JPH0749016B2 - Improved mirror - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to an improved mirror which is remarkably excellent in corrosion resistance, particularly salt spray resistance, and is also excellent in workability such as cutting and chamfering.

[Prior Art] Conventionally, in a mirror formed by plating a silver mirror surface film on the back surface of a glass substrate, in order to prevent discoloration or peeling of the silver mirror surface film due to water vapor, various corrosion resistant gases, various chemicals, or mechanical damage, It has been practiced to form a copper protective film on a silver mirror surface film, and then apply an alkyd resin paint containing Komeitan, Benji, lead cyanamide, and calcium carbonate on it to form a back coating film.

However, although each of the mirrors coated with the backing coating as described above has its own effect, it is not possible to obtain a sufficiently satisfactory performance in a bad environment existing under all conditions of use of the mirror.

From this point of view, the present inventor has tried to use an epoxy resin paint as a backing coating film in order to further improve the corrosion resistance and durability. Epoxy resin itself is generally superior in corrosion resistance and durability for the backing coating film using epoxy resin paint, and also has high adhesiveness with a metal protective film such as copper, which is sufficiently higher than conventional mirrors. And durability, but another problem was found in the processing of the mirror. That is, when using a mirror, when cutting a large-sized mirror shipped from the factory into a predetermined size, or when chamfering a cut end face of the mirror cut into a predetermined shape, a cutting portion, or It has been found that the backing coating film on the chamfered portion or the silver mirror surface film, or these films peel off at the same time, resulting in deterioration of corrosion resistance and durability. Alternatively, it has also been found that when a large-sized mirror is cut into a predetermined size, the separation is poor and the cutting workability is deteriorated.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems of a mirror having a backing coating film using various conventional paints, and to cut the mirror or chamfer it. It is an object of the present invention to provide a mirror which does not peel off the backing coating film or the silver mirror surface film of the mirror, or which has good cut-off property after cutting the mirror, corrosion resistance, especially salt water spray resistance, and workability.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and in a mirror formed by sequentially forming a silver mirror surface film on a glass substrate and a metal protective film on the film, Amino-modified epoxy resin binder (B) obtained from amino alcohols having one amino group and at least one hydroxyl group in the molecule and an epoxy compound having an epoxy equivalent of 450 to 3000 on the metal protective film. And the pigment (P) are in a weight ratio of P / B = 1.0 to 4.
An improved mirror is provided which is 6 and which is coated with a coating composition containing 5 to 15% by weight of lead sulfate in the coating composition and cured to form a backing coating film. It is a thing.

Hereinafter, the present invention will be described in more detail.

FIG. 1 shows a specific example of the mirror according to the present invention, in which 1 is a glass substrate, 2 is a silver mirror surface film formed on the glass substrate, and 3 is to enhance the chemical durability of the silver mirror surface film 2. The metal protective film 4 formed on the silver mirror surface indicates a backing coating film formed on the metal protective film in order to protect the silver mirror surface film and the metal protective film and further improve the corrosion resistance and durability.

In the above-mentioned mirror, as the silver mirror surface film, a film formed by depositing in a film form on the glass substrate surface by electroless plating is usually used, but the film is not necessarily limited to this, and vacuum deposition, sputtering A silver film formed by the method or other various film forming methods can also be used as the mirror surface film. Such a silver mirror surface film has a reflectance of 0.5 to 2 so that the reflectance required as a mirror can be sufficiently obtained and a silver mirror surface film having excellent durability can be obtained.
A film thickness of g / m ² is appropriate.

Further, the metal protective film is formed as a protective film that enhances the chemical durability of the silver mirror surface film which is easily chemically deteriorated, and has a good adhesiveness with the silver mirror surface film, and a metal having high chemical stability. Preferably, a metal that can be easily formed by a film forming method similar to the silver mirror surface film, for example, an electroless plating method is selected. A typical metal protective film is a copper protective film, and other metal protective films such as copper alloy, nickel, nickel alloy, tin and tin alloy can also be used. The metal protective film may be a single layer or two or more layers in which different kinds of metals are combined. It is appropriate that the metal protective film has a thickness of about 0.1 to 1 g / m ² so that a sufficient chemical durability effect can be obtained and the adhesion to the silver mirror surface film is not impaired.

A typical method for producing a mirror having a silver mirror surface film and a metal protective film is to prepare a glass plate having a smooth surface and no surface defects, wash this glass plate sufficiently, and then form the silver mirror surface film. The surface to be activated is subjected to an electroless plating method, for example, a silver plating solution that deposits silver by a so-called silver reaction is sprayed to form a silver mirror surface film, and then Cu is deposited on the silver mirror surface film by an electroless plating method. A method of spraying a metal plating solution for depositing a metal such as Ni or Sn or an alloy thereof to form a metal protective film, followed by washing and drying can be mentioned, but it can also be manufactured by various other methods.

In the present invention, in order to enhance the corrosion resistance and mechanical durability of the silver mirror surface film and the metal protective film on the metal protective film, the following coating material is applied and cured to form a backing coating film.

The binder in the coating composition used in the present invention includes (1) amino alcohols having one amino group and at least one hydroxyl group in the molecule, and (2) epoxy having an epoxy equivalent of 450 to 3000. The compound is an amino-modified epoxy resin obtained from

Representative examples of the amino alcohols as the component (1) include monoethanolamine, diethanolamine, N-methylmonoethanolamine, diisopropanolamine, and aminodibenzyl alcohol. These are used as one kind or as a mixture of two or more kinds.

The epoxy resin as the component (2) is, for example, a bisphenol type epoxy resin, which is generally commercially available from Yuka Shell Chemical Co., Ltd. under the trade name Epicoat 828, 834,
836, 1001, 1004, DX-255; Ciba Geigy Co., Ltd. product name Araldite GY-260; Dow Chemical Co., Ltd. product name DER330, 331, 337; Dainippon Ink and Chemicals Trade name Epicron 800; novolac type epoxy resin, for example, Yuka Shell Chemical Co., Ltd. trade name Epicoat 152, 154; Dow Chemical Co., Ltd. trade name DEN43
1, same 438; as a polyglycol type epoxy resin, for example,
Ciba Geigy Co., Ltd. product name Araldite CT508; Dow Chemical Co., Ltd. product name DER732, 736; Ester type epoxy resin, for example, Dainippon Ink and Chemicals Co., Ltd. product name Epicron 200, 400 ; As epoxidized polybutadiene, trade name BF-10 manufactured by Nippon Soda Co., Ltd.
00; Sumika oil # 50 manufactured by Sumitomo Chemical Co., Ltd .; epoxidized oils such as ADEKA SIZER 0-180 and 0-130P manufactured by Adeka Argus Chemical Co., Ltd. may be used.

Further, it should be noted that the epoxy compounds and analogs of the above-mentioned epoxy resins which are easily inferred from these compositions are also included in the scope of the present invention. For example, polyol type epoxy resin, alicyclic epoxy resin, halogen-containing epoxy resin and the like are included.

These can be used as one kind or as a mixture of two or more kinds.

The epoxy resin needs to have an epoxy equivalent in the range of 450 to 3000, and further has a weight average molecular weight of 600 to 8000.
Those in the range are preferred.

The amino-modified epoxy resin used in the present invention preferably contains 0.5 to 0.5 amino groups per 1 chemical equivalent of epoxy groups.
The components (1) and (2) are mixed at a ratio of 2.0, preferably 0.8 to 1.5 chemical equivalents, and heated at 50 to 250 ° C, preferably 80 to 200 ° C in the presence or absence of a solvent. By doing so, the intended product can be obtained.
The amino-modified epoxy resin used in the present invention can be easily produced as described above, and is, for example, Epiclon H-303.
-45, Epicron EXA-123, Epicron H-371-i, Epicron H-360, Epicron H-353, Epicron H-157
Commercial products such as the above (trade names, manufactured by Dainippon Ink and Chemicals, Inc.) may be used.

The amino-modified epoxy resin has a weight average molecular weight of about 2000.
Those having a hydroxyl value of about 0 to 40,000 and about 70 to 140 are preferable.

The amino-modified epoxy resin itself is sufficiently useful as a coating material, but if necessary, other epoxy resin, alkyd resin, polyester resin, acrylic resin,
Binders such as polyvinyl butyral, rosin and petroleum resin may be used in combination.

Further, the coating composition used in the present invention includes extenders such as talc, barium sulfate, mica, calcium carbonate, and barite powder; titanium oxide, zinc white, rouge, yellow lead, chromium oxide, iron oxide, ultramarine blue, Coloring pigments such as phthalocyanine blue, carbon black, iron black; rust-preventive pigments such as calcium leadate, basic lead chromate, lead tin, cyanamide lead, lead sulfate, etc. are used together, and Lead sulphate is used in 5 to 15% by weight of the total coating composition.

The reason for using lead sulfate in this way is as follows.
That is, the anticorrosion pigments are roughly classified into soluble pigments and basic pigments.

Soluble anti-corrosion pigments are generally considered to have a high anti-corrosion effect, but they are easily dissolved in water, and blisters occur in the coating film due to the action of the dissolved substances.

In addition, since basic pigments are generally difficult to elute in water, the problem of blistering in coating films is small, but there are many problems in stability in coating compositions due to their activity and the like.

Then, in the present invention, as a result of various comparative studies on prevention of blistering of the coating film and stability in the composition, it was confirmed that lead sulfate is the most suitable, although it is one of the basic pigments.

Therefore, in the coating composition of the present invention, it is necessary that the binder (P) and the pigment (B) are in a weight ratio of P / B = 1.0 to 4.6. If P / B is less than 1.0, blisters are likely to occur in the water resistance test, and if P / B exceeds 4.6, acid resistance is reduced and pitting corrosion is likely to occur.

On the other hand, when the content of lead sulfate is less than 5% by weight in the total coating composition, the salt spray resistance tends to decrease, and conversely, when it exceeds 15% by weight, the primary physical properties decrease and the cut property decreases. Sometimes the coating film is easily peeled off.

As the lead sulfate, commercially available Sakai Chemical Industry Co., Ltd. trade name Tribase 5000, Shinagawa Kako Co. Ltd. trade name Shinaga Red TS-G-102, Kikuchi Dye Industry Co., Ltd. tribasic lead sulfate. The trade name TS manufactured by Katsuta Kako Co., Ltd. and the trade name Stavinex TCA manufactured by Mizusawa Chemical Industry Co., Ltd. can be used, and these can be used as one kind or as a mixture of two or more kinds.

Further, particularly as an extender pigment, use precipitated barium sulfate and talc in an amount of 10 to 20% by weight based on the total solid content of the composition, and use precipitated barium sulfate and talc in a weight ratio of 30 to 70/70 to 30. By doing so, the adhesion of the coating film, salt spray resistance,
Also, the chamfering workability can be further improved.

The coating composition 12 used in the present invention further comprises a reinforcing material such as glass fiber, glass flakes, mica powder, asbestos and synthetic silica, if necessary; other thickeners, rust preventives, precipitation inhibitors, curing accelerators. Additives and the like generally used in paints can be added.

In addition, as a matter of course, in order to dissolve or disperse the resin, a known solvent such as an aromatic hydrocarbon type, an aliphatic hydrocarbon type, an ester type, an ether type, a ketone type, or an alcohol type is used in a necessary amount as necessary. be able to.

The coating composition thus obtained has a dry film thickness of 30 to 30 on the back surface of the mirror by a method such as brush, roller, spray or flow coater.
Apply it to about 100 μm. Then, it is heated and dried at room temperature or about 250 ° C or less to finish.

The backing coating film of the present invention has its adhesive strength so that the silver mirror surface film, the backing coating film, or these may not be simultaneously peeled off at the time of cutting or chamfering, or that the separability at the time of cutting is good. Is in the range of 5 to 13 kg / cm ² , and the elongation rate is 0.05
~ 0.5%, stress 1.0 ~ 2.5kg / mm ² , elastic modulus 500 ~ 1000kg
The optimum range is / mm ² .

Next, examples of the present invention will be described.

[Example] A glass substrate that has been thoroughly washed (size: 72 mm x 36 mm x 5 m
m) surface is sprayed with a silver plating solution of a solution containing silver nitrate that deposits silver by a silver mirror reaction and a reducing solution that reduces silver to form a 1g / m ² thick silver mirror surface film, and this film surface is washed with water. After that, a copper plating solution of a solution containing copper sulfate that deposits copper by an electroless plating method and a reducing solution that reduces copper is sprayed to form a metal protective film made of copper having a thickness of 0.30 g / m ² , and then. It was washed with water and dried.

Coating compositions (Examples 1 to 5 and Comparative Examples) of various formulations shown in Table 1 were dried on the copper protective film of the glass plate on which the silver mirror surface film and the copper protective film were formed by a flow coater method. Coated to a thickness of 30 μm, glass plate temperature 80 ℃
Bake for 5 minutes to form a dry film of 25 μm, and then bake for 5 minutes at a glass plate temperature of 135 ° C.
Various test pieces were obtained.

Table 2 shows the results of various performance tests performed on these various test pieces.

Performance test method 1. Cross-cut test; performed according to JIS K5400 6.15.
A rating of 10 points.

2. Immersion in warm water; When immersing in pure water at 60 ℃ for 240 hours and taking it out, no abnormality should be observed on the silver surface.

3. Water vapor test; when exposed to steam at 60 ° C for 240 hours and taken out,
No abnormality on the silver surface.

4. Hydrogen sulfide gas test: No abnormality on the silver surface when exposed at 20 ° C for 48 hours in a desiccator saturated with hydrogen sulfide gas.

5. Hydrochloric acid dipping; dip in 0.5% wt hydrochloric acid (first-grade reagent) water at 20 ° C for 72 hours, and take out no abnormalities on the silver surface. However, the four sides of the test piece were sealed.

6. Caustic soda soaked in water; 4% wt, caustic soda (reagent 1
Grade) When immersed in water at 20 ℃ for 48 hours and taken out, no abnormality should be observed on the silver surface.

7. Immersion in ammonia water: No abnormality is observed on the silver surface when immersed in a mixture of 50 parts by weight of ammonia water (reagent first grade) and 50 parts by weight of pure water at 20 ° C for 48 hours and taken out.

8. Immerse in formalin; formalin (first-grade reagent) at 20 ℃, 24
No abnormalities should be observed on the silver surface when immersed for 0 hours and taken out.

9. Bleaching agent immersion: No abnormalities on the silver surface when immersed in “Kitchen Bright”, a product of Lion Corporation, at 20 ° C for 48 hours and taken out. However, the four sides of the test piece were sealed.

10. Soaking in detergent; Sun Paul Co., Ltd. product "Sun Paul"
(Patent No. 1249719) When immersed in 20 ° C for 48 hours and taken out,
No abnormality on the silver surface. However, the four sides of the test piece were sealed.

11. Salt spray test; 360 ° salt spray test according to JIS Z2371
No abnormalities should be observed on the silver surface after time.

12. Accelerated weathering test; Accelerated weathering test according to JIS K5400 6.17
No abnormality was observed on the silver surface after 240 hours, and the coating film had no wrinkles, blisters, cracks, or peeling, and the degree of chalking was small.

13. Cut-off test; 24 ″ × 18 ″ (5 thick
mm) When the test piece is divided into 4 parts up to 12 ″ × 9 ″, after inserting the cutting line, place the nail lifting branch under the cutting line and fold the holding plate from the top. 50 mm or less was accepted.

14. Chamfering processing test: After heating at 120 ° C for 1 hour, backside chamfer width 3
Chamfering is performed at a speed of 25 mm / min for 25 mm / min to determine whether or not the edge has peeled. (No peeling: Pass, peeling: Fail) 15. Pot life; JIS K5664 Tar epoxy resin paint 5.8 Test with pot life.

16. Immersion in boiling water; No abnormality on the silver surface when immersed in pure water at 100 ° C for 18 hours and taken out.

[Operation / Effect of Invention] The mirror according to the present invention has good adhesion to a metal protective film, and has chemical durability such as steam resistance, water resistance, alkali resistance, acid resistance, formalin resistance, and hydrogen sulfide resistance. It has a backing coating film that is excellent in mechanical properties such as adhesive strength, breaking strength, impact resistance, etc., and since the epoxy resin is modified with amino alcohol, it is suitable for the coating film. Flexibility, elasticity, extensibility, and releasability are added, and the hardness of the backing coating film, the extreme adhesion with the metal protective film, the residual stress, the coefficient of thermal expansion, etc. are adjusted. At the time of cutting or chamfering, or a backing coating on the chamfered part,
Metal protective film or silver mirror surface film does not peel off,
Also, the mirror is easy to separate after cutting and less mechanically damaged.

Further, the coating composition used in the present invention is a one-pack type and has no limitation in pot life, and more particularly, it has better salt spray resistance than the conventional two-pack type epoxy resin coating film. It has improved the sex.

As described above, according to the present invention, it is possible to obtain a mirror having excellent corrosion resistance, durability and workability.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a mirror according to an embodiment of the present invention. 1: Glass substrate, 2: Silver mirror surface film, 3: Metal protective film, 4: Back coating film

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yukio Kimura 5-1 Chute Chuo, Kamisu Town, Kashima District, Ibaraki Prefecture (56) Reference JP-A-63-184702 (JP, A)

Claims (2)

[Claims] 1. A mirror formed by sequentially forming a silver mirror surface film on a glass substrate and a metal protective film on the film, and comprising:
Amino alcohols having one amino group and at least one hydroxyl group in the molecule, and an epoxy equivalent of 450 to 300
The amino-modified epoxy binder (B) obtained from the epoxy compound of 0 and the pigment (P) are in a weight ratio of P / B = 1.0.
An improved mirror, characterized in that a backing coating is formed by applying a coating composition which is -4.6 and which contains 5 to 15% by weight of lead sulfate in the coating composition and cures. 2. The coating composition is a composition containing 10 to 20% by weight of an extender pigment composed of precipitated barium sulfate and talc in a ratio of 30 to 70/70 to 30 (weight ratio). ) An improved mirror as described.