JPS621858A - Formation of hardened silicone resin film - Google Patents

Abstract

PURPOSE:To form a film of a uniform thickness with Angstrom unit at a high speed by simultaneously vacuum-depositing silicone resin and a metal from different evaporating sources. CONSTITUTION:Silicone resin and a metal are simultaneously vacuum-deposited on the surface of a substrate from different evaporating sources placed in a vacuum evaporating pot to form a hardened silicone resin film. Silicone resin having vinyl groups, silicone resin having hydrogen groups bonded directly to Si atoms or a mixture of such silicone resins is preferably used as the silicone resin. The metal may be Pt, Pd, Ni, Cr, Zr, Ti, Sn, Zn, Cu, Al, Ag or Au, and a mixture or alloy of such metals may be used. The evaporating sources are placed so that vapors are mixed with each other before deposition on the substrate. By this method, the surface function of the film can be freely regulated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for forming a cured silicone coating on the surface of a substrate.

[Prior Art] Molded products coated with cured silicone are used by taking advantage of the unique surface functions of silicone. For example, there are release paper and release film that take advantage of its release properties.
It can be treated with fabric to make it highly water-repellent, such as umbrella fabric and raincoat fabric, coated on wallpaper etc. to prevent dirt from adhering to it, treated with hygroscopic powder to prevent caking, and treated on the inner surface of catheters, etc. It is useful for preventing blood coagulation and for hardening and thinning the surfaces of plastic lenses, plastic sheets, and films.

Conventional methods for imparting the various functions of silicone resins mentioned above to the surfaces of various substrates include applying silicone resins as they are,
Alternatively, dipping method, roll coating method, dipping method, roll coating method, etc.
It is applied by brush coating, spray coating, spin cord, bar coating, or cascade coating, and is cured by heating and drying.

[Problems to be Solved by the Invention] The silicone coating coated by the above conventional method has the following problems.

(1) The coating film thickness is on the μ order, making it difficult to obtain a thin film with a uniform thickness for each person.

(2) Drying and curing of the coating film requires heat treatment at high temperatures for a long time, resulting in slow processing speed and poor productivity.

(3) The treatment is usually carried out in the atmosphere, and because of the hydrophobic nature of the coating, it tends to become electrostatically charged and attract dust, making it difficult to obtain a clean finish.

(4) In the case of coating on a porous substrate, the amount of silicone resin absorbed deep into the substrate increases, and the proportion of the resin remaining on the surface of the substrate and effective for imparting surface functionality decreases; This leads to an increase in processing costs.

[Means for Solving the Problems] As a result of intensive study to improve the problems caused by the above-mentioned conventional methods, a complete solution was found by using a multi-source vapor deposition method of silicone resin and metal.

That is, the present invention provides a method for forming a cured silicone resin film, which is characterized in that a silicone resin (B) and a metal (C) are simultaneously vacuum-deposited on the surface of a substrate (A) from different evaporation sources. is.

The base material (A) in the present invention is not particularly limited, but is made of a material such as an organic resin, an inorganic resin, a metal, or a ceramic, and preferably a sheet-like material such as a resin film, paper, or cloth.

Examples of resin films include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6, nylon 66, and nylon 12, polynitrocellulose, and polyacetic acid. There are films made of organic resins such as cellulose, such as cellulose, polyvinyl alcohol carbonate, polymethyl methacrylate, polyimide, vinyl chloride, and vinylidene chloride. good.

Examples of paper include parchment paper, glassine paper, clay coat paper, and polyethylene resin laminated paper, which are used as base materials for release paper.

Fabrics include polyamide fibers such as nylon 6, nylon 66, nylon 12, and nylon 11 used for umbrella fabrics, raincoats, etc., polyester fibers such as polyethylene terephthalate, polyacrylic fibers, cotton, wool,
Examples include plain woven fabrics made of silk alone or blended yarns, but are not particularly limited thereto.

In the present invention, vacuum deposition refers to 10-1111111
H (refers to resistance heating@deposition, high frequency heating evaporation, electron beam evaporation, sputtering evaporation, ion blating, etc. performed in a high vacuum of J or less.However, silicone resin,
The method is not particularly limited to these as long as it is a vacuum coating method in which metal is vapor-deposited.

The silicone resin (B) in the present invention is preferably a silicone resin (B') having a vinyl group, or a silicone resin (B'') having a hydrogen group directly bonded to a silicon atom, each singly or a mixture thereof.

Silicone resin (B'
) is a resin whose main chemical structure is polysiloxane, and usually has the following chemical structural units [I], [n], [
III], [IV] A polymer consisting of H3 ○ with an average degree of polymerization in the range of 5 to 4,000, which has an @ structure in which the CH3 group bonded to 3i is partially substituted with a vinyl group. .

Moreover, the silicone resin (B'') having a hydrogen group directly bonded to a silicon atom in the above is, for example, the above-mentioned [I]
, [II], [■ko, ['IV] average degree of polymerization 5
CH bound to Sl in polymers ranging from ~4.000
It is a silicone resin having a structure in which three groups are partially substituted with one group. Incidentally, the number of -H groups is preferably two or more.

The metal (C) in the present invention includes platinum, palladium, nickel, chromium, zirconium, titanium, tin, zinc,
Copper, aluminum, silver, gold, etc., more preferably platinum,
A metal selected from palladium, nickel, chromium, zirconium, and titanium, which may be used alone or as a mixture or alloy of two or more.

In the present invention, the silicone resin (B) described above
and metal (C) are separately evaporated simultaneously from different evaporation sources in the same vacuum deposition pot.

Regarding the silicone resin (B), when a silicone resin (B') having a vinyl group and a silicone resin (B'') having a hydrogen group directly bonded to a silicon atom are used together,
(B'), (B''), the metal (C) is separately obtained from different evaporation sources, or the silicone resin (B'), (B
``) is evaporated in a mixed state separately from the metal (C) in the same vacuum evaporation pot.

The silicone resin (B) and the metal (C) are evaporated from different evaporation sources and need to be mixed together in a vapor phase before being deposited on the substrate (A). A plurality of evaporation sources of the resin (B) ((B') and (B"), or a mixture thereof) and the metal (C) are alternately arranged under the base material (A>, or The particles are arranged at an angle such that the focal point in the scattering direction connects to the surface of the substrate, and the two are mixed in a gas phase and then vapor deposited.

[Function] In order to simultaneously vapor deposit silicone resin and metal curing catalyst, a large-sized silicone cured coating film of uniform thickness is formed on the surface of the substrate at high speed and in a clean state without adhesion of dust. , good and even mold release, water repellency, stain resistance, biocompatibility, moisture resistance, and high hardness surface are added.

In particular, when the base material (A) is porous such as paper or fabric and has a coating resin exhaustion property, the proportion of the resin that is impregnated deep into the base material and does not contribute to surface activity is reduced, and the resin This will lead to improved utilization rates and reduced processing costs.

[Example] Example 1 A biaxially oriented polyethylene terephthalate film with a thickness of 25μ was installed in a Pelger vapor deposition machine with a vacuum level of 1 The two types of silicone oils [V] and [VI] shown were 75 and 2, respectively.
Mixed oil mixed at a ratio of 5% by weight was separately filled and energized, and vapor deposited on one surface of the film by so-called resistance heating of the port.

A cured silicone resin film approximately 800 mm thick is formed on the surface of the 1% film, which prevents adhesive tape coated with acrylic adhesive from sticking, and which has a good contact angle of 108 degrees with water droplets measured by a goniometer. Showed water-based.

Example 2 A biaxially oriented polyethyl film having a thickness of 38μ and a width of 1-000mm was placed in a five-source carbon crucible arranged in a line perpendicular to the running direction, and platinum and the chemical structure represented by the following formulas [■] and [■] were alternately placed in a five-source carbon crucible. filled with a mixture of 850% by weight silicone oil,
The film was deposited on one side while being wound up at a running speed of 200 m/min.

A cured silicone resin film with a thickness of about 500 mm was formed on the surface of the obtained film, and a clean release film with light peel resistance and no dirt adsorption, which is suitable as a separator for adhesive film for window application, was obtained.

Example 3 Taffeta fabric 5 x 10'm using nylon filament
A Pelger type evaporator with mHCl vacuum was installed, and a mixture of nickel and the following two types of silicone oils each at 50% by weight was simultaneously evaporated from a two-source molybdenum boat.

o O 1F Nylon taffeta has a slimy texture unique to silicone, and was water-repellent with no water droplets left in the 45 degree spray-type book repellent test.

No chalk marks were observed even when the surface was scratched with a fingernail, and the appearance was superior to that obtained by conventional coating methods.

Example 4 200m of 50μ thick parchment paper with a width of 120mm
2 x 1 length roll with attached winding device
While winding up the parchment paper in a high-vacuum vapor deposition machine (Q-4mmHc), metal palladium and two types of silicone resins represented by the following formulas were heated at a processing speed of 50 m/min from three separate graphite crucibles. Evaporated and deposited using high frequency heating method.

The treated parchment paper had a good surface smoothness, the acrylic adhesive tape did not stick to it, and the silicone coating did not fall off even if the surface was frozen with the pad of a finger.

Example 5 A 25μ thick biaxially oriented polypropylene film was
It was installed in a Pelger vapor deposition machine with a vacuum level of 1 o-4 mmHg, and in two molybdenum vapor deposition boats, metal nickel and 80% by weight and 20% by weight of the silicone oils [V] and [H described in Example 1 were added. A mixture of the same proportions was separately filled, energized, and deposited on one side of the film by so-called boat resistance heating.

A cured silicone resin film with a thickness of approximately 600 mm was formed on the surface of the obtained film, and exhibited excellent mold releasability against acrylic adhesives.

[Effects of the Invention] Since the silicone cured film is formed by a vapor deposition method, the problems of those coated by the conventional method can be significantly improved as follows.

(1) Since a uniform coating film thickness can be obtained in large units, only a small amount of silicone is deposited per unit area, which is economical.

(2) Since the curing reaction of silicone resin is carried out in a vacuum phase system, the speed is fast and productivity is increased.

(3) Since the treatment is performed in a dust-free state in a vacuum pot, the surface of the substrate after treatment has a clean finish.

(4) By changing the processing speed in the base material winding type vapor deposition machine, the coating thickness of the silicone resin can be increased or decreased, and the surface functions of the silicone coating, such as water polishability, mold releasability, and smoothness, can be improved. Can be adjusted freely.

(5) Even if the resin is porous and easily penetrates deep into the base material, such as paper or cloth, it remains on the surface of the base material, increasing the utilization rate of the resin and reducing processing costs.

Claims (1)

[Claims] Silicone resin (B) and metal (C) on the surface of the base material (A)
1. A method for forming a cured silicone resin film, characterized by simultaneously performing vacuum evaporation from different evaporation sources.