CN1680503A - Coating material and mirror coated therewith - Google Patents
Coating material and mirror coated therewith Download PDFInfo
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- CN1680503A CN1680503A CN 200510059032 CN200510059032A CN1680503A CN 1680503 A CN1680503 A CN 1680503A CN 200510059032 CN200510059032 CN 200510059032 CN 200510059032 A CN200510059032 A CN 200510059032A CN 1680503 A CN1680503 A CN 1680503A
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Abstract
The invention provides an edge coating solution for a mirror, which comprises (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. The present invention relates to a water-based edge coating solution, which contains an acrylsilicone resin emulsion obtained by dispersing an acrylsilicone resin into water.
Description
Technical field
The present invention relates to the protection of silver mirror film, silver mirror film is stacked gradually mirror on glass substrate with metal protective film, the back protection film of formations such as copper; Perhaps in the mirror that silver mirror film, back protection film is stacked gradually on glass substrate; for the edge that prevents the mirror that above-mentioned silver mirror film, metal protective film expose is corroded, and the mirror that applies thereon is with edge coating and to be coated with the mirror of this mirror with edge coating lining edge.
Background technology
In the manufacturing of mirror, when applying the edge that silver mirror film, copper film expose, known method is after this ora terminalis is carried out chamfer machining, is coated with edge coating thereon, makes it dry and be covered.Usually, these linings are to adopt hand-manipulated carrying out in system mirror institute or mirror processing.
For example: in patent documentation 1, disclose and a kind ofly adopt traditional manual operations, can apply simply and good, the corrosion resistant edge coating of rapid-drying properties.
The copper film that above-mentioned metal protective film uses will be corroded if be exposed in moisture, carbonic anhydride or the sulphurous acid gas, and in above-mentioned mirror, the corrosion of copper film is propulsive to the inside by the edge.
In order to prevent similar corrosion, in patent documentation 2, disclose a kind of protection against corrosion, in other words be exactly mirror edge coating with erosion resistance.The mirror of patent documentation 2 record contains the solidifying agent that contains ammonia of bisphenol-type epoxy resin and the reaction of this bisphenol-type epoxy resin and the silane coupling agent that inorganic materials and organic materials are had reactivity or affinity with applying coatings, silver mirror film, copper film and glass substrate side had firm adherence,, because only used the bisphenol type solid epoxy resin, so need the very long dry solidification time, in other words, just rapid-drying properties is not poor, and anti-ornamental also bad, there is the problem of overlay film albefaction.And the pigment that uses in the protective membrane includes lead and unleaded overleaf, the relevant back protection film that lead is arranged, and as internal hanging coating, relevant unleaded back protection film is on the books in patent documentation 3 in the embodiment of patent documentation 2.
[patent documentation 1] spy opens flat 9-313316 communique
[patent documentation 2] spy opens flat 2000-191978 communique
No. the 3206852nd, [patent documentation 3] special permission
Summary of the invention
The objective of the invention is to, provide following mirror to be: metal protective film, the back protection film of formations such as silver mirror film, copper are stacked gradually on glass substrate, form mirror with edge coating and mirror; Perhaps silver mirror film, back protection film are stacked gradually on glass substrate, make in the process of mirror, it is coated on mirror edge coating on the edge of the mirror that above-mentioned metal protective film exposes.Its time of drying is short, and metal protective film, the back protection film of formations such as the glass surface at glass substrate edge, silver mirror film, copper had firm adherence, and excellent corrosion resistance has superior corrosion resistance for a long time.
According to the 1st feature of the present invention, the invention provides a kind of mirror edge coating, it is characterized in that this mirror contains (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300), (B) bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300), (C) o-Hydroxytoluene Novolac (novolac) type Resins, epoxy (epoxy equivalent (weight) 180～300), (D) epoxy hardener, (E) silane coupling agent with edge coating.
According to the 1st feature of the present invention, the present invention can provide a kind of mirror, is silver mirror film, metal protective film, back protection film are stacked gradually after on the glass substrate, is coated with above-mentioned mirror edge coating at ora terminalis, and dry solidification forms then.
According to the 2nd feature of the present invention, the present invention can provide a kind of water-based mirror edge coating, it is characterized in that this water-based mirror contains the acrylic silicon resin emulsion that acrylic silicon resin is scattered in the water and form with edge coating.
According to the 2nd feature of the present invention; the present invention can provide a kind of mirror; this mirror is that silver mirror film, metal protective film, back protection film are stacked gradually after on the glass substrate, and the ora terminalis that has at the glass substrate periphery is coated with the tunicle that above-mentioned water-based mirror is solidified to form with the edge coating after drying.
Description of drawings
Fig. 1 is based on the of the present invention the 1st or the 2nd feature, is scribbling mirror with forming by the section of an example of the mirror of overlay film on the edge of edge coating.
Embodiment
Below, the 1st feature about the invention described above is elaborated for example.
Mirror edge coating with the present invention's the 1st feature is realized by following means: can finish at short notice in order to obtain dry solidification; in other words; rapid-drying properties is good; glass surface to the glass substrate edge; the silver mirror film; the metal protective film that copper film constitutes; the adhesivity of back protection film (internal hanging coating) is strong; the long lasting mirror of excellent corrosion resistance is with edge coating and mirror; except that using the bisphenol type solid epoxy resin; add bisphenol type liquid-state epoxy resin and o-cresol phenolic epoxy varnish, rapid-drying properties is to have adjusted the epoxy equivalent (weight) of each resin and weight ratio thereof.
Mirror edge coating with the present invention's the 1st feature; owing to except that containing the bisphenol type solid epoxy resin, also contain bisphenol type liquid-state epoxy resin and o-cresol phenolic epoxy varnish and make rapid-drying properties good; owing to the weight ratio of having adjusted epoxy equivalent (weight) and each Resins, epoxy makes the adhesivity of its metal protective film that glass surface, silver mirror film and copper etc. are constituted, back protection film (internal hanging coating) strong, improved erosion resistance.
According to the present invention the mirror edge coating of the 1st feature be; metal protective film, the back protection film of formations such as silver mirror film, copper stacked gradually on glass substrate, make mirror or silver mirror film, reverse side protective layer layer are successively spread on the glass substrate in the manufacturing processed that forms mirror; it is coated on mirror edge coating on the ora terminalis of the mirror that above-mentioned metal protective film exposes; it is short that it has the dry solidification time, the metal protective film that the glass surface at glass substrate edge, silver mirror film, copper etc. are constituted, the strong feature of adhesivity of back protection film.Use mirror edge coating of the present invention, can access mirror with long-term good anticorrosion ability.
Fig. 1 forms by the section of an example of the mirror of overlay film at the ora terminalis that scribbles mirror usefulness edge coating.
As shown in Figure 1; this mirror is on glass substrate G; the mirror that stacks gradually metal protective film 2 that the protection of silver mirror film 1, silver mirror constitutes with copper etc., back protection film 3 and form, coating mirror with edge coating after, make it dry solidification and being formed of obtaining by the edge of overlay film 4 at mirror.
At present, on glass substrate G, stack gradually the protection of silver mirror film 1, silver mirror film with the metal protective film 2 of formation such as copper, back protection film 3 and the mirror of formation is a main flow.But; along with the corrosion resistance nature of silver mirror film 1 constantly being improved owing to back protection film 3; can envision in the future; in order to protect environment; will remove the metal protective film of the formations such as copper of silver mirror film protection usefulness, and for the mirror upward to form in glass substrate G by silver mirror film 1, back protection film 3 stacked above one another.Mirror edge coating of the present invention when being used by overlay film 4, can give the silver mirror film 1 superior corrosion resistance, even for not comprising the metal protective film 2 that copper etc. constitutes, but presses the mirror of the sequential cascade of silver mirror film 1, back protection film 3, also is effective.In addition, in the protective membrane 3, not only use being had the back protection film 3 of lead pigments overleaf, also is effective to the unleaded mirror of the unleaded back protection film 3 that uses lead-free pigment.
In the 1st feature of the present invention, silver mirror film 1 is silverskin or similar with it reflectance coating, presents the effect of mirror, and will protect it not weather, and the metallizing protective membrane 2 thereon, as copper film.These silver mirror films 1, metal protective film 2 normally adopt the chemical plating method plated film, but are not limited to this, also can adopt other one-tenth membrane means such as physical vapor deposition, sputtering process.
Silver mirror film 1 and metal protective film 2 can be because corrosive gases such as moisture, carbonic anhydride, sulphur dioxide and being corroded slowly.Thereby, in order to prevent corrosion, on metal protective film 2, hang coating in the coating, form back protection film 3.
About the ora terminalis of mirror, adopt conventional chamfer machining after, on the oblique section 5 that silver mirror film 1 and metal protective film 2 expose, coating mirror edge coating makes it to form corrosion protection covering film 4.
Mirror with the present invention's the 1st feature contains (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300), (B) bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300), (C) o-cresol phenolic epoxy varnish (epoxy equivalent (weight) 180～300), (D) epoxy hardener, (E) silane coupling agent with edge coating.
Mirror with the present invention's the 1st feature uses at normal temperatures with (A) bisphenol type liquid-state epoxy resin that edge coating contained, and promptly room temperature is a liquid for about 20 ℃, and epoxy equivalent (weight) is in 150～300 scopes, preferred 180～250 scope person.During epoxy equivalent (weight) less than 150, promptly allow to obtain the overlay film 4 that forms with the edge coating dry solidification by the mirror of coating the mirror edge, also can not reach long-acting good corrosion protection result because of its water tolerance, resistance to acids and bases difference.Preferred more than 180.Epoxy equivalent (weight) will become the very big mucus or the solid of viscosity of non-liquid state greater than 300 o'clock, and the coating mirror solidifies resulting overlay film with the edge coating after drying and can become fragile, and the crack takes place, and can not get good anticorrosion ability.Preferred below 250.
Can enumerate as such (A) bisphenol type liquid-state epoxy resin: Mitsui Chemicals, Inc's system, trade(brand)name エ Port ミ ッ Network R140, エ Port ミ ッ Network R144, big Japanese ink chemical industry system, trade(brand)name エ ピ Network ロ Application 840, エ ピ Network ロ Application 850, エ ピ Network ロ Application 860 etc., a kind of single use or two or more mixing are used and all can.
Mirror with the present invention's the 1st feature is with (B) bisphenol type solid epoxy resin that edge coating contained, and using is solid at normal temperatures, and epoxy equivalent (weight) is in 450～3300 scopes, preferred 450～2200 scope persons.During epoxy equivalent (weight) less than 450, Resins, epoxy is in a liquid state.Epoxy equivalent (weight) was greater than 3300 o'clock, and the coating mirror solidifies resulting overlay film 4 with the edge coating after drying and can become fragile, and the bonding force of generation crack etc. and mirror edge section dies down, and can not get good anticorrosion ability.
Can enumerate as such (B) bisphenol type solid epoxy resin: Mitsui Chemicals, Inc's system, trade(brand)name エ Port ミ ッ Network R301, エ Port ミ ッ Network R304, エ Port ミ ッ Network R304, エ Port ミ ッ Network R307, エ Port ミ ッ Network R309, Dainippon Ink. ﹠ Chemicals Inc's system, trade(brand)name エ ピ Network ロ Application 1050, エ ピ Network ロ Application 2055, エ ピ Network ロ Application 3055, エ ピ Network ロ Application 4050, エ ピ Network ロ Application 7050, エ ピ Network ロ Application 9050 etc., these bisphenol type solid epoxy resins can a kind of independent use, also can two or more mixing use.
Mirror with the present invention's the 1st feature with (A) bisphenol type liquid-state epoxy resin that is contained in the edge coating and (B) weight ratio of bisphenol type solid epoxy resin at (A): (B)=30: 70～90: 10 scope, preferred (A): (B)=40: 60～80: 20 scope.When (A) bisphenol type liquid-state epoxy resin less than 30 weight %, (B) the bisphenol type solid epoxy resin is greater than 70 weight %, after using the interior mirror of this scope with the edge coating coating, the formed overlay film 4 of dry solidification, water tolerance reaches the adhesivity inequality to the mirror edge.
On the other hand; when the weight ratio of (A) bisphenol type liquid-state epoxy resin greater than 90.0 weight %; when (B) weight ratio of bisphenol type solid epoxy resin was less than 10.0 weight %, formed overlay film will become insufficient to the cohesive strength of silver mirror film 1, metal protective film 2, back protection film 3.
With in the edge coating, add (B) bisphenol type solid epoxy resin, (C) o-cresol phenolic epoxy varnish if mix (A) bisphenol type liquid-state epoxy resin at the mirror with the present invention's the 1st feature, drying property will significantly must improve.
At contained (C) o-cresol phenolic epoxy varnish in the edge coating of the mirror with the present invention's the 1st feature, using its epoxy equivalent (weight) is 180～300, preferred 195～230 scope person.Epoxy equivalent (weight) behind coating mirror edge, when dry solidification forms overlay film 4, because curing speed is too fast, and tailed off the coating time less than 180 o'clock, and the coating operation is harsh.Preferred epoxy equivalent (weight) is more than 195.Epoxy equivalent (weight) was greater than 300 o'clock, and the viscosity in the time of can making dissolving uprises, and when modulating mirror is used edge coating, can not make it uniform mixing.
Can enumerate as such (C) o-cresol phenolic epoxy varnish: Toto Kasei KK's system, trade(brand)name YDCN-701, YDCN-702, YDCN-703, big Japanese ink Co., Ltd. system, trade(brand)name エ ピ Network ロ Application N-665, エ ピ Network ロ Application N-670, エ ピ Network ロ Application N-680, エ ピ Network ロ Application N-690, エ ピ Network ロ Application N-695 etc.These o-cresol phenolic epoxy varnish can a kind of independent use, also can two or more mixing use.
Have the amount of the mirror of the present invention's the 1st feature with (C) o-cresol phenolic epoxy varnish in the edge coating, is the scope of 1.0 weight %～20.0 weight % with respect to (A) bisphenol type liquid-state epoxy resin with (B) bisphenol type solid epoxy resin sum (A)+(B), the scope of preferred 2.0 weight %～15.0 weight %, during amount less than 1 weight %, the drying property of the overlay film that forms is inadequate, during greater than 20 weight %, the erosion resistance variation of filming.
Mirror with the present invention's the 1st feature with (D) epoxy hardener that contains in the edge coating be for Resins, epoxy in epoxy group(ing) generation addition reaction and use, contain amino amine curing agent, this solidifying agent is combined with reactive hydrogen atom at least 2 nitrogen-atoms in 1 molecule.For example: use as amine shape solidifying agent with amine adduct resin, polyamide resin, polyamines.
Can enumerate with suitable (D) epoxy hardener that uses in the edge coating as the mirror with the present invention's the 1st feature: Fuji changes into Industrial Co., Ltd's system, trade(brand)name ト one マ イ De 238, Off ジ キ ュ ア 1, rising sun electrification Co., Ltd., the amine adduct resin of trade(brand)name ア デ カ Ha one De-Na EH531 etc., Fuji changes into Industrial Co., Ltd's system, trade(brand)name ト one マ イ De 210, ト one マ イ De 225, ト one マ イ De 245, ト one マ イ De 410N, ト one マ イ De 423, ト one マ イ De 437, Sanwa Chemical Co., Ltd's system, trade(brand)name サ Application マ イ De 320, the polyamide resin of サ Application マ イ De 330 grades, also has commercially available Diethylenetriaminee (DETA) as chemical reagent in addition, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, diethylaminopropylamine, the menthane diamines, isophorone diamine, between benzene two methanediamines, diaminodiphenyl-methane, the polyamines class of mphenylenediamine etc., can a kind of independent use, also can two or more mixing use.
At the mirror with the present invention's the 1st feature with in the edge coating, as (A), (B) of host, (C) each Resins, epoxy and (D) epoxy hardener to use preceding mixing.After the mixing, owing to the epoxy group(ing) in above-mentioned each Resins, epoxy that is coated with and (D) the reactive hydrogen generation addition reaction of the amino in the epoxy hardener form solidified overlay film 4, epoxy group(ing) and amino ratio of mixture are in molar equivalent ratio epoxy group(ing) preferably: amino=1: 2～2: 1 scope.If outside the scope of above-mentioned ratio of mixture, the curing of overlay film 4 will be insufficient so.
(E) silane coupling agent is on the oblique section 5 of Fig. 1; when the mirror that coating has the present invention's the 1st feature is used edge coating; when dry solidification forms overlay film 4, for make overlay film 4 more firmly be adhered to glass substrate G, silver mirror film 1, as containing on the copper film of metal protective film 2 and the back protection film 3.(E) silane coupling agent has for glass substrate G, silver mirror film 1, as the functional group that addition reaction or affinity can take place the copper film of metal protective film 2, has also that back protection film 3 employed resins for organic materials can react or the functional group of affinity.As the functional group that addition reaction can take place or have affinity, can enumerate straight chain or have the alkoxyl group of methoxyl group, oxyethyl group etc. of side chain or silanol group etc. for glass substrate G.On the other hand, as the functional group that addition reaction can take place or have affinity, can enumerate vinyl, epoxy group(ing), methylpropenyl, amino, sulfydryl etc. for organic materials.
As (E) silane coupling agent with functional group like this, can enumerate γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyl triethoxyl silane, N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan, γ-sulfydryl propyl group methoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane or γ-r-chloropropyl trimethoxyl silane etc.
(E) silane coupling agent is (A)+(B)+(C)+(D) with respect to (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300), (B) bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300), (C) o-cresol phenolic epoxy varnish (epoxy equivalent (weight) 180～300), (D) epoxy hardener sum, uses the value of 0.5 weight %～10.0 weight % scopes to be mixed.During silane coupling agent less than 0.5 weight %, overlay film 4 can not be bonded on glass substrate G, silver mirror film 1, the copper film as metal protective film 2.In addition,, will increase with edge coating viscosity, gelation takes place and make the coating difficulty owing to mirror if greater than 10.0%.
For the mirror that (A), (B), (C) each Resins, epoxy is dissolved in have the present invention's the 1st feature with in the edge coating, can suitably use known organic solvents such as hydro carbons, ester class, ethers, ketone, alcohols, in addition, the aesthetic property of the outward appearance after operability when being coated with operation in order to improve and coating are finished, interpolation levelling agent that can be suitable, defoamer, rheology inhibitor.
At (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300), (B) bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300), (C) o-cresol phenolic epoxy varnish (epoxy equivalent (weight) 180～300), (D) epoxy hardener, (E) suitably add organic solvent in the silane coupling agent, levelling agent, defoamer, rheology inhibitor and the edge coating of the mirror with the present invention's the 1st feature that obtains, adopt roller coat, modes such as bristle coating, according to making dry film thickness be about the specification about 50 μ m～250 μ m, inclination position 5 to the mirror dorsal edge of doing chamfered applies, then at dry solidification below 200 ℃, preferably at 180 ℃, dry solidification 5 minutes, form overlay film 4, thus the mirror that the ora terminalis that obtains mirror has been covered.
In the 1st feature of the present invention, epoxy equivalent (weight) is per 1 equivalent of epoxy group(ing), is benchmark with the epoxy equivalent (weight) test method(s) of JISK7236 (2001) Resins, epoxy, and unit is g/equiv.
Below, to the 2nd feature of the invention described above detailed description of giving an example.
In the 2nd feature of the present invention; owing to use in the edge coating at mirror; used the acrylic silicon resin emulsion resin; so can obtain when having water-based; in the short time, just can solidify; the overlay film of mirror edge forms easily, and metal protective film, the back protection film of formations such as the glass surface at glass substrate edge, silver mirror film, copper had firm adherence, the mirror edge coating of fast drying.Use has the resulting mirror of edge coating of the present invention's the 2nd feature, and excellent corrosion resistance has long lasting preservative effect.
Water-based mirror with the present invention's the 2nd feature is compared with edge coating with the mirror that edge coating forms with adopting traditional organic solvent; because be the mirror edge coating of water-based; so there is not the danger of presence of fire; and; with the silver mirror film; the metal protective film that copper etc. constitute; back protection film stacks gradually on glass substrate; perhaps with the silver mirror film; back protection film stacks gradually in the manufacturing of the mirror on glass substrate; when the edge of the mirror that exposes of the above-mentioned metal protective film of coating forms overlay film; not only not having influences the problem of operator's health owing to sucking, and does not have environmental pollution problems.
Water-based mirror edge coating with the present invention's the 2nd feature; can finish at short notice set time when having water-based; the overlay film at mirror edge forms easily; and; when adopting pen type edge coating tool, pen etc. that the glass substrate edge is applied, metal protective film, the back protection film of formations such as the glass surface at glass substrate edge, silver mirror film, copper had firm cementability.
Water-based edge coating with the present invention's the 2nd feature is used for mirror, can accesses mirror with long life anti corrosion effect.
Basic comprising with mirror of the present invention's the 2nd feature is because be identical with the mirror with the 1st feature, so omit its record.
Have the water-based edge coating of the present invention's the 2nd feature, contain the acrylic silicon resin emulsion.
As being used for water-based mirror edge coating, the candidate of water soluble resin, can enumerate polyvinyl alcohol, polyacrylamide, water-soluble acrylic polymer, water-soluble urethane polymkeric substance, water-soluble fluorine resin etc., as emulsion, can enumerate Emulsion acrylic resin, the acrylic silicon resin emulsion, the carbamate resins emulsion, fluoro-resin emulsion, the styrene butadiene resin emulsion, the acrylonitrile butadiene resin emulsion, the styrene isoprene resin emulsion, the vinyl chloride resin emulsion, the ethylene vinyl acetate resin emulsion, ethene vinyl chloride resin emulsion and caoutchouc resin emulsion etc.
In these compounds, as the emulsion of using edge coating owing to mirror with the present invention's the 2nd feature, coating after fixing speed is fast, the overlay film of mirror edge forms easily, when making it be solidified into mirror edge overlay film 4, overlay film 4 will be imbued with weather resistance and resistance to chemical reagents, in addition, in order to obtain good overlay film 4, when the polymerization of resin, because the degree of freedom height of resin design, so the acrylic silicon resin emulsion is selected, the acrylic silicon resin emulsion that obtains by the acrylic monomer emulsion polymerization that only will contain silicon, perhaps the acrylic silicon resin emulsion that obtains of the acrylic monomer by containing silicon and other not siliceous monomer emulsion polymerization is to be fit to use.
As the above-mentioned acrylic monomer that contains silicon, can enumerate γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane etc. and contain ethene base system monomer of water-disintegrable silyl etc.
As being monomer generation polymerization with aforesaid propylene acid but not containing other monomers of silicon, can enumerate aromatic hydrocarbons vinyl monomers such as vinylbenzene, vinyl toluene, chlorostyrene, Vinyl toluene; The α of toxilic acid, methylene-succinic acid, Ba Dousuan, fumaric acid, methyl-maleic acid etc., β-ethene unsaturated carboxylic acid; Styrene sulfonic acid, vinyl sulfonic acid etc. contain the vinyl monomer of sulfonic acid; Acid anhydrides such as maleic anhydride, itaconic anhydride; Vinylchlorid, vinylidene chloride, chloroprene etc. contain the monomer of chlorine; Hydroxyethyl vinyl ether, hydroxypropyl vinyl ether etc. contain the alkyl vinyl ether of hydroxyl; The alkyl diol mono allyl ether of ethylene glycol monoallyl ether, propylene glycol mono allyl ether, Diethylene Glycol mono allyl ether etc.; The alpha-olefins of ethene, propylene, iso-butylene etc.; The vinyl acetate of vinyl acetate, propionate, vinyl propionate, trimethylacetic acid vinyl acetate etc.; The Vinyl Ether of methylvinylether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether etc.; The allyl ethers of ethyl allyl ether, butyl allyl ethers etc. etc.
Aforesaid propylene acid resin emulsion obtains by for example emulsion polymerization method.Have no particular limits about emulsion polymerization method, it is the method that adopts conventional known, reaching in the dispersed system of other additives as ultimate constituent that uses in case of necessity with above-mentioned monomer, chain-transfer agent, tensio-active agent, radical polymerization initiator in aqueous medium makes monomer polymerization make emulsion.
In the 2nd feature of the present invention,, can enumerate organoalkoxysilane and/or organoalkoxysilane as the example of other additive components that use in case of necessity.Can enumerate the tetraalkoxysilane class of tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane etc. as concrete example; Methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, normal-butyl trimethoxy butane, ne-butyltriethoxysilaneand, the n-pentyl Trimethoxy silane, the n-hexyl Trimethoxy silane, the n-heptyl Trimethoxy silane, the n-octyl Trimethoxy silane, vinyltrimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 2-hydroxyethyl Trimethoxy silane, 2-hydroxyethyl triethoxyl silane, 2-hydroxypropyl Trimethoxy silane, 3-hydroxypropyl Trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, Deng trialkoxysilanes; Dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, di dimethoxy silane, the di diethoxy silane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, di-n-butyl dimethoxy silane, the di-n-butyl diethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, the di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, the di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, the dialkoxy silicane class of phenylbenzene diethoxy silane etc., the trimethylammonium methoxy silane, the monoalkoxy silicane of trimethylethoxysilane etc.These organoalkoxysilanes and/or organoalkoxysilane can a kind of independent uses, also can two or more mixing use.
The acrylic silicon resin that is contained in the edge masking liquid at water-based mirror with the present invention's the 2nd feature, the monomer that constitutes its resin is cyclohexyl methacrylate, butyl acrylate, methyl methacrylate, butyl methacrylate and the above-mentioned acrylic monomer of silicon or the not siliceous monomeric silicon monomer of containing, as constituting monomer, preferably these compounds are all used.The polymerization of acrylic silicon resin emulsion carries out easily, have good corrosion protection result becoming the corrosion protection mirror that the water-based mirror applies easily, obtains when with edge coating.
Water-based mirror with the present invention's the 2nd feature is with the acrylic silicon resin emulsion that is contained in the edge coating, and the number-average molecular weight of the polystyrene conversion that obtains with GPC (gel permeation chromatography) is preferred more than 10,000, and 5,000, below 000.More preferably more than 50,000,1,000, below 000.Number mean molecule quantity not sufficient 10,000 o'clock, the overlay film 4 behind the dry solidification becomes fragile, and not only peels off but also can not get corrosion protection result easily, surpasses at 5,000,000 o'clock, and viscosity is too high, is difficult to form overlay film 4 during coating.
Water-based mirror with the present invention's the 2nd feature is with the upper limit of the concentration of the acrylic silicon resin in the edge coating, and as 100%, preferable amount is below 45 weight % with the gross weight of water-based edge coating.When coating water-based edge coating of the present invention, the known pen type edge coating tool of the coating part Off エ Le ト system of record in the above-mentioned patent documentation 1 that the applicant quoted is to be fit to use.Adopt under the situation that a uniform thickness is coated with, even concentration greatly also has no relations, when adopting pen type edge coating tool, if the concentration of acrylic silicon resin greater than 45.0 weight %, acrylic silicon resin extends very difficult equably, is difficult to obtain the overlay film 4 of thickness homogeneous.Preferably below the 43 weight %.In addition, water-based mirror of the present invention is with the lower limit of the concentration of the acrylic silicon resin in the edge coating, and as 100%, preferable amount is more than 10 weight % with the gross weight of water-based edge coating.If the concentration of acrylic silicon resin is littler than 10.0 weight %, just can not get the thickness of the necessary overlay film 4 of erosion resistance of silver mirror film 1, copper film 2 etc., metal exposed portions serve.
Use in the edge coating at water-based mirror with the present invention's the 2nd feature, as the vitrifying tansition temperature (being designated hereinafter simply as Tg) that is scattered in the employed acrylic silicon resin of emulsion that forms in the water, preferred more than 0 ℃, below 80 ℃, more preferably more than 20 ℃, the scope below 80 ℃.During 20 ℃ of the vitrifying tansition temperature deficiencies of acrylic resin, manifest adhesivity and solidify easily, in other words, caking if surpass 80 ℃, in the overlay film 4 that obtains in that edge coating is applied to mirror edge dry solidification, is easy to generate crackle easily.
At the mirror with the present invention's the 2nd feature with in the edge coating, acrylic silicon resin in being scattered in water when, what its number average bead diameter was fit to use is more than the 30nm, below the 800nm, more than the preferred 50nm, below the 400nm.During number average bead diameter when making it to be scattered in the water is not enough 30nm, can owing to mirror with the too high level and smooth overlay film 4 that can not get of the viscosity of edge coating.If number average bead diameter surpasses 800nm, after the coating mirror is with edge coating, form when the overlay film 4, the rapid-drying properties variation, dry solidification is slack-off.
Use in the water soluble resin of edge coating at water-based mirror with the present invention's the 2nd feature, suitably add water, in addition, for the outward appearance of finishing after the operation that improves when coating, the coating, the additive that the defoamer that can be mixed, tackifier, mould inhibitor, sanitas, antiseptic-germicide, UV light absorber, photostabilizer, levelling agent, antiseize paste, slip-off preventing agent, antioxidant and thermo-stabilizer etc. use in the water-borne coatings usually.
The mirror edge coating of the present invention that suitable interpolation water, film coalescence aid, levelling agent, defoamer obtain in the acrylic silicon resin emulsion, adopt modes such as roller coating, bristle coating, more than dry film thickness 10 μ m, the specification that 250 μ m are following applies the inclination position 5 of the mirror dorsal edge of doing chamfered.And it is being promoted drying below 80 ℃, preferred Air drying forms overlay film 4, and coating mirror edge forms overlay film 4, thereby finishes the corrosion protection mirror.
By following embodiment 1～12, to the 1st feature of the present invention detailed description of giving an example.
[embodiment 1～12 and corresponding comparative example 1～10 thereof] with the present invention's the 1st feature
In these embodiment 1～12 and comparative example 1～10, adopt known means, as shown in Figure 1, stack gradually silver mirror film 1, copper film, back protection film 3 as metal protective film 2 in the one side of glass substrate G, making thickness is large-sized mirror of 5mm.Concrete operation is as follows: the one side at the glass substrate G that cleans up sprays the silver plating solution that is made of with reduced liquid silver nitrate solution and reduction silver, forms 1.0g/m by silver mirror reaction
2Thick silver mirror film 1, behind clean this face, spraying is by copper-bath and go back the copper electrolyte that native copper constitutes with reduced liquid, forms 0.3g/m
2The metal protective film 2 that forms of copper, the washing after drying.On this metal protective film 2; adopt the flow coat coating machine; according to the standard that obtains homogeneous film thickness; coating back protection film coating; being constructed as follows of the protective layer used coating of this face: Resins, epoxy and solidifying agent 85 weight parts; hexanaphthene-formaldehyde resin 15 weight parts, tackiness agent of hexanaphthene-formaldehyde resin (B) and pigment (P) weight ratio are P/B=2, contain in the color compositions 6.0 weight % lead sulfate lead pigments arranged.After the coating, solidified 6 minutes in drying oven, the temperature of glass substrate G is 140 ℃, and forming dry film thickness is the back protection film 3 of 50 μ m.
In addition; the resin that uses in the protective membrane 3 is except that Resins, epoxy overleaf; also can enumerate melamine resin; Synolac; contain the having the lead pigments of lead sulfate for pigment except that using; also can enumerate by what lead carbonate constituted has lead pigments, a lead-free pigment, has used Resins, epoxy in the present embodiment, the sulfur-bearing lead plumbate lead pigments arranged.Pigment can use the antirust raw material that has rust-proof effect for metal protective film 2.
It is square that the mirror that obtains with aforesaid method is cut off 200mm, after its edge carried out combination processing, on the inclination position 5 that above-mentioned silver mirror film, copper film expose, adopt the known pen type of the coating part Off エ Le ト system edge coating tool of record in the above-mentioned patent documentation 1 that the applicant quoted, manual coating mirror edge coating.The mirror of coating is shown in table 1 with the composition of edge coating, and unit is weight part.
(table 1)
| Embodiment | Comparative example | ||||||||||||||||||||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 | ??11 | ??12 | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 | ||
| Host | ??((A)+(B))∶(C) | ||||||||||||||||||||||
| ??(A)+(B) | |||||||||||||||||||||||
| (A) the liquid-state epoxy resin epoxy equivalent (weight) 184～194 | ??40 | ??70 | ??90 | ??70 | ??70 | ??70 | ??30 | ??50 | ??80 | ??- | ??- | ??- | ??100 | ??20 | ??- | ??70 | ??70 | ??20 | ??10 | ??- | ??- | ??- | |
| (A) the liquid-state epoxy resin epoxy equivalent (weight) 230～280 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??40 | ??70 | ??90 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??20 | ??100 | ??- | |
| (B) the solid epoxy resin epoxy equivalent (weight) 900～1000 | ??60 | ??30 | ??10 | ??30 | ??30 | ??30 | ??70 | ??50 | ??- | ??60 | ??30 | ??- | ??- | ??80 | ??100 | ??30 | ??30 | ??80 | ??90 | ??- | ??- | ??- | |
| (B) the solid epoxy resin epoxy equivalent (weight) 2400～3300 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??20 | ??- | ??- | ??10 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??80 | ??- | ??100 | |
| (C) the o-cresol phenolic resin varnish epoxy equivalent (weight) 205～230 | ??3 | ??3 | ??3 | ??1 | ??10 | ??20 | ??5 | ??3 | ??8 | ??3 | ??3 | ??8 | ??2 | ??1 | ??3 | ??- | ??30 | ??10 | ??3 | ??3 | ??- | ??20? | |
| Rheology inhibitor levelling agent defoamer MIBK methyl propanediol n-butanol dimethylbenzene | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | ??4 | |
| ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ||
| ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ||
| ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??20 | ??10 | ??10 | ??20 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??20 | ??10 | ??20 | ||
| ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??20 | ??10 | ??10 | ??20 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??10 | ??20 | ??10 | ??20 | ||
| ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??10 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??5 | ??10 | ??5 | ??10 | ||
| ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??40 | ??20 | ??20 | ??40 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??40 | ??20 | ??40 | ||
| Solidifying agent | The polyamines resin | ??43 | ??63 | ??73 | ??62 | ??70 | ??87 | ??40 | ??50 | ??70 | ??43 | ??50 | ??62 | ??82 | ??30 | ??18 | ??61 | ??82 | ??30 | ??24 | ??15 | ??60 | ??20 |
| Silane coupling agent | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??5 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | ??2 | |
Polyamines resin ト one マ イ De 437 amine values 235～265 reactive hydrogen equivalents 150
Embodiment 1～12nd, the mirror of the present invention preferred ratio of components of edge coating, comparative example 1～10th, the mirror of the present invention preferred ratio of components example in addition of edge coating.
Next, adopt the mirror edge coating of the composition of embodiment 1～12 and comparative example 1～10, each square mirror of coating 200mm is placed on inherent 180 ℃ of drying oven, heating 5 minutes, makes its dry solidification, obtains the overlay film at 5 places, position.
Adopt test method shown in the table 2 and metewand then, carry out pencil hardness test, the test of connecting airtight property, acid resisting test, alkaline resistance test, the test of heatproof water-based, CASS test and drying property test.
(table 2)
| Test subject | Test method | Metewand |
| Pencil hardness | The JIS-K-5401 damage method | More than the H |
| Connecting airtight property | In the part of coating mirror with edge coating, 2mm cuts 10 otch with cutter knife at interval, and fiber band is peeled off | Peel off area below 10% |
| Acid resistance | Under 20 ℃, in the hydrochloric acid of 10Vol%, soaked 72 hours | It is no abnormal to be coated with the membrane stage outward appearance |
| Corrosion does not take place to invade in edge surface | ||
| The outward appearance of silver face is no abnormal | ||
| Alkali resistance | Under 20 ℃, in the caustic soda of 10Vol%, soaked 72 hours | It is no abnormal to be coated with the membrane stage outward appearance |
| The outward appearance of silver face is no abnormal | ||
| The heatproof water-based | In 60 ℃ water, soaked 10 days | It is no abnormal to be coated with the membrane stage outward appearance |
| Corrosion does not take place to invade in edge surface | ||
| The outward appearance of silver face is no abnormal | ||
| The CASS test | According to JIS D 0201, sprayed 240 hours | It is no abnormal to be coated with the membrane stage outward appearance |
| Corrosion does not take place to invade in edge surface | ||
| The outward appearance of silver face is no abnormal | ||
| Drying property | 180 ℃ of warm air dryings were positioned over flawless indoor 1 hour after 5 minutes | No abnormal |
At inclination position 5, the mirror shown in coating embodiment 1～12, the comparative example 1～10 forms overlay film with the edge coating composition, and the mirror with this overlay film is estimated, and its evaluation result is shown in table 3, and for metewand, qualified is zero, underproofly be *.
(table 3) test-results
| Embodiment | Comparative example | |||||||||||||||||||||
| Project | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Pencil hardness | 2H | 2H | 3H | 2H | 2H | 2H | H | 2H | 2H | 2H | 2H | 3H | 2H | H | H | 3H | 3H | 2H | H | H | 2H | H |
| Connecting airtight property | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | ○ | ○ | ○ | ○ | × | ○ | × |
| Acid resistance is coated with corrosion silver face unusual of membrane stage edge surface | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ × | ? ○ ○ × | ? ○ ○ × | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ × | ? ○ ○ × | ? ○ ○ × ? | ? ○ ○ × | ? ○ ○ × |
| Alkali resistance is coated with the unusual of membrane stage silver face | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ |
| The heatproof water-based is coated with corrosion silver face unusual of connecting airtight property of membrane stage edge surface | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? ○ ○ ○ ○ | ? ? × ○ ○ × | ? ? × × × × | ? ? × × ○ × | ? ? ○ ○ ○ ○ | ? ? × × ○ ○ | ? ? × ○ ○ × | ? ? × × × × | ? ? × × ○ × | ? ? ○ ○ ○ ○ | ? ? × × ○ ○ |
| CASS test is coated with corrosion silver face unusual of membrane stage edge surface | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ × × | ? ? × × × | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ ○ ○ | ? ? ○ × × | ? ? × × × | ? ? ○ ○ ○ | ? ? ○ ○ ○ |
| The drying property slight crack | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | ○ | × | ○ | ○ | × | ○ | × | ○ |
Use has the present invention's the 1st combination of features than embodiment 1～12 resulting mirror of scope scope with edge coating, all qualified in whole tests, the result is good, has the present invention's the 1st combination of features than comparative example 1～10 resulting mirror of mirror in addition and use with edge coating, have underproof situation, the result is undesirable.
More than; by the foregoing description 1～10; use with (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300) and (B) weight ratio of bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300) be (A): (B)=30: 70-90: 10; (C) o-cresol phenolic epoxy varnish (epoxy equivalent (weight) 180～300) is ((A)+(B)) with respect to the weight ratio of (A)+(B): (C)=be the mirror of feature edge coating in 100: 1～100: 20; the mirror that applies the mirror edge and obtain; confirmed that this coating has following advantage: its coating silver mirror film 1; the drying at the edge of the mirror that exposes as the copper film of metal protective film 2 can be finished at short notice; the basic G of glass to the inclination position 5 at glass substrate G edge; silver mirror film 1; copper film as metal protective film 2; back protection film has firm adherence, long-acting superior corrosion resistance.
By following embodiment 1～3, to the 2nd feature of the present invention detailed description of giving an example.
[embodiment 1～3 and corresponding comparative example 1～3 thereof] with the present invention's the 2nd feature
In these embodiment 1～3 and comparative example 1～3, adopt the method identical with above-mentioned embodiment with the present invention's the 1st feature 1～12, be coated with water-based mirror edge coating.The water-based mirror that is coated with is shown in table 4 with the composition of edge coating.
[table 4]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Acrylic silicon resin emulsion (TG20 ℃, nonvolatile component 46.0wt%) | ??70.0 | ??- | ??- | ??- | ??- | ??- |
| Acrylic silicon resin emulsion (TG80 ℃, nonvolatile component 46.0wt%) | ??- | ??70.0 | ??- | ??- | ??- | ??- |
| Acrylic silicon resin emulsion (TG80 ℃, nonvolatile component 46.0wt%)+silane monomer 20.0wt% | ??- | ??- | ??70.0 | ??- | ??- | ??- |
| Emulsion acrylic resin (nonvolatile component 43.0wt%) | ??- | ??- | ??- | ??80.0 | ??- | ??- |
| Ester-polyurethane resin emulsion (nonvolatile component 46.0wt%) | ??- | ??- | ??- | ???- | ??75.0 | ??- |
| Ethylene vinyl acetate resin emulsion (nonvolatile component 50.0%) | ??- | ??- | ??- | ???- | ??- | ??80.0 |
| Water | ??25.0 | ??25.0 | ??25.0 | ??14.0 | ??20.0 | ??14.0 |
| Film coalescence aid TEXAN0L | ??4.0 | ??4.0 | ??4.0 | ??5.0 | ??4.0 | ??7.0 |
| Levelling agent | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 |
| Water | ??0.9 | ??0.9 | ??0.9 | ??0.9 | ??0.9 | ??0.9 |
| Add up to | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ??100.0 |
Numerical value in the table 4 is represented with weight %, modulates each mirror coating of water-based to add up to 100%.
Water-based mirror coating among the embodiment 1, use TG20.0 ℃ acrylic silicon resin emulsion (Asahi Chemical Corp's system, trade(brand)name Port リ デ ュ レ ッ Network ス G623, nonvolatile component is 46.0 weight %, in water, modulate), modulate with the amount of coating gross weight in the water-based mirror with 70%.Water-based mirror coating among the embodiment 2, use TG50.0 ℃ acrylic silicon resin emulsion (East Asia synthetic chemistry Co., Ltd. system, trade(brand)name シ-ラ ス PC100, nonvolatile component is modulated to 46.0 weight %), modulate with the amount of coating gross weight in the water-based mirror with 70%.Water-based mirror coating among the embodiment 3, use is at TG20.0 ℃ acrylic silicon resin emulsion (Asahi Chemical Corp's system, trade(brand)name Port リ デ ュ レ ッ Network ス G620, nonvolatile component is modulated to 46.0 weight %) in, add the mixture of 20% silane monomer (eastern beautiful DOW CORNING silicon Co., Ltd. system, trade(brand)name SH6040), modulate with the amount of coating full weight amount in the water-based mirror with 70%.The concentration of the acrylic silicon resin that contains in edge coating at the water-based mirror shown in the embodiment 1,2, with the water-based mirror with the full weight amount of edge coating as 100%, be 32.2%.The concentration of the acrylic silicon resin shown in the embodiment 3 is 100% with the water-based mirror with the full weight amount of edge coating, is 25.8%.
Corresponding to this, water-based mirror edge coating in the comparative example 1, use Emulsion acrylic resin (Mitsui Chemicals, Inc's system, trade(brand)name テ Le マ テ ッ Network ス E293, nonvolatile component is modulated into 43.0%), modulate with the amount of edge coating full weight amount in the water-based mirror with 80%.Water-based mirror edge coating in the comparative example 2, use ester-polyurethane resin emulsion (Dainippon Ink. ﹠ Chemicals Inc's system, trade(brand)name ボ Application コ one ト CG5060, nonvolatile component is modulated into 46.0%), modulate with the amount of edge coating full weight amount in the water-based mirror with 80%.The water-based mirror edge coating of comparative example 3, use ethylene vinyl acetate resin emulsion (Dainippon Ink. ﹠ Chemicals Inc's system, trade(brand)name エ バ デ イ ッ Network EV-15, nonvolatile component is modulated into 50.0%), modulate with the amount of edge coating full weight amount in the water-based mirror with 70%.As shown in table 4, the water of interpolation 14.0 weight %～25.0 weight % adds water in film coalescence aid (イ one ス ト マ Application Co., Ltd. system, trade(brand)name TEXAN0L) and levelling agent in above each emulsion, mixes above-mentioned substance and is modulated into water-based mirror coating.
Next, the mirror edge coating that adopts embodiment 1～3 and comparative example 1～3 to form, each square mirror of coating 200mm is placed on inherent 180 ℃ of drying oven, heating 5 minutes, makes its dry solidification, obtains the overlay film at 5 places, position.
Adopt test method shown in the table 5 and metewand then, carry out pencil hardness test, the test of connecting airtight property, acid resisting test, alkaline resistance test, the test of heatproof water-based, CASS test and drying property test.
[table 5]
| Test subject | Test method | Metewand |
| Pencil hardness | The JIS-K-5401 damage method | More than the H |
| Connecting airtight property | In the part of coating mirror with edge coating, 2mm cuts 10 otch with cutter knife at interval, and fiber band is peeled off | Peel off area below 10% |
| Acid resistance | Under 20 ℃, in the hydrochloric acid of 1Vol%, soaked 72 hours | It is no abnormal to be coated with the membrane stage outward appearance |
| Corrosion does not take place to invade in edge surface | ||
| The outward appearance of silver face is no abnormal | ||
| Alkali resistance | Under 20 ℃, in the caustic soda of 5Vol%, soaked 72 hours | It is no abnormal to be coated with the membrane stage outward appearance |
| The outward appearance of silver face is no abnormal | ||
| The heatproof water-based | In 60 ℃ water, soaked 10 days | It is no abnormal to be coated with the membrane stage outward appearance |
| Corrosion does not take place to invade in edge surface | ||
| The outward appearance of silver face is no abnormal | ||
| The CASS test | According to JIS D 0201, sprayed 24 hours | It is no abnormal to be coated with the membrane stage outward appearance |
| Corrosion does not take place to invade in edge surface | ||
| The outward appearance of silver face is no abnormal | ||
| Drying property | 180 ℃ of warm air dryings were positioned over flawless indoor 1 hour after 5 minutes | No abnormal |
At inclination position 5, the mirror shown in coating embodiment 1～3, the comparative example 1～3 forms overlay film with the edge coating composition, and the mirror with this overlay film is estimated, and its evaluation result is shown in table 6, and for metewand, qualified is zero, underproofly be *.
[table 6]
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Pencil hardness | H | HB | H | H | H | H |
| Connecting airtight property | ○ | ○ | ○ | × | × | × |
| Acid resistance is coated with corrosion silver face unusual of membrane stage edge surface | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ × | ? ○ ○ × | ? ○ ○ × |
| Alkali resistance is coated with the unusual of membrane stage silver face | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? ○ ○ | ? × × |
| The heatproof water-based is coated with corrosion silver face unusual of connecting airtight property of membrane stage edge surface | ? ○ ○ ○ ○ | ? ○ ○ ○ ○ | ? ○ ○ ○ ○ | ? × ○ ○ × | ? × × × × | ? × × ○ × |
| CASS test is coated with corrosion silver face unusual of membrane stage edge surface | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ ○ ○ | ? ○ × × | ? × × × |
| The drying property slight crack | ○ | ○ | ○ | × | × | ○ |
Use has the water-based mirror edge coating that is formed as combination by the acrylic silicon resin emulsion of the present invention's the 2nd feature, embodiment 1～3 resulting mirror, all qualified in whole tests, the result is good, and use combination of the present invention than comparative example 1～3 resulting mirror of mirror in addition with edge coating, have underproof situation, the result is undesirable.
More than; by having the embodiment 1～3 of the present invention's the 2nd feature; make use mirror edge coating; this coating has following feature: contain the acrylic silicon resin emulsion that the acrylic silicon resin with the present invention's the 2nd feature is scattered in the water and form; particularly the aforesaid propylene silicon acid resinous is; the acrylic silicon resin emulsion that the acrylic monomer that contains silicon is obtained by emulsion polymerization; perhaps; to contain the acrylic monomer of silicon and not contain the acrylic silicon resin emulsion that the acrylic monomer of silicon obtains by emulsion polymerization; the mirror that applies the mirror edge and obtain; confirmed that this coating has following advantage: to silver mirror film 1; copper film as metal protective film 2; back protection film 3; has firm adherence, long-acting superior corrosion resistance.
Claims (7)
1, mirror edge coating is characterized in that containing (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300), (B) bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300), (C) o-cresol phenolic epoxy varnish (epoxy equivalent (weight) 180～300), (D) epoxy hardener and (E) silane coupling agent.
2, the described mirror edge coating of claim 1, it is characterized in that (A) bisphenol type liquid-state epoxy resin (epoxy equivalent (weight) 150～300) and (B) weight ratio of bisphenol type solid epoxy resin (epoxy equivalent (weight) 450～3300) be (A): (B)=30: 70～90: 10, (A)+(B) and (C) weight ratio of o-cresol phenolic epoxy varnish (epoxy equivalent (weight) 180～300) is ((A)+(B)): (C)=100: 1～100: 20.
3, mirror is that silver mirror film, metal protective film and back protection film are stacked gradually after on the glass substrate, and the mirror of record in claim 1 or 2 is coated the edge with edge coating, dry solidification then, thereby form.
4, water-based mirror edge coating is characterized in that containing that the handlebar acrylic silicon resin is scattered in the water and the acrylic silicon resin emulsion that forms.
5, the described water-based mirror of claim 4 edge coating, it is characterized in that the aforesaid propylene silicon acid resinous is the acrylic silicon resin emulsion that is only obtained by the acrylic monomer emulsion polymerization that contains silicon, perhaps the acrylic silicon resin emulsion that obtains by acrylic monomer that contains silicon and other monomer emulsion polymerization.
6, claim 4 or 5 described water-based mirror edge coatings is characterized in that above-mentioned acrylic silicon resin composition is cyclohexyl methacrylate, butyl acrylate, methyl methacrylate and butyl methacrylate, silicon monomer.
7, mirror is that silver mirror film, metal protective film and back protection film are stacked gradually after on the glass substrate, and the water-based mirror that each is put down in writing in the claim 4 to 6 is applied to the glass substrate surrounding edge with edge coating, forms behind the dry solidification.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004085881 | 2004-03-24 | ||
| JP2004085881 | 2004-03-24 | ||
| JP2005035206 | 2005-02-10 | ||
| JP2005035206A JP4807957B2 (en) | 2005-02-10 | 2005-02-10 | Aqueous mirror coating liquid and mirror using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610172440 Division CN101033361A (en) | 2004-03-24 | 2005-03-24 | Edge coating for mirror and mirror coated with the edge coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1680503A true CN1680503A (en) | 2005-10-12 |
| CN100345921C CN100345921C (en) | 2007-10-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510059032XA Expired - Fee Related CN100345921C (en) | 2004-03-24 | 2005-03-24 | Coating material and mirror coated therewith |
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| Country | Link |
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| CN (1) | CN100345921C (en) |
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| CN101809068A (en) * | 2007-04-24 | 2010-08-18 | 莫门蒂夫性能材料股份有限公司 | Method of applying an anti-corrosion and/or adhesion promoting coating to a metal and resulting coated metal |
| CN102101963A (en) * | 2010-11-30 | 2011-06-22 | 高鼎实业股份有限公司 | Mirror and back coating composition thereof |
| CN104327625A (en) * | 2014-10-14 | 2015-02-04 | 马鞍山市恒毅机械制造有限公司 | Water and corrosion resistant quick-drying aqueous coating for glass doors, and its preparation method |
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| JPH0627181B2 (en) * | 1988-02-16 | 1994-04-13 | ソマール株式会社 | Flexible epoxy resin composition |
| JPH0275619A (en) * | 1988-09-12 | 1990-03-15 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
| JP2580444B2 (en) * | 1992-07-10 | 1997-02-12 | ソマール株式会社 | Flexible epoxy resin composition |
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| JP4047991B2 (en) * | 1998-12-28 | 2008-02-13 | 旭硝子株式会社 | Mirror edge coating composition and mirror |
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