阅读说明：本技术 涂装的铝材及其制造方法 (The aluminium and its manufacturing method of coating ) 是由 高泽令子 兼子彬 于 2018-02-08 设计创作，主要内容包括：本发明提供一种涂装的铝材,其在铝材的表面具有涂膜,为无铬且在极端的使用条件下也可以发挥优异的耐腐蚀性能。该涂装的铝材是在铝材的表面隔着包含水分散性二氧化硅、磷化合物和硅烷偶联剂的含二氧化硅皮膜形成涂膜的涂装的铝材,含二氧化硅皮膜以0.5～35质量％的比例包含硅烷偶联剂,且Si含量在2～60mg/m<Sup>2</Sup>的范围内,P含量在0.1～6.0mg/m<Sup>2</Sup>的范围内,且所述P含量与Si含量的P/Si质量比在0.02～0.15的范围内,此外,本发明还提供如上所述的涂装的铝材的制造方法。(The present invention provides a kind of aluminium of coating, has film on the surface of aluminium, for Chrome-free and can also play excellent corrosion resistance under extreme use condition.The aluminium of the coating is the aluminium for forming the coating of film across the epithelium containing silica comprising water-dispersible silica, phosphorus compound and silane coupling agent on the surface of aluminium, epithelium containing silica includes silane coupling agent with the ratio of 0.5~35 mass %, and Si content is in 2~60mg/m 2 In the range of, P content is in 0.1~6.0mg/m 2 In the range of, and the P/Si mass ratio of the P content and Si content is in the range of 0.02~0.15, in addition, the present invention also provides the manufacturing methods of the aluminium of coating as described above.)

1. a kind of aluminium of coating, which is characterized in that be on the surface for the aluminium being made of aluminum or aluminum alloy across containing titanium dioxide Siliceous skin film is formed with the aluminium of the coating of film, and the epithelium containing silica includes water-dispersible silica, phosphorus compound And silane coupling agent,

The epithelium containing silica includes the silane coupling agent with the ratio of 0.5~35 mass %, and Si content 2~ 60mg/m²In the range of, P content is in 0.1~6.0mg/m²In the range of and the P/Si mass ratio of the P content and Si content exist In the range of 0.02~0.15.

2. a kind of aluminium of coating, which is characterized in that the water-dispersible silica is colloidal silicon dioxide.

3. a kind of manufacturing method of the aluminium of coating, which is characterized in that be the surface for the aluminium being made of aluminum or aluminum alloy every Epithelium containing silica be formed with film coating aluminium manufacturing method, the epithelium containing silica include water dispersion Property silica, phosphorus compound and silane coupling agent,

Epithelium containing silica is formed on the surface of the aluminium, next forms the painting on the epithelium containing silica Film, the epithelium containing silica include the silane coupling agent with the ratio of 0.5~35 mass %, and Si content 2~ 60mg/m²In the range of, P content is in 0.1~6.0mg/m²In the range of.

Technical field

The present invention relates to have corrosion resistance and adaptation excellent on the surface for the aluminium being made of aluminum or aluminum alloy The aluminium and its manufacturing method of the coating of film.

Background technique

Corrosion resistance processing for aluminium, well-known has using chromium such as chromic acid salt treatment, the processing of phosphoric acid chromate It is the method for surface treating agent, these methods are also widely used (referenced patent document 1~3) now.

However, in recent years, limitation is grown to even greater heights using the trend of the substance caused environmental damage in the whole world, such as European Union starts to carry out legal restriction to 6 valence chromium by abandoned car instruction etc..

In this context, the inventors of the present invention propose a kind of aluminium (patent document 4) of following coating, the coating Aluminium across with 5~200mg/m of silicon amount²With the range of 25~46.7 mass % of silicon containing ratio contain Si oxide and with 0.1~20mg/m of phosphorus amount²Contain the inorganic epithelium of phosphorus compound (containing titanium dioxide with the range of 0.2~10 mass % of phosphorus containing ratio Siliceous skin film) on the surface of aluminium form film.Furthermore, it is also proposed that a kind of aluminium (patent document 5) of following coating, it should The aluminium of coating is across with 5~200mg/m of silicon amount²Contain silicon compound, simultaneously with the range of 30~46.7 mass % of silicon containing ratio And with 0.1~20mg/m of phosphorus amount²Contain phosphorus compound with the range of 0.2~10 mass % of phosphorus containing ratio and with 35 mass % or less The range inorganic epithelium (epithelium containing silica) that contains organic binder form film on the surface of aluminium.Moreover, this The aluminium of a little coatings is substantially entirely free of 6 valences and trivalent chromium, i.e., so-called " Chrome-free ", environmentally friendly, and corrosion resistance is excellent Multiple fields that are different, being used in headed by automobile industry for the aluminium for requiring the coating of excellent corrosion resistance etc..

In turn, patent document 6 proposes a kind of surface-treated metal plate, and the surface-treated metal plate is in cold-rolled steel sheet, plating Chemical treatment epithelium (epithelium containing silica) and adhesive layer, above-mentioned chemical treatment are stacked gradually on the metal substrates such as zinc steel plate Epithelium (epithelium containing silica) includes colloidal silicon dioxide (colloidal silica) and thermohardening type resin, and can be with It include silane coupling agent, phosphoric acid class with defined ratio, the surface-treated metal plate is excellent in adhesion with resin (plastics), this It also proposed outside and be preferred for automobile, household appliances, OA (office using the surface-treated metal plate is obtained Automatic) the metal plate compound resin moldings of the purposes such as equipment.

Summary of the invention

Problems to be solved by the invention

However, according to its purposes mostly in outdoor application, therefore being compared in fields such as such as building materials, transport, motor, electronics In in other fields the case where, various products manufactured by the aluminium using coating are sometimes under more extreme moist environment Use, in addition, may require that sometimes and the aluminium of coating is carried out the processing such as suppressing and then be existed in the fields such as motor, electronics, transport It is thus obtained with total 30 μm or more and then 40 μm that coatings such as (post coat) are coated with after the processing after its surface carries out The aluminium of the coating of the above thick film thickness film, in addition, also have even if film thickness less than 30 μm but for 5 μm or more be in turn 10 μm Above compared with the film of thick film thickness and such as above-mentioned the case where use is overlapped under extreme moist environment.Moreover, in such pole Under the moist environment at end in the case where use, require film thickness individually or add up to 30 μm or more thick film it is thick in the case where, into And compared with thick film thickness film with use is overlapped under extreme moist environment in the case where (hereinafter, these situations are claimed sometimes For " under extreme use condition "), the adaptation between aluminium and film reduces sometimes, and then also requires excellent corrosion resistance Energy.

Therefore, the aluminium of the coating in above patent document 4 and 5 is further improved to meet in the inventors of the present invention Such demand about the evaluation of corrosion resistance is made all the time using what the appearance of observation corrosion was evaluated Resistance to filiform corrosion test, but use the wet case examination that can evaluate the adaptation between aluminium and film under extreme conditions (humidity cabinet test) is tested, can also play excellent corrosion resistance in the humidity cabinet test to develop The aluminium of coating have made intensive studies, as a result have been surprisingly found that, being formed on the surface of aluminium includes water-dispersible silica When with the epithelium containing silica of phosphorus compound, the content and containing ratio of silicon (Si), phosphorus (P) are not only controlled, but also makes silane Coupling agent is coexisted with defined ratio and controls the P/Si mass ratio of P content and Si content in certain particular range, thus for Chrome-free and excellent corrosion resistance is played under above-mentioned extreme use condition, completes the present invention.

Therefore, the purpose of the present invention is to provide a kind of aluminiums of coating, in the aluminium table being made of aluminum or aluminum alloy Face has film, for Chrome-free and can play excellent corrosion resistance under extreme use condition.

The solution to the problem

That is, the present invention is a kind of aluminium of coating, which is characterized in that be on the surface for the aluminium being made of aluminum or aluminum alloy The aluminium of the coating of film is formed with across epithelium containing silica, above-mentioned epithelium containing silica includes water dispersible titanium dioxide Silicon, phosphorus compound and silane coupling agent, above-mentioned epithelium containing silica include that above-mentioned silane is even with the ratio of 0.5~35 mass % Join agent, and Si content is in 2~60mg/m²In range, P content is in 0.1~6.0mg/m²In range and above-mentioned P content contains with Si The P/Si mass ratio of amount is in 0.02~0.15 range.

In addition, the present invention is a kind of manufacturing method of the aluminium of coating, which is characterized in that constituted by aluminum or aluminum alloy Aluminium surface be formed with across epithelium containing silica film coating aluminium manufacturing method, it is above-mentioned contain silica Epithelium includes water-dispersible silica, phosphorus compound and silane coupling agent, is formed on the surface of above-mentioned aluminium and contains silica Next epithelium forms above-mentioned film on the epithelium containing silica, above-mentioned epithelium containing silica is with 0.5~35 mass % Ratio include silane coupling agent, and Si content is in 2~60mg/m²In range, P content is in 0.1~6.0mg/m²In range.

In addition, in explanation of the invention below, about " film thickness of film ", in the film that the surface of aluminium is laminated In the case where face painting (top coating) film for single layer, the film thickness of the film indicates that the face applies the film thickness of film, in addition, Also to include that 2 layers or more of the face of priming paint (primer) film applies multilayer film made of film stacking, the film Film thickness indicate its total film thickness, sometimes referred to as " always applying film thickness " of film.

In the present invention, as aluminium, the rolling stock being made of aluminum or aluminum alloy can be enumerated, be extruded into profile, die casting These materials by rapidoprint obtained from these appropriate processing and then are carried out appropriately combined and obtained by material, founding materials etc. The combined material etc. arrived.

In addition, in the present invention, being formed by epithelium containing silica about the surface in aluminium, needing silicone content (Si Content) it is 2mg/m²Above and 60mg/m²It below, is preferably 2mg/m²Above and 45mg/m²Below, it is more preferably 4mg/m²More than And 40mg/m²Range below；Phosphorus content (P content) is 0.1mg/m²Above and 6.0mg/m²It below, is preferably 0.3mg/m²With Upper and 5mg/m²Below, it is more preferably 0.3mg/m²Above and 3.0mg/m²Range below, also, these P contents and Si content P/Si mass ratio be 0.02 or more and 0.15 or less, preferably 0.02 or more and 0.13 or less, more preferably 0.04 or more and 0.13 range below, in addition, it is expected that the containing ratio of silane coupling agent be 0.5 mass % or more and 35 mass % hereinafter, it is preferred that For 1 mass % or more and 25 mass % hereinafter, more preferably 4 mass % or more and 21 mass % or less.In the present invention, when this When 4 conditions do not meet simultaneously, under above-mentioned extreme use condition, corrosion resistance is reduced, closely sealed between aluminium and film Property reduce, the durability of the aluminium of coating is impaired.

Moreover, the film thickness about the epithelium containing silica, its usual film thickness is 5nm or more and 500nm is hereinafter, can be excellent 20nm or more is selected as and 300nm hereinafter, in addition, the silicon containing ratio (Si containing ratio) contained in silica epithelium is 30 mass % Above and 50 mass % are hereinafter, can be preferably 35 mass % or more and 45 mass % hereinafter, phosphorus containing ratio (P containing ratio) is 0.8 mass % or more and 5.5 mass % are hereinafter, can be preferably 1 mass % or more and 5 mass % or less.When the inorganic epithelium Film thickness ratio 5nm it is thin when, filiform corrosion resistance may be insufficient, conversely, adaptation may be insufficient when thicker than 500nm.In addition, When the Si containing ratio in epithelium containing silica is fewer than 30 mass %, filiform corrosion resistance be may be decreased, conversely, when than 50 matter Amount % is difficult with general raw material when more to form epithelium, and cost is got higher.In turn, when the P in epithelium containing silica contains When rate % fewer than 0.8 mass, corrosion resistance be may be decreased, conversely, adaptation possible deviation when more than 5.5 mass %.

Here, as the water-dispersible silica of the invention used in epithelium containing silica, for example, glue Body silica, fumed silica etc., preferably colloidal silicon dioxide.Moreover, as the colloidal silicon dioxide, without special It limits, specifically for example can enumerate Nissan Chemical Ind Ltd SNOWTEX- as spherical colloidal silicon dioxide C, SNOWTEX-O, SNOWTEX-N, SNOWTEX-S, SNOWTEX-OL, SNOWTEX-XS, SNOWTEX-XL etc., in addition, conduct The colloidal silicon dioxide of chain can enumerate Nissan Chemical Ind Ltd SNOWTEX-UP, SNOWTEX-OUP etc..In addition, As fumed silica, Japanese AEROSIL corporation AEROSIL 130, AEROSIL 200, AEROSIL can be enumerated 200CF, AEROSIL 300, AEROSIL300CF, AEROSIL 380, AEROSIL MOX80 etc..

In addition, the phosphorus compound used in the epithelium containing silica, is to further increase corrosion resistance etc. and be Purpose and add, be not particularly limited, be preferably able to enumerate for example selected from orthophosphoric acid, phosphonic acids, pyrophosphoric acid, tripolyphosphate and it Salt in one kind or two or more mixture, specifically, can example phosphoric acid, triammonium phosphate, tertiary sodium phosphate, aluminum phosphate, Trbasic zinc phosphate, magnesium phosphate etc..

In turn, the silane coupling agent used in the epithelium containing silica is to assign adaptation and corrosion resistance etc. For the purpose of and add, be not particularly limited, it is however preferred to have vinyl, epoxy group, styryl, methylacryloyl, third Enoyl-, amino, urea groups, sulfydryl, thioether group, isocyanate group, thiocarbonyl, halogen group, triazine thiol base isoreactivity Silane coupling agent of the functional group as reactive group, as long as finally showing the silane coupling agent of reactive silanol group does not have then It is particularly limited to, can specifically enumerate such as vinyltrimethoxysilane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy Base silane, 3- epoxy propoxy propyl triethoxysilane, p- styryltrimethoxysilane, 3- methacryloxy Propyl trimethoxy silicane, 3- acryloyloxypropyltrimethoxysilane, 3- TSL 8330,3- aminopropan Ethyl triethoxy silicane alkane, 3- ureidopropyltriethoxysilane, 3- mercapto propyl methyl dimethoxy silane, 3- mercaptopropyi three Methoxy silane, bis- (triethoxysilylpropyltetrasulfide) tetrasulfides, 3- isocyanate group propyl-triethoxysilicane etc..It closes It in these silane coupling agents, can be used alone, furthermore can also mix two or more use.Furthermore, it is possible to be to have alkoxy concurrently The alkoxy oligomer of silicyl and above-mentioned reactive functional groups, and then can be intramolecular having with triazine thiol base Machine siloxy oligomer etc..

Moreover, about formed these water-dispersible silicas of the epithelium of the invention containing silica, phosphorus compound and Silane coupling agent is prepared to epithelium when aluminium material surface forms epithelium containing silica and forms treatment fluid, but the epithelium is formed Treatment fluid is desirably made aqueous solution or alcoholic solution, at this point it is possible to be added as needed surface conditioner, antibacterial agent, mould inhibitor, The thirds ingredients such as the solvent other than water removal, alcohol.Therefore, in above-mentioned epithelium containing silica of the invention, in addition to water dispersible two Other than silica, phosphorus compound and silane coupling agent, there is also come from these ternary ingredients sometimes.

In the present invention, film is formed by across epithelium containing silica on the surface of aluminium can be directly be painted on This is formed by the outermost face painting film of aluminium that film forms coating on epithelium containing silica, be also possible to across conduct The face for the primer coating film institute coating that prime coat functions applies film, furthermore can also be that these faces apply film and are laminated 2 layers or more Multilayer film.It, can be according to the use of the aluminium of coating about the total painting film thickness for being formed by film on epithelium containing silica Purpose etc. is suitably selected and is determined, is not particularly limited, and usually 0.5 μm or more and 200 μm hereinafter, can be preferably 2 μm Above and 150 μm hereinafter, can be closely sealed after humidity cabinet test and after boiling water immersion test especially with regard to its lower limit value Property in make that effect of the invention shows 5 μm or more, can be preferably 10 μm or more, more preferably 30 μm or more.When the film It is 0.5 μm of total film thickness rate thin when, sufficient corrosion resistance cannot be played, on the contrary when more than 200 μm adaptation drop sometimes It is low.

Here, being formed by film across epithelium containing silica about in aluminium material surface, it is not particularly limited, can be On the epithelium containing silica of aluminium material surface coating be selected from for example Acrylic coatings, Polyester coating, polyurethane series coating, Acroleic acid polyurethane system coating, acrylic polyester system coating, epoxy coating, fluorine system coating, acrylic acid silicon systems coating, polyurethane The organic systems such as silicon systems coating, acroleic acid polyurethane silicon systems coating, ceramics system coating, TiO 2 series coating, it is inorganic system or it is organic, Any coating (film forms coating) in the coating such as inorganic mixed stocker is formed by film, can be preferably acrylic acid series Coating, Polyester coating, polyurethane series coating, epoxy coating etc..

Hereinafter, manufacturing method when to the aluminium for manufacturing coating of the invention is illustrated.

The manufacture of aluminium about coating of the invention preferably forms the epithelium of the epithelium containing silica on the surface of aluminium The pre-treatments such as ungrease treatment, surface modulation processing are carried out in advance to the surface of aluminium before formation processing, at above-mentioned degreasing Reason can enumerate the cleaning of the solvent such as using coating dilution, using the ungrease treatment of commercially available acid or alkaline defatting agent, In addition, handling as above-mentioned surface modulation, the acid processing using acid solution, preferably pH6 acid solution below can be enumerated； And/or use aqueous slkali, the alkali process of the preferably aqueous slkali of pH8 or more etc..Here, at as the acid handled for surface modulation The acid solution of reason is able to use the acid solution for example prepared using above-mentioned commercial acid degreasing agent；Use sulfuric acid, nitric acid, hydrogen The inorganic acids such as fluoric acid, phosphoric acid, the acid solution prepared using organic acids such as acetic acid, citric acids；Using by by these inorganic acids, organic Acid-mixed closes the acid solution etc. of the acid reagent preparation of the compositions such as obtained mixed acid, in addition, being able to use for example as aqueous slkali The aqueous slkali prepared using commercially available alkaline defatting agent；The aqueous slkali prepared using base reagents such as caustic soda；Use sodium metasilicate system Degreasing agent preparation aqueous slkali；Use the aqueous slkali etc. for mixing these aqueous slkalis and preparing.

Surface modulation about the above-mentioned pre-treatment carried out using acid solution and/or aqueous slkali is handled, can using with It is all the time identical with treatment conditions using operating method conducted in the processing of the surface modulation of this kind of acid solution or aqueous slkali Method, for example, can be implemented in following treatment conditions by the methods of infusion process, spray coating method: treatment temperature is from room temperature To 90 DEG C, preferably from room temperature to 70 DEG C, the processing time is every 1 process 1 second to 15 minutes or so, preferably 2 seconds to 10 minutes Left and right, more preferably 2 seconds to 3 minutes or so, process number was usual 2 or more and 6 hereinafter, preferably 2 or more and 4 or less.In addition, In the surface modulation processing of the preceding processing carried out using the acid solution and/or aqueous slkali, the surface of aluminium can be etched, It can not be etched.

Moreover, can according to need carry out washing process, in the water after implementing above-mentioned preceding processing on the surface of aluminium It washes in processing and is able to use industrial water, underground water, tap water, ion exchange water etc., it can be according to the aluminium of manufactured coating Appropriate selection.In turn, it about the aluminium for carrying out pre-treatment, can be dried as needed, it, can about the drying process To be the natural drying placed in room temperature, furthermore can be using air blast, drier, far-infrared heater, baking oven etc. into Capable force drying.

On the surface for the aluminium for having carried out preceding processing as needed like this, it is coated with above-mentioned comprising water dispersible titanium dioxide The epithelium of silicon, phosphorus compound and silane coupling agent forms treatment fluid, forms above-mentioned epithelium containing silica of the invention.Here, When preparing epithelium formation treatment fluid, in a manner of it can be realized following condition, by above-mentioned water-dispersible silica, phosphorus Compound and silane coupling agent cooperate together with the third ingredient of needs in water or alcohol equal solvent, the condition are as follows: in aluminium It is 2mg/m that surface, which is formed by the Si content in epithelium containing silica,²Above and 60mg/m²Hereinafter, P content is 0.1mg/m² Above and 6.0mg/m²Hereinafter, and these P contents and the P/Si mass ratio of Si content are 0.02 or more and 0.15 hereinafter, silane The containing ratio of coupling agent is 0.5 mass % or more and 20 mass % or less.

It, can be by using roller about the epithelium formation processing when the surface of the aluminium forms epithelium containing silica The pre-coating methods of coating, spray coating method, infusion process, stick coating method, electrostatic coating processes etc. is implemented, or by using spray coating method, spin coating The rear rubbing method of method, infusion process, electrostatic coating processes etc. is implemented, in addition, place can be dried after coating as needed at this time Reason, about the drying process, can be the natural drying placed in room temperature, be furthermore also possible to using air blast, drier, The force drying of the progress such as far-infrared heater, baking oven.It, usually can be in room temperature~250 in the case where carrying out force drying DEG C temperature, preferably 2 seconds to 5 minutes or so 1 second~10 minutes or so condition carry out.

In the present invention, above-mentioned film is coated on being formed by epithelium containing silica like this to be formed with painting Material is to form film, about coating process at this time, can be and for example utilizes rolling method, spray coating method, infusion process, stick coating method, quiet Furthermore the pre-coating method of electric finishing etc. can be the rear coating using spray coating method, spin-coating method, infusion process, electrostatic coating processes etc. Method.Moreover, about the drying process after coating, if using the drying means for corresponding to coating, can example for example make The method carried out with air blast, drier, baking oven etc. in room temperature~300 DEG C and 5 seconds~24 hours drying conditions.

In addition, the case where above-mentioned film is multilayer film, is made face apply film and is formed with common painting coating is coated with The case where it is identical, such as rolling method, spray coating method, infusion process, stick coating method, electrostatic can be passed through on being formed by the 1st coating film The pre-coatings such as finishing method is coated with painting coating by the rear rubbing method such as spray coating method, spin-coating method, infusion process, electrostatic coating processes, connects Get off and is dried by corresponding to the drying means of be coated with painting coating.

Invention effect

Be capable of providing a kind of aluminium of coating according to the present invention, aluminium material surface have film, be Chrome-free and even if Excellent corrosion resistance can be also played under extreme use condition.

In addition, in accordance with the invention it is possible to being easily manufactured such for Chrome-free and even if under extreme use condition Also the aluminium of the coating of excellent corrosion resistance can be played.

Specific embodiment

Hereinafter, the preferred embodiment of the present invention is specifically described based on embodiment and comparative example.

[Examples 1 to 10 and comparative example 1~8]

Prepare size 70mm × 150mm × 1.0mm aluminium sheet (JIS 5052-H18) and be used as aluminium, to each reality of the preparation It applies example and the aluminium sheet of comparative example carries out pre-treatment as shown below, the epithelium formation of the epithelium containing silica is handled and the shape of film At being prepared for the aluminium of the coating of each embodiment and comparative example.

[pre-treatment]

In each embodiment and comparative example, pre-treatment below is implemented to above-mentioned aluminium sheet.

That is, having carried out that aluminium sheet is immersed in the degreasing agent (Nippon containing sodium metasilicate in 60 DEG C and 30 seconds of condition Paint Surf Chemicals Co., Ltd. system, trade name: SURFCLEANER 155) 2 mass % aqueous solutions in it is de- After rouge processing, washing is made it dry.

[epithelium formation processing]

As the treatment fluid for being used to form the epithelium containing silica, set using colloidal silicon dioxide shown in table 1 and addition Phosphorus compound shown in rouge etc. and table 2, silane coupling agent and water or isopropanol (iso-PrOH) as solvent, are prepared for The epithelium formed shown in table 2 forms treatment fluid.

[table 1]

The type of colloidal silicon dioxide and addition resin etc.

[table 2]

The composition of epithelium formation treatment fluid

In the above embodiments 1,3 and 5~9 and comparative example 1~7, after preceding processing, using rod coaters, with Coating weight becomes 1g/m²Mode coating table 2 shown in form epithelium formed treatment fluid, next in maximum temperature reached 180 DEG C of (PMT:Peak metal temperature) makes it dry 1 minute, forms siliceous skin containing titanium dioxide on the surface of aluminium sheet Film.

In addition, after preceding processing, using rod coaters, becoming 2.5g/m in the above embodiments 2 with coating weight² Mode coating table 2 shown in form epithelium formed treatment fluid, next made it dry at PMT180 DEG C 1 minute, in aluminium sheet Surface forms epithelium containing silica.

In turn, in the above embodiments 4, after preceding processing, using spray gun, 25g/m is become with coating weight²Side The epithelium formed shown in formula coating table 2 forms treatment fluid, makes it dry at PMT180 DEG C 1 minute, forms on the surface of aluminium sheet Epithelium containing silica.

And then in addition, after preceding processing, using spray gun, 50g/m is become with coating weight in embodiment 10²Side The epithelium formed shown in formula coating table 2 forms treatment fluid, makes it dry at PMT180 DEG C 1 minute, forms on the surface of aluminium sheet Epithelium containing silica.

Then, in comparative example 8, after preceding processing, using rod coaters, 1g/m is become with coating weight²Mode apply It fills the epithelium formed shown in table 2 and forms treatment fluid, next make it dry at PMT100 DEG C 1 minute, formed on the surface of aluminium sheet Containing silica epithelium.

For being formed by the epithelium containing silica of each embodiment and comparative example executed as described above, pass through fluorescent X-ray point Analysis determines (the Si content: mg/m of silicone content contained in epithelium unit area respectively²) and phosphorus content (P content: mg/m²).In When the measurement, same method, production contain the case where use on the plate of 99.999% fine aluminium is with each embodiment and comparative example Silica epithelium, to silicone content (the Si content: mg/m contained in the unit area of the epithelium containing silica²) and phosphorus Content (P content: mg/m²) carry out quantitative analysis.

[formation of film]

Painting shown in following tables 3 is used across the film that above-mentioned epithelium containing silica is laminated on the surface of aluminium sheet Film, which is formed, uses coating, and the film of each film thickness shown in table 3 is respectively formed according to the sequence of the 1st layer, layers 2 and 3.

[table 3]

Coating is used in film formation

	Coating name	Manufacturer	Resin system	Color
					A	Precolor TX4427	B A S F	Polyester	It is white
B	V-NITTO#120	Big Japanese coating (strain)	Epoxy base system	It is transparent
					C	V-NITTO #500	Big Japanese coating (strain)	Polyester	It is transparent
D	V-PET #4000W	Big Japanese coating (strain)	Polyester	Ash
					E	V-top H floating coat	Big Japanese coating (strain)	Polyurethane series	It is white
F	V-top H finishing coat	Big Japanese coating (strain)	Polyurethane series	It is white

For having carried out above-mentioned pre-treatment and the aluminium sheet of epithelium form that treated each embodiment and comparative example, under The method stated forms film, is prepared for the test film (aluminium of coating) of each embodiment and comparative example.

In embodiment 1, stick applies coating process A, and 60 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film of 30 μm of film thickness (total coating thickness).

In example 2, stick applies coating process B, and 60 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 5 μm of film thickness is burnt next, forming 50 μm of film using spray gun coating process E with the heating furnace for being set as 80 DEG C Knot 5 minutes, and then spray gun coating process F is used, 50 μm of film is formed, is sintered 10 minutes with the heating furnace for being set as 80 DEG C, It is prepared for the test film (aluminium of coating) of 105 μm of total coating thickness.

In embodiment 3, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 10 μm of film thickness carries out 60 seconds sintering processes at PMT225 DEG C, makes it dry, shape next, stick applies coating process C At 30 μm of film of film thickness, it is prepared for the test film (aluminium of coating) of 40 μm of total coating thickness.

In example 4, electrostatic powder body coating coating D is sintered 30 minutes with the heating furnace for being set as 180 DEG C, forms film The film that 100 μm of thick (total coating thickness), is prepared for test film (aluminium of coating).

In embodiment 5, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 2 μm of film thickness carries out 60 seconds sintering processes at PMT210 DEG C, makes it dry next, stick applies coating process A, is formed The film that 30 μm of film thickness is prepared for the test film (aluminium of coating) of 32 μm of total coating thickness.

In embodiment 6, stick applies coating process C, and 60 seconds sintering processes are carried out at PMT225 DEG C, are made it dry, and is formed The film of 20 μm of film thickness (total coating thickness).

In embodiment 7, stick applies coating process B, and 60 seconds sintering processes are carried out at PMT225 DEG C, are made it dry, and is formed The film of 5 μm of film thickness (total coating thickness), is prepared for test film (aluminium of coating).

In embodiment 8, stick applies coating process C, and 60 seconds sintering processes are carried out at PMT225 DEG C, are made it dry, and is formed The film of 35 μm of film thickness (total coating thickness).

In embodiment 9, stick is applied into coating process B, 60 seconds sintering processes are carried out at PMT225 DEG C, are made it dry, shape At 40 μm of film of film thickness (total coating thickness), it is prepared for test film (aluminium of coating).

In embodiment 10, electrostatic powder body coating coating D is sintered 30 minutes with the heating furnace for being set as 180 DEG C, forms film The film that 50 μm of thick (total coating thickness), is prepared for test film (aluminium of coating).

In comparative example 1, electrostatic powder body coating coating D is sintered 30 minutes with the furnace for being set as 180 DEG C, it is (total to form film thickness Coating thickness) 100 μm of film, it is prepared for test film (aluminium of coating).Although the aluminium of the coating of the comparative example 1 have with The epithelium containing silica of substantially the same P/Si mass ratio of the aluminium of coating documented by the embodiment 2 of patent document 4, but Do not add silane coupling agent.

In comparative example 2, electrostatic powder body coating coating D is sintered 30 minutes with the furnace for being set as 180 DEG C, it is (total to form film thickness Coating thickness) 100 μm of film, it is prepared for test film (aluminium of coating).The silane coupled agent content of comparative example 2 is more than the upper limit Value.

In comparative example 3, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film of 5 μm of film thickness (total coating thickness), is prepared for test film (aluminium of coating).Though the aluminium of the coating of the comparative example 3 The P/Si mass ratio for so having the aluminium of coating documented by the embodiment 9 with patent document 4 substantially the same contains titanium dioxide Siliceous skin film, but without addition silane coupling agent.

In comparative example 4, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 5 μm of film thickness carries out 60 seconds sintering processes at PMT225 DEG C, makes it dry next, stick applies coating process C, is formed The film that 30 μm of film thickness is prepared for the test film (aluminium of coating) of 35 μm of total coating thickness.Under the P/Si ratio of comparative example 4 is less than Limit value.

In comparative example 5, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 5 μm of film thickness carries out 60 seconds sintering processes at PMT225 DEG C, makes it dry next, stick applies coating process C, is formed The film that 10 μm of film thickness is prepared for the test film (aluminium of coating) of 15 μm of total coating thickness.Under the P/Si ratio of comparative example 5 is less than Limit value.

In comparative example 6, stick applies coating process B, and 60 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 5 μm of film thickness is burnt next, forming 50 μm of film using spray gun coating process E with the heating furnace for being set as 80 DEG C Knot 5 minutes, and then spray gun coating process F is used, 50 μm of film is formed, is sintered 10 minutes with the heating furnace for being set as 80 DEG C, It is prepared for the test film (aluminium of coating) of 105 μm of total coating thickness.The P/Si mass ratio of the aluminium of the coating of the comparative example 6 is super Cross its upper limit.

In comparative example 7, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 5 μm of film thickness, next, electrostatic powder body coating coating D, is sintered 30 minutes with the heating furnace for being set as 180 DEG C, forms film Thick 50 μm of film, is prepared for the test film (aluminium of coating) of 55 μm of total coating thickness.Although the comparative example 7 has and patent The epithelium containing silica of substantially the same P/Si mass ratio of the aluminium of coating documented by the embodiment 2 of document 5, but do not have Add silane coupling agent.

In comparative example 8, stick applies coating process B, and 40 seconds sintering processes are carried out at PMT210 DEG C, are made it dry, and is formed The film that 5 μm of film thickness, next, electrostatic powder body coating coating D, is sintered 30 minutes with the heating furnace for being set as 180 DEG C, forms film Thick 70 μm of film, is prepared for the test film (aluminium of coating) of 75 μm of total coating thickness.The aluminium of coating about the comparative example 8 Material does not add phosphorus compound in epithelium containing silica, and P/Si mass ratio is zero (0), and the addition of silane coupling agent is more than 21 mass %.

[corrosion resistance test]

For the test film of prepared each embodiment and comparative example executed as described above, carries out following salt spray tests, moistens Case test and boiling water immersion test, have probed into adaptation, have had rated corrosion resistance.

In salt spray test, the test film of each embodiment and comparative example intersect according to the method for JIS K5600 and is cut It cuts, implements the test of 1000 hours (hr).In the salt spray test, in film after 1000 hours, commented according to following Price card standard is evaluated, ◎: burn into expansion etc. absolutely not occurs for cutting part, and the adaptation of cutting part is good；〇: cutting part Corrosion within 1mm, do not expand, adaptation is good；And ×: the corrosion of cutting part is 1mm or more or expands, Or that adaptation has occurred is bad etc. abnormal.

In humidity cabinet test, by the test film of each embodiment and comparative example in 50 DEG C and 95%RH of climatic chamber After standing 1000 hours (hr), the adaptation of film is evaluated.According to the method for the adhesion (cross-hatching) of JIS K5600, the painting The adaptation of film is evaluated according to following benchmark: will generate removing cross-cut portion area be 5% or less (classification 1 with Under) the case where evaluation be used as ◎；〇 will be evaluated as more than 5% and for 15% or less situation；To be more than 15% and for 35% with Under situation the case where being evaluated as Δ, will being more than 35% be evaluated as ×.

About boiling water immersion test, the test film of each embodiment and comparative example is immersed in boiling water after 5 hours, and it is above-mentioned Humidity cabinet test the case where be carried out similarly, the adaptation of film is had rated with same evaluation criterion.

The result of the adaptation after adaptation and boiling water immersion test after above-mentioned salt spray test, humidity cabinet test is shown in Table 4.

[table 4]