WO2014103894A1 - 裏止め塗料組成物および鏡 - Google Patents
裏止め塗料組成物および鏡 Download PDFInfo
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- WO2014103894A1 WO2014103894A1 PCT/JP2013/084155 JP2013084155W WO2014103894A1 WO 2014103894 A1 WO2014103894 A1 WO 2014103894A1 JP 2013084155 W JP2013084155 W JP 2013084155W WO 2014103894 A1 WO2014103894 A1 WO 2014103894A1
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- silicone oil
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the present invention relates to a back coating composition for forming a back coating film on the back surface of the mirror, and a mirror having a back coating film formed on the back surface.
- a copper protective film is formed on the silver mirror surface film and a backing coating film is further formed on the copper protective film in order to prevent corrosion of the silver mirror surface film.
- a back coating composition for forming the back coating film a composition containing a thermosetting resin (epoxy resin, alkyd resin, etc.) and a pigment (external pigment, rust preventive pigment, etc.) is usually used ( (See Patent Documents 1 and 2).
- the conventional back coating film cannot sufficiently suppress erosion by acid, and in mirrors installed in bathrooms, bathrooms, washrooms, etc., the silver mirror film may be corroded by highly acidic chemicals. is there. Therefore, it is desired to develop a back coating composition that can form a back coating film that is not easily eroded by acid for mirrors installed in bathrooms, bathrooms, washrooms, and the like.
- a backing coating composition comprising a thermosetting resin, a pigment, and a dispersant, and an amino group-containing polymer having an amine value of 20 mgKOH / g or more and having no acid group as the dispersant (patent) Reference 3).
- a coating film made of a backing coating composition containing the amino group-containing polymer is likely to have appearance problems such as formation of dents and distortion skin.
- problems such as water resistance (moisture resistance) are likely to occur, such as peeling of the silver mirror film at the periphery (cut surface) of the mirror.
- An object of the present invention is to provide a backing coating composition that is less susceptible to acid erosion, has a good appearance, and can form a backing coating film that is excellent in water resistance, and a mirror that is excellent in acid resistance, appearance on the back surface, and water resistance. Is to provide.
- the back coating composition of the present invention is a back coating composition for forming a back coating film on the back surface of a mirror, and comprises a thermosetting resin, a pigment, a dispersant, a reactive silicone oil,
- a thermosetting resin an epoxy resin (excluding reactive silicone oil having an epoxy group) and an amine-based curing agent, and as the dispersant, the amine value is 20 mgKOH / g or more, And an amino group-containing polymer having no acid group, and the reactive silicone oil includes an epoxy-modified silicone oil having an epoxy group and no polyoxyalkylene chain.
- the epoxy resin is preferably a bisphenol A type epoxy resin.
- the amine curing agent is preferably dicyandiamide or organic acid dihydrazide.
- the amine value of the amino group-containing polymer is preferably 20 to 70 mgKOH / g.
- the proportion of the amino group-containing polymer is preferably 20 to 100% by mass in the dispersant (100% by mass).
- the functional group equivalent of the epoxy group in the epoxy-modified silicone oil is preferably 1000 g / mol or less.
- the backing coating composition of the present invention preferably further contains at least one curing accelerator selected from the group consisting of organotin compounds, urea derivatives and imidazoles as the thermosetting resin.
- the ratio of the thermosetting resin is 30 to 50% by mass in the solid content (100% by mass) of the backing coating composition obtained by removing the solvent from the backing coating composition. %,
- the ratio of the pigment is 50 to 70% by mass, the ratio of the dispersant is 1 to 13% by mass, and the ratio of the reactive silicone oil is 0.001 to 0.5% by mass. % Is preferred.
- the backing coating composition of the present invention preferably contains an extender pigment as the pigment.
- the back coating composition of the present invention preferably contains a rust preventive pigment as the pigment.
- the mirror of the present invention has a glass substrate, a metal film formed on the glass substrate, and a back coating film formed on the metal film using the back coating composition of the present invention. It is characterized by.
- the film thickness of the backing coating film is preferably 30 to 100 ⁇ m.
- the metal film may be composed of a silver mirror film formed on the glass substrate and a metal protective film formed on the silver mirror film, and is a silver mirror film formed on the glass substrate. May be.
- the mirror of the present invention is a mirror having a glass substrate, a metal film formed on the glass substrate, and a back coating film formed on the metal film.
- the backing coating composition of the present invention it is possible to form a backing coating film that is hardly eroded by acid, has a good appearance, and is excellent in water resistance. Further, the mirror of the present invention is excellent in acid resistance, the appearance of the back surface, and water resistance.
- thermosetting resin means a resin that cures when heated.
- the thermosetting resin includes a curing agent that cures the thermosetting resin, a curing accelerator that accelerates the curing of the thermosetting resin, and a relatively low molecular weight reactive diluent that can react with the thermosetting resin.
- the dispersant means a compound having an action capable of dispersing the pigment in the backing coating composition and stabilizing the dispersion state. Having no acid group means not having an acid group such as a carboxy group or a phosphate group in the molecule, and having no acid group can be confirmed by the presence or absence of an acid value.
- the amine value is a value measured according to JIS K7237.
- the acid value is a value measured according to JIS K2501.
- the reactive silicone oil means a modified silicone oil having a dimethylpolysiloxane skeleton and having a reactive organic group introduced into one or both of a side chain and a terminal.
- the functional group equivalent of an epoxy group means the molecular weight of the epoxy-modified silicone oil per functional group (epoxy group).
- the solvent means a compound that can dissolve or disperse the thermosetting resin or pigment, but does not react with other components.
- the solid content of the backing coating composition means a component obtained by removing the solvent from the backing coating composition, and includes thermosetting resins and other resins. “ ⁇ ” in a numerical range means that numerical values described before and after that are included as a lower limit value and an upper limit value unless otherwise specified.
- the back coating composition of the present invention is a back coating composition for forming a back coating film on the back surface of a mirror, and includes a thermosetting resin, a pigment, a dispersant and a reactive silicone oil. Depending on the case, it may contain a solvent, other additives, other resins and the like.
- thermosetting resin examples include an epoxy resin, an alkyd resin, a phenol resin, and a melamine resin.
- the back coating composition of the present invention is an epoxy resin (however, a reactive silicone oil having an epoxy group is used as at least a part of the thermosetting resin from the point that it is less likely to be eroded by acid when used as a back coating film. And a curing agent for the epoxy resin.
- epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, amino-modified epoxy resin (see Japanese Patent Laid-Open No. 3-75006), and esterified bisphenol type epoxy resin (Japanese Patent Laid-Open No. Bisphenol A type epoxy resin is particularly preferable from the viewpoint of corrosion resistance and durability.
- the curing agent examples include amine-based curing agents and acid anhydride-based curing agents.
- the backing coating composition of the present invention is characterized by containing an amine-based curing agent as at least a part of the curing agent from the viewpoint of good adhesion of the coating film.
- amine curing agents include aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, dicyandiamide curing agents, polyamide amine curing agents, organic acid dihydrazides, and the like. From the viewpoint of rapidly curing by heating, dicyandiamide, organic acid dihydrazide or polyamidoamine type curing agent is preferable, and dicyandiamide or organic acid dihydrazide is particularly preferable.
- the backing coating composition of the present invention may further contain a curing accelerator (curing catalyst) as at least a part of the thermosetting resin.
- a curing accelerator curing catalyst
- the curing accelerator include organotin compounds, imidazoles, urea derivatives, tertiary amines, onium salts, and the like, and are composed of organotin compounds, urea derivatives, and imidazoles because the temperature required for curing can be reduced. At least one selected from the group is preferred.
- the backing coating composition of the present invention may further contain a reactive diluent as part of the thermosetting resin for the purpose of adjusting the viscosity and the like of the backing coating composition.
- a reactive diluent include an epoxy compound having a relatively low molecular weight such as glycidyl ethers.
- the pigment examples include extender pigments, rust preventive pigments, and colored pigments.
- the backing coating composition of the present invention preferably contains an extender pigment as at least a part of the pigment from the viewpoint of imparting necessary properties to the coating film.
- the back coating composition of this invention contains a rust preventive pigment as at least one part of a pigment from the point which protects the metal film as a mirror surface effectively.
- Examples of extender pigments include talc, barium sulfate, mica, calcium carbonate, and the like. Talc, calcium carbonate, and barium sulfate are preferable, and talc or barium sulfate is more preferable.
- Examples of the rust preventive pigment include cyanamide zinc, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, and cyanamide zinc calcium. Zinc molybdate, barium borate, and calcium cyanamide zinc are preferable, and cyanamide Zinc or zinc oxide is more preferred.
- Examples of the color pigment include titanium oxide, carbon black, and iron oxide. Carbon black or titanium oxide is preferable, and iron oxide is more preferable.
- the backing coating composition of the present invention is an amino group-containing polymer (hereinafter referred to as a specific amino group-containing polymer) having an amine value of 20 mgKOH / g or more and having no acid group as at least a part of the dispersant. .).
- the amine value of the specific amino group-containing polymer is 20 mgKOH / g or more, more preferably 20 to 70 mgKOH / g, and particularly preferably 40 to 70 mgKOH / g.
- the amine value is 20 mgKOH / g or more and it has no acid group, a backing coating film that is hardly eroded by an acid can be formed. Further, if the amine value is 70 mgKOH / g or less, the hydrophilic amino group remaining in the coating film without causing an addition reaction with the epoxy resin is reduced, and the water resistance of the backing coating film is not adversely affected. .
- the specific amino group-containing polymer in the present invention preferably has no acid group is as follows. Since the dispersant is usually used for the purpose of improving the dispersibility of the pigment or the like, the dispersant needs to have a specific adsorption action on the pigment. Accordingly, dispersants having both acid groups and amino groups are widely known. On the other hand, the dispersant (specific amino group-containing polymer) in the present invention has an action as a curing catalyst for thermosetting resins (particularly epoxy resins) as well as adsorption to pigments and improved affinity with thermosetting resins. Have. The specific amino group-containing polymer in the present invention does not have an acid group and is preferable from the viewpoint of proceeding curing of the thermosetting resin.
- Examples of the specific amino group-containing polymer include the following dispersants manufactured by BYK. Each amine value and acid value are as shown in parentheses. DISPERBYK (registered trademark) -116 (amine value: 65 mgKOH / g, acid value: 0 mgKOH / g, acrylic copolymer), DISPERBYK (registered trademark) -2155 (amine value: 48 mgKOH / g, acid value: 0 mgKOH / g, block copolymer), DISPERBYK (registered trademark) -9077 (amine value: 48 mgKOH / g, acid value: 0 mgKOH / g, polymer copolymer) and the like.
- dispersant another dispersant other than the specific amino group-containing polymer may be used in combination.
- examples of other dispersants include the following dispersants manufactured by BYK. DISPERBYK (registered trademark) -167 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g, block copolymer), DISPERBYK (registered trademark) -163 (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g, block copolymer), DISPERBYK (registered trademark) -164 (amine value: 18 mgKOH / g, acid value: 0 mgKOH / g, block copolymer), DISPERBYK (registered trademark) -110 (amine value: 0 mgKOH / g, acid value: 53 mgKOH / g, copolymer having an acid group), DISPERBYK (registered trademark) -106 (amine value:
- reactive silicone oil examples include amine-modified silicone oil, epoxy-modified silicone oil, alicyclic epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxy-modified silicone oil, hydrogen-modified silicone oil, and methacryl-modified silicone. Examples thereof include oil, polyether-modified silicone oil, phenol-modified silicone oil, silanol-modified silicone oil, and diol-modified silicone oil.
- the reactive organic group examples include an amino group, an epoxy group, a (meth) acryloyl group, a mercapto group, a carboxy group, a hydroxyl group, and a hydrogen atom.
- the back coating composition of the present invention has an epoxy group as at least a part of the reactive silicone oil and has a good appearance and can form a back coating film having excellent water resistance.
- An epoxy-modified silicone oil having no chain (hereinafter referred to as a specific epoxy-modified silicone oil) is included.
- the reactive silicone oil has an epoxy group, the compatibility with the thermosetting resin is improved, and a backing film having a good appearance can be formed.
- the reactive silicone oil has water repellency, a backing coating film excellent in water resistance can be formed.
- the polyoxyalkylene chain has a polyoxyalkylene chain
- the polyoxyalkylene chain is derived from the hydrophilic part of the molecular structure, has a good appearance, and It is difficult to form a backing film with excellent water resistance.
- the functional group equivalent of the epoxy group in the specific epoxy-modified silicone oil is preferably 1000 g / mol or less, more preferably 200 to 700 g / mol. If the functional group equivalent of the epoxy group is 1000 g / mol or less, the number of epoxy groups per molecule of the specific epoxy-modified silicone oil is sufficiently large, and (i) compatibility with the thermosetting resin is increased. Further, (ii) the reaction with the thermosetting resin sufficiently occurs and the reactive silicone oil is sufficiently fixed in the coating film, so that the bleed-out of the reactive silicone oil is suppressed.
- the functional group equivalent of the epoxy group is 200 g / mol or more, the number of epoxy groups per molecule of the specific epoxy-modified silicone oil does not increase too much, and the surface tension of the paint is imparted while performing addition polymerization on the epoxy resin. And it is preferable from the point which gives water resistance to a coating film.
- a modified silicone oil other than the specific epoxy-modified silicone oil may be used in combination.
- the back coating composition of the present invention may contain a solvent.
- the solvent include aromatic hydrocarbons, aliphatic hydrocarbons, esters, ethers, ketones, alcohols and the like. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols and the like are preferable.
- the backing coating composition of the present invention may contain an additive other than the dispersant.
- the additive include a reinforcing material, a thickener, a rust inhibitor, an anti-settling agent, an antifoaming agent, a surfactant, and a rheology control agent.
- the backing coating composition of the present invention may contain a resin other than the thermosetting resin.
- resins include polyester, acrylic resin, styrene resin, vinyl resin, ketone resin, and rosin.
- composition ratio The solid content concentration of the backing coating composition of the present invention is preferably 60 to 100% by mass, more preferably 70 to 90% by mass. If the solid content concentration is 60% by mass or more, a sufficient film thickness can be obtained.
- the proportion of the thermosetting resin (including the curing agent, curing accelerator and reactive diluent) in the solid content (100% by mass) of the backing coating composition is preferably 30 to 50% by mass, 45 mass% is more preferable.
- the ratio of the thermosetting resin is 30% by mass or more, the film-forming property is good, and sufficient hardness and adhesion of the coating film can be obtained.
- the ratio of a thermosetting resin is 50 mass% or less, the ratio of functional pigments, such as a rust preventive pigment, will increase, and the acid resistance etc. of a coating film will improve.
- the proportion of the pigment in the solid content (100% by mass) of the backing coating composition is preferably 50 to 70% by mass, and more preferably 52 to 68% by mass.
- the proportion of the pigment is 50% by mass or more, the acid resistance of the coating film is improved.
- the proportion of the pigment is 70% by mass or less, the resin component as the film-forming component is increased, and sufficient hardness and adhesion of the coating film can be obtained.
- the proportion of the dispersant in the solid content (100% by mass) of the backing coating composition is preferably 1 to 13% by mass, and more preferably 1.2 to 11% by mass.
- the ratio of the dispersant is 1% by mass or more, the effect of the dispersant is sufficiently obtained. If the ratio of a dispersing agent is 13 mass% or less, the fall of the fluidity
- the proportion of the reactive silicone oil in the solid content (100% by mass) of the backing coating composition is preferably 0.001 to 0.5% by mass, and more preferably 0.002 to 0.4% by mass.
- the ratio of the reactive silicone oil is 0.001% by mass or more, the effect of the reactive silicone oil can be sufficiently obtained. If the ratio of reactive silicone oil is 0.5 mass% or less, it is preferable from the viewpoint that the surface tension of the coating can be reduced and a good coating surface can be formed.
- the proportion of the epoxy resin in the thermosetting resin (including a curing agent, a curing accelerator and a reactive diluent) (100% by mass) is preferably 70 to 90% by mass, and more preferably 80 to 88% by mass. . If the ratio of an epoxy resin is 70 mass% or more, the acid resistance of a coating film will improve further. If the ratio of the epoxy resin is 90% by mass or less, it is preferable because it becomes a blending ratio with a sufficient curing agent and curing accelerator, and a dense coating film can be formed.
- the proportion of the amine curing agent in the thermosetting resin (including a curing agent, a curing accelerator and a reactive diluent) (100% by mass) is preferably 5 to 12% by mass, and 7 to 10% by mass. More preferred.
- the proportion of the amine curing agent is 5% by mass or more, the adhesion of the coating film is further improved.
- the proportion of the amine curing agent is 12% by mass or less, the appearance of the coating film is improved.
- curing agent which remains in a coating film is reduced, and acid resistance improves.
- the proportion of the curing accelerator in the thermosetting resin (including a curing agent, a curing accelerator and a reactive diluent) (100% by mass) is preferably 3 to 6% by mass, and preferably 3.5 to 5.5%. The mass% is more preferable. If the ratio of a hardening accelerator is 3 mass% or more, sufficient hardening acceleration will arise and a dense coating film can be formed. If the ratio of a hardening accelerator is 6 mass% or less, the unreacted hardening accelerator remaining in a coating film can be reduced and acid resistance will improve.
- the proportion of the extender pigment in the pigment (100% by mass) is preferably 48 to 68% by mass, and more preferably 53 to 63% by mass.
- the proportion of the extender pigment is 48% by mass or more, a decrease in fluidity of the backing coating composition can be suppressed.
- the proportion of the extender pigment is 68% by mass or less, other rust preventive pigments are increased and the acid resistance of the coating film is improved.
- the proportion of the rust preventive pigment in the pigment (100% by mass) is preferably 24 to 44% by mass, and more preferably 29 to 39% by mass.
- the proportion of the rust preventive pigment is 24% by mass or more, a sufficient rust preventive effect is obtained. If the ratio of a rust preventive pigment is 44 mass% or less, the fall of the fluidity
- the proportion of the specific amino group-containing polymer in the dispersant (100% by mass) is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and particularly preferably 100% by mass.
- the ratio of the specific amino group-containing polymer is 20% by mass or more, a sufficient effect as a curing catalyst for the thermosetting resin can be obtained.
- the proportion of the specific epoxy-modified silicone oil in the reactive silicone oil (100% by mass) is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 100% by mass.
- the ratio of the specific epoxy-modified silicone oil is 20% by mass or more, the effect of the epoxy-modified silicone oil can be sufficiently obtained.
- the backing coating composition of the present invention since it contains an amino group-containing polymer having an amine value of 20 mgKOH / g or more and having no acid group as a dispersant, it is less susceptible to acid attack. A back coating film can be formed.
- the reactive silicone oil includes an epoxy-modified silicone oil having an epoxy group and not having a polyoxyalkylene chain, a backing coating film having a good appearance and excellent water resistance can be formed.
- FIG. 1 is a cross-sectional view showing a first embodiment of the mirror of the present invention.
- the mirror 10 includes a glass substrate 11, a silver mirror film 12 (metal film) formed on the glass substrate 11, a metal protective film 13 (metal film) formed on the silver mirror film 12, and the metal protective film 13. And a back coating film 14 formed.
- FIG. 2 is a sectional view showing a second embodiment of the mirror of the present invention.
- the mirror 10 includes a glass substrate 11, a silver mirror film 12 (metal film) formed on the glass substrate 11, and a backing coating film 14 formed on the silver mirror film 12.
- Glass substrate As a glass substrate, the well-known glass for mirrors can be used, For example, soda-lime glass etc. are mentioned.
- the silver mirror film examples include electroless plating, vacuum deposition, and sputtering.
- the silver mirror film preferably has a film thickness such that the silver mirror film is in the range of 0.5 to 2 g / m 2 , preferably 0.6 to 1.5 g / m 2 .
- the metal protective film is a metal film formed for corrosion protection of the silver mirror film.
- the metal protective film include metal protective films made of copper, copper alloy, nickel, nickel alloy, tin, tin alloy, and the like, and a copper protective film is usually preferable.
- the method for forming the metal protective film include an electroless plating method.
- the metal protective film preferably has a thickness such that the metal protective film is in the range of 0.1 to 1 g / m 2 , preferably 0.2 to 0.8 g / m 2 .
- the mirror of the present invention may have two or more metal protective films made of different metals. Further, since the mirror of the present invention has a back coating film which is formed using the back coating composition of the present invention and is not easily eroded by acid, as shown in FIG. 2, it does not have a metal protective film. May be.
- the back coating film is a film formed to prevent corrosion of the silver mirror surface film and the metal protective film and to improve mechanical durability.
- the back coating film is formed by applying the back coating composition of the present invention to the surface of a metal film (silver mirror surface film or metal protective film) and thermally curing it.
- the back coating composition can be carried out using a brush, roller, spray, flow coater, applicator or the like, with a flow coater, roll coater or the like being preferred.
- the coating amount of the back coating composition is such that the dry film thickness is 30 to 100 ⁇ m, preferably 30 to 60 ⁇ m.
- the temperature at the time of thermosetting the backing coating composition is usually from room temperature to 250 ° C., preferably from 150 to 180 ° C.
- the mirror of the present invention described above has a back coating film formed using the back coating composition of the present invention, it is excellent in acid resistance, appearance on the back surface, and water resistance. Specifically, (a) after immersing the cut mirror of the present invention in 10 mass% hydrochloric acid (reagent grade 1) at 20 ° C. for 48 hours, peeling from the cut section of the metal film is 5 mm or less. Has acid resistance. And (b) a step of leaving the cut mirror of the present invention in an atmosphere of a temperature of 60 ° C. and a relative humidity of 95% for 8 hours, and a step of standing in an atmosphere of a temperature of 25 ° C. and a relative humidity of 60% for 16 hours. After repeating the cycle consisting of 40 times, the metal film has water resistance such that peeling from the cut section of the metal film is 5 mm or less.
- Example 1 Each raw material was weighed in a paint shaker (Paintshaker) so as to have the composition ratio shown in the column of Example 1 in Table 1, and shaken for 15 minutes to prepare a back coating composition.
- a solution containing silver nitrate (an aqueous solution having a silver concentration of 0.08 mol / L) and a reducing solution for reducing silver (a solution of a compound containing an aldehyde group) on the surface of a sufficiently cleaned glass substrate (size 90 mm ⁇ 40 mm ⁇ 5 mm) ) was sprayed, and silver was deposited by a silver mirror reaction to form a film having a silver mirror film of 1.0 g / m 2 .
- a copper plating comprising a solution containing copper sulfate (aqueous solution having a copper sulfate concentration of 0.15 mol / L) and a reducing solution (suspension of base metal powder) for reducing copper is applied to the surface.
- the liquid was sprayed and copper was deposited by an electroless plating method to form a film having a copper protective film of 0.3 g / m 2 .
- the surface of the copper protective film was washed with water and dried, and then the temperature of the glass substrate was set to room temperature.
- the backing coating composition is applied to the surface of the copper protective film by a flow coating method so that the dry film thickness becomes 55 ⁇ m, and the glass substrate is heated for 3 minutes in a drying furnace so that the temperature of the glass substrate becomes 135 ° C.
- a coating film was formed to obtain a mirror (with a copper protective film).
- a silver plating solution comprising: was sprayed and silver was deposited by a silver mirror reaction to form a film having a silver mirror surface film of 1.0 g / m 2 . The surface of the silver mirror film was washed with water and dried, and then the temperature of the glass substrate was set to room temperature.
- the backing coating composition is applied to the surface of the silver mirror film by a flow coating method so that the dry film thickness becomes 55 ⁇ m, and the glass substrate is heated for 3 minutes in a drying furnace so that the temperature of the glass substrate becomes 135 ° C. A film was formed to obtain a mirror (no copper protective film).
- Examples 2 to 32 Each raw material was prepared so that the composition ratios shown in the columns of Examples 2 to 32 in Tables 1 to 6 were obtained, and a backing coating composition having the composition described in each column was prepared. A mirror (with and without a copper protective film) was obtained in the same manner as in Example 1 except that the backing coating composition was changed.
- Tables 1 to 6 show the evaluation results of the coating film appearance, the hydrochloric acid test results, and the water vapor cycle test results for the mirrors of Examples 1 to 32, respectively.
- the evaluation method is as follows.
- MIBK methyl isobutyl ketone.
- jER828 bisphenol A type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., jER828.
- DICY Dicyandiamide, manufactured by SKW Trostberg AG, Dyhard (registered trademark) 100SF.
- SDH Sebacic acid dihydrazide, manufactured by Nippon Fine Chemical Co., Ltd.
- ADH adipic acid dihydrazide, manufactured by Nippon Fine Chemical Co., Ltd.
- DY-T Trimethylolpropane triglycidyl ether, Araldite (registered trademark) DY-T, manufactured by Ciba Specialty Chemicals.
- DBTDL Dibutyltin dilaurate.
- UR500 urea curing accelerator, manufactured by SKW Trostberg AG, Dyhard (registered trademark) UR500.
- 2E4MZ 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.
- IBMI-12 1-isobutyl-2-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.
- BYK116 manufactured by BYK, DISPERBYK (registered trademark) -116 (amine value: 65 mgKOH / g, acid value: 0 mgKOH / g, acrylic copolymer).
- BYK2163 manufactured by BYK, DISPERBYK (registered trademark) -2163 (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g, block copolymer).
- BYK2155 DISPERBYK (registered trademark) -2155 manufactured by BYK (amine value: 48 mgKOH / g, acid value: 0 mgKOH / g, block copolymer).
- BYK110 manufactured by BYK, DISPERBYK (registered trademark) -110 (amine value: 0 mgKOH / g, acid value: 53 mgKOH / g, copolymer having an acid group).
- BYK106 DISPERBYK (registered trademark) -106 manufactured by BYK (amine value: 74 mgKOH / g, acid value: 132 mgKOH / g, polymer salt having an acid group).
- Cyanamide zinc calcium manufactured by Kikuchi Color Co., Ltd., ZK-S2.
- Talc SG-95, manufactured by Nippon Talc.
- Barium sulfate W-10 manufactured by Takehara Chemical Industries, Ltd. Titanium oxide: R-650, manufactured by Sakai Chemical Industry Co., Ltd.
- Carbon black CP carbon black manufactured by Sigma-Aldrich Japan.
- X-22-2000 manufactured by Shin-Etsu Chemical Co., Ltd., X-22-2000 (functional group equivalent of epoxy group: 620 g / mol, epoxy-modified silicone oil).
- X-22-4741 manufactured by Shin-Etsu Chemical Co., Ltd., X-22-4741 (functional group equivalent of epoxy group: 2500 g / mol, epoxy-modified silicone oil, with polyoxyalkylene chain).
- KF-101 manufactured by Shin-Etsu Chemical Co., Ltd., KF-101 (functional group equivalent of epoxy group: 350 g / mol, epoxy-modified silicone oil).
- KF-105 manufactured by Shin-Etsu Chemical Co., Ltd., KF-105 (functional group equivalent of epoxy group: 490 g / mol, epoxy-modified silicone oil).
- the mirrors of Examples 2-9, 11-16, 21, and 28-32 are resistant to acid resistance because the back coating composition contains a specific amino group-containing polymer and a specific reactive silicone oil.
- the coating film appearance and water resistance were excellent.
- the back coating composition when the back coating composition does not contain a specific amino group-containing polymer, the acid resistance is poor, and the back coating composition When no specific reactive silicone oil was contained, the coating film appearance and water resistance tended to be inferior.
- a mirror having a back coating film formed using the back coating composition of the present invention is excellent in acid resistance, appearance on the back and water resistance, and is useful as a mirror installed in a bathroom, a restroom, a washroom, etc. It is.
- the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2012-284687 filed on December 27, 2012 are cited here as disclosure of the specification of the present invention. Incorporated.
Abstract
Description
裏止め塗膜を形成するための裏止め塗料組成物としては、通常、熱硬化性樹脂(エポキシ樹脂、アルキド樹脂等)と、顔料(体質顔料、防錆顔料等)を含むものが用いられる(特許文献1、2参照)。
熱硬化性樹脂と、顔料と、分散剤とを含み、前記分散剤として、アミン価が20mgKOH/g以上であり、かつ酸基を有さないアミノ基含有ポリマーを含む裏止め塗料組成物(特許文献3参照)。
前記エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂が好ましい。
また、前記アミン系硬化剤としては、ジシアンジアミドまたは有機酸ジヒドラジドが好ましい。
前記アミノ基含有ポリマーの割合は、前記分散剤(100質量%)のうち20~100質量%であることが好ましい。
前記エポキシ変性シリコーンオイルにおける、エポキシ基の官能基当量は、1000g/mol以下であることが好ましい。
本発明の裏止め塗料組成物は、前記熱硬化性樹脂として、有機錫化合物、尿素誘導体およびイミダゾール類からなる群から選ばれる少なくとも1種の硬化促進剤をさらに含むことが好ましい。
本発明の裏止め塗料組成物は、前記顔料として、体質顔料を含むことが好ましい。
本発明の裏止め塗料組成物は、前記顔料として、防錆顔料を含むことが好ましい。
前記裏止め塗膜の膜厚は、30~100μmが好ましい。
前記金属膜は、前記ガラス基板上に形成された銀鏡面膜と、該銀鏡面膜上に形成された金属保護膜とからなるものであってもよく、前記ガラス基板上に形成された銀鏡面膜であってもよい。
(a)前記鏡を20℃の10質量%塩酸に48時間浸漬した後における前記金属膜の切断断面からの剥離が5mm以下である。
(b)前記鏡を、温度60℃相対湿度95%の雰囲気下に8時間静置するステップと、温度25℃相対湿度60%の雰囲気下に16時間静置するステップとからなるサイクルを40回繰り返した後における前記金属膜の切断断面からの剥離が5mm以下である。
また、本発明の鏡は、耐酸性、裏面の外観、および耐水性に優れる。
熱硬化性樹脂とは、加熱すると硬化する樹脂を意味する。熱硬化性樹脂を硬化させる硬化剤、熱硬化性樹脂の硬化を促進させる硬化促進剤、および熱硬化性樹脂と反応し得る比較的低分子量の反応性希釈剤は、熱硬化性樹脂に包含される。
分散剤とは、裏止め塗料組成物に顔料を分散させ、かつ分散状態を安定化させうる作用を有する化合物を意味する。
酸基を有さないとは、分子中にカルボキシ基、リン酸基等の酸基を有さないことを意味し、酸基を有さないことは、酸価の有無によって確認できる。
アミン価は、JIS K7237に準拠して測定される値である。
酸価は、JIS K2501に準拠して測定される値である。
反応性シリコーンオイルとは、ジメチルポリシロキサン骨格を有し、かつ側鎖および末端のうちの一方または両方に反応性有機基を導入した変性シリコーンオイルを意味する。
エポキシ基の官能基当量とは、官能基(エポキシ基)の1つあたりのエポキシ変性シリコーンオイルの分子量を意味する。
溶剤とは、熱硬化性樹脂や顔料を溶解または分散させ得るが、他の成分と反応しない化合物を意味する。
裏止め塗料組成物の固形分とは、裏止め塗料組成物から溶剤を除いた成分を意味し、熱硬化性樹脂、その他の樹脂も含む。
数値範囲における「~」とは、特段の定めがない限り、その前後に記載される数値を下限値および上限値として含むことを意味する。
本発明の裏止め塗料組成物は、鏡の裏面に裏止め塗膜を形成するための裏止め塗料組成物であって、熱硬化性樹脂、顔料、分散剤および反応性シリコーンオイルを含み、必要に応じて溶剤、他の添加剤、他の樹脂等を含んでいてもよい。
熱硬化性樹脂としては、エポキシ樹脂、アルキド樹脂、フェノール樹脂、メラミン樹脂等が挙げられる。本発明の裏止め塗料組成物は、裏止め塗膜とした際に酸に侵食されにくい点から、熱硬化性樹脂の少なくとも一部として、エポキシ樹脂(ただし、エポキシ基を有する反応性シリコーンオイルを除く。)、および該エポキシ樹脂の硬化剤を含むことを特徴とする。
アミン系硬化剤としては、脂肪族アミン系硬化剤、脂環族アミン系硬化剤、芳香族アミン系硬化剤、ジシアンジアミド系硬化剤、ポリアミドアミン系硬化剤、有機酸ジヒドラジド等が挙げられ、潜在性を有し、加熱によって急速に硬化する点から、ジシアンジアミド、有機酸ジヒドラジドまたはポリアミドアミン系硬化剤が好ましく、ジシアンジアミドまたは有機酸ジヒドラジドが特に好ましい。
顔料としては、体質顔料、防錆顔料、着色顔料が挙げられる。本発明の裏止め塗料組成物は、塗膜に必要な特性を付与しうる点から、顔料の少なくとも一部として、体質顔料を含むことが好ましい。また、本発明の裏止め塗料組成物は、鏡面としての金属膜を有効に保護する点から、顔料の少なくとも一部として、防錆顔料を含むことが好ましい。
防錆顔料としては、シアナミド亜鉛、酸化亜鉛、リン酸亜鉛、リン酸カルシウムマグネシウム、モリブデン酸亜鉛、ホウ酸バリウム、シアナミド亜鉛カルシウム等が挙げられ、モリブデン酸亜鉛、ホウ酸バリウムまたはシアナミド亜鉛カルシウムが好ましく、シアナミド亜鉛または酸化亜鉛がより好ましい。
着色顔料としては、酸化チタン、カーボンブラック、酸化鉄等が挙げられ、カーボンブラックまたは酸化チタンが好ましく酸化鉄がより好ましい。
分散剤としては、顔料用分散剤等が挙げられる。本発明の裏止め塗料組成物は、分散剤の少なくとも一部として、アミン価が20mgKOH/g以上であり、かつ酸基を有さないアミノ基含有ポリマー(以下、特定のアミノ基含有ポリマーと記す。)を含むことを特徴とする。
分散剤は、通常、顔料等の分散性を向上させる目的で用いられることから、分散剤には顔料への特異な吸着作用が必要とされる。したがって、分散剤としては、酸基およびアミノ基の両方を有するものが広く知られている。
一方、本発明における分散剤(特定のアミノ基含有ポリマー)は、顔料への吸着および熱硬化性樹脂との親和性の向上とともに、熱硬化性樹脂(特にエポキシ樹脂)の硬化触媒としての作用も有している。本発明における特定のアミノ基含有ポリマーは、酸基を有しておらず、熱硬化性樹脂の硬化を進行させる点から好ましいものである。
DISPERBYK(登録商標)-116(アミン価:65mgKOH/g、酸価:0mgKOH/g、アクリル系共重合物)、
DISPERBYK(登録商標)-2155(アミン価:48mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)、
DISPERBYK(登録商標)-9077(アミン価:48mgKOH/g、酸価:0mgKOH/g、高分子共重合体)等。
DISPERBYK(登録商標)-167(アミン価:13mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)、
DISPERBYK(登録商標)-163(アミン価:10mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)、
DISPERBYK(登録商標)-164(アミン価:18mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)、
DISPERBYK(登録商標)-110(アミン価:0mgKOH/g、酸価:53mgKOH/g、酸基を有する共重合物)、
DISPERBYK(登録商標)-106(アミン価:74mgKOH/g、酸価:132mgKOH/g、酸基を有するポリマー塩)、
DISPERBYK(登録商標)-2163(アミン価:10mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)、
DISPERBYK(登録商標)-2164(アミン価:14mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)等。
反応性シリコーンオイルとしては、アミン変性シリコーンオイル、エポキシ変性シリコーンオイル、脂環式エポキシ変性シリコーンオイル、カルビノール変性シリコーンオイル、メルカプト変性シリコーンオイル、カルボキシ変性シリコーンオイル、ハイドロジェン変性シリコーンオイル、メタクリル変性シリコーンオイル、ポリエーテル変性シリコーンオイル、フェノール変性シリコーンオイル、シラノール変性シリコーンオイル、ジオール変性シリコーンオイル等が挙げられる。反応性有機基としては、アミノ基、エポキシ基、(メタ)アクリロイル基、メルカプト基、カルボキシ基、水酸基、水素原子等が挙げられる。
反応性シリコーンオイルがエポキシ基を有することによって、熱硬化性樹脂との相溶性がよくなり、外観が良好な裏止め塗膜を形成できる。また、反応性シリコーンオイルが撥水性を有するため、耐水性に優れた裏止め塗膜を形成できる。なお、反応性シリコーンオイルがエポキシ基を有する場合であっても、ポリオキシアルキレン鎖を有する場合、ポリオキシアルキレン鎖が分子構造上有している親水性部位に由来し、外観が良好で、かつ耐水性に優れた裏止め塗膜を形成しにくい。
なお、外観が良好で、かつ耐水性に優れた裏止め塗膜を形成する点からは、ポリオキシアルキレン鎖を有するポリエーテル変性シリコーンオイルを含まないことが好ましい。
本発明の裏止め塗料組成物は、溶剤を含んでいてもよい。溶剤としては、芳香族炭化水素類、脂肪族炭化水素類、エステル類、エーテル類、ケトン類、アルコール類等が挙げられる。なかでも、芳香族炭化水素類、脂肪族炭化水素類、アルコール類等が好ましい。
本発明の裏止め塗料組成物は、分散剤以外の他の添加剤を含んでいてもよい。添加剤としては、補強材、増粘剤、防錆剤、沈降防止剤、消泡剤、界面活性剤、レオロジーコントロール剤等が挙げられる。
本発明の裏止め塗料組成物は、熱硬化性樹脂以外の他の樹脂を含んでいてもよい。他の樹脂としては、ポリエステル、アクリル系樹脂、スチレン系樹脂、ビニル系樹脂、ケトン樹脂、ロジン等が挙げられる。
本発明の裏止め塗料組成物の固形分濃度は、60~100質量%が好ましく、70~90質量%がより好ましい。固形分濃度が60質量%以上であれば、充分な膜厚が得られる。
以上説明した本発明の裏止め塗料組成物にあっては、分散剤として、アミン価が20mgKOH/g以上であり、かつ酸基を有さないアミノ基含有ポリマーを含むため、酸に侵食されにくい裏止め塗膜を形成できる。また、反応性シリコーンオイルとして、エポキシ基を有し、ポリオキシアルキレン鎖を有さないエポキシ変性シリコーンオイルを含むため、外観が良好で、かつ耐水性に優れた裏止め塗膜を形成できる。
図1は、本発明の鏡の第1の実施形態を示す断面図である。鏡10は、ガラス基板11と、ガラス基板11上に形成された銀鏡面膜12(金属膜)と、銀鏡面膜12上に形成された金属保護膜13(金属膜)と、金属保護膜13上に形成された裏止め塗膜14とを有する。
ガラス基板としては、鏡用の公知のガラスを用いることができ、たとえば、ソーダライムガラス等が挙げられる。
銀鏡面膜の形成方法としては、無電解メッキ法、真空蒸着法、スパッタ法等が挙げられる。
銀鏡面膜としては、銀鏡面膜が0.5~2g/m2の範囲、好ましくは0.6~1.5g/m2となるような膜厚となることが好ましい。
金属保護膜は、銀鏡面膜の防食のために形成される金属製の膜である。金属保護膜としては、銅、銅合金、ニッケル、ニッケル合金、錫、錫合金等からなる金属保護膜が挙げられ、通常は、銅保護膜が好ましい。
金属保護膜の形成方法としては、無電解メッキ法等が挙げられる。
金属保護膜としては、金属保護膜が0.1~1g/m2の範囲、好ましくは0.2~0.8g/m2となるような膜厚となることが好ましい。
また、本発明の鏡は、本発明の裏止め塗料組成物を用いて形成された、酸に侵食されにくい裏止め塗膜を有するため、図2に示すように、金属保護膜を有さなくてもよい。
裏止め塗膜は、銀鏡面膜および金属保護膜の防食、ならびに機械的耐久性向上のために形成される膜である。
裏止め塗膜は、金属膜(銀鏡面膜または金属保護膜)の表面に本発明の裏止め塗料組成物を塗布し、熱硬化させることによって形成される。
裏止め塗料組成物の塗布量は、乾燥膜厚が30~100μm、好ましくは30~60μmとなるように行う。
裏止め塗料組成物の熱硬化の際の温度は、通常、常温~250℃、好ましくは150~180℃である。
以上説明した本発明の鏡にあっては、本発明の裏止め塗料組成物を用いて形成された裏止め塗膜を有するため、耐酸性、裏面の外観、および耐水性に優れる。
具体的には、(a)切断した本発明の鏡を20℃の10質量%塩酸(試薬1級)に48時間浸漬した後における、金属膜の切断断面からの剥離が5mm以下となるような耐酸性を有する。また、(b)切断した本発明の鏡を、温度60℃相対湿度95%の雰囲気下に8時間静置するステップと、温度25℃相対湿度60%の雰囲気下に16時間静置するステップとからなるサイクルを40回繰り返した後における、金属膜の切断断面からの剥離が5mm以下となるような耐水性を有する。
例2~9、11~16、21、および28~32は実施例であり、例1、10、17~20、および22~27は比較例である。
表1の例1の欄に示す組成比となるように、各原料をペイントシェーカー(Paintshaker)に量り取り、15分間シェイクし、裏止め塗料組成物を調製した。
銀鏡面膜の表面を水洗した後、該表面に、硫酸銅を含む溶液(硫酸銅濃度0.15mol/Lの水溶液)と銅を還元させる還元液(卑金属粉末の懸濁液)とからなる銅メッキ液をスプレーし、無電解メッキ法によって銅を析出させて、銅保護膜が0.3g/m2となるような膜を形成した。
銅保護膜の表面を水洗し、乾燥した後、ガラス基板の温度を常温とした。
銅保護膜の表面に、前記裏止め塗料組成物をフローコート法によって乾燥膜厚が55μmとなるよう塗布し、乾燥炉にてガラス基板の温度が135℃になるよう3分間加熱して裏止め塗膜を形成し、鏡(銅保護膜あり)を得た。
銀鏡面膜の表面を水洗し、乾燥した後、ガラス基板の温度を常温とした。
銀鏡面膜の表面に、前記裏止め塗料組成物をフローコート法によって乾燥膜厚が55μmとなるよう塗布し、乾燥炉にてガラス基板の温度が135℃になるよう3分間加熱して裏止め塗膜を形成し、鏡(銅保護膜なし)を得た。
表1~6の例2~32の欄に示す組成比となるように、各原料を用意し、各欄記載の組成を有する裏止め塗料組成物をそれぞれ調製した。
裏止め塗料組成物を変更した以外は、例1と同様にして、鏡(銅保護膜ありおよび銅保護膜なし)を得た。
例1~32の鏡について、塗膜外観の評価結果、塩酸試験の結果、および水蒸気サイクル試験の結果を、それぞれ表1~6に示す。
評価方法は、下記のとおりである。
裏止め塗膜を目視にて観察し、下記の基準にて評価した。
合格:下記の不合格以外のもの。
不合格:円形状の凹みが顕著であり、凹みの直径が1mm以上の欠陥として認識できるもの。
サイズ90mm×40mmの鏡を、サイズ45mm×40mmの鏡が得られるように2つに切断した。切断した鏡を20℃の0.5質量%塩酸(試薬1級)に48時間浸漬した後、取り出して下記の基準にて評価した。
合格:銀鏡面膜に異常がなく、かつ切断断面からの侵食による金属膜の剥離が5mm以下である。
不合格:銀鏡面膜に異常がある、または、切断断面からの侵食による金属膜の剥離が5mmを超える。
サイズ90mm×40mmの鏡を、サイズ45mm×40mmの鏡が得られるように2つに切断した。切断した鏡を、温度60℃相対湿度95%の雰囲気下に8時間静置するステップと、温度25℃相対湿度60%の雰囲気下に16時間静置するステップとからなるサイクルを繰り返し行った。切断断面からの侵食による金属膜の剥離が5mmを超えた時点で試験を中止し、金属膜の剥離が5mm以下を維持できたサイクル数を記録した。
*2:反応性シリコーンオイルの略号の後ろの括弧内の数値は、エポキシ官能基当量(g/mol)であり、括弧内の「有」または「無」は、ポリオキシアルキレン鎖の有無である。
MIBK:メチルイソブチルケトン。
jER828:ビスフェノールA型エポキシ樹脂、ジャパンエポキシレジン社製、jER828。
DICY:ジシアンジアミド、SKW Trostberg AG社製、Dyhard(登録商標)100SF。
SDH:セバチン酸ジヒドラジド、日本ファインケミカル社製。
ADH:アジピン酸ジヒドラジド、日本ファインケミカル社製。
DY-T:トリメチロールプロパントリグリシジルエーテル、Ciba Specialty Chemicals社製、Araldite(登録商標)DY-T。
DBTDL:ジブチル錫ジラウレート。
UR500:尿素系硬化促進剤、SKW Trostberg AG社製、Dyhard(登録商標)UR500。
2E4MZ:2-エチル-4-メチルイミダゾール、四国化成社製。
IBMI-12:1-イソブチル-2-メチルイミダゾール、四国化成社製。
BYK2163:BYK社製、DISPERBYK(登録商標)-2163(アミン価:10mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)。
BYK2155:BYK社製、DISPERBYK(登録商標)-2155(アミン価:48mgKOH/g、酸価:0mgKOH/g、ブロック共重合物)。
BYK110:BYK社製、DISPERBYK(登録商標)-110(アミン価:0mgKOH/g、酸価:53mgKOH/g、酸基を有する共重合物)。
BYK106:BYK社製、DISPERBYK(登録商標)-106(アミン価:74mgKOH/g、酸価:132mgKOH/g、酸基を有するポリマー塩)。
タルク:日本タルク社製、SG-95。
硫酸バリウム:竹原化学工業社製、W-10。
酸化チタン:堺化学工業社製、R-650。
カーボンブラック:シグマアルドリッチジャパン社製、CPカーボンブラック。
X-22-4741:信越化学工業社製、X-22-4741(エポキシ基の官能基当量:2500g/mol、エポキシ変性シリコーンオイル、ポリオキシアルキレン鎖あり)。
KF-101:信越化学工業社製、KF-101(エポキシ基の官能基当量:350g/mol、エポキシ変性シリコーンオイル)。
KF-105:信越化学工業社製、KF-105(エポキシ基の官能基当量:490g/mol、エポキシ変性シリコーンオイル)。
例1、10、17~20、および22~27(比較例)の鏡においては、裏止め塗料組成物が特定のアミノ基含有ポリマーを含まない場合は、耐酸性に劣り、裏止め塗料組成物が特定の反応性シリコーンオイルを含まない場合は、塗膜外観および耐水性に劣る傾向が見られた。
なお、2012年12月27日に出願された日本特許出願2012-284687号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
11 ガラス基板
12 銀鏡面膜(金属膜)
13 金属保護膜(金属膜)
14 裏止め塗膜
Claims (15)
- 鏡の裏面に裏止め塗膜を形成するための裏止め塗料組成物であって、
熱硬化性樹脂と、顔料と、分散剤と、反応性シリコーンオイルとを含み、
前記熱硬化性樹脂として、エポキシ樹脂(ただし、エポキシ基を有する反応性シリコーンオイルを除く。)およびアミン系硬化剤を含み、
前記分散剤として、アミン価が20mgKOH/g以上であり、かつ酸基を有さないアミノ基含有ポリマーを含み、
前記反応性シリコーンオイルとして、エポキシ基を有し、ポリオキシアルキレン鎖を有さないエポキシ変性シリコーンオイルを含むことを特徴とする裏止め塗料組成物。 - 前記アミノ基含有ポリマーのアミン価が、20~70mgKOH/gである、請求項1に記載の裏止め塗料組成物。
- 前記アミノ基含有ポリマーの割合が、前記分散剤(100質量%)のうち20~100質量%である、請求項1または2に記載の裏止め塗料組成物。
- 前記エポキシ変性シリコーンオイルにおける、エポキシ基の官能基当量が、1000g/mol以下である、請求項1~3のいずれか一項に記載の裏止め塗料組成物。
- 前記エポキシ樹脂がビスフェノールA型エポキシ樹脂である、請求項1~4のいずれか一項に記載の裏止め塗料組成物。
- 前記アミン系硬化剤がジシアンジアミドまたは有機酸ジヒドラジドである、請求項1~5のいずれか一項に記載の裏止め塗料組成物。
- 前記熱硬化性樹脂として、有機錫化合物、尿素誘導体およびイミダゾール類からなる群から選ばれる少なくとも1種の硬化促進剤をさらに含む、請求項1~6のいずれか一項に記載の裏止め塗料組成物。
- 前記裏止め塗料組成物から溶剤を除いた裏止め塗料組成物の固形分(100質量%)のうち、
前記熱硬化性樹脂の割合が、30~50質量%であり、
前記顔料の割合が、50~70質量%であり、
前記分散剤の割合が、1~13質量%であり、
前記反応性シリコーンオイルの割合が、0.001~0.5質量%である、請求項1~7のいずれか一項に記載の裏止め塗料組成物。 - 前記顔料として、体質顔料を含む、請求項1~8のいずれか一項に記載の裏止め塗料組成物。
- 前記顔料として、防錆顔料を含む、請求項1~9のいずれか一項に記載の裏止め塗料組成物。
- ガラス基板と、
該ガラス基板上に形成された金属膜と、
該金属膜上に、請求項1~10のいずれか一項に記載の裏止め塗料組成物を用いて形成された裏止め塗膜と
を有する、鏡。 - 前記裏止め塗膜の膜厚が30~100μmである、請求項11に記載の鏡。
- 前記金属膜が、前記ガラス基板上に形成された銀鏡面膜と、該銀鏡面膜上に形成された金属保護膜とからなる、請求項11または12に記載の鏡。
- 前記金属膜が、前記ガラス基板上に形成された銀鏡面膜である、請求項11または12に記載の鏡。
- ガラス基板と、該ガラス基板上に形成された金属膜と、該金属膜上に形成された裏止め塗膜とを有する鏡であって、下記の条件(a)および(b)を満足する、鏡。
(a)前記鏡を20℃の10質量%塩酸に48時間浸漬した後における前記金属膜の切断断面からの剥離が5mm以下である。
(b)前記鏡を、温度60℃相対湿度95%の雰囲気下に8時間静置するステップと、温度25℃相対湿度60%の雰囲気下に16時間静置するステップとからなるサイクルを40回繰り返した後における前記金属膜の切断断面からの剥離が5mm以下である。
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JP2016176065A (ja) * | 2015-03-19 | 2016-10-06 | ナガセケムテックス株式会社 | 屋外電気絶縁用エポキシ樹脂組成物及び屋外電気絶縁用部材 |
JP2020525625A (ja) * | 2017-07-05 | 2020-08-27 | ヴェナートア・ジャーマニー・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | 処理された硫酸バリウム粒子及びそれらの使用 |
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