In general, fluorine atoms have a high molecular density and low surface energy, and are therefore known to exhibit water and oil repellency at high elevations. The present invention utilizes such characteristics of fluorine atoms, and by introducing fluorine atoms or organic groups that remove fluorine substituents onto the surface of the inorganic coated film, it is possible to prevent fading and improve the vM7f properties of the film. Since the above is possible, the friction coefficient of the surface is reduced by 7:J3, and the wear resistance is also improved.

The present invention will be described in detail below based on Examples, but the present invention is not limited thereto.

〔Example〕

Example-1 A synthetic resin lens made of diethylene glycol bis(allyl carbonate) resin was cleaned with acetone, and then an antireflection treatment was applied to the surface of the synthetic resin lens using a vacuum evaporation method at a multi-substrate temperature of 50°C. The configuration is 810tll from the lens side is λ./4°Z r O2+- and S10.
+g total film thickness or λ6/4eZr02 layer 7! J3λo/
4. The top layer 8108 is λ. /4. Next, this lens was washed with inpropyl alcohol, thoroughly dried, and then dehydrated with 5% 3@314#4.5,5.5-
In a hexane solution of hebutafluoroisocyanate, 10
℃ for 30 seconds.

Thereafter, the lens was left in dry air at -30°C for 1 minute, immersed in Improper Tool to wash away unreacted incyanate, and then steam washed with Improper Tool and dried. . Appearance of the lens after cleaning and drying,
No significant change was observed in antireflection properties.

The obtained coated film was evaluated using the method shown below. 90■ Stain resistance: Tap water was poured onto the surface of the coated film to dry it, and then the residue was wiped off with a cloth. If any residue remained, it was evaluated as C1. If it was completely removed, it was evaluated as A, and if some remained, it was evaluated as B.

■ Abrasion resistance: The surface of the coated film was rubbed with a cloth 1000 times under a load of 1111. The evaluation was divided into 3 stages: all scratches on the stand.

A: No scratches at all B = 1 to 10 fine scratches C: Numerous fine IC scratches ■ Adhesion: After being immersed in pure water at 37°C for one week, the dense layer property of the coating film was measured. Examined. The adhesion of the coating film is J Engineering EI.
A cross-cut tape test was conducted according to D-0202. That is, using a knife, incisions are made on the lens surface at 1 inch intervals to form 1-squares of 10Od.

Next, apply cellophane adhesive tape (manufactured by Nitto Chemical Co., Ltd.) on top of it.
After strongly pressing the cellophane tape ("cellotape") and then suddenly pulling it off from the 5th surface in the 900 direction, the number of squares remaining in the coating film was taken as an adhesion index.

(2) Contact angle: Measured by the droplet method using a contact angle (C!A-D manufactured by Kyowa Kagaku ■).

The results of each test are shown in Table 1. 〇Example 2 After ion blating aluminum oxide with a refractive index of 1.60 from the lens side to a thickness of 1 μm in argon plasma on the lens surface made of crown glass, Crfα0
An antireflection layer was formed thereon by vacuum evaporation to a thickness of 0.02 μm and ion blasting in MgF, io, and 12 μm argon plasma. After washing the lens obtained in this way with pure water, thoroughly drain the water and dry it. After that, 10%
3.3,4,4,5,5,6,6.6-nonafluorohexyldimethylammonium iodide was immersed in a tetrahydrofuran CTHF II solution at 25°C for 1 minute, then pulled out and placed in dry air at 60°C. , and left for 10 minutes. Subsequently, it was optically cleaned with pure water and then dried. The appearance after treatment was almost the same as before treatment.

Example 3 After forming the uppermost Sin layer in Example 1, the surface was treated with argon gas plasma for 1 minute, and then the lens was immediately treated with 10% perfluoro(2-methyl-3-
oxohexanoyl fluoride) for 2 minutes at 50°C. After being pulled up, it was washed with THF and pure water and dried, but no change in appearance was observed.

Example-4 Diethylene f I washed with inpropyl alcohol
A lens made of J.Coalbis (allyl carbonate) was treated with a 5% aqueous sodium hydroxide solution for 5 minutes at room temperature, and the coating solution described below was applied by dipping.
The liquid @5C1 was applied at a pulling speed of 40 cm/m. Next, in a hot lice drying oven at 80°C for 50 minutes,
C. for another 2 hours.

The coating liquid is prepared as follows.

In a reaction vessel equipped with a stirring device, 206 parts of ethanol, 396 parts of ethanol-dispersed colloidal silica (solid content of ``Oscar 1252'' manufactured by Catalysts & Chemicals Co., Ltd. 50%), γ-
312 parts of a partial hydrolyzate of glycidoxypropyltrimethoxysilane, 0.2 n of a flow control agent (Nippon Unicar @g" Lake 6114') and 86 parts of α05N acetic acid aqueous solution were added, and the mixture was stirred at room temperature for 5 hours. It was used as a coating liquid.

The lens obtained as described above was prepared using 250 to 300 meshes of fluorite (containing 20% CaF).

It was immersed in 96% & sulfuric acid at 35°C for 5 seconds. The lens was washed with water, saturated Na HO₂, a water bath solution, and then with pure water, and then dried. Almost no changes in appearance were observed.

Example-5 810. of the top layer in Example-1. After forming the layer, the lens was immersed in 15% hydrofluoric acid for 5 seconds at 10°C. The lens was then washed with water and saturated NaHCo! It was washed with an aqueous solution and then with pure water, and then dried.

Almost no change in appearance was observed.

Comparative Example The lens obtained in Example-1 before incyanate treatment was designated as Comparative Example-1, and the lens obtained in Example-2 before ammonium salt treatment was designated as Comparative Example-2.O [Effects of the Invention] As described above, by reacting the inorganic coated film with a reactive organic compound having fluorine [i[L group 1] or hydrogen fluoride and/or gold-fluoride, the hydrophilicity of the surface decreases. As a result, the fading phenomenon was prevented, and the water resistance and dense layer properties of the film were improved.

Furthermore, because the surface energy has been reduced, it is now possible to easily remove stains from organic substances such as sweat, fat, and negative oil secreted from the human body by simply wiping with tissue paper. It also has the effect of lowering the friction coefficient of one surface and improving wear resistance.

The present invention provides (1) synthetic resin and glass eyeglass lenses, optical lenses for treetop saw equipment, display panels, watch cover glasses,
This method is widely applicable to products using inorganic coated films such as window glass, and its applications will likely be further expanded.

Table-1 that's all

Claims (1)

[Claims] A method for surface modification of an inorganic coat film, which comprises reacting the inorganic coat film with a reactive organic compound having a fluorine substituent, hydrogen fluoride and/or a metal fluoride.