CN102497982A - Coated metallic material and manufacturing method for same - Google Patents

Abstract

Disclosed is a coated metallic material having a coating layer comprising at least two layers: a first coating film layer which is located on part or all of the surface of a metallic material and which contains rutile titanium oxide at a solid volume concentration of 35-70%; and a second coating film layer which is laminated onto the surface side of the first coating film layer. The centre line average roughness (Ra) of the boundary surface between the first coating film layer and the second coating film layer is not less than 0.8[mu]m. The disclosed coated metallic material has a higher total light reflectance than has previously been achieved and has excellent moldability. Also disclosed is a method for manufacturing the coated metallic material.

Description

Coating metal material and manufacturing approach thereof

Technical field

The present invention relates to have the coating metal material and the manufacturing approach thereof of high reflectivity.

Background technology

Utilize the various device (for example ligthing paraphernalia, AV equipment, electronic equipment, movable equipment, LCD TV, plasma display etc.) of visible light, have through send visible light illuminate around, transmit optical signal, or demonstrate the function of light image etc.In these equipment, also have and carried out around light source and/or reflecting plate is set behind, improve the equipment of briliancy and/or the change direction of light etc. of light through making this baffle reflection light.Under this situation,, reduce the visible reflectance high for fear of light quantity to the reflecting plate surface requirements at reflecting plate glazing reflex time.Therefore, all the time, as the means of the reflectivity that improves the reflecting plate surface, carried out the coating etc. that abrasive metal becomes minute surface, white color system that the application reflectivity is high.

Means as such raising reflectivity; For example; In patent documentation 1; Once disclosed the technology of following light reflective film: at a surperficial stacked above one another metal film layer of base film, contain the resin bed of inorganic particles, this metal foil skin membrane is made up of aluminium, constitutes the refractive index n of the inorganic particles of the resin bed that contains inorganic particles _fRefractive index n with the resin that constitutes this layer _bBe n _f-n _b>=0.4.

In addition; For example, in patent documentation 2, the backplate of effect LCD is used; The technology of the high scattered reflection coated metal plate that the backplate of following LCD uses was once disclosed: on aluminium sheet; Be formed with the priming coat that contains thickness 50～100 μ m of titanium oxide pigments 150～300 mass parts with respect to resin 100 mass parts, and on this priming coat, be formed with the titanium oxide pigments that contains 100～250 mass parts with respect to resin 100 mass parts; Gloss is below 15, and thickness is the last coating of 10～30 μ m.

In addition; For example; In patent documentation 3; The technology of the lining material with high diffuse reflectance was once disclosed, this lining material have one deck at least with respect to adhesive 100 parts by volume contain more than 150 parts by volume and be lower than the Chinese white of 1500 parts by volume the high concentration coat of colo(u)r, or contain adhesive and Chinese white, and the voidage of its coating is that 5 volume % are above and be lower than the low-density layer of 35 volume %.

In addition; For example; In patent documentation 4; Once disclosed following technology with lining material of high diffuse reflectance, this lining material has by adhesive, Titanium Dioxide Rutile Top grade and the low particle of refractive index ratio Titanium Dioxide Rutile Top grade and constitutes and the concentration of rutile-type oxide is the visible light reflecting layer of 35 volume %～70 volume %.

The prior art document

Patent documentation 1: japanese kokai publication hei 10-730 communique

Patent documentation 2: TOHKEMY 2002-172735 communique

Patent documentation 3: TOHKEMY 2006-192660 communique

Patent documentation 4: TOHKEMY 2008-145942 communique

Summary of the invention

Yet, for the reflecting plate of the electric product that is used for ligthing paraphernalia and LCD etc., in recent years, with electric product and structure and complex designization etc. together, the demand that different shape uses is processed in reflecting plate moulding (shaping) has improved.And, demand more doughtily equably the tendency of catoptrical reflecting plate constantly strengthen.

Under such present situation; As the technology that above-mentioned patent documentation 1 is put down in writing; Using under the situation of film as base material; Be difficult to range upon range of metal foil skin membrane and/or the film forming after containing the resin bed of inorganic particles is the shape of target, need be after the shape that film is shaped in advance target laminated metal thin skin rete and/or contain the resin bed of inorganic particles.At this moment, under the forming shape complicated situation of reflecting plate, exist in the processing part and be difficult to make epithelium with the range upon range of such unfavorable condition of uniform thickness.

In addition; In the technology that above-mentioned patent documentation 2 is put down in writing; Can carry out processing and forming after painting bottom coating (prime coat) and the last coating (top coat layer) in advance on the aluminium sheet, but in the application on general field application production line, the priming coat (50～100 μ m) that utilizes 1 this thickness of application is difficulty very; Need being coated with again more than 2 times, therefore have the low shortcoming that waits of productivity ratio.

In addition; In the technology that above-mentioned patent documentation 3 and 4 is put down in writing; Also can obtain high diffuse reflectance even coating is thin; Even 1 application on general field application production line also can be made the precoated metal sheet with high diffuse reflectance, but, therefore there are machinability and the such shortcoming of poor adhesion because the adhesive in the coating is very few.

To such situation, low pigment concentration layer improves machinability and adhering technology is discussed for forming through the levels at above-mentioned high concentration coat of colo(u)r, low-density layer, visible light reflecting layer.And, for through using the big mylar of molecular weight to improve machinability and adhering technology is also discussed as adhesive resin.

But, even adopt any above-mentioned technology, corresponding to the complicated processing and forming that accompanies of the structure of electric product and design to different shape in, machinability and adhesiveness are all also insufficient.In addition, adopt these fabrication techniques the full light reflectance (total light reflectance) of coating metal material, for the desired reflectivity of the reflecting plate of electric product, also may not can be described as the situation of sufficient reflectivity.

As above-mentioned, start from the structure of electric product and the reason in the design, need reflecting plate complicated ground processing and forming be used sometimes.Under this situation; To the high mouldability of coating metal material requirements, full light reflectance, productivity ratio etc.; But the coating metal material of being put down in writing in above-mentioned patent documentation 1～4 grade is not the material that can satisfy the performance of mouldability (machinability, adhesiveness) and full light reflectance etc.

The present invention accomplishes in view of above-mentioned present situation, its objective is that providing a kind of has than higher in the past full light reflectance and excellent coating metal material and the manufacturing approach thereof of mouldability.

Present inventors for solve above-mentioned problem repeatedly attentively the result of research find: through the part of metal material surface or all lining comprise and contain the 1st of Titanium Dioxide Rutile Top grade with high concentration and be coated with the 2nd of rete and its upper strata and be coated with the coating more than rete two-layer; And increase the 1st and be coated with the roughness that rete and the 2nd is coated with the boundary face of rete; Can have high full light reflectance and excellent mouldability thus concurrently, thereby accomplish the present invention based on this opinion.

Promptly; According to the present invention; A kind of coating metal material is provided, and it is in the part of metal material surface or all have and comprise the 1st and be coated with the two-layer at least coating that rete and the 2nd is coated with rete, and the said the 1st is coated with rete contains and count 35%～70% Titanium Dioxide Rutile Top grade by the solid constituent volumetric concentration; The said the 2nd film layer be laminated in the above-mentioned the 1st be coated with rete the top layer side, the above-mentioned the 1st to be coated with the center line average roughness Ra that rete and the above-mentioned the 2nd is coated with the boundary face of rete be more than the 0.8 μ m.

At this, preferred: be coated with boundary member that rete and the above-mentioned the 2nd is coated with rete the above-mentioned the 1st and exist the above-mentioned the 1st composition and the above-mentioned the 2nd that is coated with in the rete to be coated with the mixed layer that the composition in the rete mixes, above-mentioned mixed layer has the thickness of 3 μ m～12 μ m.

Preferably: the most surperficial filtering center line percent ripple W of above-mentioned coating _CABe below the 2 μ m.

Being coated with rete and also can containing silicones or fluororesin of top layer among the above-mentioned coating.

Top layer among the above-mentioned coating be coated with rete, also can in the resin matrix that formation is filmed, have-the Si-O-Si-key.

In addition, the average grain diameter of preferred above-mentioned Titanium Dioxide Rutile Top grade is 200nm～400nm.

The above-mentioned the 1st is coated with rete can also contain the particle that the above-mentioned Titanium Dioxide Rutile Top grade of size ratio is big and have the refractive index lower than above-mentioned Titanium Dioxide Rutile Top grade.

Preferably: be coated with the above-mentioned the 1st and have the space in the rete, the containing ratio in above-mentioned space is the above-mentioned the 1st to be coated with 0.05 times～0.9 times of solid constituent volume in the rete.

The preferred the above-mentioned the 1st be coated with rete thickness be 10 μ m～80 μ m.

The preferred the above-mentioned the 2nd be coated with rete thickness be 5 μ m～30 μ m.

Above-mentioned coating also can also contain and is laminated in above-mentioned metal material and the above-mentioned the 1st and is coated with the 3rd between the rete and is coated with rete.

The preferred the above-mentioned the 3rd be coated with rete thickness be 5 μ m～30 μ m.

In addition; According to the present invention; A kind of manufacturing approach of coating metal material is provided; This manufacturing approach is the manufacturing approach of above-mentioned coating metal material, wherein, adopt multilayer to be coated with simultaneously or wet-wet (wet on wet) mode the part of metal material surface or all be coated with the above-mentioned the 1st be coated with the formation usefulness of rete coating and the above-mentioned the 2nd be coated with the coating of the formation usefulness of rete.

According to the present invention, also provide a kind of with above-mentioned coating metal material be used to the to throw light on ligthing paraphernalia of reflecting plate.

According to the present invention, a kind of electronic equipment of reflecting plate of reflecting plate or the image displaying part that above-mentioned coating metal material is used for luminous component is provided also.

According to the present invention, can provide to have than higher in the past full light reflectance and excellent coating metal material and the manufacturing approach thereof of mouldability.

Description of drawings

Fig. 1 is the cross section ideograph of an example of the briliancy determinator representing to use in the present embodiment.

Fig. 2 is an ideograph of observing the briliancy determinator of Fig. 1 from top.

Fig. 3 be the expression film boundary face concavo-convex state one the example figure.

The specific embodiment

Following one side is with reference to accompanying drawing, and at length explain for preferred implementation of the present invention on one side.Moreover, in this specification and accompanying drawing, through omitting repeat specification for the subsidiary identical mark of the inscape that has the identical functions formation in fact.

< formation of coating metal material >

The formation of the coating metal material that at first, relates to for an embodiment of the present invention describes.

The coating metal material that this embodiment relates to is in the part on the surface of the metal material that becomes base material or all have two-layer at least coating.Specifically; This coating have comprise at least with high concentration contain the 1st of Titanium Dioxide Rutile Top grade be coated with rete (below; Be called " high concentration coat of colo(u)r ") and be laminated in the 1st be coated with rete the top layer side the 2nd be coated with rete (below, be called " go up coating ") laminated construction.In addition; The coating metal material that this embodiment relates to, as coating, can also be in the internal layer side of high concentration coat of colo(u)r, be have between metal material and the high concentration coat of colo(u)r the 3rd be coated with rete (below; Be called " priming coat "); And then, can also have other be coated with rete (for example, be laminated in coating more top layer side be coated with rete).Below, by the order of high concentration coat of colo(u)r, last coating, priming coat, at length explain for the formation that respectively is coated with rete.

" high concentration coat of colo(u)r " (summary)

The high concentration coat of colo(u)r that this embodiment relates to is to contain the layer of counting 35%～70% Titanium Dioxide Rutile Top grade by the solid constituent volumetric concentration as Chinese white, is positioned at the internal layer side of coating, i.e. a side of more approaching metal material as base material.But, be under the situation of the 3-tier architecture that constitutes by priming coat, high concentration coat of colo(u)r and last coating at coating, the high concentration coat of colo(u)r becomes the layer that is positioned at the part that contacts with last coating with priming coat and be held.In addition; Have at coating under the situation of the sandwich construction more than 4 layers of the layer more than 1 layer that also contains other 3 layers except priming coat, high concentration coat of colo(u)r and last coating; Will be between last coating and priming coat; And, contain count 35%～70% Titanium Dioxide Rutile Top grade by the solid constituent volumetric concentration whole layers as the high concentration coat of colo(u)r.In addition, the concentration of Titanium Dioxide Rutile Top grade changes continuously in coating, and under the indefinite situation in the border of each layer, the scope that with the solid constituent volumetric concentration that satisfies Titanium Dioxide Rutile Top grade is 35%～70% condition is all as the high concentration coat of colo(u)r.

Moreover; Said " the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade "; Being meant the ratio of the shared volume of Titanium Dioxide Rutile Top grade in the filming of high concentration coat of colo(u)r with respect to all shared volumes of the solid constituent that contains resin (adhesive) composition and pigment composition, is the ratio (assay method for this " the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade " is narrated later on) the shared volume in space in filming.

The high concentration coat of colo(u)r that this embodiment relates to; Through in dry, filming after solidifying; Contain Titanium Dioxide Rutile Top grade with high concentration; Make the particle of Titanium Dioxide Rutile Top grade exist, be formed at the volume of the volume in the interparticle space of Titanium Dioxide Rutile Top grade thus greater than adhesive resin with the mode that becomes more than the closeest filling.Therefore, the high concentration coat of colo(u)r that this embodiment relates to is different to become the concentration that is lower than the closeest filling and contains such the filming of pigment, can the part that does not have adhesive resin be present in as the space to film.At this, the refractive index of general air is lower than the refractive index as the resin of adhesive, so the refringence in Titanium Dioxide Rutile Top grade and space, and is bigger than the refringence of Titanium Dioxide Rutile Top grade and resin.In addition, the high concentration coat of colo(u)r that this embodiment relates to also can reflect the light that the high concentration coat of colo(u)r is accepted at the interface in adhesive resin and space.Like this; Because the high concentration coat of colo(u)r that relates to of this embodiment, in the refringence at catoptrical interface than to contain filming of pigment big to become the concentration that is lower than the closeest filling, and; It is big that area that can catoptrical interface becomes, and therefore can access high full light reflectance.

Below, at length explain for each composition that the high concentration coat of colo(u)r is contained.

(Titanium Dioxide Rutile Top grade)

In this embodiment, the pigment as the high concentration coat of colo(u)r is contained uses Titanium Dioxide Rutile Top grade.Its reason is that general other Chinese whites that use of the refractive index ratio of Titanium Dioxide Rutile Top grade are high; Can increase and resin that uses as adhesive and the refringence that is present in the air in the space in filming, therefore can improve at the interface of pigment and resin more and the full light reflectance at the interface of pigment and air.Moreover anatase-type titanium oxide also has than higher refractive index, but photocatalytic is higher, in the light time that receives fluorescent lamp etc., and the possibility that has adhesive resin to decompose, therefore not preferred.

The coating metal material that this embodiment relates to is the main starting point with reflect visible light, so the full light reflectance height of the high wavelength region may of the susceptibility of human eye becomes important.Though human eye has individual difference, can experience the light of the wavelength of 380nm～780nm, the peak of its susceptibility is near 555nm.Therefore, preferably also to reflect consumingly with 555nm be the light of the wavelength at center to the coating metal material that relates to of this embodiment, therefore preferably considers also that for the particle diameter of the pigment that is used for the high concentration coat of colo(u)r (Titanium Dioxide Rutile Top grade) this point selectes.

The average grain diameter of the Titanium Dioxide Rutile Top grade that uses as pigment; Because its hour surface area change of per unit volume is big; Area as the interface of the resin of light reflection surface or space and pigment becomes big, and therefore full light reflectance also uprises, if but the average grain diameter of pigment too diminish; Then long wavelength's light transmission, therefore full light reflectance reduces.At this, general knownly there is the big so-called Mie scattering region of scattering of light in particle size range with the wavelength par, be that 1/2 front and back light scattering of wavelength becomes the highest at particle diameter.Thus, in this embodiment, the average grain diameter of the Titanium Dioxide Rutile Top grade that preferably will use as pigment is made as the only about half of 200nm of the being～400nm of visible wavelength, more preferably is made as 250nm～350nm.

Moreover; The average grain diameter of so-called Titanium Dioxide Rutile Top grade in this embodiment; Be to adopt electron microscope (SEM) 10; Observe down the part that wanting of filming confirmed for 000 times, among the Titanium Dioxide Rutile Top grade particle that in the visual field, demonstrates, removed from the little side of particle diameter and begin to be equivalent to 20% part and the arithmetic mean of instantaneous value of the particle diameter of the Titanium Dioxide Rutile Top grade particle that begins from the big side of particle diameter to be equivalent to be left behind the particle of 5% part by quantity by quantity.

< condition determination >

Observe preparation method: sample is imbedded in the resin, ground the vertical cross-section of sample, made sample thus with sample.

The visual field of observing: observe through about 500 times～1000 times light microscope or electron microscope (SEM) in advance, selection is equivalent to the position arbitrarily of the layer of high concentration coat of colo(u)r.

Ask the system of selection of the Titanium Dioxide Rutile Top grade particle of arithmetic mean of instantaneous value: take the image of under 10000 times multiplying power, observing the visual field of selecting through electron microscope (SEM).For all particle assay particle diameters of Titanium Dioxide Rutile Top grade that in the image of taking, demonstrate.

The assay method of the particle diameter of each Titanium Dioxide Rutile Top grade particle: in the particle size determination of Titanium Dioxide Rutile Top grade particle, measure the longest diameter and the shortest diameter of each particle, 1 Titanium Dioxide Rutile Top grade particle diameter=(longest diameter+the shortest diameter)/2.

Arithmetic mean of instantaneous value average (?): at random select 3 places above-mentioned " visual field of observation ", will carry out arithmetic average again by " arithmetic mean of instantaneous value " that these visual fields obtain respectively.

The Titanium Dioxide Rutile Top grade particle that in this embodiment, uses just can especially restrictedly not use as long as satisfy above-mentioned condition.In addition; The Titanium Dioxide Rutile Top grade particle that in this embodiment, uses; Can be the particle monomer of Titanium Dioxide Rutile Top grade, perhaps also can be to utilize silica, aluminium oxide, zirconia, zinc oxide, antimony oxide, various organic matters etc. to implement the particle that applies to Titanium Dioxide Rutile Top grade.Organic matter as the coating that is used for Titanium Dioxide Rutile Top grade; Not special the qualification can be enumerated the silicon-type compound etc. of the alkanolamine based compound, silicones, alkylchlorosilane etc. of polyalcohol based compound, the triethanolamine of for example pentaerythrite, trimethylolpropane etc., the acylate of trihydroxy methyl amine etc.

In this embodiment; As Titanium Dioxide Rutile Top grade; Also commercially available article can be used, for example, the former industry corporate system of stone " タ イ ペ one Network (registration mark) " series, Fuji's titanium corporate system " TA " series, テ イ カ corporate system " TITANIX (registration mark) " series etc. can be used.

In addition, the Titanium Dioxide Rutile Top grade as above-mentioned, the solid constituent volumetric concentration in the high concentration coat of colo(u)r is more than 35%.If the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade is more than 35%; Then as above-mentioned; In dry, filming after solidifying, the particle of Titanium Dioxide Rutile Top grade exists with the mode that becomes more than the closeest filling, therefore can make to have the non-existent space of adhesive resin in filming.Thus, can improve the full light reflectance of high concentration coat of colo(u)r.Under situation, the Titanium Dioxide Rutile Top grade of the above-mentioned average grain diameter with 200nm～400nm is made as by the solid constituent volumetric concentration counts more than 50% the higher reflecting properties of coating metal material requirements.Under this situation, the interface of the Titanium Dioxide Rutile Top grade in filming and the interface in space, Titanium Dioxide Rutile Top grade and resin and the interface in resin and space help full light reflectance efficiently, can obtain high total reflectivity, and be therefore preferred.

On the other hand; If the solid constituent volumetric concentration of the Titanium Dioxide Rutile Top grade in the high concentration coat of colo(u)r surpasses 70%; The shared ratio in Titanium Dioxide Rutile Top grade in then filming and space too becomes many; Therefore be difficult to guarantee the continuity of filming (state that keeps film) that caused by adhesive resin, the high concentration coat of colo(u)r itself becomes fragile.Therefore, the solid constituent volumetric concentration with the Titanium Dioxide Rutile Top grade in the high concentration coat of colo(u)r is made as below 70%.From guaranteeing the viewpoint of stable coating strength, the more preferably scope of the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade is below 65%.

At this, describe for the assay method of the solid constituent volumetric concentration in the coating in this embodiment.As an example, be that the assay method of solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade of the situation of the 3-tier architecture that is made up of last coating, high concentration coat of colo(u)r, priming coat is narrated for coating.

(assay method of the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade)

At first, the mode that will become the above coating of coating, high concentration coat of colo(u)r, the priming coat of determination object from sample is cut by each layer and is got, and measures and cuts the area A of filming 1 and mass M 1 of having got.Then, that has used crucible to cut to get films 500 ℃ of heating 1 hour, and resinous principle is decomposed.Owing to can undecomposed and residual part be thought of as Titanium Dioxide Rutile Top grade, therefore measure this residual mass M 2.

The density of general Titanium Dioxide Rutile Top grade pigment is 3800～4200kgm ^-3About, therefore the density with Titanium Dioxide Rutile Top grade pigment is assumed to 4000kgm ^-3, in addition, the density of general mylar is 1150～1250kgm ^-3About, therefore the density with mylar is assumed to 1200kgm ^-3, as V1=(M1-M2)/1200kgm ^-3Obtain the volume V1 of mylar, as V2=M2/4000kgm ^-3Obtain the volume V2 of Titanium Dioxide Rutile Top grade.

Can obtain the volumetric concentration C1 of Titanium Dioxide Rutile Top grade as C1=V2/ (V1+V2) * 100 (volume %) from the volume V1 of the mylar obtained like this, the volume V2 of Titanium Dioxide Rutile Top grade.

With the mensuration of above-mentioned C1, measure 3 times for 1 determination object (for example, the high concentration coat of colo(u)r), obtain its arithmetic mean of instantaneous value.

(interpolations of other particles)

In the high concentration coat of colo(u)r that this embodiment relates to; If with Titanium Dioxide Rutile Top grade and with the above-mentioned Titanium Dioxide Rutile Top grade of size ratio greatly and have low refractive index particle (below; Be sometimes referred to as " low-refraction particle "); Then can improve full light reflectance more efficiently, therefore preferred.Through further add the big particle of size ratio Titanium Dioxide Rutile Top grade to the high concentration coat of colo(u)r, the interparticle space in the high concentration coat of colo(u)r becomes big, can contain more space, and full light reflectance is improved.And; With the big particle of the particle diameter of Titanium Dioxide Rutile Top grade and usefulness be the particle of low-refraction; Therefore at the contact interface at the position that this low-refraction particle contacts with the Titanium Dioxide Rutile Top grade particle; Because the refringence of Titanium Dioxide Rutile Top grade particle and low-refraction particle and can reverberation, thereby can help the raising of full light reflectance.

The particle diameter of above-mentioned low-refraction particle with respect to the excessively big situation of the particle diameter of Titanium Dioxide Rutile Top grade under; Be difficult to performance and make and contain the space in the high concentration coat of colo(u)r efficiently, and then obtain light at the contact interface of low-refraction particle and titanium oxide efficiently and reflect such effect.From such viewpoint, the average grain diameter of low-refraction particle is preferably 1 μ m～10 μ m, more preferably 3 μ m～8 μ m.

The ratio R of the arithmetic mean diameter of this low-refraction particle and Titanium Dioxide Rutile Top grade _L, be R _L=(arithmetic mean diameter of low-refraction particle)/(arithmetic mean diameter of Titanium Dioxide Rutile Top grade) is preferably more than 1/40, more preferably 1/40～12/40 (especially preferably 3/40～10/40).

Moreover; The average grain diameter of so-called low-refraction particle in this embodiment; Same with Titanium Dioxide Rutile Top grade; Be to adopt electron microscope to observe the part that wanting of filming confirmed down, among the low-refraction particle that in the visual field, demonstrates at 10,000 times; Removed from the little side of particle diameter and begun to be equivalent to 20% part and to begin to be equivalent to the arithmetic mean of instantaneous value (that is, the arithmetic mean of instantaneous value of the particle diameter of low-refraction particle also can likewise be measured with the situation of above-mentioned " Titanium Dioxide Rutile Top grade ") of the particle diameter of low-refraction particle remaining behind the particle of 5% part from the big side of particle diameter by quantity by quantity.

As above-mentioned low-refraction particle; Do not limit so long as the particle of the refractive index lower than Titanium Dioxide Rutile Top grade is just special; But the refringence of preferred and Titanium Dioxide Rutile Top grade is more than 1; More preferably there is not strong absorption, the particle that under pulverulence, is white in color with respect to the light of visible region.Specifically, as above-mentioned low-refraction particle, for example can use the inorganic particulate of silica, calcium carbonate, barium sulfate, zinc oxide etc.In addition, in addition,, also can use toner etc. as above-mentioned low-refraction particle.Do not limit for the kind of toner is special,, for example can use acrylic resin powder, polyester resin powder, PTFE (polytetrafluoroethylene (PTFE)) powder etc. as toner.

The effect of above-mentioned low-refraction particle as above-mentioned, can contain the space efficiently in the high concentration coat of colo(u)r, and then at the contact interface reverberation of low-refraction pigment and titanium oxide, thereby obtain high reflectivity.Therefore; Even the addition of low-refraction particle is a small amount of; Also can only depend on the part performance effect that contains; Therefore the least concentration for the low-refraction particle there is no need special qualification, but when (volume of the volume/Titanium Dioxide Rutile Top grade of low-refraction particle) when being lower than 0.05, the raising effect of the full light reflectance of interpolation low-refraction particle is few.Therefore, the least concentration as the low-refraction particle is preferably (volume of the volume/Titanium Dioxide Rutile Top grade of low-refraction pigment) and becomes the concentration more than 0.05.

On the other hand; Upper limit concentration for the low-refraction particle; At (volume of the volume/Titanium Dioxide Rutile Top grade of low-refraction pigment) when being the scope below 0.2; The reflection of light rate follow the low-refraction particle addition rising and rise, can confirm the additive effect of low-refraction particle, if but surpass this scope and add then can confirm the tendency that the performance (machinability, corrosion resistance etc.) beyond the reflectivity of bright dipping reduces.Therefore, the upper limit concentration as the low-refraction particle, being preferably (volume of the volume/Titanium Dioxide Rutile Top grade of low-refraction pigment) is the concentration below 0.2.

In addition, above-mentioned low-refraction particle except full light reflectance improves such effect, also has the such effect of roughness of the boundary face of control high concentration coat of colo(u)r and last coating, narrates later on for details.

(space in filming)

The containing ratio in the space in the high concentration coat of colo(u)r is preferably 0.05 times～0.9 times of solid constituent volume.Reason is that the containing ratio in the space is when being lower than 0.05 times of solid constituent volume; Raising effect by containing the full light reflectance that brings in the space is few; If the containing ratio in space surpasses 0.9 times of the solid constituent volume; Then the high concentration coat of colo(u)r becomes fragile (mechanical strength reduction), and the possibility of machinability and poor adhesion is arranged.Being somebody's turn to do the method for stating after " containing ratio in space " can adopt measures.

The control of the containing ratio in the space in the high concentration coat of colo(u)r is as above-mentioned; The concentration that contains of pigment that can be through Titanium Dioxide Rutile Top grade and low refraction particle etc. is controlled; In addition, for example also can control through the dispersity that adjustment is used to form the coating of high concentration coat of colo(u)r.That is, the dispersing of pigments state in coating better (even more), then adhesive resin is adsorbed in pigment, and the containing ratio in the space between the landfill pigment particles, so space efficiently is few more.Therefore, in order to obtain higher full light reflectance, preferably in the stable no problem scope of coating and coating, be limited in MIN dispersity (inhomogeneous as much as possible in the stable no problem scope of coating and coating).Moreover the dispersing of pigments state in coating can wait and control through kind, jitter time, the kind of dispersant, the addition of adjustment dispersion machine.

The size in the space in the high concentration coat of colo(u)r is not special to be limited; But if the space of extremely big size is arranged, and then become paint film defect, the anxiety of the film performance reduction of machinability of making and corrosion resistance etc. is arranged; Therefore not preferred; In addition, because the surface area of the per unit area in space diminishes, therefore not preferred from the viewpoint of the raising effect of full light reflectance.On the other hand, the size in space hour, it is big that the surface area of the per unit area in space becomes; It is big that the area at reflection of light interface becomes, and therefore full light reflectance also uprises, if but the size in space is too terrifically little; Therefore the light transmission of then long wavelength has the anxiety of full light reflectance reduction.

Therefore, the size in the space in the high concentration coat of colo(u)r is preferably the only about half of 200nm of the being～400nm as visible wavelength, more preferably 250nm～350nm from the viewpoint of the raising of reflection of light rate.But because the size in control space, the consistent size that particularly makes the space in filming is difficulty, and the therefore problem of short of paint film defect as above-mentioned etc. and the extreme influence to reflectivity just do not have special problem for the size in space.Moreover, in this embodiment,, use as the suitable footpath of the equal-volume ball of the diameter of ball with volume identical with the space as the size in space.In fact can pass through scanning electron microscope (SEM) is taken the vertical cross-section in the high concentration coat of colo(u)r under 10000 times multiplying power position arbitrarily; Be chosen in the viewed space arbitrarily of this photographic images; The diameter that will have the ball that is defined as with the diameter of a circle of this area area identical and has the volume identical with the space is identical, thereby obtains.Can among the viewed space in the electron microscope photographic images, diameter is calculated in 10 spaces arbitrarily, with the diameter of its arithmetic mean of instantaneous value as the space.

At this, describe for the assay method of the volume in the space in the coating in this embodiment.

At first; From sample cut get the coating that becomes determination object after; With respect to by vertical this coating of face cutting of clad can (face that is parallel to metal material surface), utilize * * light microscope, electron microscope etc. to observe this cross section, perhaps use electromagnetism film thickness gauge * * to obtain the thickness T1 of coating.In addition, likewise obtain with the occasion of the volumetric concentration of obtaining Titanium Dioxide Rutile Top grade and cut the area A of filming 1, the volume V1 of adhesive resin (for example, mylar) and the volume V2 of pigment (for example, Titanium Dioxide Rutile Top grade) that has got.From A1, V1 and the V2 that has obtained, obtain the thickness T2 of the coating of the occasion that does not have the space as T2=(V1+V2)/A1.Can obtain the volume V3 in space by the formula of V3=(V1+V2) * (T1-T2)/(T1+T2) from V1, V2, T1 and the T2 that obtains like this.

The assay method of above-mentioned thickness T1 is from measuring the precision aspect, the preferred method of having used light microscope or electron microscope (SEM) that adopts.In addition, above-mentioned voidage is measured 5 times for same sample (that is, coating), obtains its arithmetic mean of instantaneous value.

(adhesive resin)

As the adhesive resin that uses in the high concentration coat of colo(u)r that relates at this embodiment; Not special the qualification; Can use general employed adhesive resin, for example mylar, urethane resin, epoxy resin, acrylic resin, silicones, fluororesin etc.But; Because in the high concentration coat of colo(u)r that this embodiment relates to; Add the Titanium Dioxide Rutile Top grade particle that becomes the above amount of the closeest filling; Therefore filming becomes fragile easily, therefore as the adhesive resin that in the high concentration coat of colo(u)r, uses, preferably uses the excellent resin of machinability and adhesiveness.Specifically, as adhesive resin, preferably using number-average molecular weight for example is 19000～28000 mylar A.This is based on following reason.

In the coating metal material that this embodiment relates to; Therefore to obtain high full light reflectance is purpose, need the Titanium Dioxide Rutile Top grade particle that in the high concentration coat of colo(u)r, adds as Chinese white be made as and count 35%～70% high concentration by the solid constituent volumetric concentration.Therefore, according to the kind of the adhesive resin that is used for coating, adhesive power sometimes that pigment particles is bonded to one another is not enough, therefore exists the machinability of coating metal material to reduce such problem.Therefore; Present inventors guarantee that with a spot of adhesive resin the formation of the coating of machinability carried out the result of wholwe-hearted investigation and found for being used for: with pigment particles with as the excellent mylar of adhesiveness of the metal material of base material is best; And; Number-average molecular weight through with mylar is made as 19000～28000; Embodying the excellent performance of ductility and intensity balance, is 19000～28000 mylar A thus through the use number-average molecular weight, can obtain good machinability.The number-average molecular weight of mylar can adopt " GPC " to measure.Under the situation of using commercially available resin, value that can the disclosed number-average molecular weight of application manufacturer.

At this, usually, used molecular weight be high molecular weight polyester resins more than 19000 as the coating of adhesive, viscosity uprises easily, therefore in order to ensure the viscosity that is suitable for application, need the solid constituent viscosity in the coating be suppressed for lower.Therefore, think that the painting defect that is called as convexity (foaming) is easy to generate in the purposes of the thick film application that the present invention mainly is suitable for, the application of high molecular weight polyester resins is difficulty.But, in this embodiment, owing to add Titanium Dioxide Rutile Top grade in large quantities as Chinese white, so the viscosity of adhesive resin step-down relatively, even the solid component concentration in the coating is suppressed to be the too low viscosity that also can guarantee to be suitable for application.Therefore, the adhesive of the high concentration coat of colo(u)r that relates to as this embodiment even use the mylar A of HMW, can not produce convexity yet and carries out the application of thick film, can have coating and machinability concurrently.

In addition; Number-average molecular weight at mylar A is lower than at 19000 o'clock; Mouldability guarantee to become difficulty, the preferable range of the number-average molecular weight of the mylar A that will use as the adhesive resin that uses in the high concentration coat of colo(u)r that relates at this embodiment together with above-mentioned reason thus is made as more than 19000.

On the other hand; If the number-average molecular weight of mylar A surpasses 28000; Then film coated surface becomes too soft; The anxiety that the scratch resistance deterioration is arranged, the preferable range of the number-average molecular weight of the mylar A that therefore will use as the adhesive resin that uses in the high concentration coat of colo(u)r that relates at this embodiment is made as below 28000.

Addition for the mylar A as above-mentioned; If mylar A is with respect to more than all concentration 20 quality % of adhesive resin; Then can not produce convexity and carry out the application of thick film; Can have coating and machinability concurrently, the therefore preferred concentration that mylar A is all with respect to adhesive resin is made as more than the 20 quality %.

In addition; Present inventors find; Through making the adhesive resin in the high concentration coat of colo(u)r, except above-mentioned mylar A, also contain number-average molecular weight and be 2000～6000 and hydroxyl value be the mylar B more than 20; And mylar A and mylar B count 0.25≤(mylar B)/(mylar A)≤4 by mass ratio, can obtain more excellent mouldability thus.

As above-mentioned; Number-average molecular weight is the excellent workability of the mylar A of 19000～28000 HMW; But the high concentration coat of colo(u)r of this embodiment contains the pigment of Titanium Dioxide Rutile Top grade etc. with high concentration, and therefore having adhesive resin is dispersed in the structure between the pigment.In such structure, even contain the coating of high molecular weight polyester resins A, compare with the coating that pigment concentration is low, the tendency of its machinability step-down is also arranged, require the further raising of machinability.

Therefore; The result that present inventors have carried out wholwe-hearted investigation for the further raising of machinability finds: through the mylar A and the low-molecular-weight mylar B of combination use HMW, compare the processing characteristics that can obtain excellence with the independent situation of the mylar A of HMW.That is, when high molecular weight polyester resins A was independent, resin can not enter into the gap of the pigment that exists with high concentration fully, became insufficient as the function of adhesive, therefore had machinability that the possibility of reduction is arranged slightly.Relative therewith; Think through making up the mylar A and the low-molecular-weight mylar B of use HMW; Low-molecular-weight mylar B enters between the pigment and pigment that the mylar A of HMW can not get into; As the adhesive performance function of the mylar A of pigment and pigment or pigment and HMW, the intensity that coating is all improves with adhesiveness, therefore can obtain the machinability of excellence.In addition, the hydroxyl value of low-molecular-weight mylar B is high more, just has more crosslinking points more, can obtain the adhesiveness of higher epithelium.

From above viewpoint, preferred: the number-average molecular weight of low-molecular-weight mylar B is 2000～6000, and hydroxyl value is more than 20.If the number-average molecular weight of mylar B is lower than 2000; The anxiety that the insufficient and machinability reduction of epithelium intensity is then arranged; If number-average molecular weight surpasses 6000, then mylar B is difficult to get between pigment and the pigment, and therefore the anxiety of adhering raising effect reduction is arranged.In addition, if the hydroxyl value of mylar B is lower than 20, then the crosslinking points of pigment and pigment tails off, and the anxiety of adhering raising effect reduction is arranged.In addition, from the viewpoint of epithelium performance, need not confirm the higher limit of the hydroxyl value of mylar B especially, from the viewpoint of the stability of easy to be acquired, the coating of resin, the hydroxyl value of preferred polyester resin B is below 200.

In addition,, the mixed proportion of mylar A and mylar B can obtain excellent adhesiveness and machinability if counting 0.25≤(mylar B)/(mylar A)≤4 by mass ratio.If the mass ratio of (mylar B)/(mylar A) is lower than 0.25; Then the function embodiment of mylar B becomes insufficient; The anxiety that therefore the adhesiveness reduction is arranged; If greater than 4, then the function embodiment of mylar A becomes insufficient to (mylar B)/(mylar A), therefore the anxiety of machinability reduction is arranged.

(thickness)

In order to obtain high full light reflectance, the thickness of the high concentration coat of colo(u)r that this embodiment relates to is preferably more than the 10 μ m, under the situation that requires higher full light reflectance more preferably more than the 40 μ m.On the other hand, if the thickness of high concentration coat of colo(u)r surpasses 80 μ m, the anxiety of the machinability reduction of filming is arranged then, therefore, the thickness of high concentration coat of colo(u)r is preferably below the 100 μ m, under the situation that requires higher machinability, more preferably below the 15 μ m.At this, the thickness of the high concentration coat of colo(u)r in this embodiment can be measured as follows.That is, with respect to respectively be coated with rete by the vertical face of clad can cutting sample, utilize light microscope, its cross section of electron microscope observation, can obtain the thickness that is coated with rete thus.In this " thickness " is measured, be decided to be the thickness of (arithmetic) mean value of measuring for 5 positions arbitrarily.

Moreover, after the last coating stated and the thickness of priming coat also can likewise measure with the thickness of high concentration coat of colo(u)r.In addition, narrate later on for the situation that is formed with mixed layer in the boundary portion that respectively is coated with rete.

[going up coating]

More than, the high concentration coat of colo(u)r that relates to for this embodiment specifies, and then, the last coating that relates to for this embodiment describes.

(summary)

The last coating that this embodiment relates to, be the top layer side of above-mentioned high concentration coat of colo(u)r, promptly apart from as the farther side of the metal material of base material range upon range of coating.At this; Under the situation of coating for the double-layer structure that constitutes by high concentration coat of colo(u)r and last coating, also contain under the situation of 3-tier architecture of priming coat on this basis and exist under the situation of the structure more than 4 layers of high concentration coat of colo(u)r of multilayer, last coating is positioned at top layer.But, as long as go up the top layer side that coating directly is laminated in the high concentration coat of colo(u)r, then may not be positioned at top layer, also can be on the more top layer of last coating side is range upon range of that other coating arranged.

(adhesive)

As the resin that the adhesive of last coating uses, not special the qualification, from the adhesiveness of high concentration coat of colo(u)r, after the viewpoint of formation, commonization of coating raw material etc. of the mixed layer stated, preferably contain the resin identical and use with the high concentration coat of colo(u)r.Therefore, because as the adhesive of high concentration coat of colo(u)r, preferably using number-average molecular weight is 19000～28000 mylar A, therefore in last coating, also preferably uses mylar A as adhesive.The number-average molecular weight of the mylar that uses as the adhesive of last coating is lower than at 19000 o'clock, and the anxiety of machinability and adhesiveness reductions is arranged, if number-average molecular weight above 28000, film coated surface softness too then has the anxiety of scratch resistance and anti-adhesive deterioration.

Moreover; For the addition of the mylar A of coating upwards; If mylar A is with respect to more than all concentration 80 quality % of adhesive resin; Then can bring into play and improve machinability and the such effect of adhesiveness, the therefore preferred concentration that mylar A is all with respect to adhesive resin is made as more than the 80 quality %.

(pigment)

Last coating is different with the high concentration coat of colo(u)r, and the interpolation of pigment is unessential, through the kind of adjusting the pigment that has or not, adds that pigment adds according to purposes, the concentration of pigment etc., gives and the corresponding reflection characteristic of purpose and other characteristics.

At first, for example adding the situation of Titanium Dioxide Rutile Top grade for coating upwards as pigment narrates.Add Titanium Dioxide Rutile Top grade through the coating that makes progress, can improve full light reflectance, Titanium Dioxide Rutile Top grade concentration height is then favourable to reflecting properties.But the main effect of last coating is that the protective covering layer is all, and therefore too crisp filming is not preferred.Therefore, the Titanium Dioxide Rutile Top grade concentration in the last coating from the viewpoint of the flexibility guaranteeing to film, is preferably counted below 35% by the solid constituent volumetric concentration.On the other hand, the lower limit for the Titanium Dioxide Rutile Top grade concentration in the last coating does not need special qualification, comprises the situation that does not contain Titanium Dioxide Rutile Top grade fully.That is, the Titanium Dioxide Rutile Top grade concentration in the last coating that this embodiment relates to preferably counts 0%～35% by the solid constituent volumetric concentration.In addition; Under the situation that requires higher full light reflectanceization; Be made as by the solid constituent volumetric concentration and count 20%～30% through going up Titanium Dioxide Rutile Top grade concentration in the coating, can have defencive function and the highly reflective ability of bringing by last coating all concurrently with high level to coating.

Moreover; Said " the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade " is meant: go up the ratio of the shared volume of Titanium Dioxide Rutile Top grade in the filming of coating with respect to all shared volumes of the solid constituent that contains resin (adhesive) composition and pigment composition.

The average grain diameter of this Titanium Dioxide Rutile Top grade under the situation of having used Titanium Dioxide Rutile Top grade as pigment; Its hour, it is big that the surface area of per unit volume becomes, and becomes greatly as the area at the interface of the resin of light reflection surface or space and pigment; Therefore full light reflectance also uprises; If but the average particle diameter became of pigment is too small, then long wavelength's light transmission, therefore full light reflectance reduces.Therefore, same with the situation of high concentration coat of colo(u)r, the average grain diameter of the Titanium Dioxide Rutile Top grade that uses as the pigment in the last coating preferably is made as 200nm～400nm, more preferably is made as 250nm～350nm.

(adding ingredient beyond the pigment)

In last coating, except Titanium Dioxide Rutile Top grade, can also add for example delustering agent with appending.Add through coating upwards and to count 3%～15% delustering agent, can under the state of the full light reflectance of the degree identical, do not had the reflection characteristic of normal reflection composition basically with the situation of not using delustering agent by the solid constituent volumetric concentration.Under the situation of the coating metal material that will have such reflection characteristic as the reflecting plate use of ligthing paraphernalia; Have nothing to do in the distance of light source, angle and can obtain certain reverberation; Therefore under the big situation in the interval between few or light source, also can access uniform reverberation in the quantity of light source.But, through the interpolation of delustering agent, form fine concavo-convexly on the surface of last coating, fine accumulate polluter easily in concavo-convex at this, and, even this polluter also is difficult to be removed through erasing, therefore the anxiety of stain resistance reduction is arranged.Therefore, the addition of preferred delustering agent is considered suitable amount is confirmed in the influence of the reduction of catoptrical uniformity and stain resistance.

In addition, as the delustering agent that in this embodiment, uses, not special the qualification, for example, preferable particle size is the silica of 3 μ m～9 μ m.

(thickness)

Add under the situation of Titanium Dioxide Rutile Top grade in the coating that makes progress, the thickness of last coating is thick more, just can obtain high more machinability, adhesiveness and full light reflectance.But, surpass 30 μ m if go up the thickness of coating, then be easy to generate convexity during application, so the coating deterioration, and, not preferred aspect the coating cost yet.On the other hand, when the thickness of last coating was lower than 5 μ m, the raising effect of the machinability of being brought by last coating, adhesiveness and full light reflectance diminished, and the thickness that therefore preferably will go up coating is made as 5 μ m～30 μ m.From guaranteeing the viewpoint of stable machinability, adhesiveness, full light reflectance and coating, the preferred thickness of going up coating is 10 μ m～25 μ m.

Upwards coating is added the scope of thickness of last coating of counting the occasion of 3%～15% delustering agent by the solid constituent volumetric concentration, and is same with the occasion of coating interpolation Titanium Dioxide Rutile Top grade upwards, preferably is made as 5 μ m～30 μ m.If the thickness of last coating surpasses 30 μ m, then when application, be easy to generate convexity, so the coating deterioration, and, not preferred aspect the coating cost yet.On the other hand, when the thickness of last coating is lower than 5 μ m, have almost to can not get machinability, adhering raising effect of bringing by last coating and the anxiety that does not have the reflection characteristic of normal reflection composition basically.From guaranteeing the viewpoint of stable machinability, adhesiveness, reflection characteristic and coating, the preferred thickness that has added the last coating of delustering agent is 10 μ m～25 μ m.

[for the rough interface degree of high concentration coat of colo(u)r and last coating]

In the coating metal material that this embodiment relates to, the center line average roughness Ra of the above-mentioned high concentration coat of colo(u)r and the boundary face of last coating need be for more than the 0.8 μ m.The Ra of the boundary face through increasing high concentration coat of colo(u)r and last coating in this wise, therefore the boundary face roughening of high concentration coat of colo(u)r and last coating can improve diffuse reflectance.If the Ra of the boundary face of high concentration coat of colo(u)r and last coating is lower than 0.8 μ m, then can not obtain above-mentioned adhering raising effect and the effect that improves reflectivity fully.If be more than the 0.9 μ m then reflectivity is higher, therefore more preferably.More preferably more than the 2.0 μ m.

The Ra of the boundary face of floating coat and last coating; Be through cutting off filming of each embodiment; Grind after in being embedded to resin, make cross section smoothed thus, utilize the photo of having taken by scan microscope (1000 times of multiplying powers) to estimate perpendicular to the surface of filming.On photo, cover the slide be used for OHP, critically behind scanning boundary face concavo-convex; As shown in Figure 3; Direction along the average line of boundary face curve is only extracted datum length l, is the X axle with the direction along the average line of this extraction part, is the Y axle along vertical multiplying power direction; During with y=f (x) expression border curve, the value that will obtain through number l is as the Ra of boundary face.Moreover, in the application invention, be decided to be the mean value that adopts the Ra that above-mentioned method measured for the cross section arbitrarily in filming 5 positions.

$\mathrm{Ra}=\frac{1}{l}{\&Integral;}_0^l\left|f\left(x\right)\right|\mathrm{dx}$

(control method of the Ra of boundary face)

The Ra of the boundary face of high concentration coat of colo(u)r and last coating can form viscosity and surface tension under the low-shearing force of coating of usefulness through the coating process of high concentration coat of colo(u)r and last coating, pigment type (the low-refraction particle of Titanium Dioxide Rutile Top grade, silica etc. etc.), high concentration coat of colo(u)r and the last coating of concentration, high concentration coat of colo(u)r of pigment (Titanium Dioxide Rutile Top grade) in the high concentration coat of colo(u)r and wait and control.Moreover the high concentration coat of colo(u)r in so-called this exploitation and the boundary face of last coating are meant boundary face (boundary line) visually visible when utilizing light microscope or electron microscope to take the cross section of filming.

Specifically; Method as the Ra of the boundary face that is used to increase high concentration coat of colo(u)r and last coating has following method etc.: (1) be employed in range upon range of high concentration coat of colo(u)r under the undried state form the coating of usefulness and coating that last coating forms usefulness, so-called wet-on-wet or multilayer rubbing method simultaneously; (2) pigment concentration in the last coating improves the pigment (Titanium Dioxide Rutile Top grade etc.) in the high concentration coat of colo(u)r; (3) in the high concentration coat of colo(u)r, add the big particle (silica etc.) of particle diameter; (4) the high concentration coat of colo(u)r under the reduction low-shearing force forms the viscosity of the coating of usefulness; (5) reducing the high concentration coat of colo(u)r, to form the surface tension of the coating of usefulness and the coating that last coating forms usefulness poor.

At first; For above-mentioned method (1); Form the coating of usefulness and the coating of last coating formation usefulness through range upon range of high concentration coat of colo(u)r under undried state; The Titanium Dioxide Rutile Top grade particle plays a role in boundary face from the make progress power of coating diffusion of high concentration coat of colo(u)r thus, and the Ra that is coated with the boundary face of rete becomes big.At this moment; As method (2); Be made as high concentration, particularly be made as concentration more than the closeest filling through concentration the Titanium Dioxide Rutile Top grade in the high concentration coat of colo(u)r; It is big that the concentration difference of itself and last coating film becomes, and the make progress power of coating diffusion of Titanium Dioxide Rutile Top grade acts on consumingly, so the Ra of boundary face becomes bigger.

In addition; For method (3),, the particle of this big particle diameter is present near the boundary face of high concentration coat of colo(u)r and last coating through in the high concentration coat of colo(u)r, adding the big particle of particle diameter; Form concavo-convex that particle by big particle diameter causes in boundary face, so the Ra of boundary face becomes big.At this moment; As method (1); Form the coating of usefulness and the coating of last coating formation usefulness through range upon range of high concentration coat of colo(u)r under undried state; The particle of big particle diameter is from the coating diffusion that makes progress of high concentration coat of colo(u)r, and the particle of therefore big particle diameter is present near the boundary face of high concentration coat of colo(u)r and last coating easily.

In addition, for method (4), through reducing the viscosity that low-shearing force high concentration coat of colo(u)r down forms the coating of usefulness, the Titanium Dioxide Rutile Top grade in the high concentration coat of colo(u)r is upwards coating diffusion easily, so the Ra of boundary face becomes greatly.Promptly; Opinion according to present inventors; Add the coating of particulate (under this situation, being Titanium Dioxide Rutile Top grade) to become concentration such more than the closeest filling after drying, the curing, become the non-newtonian fluid that is commonly referred to as dense disperse system coating; Become when utilizing rotary viscosity design determining viscosity, have the coating of so-called shear thinning (shear thinning) characteristic that viscosity is high, viscosity is low when height rotates when low rotation.In dense disperse system coating, because the distance between the pigment particles in the coating is short, therefore molecular separating force is had an effect between particle.Therefore, the shearing force that when low rotation, puts on coating is little, and therefore the viscosity that influences through this molecular separating force uprises.On the other hand, the shearing force that when height rotates, puts on coating becomes big, if this shearing force surpasses molecular separating force then viscosity.In the application operability during in base material with such paint spraying, high rotation viscosity down produces considerable influence to it, and on the other hand, low rotation viscosity down is to mobile generation considerable influence in the film of the coating in the drying after application, the baking-curing operation.Therefore, the dope viscosity that is adjusted under the low rotation is important to the control of the Ra of the boundary face of high concentration coat of colo(u)r and last coating.

At this,, can adjust through the quantity of solvent in the change coating and the maintaining requirement (between storage humidity and maintaining period) of coating for the dope viscosity under the low rotation.As the maintaining requirement of coating, storage humidity is high more, and is long more between maintaining period in addition, and then thixotropy is just low more, so the dope viscosity under the low-shearing force improves.The wetability of elongated then surface of pigments and coating improves between maintaining period if this is, more resin adsorption is in surface of pigments, so the molecular separating force between pigment weakens, so the thixotropy step-down.

In addition, also can adjust the dope viscosity under the low-shearing force through the additive that in coating, adds dispersant etc.

In addition, for method (5), to form the surface tension of the coating of usefulness and the coating that last coating forms usefulness poor if reduce the high concentration coat of colo(u)r, and under drying regime not range upon range of these coating, side by side carry out drying and baking-curing, then the Ra of boundary face becomes big.But; It is poor that the high concentration coat of colo(u)r forms the surface tension of the coating of usefulness and the coating that last coating forms usefulness, according to different, the suitable value difference of the resin kind of each layer and solvent species etc.; Therefore can not stipulate entirely, need confirm optimum value the investigation in advance of each coating.At this, the surface tension of coating can be adjusted through the additive that uses levelling agent, antifoaming agent etc. to be commonly referred to as surfactant, also can adjust through changing solvent types.

Yet; In the coating metal material that this embodiment relates to; Need the center line average roughness Ra of the boundary face of high concentration coat of colo(u)r and last coating be made as more than the 0.8 μ m; As the effective method that is used for this; Can be exemplified below the method for stating: in the high concentration coat of colo(u)r, become the Titanium Dioxide Rutile Top grade that mode more than the closeest filling is added particle diameter 200nm～400nm with the volume with respect to dried coating, range upon range of this high concentration coat of colo(u)r forms to form with last coating with coating and use coating under undried state, drying, curing side by side under range upon range of state.Through in the high concentration coat of colo(u)r, adding the Titanium Dioxide Rutile Top grade more than the closeest filling; And it is range upon range of under drying regime not with last coating; Produce the concentration gradient of Titanium Dioxide Rutile Top grade particle at the interlayer of respectively filming, produce the make progress effect of coated side diffusion of Titanium Dioxide Rutile Top grade particle in the high concentration coat of colo(u)r, and then in dry, curing process, apply heat; Therefore this heat becomes driving force, and it is remarkable that the effect that Titanium Dioxide Rutile Top grade will spread becomes.On the other hand,, then cause the cross-linking reaction that forms the resin of filming, therefore produce the mobile effect of the inter-level diffusion that suppresses the Titanium Dioxide Rutile Top grade particle if in drying, curing process, apply heat.Therefore, the boundary face of high concentration coat of colo(u)r and last coating becomes coarse state, and it is big that Ra becomes.

In addition; Through the following coating film layer that high concentration coat of colo(u)r that this embodiment relates to is used as coating is set, the Ra that can make the boundary face of high concentration coat of colo(u)r and last coating is more than the 0.8 μ m, as above-mentioned (4); When the Ra of the boundary face of controlling high concentration coat of colo(u)r and last coating; Dope viscosity influence under the low-shearing force is bigger, through reducing the dope viscosity under the low-shearing force, can further increase the Ra of the boundary face of high concentration coat of colo(u)r and last coating.

[mixed layer]

In the coating metal material that this embodiment relates to; Use coating through adopting the rubbing method application high concentration coat of colo(u)r formation simultaneously of wet-on-wet or multilayer to form with coating and last coating; The high concentration coat of colo(u)r forms with the Titanium Dioxide Rutile Top grade in the coating thus; The interface that surpasses each layer coating that makes progress forms and spreads down with coating, therefore at the near interface of high concentration coat of colo(u)r and last coating, forms the concentration gradient layer of Titanium Dioxide Rutile Top grade.In the present invention, the concentration gradient layer with this titanium oxide is called mixed layer.Under this situation, the mixed layer of the boundary member through being present in high concentration coat of colo(u)r and last coating can make the adhesiveness between high concentration coat of colo(u)r and the last coating improve.In addition, under the situation that is precoated metal materials, the processing of the full light reflectance of coating metal material after because of application sometimes reduces, but through there being mixed layer, adhesiveness improves, the reduction of the full light reflectance after therefore can suppressing to process.

(definition of mixed layer)

At this, " mixed layer " that so-called this embodiment relates to is meant that the Titanium Dioxide Rutile Top grade through the high concentration coat of colo(u)r upwards is coated with the rete diffusion, and the concentration of Titanium Dioxide Rutile Top grade becomes the layer of inclination (gradient) structure.More particularly, in this embodiment, if be conceived to Titanium Dioxide Rutile Top grade, when the Ti amount note of the Ti amount note of high concentration coat of colo(u)r being made x, will go up coating is made y, with the part of [x+0.05 * (x-y)]～[y-0.05 * (x-y)] as mixed layer.The analytical method of stating after each Ti amount can adopt is obtained, and can the mensuration intensity amount of regarding as when utilizing each analyzer to measure Ti calculate.

Moreover, sometimes after form mixed layer between the priming coat stated and the high concentration coat of colo(u)r, under this situation, the definition of mixed layer and the definition of boundary face, and the mixed layer between high concentration coat of colo(u)r and the last coating is same.

In the high concentration coat of colo(u)r, contain under the situation of low-refraction particle; The low-refraction particle is with respect to the volume ratio of Titanium Dioxide Rutile Top grade; If the low-refraction particle is for example inorganic pigment, then can be through obtaining with the same operation of the volumetric concentration of obtaining Titanium Dioxide Rutile Top grade.With the difference of Titanium Dioxide Rutile Top grade be; For example; Can use that Titanium Dioxide Rutile Top grade does not dissolve and only dissolves the medicine of the acid etc. of low-refraction particle among the heating nubbin, only dissolve the low-refraction particle, from the quality of obtaining the low-refraction particle of poor quality of dissolving nubbin and heating nubbin; From this quality and low-refraction Particle Density, can obtain the volume of low-refraction particle.

On the other hand; At the low-refraction particle for example as resin bead under the diverse situation of the transmittance of electron beam and Titanium Dioxide Rutile Top grade; Have and utilize scanning electron microscope to observe to be coated with the cross section of rete or utilize ultramicrotome (microtome) etc. to cut to get to be coated with rete, utilize transmission electron microscope (about 10000 times of multiplying powers) to its method of observing etc. than unfertile land.Specifically, can obtain through counting quantity of certifiable Titanium Dioxide Rutile Top grade and low-refraction particle in the visual field.But, when quantity after a little while error become big, therefore preferably have the quantity of the scope counting particle more than 100 at Titanium Dioxide Rutile Top grade at least.

In addition; Electron beam transmittance and Titanium Dioxide Rutile Top grade at the low-refraction particle not too have difference; Be difficult to know under the condition of different of low-refraction particle and Titanium Dioxide Rutile Top grade under scanning electron microscope and the transmission electron microscope; Can confirm to form, obtain the ratio of Titanium Dioxide Rutile Top grade and other low-refraction particle from the composition of confirming at the element in the cross section that is coated with rete.The element composition can use EPMA (electron probe microanalyzer), GDS (glow discharge emission spectrographic analysis device) etc. to confirm.

(thickness of mixed layer)

In this embodiment, under the situation that has above-mentioned mixed layer, this mixed layer preferably has the thickness of 3 μ m～12 μ m.Thickness at mixed layer is lower than under the situation of 3 μ m, the anxiety that has the high concentration coat of colo(u)r that can not stably obtain being caused by mixed layer and the adhesiveness between the last coating to improve effect.On the other hand, if the thickness of mixed layer surpasses 12 μ m, then be difficult to guarantee fully to share the high concentration coat of colo(u)r of necessary function and the thickness of filming of last coating.Therefore; In last coating is under the situation on top layer; Bad order that thickness deficiency by top layer causes etc. takes place easily; Be difficult to keep the performance of high concentration coat of colo(u)r and last coating itself, become in fact and form with what coating and last coating formed that coating with coating forms and be coated with the identical performance of rete through mixing the high concentration coat of colo(u)r, thus can not get need original high concentration coat of colo(u)r and the performance of last coating.Moreover, the THICKNESS CONTROL of mixed layer is come down to difficulty for the thickness that surpasses 12 μ m.

(the Determination of thickness method of mixed layer)

The thickness of mixed layer can be obtained through the distribution of film thickness direction of analyzing the high concentration coat of colo(u)r or going up the composition that only any one comprised of coating.As analytical method; Can use known analytical method; For example can utilize * * X ray probe-microanalyser, electron probe microanalyzer (EPMA), x-ray photoelectron spectroscopy analysis (XPS), Auger electron spectroscopy analysis (AES), glow discharge optical emission spectrometry analysis (GDS) * * to wait the concentration of element of analyzing the depth direction of filming; The thickness of mixed layer is obtained in the perhaps constituent analysis through the cross section of filming from the CONCENTRATION DISTRIBUTION of the composition that becomes object.The kind of the constituent analysis that is suitable for and method can be according to thickness, becomes component to wait suitable selection to carry out.Even the method beyond EPMA, XPS, AES, the GDS so long as can carry out the method for the constituent analysis of depth direction, also can suitably be selected.Moreover, as operable composition in the analysis of mixed layer, also can be the composition beyond the Ti.Among this analytical method, on one side GDS analyze in the depth direction sputter on one side from the argon ion of the surface by utilizing inertia of filming, can precision the concentration of the depth direction of comparative measurements element well, therefore preferred.The thickness of the mixed layer in the application invention is for 5 average thickness that the position is measured arbitrarily.

(control method of the thickness of mixed layer)

The thickness of mixed layer can mainly be controlled through coating process, stoving time.Through adopt wet-on-wet, multilayer rubbing method simultaneously as coating process, mixed layer forms easily.In addition, be used for the time that mixed layer forms through prolonging stoving time, can prolonging fully, therefore can increase the thickness of mixed layer, specifically, through stoving time being made as about 60 seconds～180 seconds, the thickness that can make mixed layer is 3 μ m～12 μ m.

In addition; In order to form stable mixed layer; Preferably: the high concentration coat of colo(u)r that control forms mixed layer forms poor (the Δ σ=σ 2-σ 1) that form with the surface tension (σ 2) of coating with the surface tension (σ 1) of coating and the last coating that forms mixed layer makes it become 0.5～8mN/m, and the high concentration coat of colo(u)r formation of control formation mixed layer makes it with the last coating formation of the viscosity (φ 1) of coating and formation mixed layer with poor (the Δ φ=φ 2-φ 1) of the viscosity (φ 2) of coating and becomes-100～4000mPas.Like this; Through corresponding to the kind of coating and application condition with the high concentration coat of colo(u)r that forms mixed layer and go up the surface tension of coating material and the relation of viscosity suitably is adjusted into the suitable value in the above-mentioned condition; Also can carry out the generation of stable mixed layer and the control of thickness, and then the most surperficial shape of control.

That is, through make Δ σ be below the 8mN/m, or to make Δ φ be below the 4000mPas, can form the mixed layer of thickness sufficient, so interlayer adhesion improves further.On the other hand, through make Δ σ be more than the 0.5mN/m, or make Δ φ for-more than the 100mPas, the thickness of high concentration coat of colo(u)r and last coating becomes sufficient thickness, and the shape on surface also becomes suitable, can more stably guarantee performance.Moreover in this embodiment, the platinum loop czochralski method that the surface tension of coating can be employed under 20 ℃ is measured (about the details of such surface tension test, can " take turns around-France " according to JIS.K.3362.8.4.2 and carry out).In addition, dope viscosity can use Brookfield viscometer, under 20 ℃, * * 6mpm**, measures (about the details of such viscosimetric analysis, can " adopt the viscosity measurement of single cylindrical shape rotation viscometer " according to JIS.Z.8803.8 and carry out).

Moreover, when adjusting the surface tension of coating, preferably utilize surfactant (also comprising antifoaming agent, levelling agent).As surfactant, can use known surfactant, as commercially available article, the エ Le マ ゲ Application of the BYK-333 of known BYK company, BYK-307, KAO. Corp. SA etc. also have much in addition, can suitably add according to paint ingredient.In addition, can also adopt dilution or the method for mixing beyond the surfactant of other solvents etc. is carried out the capillary adjustment of coating.Moreover if surface tension is excessive, therefore the possibility that then has coating to worsen preferably all is made as the surface tension of high concentration coat of colo(u)r with coating, last coating material below the 40mN/m.

In addition, during the viscosity of adjustment coating, preferably utilize tackifier (comprising rheology adjustment agent, viscosity modifier).As tackifier, can use known tackifier, as commercially available article, the BYK-411 of known BYK company, BYK-425 etc. also have much in addition, can suitably add according to paint ingredient.In addition, can also adopt dilution or mix other solvents, or make the method beyond the tackifier of ratio increase etc. of solid constituent carry out the adjustment of the viscosity of coating.

In addition, the thickness of mixed layer can be controlled with the difference of the pigment concentration in pigment concentration in the coating and the last coating material through adjustment high concentration coat of colo(u)r.That is, big if the difference of pigment concentration becomes, then pigment accelerates from the make progress diffusion velocity of coating of high concentration coat of colo(u)r, therefore can be dry with coating and last coating material at the high concentration coat of colo(u)r, solidify before the mixed layer of formation thickness sufficient.

(about the most surperficial percent ripple (fluctuating))

In the coating metal material that this embodiment relates to, the most surperficial filtering center line percent ripple W of preferred coating _CABe below the 2 μ m.Through reducing the most surperficial W of coating in this wise _CA, can improve the definition of coating metal material, and obtain not having tiny concavo-convex smooth surface, so polluter is difficult to accumulate at the coating metal material surface, therefore can improve stain resistance.If the most surperficial W of coating _CASurpass 2 μ m, the anxiety of definition and stain resistance reduction is then arranged.On the other hand, for the W on surface of coating _CAThe preferred lower limit value do not need special qualification, but make the W on surface of coating _CABe lower than 0.2 μ m and be difficult to control in fact, therefore from such viewpoint, the most surperficial W of preferred coating _CABe below the 0.2 μ m.Moreover, the W of the application's invention _CA, be decided to be the mean values of measuring for 5 positions arbitrarily.

Moreover, in that this is said " coating surface ", be meant the surface that is coated with rete on the top layer in the coating.For " top layer be coated with rete ", as above-mentioned, be meant the last coating that this embodiment relates to, perhaps, on the top layer of last coating side further range upon range of when being coated with rete, be meant that this is coated with rete.

(the most surperficial W _CAControl method)

The most surperficial W of coating _CABecause of the influence of the Ra of the boundary face of high concentration coat of colo(u)r and last coating changes.Therefore, the most surperficial W of coating _CAMainly control through the dope viscosity under coating process, the low-shearing force.Specifically, be wet-on-wet, multilayer rubbing method simultaneously through making coating process, Titanium Dioxide Rutile Top grade is from the coating diffusion that makes progress of high concentration coat of colo(u)r, and therefore, it is big that the Ra of the boundary face of high concentration coat of colo(u)r and last coating becomes, the W on the surface of coating _CAAlso become big.In addition, through reducing the dope viscosity that low-shearing force high concentration coat of colo(u)r down forms usefulness, the upwards coating diffusion easily that becomes of the Titanium Dioxide Rutile Top grade in the high concentration coat of colo(u)r, so the Ra of boundary face becomes big, the most surperficial W of coating _CAAlso become big.

As above-mentioned,, preferably bigger for the Ra of the boundary face of high concentration coat of colo(u)r and last coating; The most surperficial WCA for coating; Preferably less, therefore, preferred: the balance of considering both confirms that the high concentration coat of colo(u)r under the low-shearing force forms the desired value of the dope viscosity of usefulness.

[giving of the water proofing property of being filmed in top layer, grease proofness]

In addition, in the coating metal material that this embodiment relates to, be formed at the rete that is coated with on top layer among the coating on the metal material, also can contain silicones or fluororesin.At this, so-called " top layer be coated with rete ", to form under the situation on top layer be coating on this to coating on above-mentioned, also range upon range of to have under the situation that is coated with rete be that this is coated with rete to side on the top layer of last coating.Be applied under the situation of precoated metal sheet at the coating metal material that this embodiment is related to, worry reduction by the full light reflectance that causes adhering to of the dirt that adds man-hour etc.Be directed to this; The part of the adhesive that is coated with rete on the top layer through the coating metal material that relates to as this embodiment or all use silicones or fluororesin can be given grease proofness (dialling oiliness, grease resistance) and water proofing property (water-repellancy, water-resistance) to film coated surface.The surface that is coated with rete on surface becomes grease proofness and water proofing property through making like this, and dirt is difficult to be attached to film coated surface, and the reduction of full light reflectance is suppressed, and is therefore preferred.

As the method that contains silicones or fluororesin in the rete that is coated with that makes above-mentioned top layer, being coated with method that rete adds silicones or fluororesin, using the method that contains the material of silicones or fluororesin as main resin of oriented top layer.

As the silicones that adds in the rete that is coated with on top layer; In commercially available article; " BYK (registration mark)-306 " of known for example BYK corporate system, " BYK (registration mark)-378 " etc. are as the fluororesin in the rete that is coated with that adds top layer to, in commercially available article known for example BYK corporate system " BYK (registration mark)-340 " etc.; Other also have a lot, can suitably add according to paint ingredient.

In addition; As the main resin that comprises silicones or fluororesin; (for example can use commercially available polysiloxanes-acrylic copolymeric resin; East Asia Synesis Company system " サ イ マ Star Network (registration mark) " series, " レ ゼ ダ (registration mark) " series, ト Network シ キ corporate system " SQ (registration mark) 100 etc.), commercially available polysiloxanes-fluorine copolymer resins (for example, Fuji changes into industrial group's system " ZX-001 " etc.).

In addition, above-mentioned polysiloxanes-acrylic copolymeric resin or polysiloxanes-fluorine copolymer resins also can use general known crosslinking agent, for example isocyanates, melmac to carry out crosslinked as required.Under this situation; As isocyanates; General commercially available product be can use, バ イ エ Le corporate system " ス ミ ジ ユ one Le (registration mark) " series, " デ ス モ ジ ユ one Le (registration mark) " series, the military field of Mitsui ケ ミ カ Le corporate system " タ ケ ネ one ト (registration mark) " series etc. for example firmly changed.As melmac; Can use general commercially available product, for example Mitsui サ イ テ Star Network corporate system " サ イ メ Le (registration mark) " series, " マ イ コ one ト (registration mark) " series, big Japanese イ Application キ chemical industrial company's system " ベ Star カ ミ Application (registration mark) " series, " ス one パ one ベ Star カ ミ Application (registration mark) " series etc.

As above-mentioned, the coating metal material that contains silicones or fluororesin in the rete that is coated with on top layer except the purposes of the reflecting plate of ligthing paraphernalia, also is fit to be applied to the purposes of indoor ceiling, wall material etc.In addition; Being coated with under the situation in the purposes that the coating metal material that contains silicones or fluororesin in the rete is applied to indoor ceiling, wall material etc. of top layer; Because therefore indoor ceiling, the effect that wall material itself is also born reflecting plate can make indoor bright with light quantity still less.

[hydrophilic the giving of being filmed in top layer]

In addition, in the coating metal material that this embodiment relates to, be formed at the rete that is coated with on top layer among the coating on the metal material, also can in the resin matrix that formation is filmed, have-the Si-O-Si-key.At this, so-called " top layer be coated with rete ", to form under the situation on top layer be coating on this to coating on above-mentioned, also range upon range of to have under the situation that is coated with rete be that this is coated with rete to side on the top layer of last coating.In addition, the Si in-Si-O-Si-key derives from the hydrolytic condensate of alkoxy silane or alkoxy silane.

Be applied under the situation of precoated metal sheet at the coating metal material that this embodiment is related to, worry reduction by the full light reflectance that causes adhering to of the dirt that adds man-hour etc.Be directed to this; Middle formation-the Si-O-Si-that films on the top layer through the coating metal material that relates at this embodiment; Even it contains the Si of the hydrolytic condensate that derives from alkoxy silane or alkoxy silane, can not damage gloss and the machinability on surface thus and give hydrophily film coated surface.Like this, be hydrophily through the surface that is coated with rete that makes top layer, the attachment that will be attached to film coated surface easily waits through the water wiping to be wiped, and the reduction of full light reflectance is suppressed, and is therefore preferred.

For formation-Si-O-Si-key in the resin matrix of filming in formation, the hydrolytic condensate of preferably in the coating that forms usefulness of filming on this top layer, adding alkoxy silane or alkoxy silane.As using alkoxy silane this moment; Can enumerate general known alkoxy silane, for example tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, MTMS, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, dimethoxy diethoxy silane, dimethoxy dipropoxy silane etc.In addition, as the hydrolytic condensate of alkoxy silane, can give an example as more than the hydrolytic condensate of illustrative alkoxy silane.

As above, in the filming of top layer, formed-the coating metal material of Si-O-Si-, except the purposes of the reflecting plate of ligthing paraphernalia, also be fit to be applied to the purposes of indoor ceiling, wall material etc.In addition; To in the filming of top layer, form-the coating metal material of Si-O-Si-is applied under the situation of purposes of indoor ceiling, wall material etc.; Because therefore the effect that indoor ceiling and wall material itself are also brought into play reflecting plate can make indoor bright with light quantity still less.

[thickness that is coated with rete on top layer]

Moreover; The coating metal material that relates to when this embodiment; What side also had top layer on the top layer of last coating (for example is coated with rete; The above-mentioned rete that is coated with that contains being coated with rete, in the resin matrix that formation is filmed, having of silicones or fluororesin-Si-O-Si-key) under the situation; For the thickness that is coated with rete on this top layer, so long as can obtain just not special qualification of degree of the characteristic of above-mentioned water proofing property, grease proofness, hydrophily etc., the thickness that is coated with rete on preferred top layer is 1 μ m～25 μ m.If the thickness that is coated with rete on above-mentioned top layer is lower than 1 μ m, water proofing property, grease proofness, possibility that hydrophily is not enough are then arranged, if surpass 25 μ m, the possibility of machinability difference is arranged then, and not preferred from the cost aspect yet.

[priming coat] (summary)

The coating that the coating metal material that this embodiment relates to has except the high concentration coat of colo(u)r of above explanation with the last coating, can also contain priming coat.This priming coat is the rete that is coated with that is formed between metal material and the high concentration coat of colo(u)r, on coating is served as reasons under the situation of coating, high concentration coat of colo(u)r and these 3 layers of formations of priming coat, becomes and the rete that is coated with as the immediate side of the metal material of base material.But; Under this situation; Even layer apart from the nearest side of metal material; The coating that is lower than 1 μ m with the thickness that the metal material and the adhesiveness of filming improve and corrosion resistance rises to the purpose setting is not equivalent to the priming coat that this embodiment relates to yet, and the coating of top layer side of coating that thickness is lower than 1 μ m is as priming coat.

(adhesive)

Not special qualification of resin of using as the adhesive of priming coat, but from the viewpoint of the adhesiveness of high concentration coat of colo(u)r, commonization of coating raw material etc., preferably contain the resin identical and use with the high concentration coat of colo(u)r.Therefore, preferably using number-average molecular weight from the adhesive as the high concentration coat of colo(u)r is 19000～28000 mylar A, in priming coat, also preferably uses mylar A as adhesive.The number-average molecular weight of the mylar that uses as the adhesive of priming coat is lower than at 19000 o'clock; The anxiety that machinability and adhesiveness reduction are arranged; If number-average molecular weight surpasses 28000, then film coated surface becomes too soft, and the anxiety of scratch resistance and anti-adhesive deterioration is arranged.

Moreover; For the addition of mylar A to priming coat; If the mylar A concentration all with respect to adhesive resin is more than the 80 quality %; Then can bring into play and improve machinability and adhering effect, the therefore preferred concentration that mylar A is all with respect to adhesive resin is made as more than the 80 quality %.

(pigment)

Count 20%～35% Titanium Dioxide Rutile Top grade as pigment if in priming coat, add by the solid constituent volumetric concentration, then reflectivity improves more, thereby preferred.Reason as the preferred Titanium Dioxide Rutile Top grade of pigment that adds to priming coat; With the occasion of high concentration coat of colo(u)r be same; Because other general employed pigment of the refractive index ratio of Titanium Dioxide Rutile Top grade are high; Resin that can increase and use as adhesive and the refringence that is present in the air of the gap between pigment particles thus, can improve the light reflectivity at interface of interface, pigment and the air of pigment and resin.

Average grain diameter at this Titanium Dioxide Rutile Top grade of the occasion of using Titanium Dioxide Rutile Top grade as pigment; Its hour surface area change of per unit volume is big; Area as the interface of the resin of light reflection surface or space and pigment becomes big, and therefore full light reflectance also uprises, if but the average grain diameter of pigment is too small; Then long wavelength's light transmission, therefore full light reflectance reduces.Therefore, with the occasion of high concentration coat of colo(u)r likewise, the average grain diameter of the Titanium Dioxide Rutile Top grade that uses as the pigment in the priming coat is preferably 200nm～400nm, more preferably 250nm～350nm.

(thickness)

For the thickness of priming coat, thickness is thick more, then can obtain high more machinability and adhesiveness; And; Having added as pigment under the situation of Titanium Dioxide Rutile Top grade,, also be that thickness is thick more favourable more for reflecting properties; Therefore from these aspect of performances, need not set the higher limit of the thickness of priming coat.But, then different if the thickness of priming coat surpasses 30 μ m with the high concentration coat of colo(u)r, because the pigment concentration in the coating is low, therefore when application, be easy to generate convexity, the coating deterioration, and, not preferred from the viewpoint of coating cost yet.Therefore, the thickness of priming coat is preferably below the 30 μ m.On the other hand, when the thickness of priming coat was lower than 5 μ m, the raising effect of machinability, adhesiveness and the reflecting properties that is brought by priming coat diminished, so the thickness of priming coat is preferably more than the 5 μ m.From guaranteeing the viewpoint of stable machinability, adhesiveness, reflection characteristic and coating, the thickness of preferred priming coat is 10 μ m～25 μ m.

[base material (metal material)]

Metal material as the base material that is used for the coating metal material that this embodiment relates to can use general known metal material or alloy material.Specifically, as metal material, can enumerate for example steel plate, corrosion resistant plate, aluminium sheet, aluminium alloy plate, titanium plate, copper coin etc.Also can apply coating on the surface of these metal materials or alloy material.As the kind of coating, can enumerate zinc coat, aluminium coated, copper plate, nickel coating etc., also can be their alloy layer.In addition; Using under the situation of steel plate as metal material, can use hot-dip galvanized steel sheet, plated steel sheet, zinc-plated-nickel alloy steel plate, alloyed hot-dip galvanized steel plate, aludip, aluminize-the general known steel plate and the clad steel sheets such as steel plate of kirsite.

In addition,, the surface of the metal material that uses in this embodiment handles if being implemented chemical conversion, then raisings such as metal material and the adhesiveness that is coated with rete and corrosion resistance, so more preferably.Handle as such chemical conversion; Can use the processing of generally being implemented; Specifically, for example can use trbasic zinc phosphate is that chemical conversion processing, chromate-free are that chemical conversion processing, application type chromate are handled, the electrolysis chromic acid is handled, react chromate processing etc.Wherein, the application type chromate is handled, the electrolysis chromic acid is handled, the reaction chromate is handled owing to containing 6 valency chromium as the carrying capacity of environment material, and is therefore not too preferred.In addition, trbasic zinc phosphate is that chemical conversion is handled, and compares the anxiety that the processing poor adhesion is also arranged with other processing.Therefore, handle as the chemical conversion that the metal material that this embodiment is related to is implemented, preferred chromate-free is to handle.

As chromate-free is that chemical conversion is handled, and the processing of the chemical conversion treating agent that uses inorganic system is arranged and use the processing of the chemical conversion treating agent of organic system, but any processing can.Specifically; As chromate-free is that chemical conversion is handled; Known use contains the processing of aqueous solution of for example silane coupling agent, zirconium compounds, titanium compound, tannin or tannic acid, resin, silica etc. etc., the technique known that also can use japanese kokai publication sho 53-9238 communique, japanese kokai publication hei 9-241576 communique, TOHKEMY 2001-89868 communique, TOHKEMY 2001-316845 communique, TOHKEMY 2002-60959 communique, TOHKEMY 2002-38280 communique, TOHKEMY 2002-266081 communique, TOHKEMY 2003-253464 communique etc. to be put down in writing.In addition; In these chemical conversions were handled, the 3 valency chromium that can use the chromate inorganic agent " ZM-1300AN " of for example Japanese パ one カ ラ イ ジ Application グ corporate system, the chromate-free chemical conversion treating agent " CT-E300N " of Japanese パ one カ ラ イ ジ Application グ corporate system, Japanese ペ イ Application ト corporate system were the commercially available chemical conversion treating agent of chemical conversion treating agent " サ one Off コ, one ト (registration mark) NRC1000 " etc.

[for back matel coated material]

In above explanation, mainly based on the example shows that is applied to precoated metal materials the present invention, but the invention is not restricted to precoated metal materials, also can be applied to back matel coated material.Under the situation of back matel coated material, different with precoated metal materials, may not require to process adhesiveness etc., but under situation about using, need have high full light reflectance as reflecting plate.

Under the situation of back matel coated material; Through in the high concentration coat of colo(u)r, adding low-refraction particle with particle diameter bigger than Titanium Dioxide Rutile Top grade; If the solid component concentration of this low-refraction particle is high, the Ra that then can make the boundary face of high concentration coat of colo(u)r and last coating is more than the 0.8 μ m.In addition; After having formed the high concentration coat of colo(u)r on the metal material after the processing; Surface physics ground at the high concentration coat of colo(u)r that forms adds cut etc., and roughening makes surperficial Ra become more than the 0.8 μ m, thereafter; Even coating material in the coating, the Ra that also can make the boundary face of high concentration coat of colo(u)r and last coating are more than the 0.8 μ m.

< for the manufacturing approach of coating metal material >

More than, the formation of the coating metal material that relates to for this embodiment at length is illustrated.Then, at length explain for the manufacturing approach of the coating metal material of formation with above-mentioned that kind.

The manufacturing approach of the coating metal material that this embodiment relates to; Be to form the two-layer at least coating comprise the high concentration coat of colo(u)r and the last coating of the top layer side that is laminated in the high concentration coat of colo(u)r to make that the center line average roughness Ra of boundary face of high concentration coat of colo(u)r and last coating is the method more than the 0.8 μ m, this high concentration coat of colo(u)r contains counts 35%～70% Titanium Dioxide Rutile Top grade by the solid constituent volumetric concentration.Below, being divided into situation that the coating metal material is a precoated metal materials and being the situation of back matel coated material, the details of the manufacturing approach of the coating metal material that this embodiment is related to describe.

[situation of precoated metal materials]

At first, describe for the manufacturing approach that at the coating metal material is the coating metal material that relates to of this embodiment under the situation of precoated metal materials.The processing that the paint line that the coating metal material that this embodiment relates to can be used through general continuous paint line (being called as " CCL "), cutting plate suitably selects needs, the processing of having implemented to select, manufacturing thus.Representational manufacturing process as paint line; Be " washing " → " drying " → " chemical conversion processing " → " drying " → " application " → " dry, baking " → " cooling " → " drying ", but the manufacturing process of the coating metal material in this embodiment is not limited to this.

In addition; The coating metal material that this embodiment relates to; Also can carry out application repeatedly by each coating and make through as carrying out usually with dry baking, but from the aspect of performance of each layer and the aspect of productivity ratio; Preferably: adopt multilayer to be coated with simultaneously or wet-wet mode, in the part of metal material surface or all be coated with the coating that the high concentration coat of colo(u)r forms usefulness and make with the coating that last coating forms usefulness.Equally; Side also has top layer to the coating metal material that relates to when this embodiment on the top layer of last coating (for example is coated with rete; The above-mentioned rete that is coated with that contains silicones or fluororesin) under the situation; Preferred adopt multilayer to be coated with simultaneously or wet-wet mode, metal material surface coating high concentration coat of colo(u)r form usefulness coating, on coating form usefulness coating and top layer be coated with the coating that rete forms usefulness.

Moreover; Metal material at this embodiment is that zinc is under the situation of clad steel sheet; Behind the plating process in continuous electroplating steel plate equipment or continuous hot-dipping galvanizing steel plate equipment; That utilization has is wet-wet coating equipment or simultaneously the production line of multi-layer coated equipment make, be coated with before can forming at the oxide scale film of metallized surfaces, can prevent the depression bad order that causes by oxide scale film.

At this; So-called multilayer is coated with simultaneously; Be that the parallel slit more than 2 etc. of curtain formula coating machine etc. through can being coated with machine or slip hopper formula from slit die is with the spue device of different coating of range upon range of mode; Coat base material under the state of a plurality of masking liquids of laminated at the same time, the method that the masking liquid that this is range upon range of side by side carries out drying, baking.

In addition, so-called wet-wet application, be in application on the base material behind masking liquid, further be coated with other masking liquids under the wet condition before this masking liquid drying above that, the method for the masking liquid of range upon range of multilayer is side by side dry, baking.Specifically; Method as wet-wet application; For example can enumerate following method etc.: the coating process that adopts roller coat, dipping, the mobile coating of curtain formula, the coating of roll-type curtain etc.; Application 1 layer be coated with rete after, before this is coated with rete in drying baking, more above that; Adopt the curtain formula to flow coating, the coating of roll-type curtain, the coating of slip hopper formula, slit die be coated with etc. can with the discontiguous state of base material under after the method for application implements the 2nd layer application, side by side dry, baking the method etc. of multilayer film of range upon range of wet condition.

In this embodiment; Carried out as baking side by side that multilayer is coated with simultaneously or the method for filming of wet-wet application; Can use general known coating to use oven, for example hot-air drying stove, full run-down type heating furnace, induction heater, infrared furnace or and used their stove etc.

Like this, be coated with the not masking liquid of drying regime simultaneously, mix a little, can form the mixed layer that the composition of each layer mixes thus, thus, interlayer adhesion is improved at the masking liquid of each layer of boundary portion of masking liquid through range upon range of ground.In addition, because the drying process that will be undertaken by each layer carries out uniformly in the past, be favourable aspect productivity ratio and the manufacturing cost therefore, and also having the so less advantage of drying equipment.

[situation of back matel coated material]

The manufacturing approach of the coating metal material that then, relates to for this embodiment of the situation of back matel coated material for the coating metal material describes.

The coating metal material that is coated with after the employing that this embodiment relates to; After the metal material as above-mentioned having been implemented chemical conversion processing etc.; After being shaped to the shape of illumination reflecting plate, the reflecting plate of luminous component or the reflecting plate of image displaying part etc. of the coating metal material that to be used embodiment relate to; Through after be coated with application, make thus.As the forming method of metal material, can use known method.In addition, as after the method that is coated with, can adopt the flow known method of application, brush painting, electrostatic spraying etc. of coating machine of spraying, dipping coating, employing curtain formula.In addition, under the situation of back matel coated material, also can wait the application of wetting-wet through spraying.

(summary)

In the electronic equipment of the coating metal material that uses this embodiment as described above to relate to; This coating metal material has high full light reflectance and mouldability concurrently high-levelly; Therefore brighter than in the past under the situation of same light source, and, even the quantity of light source is than lacked in the past; Or reduce and drop into power, also can guarantee and equal in the past lightness.In addition; The coating metal material that this embodiment relates to; Have and easily to be shaped to different shape, or to be shaped to the characteristic of complicated shape, therefore can expect the expansion of applicable electronic equipment object and effect that the productivity ratio of the parts used improves.

As the electronic equipment that can bring into play such characteristic, not special the qualification can be used in the reflecting plate of the reflecting plate that for example throws light on, luminous component or the reflecting plate of image displaying part etc.As their example more specifically, can enumerate ligthing paraphernalia, lamp decoration, AV (audiovisual) equipment, movable equipment, various displays etc., the reflecting plate in the reflecting plate that is preferred for throwing light on, the interior trim label, Backlight For Liquid Crystal Display Panels reflecting plate etc.

[embodiment]

Then, use embodiment that the present invention more specifically is described, but the present invention is not limited to following embodiment.

[coating]

At first, at length explain for the coating that uses in the present embodiment.In the present embodiment; As the coating metal material; Use is becoming the galvanized steel sheet surface of base material; Be coated with the pre-coated steel plate of following coating, the priming coat that this coating has had from this steel plate side stacked above one another, high concentration coat of colo(u)r (floating coat), go up the three-decker of coating, perhaps the four-layer structure of priming coat, floating coat, two-layer last coating.Below, describe for the paint ingredient that uses with coating (be called " in coating "), the order that goes up coating material (being called " coating ") with coating (being called " bottom-coating "), high concentration coat of colo(u)r (floating coat) by priming coat.

(bottom-coating)

For bottom-coating shown in below table 1; As adhesive; " バ イ ロ Application (registration mark) 630 " (number-average molecular weight 23000, hydroxyl value 5) of the amorphous polyester resin of corporate system spun in use as Japan; As pigment; Use that (refractive index: 2.5), 25% the mode of becoming with the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade is mixed with adhesive, has made bottom-coating (primary coat-1) as the former industry corporate system of the stone of the Titanium Dioxide Rutile Top grade of 280nm " タ イ ペ one Network (registration mark) CR95 " as average grain diameter.

Table 1

(in coating)

For in coating; As shown in table 1; As base resin, use as Japan spin corporate system amorphous polyester resin " バ イ ロ Application (registration mark) " series and as " デ ス モ Off エ Application (registration mark) " series of firmly changing the amorphous polyester resin of バ イ エ Le ウ レ タ Application corporate system.For example; In be coated with in-1～20, using will " バ イ ロ Application (registration mark) 630 " (number-average molecular weight 23000, hydroxyl value 5) and be dissolved in the material that organic solvent (solvent that ソ Le ベ Star ソ 150 and cyclohexanone are mixed with mass ratio at 1: 1) forms as " デ ス モ Off エ Application (registration mark) 690 " (number-average molecular weight 3500, hydroxyl value 46) of the amorphous polyester resin of firmly changing バ イ エ Le ウ レ タ Application corporate system at 1: 1 with mass ratio.Crosslinking agent; Solid constituent 100 mass parts with respect to mylar; " the サ イ メ Le (registration mark) 303 " of the commercially available Mitsui サ イ テ Star Network corporate system as hexa methoxy-methylated melamine of adding 15 mass parts; And then " キ ヤ タ リ ス ト (registration mark) 6003B " of the commercially available Mitsui サ イ テ Star Network corporate system as acidic catalyst of adding 0.5 mass parts, having obtained polyester thus is clear dope.

As Titanium Dioxide Rutile Top grade, use average grain diameter to be the former industry corporate system of the stone of 280nm " タ イ ペ one Network (registration mark) CR95 " (refractive index: 2.5).

In addition, as the low-refraction particle that in floating coat, contains, use Asahi Glass corporate system silica " サ Application ス Off エ ア (registration mark) H-31 " (average grain diameter 3 μ m).

In addition; 1.6), average grain diameter is zinc oxide " the micronized zinc oxide " (refractive index: 2.0) of the Sakai chemical industrial company system of 290nm as the comparative material of the pigment that in floating coat, contains, use average grain diameter to be the barium sulfate " BARIACE (registration mark) B-30 " of the Sakai chemical industrial company system of 300nm (refractive index:.

In addition, adjust between the storage humidity through change quantity of solvent and coating, maintaining period in dope viscosity under the low-shearing force of coating.Moreover, as the viscosity under the low-shearing force, adopt the Brookfield viscometer (model: the value of B-8L) under rotating speed 6rpm, measuring of using Tokyo gauge corporate system.

The details of coating in making are shown in below table 2.

(coating)

For coating; Use is shown in below table 3; As adhesive, use the amorphous polyester resin " バ イ ロ Application (registration mark) 630 " (number-average molecular weight 23000, hydroxyl value 5) that corporate system is spun by Japan to be dissolved in the material that organic solvent (solvent that ソ Le ベ Star ソ 150 and cyclohexanone are mixed with mass ratio at 1: 1) forms.Crosslinking agent; With respect to solid constituent 100 mass parts of mylar add the commercially available Mitsui サ イ テ Star Network corporate system of 15 mass parts complete alkyl type methylated melamine resin (below; Be called methylated melamine) " サ イ メ Le (registration mark) 303 "; And then " キ ヤ タ リ ス ト (registration mark) 6003B " of the commercially available Mitsui サ イ テ Star Network corporate system as acidic catalyst of adding 0.5 mass parts obtained clear dope thus.Use this clear dope; As pigment; Use average grain diameter to be the former industry corporate system of the stone of the Titanium Dioxide Rutile Top grade of 280nm " タ イ ペ one Network (registration mark) CR95 " (refractive index: 2.5); 25% the mode of becoming with the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade is mixed with adhesive, has made coating (on be coated with-1).

In addition; Also made: use with above-mentioned on be coated with-1 identical adhesive resin and pigment, and added with respect to the total of adhesive resin and pigment and measured the coating (on be coated with-2), coating that the fluorine that added the BYK company of 0.5 mass parts is additive B YK-340 (on be coated with-3) of silicon-type additive B YK-306 that 100 mass parts are the BYK company of 1 mass parts.

In addition; Base resin as adhesive; Using commercially available polysiloxanes-acrylic copolymeric resin is the polysiloxane-modified acrylic resin " サ イ マ Star Network (registration mark) US-380 " of East Asia Synesis Company system; As crosslinking agent, used the crosslinking agent that the methylated melamine " サ イ メ Le (registration mark) 303 " of the butylated melamine resins " ス one パ one ベ Star カ ミ Application (registration mark) J830 " of commercially available big Japanese イ Application キ chemical industrial company system and Mitsui サ イ テ Star Network corporate system has been mixed with mass ratio at 1: 1.These adhesive resins and crosslinking agent are pressed the solid constituent mass ratio mix at 100: 30, obtained clear dope (on be coated with-4).In addition, use this clear dope, with on be coated with-1 same; As pigment; Use " タ イ ペ one Network (registration mark) CR95 " of the former industry corporate system of stone, 25% the mode of becoming with the solid constituent volumetric concentration of Titanium Dioxide Rutile Top grade is mixed with adhesive, has made coating (on be coated with-5).

In addition, also made except using " the デ ス モ Off エ Application BL3175 (trade name) " firmly change バ イ エ Le ウ レ タ Application corporate system (below, be called HDI) as crosslinking agent in addition, with on be coated with-4,5 coating (on be coated with-6,7) likewise made.

In addition, also made except " ZX-001 " of polysiloxanes-fluorine copolymer resins of using industrial group of Fuji system as the base resin of adhesive, with on be coated with-4,5 coating (on be coated with-8,9) likewise made.

In addition, also made use with above-mentioned on be coated with-1 same adhesive resin and pigment, and added with respect to the total of adhesive resin and pigment and measured the coating that 100 mass parts are the tetraethoxysilane of 20 mass parts (on be coated with-10).

Moreover, on above-mentioned, be coated with in-1～10, as retarder thinner, all used by quality ratio cyclohexanone and ソ Le ベ Star ソ 150 by the solvent that mixes at 1: 1.

(precoated metal sheet)

Then, at length explain for the precoated metal sheet that uses in the present embodiment.

The hot-dip galvanized steel sheet " シ Le バ one ジ Application Network (registration mark) " (below, be called GI) of having prepared Nippon Steel Manufacturing Corp is as raw sheet.Use the plate of thickness of slab as 0.6mm.Use the plating adhesion amount to be single face 60mg/m ²Plate.

Then; With ready raw sheet through the degreasing of spraying of 2 quality % concentration, 50 ℃ of aqueous solution of the alkaline degreaser " FC-4336 " of Japanese パ one カ ラ イ ジ Application グ corporate system; Carry out drying after the washing; Thereafter " CT-E300N " that handles as the chromate-free chemical conversion of Japanese パ one カ ラ イ ジ Application グ corporate system through the roll coater coating is dry through hot-air oven.Drying condition in hot-air oven is that to make the arrival plate temperature of steel plate be 60 ℃.The adhesion amount of handling in chromate-free adheres to 200g/m by the total solids composition ²Mode carry out application.

Then; A face at the metallic plate of having implemented the chemical conversion processing; With the bottom-coating of producing is that the mode of 20 μ m is carried out application with roll coater with dried thickness; At another face; To be that the mode of 5 μ m is coated with roll coater with dried thickness as the grey of " FL100HQ " of the CB coating of Japanese Off ア イ Application コ one テ イ Application グ ス corporate system, using the induction heater that has been blown into hot blast thereafter be dry baking-curing under 230 ℃ the condition in the arrival plate temperature of metallic plate.And, after drying baking, with the metallic plate water spray from sprayer to application, carry out water-cooled.

Then; Use the curtain of slip hopper formula to be coated with machine; Be coated with the surface of rete in primary coat; Will in coating and coating side by side carry out the two-layer laminate application, the induction heater that use has been blown into hot blast is under 220 ℃ the condition in the arrival plate temperature of metallic plate, with the range upon range of side by side dry baking-curing of filming.And, after drying baking, with the metallic plate water spray from sprayer to application carry out water-cooled, made the precoated metal sheet (after, will the coating process in this step be called " coating process (i) ") of coating thus with three-decker.

In addition; As required; Use surface that roll coater is coated with rete to primary coat only 1 layer of application in coating, after above-mentioned main points baking, reuse 1 layer of coating of external coating that roll coater centering is coated with rete; By the baking of above-mentioned main points, made the precoated metal sheet (will the coating process in this step be called " coating process (ii) ") of coating with three-decker.

In addition; As required; Use the curtain of slip hopper formula to be coated with machine coating and coating in the application on primary coat is coated with rete, application coating on it again, thus carry out three folded layer by layer applications simultaneously; The induction heater that utilization has been blown into hot blast is under 220 ℃ the condition in the arrival plate temperature of metallic plate, with the range upon range of side by side dry baking-curing of filming.And, after the dry baking, with the metallic plate water spray from sprayer to application carry out water-cooled, made the precoated metal sheet (below, will the coating process in this step be called " coating process iii ") of coating thus with four-layer structure.

(evaluation method)

Then, the details to the evaluation method of the precoated metal sheet as above-mentioned, made describe.1) the full light reflectance of precoated metal sheet is measured

Use has been installed the instrument of integrating sphere reflection auxiliary equipment to the spectrophotometer " UV265 " of Shimadzu Seisakusho Ltd.'s corporate system, uses as datum plate the barium sulfate powder is pressed solidly the datum plate that forms.Be determined at as the full light reflectance under the 555nm of the highest wavelength of the susceptibility of human eye, estimate according to following benchmark.

◎: full light reflectance is the situation more than 99%

◎～zero: full light reflectance is more than 97% and is lower than 99% situation

Zero: full light reflectance is more than 95% and is lower than 97% situation

Zero～△: full light reflectance is more than 93% and is lower than 95% situation

△: full light reflectance is more than 91% and is lower than 93% situation

△～*: full light reflectance is more than 89% and is lower than 91% situation

*: full light reflectance is lower than 89% situation

2) briliancy of ligthing paraphernalia is measured

Fig. 1 and Fig. 2 represent the summary of experimental provision.With the lining substrate forming is the both ends longitudinally as depicted in figs. 1 and 2 shapes of lateral buckling upward, as reflecting plate 1.2 commercially available fluorescent illumination implements 2 are installed therein side by side, the cover 3 that is formed by frosted glass is installed above that.Vertically brightness photometer 6 is being set apart from measuring point apart from the place of 50cm; Measure this cover 3 middle body (below; Be called " briliancy determination part ") 4 and from squint the laterally briliancy of part (below, be called " the uniformity comparative measurements portion of briliancy ") 5 of 1.5cm of middle body 4.As fluorescent illumination implement 2, use 16 types, lamp power output fluorescent lamp as 16W.

The evaluation of briliancy is estimated through the briliancy determination part 4 of measuring cover 3.During mensuration, the light beyond the fluorescent illumination implement 2 is all isolated, measure the briliancy of the benchmark reflecting plate of producing as follows, relative therewith, measure the briliancy the when reflecting plate 1 that lining base material that use goes out makes has been installed.Then; Briliancy when the briliancy when utilizing the benchmark reflecting plate to measure is measured with the reflecting plate that utilizes the lining base material of producing 1; Be defined as luminance variations rate=([briliancy in the reflecting plate 1 of the lining base material that employing is produced]-[briliancy in the benchmark reflecting plate]) * 100/ [briliancy in the benchmark reflecting plate], estimate by following benchmark through the luminance variations rate.

◎: the luminance variations rate is the situation more than 30%

◎～zero: the luminance variations rate is more than 25% and is lower than 30% situation

Zero: the luminance variations rate is more than 20% and is lower than 25% situation

Zero～△: the luminance variations rate is more than 15% and is lower than 20% situation

△: the luminance variations rate is more than 10% and is lower than 15% situation

*: the luminance variations rate is lower than 10% situation

The benchmark reflecting plate is to make through the method for the coating of the high white color system of the application reflectivity of the means of the reflectivity on conduct raising reflecting plate surface in the past.Coating shown in the table 4 is adopted the same method made from above-mentioned primary coat coated plate, is that the mode of 10 μ m is carried out application with thickness after the drying, and dry solidification.Use above that roll coater once more with the described coating of table 4 with drying after thickness be the mode application of 20 μ m, using the induction heater be blown into hot blast is dry solidification under 230 ℃ the condition in the arrival plate temperature of metallic plate.And, after drying baking, with the metallic plate water spray from sprayer to application carry out water-cooled.

In addition; The inhomogeneity evaluation of briliancy is to measure the briliancy determination part 4 of cover and from the briliancy at two positions of the uniformity comparative measurements portion 5 of the briliancy of briliancy determination part 4 skew 1.5cm; Be defined as the uniformity=100-([briliancy of the uniformity comparative measurements portion 5 of briliancy]-[briliancy of briliancy determination part 4])/[briliancy of briliancy determination part 4] * 100 of briliancy, estimate by following benchmark with the uniformity of briliancy.

◎: the uniformity of briliancy is the situation more than 90%

Zero: the uniformity of briliancy is more than 85% and is lower than 90% situation

△: the uniformity of briliancy is more than 70% and is lower than 85% situation

*: the uniformity of briliancy is lower than 70% situation

3) machinability and adhesiveness

The precoated metal sheet of producing is clipped betwixt under the state of sample of any piece of number and carry out 180 ° of bending processes (adhesion bending machining),, investigated having or not of the crackle of filming with filming of visualization processing portion.Moreover, to carry out 180 ° of whens bending, the mode that becomes the crooked outside with the surface of precoated metal sheet bends, and adheres to bending (situation of general known not clamped sample is that 0T is crooked, and the situation of 1 piece of sample of clamping is that 1T is crooked).And, use the visualization processing portion, estimate by following benchmark.

◎ ◎: under the 0T bending, do not have crackle and peel off

◎: under the 1T bending, do not have crackle and peel off

◎～zero: under the 2T bending, do not have crackle and peel off

Zero: under the 2T bending a little crackle and/or peel off, under the 3T bending, do not have crackle with peel off

Zero～△: under the 2T bending, have to arrive primary coat and be coated with the crackle of rete or raw sheet and/or peel off, under 3T, do not have crackle and peel off

△: under the 3T bending a little crackle and/or peel off, under 4T, do not have crackle with peel off

△～*: under the 2T bending, have to arrive primary coat and be coated with the crackle of rete or raw sheet and/or peel off, under the 3T bending, do not have crackle and peel off

*: crackle is arranged under the 4T bending and/or peel off

In addition, also implement processing portion adhesiveness test that the processing portion Continuous pressing device for stereo-pattern is peeled off again,, estimate by following benchmark with the adhesiveness behind the visualization tape stripping.

◎ ◎: under the 0T bending, do not peel off

◎: under the 1T bending, do not peel off

◎～zero: under the 2T bending, do not peel off

Zero: the total length with respect to processing portion under the 2T bending is peeled off in the length existence that total is lower than half, under the 3T bending, does not peel off

Zero～△: the total length with respect to processing portion under the 2T bending is peeled off in the length existence that total is lower than half, under the 3T bending, does not peel off

△: under the 3T bending a little crackle and/or peel off, under the 4T bending, do not have crackle with peel off

△～*: under the 2T bending, exist and peel off adding up to length over half, under the 3T bending, do not peel off with respect to total length

*: under the 4T bending, peel off

4) overall merit

Scoring be the situation with ◎ ◎ be 8 minutes, with the situation of ◎ be 7 minutes, with ◎～zero situation be 6 minutes, situation with zero be 5 minutes, with the situation of zero～△ be 4 minutes, with the situation of △ be 3 minutes, with △～* situation be 2 minutes, with * situation be 1 minute; Add up to the scoring of full light reflectance and machinability; Calculate it and add up to, estimate by following benchmark.

◎: the adding up to more than 11 minutes of scoring

Zero: the adding up to more than 9 minutes and be lower than 11 fens of scoring

△: the adding up to more than 7 minutes and be lower than 9 fens of scoring

*: the total of scoring is lower than 7 fens

5) mensuration of boundary face Ra

The Ra of the boundary face of floating coat and last coating is through cutting off filming of each embodiment, grinds after imbedding resin, make the cross section smoothed perpendicular to the surface of filming thus, utilizes the photo of having taken with 3500 times scan microscope to estimate.On photo, cover the transparent film be used for OHP, critically behind scanning boundary face concavo-convex; As shown in Figure 3; Direction along the average line of boundary face curve is only extracted datum length l, is taken as the X axle along the direction of the average line of this extraction part, is taken as the Y axle along vertical multiplying power direction; With y=f (x) expression border curve the time, will represent with micron (μ m) through the value that following formula is obtained.Moreover, 5 positions are arbitrarily measured, obtain its mean value.

$\mathrm{Ra}=\frac{1}{l}{\&Integral;}_0^l\left|f\left(x\right)\right|\mathrm{dx}$

6) W on surface _CAMensuration

The most surperficial W of coating _CAMeasure through the bright 3 D surface shape determinator of stretching industrial group's system.Evaluation length when measuring is to measure under the condition of 40mm, intercepting value (cut off) 8mm.Details are measured according to JIS B0601 standard.5 positions are arbitrarily measured, obtained its mean value.

7) mixed layer Determination of thickness

Utilize GDS (glow discharge emission spectrographic analysis device) near the boundary face of floating coat and last coating, to measure the distribution of the Ti of depth direction.More particularly, the Ti concentration with floating coat be x, on the Ti concentration of coating when being y, will [x+0.05 * (x-y)]～thickness of the part of [y-0.05 * (x-y)] measures as mixed layer thickness.5 positions are arbitrarily measured, obtained its mean value.

6) the most surperficial W _CAMensuration

The most surperficial W of coating _CAMeasure through the bright 3 D surface shape determinator of stretching industrial group's system.

7) mixed layer Determination of thickness

Utilize GDS (glow discharge optical emission spectrometry analytical equipment) near the boundary face of floating coat and last coating, to measure the distribution of the Ti of depth direction.More particularly, the Ti concentration with floating coat be x, on the Ti concentration of coating when being y, will [x+0.05 * (x-y)]～thickness of the part of [y-0.05 * (x-y)] measures as " mixed layer thickness ".

8) stain resistance

In addition; With the coating of Mitsubishi Chemical Ind's system 10% suspension with carbon " カ of Mitsubishi one ボ Application MA100 "; Coat the film coated surface of the precoated metal sheet of as above producing; After 1 hour,,, estimate by following benchmark with the change in color that the Δ E that adopts spectral photometric colour measuring meter (ス ガ exerciser system, model MSC-45-2B) to obtain obtains the test front and back through the white メ リ of the Network リ one ニ Application グ ヤ ス ウ エ ス erasing of Japanese ウ エ ス corporate system.

◎: Δ E is lower than 0.2

◎～zero: Δ E is more than 0.2 and is lower than 0.5

Zero: Δ E is more than 0.5 and is lower than 1

△: Δ E is more than 1 and is lower than 2

*: Δ E is more than 2

(evaluation result)

The formation and its evaluation result of table 4～precoated metal sheet that 6 expressions are produced in the present embodiment.

By the precoated metal sheet (NO.1～42,48～62) that embodiments of the invention obtain, be full light reflectance, briliancy, the machinability of filming, result that stain resistance is all good.

Can know like NO.1～42, shown in 48～62; Be made as more than 35% through volumetric concentration the Titanium Dioxide Rutile Top grade in the floating coat; The Ra of the boundary face of floating coat and last coating is more than the 0.8 μ m, and the area that can help to reflect increases, and therefore can obtain high full light reflectance.And, can know because the contact area of floating coat and last coating increases, can obtain excellent adhesiveness.

Pigment in the floating coat is not the metallic plate (NO.43,44) of titanium oxide, and is because full light reflectance is poor, therefore not preferred.The volumetric concentration of the Titanium Dioxide Rutile Top grade in the floating coat is lower than 35% metallic plate (NO.45), and is because full light reflectance is poor, therefore not preferred.The solid constituent volumetric concentration of the Titanium Dioxide Rutile Top grade in the floating coat surpasses 70% metallic plate (NO.46), because machinability and poor adhesion are therefore not preferred.The Ra of the boundary face of floating coat and last coating is lower than the metallic plate (NO.47) of 0.8 μ m, because machinability and poor adhesion are therefore not preferred.

Can know shown in NO.6～42; Through in floating coat, together containing the big low-refraction pigment of size ratio Titanium Dioxide Rutile Top grade with Titanium Dioxide Rutile Top grade; The Ra of the boundary face of floating coat and last coating can be improved, higher full light reflectance and more excellent adhesiveness can be obtained.

Can know shown in NO.13～16,, can improve the Ra of the boundary face of floating coat and last coating, can obtain higher full light reflectance and more excellent adhesiveness through the viscosity under the low-shearing force of coating in reducing.But, if the viscosity under the low-shearing force of coating in too reducing, the most surperficial W _CABe 4 μ m (NO.16), the poor slightly tendency of stain resistance is then arranged.Therefore, can know more preferably the most surperficial W _CABe below the 2 μ m.

Can know shown in NO.17～42,, then be present in the mixed layer thickening of the boundary portion of floating coat and last coating, can obtain higher full light reflectance and more excellent adhesiveness if increase the coating baking time.The thickness of mixed layer that can know the boundary portion that is present in floating coat and last coating is more preferably more than the 3 μ m.

Can know that shown in NO.48～56, the thickness of floating coat is thin more, full light reflectance just falls lowly more, but the machinability of filming improves.Can know that the precoated metal sheet that is obtained by embodiments of the invention all is that the balance of full light reflectance and machinability is excellent.

Can know that shown in NO.57～80 if on the precoated metal sheet that is obtained by embodiments of the invention, contain silicones or fluororesin (NO.58～62,64～80) in the adhesive on coating or top layer, then stain resistance improves, thereby more preferably.

Can know that like NO.81, shown in 82 if on the precoated metal sheet that is obtained by embodiments of the invention, contain the Si of the hydrolytic condensate that derives from alkoxy silane or alkoxy silane in the coating, then stain resistance improves, thereby more preferably.In addition, can know also in the thicker NO.81 of the thickness of floating coat that full light reflectance is excellent especially with briliancy, in the thin NO.82 of the thickness of floating coat, machinability and adhesiveness be excellence especially.

More than, with reference to accompanying drawing on one side for of the present invention preferred implementation be illustrated on one side, be much less but the present invention is not limited to these examples.If those skilled in the art, then in the described scope of the scope that patent is asked for protection, can expect various change examples or revise example is significantly, can be regarded as for these examples to belong to technical scope of the present invention certainly.

Description of reference numerals

1: reflecting plate, 2: fluorescent illumination implement, 3: cover, 4: briliancy determination part, 5: the uniformity comparative measurements portion, 6 of briliancy: brightness photometer

Claims (15)

1. a coating metal material is characterized in that,

In the part of metal material surface or all have and comprise the 1st and be coated with the two-layer at least coating that rete and the 2nd is coated with rete; The said the 1st is coated with rete contains and counts 35%～70% Titanium Dioxide Rutile Top grade by the solid constituent volumetric concentration; The said the 2nd film layer be laminated in the said the 1st be coated with rete the top layer side

The said the 1st to be coated with the center line average roughness Ra that rete and the said the 2nd is coated with the boundary face of rete be more than the 0.8 μ m.

2. coating metal material according to claim 1 is characterized in that,

Be coated with the boundary member that rete and the said the 2nd is coated with rete the said the 1st, exist the said the 1st composition and the said the 2nd that is coated with in the rete to be coated with the mixed layer that the composition in the rete mixes,

Said mixed layer has the thickness of 3 μ m～12 μ m.

3. coating metal material according to claim 1 and 2 is characterized in that, the most surperficial filtering center line percent ripple W of said coating _CABe below the 2 μ m.

4. according to each described coating metal material of claim 1～3, it is characterized in that the rete that is coated with on the top layer among the said coating contains silicones or fluororesin.

5. according to each described coating metal material of claim 1～3, it is characterized in that being coated with rete and in the resin matrix that formation is filmed, having-the Si-O-Si-key of the top layer among the said coating.

6. according to each described coating metal material of claim 1～5, it is characterized in that the average grain diameter of said Titanium Dioxide Rutile Top grade is 200nm～400nm.

7. according to each described coating metal material of claim 1～6, it is characterized in that the said the 1st is coated with rete also contains the particle that the said Titanium Dioxide Rutile Top grade of size ratio is big and have the refractive index lower than said Titanium Dioxide Rutile Top grade.

8. according to each described coating metal material of claim 1～7, it is characterized in that,

Be coated with the said the 1st and have the space in the rete,

The containing ratio in said space is the said the 1st to be coated with 0.05 times～0.9 times of solid constituent volume in the rete.

9. according to each described coating metal material of claim 1～8, it is characterized in that, the said the 1st be coated with rete thickness be 10 μ m～80 μ m.

10. according to each described coating metal material of claim 1～9, it is characterized in that, the said the 2nd be coated with rete thickness be 5 μ m～30 μ m.

11. each the described coating metal material according to claim 1～10 is characterized in that, said coating also contains and is laminated in said metal material and the said the 1st and is coated with the 3rd between the rete and is coated with rete.

12. coating metal material according to claim 11 is characterized in that, the said the 3rd be coated with rete thickness be 5 μ m～30 μ m.

13. the manufacturing approach of a coating metal material is the manufacturing approach of each described coating metal material of claim 1～12, it is characterized in that,

Adopt multilayer to be coated with simultaneously or wet-wet mode the part of metal material surface or all be coated with the said the 1st be coated with the formation usefulness of rete coating and the said the 2nd be coated with the coating of the formation usefulness of rete.

14. a ligthing paraphernalia is used to the reflecting plate that throws light on each described coating metal material of claim 1～12.

15. an electronic equipment is used for the reflecting plate of luminous component or the reflecting plate of image displaying part with each described coating metal material of claim 1～12.

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