JPS5939714A - Formation of silicon oxide coat - Google Patents

Abstract

PURPOSE:To form easily a favorable silicon oxide coat on the surface of a substrate at a low temp. close to room temp. while arbitrarily increasing or decreasing org. groups by treating the surface of the substrate with a silane isocyanate compound having Si-NCO bonds in the molecule. CONSTITUTION:A silane isocyanate compound having Si-NCO bonds in the molecule such as a compound represented by formula I or II (where R is optionally substituted hydrocarbon, and (n) is 1-3) or a condensation product of the compound is prepared. The surface of a substrate of plastics, glass, metal or the like is treated with the silicon compound by casting, spraying, vapor deposition or other method to form a silicon oxide coat on the surface of the substrate. The surface of the substrate may be treated with the silicon compound combined with a multivalent metallic compound or a heterocyclic compound capable of forming an Si-O-M bond (M is a metallic or nonmetallic element) by a reaction with the silicon compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for forming a silicon oxide coating, particularly a method for forming a silicon oxide coating on the surface of a substrate, in which organic groups can be arbitrarily increased or decreased at a low temperature around room temperature.

Insulating films for electronic components, surface stabilization of plastics and glass, metal plating, thin film surface protection and laminates.

It is widely known to form and use a highly pure silicon oxide coating on a substrate for the purpose of surface treatment of a liquid crystal cell surface alignment film, etc.

These coatings are formed by spucking of 5jO2, vacuum evaporation, CVD of silane, or thermal oxidation when the substrate is silicon. Furthermore, recently, a solution method classified as a sol/gel method has been attracting attention because it is easy to handle and suitable for large area processing. This solution method has the advantage of being able to safely treat a wide surface area without using special treatment equipment like other methods, and the treatment agent used for this purpose is hydrolysis of halogenated silanes and alkyl silicates, or alcohol- This method uses a sol/gel in which some or all of the bonding groups of a silicon compound are hydrolyzed by adding an acid aqueous solution, and is disclosed in Japanese Patent Publication No. 52-16488. % public 52-2082
5. JP-A-55-34g76, JP-A-57-74370
, JP-A-57-105463, JP-A-57-10094
0-44, the chain side is disclosed.

However, even in these sol/gel methods, film formation usually takes 2
Since the oxide film will not be formed unless it is fired at a high temperature of 00＼600℃, there will be a lack of continuity in the work and there will be restrictions on the applicable materials, so the silicon oxide coating treatment will be carried out at room temperature or at a low temperature range where continuous processing is possible. The development of a method was requested. Therefore, as a result of research on a method of forming a silicon oxide coating at a low temperature near room temperature, it was found that a method of treating the thread body with silane isocyanate containing a 5i-NGO bond in the molecule was effective, leading to the present invention.

Thus, the present invention provides a method for safely forming silicon oxide, which comprises treating the surface of a substrate made of various materials with a silane isocyanate compound having an S l -Neo bond in its molecule.

In the present invention, such a silane isocyanate compound and a polyvalent metal compound or a hetero element compound capable of reacting with this compound to form an Si-0-M bond (M is a metal or a non-metal element) are used in combination to form a substrate surface. A silicon oxide coating can also be formed by processing. In the present invention, the silane isocyanate compound mainly contains St in the molecule.
A compound containing at least two NCO groups directly connected to is used.

To explain the present invention in more detail, the silane incyanate compound used herein is of formula 5i (NCO
)4, RH8i (NCO)4-n, (RO), Si
-(NCO)4-n (wherein R is a hydrocarbon group with or without a substituent, n = l, 2 or 3).

Or condensates of these compounds can be mentioned. Also, S condensed with silicic anhydride or polysiloxane compound and the compound of the above formula
Compounds containing two or more NCO groups directly linked to i can also be used in the present invention. Such silicon compounds can be used alone or in combination of two or more.

In the above formula, R is methyl.

Ethyl, vinyl, phenyl, and other unsubstituted or substituted saturated or unsaturated aliphatic or aromatic hydrocarbon groups, and such mechanical differences can be arbitrarily selected, increased or decreased depending on the desired physical properties, etc. A silicon oxide coating incorporating these can be formed. Further, in the above formula, a compound where n = 1 to 2 is used as a substitute for a compound where n = 1 to 3, but a compound where n = 3 has the effect of alkylsilylation treatment on the surface of the substrate.

When treating the surface of plastic, glass, metal, and other various materials with these silicon compounds, so-called casting methods, spinner methods, spray methods, nine-coat methods, vapor deposition methods, CVD methods, etc. are used. Various methods are used. When applying and depositing the silicon compound by treating the surface of the substrate using these methods, 5i-N is added to the molecule as described above.
The NCO group directly connected to St in the compound that forms the GO bond easily reacts with moisture in the air, moisture on the surface of the substrate, or OH groups at room temperature to form a siloxane bond without using a special catalyst. Therefore, by simply treating the surface of the chain in a normal atmosphere with a compound containing such silane isocyanate, it is possible to cure and easily form a silicon oxide coating on the surface of the substrate.

This silane isocyanate compound can be used in combination with other compounds if necessary. For example, a compound that does not contain active hydrogen that reacts with NCO groups can be used in combination as a solvent. Examples of compounds that can be used as solvents include n-hexane, benzene, toluene, xylene, methylene chloride, trichloroethylene (triclene),
Fluorinated hydrocarbons (Freon), dimethylformamide (
DMF), dimethy/l/, X/l/phoxyto(DM
SO), nitrobenzene, methyl acetate, ethyl acetate, dithyl acetate, and the like.

In addition, in order to provide adhesion, prevent alkali migration, and other functions during treatment, it reacts with Si in the silane isocyanate compound to form an S-nee O-M bond (M is a metal or nonmetal element as shown below). A polyvalent metal compound or a petroelement compound that can be used may also be used in combination. Compounds that can be used for this purpose include Mg, Ca, Zn%B, AI%Sn, Ti,
Zr, Sb, In%V%Ta.

Compounds containing metal or nonmetallic elements such as As, P, Fe, Co, Ni, and Cr can be mentioned. These compounds include alkoxides, chelates, acylates,
A variety of compounds such as hydroxides can be used, but they must be non-aqueous and soluble in a solution consisting of a silane isocyanate compound or the above-mentioned solvent.

In the method of the present invention, as described above, a good silicon oxide coating is formed by processing in an atmosphere at normal room temperature, but it is of course possible to perform the processing under heating if necessary. This is preferable because it can promote stabilization.

(Thus, according to the method of the present invention, a silicon oxide coating can be formed on the substrate by a moisture curing method at or near room temperature. It is industrially useful because it can form an oxide coating.

Examples of the present invention are shown below. The middle part of the example shows the N position.

Example 1-6 A hard glass slide was optically cleaned with detergent and alcohol to prepare a specimen. This specimen was treated with the compounds of the following examples using a dipping/pulling method at a rate of 1 Qcz/min and cured in an atmosphere of 65% RH at ℃, and the physical properties of the formed coating were measured.

Example Compound Curing time Appearance I
5i (NCO) 450 16 minutes Colorless transparent CH5i (NCO) 350 2 CH2=CH81 (NGO) 350 1
7 minutes 〃S + (NGO) , + 10 (CH3)2Si(NCO)240 3 (CH30)S+ (NGO)390
18 minutes 〃(CH) 5t(NGO)210 2 4 (CH30)Si(NCO)380 1
0 minutes 〃CM = CH8i (NGO) 318 TAA-1002 5 condensate i11 30 10 minutes 〃(C
H)Si(NGO)340 s・1(INco>2,.27 B(OC2H5)33 6 condensate +21*33(115 min 〃5i(
NGO) 415 (CH3)3Si(NCO)5 TAA-1003 Ethyl acetate 47 Boiling test I-*4 Cetonatotitanate 13 hours 13 hours cH3G(3a(31 *Changes in appearance appear after boiling in 45% saline solution1) Example 7 5i (NGO) was placed in a sealed glass flask equipped with a submerged gas inlet pipe and a vaporized gas outlet pipe, and thoroughly dried with N2.
The flask temperature was raised to 80''C while passing gas.

In this state, N2 gas containing Si (NCO) 4 vapor discharged from the outlet tube was sprayed onto the surfaces of various substrates, and the substrates were cured in ambient air at 65% RH and 25°C.

The resulting coating showed good physical properties.

Slide glass Colorless transparent 8 minutes 15 Gloss chrome metal 〃 〃 18 Copper surface 〃 〃 12 Polyester film 〃 9 minutes 10 Illuminated polyvinyl chloride 〃 〃 10 Film disaster example 8 CH3S;, (NCO) 310 parts, 5i (NCO)
) 490 parts of the mixture was placed on a silicon single crystal plate at 200 or
After coating with a spinner at 5° C. and 65% RH for a few minutes, the film was heated to 160° C. for 5 minutes using an infrared lamp to obtain a uniform film.

The surface resistance of the treated film C was 10 Ω 7 μm, and the boiling test was 25 hours.

Claims (1)

[Claims] 1. A method for forming a silicon oxide coating, which comprises treating the surface of a substrate with a silane isocyanate compound containing an S i -NCO bond in the molecule. 2. The method according to claim 1, wherein the silane isocyanate compound contains a compound containing at least two NGO groups directly connected to Si in the molecule. 3. The method according to claim 1, wherein the silane isocyanate compound contains a compound containing at least two NGO groups directly bonded to Si. silane isocyanate compound, react with this compound to form Si-0-M
2. The method according to claim 1, which comprises treating the groove surface using a polyvalent metal compound or a hetero element compound capable of forming a bond (M is a metal or a non-metal element).