JP2005307179A - Mirror coating liquid and mirror coated with the coating liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an edge coating solution for a mirror, capable of shortening a time for drying a covering of an edge of the mirror of which the metallic protective film is exposed, when the mirror is produced by sequentially laminating a silver mirror film, the metallic protective film, and a back surface protective film on a glass base plate, capable of being strongly adhered to a glass surface, the silver mirror film, the metallic protective film formed out of copper, etc., and the back surface protective layer at the edge of the glass base plate, excellent in corrosion resistance, and having an excellent corrosion-resistant effect for a long period. <P>SOLUTION: This edge coating solution for the mirror contains (A) a bisphenol-type liquid epoxy resin (having an epoxy equivalent of 150-300), (B) a bisphenol-type solid epoxy resin (having an epoxy equivalent of 450-3,300), (C) an o-cresol-novolak-type epoxy resin (having an epoxy equivalent of 180-300), (D) an epoxy curing agent, and (E) a silane coupling agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  In the present invention, a silver mirror film on a glass substrate, a metal protective film made of copper or the like for protecting the silver mirror film, a mirror in which a back surface protective film is sequentially laminated, or a silver mirror film and a back surface protective film are sequentially laminated on a glass substrate. The present invention relates to a mirror mirror coating film for coating the edge of the mirror with the silver mirror film and the metal protective film exposed thereto for corrosion prevention, and a mirror coated with the mirror edge coating liquid and coated with the edge.

  Silver mirror film, metal protective film made of copper or the like for protecting the silver mirror film, manufacture of mirrors in which the back surface protective film is sequentially laminated, or manufacture of mirrors in which the silver mirror film and back surface protective film are sequentially laminated on the glass substrate, When coating the exposed edges of the film and copper film, it is known that after chamfering the edges, the edge coating liquid is applied to the edges and dried to coat. This is done manually at mirrors and mirror shops.

  For example, Patent Document 1 discloses a rim coating liquid that can be easily rim coated by manual operation, has excellent quick-drying properties, and has corrosion resistance.

  The copper film used for the metal protective film corrodes when exposed to moisture, carbon dioxide gas or sulfurous acid gas, and the corrosion of the copper film proceeds inward from the edge of the mirror in the mirror.

In order to prevent such corrosion, Patent Document 2 discloses a mirror edge coating that prevents corrosion, in other words, has corrosion resistance. The mirror coating composition described in Patent Document 2 is a bisphenol type epoxy resin, an amine-containing curing agent that reacts with the bisphenol type epoxy resin, and a silane having reactivity or affinity for inorganic and organic materials. Contains a coupling agent and adheres firmly to the silver mirror film, copper film, and glass substrate side, but uses only bisphenol-type solid epoxy resin, so it takes a long time to dry and cure, in other words, it is inferior in quick-drying In addition, there was a problem that the coating was whitened due to poor decoration resistance. In addition, in the back surface protective film, there are lead and lead-free pigments to be used. As for the back surface protective film with lead, it is used as a back coating film in the embodiment of Patent Document 2, and as for the lead-free back surface protective film, Patent Document 3 is used. It is described in.
JP-A-9-313316 Japanese Unexamined Patent Publication No. 2000-191978 Japanese Patent No. 3206852

  In the manufacture of a mirror in which a silver mirror film, a metal protective film made of copper or the like, and a back surface protective film are sequentially laminated on a glass substrate, or in the manufacture of a mirror in which a silver mirror film and a back surface protective film are sequentially laminated on a glass substrate. A mirror edge coating solution for coating the exposed mirror edge of the metal protective film, which can be dried in a short period of time, a glass surface of the glass substrate edge, a silver mirror film, a metal protective film made of copper, etc. An object of the present invention is to provide a mirror edge coating liquid and a mirror that adhere firmly to a back surface protective film, have excellent corrosion resistance, and have an excellent anticorrosive effect over a long period of time.

  The mirror edge coating liquid of the present invention can be dried and cured in a short time, in other words, excellent in quick-drying properties, and is strong on a glass protective film on the edge of a glass substrate, a silver mirror film, a copper protective film, and a protective film on the back surface. In addition to bisphenol-type solid epoxy resin, bisphenol-type liquid epoxy resin and ortho-cresol-novolak are used to obtain mirror edge coating liquids and mirrors that adhere to the surface and have excellent corrosion resistance and long-term anticorrosive effect. Using a type epoxy resin, quick drying is an adjustment of the epoxy equivalent and weight ratio of each epoxy resin.

  The mirror rim coating liquid of the present invention is excellent in quick drying due to the effect of containing a bisphenol type liquid epoxy resin and an ortho-cresol novolac type epoxy resin in addition to the bisphenol type solid epoxy resin, By adjusting the epoxy equivalent and the weight ratio of each epoxy resin, the glass surface, the silver mirror film, the metal protective film made of copper, etc., and the back surface protective film were firmly fixed to enhance the corrosion resistance.

  That is, the present invention comprises (A) bisphenol type liquid epoxy resin (epoxy equivalent, 150 to 300), (B) bisphenol type solid epoxy resin (epoxy equivalent, 450 to 3300), (C) ortho-creso. -A mirror edge coating liquid characterized by containing a lenovolac type epoxy resin (epoxy equivalent 180-300), (D) an epoxy curing agent, and (E) a silane coupling agent.

  Further, in the present invention, the weight ratio of (A) bisphenol type liquid epoxy resin (epoxy equivalent, 150 to 300) and (B) bisphenol type solid epoxy resin (epoxy equivalent 450 to 3300) is (A): (B) = 30: 70 to 90:10, and the weight ratio of (C) ortho-cresol novolak type epoxy resin (epoxy equivalent 180 to 300) to (A) + (B) is ((A) + (B)): (C) = 100: 1 to 100: 20.

  Further, in the present invention, a silver mirror film, a metal protective film made of copper or the like, and a back surface protective film are sequentially laminated on the glass substrate surface, and then the above-mentioned mirror edge coating liquid is applied to the edge and then cured. It is a mirror.

  The mirror rim coating liquid of the present invention is used in the manufacture of a mirror in which a silver mirror film, a metal protective film made of copper, etc., and a back surface protective film are sequentially laminated on a glass substrate, or a silver mirror film and a back surface protective film are sequentially formed on a glass substrate. In the manufacture of laminated mirrors, it is a mirror edge coating liquid for coating the edge of the mirror where the metal protective film is exposed, and drying and curing can be done in a short time, and the glass surface of the edge of the glass substrate, silver mirror film, copper A mirror having excellent anticorrosive effect over a long period of time was obtained by using the edge coating liquid of the present invention, which adheres firmly to the metal protective film and the back surface protective film composed of, etc., and has excellent corrosion resistance.

  FIG. 1 is a cross-sectional view of an example of a mirror in which a mirror edge coating liquid is applied and a coating is formed on an edge.

  As shown in FIG. 1, the mirror is a mirror in which a silver mirror film 1, a metal protective film 2 made of copper for protecting the silver mirror film, and a back surface protective film 3 are sequentially laminated on a glass substrate G. A coating 4 formed by drying and curing after applying the liquid is formed on the mirror end.

  Currently, a mirror in which a silver mirror film 1, a metal protective film 2 made of copper or the like for protecting the silver mirror film 1 and a back surface protective film 3 are sequentially laminated on a glass substrate G is mainly used. In the future, there is no metal protective film 2 made of copper or the like for protecting the silver mirror film 1 for environmental protection due to improvement of the corrosion resistance of the silver mirror film 1 by 3 and the silver mirror film 1 on the glass substrate G. It is expected that the mirror will be replaced with the back surface protective film 3 sequentially laminated. The mirror rim coating liquid of the present invention does not have the metal protective film 2 made of copper or the like in which the silver mirror film 1 and the back surface protective film 3 are sequentially laminated in order to give the silver mirror film 1 excellent corrosion resistance when the coating 4 is used. It is also effective for mirrors. The mirror rim coating liquid of the present invention is effective not only for a mirror having a back surface protective film 3 using a leaded pigment but also for a lead-free mirror having a back surface protective film 3 using a lead-free pigment.

  In the present invention, the silver mirror film 1 is a silver film or a reflective film similar to the silver film, and exhibits a mirror action. Further, in order to protect it from erosion, a metal protective film 2 such as a copper film is applied thereon. Is done. These silver mirror film 1 and metal protective film 2 are usually formed by a chemical plating method, but not limited to this, other film forming methods such as physical vapor deposition and sputtering are employed.

  The silver mirror film 1 and the metal protective film 2 are gradually corroded and corroded by corrosive gases such as moisture, carbon dioxide gas, sulfurous acid gas and the like. Therefore, the metal protective film 2 is coated with a back coating film and coated with the back protective film 3 to prevent corrosion.

  The edge of the mirror is usually chamfered, and the mirror edge coating liquid is applied to the oblique section 5 where the silver mirror film 1 and the metal protective film 2 are exposed, and a coating 4 is formed to prevent corrosion.

  The mirror edge coating liquid of the present invention comprises (A) bisphenol type liquid epoxy resin (epoxy equivalent 150 to 300), (B) bisphenol type solid epoxy resin (epoxy equivalent 450 to 3300), and (C) ortho-. It contains a cresol novolac type epoxy resin (epoxy equivalent 180 to 300), (D) an epoxy curing agent, and (E) a silane coupling agent.

  The (A) bisphenol type liquid epoxy resin contained in the mirror rim coating liquid of the present invention is liquid at room temperature, that is, room temperature, around 20 ° C., and has an epoxy equivalent of 150 to 300, preferably 180 to 250. Use the one in the range. If the epoxy equivalent is less than 150, even if a mirror edge coating liquid is applied to the edge of the mirror and then dried and cured, the coating 4 is inferior in water resistance, acid resistance and alkali resistance, and has an excellent anticorrosive effect over a long period of time. I can't get it. Preferably it is 180 or more. If the epoxy equivalent is greater than 300, the liquid is not liquid but increases in viscosity and becomes a mucus or solid. The coating obtained by applying and applying a mirror rim coating liquid is brittle, cracks are generated, and an excellent anticorrosive effect is obtained. I can't. Preferably it is 250 or less.

  As such (A) bisphenol type liquid epoxy resin, Mitsui Chemicals, Inc., trade name, Epomic R140, Epomic R144, Dainippon Ink and Chemicals, trade names, Epicron 840, Epicron 850, Epicron 860, etc. These are used alone or in combination of two or more.

  The (B) bisphenol type solid epoxy resin contained in the mirror rim coating liquid of the present invention is solid at room temperature and has an epoxy equivalent of 450 to 3300, preferably 450 to 2200. When the epoxy equivalent is less than 450, the epoxy resin becomes liquid. When the epoxy equivalent is larger than 3300, the coating 4 obtained by applying and drying and curing the mirror edge coating liquid becomes brittle, cracks and the like occur, the adhesion to the mirror edge portion becomes weak, and an excellent anticorrosive effect. Cannot be obtained.

  As such (B) bisphenol type solid epoxy resin, manufactured by Mitsui Chemicals, Inc., trade name, EPOMIC R301, EPOMIC R304, EPOMIC R304, EPOMIC R307, EPOMIC R309, manufactured by Dainippon Ink and Chemicals, Inc. Name, Epicron 1050, Epicron 2055, Epicron 3055, Epicron 4050, Epicron 7050, Epicron 9050, and the like can be mentioned. These bisphenol-type solid epoxy resins are used singly or in combination of two or more.

  The weight ratio of (A) bisphenol type liquid epoxy resin and (B) bisphenol type solid epoxy resin contained in the mirror edge coating liquid of the present invention is (A) :( B) = 30: 70 to 90: The range is 10, preferably (A) :( B) = 40: 60 to 80:20. (A) A bisphenol liquid epoxy resin is less than 30% by weight, and (B) a bisphenol solid epoxy resin is prepared in a range larger than 70% by weight. The coating 4 formed in this way is inferior in water resistance and adhesion to the mirror end.

  On the other hand, the weight ratio of (A) bisphenol type liquid epoxy resin was more than 90.0% by weight, and the weight ratio of (B) bisphenol type solid epoxy resin was less than 10.0% by weight. The coating has insufficient adhesion strength to the silver mirror film 1, the metal protective film 2, and the back surface protective film 3.

  In addition to (A) bisphenol type liquid epoxy resin and (B) bisphenol type solid epoxy resin, (C) ortho-cresol type novolak type epoxy resin is included in the mirror edge coating liquid. Improve dramatically.

  The (C) ortho-cresol novolak epoxy resin contained in the mirror coating composition of the present invention has an epoxy equivalent of 180 to 300, preferably 195 to 230. When the epoxy equivalent is less than 180, when the coating 4 is formed by drying and curing after coating on the edge of the mirror, the curing speed becomes too fast, the coating time is reduced, and the coating work is difficult. A preferable epoxy equivalent is 195 or more. When the epoxy equivalent is greater than 300, the viscosity when dissolved is high, and it cannot be uniformly mixed when making a mirror coating liquid.

  As such (C) ortho-cresol novolac epoxy resin, Toto Kasei Co., Ltd., trade name, YDCN-701, YDCN-702, YDCN-703, Dainippon Ink Co., Ltd., trade name, Epicron N- 665, Epicron N-670, Epicron N-680, Epicron N-690, Epicron N-695 and the like. These ortho-cresol novolac epoxy resins may be used alone or in combination of two or more.

The content of (C) ortho-cresol novolac type epoxy resin in the mirror rim coating liquid of the present invention is the sum of (A) bisphenol type liquid epoxy resin and (B) bisphenol type solid epoxy resin (A) + 1.0% to 20.0% by weight with respect to (B), preferably 2.0% to 15.0% by weight with respect to (A) + (B) The coating formed at less than 1% by weight has insufficient drying properties, and if it exceeds 20.0% by weight, the corrosion resistance of the coating film deteriorates.

  The (D) epoxy curing agent contained in the mirror rim coating liquid of the present invention undergoes an addition reaction with an epoxy group in the epoxy resin, so that an amino group in which active hydrogen atoms are bonded to at least two nitrogen atoms in one molecule. An amine curing agent having the following is used: For example, an amine adduct resin, a polyamide resin, or a polyamine is used as the amine-type curing agent.

  As (D) epoxy curing agent suitable for the edge coating liquid of the present invention, Fuji Kasei Kogyo Co., Ltd., trade name, tomide 238, Fuji Cure 202, Asahi Denka Co., Ltd., trade name, Adeka Hard -Amine adduct resin such as NA-EH531, manufactured by Fuji Kasei Kogyo Co., Ltd., trade name, tomide 210, tomide 225, tomide 245, tomide 410N, tomide 423, tomide 437, Sanwa Chemical Co., Ltd. Company-made, trade name, polyamide resin such as sunmide 320, sunmide 330, or diethylenetriamine, triethylenetetramine, tetraethylenebentamine, dipropylenetriamine, diaminotriamine, commercially available as chemicals, diethylaminopropylamine, menthanediamine, isophoronediamine, m- Xylylenediamine, diaminodiphenyl ester Emissions, include polyamines such as m- Fe 2 diamine, used as a mixture of more than a single or two or.

  In the mirror edge coating liquid of the present invention, the main resins (A), (B), (C) and the epoxy resin (D) are mixed immediately before use. After mixing, coating is performed to form a coating 4 cured by an addition reaction between the epoxy group in each epoxy resin and the active hydrogen of the amino group in (D) epoxy curing agent. The mixing ratio of epoxy group and amino group Is preferably in the range of epoxy group: amino group = 1: 2 to 2: 1 in molar equivalent ratio. Outside the above mixing ratio range, the coating 4 is not sufficiently cured.

  (E) The silane coupling agent is obtained by applying the mirror edge coating liquid of the present invention to the oblique section 5 of FIG. 1 and drying and curing to form the coating 4 as the glass substrate G, the silver mirror film 1, and the metal protective film. In order to make it adhere to the copper film and back surface protective film 3 as 4 more firmly. (E) A silane coupling agent is used for the glass substrate G, the silver mirror film 1, the functional group having an addition reaction or affinity for the copper film as the metal protective film 2, and the back surface protective film 3 which is an organic material. It has a functional group having a reaction or affinity with the resin. Examples of the functional group that undergoes an addition reaction with the glass substrate G or has an affinity include a linear or branched alkoxy group such as a methoxy group or an ethoxy group, or a silanol group. On the other hand, examples of the functional group that undergoes addition reaction or affinity with an organic material include a vinyl group, an epoxy group, a methacryl group, an amino group, and a mercapto group.

Examples of the (E) silane coupling agent having such a functional group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N- β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-mercaptopropylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc. .

  (E) Silane coupling agents are (A) bisphenol type liquid epoxy resin (epoxy equivalent 150-300), (B) bisphenol type solid epoxy resin (epoxy equivalent 450-3300), (C) ortho- Cresol-novolak type epoxy resin (epoxy equivalent 180 to 300), (D) 0.5 wt% to 10 wt% based on the total of epoxy curing agent (A) + (B) + (C) + (D). It mix | blends in the range of 0 weight%. (E) If the silane coupling agent is less than 0.5% by weight, the coating 4 does not adhere to the glass film G, the silver mirror film 1 and the copper film as the metal protective film 2. On the other hand, if it is larger than 10.0% by weight, the mirror edge coating liquid is thickened, gelled, and difficult to apply.

  In addition, in order to dissolve each epoxy resin (A), (B), (C) in the mirror rim coating liquid of the present invention, hydrocarbon-based, ester-based, ether-based, ketone-based, alcohol-based A known organic solvent such as a silver base is appropriately used, and a leveling agent, an antifoaming agent, a rheology control agent, etc. are appropriately added in order to improve the workability during coating and the finished appearance of the coating.

  (A) Bisphenol type liquid epoxy resin (epoxy equivalent 150 to 300), (B) Bisphenol type solid epoxy resin (epoxy equivalent 450 to 3300), (C) Ortho-cresol novolac type epoxy resin (epoxy equivalent) 180-300), (D) Epoxy curing agent, (E) Mirror coupling of the present invention obtained by appropriately adding an organic solvent, a leveling agent, an antifoaming agent, and a rheology control agent to a silane coupling agent The edge coating liquid is applied to the inclined portion 5 on the edge of the mirror back surface that has been chamfered by a roll coater, brush coating, or the like so that the dry film thickness is about 50 μm to 250 μm, and then 200 ° C. or less. Dry and cure, preferably at 180 ° C. for 5 minutes to form a coating 4 to complete the mirror with the mirror edges coated.

  In addition, in this invention, an epoxy equivalent is an equivalent per epoxy group, and based on the epoxy equivalent test method of JISK7236 (2001) epoxy resin, a unit is g / equiv.

  As shown in FIG. 1, a silver mirror film 1, a copper film as a metal protective film 2, and a back surface protective film 3 are sequentially laminated on one side of a glass substrate G by a known means to produce a large mirror having a thickness of 5 mm. did.

Specifically, a silver plating solution composed of a silver nitrate solution and a reducing solution for reducing silver is sprayed on one side of a glass substrate G that has been cleaned, and a silver mirror film having a thickness of 1.0 g / m ^{2 is obtained} by a silver mirror reaction. 1 is formed, thereafter the film surface was washed with water, and spraying the copper plating solution comprising a reducing solution for that reduces copper sulfate solution and copper, the metal protective layer consisting of 0.3 g / m ² thick copper 2 Was formed, washed with water and dried. On this metal protective film 2, 85 parts by weight of epoxy resin and curing agent and 15 parts by weight of cyclohexane-formaldehyde resin are H / F = 2.0 by weight ratio of binder (F) and pigment (H). In addition, after applying a coating film for a back surface protection film comprising a leaded pigment containing 6% by weight of lead sulfate in the pigment composition to a uniform film thickness with a flow coater, the glass substrate is heated for 6 minutes in a drying furnace. The back surface protective film 3 having a dry film thickness of 50 μm was formed by curing so that the temperature of G was 140 ° C.

In addition to the epoxy resin, the resin used for the back surface protective film 3 includes melamine resin and alkyd resin. In addition to the leaded pigment containing lead sulfate, the pigment includes a leaded pigment made of lead carbonate and a leadless pigment. In this example, a leaded pigment containing an epoxy resin and lead sulfate was used.
As the pigment, a rust preventive pigment having a rust preventive effect on the metal protective film 2 is used.

  The mirror manufactured in this manner is cut into 200 mm square, and the edge portion is seamed, and then the silver mirror film 1 and the inclined portion 5 where the copper film is exposed are applied to a known pen made of felt. Using a mold edge coater, the mirror edge coating liquid was applied manually. Table 1 shows the composition of the applied mirror edge coating liquid. All units are parts by weight.

  Examples 1-12 are the preferable composition ratios of the mirror edge coating liquid of this invention, and Comparative Examples 1-10 remove | deviate from the preferable composition ratio of the mirror edge coating liquid of this invention.

  Next, 200 mm square mirrors coated with mirror coating compositions of Examples 1 to 12 and Comparative Examples 1 to 10 were heated in a drying oven at 180 ° C. for 5 minutes to be dried and cured, and the inclined portion 5 was formed. A coating 4 was obtained.

  Next, a pencil hardness test, an adhesion test, an acid resistance test, an alkali resistance test, a warm water resistance test, a cast test and a drying test, which are the test methods and evaluation criteria shown in Table 2, were performed.

  The evaluation result of the mirror which applied the edge coating liquid of the composition shown in Examples 1-12 and Comparative Examples 1-10, and made the coating | coated 4 to the inclination part 5 was set to (circle) and the rejection to x to the evaluation criteria. Table 3 shows.

  The mirrors of Examples 1-12 using the mirror rim coating liquid of the composition ratio of the present invention passed all the tests and were excellent, but used the mirror rim coating liquid outside the composition ratio range of the present invention. The mirrors of Comparative Examples 1 to 10 are inferior because there are tests that do not pass.

  As described above, according to the examples, the weight ratio of A) bisphenol liquid epoxy resin (epoxy equivalent, 150 to 300) and (B) bisphenol solid epoxy resin (epoxy equivalent 450 to 3300) is (A) :( B) = 30: 70 to 90:10, and the weight ratio of (C) ortho-cresol novolak type epoxy resin (epoxy equivalent 180 to 300) to (A) + (B) is ((A) + ( B)): (C) = 100: 1 to 100: 20 The mirror which coat | covered the edge of a mirror using the edge coating liquid characterized by the above as the silver mirror film 1 and the metal protective film 2 It takes a short time to coat and dry the exposed mirror edge of the copper film, the glass substrate G of the inclined portion 5 at the edge of the glass substrate G, the silver mirror film 1, the copper film as the metal protective film 2, and the back surface protection It adheres firmly to the membrane 3 and has excellent corrosion resistance over a long period of time. It was confirmed that the anti-corrosion effect that was.

It is sectional drawing of the mirror by which the edge coating liquid for mirrors was apply | coated and the coating | cover was formed in the edge.

Explanation of symbols

G glass substrate 1 silver mirror film 2 metal protective film 3 back surface protective film 4 coating 5 inclined portion

Claims (3)

(A) Bisphenol type liquid epoxy resin (epoxy equivalent, 150 to 300), (B) Bisphenol type solid epoxy resin (epoxy equivalent, 450 to 3300), (C) Ortho-cresol novolac type epoxy resin ( Epoxy equivalent, 180-300), (D) epoxy curing agent, and (E) silane coupling agent. The weight ratio of (A) bisphenol type liquid epoxy resin (epoxy equivalent, 150 to 300) and (B) bisphenol type solid epoxy resin (epoxy equivalent 450 to 3300) is (A) :( B) = 30: 70-90: 10, and the weight ratio of (C) ortho-cresol-novolak type epoxy resin (epoxy equivalent 180-300) to (A) + (B) is ((A) + (B)) :( 2. The mirror rim coating liquid according to claim 1, wherein C) = 100: 1 to 100: 20. A mirror formed by sequentially laminating a silver mirror film, a metal protective film, and a back surface protective film on a glass substrate, and then applying the edge coating liquid according to claim 1 or 2 to an edge, followed by drying and curing.