WO2011034216A1 - 塗装金属材とその製造方法 - Google Patents

塗装金属材とその製造方法 Download PDF

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Publication number
WO2011034216A1
WO2011034216A1 PCT/JP2010/066638 JP2010066638W WO2011034216A1 WO 2011034216 A1 WO2011034216 A1 WO 2011034216A1 JP 2010066638 W JP2010066638 W JP 2010066638W WO 2011034216 A1 WO2011034216 A1 WO 2011034216A1
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Prior art keywords
layer
coating
coating layer
metal material
titanium oxide
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PCT/JP2010/066638
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English (en)
French (fr)
Japanese (ja)
Inventor
智明 細川
浩平 植田
郁也 井上
裕樹 小原
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新日本製鐵株式会社
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Application filed by 新日本製鐵株式会社 filed Critical 新日本製鐵株式会社
Priority to KR1020127006749A priority Critical patent/KR101365279B1/ko
Priority to CN201080041439.9A priority patent/CN102497982B/zh
Priority to IN2298DEN2012 priority patent/IN2012DN02298A/en
Priority to JP2011508730A priority patent/JP4897109B2/ja
Publication of WO2011034216A1 publication Critical patent/WO2011034216A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material

Definitions

  • the present invention relates to a coated metal material having a high reflectance and a method for producing the same.
  • Various devices that use visible light (for example, lighting equipment, AV equipment, electronic devices, mobile devices, liquid crystal televisions, plasma displays, etc.) emit visible light to brighten the surroundings, transmit optical signals, or It has functions such as projecting optical images.
  • a reflector is provided around or behind the light source, and the light is reflected on the reflector to improve the brightness of the light or change the direction of the light.
  • a high visible light reflectance is required on the reflecting plate surface. Therefore, conventionally, as means for increasing the reflectivity of the reflecting plate surface, metal has been polished into a mirror surface, or a white paint having a high reflectivity has been applied.
  • Patent Document 1 As a means for increasing the reflectance, for example, in Patent Document 1, a metal thin film layer and a resin layer containing inorganic fine particles are sequentially laminated on one surface of a base film, and the metal thin film layer is made of aluminum, art light reflecting film and the refractive index n b of the refractive index n f and the resin constituting the same layer of the inorganic fine particles are set to be n f -n b ⁇ 0.4 which constitutes the resin layer containing inorganic fine particles Is disclosed.
  • a back panel of a liquid crystal display comprising 100 to 250 parts by mass of a titanium oxide pigment with respect to 100 parts by mass of the resin, an overcoat layer having a gloss of 15 or less and a film thickness of 10 to 30 ⁇ m formed on the undercoat layer.
  • a high-concentration pigment layer containing a white pigment in an amount of 150 parts by volume or more and less than 1500 parts by volume or a binder and a white pigment with respect to 100 parts by volume of a binder, and further a void in the coating layer A technique of a coating material having a high diffuse reflectance having at least one low-density layer having a rate of 5% by volume or more and less than 35% by volume is disclosed.
  • the undercoating layer and the overcoating layer can be formed after being applied on the aluminum plate in advance, but in a general pre-coating line, it can be performed once. It is very difficult to coat the undercoat layer (50 to 100 ⁇ m) with such a film thickness, and it requires two or more times of overcoating, resulting in low productivity.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a coated metal material having a higher total light reflectivity than before and excellent in formability and a method for producing the same.
  • a first coating layer containing a high concentration of rutile-type titanium oxide on part or all of the metal material surface and an upper layer thereof
  • a first coating layer containing a high concentration of rutile-type titanium oxide on part or all of the metal material surface By coating two or more coating layers including the second coating layer, and increasing the roughness of the interface between the first coating layer and the second coating layer, high total light reflection It has been found that both the rate and excellent moldability can be achieved, and the present invention has been completed based on this finding.
  • the first coating layer containing 35% to 70% of rutile-type titanium oxide in solid content volume concentration on a part or all of the metal material surface, and the first coating layer And a second coating layer laminated on the surface layer side of the first coating layer, and the center line average of the boundary surface between the first coating layer and the second coating layer
  • a coated metal material having a roughness Ra of 0.8 ⁇ m or more is provided.
  • a component in the first coating layer and a component in the second coating layer are mixed in the boundary portion between the first coating layer and the second coating layer.
  • a mixed layer is present, and the mixed layer preferably has a thickness of 3 ⁇ m to 12 ⁇ m.
  • the filtering center line waviness W CA on the outermost surface of the coating layer is 2 ⁇ m or less.
  • the outermost coating layer of the coating layer may contain a silicone resin or a fluorine resin.
  • the outermost coating layer of the coating layer may have —Si—O—Si— bonds in the resin skeleton forming the coating.
  • the average particle size of the rutile titanium oxide is preferably 200 nm or more and 400 nm or less.
  • the first coating layer may further contain particles having a particle size larger than that of the rutile titanium oxide and having a refractive index lower than that of the rutile titanium oxide.
  • the content of the voids is 0.05 times or more and 0.9 times or less of the solid content volume in the first coating layer. preferable.
  • the film thickness of the first coating layer is preferably 10 ⁇ m or more and 80 ⁇ m or less.
  • the film thickness of the second coating layer is preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the multi-layer may further include a third coating layer laminated between the metal material and the first coating layer.
  • the film thickness of the third coating layer is preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • a method for producing a coated metal material as described above wherein a coating material for forming the first coating film layer and a coating material for forming the second coating film layer are multilayered.
  • a method for producing a coated metal material which is applied to a part or all of a metal material surface by simultaneous application or wet-on-wet method.
  • an electronic apparatus in which the above-described painted metal material is used for a light-emitting component reflector or an image display reflector.
  • the present invention it is possible to provide a coated metal material having a higher total light reflectivity than before and excellent in formability and a method for producing the same.
  • the coated metal material according to the present embodiment has at least two coating layers on part or all of the surface of the metal material serving as the base material.
  • the coating layer includes a first coating layer containing rutile-type titanium oxide at a high concentration (hereinafter referred to as “high concentration pigment layer”), and a surface layer side of the first coating layer. And a second coating layer (hereinafter referred to as “overcoat layer”) laminated at least.
  • the coated metal material according to the present embodiment has a third coating layer (hereinafter referred to as “undercoat layer”) as a coating layer, on the inner layer side of the high concentration pigment layer, that is, between the metal material and the high concentration pigment layer.
  • each coating layer may be further included, and another coating layer (for example, a coating layer laminated on the surface layer side of the top coating layer) may be further included.
  • a coating layer laminated on the surface layer side of the top coating layer may be further included.
  • the configuration of each coating layer will be described in detail in the order of the high-concentration pigment layer, the overcoat layer, and the undercoat layer.
  • the high-concentration pigment layer according to the present embodiment is a layer containing, as a white pigment, rutile-type titanium oxide in a solid content volume concentration of 35% or more and 70% or less, and is an inner layer side of the topcoat layer, that is, a base material. Located closer to the metal.
  • the coating layer has a three-layer structure including an undercoat layer, a high-concentration pigment layer, and an overcoat layer
  • the high-concentration pigment layer is a layer located in a portion sandwiched between the undercoat layer and the overcoat layer.
  • the coating layer has a multi-layer structure of four or more layers including one or more other layers in addition to the three layers of the undercoat layer, the high concentration pigment layer and the topcoat layer, the topcoat layer and the undercoat layer And all layers containing rutile-type titanium oxide in a solid content volume concentration of 35% or more and 70% or less as high-concentration pigment layers. Furthermore, when the concentration of the rutile type titanium oxide continuously changes in the coating layer and the boundary between the layers is unclear, the solid volume concentration of the rutile type titanium oxide is in a range that satisfies the condition of 35% to 70%. All are high-concentration pigment layers.
  • volume concentration of solid content of rutile type titanium oxide refers to the rutile type titanium oxide relative to the volume occupied by the entire solid content including the resin (binder) component and the pigment component in the coating film in the high concentration pigment layer. This refers to the proportion of the volume occupied, excluding the volume occupied by the voids in the coating film (the method for measuring this “volume concentration of solid content of rutile titanium oxide” will be described later).
  • the rutile-type titanium oxide is contained at a high concentration so that the particles of the rutile-type titanium oxide are present in the coating film after drying and curing so as to be more than the closest packing.
  • the volume of the voids formed between the rutile-type titanium oxide particles becomes larger than the volume of the binder resin. Therefore, in the high-concentration pigment layer according to the present embodiment, unlike the coating film in which the pigment is contained at a concentration that is less than the closest packing, a portion where the binder resin does not exist is present in the coating film as a void. be able to.
  • the refractive index difference between the rutile titanium oxide and the void is larger than the refractive index difference between the rutile titanium and the resin. .
  • the refractive index difference at the interface that reflects light is larger than that of the coating film containing the pigment at a concentration that is less than the closest packing, and Since the area of the interface that can reflect light is increased, a high total light reflectance can be obtained.
  • rutile type titanium oxide is used as a pigment to be contained in the high concentration pigment layer. This is because the refractive index of rutile titanium oxide is higher than that of other commonly used white pigments, and the difference in refractive index between the resin used as the binder and the air present in the voids in the coating film can be increased. This is because the total light reflectance at the interface between the pigment and the resin and at the interface between the pigment and the air can be further increased. Note that anatase-type titanium oxide also has a relatively high refractive index, but is not preferable because it has high photocatalytic properties and may decompose the binder resin when receiving light from a fluorescent lamp or the like.
  • the coated metal material according to the present embodiment is mainly intended to reflect visible light, it is important that the total light reflectance in a wavelength region where the sensitivity of the human eye is high is high.
  • the human eye can sense light with a wavelength of 380 nm to 780 nm although there are individual differences, and the peak of the sensitivity is in the vicinity of 555 nm. Therefore, it is desirable that the coated metal material according to the present embodiment also strongly reflects light having a wavelength centered at 555 nm. Therefore, this is also true for the particle size of the pigment (rutile titanium oxide) used for the high concentration pigment layer. It is preferable to select in consideration.
  • the average particle size of rutile-type titanium oxide used as a pigment is preferably about 200 nm to 400 nm, which is about half the visible light wavelength, and more preferably 250 nm to 350 nm. preferable.
  • the average particle diameter of the rutile type titanium oxide in this embodiment is the part of the rutile type titanium oxide particles that are observed 10,000 times with an electron microscope (SEM) by the electron microscope (SEM) and projected in the field of view.
  • SEM electron microscope
  • the arithmetic average value of the particle sizes of the remaining rutile-type titanium oxide particles excluding the particles corresponding to 20% from the smaller particle size and the particles corresponding to 5% from the larger particle size ⁇ measurement Conditions>
  • Preparation method of observation sample The sample was prepared by embedding the sample in a resin and polishing the vertical section of the sample.
  • Field of view Observe with an optical microscope or electron microscope (SEM) at a magnification of about 500 to 1000 times in advance, and select an arbitrary location on the layer corresponding to the high concentration pigment layer.
  • Method for selecting rutile-type titanium oxide particles for obtaining an arithmetic mean value An image obtained by observing the selected visual field with an electron microscope (SEM) at a magnification of 10,000 times is taken. The particle size is measured for all the rutile-type titanium oxide particles shown in the photographed image.
  • the rutile-type titanium oxide particles used in the present embodiment can be used without particular limitation as long as the above-described conditions are satisfied. Further, the rutile type titanium oxide particles used in the present embodiment may be a rutile type titanium oxide single particle, or rutile type titanium oxide, silica, alumina, zirconia, zinc oxide, antimony oxide, various organic substances, etc. It may be coated with a coating.
  • the organic material used for the rutile titanium oxide coating is not particularly limited, but examples thereof include polyol compounds such as pentaerythritol and trimethylolpropane, triethanololamine, and organic acid salts of trimethylolamine. Examples thereof include silicon compounds such as alkanolamine compounds, silicon resins, and alkylchlorosilanes.
  • rutile titanium oxide may be used.
  • Teika Co., Ltd. commercially available rutile titanium oxide.
  • Teika Co., Ltd. commercially available rutile titanium oxide.
  • Teipec registered trademark
  • TA series manufactured by Fuji Titanium Co., Ltd.
  • TITANIX manufactured by Teika Co., Ltd.
  • the rutile type titanium oxide as described above has a solid content volume concentration of 35% or more in the high concentration pigment layer.
  • the solid content volume concentration of rutile type titanium oxide is 35% or more, as described above, the particles of rutile type titanium oxide are present in the coated film after drying and curing so as to be more than the closest packing. Therefore, voids in which no binder resin is present can be present in the coating film. Thereby, the total light reflectance of a high concentration pigment layer can be made high.
  • the rutile-type titanium oxide having an average particle diameter of 200 nm to 400 nm is set to 50% or more in terms of solid content volume concentration.
  • the interface between the rutile-type titanium oxide and the void, the interface between the rutile-type titanium oxide and the resin, and the interface between the resin and the void in the coating effectively contribute to the total light reflectance, and the high total reflectance. Is preferable.
  • the solid content volume concentration of the rutile type titanium oxide in the high concentration pigment layer exceeds 70%, the ratio of the rutile type titanium oxide and the voids in the coating film becomes too large. It is difficult to ensure the property (maintaining the film state), and the high concentration pigment layer itself becomes brittle. Therefore, the solid content volume concentration of the rutile type titanium oxide in the high concentration pigment layer is set to 70% or less. From the viewpoint of securing stable coating strength, a more preferable range of the solid content volume concentration of rutile-type titanium oxide is 65% or less.
  • a method for measuring the solid content volume concentration in the coating layer in the present embodiment will be described.
  • a method for measuring the solid content volume concentration of rutile-type titanium oxide in the case where the coating layer has a three-layer structure including an overcoat layer, a high-concentration pigment layer, and an undercoat layer will be described.
  • the coating layer to be measured is scraped from the sample for each layer such as an overcoat layer, a high-concentration pigment layer, and an undercoat layer, and the area A1 and mass M1 of the scraped coating film are measured.
  • the scraped coating film is heated at 500 ° C. for 1 hour using a crucible to decompose the resin component. Since the portion remaining without being decomposed can be considered as the rutile type titanium oxide, the mass M2 of the remaining portion is measured.
  • the density of a general rutile type titanium oxide pigment is about 3800 to 4200 kg ⁇ m ⁇ 3
  • the density of the rutile type titanium oxide pigment is assumed to be 4000 kg ⁇ m ⁇ 3
  • the density of a general polyester resin is since about 1150 ⁇ 1250kg ⁇ m -3
  • the density of the polyester resin is assumed to 1200 kg ⁇ m -3
  • volume V1 of the polyester resin, V1 (M1-M2) / 1200kg ⁇ m -3
  • the measurement of the above C1 is measured three times for one measurement object (for example, a high concentration pigment layer), and the arithmetic average is obtained.
  • particles having a particle size larger than that of the rutile-type titanium oxide and having a lower refractive index hereinafter may be referred to as “low refractive index particles”.
  • Use in combination with rutile type titanium oxide is preferable because the total light reflectance can be increased more efficiently.
  • particles having a particle size larger than that of rutile-type titanium oxide to the high-concentration pigment layer, voids between particles in the high-concentration pigment layer are increased, and more voids can be contained. , The total light reflectance can be improved.
  • the large particle size used in combination with the rutile type titanium oxide is a low refractive index particle, so that the rutile type oxidation is also performed at the contact interface where the low refractive index particle and the rutile type titanium oxide particle are in contact with each other.
  • Light can be reflected by the difference in refractive index between the titanium particles and the low refractive index particles, which can contribute to the improvement of the total light reflectance.
  • the average particle diameter of the low refractive index particles is preferably 1 ⁇ m or more and 10 ⁇ m or less, and more preferably 3 ⁇ m or more and 8 ⁇ m.
  • the ratio R L of the low refractive index particles to the rutile titanium oxide is Is preferably 1/40 or more, more preferably 1/40 to 12/40 (particularly 3/40 to 10/40).
  • the average particle diameter of the low refractive index particles in this embodiment is the low refractive index displayed in the field of view by observing the portion of the coating film to be confirmed with an electron microscope at a magnification of 10,000 as in the case of rutile titanium oxide.
  • the arithmetic average value of the particle sizes of the remaining low refractive index particles excluding particles corresponding to 20% from the smaller particle size and 5% from the larger particle size.
  • the arithmetic average value of the particle diameters of the low refractive index particles can also be measured in the same manner as in the case of the above-mentioned “rutile titanium oxide”).
  • the low refractive index particle is not particularly limited as long as it has a lower refractive index than rutile type titanium oxide, but preferably has a refractive index difference of 1 or more from rutile type titanium oxide, Those which do not have strong absorption of light in the visible light region and exhibit a white color in a powder state are preferable.
  • inorganic particles such as silica, calcium carbonate, barium sulfate, and zinc oxide can be used as the low refractive index particles.
  • resin powder or the like can be used as the low refractive index particles.
  • the type of the resin powder is not particularly limited, and for example, acrylic resin powder, polyester resin powder, PTFE (polytetrafluoroethylene) powder, or the like can be used as the resin powder.
  • the role of the low refractive index particles is to efficiently include voids in the high-concentration pigment layer, and further reflect light at the contact interface between the low refractive index pigment and titanium oxide, thereby increasing the reflectance. Is to get. Therefore, even if the addition amount of the low refractive index particles is small, the effect can be exerted as much as the contained amount. Therefore, there is no need to particularly limit the lower limit concentration of the low refractive index particles.
  • the volume of / rutile titanium oxide is less than 0.05, the effect of improving the total light reflectance by adding the low refractive index particles is small. Therefore, the lower limit concentration of the low refractive index particles is preferably a concentration at which (volume of low refractive index pigment / volume of rutile titanium oxide) is 0.05 or more.
  • the upper limit concentration of the low refractive index particles when (volume of low refractive index pigment / volume of rutile type titanium oxide) is in the range of 0.2 or less, the reflection of light increases with the increase in the amount of low refractive index particles. The ratio increases, and the effect of adding low refractive index particles is recognized. However, if the amount is added beyond this, performance (workability, corrosion resistance, etc.) other than light reflectance tends to decrease. Therefore, the upper limit concentration of the low refractive index particles is preferably such that (volume of low refractive index pigment / volume of rutile titanium oxide) is 0.2 or less.
  • the low refractive particles have a role of controlling the roughness of the boundary surface between the high-concentration pigment layer and the topcoat layer in addition to the role of improving the total light reflectance. To do.
  • the void content in the high-concentration pigment layer is preferably 0.05 times or more and 0.9 times or less of the solid content volume.
  • the void content is less than 0.05 times the solid content volume, there is little effect of improving the total light reflectivity due to the inclusion of the void, and when the void content exceeds 0.9 times the solid volume. This is because the high-concentration pigment layer becomes brittle (the mechanical strength decreases), and the workability and adhesion may be inferior.
  • This “void content” can be measured by the method described later.
  • Control of the void content in the high-concentration pigment layer can be controlled by the content concentration of pigments such as rutile titanium oxide and low refractive particles as described above. It can also be controlled by adjusting the dispersion state of the paint for forming the pigment layer. That is, the better the dispersion state of the pigment in the paint (the more uniform), the more the binder resin is adsorbed on the pigment and efficiently fills the gaps between the pigment particles, so the void content decreases. Therefore, in order to obtain a higher total light reflectivity, the dispersion state should be kept to a minimum within a range where there is no problem in coating property and paint stability (in a range where there is no problem in coating property and paint stability). It is preferable to make it as non-uniform as possible.
  • the dispersion state of the pigment in the paint can be controlled by adjusting the type of the disperser, the dispersion time, the type of the dispersant, the amount added, and the like.
  • the size of the voids in the high-concentration pigment layer is not particularly limited, but if there is an extremely large size, it is not preferable because it may cause a coating film defect and deteriorate the coating performance such as processability and corrosion resistance, Since the surface area per unit volume of the gap is small, it is not preferable from the viewpoint of the effect of improving the total light reflectance. On the other hand, the smaller the gap size, the larger the surface area per unit volume of the gap, and the larger the area of the light reflection interface, the higher the total light reflectance, but the gap size becomes extremely small. Then, since light having a long wavelength is transmitted, the total light reflectance may be reduced.
  • the size of the voids in the high-concentration pigment layer is preferably 200 nm to 400 nm, more preferably 250 nm to 350 nm, which is about half the visible light wavelength from the viewpoint of improving the light reflectance.
  • the size of the gap is not particularly a problem.
  • an equivalent volume sphere equivalent diameter that is the diameter of a sphere having the same volume as the gap is used as the size of the gap.
  • the coating layer is cut by a plane perpendicular to the coating surface (surface parallel to the surface of the metal material), and the cross section is ** optical microscope, electron microscope
  • the film thickness T1 of the coating layer is obtained using an electromagnetic film thickness meter **.
  • the measurement method of the film thickness T1 is preferably a method using an optical microscope or an electron microscope (SEM) from the viewpoint of measurement accuracy.
  • the above void volume is measured five times for the same sample (that is, the coating layer), and the arithmetic average is obtained.
  • the binder resin used in the high-concentration pigment layer according to the present embodiment is not particularly limited, and commonly used binder resins such as polyester resins, urethane resins, epoxy resins, acrylic resins, silicone resins, fluorine resins, etc. Can be used. However, since the rutile-type titanium oxide particles in an amount exceeding the closest packing are added to the high-concentration pigment layer according to this embodiment, the coating film tends to become brittle, so that the binder resin used for the high-concentration pigment layer It is preferable to use a resin excellent in processability and adhesion. Specifically, for example, a polyester resin A having a number average molecular weight of 19000 or more and 28000 or less is preferably used as the binder resin. This is due to the following reasons.
  • rutile titanium oxide particles added as a white pigment to the high concentration pigment layer are contained in a solid content volume concentration of 35% to 70%. % Must be high.
  • the binder ability to bind the pigment particles may be insufficient, resulting in a problem that the workability of the painted metal material is lowered. Therefore, as a result of intensive studies on the configuration of the coating layer for ensuring processability with a small amount of binder resin, the present inventors have found that a polyester resin having excellent adhesion to the pigment particles and the metal material as the base material is optimal.
  • the polyester resin A having a number average molecular weight of 19000 or more and 28000 or less is obtained. It has been found that good processability can be obtained by using this.
  • the number average molecular weight of the polyester resin can be measured by “GPC”. When using a commercially available resin, the value of the number average molecular weight disclosed by the manufacturer can be applied.
  • a paint using a high molecular weight polyester resin having a molecular weight of 19000 or more as a binder tends to have a high viscosity. Therefore, in order to secure a viscosity suitable for coating, it is necessary to keep the solid content concentration in the paint low. There is. For this reason, in thick film coating applications to which the present invention is mainly applied, coating defects called boiling are likely to occur, and it has been considered difficult to apply high molecular weight polyester resins.
  • the concentration of the binder resin becomes relatively low, and the viscosity suitable for coating without reducing the solid content concentration in the paint too low. Can be secured. Accordingly, even when the high molecular weight polyester resin A is used as the binder of the high-concentration pigment layer according to the present embodiment, a thick film can be applied without causing boiling, and both paintability and workability can be achieved. .
  • the polyester resin used as the binder resin used in the high-concentration pigment layer according to this embodiment the polyester resin used as the binder resin used in the high-concentration pigment layer according to this embodiment.
  • the preferable range of the number average molecular weight of A was set to 19000 or more.
  • the number average molecular weight of the polyester resin A exceeds 28000, the surface of the coating film becomes too soft and there is a possibility that the scratch resistance may deteriorate.
  • the preferable range of the number average molecular weight of the polyester resin A is 28000 or less.
  • the concentration of the polyester resin A with respect to the entire binder resin is 20% by mass or more, a thick film can be applied without causing boiling, and paintability and workability are improved. Therefore, the concentration of the polyester resin A with respect to the whole binder resin is preferably 20% by mass or more.
  • the present inventors further added a polyester resin B having a number average molecular weight of 2000 or more and 6000 or less and a hydroxyl value of 20 or more in addition to the polyester resin A. It was found that when the polyester resin A and the polyester resin B have a mass ratio of 0.25 ⁇ (polyester resin B) / (polyester resin A) ⁇ 4, further excellent moldability can be obtained.
  • the processability of the polyester resin A having a number average molecular weight of 19000 or more and 28000 or less is excellent, but the high concentration pigment layer of the present embodiment contains a pigment such as rutile type titanium oxide at a high concentration. Therefore, it is considered that the binder resin has a structure dispersed between the pigments. In such a structure, even a coating layer containing the high molecular weight polyester resin A tends to have lower processability than a coating layer having a low pigment concentration, and further improvement in processability is required.
  • the present inventors have used a high molecular weight polyester resin A and a low molecular weight polyester resin B in combination to thereby obtain a high molecular weight polyester resin A. It has been found that superior processing performance can be obtained compared to the case of a single case. That is, when the high molecular weight polyester resin A is used alone, the resin cannot sufficiently enter the gaps between the pigments present at a high concentration, and the function as a binder becomes insufficient, so that the workability may be slightly lowered. .
  • the low molecular weight polyester resin B becomes a pigment and a pigment that the high molecular weight polyester resin A cannot enter.
  • it is possible to obtain excellent processability because it functions as a binder between the pigment and the pigment, or the pigment and the high molecular weight polyester resin A. Conceivable.
  • the low molecular weight polyester resin B preferably has a number average molecular weight of 2000 or more and 6000 or less and a hydroxyl value of 20 or more. If the number average molecular weight of the polyester resin B is less than 2000, the film strength may be insufficient and the processability may be reduced. If the number average molecular weight exceeds 6000, the polyester resin B is difficult to enter between the pigments. Therefore, there is a possibility that the effect of improving the adhesiveness is lowered. Moreover, when the hydroxyl value of the polyester resin B is less than 20, the crosslinking point between the pigment and the pigment decreases, and the effect of improving the adhesion may be reduced.
  • the hydroxyl value of the polyester resin B is 200. The following is preferable.
  • the mixing ratio of the polyester resin A and the polyester resin B is 0.25 ⁇ (polyester resin B) / (polyester resin A) ⁇ 4 in mass ratio, excellent adhesion and workability can be obtained. . If the mass ratio of (Polyester resin B) / (Polyester resin A) is less than 0.25, there is a possibility that the adhesion of the polyester resin B may be lowered due to insufficient function expression, and (Polyester resin B) If / (polyester resin A) is greater than 4, the functional expression of polyester resin A becomes insufficient, and the processability may be reduced.
  • the film thickness of the high-concentration pigment layer according to the present embodiment is preferably 10 ⁇ m or more in order to obtain a high total light reflectance, and 40 ⁇ m or more when obtaining a higher total light reflectance. Further preferred. On the other hand, if the film thickness of the high-concentration pigment layer exceeds 80 ⁇ m, the processability of the coating film may be lowered. Therefore, the film thickness of the high-concentration pigment layer is preferably 100 ⁇ m or less, and higher workability is required. In some cases, it is more preferably 15 ⁇ m or less.
  • the film thickness of the high-concentration pigment layer in the present embodiment can be measured as follows.
  • the film thickness of the coating layer can be determined by cutting the sample along a plane perpendicular to the coating surface of each coating layer and observing the cross section with an optical microscope or an electron microscope.
  • the film thickness is the average (arithmetic) film thickness measured at any five points.
  • the film thickness of the overcoat layer and undercoat layer which are mentioned later can also be measured similarly to the film thickness of the high concentration pigment layer.
  • the case where a mixed layer is formed in the boundary part of each coating film layer is mentioned later.
  • the topcoat layer according to this embodiment is a coating layer that is laminated on the surface layer side of the high-concentration pigment layer described above, that is, on the side farther from the metal material that is the base material.
  • the coating layer has a two-layer structure composed of a high-concentration pigment layer and an overcoat layer, in the case of a three-layer structure further including an undercoat layer, further, four or more layers in which a plurality of high-concentration pigment layers exist In the case of this structure, the overcoat layer is located on the outermost layer.
  • the overcoat layer is directly laminated on the surface layer side of the high-concentration pigment layer, it is not always necessary to be positioned on the outermost layer, and a separate coating layer may be laminated on the surface layer side of the overcoat layer. .
  • the resin used as the binder of the topcoat layer is not particularly limited, but from the viewpoint of adhesion with the high concentration pigment layer, formation of a mixed layer described later, common use of the coating material, and the like, It is preferable to use the same resin. Therefore, since it is preferable to use the polyester resin A having a number average molecular weight of 19000 or more and 28000 or less as the binder of the high concentration pigment layer, it is preferable to use the polyester resin A as the binder also in the overcoat layer. If the number average molecular weight of the polyester resin used as the binder of the topcoat layer is less than 19000, the workability and the adhesion may be reduced. If the number average molecular weight exceeds 28000, the surface of the coating film becomes too soft and wrinkle resistant. Property and blocking property may be deteriorated.
  • concentration of the polyester resin A with respect to the whole binder resin is 80 mass% or more, since the effect of an improvement of workability and adhesiveness can be exhibited, It is preferable that the density
  • the topcoat layer does not require the addition of a pigment, and the reflection according to the purpose is adjusted by adjusting the presence or absence of pigment addition, the type of pigment to be added, the pigment concentration, etc. according to the application. Characteristics and other characteristics are added.
  • the rutile type titanium oxide for example, is added as a pigment to the overcoat layer.
  • the total light reflectance can be improved, and a higher rutile type titanium oxide concentration is advantageous for reflection performance.
  • the rutile-type titanium oxide concentration in the overcoat layer is preferably 35% or less in terms of solid content volume concentration from the viewpoint of ensuring the flexibility of the coating film.
  • the lower limit of the rutile-type titanium oxide concentration in the overcoat layer is not particularly limited, and includes a case where no rutile-type titanium oxide is contained.
  • the rutile-type titanium oxide concentration in the overcoat layer according to this embodiment is preferably 0% or more and 35% or less in terms of solid content volume concentration. Furthermore, when a higher total light reflectivity is required, the protective function of the entire coating layer by the overcoat layer is achieved by setting the rutile-type titanium oxide concentration in the overcoat layer to 20% to 30% in terms of solid content volume concentration. It is possible to achieve both high reflection performance and high dimensions.
  • the solid content volume concentration of rutile type titanium oxide here is the volume occupied by the rutile type titanium oxide with respect to the volume occupied by the whole solid content including the resin (binder) component and the pigment component in the coating film in the overcoat layer.
  • the average particle size of the rutile titanium oxide is smaller, the surface area per unit volume is larger, and the area of the interface between the resin or the void as a light reflecting surface and the pigment is larger. Since it becomes wider, the total light reflectance also becomes high, but when the average particle diameter of the pigment becomes too small, light having a long wavelength is transmitted, so that the total light reflectance is lowered. Therefore, as in the case of the high-concentration pigment layer, the average particle size of the rutile titanium oxide used as the pigment in the overcoat layer is preferably 200 nm or more and 400 nm or less, and more preferably 250 nm or more and 350 nm or less.
  • a matting agent may be additionally added to the topcoat layer.
  • a reflection characteristic with almost no specular reflection component is obtained while maintaining the same total light reflectance as when the matting agent is not used. be able to.
  • a coated metal material having such reflection characteristics is used as a reflector of a lighting fixture, a constant reflected light can be obtained regardless of the distance and angle with the light source. Even when the interval is wide, uniform reflected light can be obtained.
  • the addition of a matting agent forms fine irregularities on the surface of the topcoat layer, and dirt substances are likely to collect on these fine irregularities, and since these dirt substances are difficult to remove even by wiping, they are resistant to contamination. May decrease. Therefore, it is desirable that the amount of the matting agent added is determined in consideration of the uniformity of reflected light and the influence on the deterioration of the stain resistance.
  • the matting agent used in the present embodiment is not particularly limited.
  • silica having a particle size of 3 ⁇ m to 9 ⁇ m is suitable.
  • the film thickness of the overcoat layer is less than 5 ⁇ m, the effect of improving the workability, adhesion and total light reflectance by the topcoat layer is reduced, and therefore the film thickness of the topcoat layer is preferably 5 ⁇ m or more and 30 ⁇ m or less. From the viewpoint of ensuring stable processability, adhesion, total light reflectance, and paintability, a more preferable film thickness of the overcoat layer is 10 ⁇ m or more and 25 ⁇ m or less.
  • the film thickness range of the topcoat layer is the same as when rutile titanium oxide is added to the topcoat layer, and is 5 ⁇ m to 30 ⁇ m. It is preferable that If the film thickness of the overcoat layer exceeds 30 ⁇ m, boiling tends to occur during coating, so that the paintability is deteriorated, and the coating cost is not preferable. On the other hand, when the film thickness of the overcoat layer is less than 5 ⁇ m, there is a possibility that almost no improvement in workability and adhesion due to the overcoat layer and reflection characteristics having almost no regular reflection component can be obtained. From the viewpoint of ensuring stable processability, adhesion, reflection characteristics, and paintability, a more preferable film thickness of the overcoat layer to which a matting agent is added is 10 ⁇ m or more and 25 ⁇ m or less.
  • the center line average roughness Ra of the boundary surface between the high-concentration pigment layer and the overcoat layer described above needs to be 0.8 ⁇ m or more.
  • the boundary surface between the high-concentration pigment layer and the topcoat layer becomes rough, so that the diffuse reflectance can be increased.
  • the Ra at the boundary surface between the high-concentration pigment layer and the overcoat layer is less than 0.8 ⁇ m, the above-described effects of improving adhesion and increasing the reflectance cannot be sufficiently obtained.
  • the Ra of the boundary surface between the intermediate coating layer and the top coating layer is obtained by cutting the coating film of each example, embedding it in a resin, and polishing it to smooth the cross section perpendicular to the surface of the coating film. Evaluation was made using photographs taken with a microscope (1000 times magnification). From the top of the photo, the transparent sheet used for OHP is covered and the unevenness of the boundary surface is traced precisely. Then, as shown in FIG. 3, the reference length l is extracted in the direction of the average line of the boundary surface curve.
  • it is set as the average of Ra measured by the above-mentioned method about five arbitrary cross sections in a coating film.
  • the Ra of the boundary surface between the high-concentration pigment layer and the topcoat layer is the coating method of the high-concentration pigment layer and the topcoat layer, the concentration of the pigment (rutile titanium oxide) in the high-concentration pigment layer, and the pigment type of the high-concentration pigment layer ( The low refractive index particles such as rutile type titanium oxide and silica, etc.), the viscosity and the surface tension of the coating for forming the high concentration pigment layer and the overcoat layer can be controlled.
  • the boundary surface between the high-concentration pigment layer and the topcoat layer in the present development refers to a boundary surface (boundary line) that can be visually seen when a cross section of the coating film is photographed with an optical microscope or an electron microscope.
  • the paint for forming the high-concentration pigment layer and the paint for forming the topcoat layer are undried.
  • the pigment such as rutile titanium oxide
  • Add large particles such as silica
  • Form the high-concentration pigment layer There are methods such as reducing the difference in surface tension between the paint for coating and the paint for forming the topcoat layer.
  • rutile type titanium oxide is formed from the high concentration pigment layer to the top coating layer by laminating the coating material for forming the high concentration pigment layer and the coating material for forming the top coating layer in an undried state.
  • the force that the particles try to diffuse acts on the boundary surface, and Ra of the boundary surface of the coating layer increases.
  • the concentration of the rutile-type titanium oxide in the high-concentration pigment layer is set to a high concentration, particularly a concentration equal to or higher than the closest packing, the concentration difference from the upper layer coating film increases. Since the rutile titanium oxide has a strong force to diffuse into the overcoat layer, Ra on the boundary surface is further increased.
  • a particle having a large particle size is added to the high concentration pigment layer, and the particle having the large particle size is present in the vicinity of the boundary surface between the high concentration pigment layer and the overcoat layer. Since the surface has irregularities due to the large particle size, Ra on the boundary surface increases.
  • the coating for forming the high concentration pigment layer and the coating for forming the overcoat layer are laminated in an undried state, whereby particles having a large particle diameter are overcoated from the high concentration pigment layer. Due to diffusion into the layer, particles having a large particle size are likely to be present in the vicinity of the interface between the high-concentration pigment layer and the overcoat layer.
  • Ra becomes larger. That is, according to the knowledge of the present inventors, a paint to which fine particles (in this case, rutile titanium oxide) are added at such a concentration that it becomes more than the closest packing after drying / curing is generally called a concentrated and highly dispersed paint.
  • the coating workability when coating such a paint on a substrate is greatly affected by the viscosity at high rotation, while the low-speed rotation is applied to the in-film flow of the paint in the drying / baking hardening process after coating.
  • the viscosity at will greatly affect. Therefore, it is important to adjust the viscosity of the paint at a low rotation speed in order to control Ra at the boundary surface between the high concentration pigment layer and the topcoat layer.
  • the viscosity of the paint at low rotation can be adjusted by changing the amount of the solvent in the paint and the storage conditions (storage temperature and storage period) of the paint.
  • the storage conditions of the paint the higher the storage temperature and the longer the storage period, the lower the thixotropic property, so that the paint viscosity with a low share improves. This is because the wettability between the pigment surface and the paint increases as the storage period becomes longer, and more resin is adsorbed on the pigment surface, so that the intermolecular force between the pigments is weakened and the thixotropic property is lowered.
  • the viscosity of the paint with a low share can be adjusted by adding an additive such as a dispersant to the paint.
  • the difference in surface tension between the paint for forming the high-concentration pigment layer and the paint for forming the topcoat layer is reduced, and these paints are laminated in an undried state, and simultaneously dried and baked. When cured, the boundary surface Ra increases.
  • the difference in surface tension between the paint for forming the high-concentration pigment layer and the paint for forming the topcoat layer varies depending on the resin type and solvent type of each layer, so it cannot be specified unconditionally. It is necessary to investigate in advance for each paint to determine the optimum value.
  • the surface tension of the paint can be adjusted by using an additive generally called a surfactant, such as a leveling agent or an antifoaming agent, but may be adjusted by changing the kind of the solvent.
  • the center line average roughness Ra of the boundary surface between the high-concentration pigment layer and the topcoat layer needs to be 0.8 ⁇ m or more.
  • a rutile type titanium oxide having a particle diameter of 200 nm to 400 nm is added to the high concentration pigment layer so as to be more than the closest packing with respect to the volume of the coating film after drying, A method of laminating the paint for forming the topcoat layer in an undried state, and simultaneously drying and curing in the laminated state can be mentioned.
  • the Ra of the boundary surface between the high-concentration pigment layer and the topcoat layer can be 0.8 ⁇ m or more.
  • the control of Ra at the boundary surface between the high-concentration pigment layer and the topcoat layer is greatly influenced by the viscosity of the paint with a low share. Ra of the boundary surface between the density pigment layer and the overcoat layer can be further increased.
  • the high-concentration pigment layer-forming paint and the topcoat layer-forming paint are applied by a wet-on-wet method or a multi-layer simultaneous coating method, so that the rutile in the high-concentration pigment layer-forming paint is applied. Since the type titanium oxide diffuses into the overcoat phase forming paint beyond the interface of each layer, a concentration gradient layer of rutile type titanium oxide is formed in the vicinity of the interface between the high concentration pigment layer and the overcoat layer. In the present invention, the concentration gradient layer of the present titanium oxide is called a mixed layer.
  • the adhesion between the high-concentration pigment layer and the topcoat layer can be improved by the mixed layer present at the boundary portion between the high-concentration pigment layer and the topcoat layer.
  • the total light reflectivity of the coated metal material may be reduced by processing after painting.
  • the presence of the mixed layer improves the adhesion, so A decrease in reflectance can also be suppressed.
  • the “mixed layer” refers to a layer in which the concentration of the rutile type titanium oxide has an inclined structure by diffusing the rutile type titanium oxide of the high concentration pigment layer into the top coat layer. . More specifically, in this embodiment, focusing on rutile-type titanium oxide, when the Ti amount of the high pigment concentration layer is x and the Ti amount of the overcoat layer is y, [x + 0.05 ⁇ (x ⁇ y)] to [y-0.05 ⁇ (xy)] are assumed to be mixed layers. Each Ti amount can be determined by an analysis method described later, and can be calculated by regarding the measured intensity when Ti is measured by each analyzer as the amount.
  • a mixed layer may be formed between the undercoat layer and the high-concentration pigment layer, which will be described later.
  • the definition of the mixed layer and the definition of the boundary surface are the same between the high-concentration pigment layer and the overcoat layer. It is the same as the mixed layer in between.
  • the volume ratio of the low-refractive-index particles to the rutile-type titanium oxide is the volume concentration of the rutile-type titanium oxide if the low-refractive-index particles are inorganic pigments, for example. It can obtain
  • rutile type titanium oxide for example, among the heating residue, rutile type titanium oxide does not dissolve, using chemicals such as acid that dissolves only low refractive index particles, dissolves only low refractive index particles,
  • the mass of the low refractive index particles can be determined from the difference in mass between the dissolved residue and the heated residue, and the volume of the low refractive index particles can be determined from the mass and the density of the low refractive index particles.
  • the cross section of the coating layer is observed with a scanning electron microscope, or the coating layer is For example, there is a method of thinly cutting with a microtome or the like and observing it with a transmission electron microscope (magnification about 10,000 times). Specifically, it can be determined by counting the number of rutile titanium oxide and low refractive index particles recognized in the visual field. However, if the number is small, the error becomes large. Therefore, it is preferable to count the number of particles in a range where at least 100 rutile-type titanium oxides are present.
  • the electron beam transmittance of low refractive index particles is not so different from that of rutile titanium oxide, and the difference between low refractive index particles and rutile titanium oxide is difficult to understand with a scanning electron microscope or transmission electron microscope.
  • the elemental composition can be confirmed using EPMA (electron beam microanalyzer), GDS (glow discharge emission spectroscopic analyzer) or the like.
  • the mixed layer when the above-described mixed layer is present, the mixed layer preferably has a thickness of 3 ⁇ m to 12 ⁇ m.
  • the thickness of the mixed layer is less than 3 ⁇ m, the effect of improving the adhesion between the high-concentration pigment layer and the topcoat layer by the mixed layer may not be stably obtained.
  • the thickness of the mixed layer exceeds 12 ⁇ m, it becomes difficult to sufficiently secure the thicknesses of the high-concentration pigment layer and the overcoat layer that share the necessary functions.
  • the topcoat layer is the outermost layer, it is difficult to maintain the performance of the high-concentration pigment layer and the topcoat layer itself, such as appearance failure due to insufficient thickness of the outermost layer, and the paint for forming the high-concentration pigment layer substantially. Therefore, the required performance of the high-concentration pigment layer and the topcoat layer cannot be obtained. In addition, it is substantially difficult to control the thickness of the mixed layer to a thickness exceeding 12 ⁇ m.
  • the film thickness of the mixed layer can be determined by analyzing the distribution state in the film thickness direction of components contained only in either the high-concentration pigment layer or the topcoat layer.
  • an analysis method a known analysis method may be used. For example, ** X-ray probe microanalyzer, electron beam microanalyzer (EPMA), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Using glow discharge emission analysis (GDS) **, etc., analyze the element concentration in the depth direction of the coating film, or analyze the composition of the mixed layer from the concentration distribution of the target component by component analysis in the coating section.
  • the film thickness can be determined.
  • the type and method of component analysis to be applied may be appropriately selected according to the film thickness, component amount, and the like. Any method other than EPMA, XPS, AES, and GDS may be selected as long as the component analysis in the depth direction is possible.
  • the component that can be used for the analysis of the mixed layer may be other than Ti. Among these analysis methods, GDS is suitable because it can be analyzed while sputtering in the depth direction with inert argon ions from the surface of the coating film, and the concentration in the depth direction of the measurement element can be compared with high accuracy.
  • the film thickness of the mixed layer in the present invention is an average film thickness measured at any five locations.
  • the thickness of the mixed layer can be controlled mainly by the coating method and baking time.
  • a coating method a mixed layer can be easily formed by employing a wet-on-wet method or a multilayer simultaneous coating method.
  • the baking time is from 60 seconds to By setting it as about 180 seconds, the thickness of a mixed layer can be 3 micrometers or more and 12 micrometers or less.
  • the type and coating conditions of the paint by appropriately adjusting the relationship between the surface tension and the viscosity of the high-concentration pigment layer forming the mixed layer and the paint for the topcoat layer to an appropriate value within the above conditions, A stable mixed layer can be generated, the film thickness can be controlled, and the shape of the outermost surface can be controlled.
  • the surface tension of the paint can be measured by a platinum ring pulling method at 20 ° C. (For details of such surface tension measurement, refer to JIS K.3362.8.4.2.
  • the viscosity of the paint can be measured with a B-type viscometer at 20 ° C. and ** 6 mpm ** (for details of such viscosity measurement, see JIS.Z.8803.8 “single cylinder type”). This can be done in accordance with the “viscosity measurement method using a rotational viscometer”).
  • a surfactant (including an antifoaming agent and a leveling agent) is preferably used for adjusting the surface tension of the paint.
  • the surfactant publicly known ones can be used, and examples of commercially available ones include BYK-333, BYK-307 from BYK and Ermagen from Kao, etc. It can be added appropriately depending on the paint component.
  • the surface tension of the coating material may be adjusted by a method other than the surfactant, such as dilution or mixing with another solvent. If the surface tension is too large, the paintability may be deteriorated. Therefore, it is preferable that the surface tension of the high-concentration pigment layer coating material and the top coating layer coating material is 40 mN / m or less.
  • a thickener including a rheology modifier and a viscosity modifier
  • a thickener including a rheology modifier and a viscosity modifier
  • known ones can be used, and examples of commercially available ones include BYK-411 and BYK-425 manufactured by BYK, but there are many others depending on the paint components. It can be added as appropriate.
  • the viscosity of the paint may be adjusted by a method other than a thickener such as dilution, mixing with another solvent, or increasing the ratio of solid components.
  • the thickness of the mixed layer can also be controlled by adjusting the difference between the pigment concentration in the high-concentration pigment layer paint and the pigment concentration in the overcoat layer paint. That is, as the difference in pigment concentration increases, the diffusion rate of the pigment from the high-concentration pigment layer to the topcoat layer increases, so before the high-concentration pigment layer paint and the topcoat layer paint are dried and cured, A mixed layer having a sufficient thickness can be formed.
  • the filtering center line waviness W CA on the outermost surface of the coating layer is 2 ⁇ m or less.
  • W CA of the outermost surface of the coating layer is more than 2 [mu] m, sharpness and stain resistance may deteriorate.
  • the preferred lower limit of the W CA of the outermost surface of the coating layer is not particularly necessary to define, it is difficult to substantially control those W CA of the outermost surface of the coating layer is less than 0.2 ⁇ m Therefore, from such a viewpoint, it is preferable that the W CA on the outermost surface of the coating layer is 0.2 ⁇ m or less.
  • W CA of the present invention is the average determined for any five locations.
  • the “outermost surface of the coating layer” here means the surface of the outermost coating layer of the coating layer.
  • the coating layer when the coating layer is further laminated on the surface of the top coating layer or the top coating layer according to this embodiment, the coating layer. Means.
  • the W CA on the outermost surface of the coating layer changes due to the influence of Ra on the boundary surface between the high-concentration pigment layer and the overcoat layer. Therefore, the W CA on the outermost surface of the coating layer can be controlled mainly by the coating method and the viscosity of the paint with a low share. Specifically, since the rubbing type titanium oxide diffuses from the high-concentration pigment layer to the topcoat layer by setting the coating method to a wet-on-wet method or a multilayer simultaneous coating method, the boundary surface between the high-concentration pigment layer and the topcoat layer the Ra is increased, the greater W CA of the outermost surface of the coating layer.
  • the rutile titanium oxide in the high concentration pigment layer is easily diffused into the overcoat layer, so that Ra on the boundary surface increases, and the coating layer The outermost surface WCA also increases.
  • the coating layer of the outermost layer of the coating layers formed on the metal material may contain silicone resin or fluorine resin.
  • the “coating layer of the outermost layer” refers to the overcoating layer when the above-described overcoating layer is formed on the outermost layer, and a coating layer is further laminated on the surface layer side of the overcoating layer. If it is, it means the coating layer.
  • oil repellency and water repellency are imparted to the coating film surface by using silicone resin or fluorine resin as part or all of the binder of the outermost coating layer of the coated metal material according to the present embodiment. can do.
  • silicone resin or fluorine resin as part or all of the binder of the outermost coating layer of the coated metal material according to the present embodiment.
  • a method of adding a silicone resin or a fluorine resin to the outermost coating layer a method of adding a silicone resin or a fluorine resin to the outermost coating layer, a method containing a silicone resin or a fluorine resin as a main resin There is a method of using.
  • Examples of commercially available silicone resins to be added to the outermost coating layer include “BYK (registered trademark) -306” and “BYK (registered trademark) -378” manufactured by BYK.
  • BYK (registered trademark) -340” manufactured by BYK is known as a commercially available fluororesin added to the outermost coating layer. There are many, and can be added as appropriate according to the paint components.
  • silicone-acrylic copolymer resins for example, “Saimak (registered trademark)” series and “Reseda (registered trademark)” series manufactured by Toa Gosei Co., Ltd. Manufactured "SQ (registered trademark) 100" or the like, and commercially available silicone-fluorine copolymer resin (for example, "ZX-001” manufactured by Fuji Kasei Kogyo Co., Ltd.) can be used.
  • the silicone / acrylic copolymer resin or silicone / fluorine copolymer resin may be crosslinked with a generally known crosslinking agent, for example, an isocyanate or a melamine resin, if necessary.
  • a generally known crosslinking agent for example, an isocyanate or a melamine resin, if necessary.
  • an isocyanate commercially available ones such as “Sumijour (registered trademark)” series, “Desmodule (registered trademark)” series manufactured by Sumika Bayer Co., Ltd., “Takenate (registered trademark)” manufactured by Mitsui Takeda Chemical Co., Ltd. Trademark) "series and the like.
  • melamine resins that are generally available on the market include, for example, “Cymel (registered trademark)” series, “My Coat (registered trademark)” series manufactured by Mitsui Cytec Co., Ltd., “Beccamin (registered trademark)” manufactured by Dainippon Ink and Chemicals, Inc. "Series”, “Super Becamine (registered trademark)” series, etc. can be used.
  • the coated metal material containing the silicone resin or fluorine resin in the outermost coating layer is suitable for use in applications such as ceilings and wall materials in the room in addition to the use as a reflector for lighting equipment. is there.
  • the ceiling or wall material itself also serves as a reflector. Since it can be carried, the room can be brightened with a smaller amount of light.
  • the coating layer of the outermost layer of the coating layers formed on the metal material has -Si-O-Si- bonds in the resin skeleton forming the coating film.
  • the “coating layer of the outermost layer” refers to the overcoating layer when the above-described overcoating layer is formed on the outermost layer, and a coating layer is further laminated on the surface layer side of the overcoating layer. If it is, it means the coating layer.
  • Si in the —Si—O—Si— bond is derived from alkoxysilane or a hydrolysis condensate of alkoxysilane.
  • the coated metal material according to the present embodiment When the coated metal material according to the present embodiment is applied to a precoated metal plate, there is a concern that the total light reflectance is reduced due to adhesion of dirt during processing.
  • -Si-O-Si- is formed in the coating film of the outermost layer of the coated metal material according to the present embodiment, that is, Si derived from alkoxysilane or a hydrolysis condensate of alkoxysilane is contained.
  • hydrophilicity can be imparted to the surface of the coating film without impairing the gloss and processability of the surface.
  • alkoxysilane or a hydrolysis condensate of alkoxysilane is added to the coating film for forming the outermost coating layer. That's fine.
  • the alkoxysilane used at this time is generally known, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxy.
  • Silane, dimethoxydiethoxysilane, dimethoxydipropoxysilane, etc. are mentioned.
  • hydrolysis condensate of an alkoxysilane the hydrolysis condensate of the alkoxysilane illustrated above is mentioned, for example.
  • the coating metal material in which -Si-O-Si- is formed in the outermost layer coating is applied to the use of the ceiling or wall material in the room in addition to the use of the reflector of the lighting fixture. It is suitable for. And, when the coated metal material in which -Si-O-Si- is formed in the outermost layer coating is applied to the use such as indoor ceiling or wall material, the indoor ceiling or wall material itself is also a reflector. The room can be brightened with a smaller amount of light.
  • the coating metal material which concerns on this embodiment is a resin skeleton which forms the coating film layer (For example, the coating layer containing the silicone resin or fluorine resin mentioned above, or a coating film further on the surface layer side of a top coat layer)
  • the above-mentioned characteristics such as water repellency, oil repellency and hydrophilicity are obtained for the film thickness of the outermost coating layer.
  • the film thickness of the coating layer of the outermost layer is 1 micrometer or more and 25 micrometers or less.
  • the film thickness of the outermost coating layer is less than 1 ⁇ m, water repellency, oil repellency and hydrophilicity may be insufficient, and if it exceeds 25 ⁇ m, processability may be inferior, and cost may be reduced. Therefore, it is not preferable.
  • the coating layer of the coated metal material according to this embodiment may include an undercoat layer in addition to the high-concentration pigment layer and the overcoat layer described above.
  • This undercoat layer is a coating layer formed between the metal material and the high-concentration pigment layer, and when the coating layer is composed of three layers of an overcoat layer, a high-concentration pigment layer, and an undercoat layer, It becomes the coating layer on the side closest to the metal material.
  • the coating layer having a film thickness of less than 1 ⁇ m provided for the purpose of improving the adhesion between the metal material and the coating film and improving the corrosion resistance is an undercoat according to this embodiment.
  • a coating layer on the surface layer side of the coating layer having a film thickness of less than 1 ⁇ m is used as the undercoat layer.
  • the resin used as the binder of the undercoat layer is not particularly limited, but it is used including the same resin as the high concentration pigment layer from the viewpoint of adhesion to the high concentration pigment layer and common use of paint raw materials. It is preferable to do. Therefore, since it is preferable to use the polyester resin A having a number average molecular weight of 19000 or more and 28000 or less as the binder of the high concentration pigment layer, it is preferable to use the polyester resin A as the binder also in the undercoat layer. If the number average molecular weight of the polyester resin used as the binder for the undercoat layer is less than 19000, the workability and adhesion may be reduced. If the number average molecular weight exceeds 28000, the surface of the coating film becomes too soft and wrinkle resistant. Property and blocking property may be deteriorated.
  • concentration of the polyester resin A with respect to the whole binder resin is 80 mass% or more, since the effect of an improvement of workability and adhesiveness can be exhibited, It is preferable that the density
  • the rutile type titanium oxide is added to the undercoat layer as a pigment in a solid content volume concentration of 20% or more and 35% or less, the reflectance is further improved, which is preferable.
  • the reason why rutile-type titanium oxide is suitable as a pigment to be added to the undercoat layer is that the refractive index of rutile-type titanium oxide is higher than that of other commonly used pigments, as in the case of the high-concentration pigment layer.
  • the difference in refractive index between the resin used and the air in the voids existing between the pigment particles can be increased, thereby increasing the light reflectivity at the pigment-resin interface and the pigment-air interface. It is.
  • the average particle size of the rutile titanium oxide is smaller, the surface area per unit volume is larger, and the area of the interface between the resin or the void as a light reflecting surface and the pigment is larger. Since it becomes wider, the total light reflectance also becomes high, but when the average particle diameter of the pigment becomes too small, light having a long wavelength is transmitted, so that the total light reflectance is lowered. Therefore, as in the case of the high-concentration pigment layer, the average particle size of the rutile titanium oxide used as the pigment in the undercoat layer is preferably 200 nm or more and 400 nm or less, and more preferably 250 nm or more and 350 nm or less.
  • the thickness of the undercoat layer Regarding the film thickness of the undercoat layer, the higher the film thickness, the higher the workability and adhesion, and the more reflective the reflective performance when rutile titanium oxide is added as the pigment, the more advantageous. Therefore, it is not necessary to set the upper limit value of the thickness of the undercoat layer from these performance aspects. However, when the film thickness of the undercoat layer exceeds 30 ⁇ m, unlike the high concentration pigment layer, the pigment concentration in the paint is low, so boiling easily occurs during painting, paintability is deteriorated, and the viewpoint of paint cost. Is also not preferable. Therefore, the thickness of the undercoat layer is preferably 30 ⁇ m or less.
  • the film thickness of the undercoat layer is less than 5 ⁇ m, the effect of improving the workability, adhesion and reflection performance by the undercoat layer is reduced, and therefore the film thickness of the undercoat layer is preferably 5 ⁇ m or less.
  • a more preferable thickness of the undercoat layer is 10 ⁇ m or more and 25 ⁇ m or less.
  • Base material metal material used for the base material of the coated metal material according to the present embodiment
  • metal materials or alloy materials can be used.
  • the metal material include a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a titanium plate, and a copper plate.
  • the surface of these metal materials or alloy materials may be plated.
  • the type of plating include zinc plating, aluminum plating, copper plating, nickel plating, and the like, and may be alloy plating thereof.
  • a hot dip galvanized steel plate an electrogalvanized steel plate, a zinc-nickel alloy plated steel plate, a hot galvanized steel plate, an aluminum plated steel plate, an aluminum-zinc alloyed plated steel plate, etc.
  • a hot dip galvanized steel plate an electrogalvanized steel plate, a zinc-nickel alloy plated steel plate, a hot galvanized steel plate, an aluminum plated steel plate, an aluminum-zinc alloyed plated steel plate, etc.
  • steel plates and plated steel plates can be applied.
  • a chemical conversion treatment on the surface of the metal material used in the present embodiment because adhesion between the metal material and the coating layer, corrosion resistance, and the like are improved.
  • chemical conversion treatment those commonly applied can be used.
  • zinc phosphate chemical conversion treatment, chromate-free chemical conversion treatment, coating-type chromate treatment, electrolytic chromic acid treatment, reaction Chromate treatment etc. can be used.
  • coating-type chromate treatment, electrolytic chromic acid treatment, and reactive chromate treatment are less preferred because they contain hexavalent chromium, which is an environmentally hazardous substance.
  • the zinc phosphate chemical conversion treatment may be inferior in work adhesion as compared with other treatments. Therefore, as the chemical conversion treatment applied to the metal material according to this embodiment, a chromate-free treatment is suitable.
  • the chromate-free chemical conversion treatment includes an inorganic chemical conversion treatment agent and an organic chemical conversion treatment agent, and any of them may be used.
  • a chromate-free chemical conversion treatment for example, a treatment using an aqueous solution containing a silane coupling agent, a zirconium compound, a titanium compound, tannin or tannic acid, a resin, silica, or the like is known.
  • the present invention is mainly described based on an example in which the present invention is applied to a precoat metal material.
  • the present invention is not limited to a precoat metal material, and may be applied to a postcoat metal material.
  • a post-coated metal material unlike a pre-coated metal material, processing adhesion and the like are not necessarily required, but when used as a reflector, it is necessary to have a high total light reflectance. .
  • the solid content concentration of the low refractive index particles is high. It is possible to set Ra of the boundary surface between the density pigment layer and the overcoat layer to 0.8 ⁇ m or more. Further, after forming a high concentration pigment layer on the processed metal material, the surface of the formed high concentration pigment layer is physically wrinkled so that the surface Ra is rough so as to be 0.8 ⁇ m or more. Then, even if the overcoat layer coating is applied thereafter, the Ra of the boundary surface between the high-concentration pigment layer and the overcoat layer can be 0.8 ⁇ m or more.
  • the method for producing a coated metal material according to the present embodiment includes a high pigment concentration layer containing rutile-type titanium oxide in a solid content volume concentration of 35% or more and 70% or less, and an overcoat layer laminated on the surface layer side of the high concentration pigment layer. Are formed such that the center line average roughness Ra of the boundary surface between the high-concentration pigment layer and the overcoat layer is 0.8 ⁇ m or more.
  • the details of the method for producing a coated metal material according to the present embodiment will be described separately for the case where the painted metal material is a pre-coated metal material and the case of a post-coated metal material.
  • the coated metal material according to the present embodiment is manufactured by appropriately selecting a necessary process using a general continuous coating line (referred to as “CCL”) and a coating line for a cut plate, and performing the selected process. it can.
  • the typical manufacturing process of the painting line is “washing” ⁇ “drying” ⁇ “chemical conversion treatment” ⁇ “drying” ⁇ “painting” ⁇ “drying / baking” ⁇ “cooling” ⁇ “drying”.
  • the manufacturing process of the coated metal material in the embodiment is not limited to this.
  • the coated metal material according to the present embodiment may be manufactured by repeating painting and drying / baking for each coating layer as usual, but a paint for forming a high concentration pigment layer, It is preferable from the viewpoint of the performance and productivity of each layer that the coating for forming the topcoat layer is applied to a part or all of the surface of the metal material using a multi-layer simultaneous application or wet-on-wet method. .
  • the coated metal material according to the present embodiment further has an outermost coating layer (for example, a coating layer containing the above-described silicone resin or fluorine resin) on the surface layer side of the topcoat layer
  • an outermost coating layer for example, a coating layer containing the above-described silicone resin or fluorine resin
  • the wet-on-wet coating facility or the simultaneous multilayer coating facility after the plating process in the continuous electroplated steel sheet facility or the continuous hot-dip galvanized steel sheet facility can be applied before the oxide film on the surface of the plated metal is formed, and the appearance of repellency due to the oxide film can be prevented.
  • multi-layer simultaneous application means that a plurality of coating liquids are simultaneously applied by a device capable of discharging different paints from two or more parallel slits such as a slot die coater or a slide hopper type curtain coater. It is a method of applying to a base material in a laminated state, and simultaneously drying and baking this laminated coating liquid.
  • wet-on-wet coating refers to a multilayered structure in which a coating liquid is once coated on a substrate and then coated with another coating liquid on the wet state before the coating liquid dries.
  • the coating liquid is simultaneously dried and baked.
  • a coating layer such as a roll coater, a dip, a curtain flow coater, or a roller curtain coater is applied, and then this coating layer is dried and baked.
  • a second layer is applied in a non-contact manner with a substrate such as a curtain flow coater, roller curtain coater, slide hopper type curtain coater, slot die coater, etc., and then laminated.
  • a method of simultaneously drying and baking the wet multilayer coating film for example, a coating layer such as a roll coater, a dip, a curtain flow coater, or a roller curtain coater is applied, and then this coating layer is dried and baked.
  • a second layer is applied in a non-contact manner with a substrate such as a curtain flow coater, roller curtain coater
  • a generally known coating baking furnace for example, a hot air drying furnace, a direct heating furnace, an induction heating furnace, infrared heating A furnace, a furnace using these in combination, or the like can be used.
  • the coating liquid of each layer is slightly mixed at the boundary of the coating liquid, thereby forming a mixed layer in which the components of each layer are mixed.
  • interlayer adhesion can be improved.
  • the drying process conventionally performed for each layer is performed collectively, it is advantageous in terms of productivity and manufacturing cost, and there is an advantage that less drying equipment is required.
  • the coated metal material by the post coat according to the present embodiment is subjected to a chemical conversion treatment or the like on the metal material as described above, and then the illumination reflector, the reflector of the light emitting component, in which the painted metal material according to the present embodiment is used, Alternatively, it is manufactured by being formed into a shape such as a reflection plate of the image display unit and then painted by post-coating.
  • a method for forming the metal material a known method can be used.
  • a method of post coating known methods such as spray coating, immersion coating, curtain flow coater coating, brush coating and electrostatic coating can be used. Even in the case of a post-coated metal material, wet-on-wet coating can be performed by spray coating or the like.
  • this painted metal material has both high total light reflectivity and formability at a high level. Even if the number of light sources is reduced or the input power is reduced, it is possible to ensure the same brightness as before. Furthermore, since the coated metal material according to the present embodiment has a characteristic that it can be easily formed into various shapes or can be formed into a more complicated shape, it can be applied to a wide range of applicable electronic devices and applied parts. The effect of improving productivity can be expected.
  • the electronic device that can make use of such characteristics is not particularly limited, and can be used, for example, as an illumination reflector, a reflector of a light emitting component, or a reflector of an image display unit. More specific examples of these include lighting fixtures, lighting, AV equipment, mobile devices, various displays, etc., but lighting reflectors, reflectors in interior signs, backlight reflectors for liquid crystal displays, etc. It is preferable to use for.
  • paint used in this example will be described in detail.
  • a coated metal material a three-layer structure of an undercoat layer, a high-concentration pigment layer (intercoat layer), and an overcoat layer laminated in order from the steel plate side on the surface of a galvanized steel plate as a base material, or A precoated steel sheet coated with a coating layer having a four-layer structure of an undercoat layer, an intermediate coat layer, and two overcoat layers was used.
  • undercoat paint paint for undercoat layer
  • paint for high-concentration pigment layer intercoat layer
  • paint for topcoat layer referred to as “overcoat paint”.
  • the paint components used are described in the order of).
  • Intermediate paint For intermediate coatings, as shown in Table 1, as a base resin, “Byron (registered trademark)” series, which is an amorphous polyester resin manufactured by Toyobo Co., Ltd., and an amorphous polyester resin manufactured by Sumika Bayer Urethane Co., Ltd. The “Desmophen®” series was used. For example, in the intermediate coating-1 to 20, “Byron (registered trademark) 630” (number average molecular weight 23000, hydroxyl value 5) and “Desmophen (registered trademark) 690, which is an amorphous polyester resin manufactured by Sumika Bayer Urethane Co., Ltd., are used.
  • Tipec registered trademark
  • CR95 reffractive index: 2.5
  • silica “Sunsphere (registered trademark) H-31” (average particle size: 3 ⁇ m) manufactured by Asahi Glass Co., Ltd. was used.
  • barium sulfate “BARIACE (registered trademark) B-30” (refractive index: 1.6) manufactured by Sakai Chemical Industry Co., Ltd. having an average particle size of 300 nm, an average particle size of 290 nm Zinc oxide “fine zinc oxide” (refractive index: 2.0) manufactured by Sakai Chemical Industry Co., Ltd. was also used.
  • the viscosity of the paint with a low share of the intermediate coating was adjusted by changing the amount of solvent, the storage temperature of the paint, and the storage period.
  • the value measured at the rotation speed of 6 rpm was used using a B-type viscometer (model: B-8L) manufactured by Tokyo Keiki Co., Ltd.
  • Top coat For the top coating, as shown in Table 3 below, “Byron (registered trademark) 630” (number average molecular weight 23,000, hydroxyl value 5), which is an amorphous polyester resin manufactured by Toyobo Co., Ltd., is used as an organic solvent (Solvesso). 150 and cyclohexanone mixed in a mass ratio of 1: 1) were used.
  • Cymel (registered trademark) 303 which is a commercially available fully alkyl methylated melamine resin (hereinafter referred to as methylated melamine) manufactured by Mitsui Cytec Co., Ltd., is 15 A clear paint was obtained by adding 0.5 parts by mass of “Catalyst (registered trademark) 6003B” manufactured by Mitsui Cytec Co., Ltd., which is a commercially available acid catalyst.
  • rutile titanium oxide using “Taipek (registered trademark) CR95” (refractive index: 2.5) manufactured by Ishihara Sangyo Co., Ltd., which is rutile titanium oxide having an average particle size of 280 nm. was mixed with a binder such that the solid content volume concentration was 25% to prepare a top coat (top coat-1).
  • top coat-1 using the same binder resin and pigment as the above-mentioned top coat-1 and further adding 1 part by mass of BYK-306, which is a silicone additive of BYK, to 100 parts by mass of the total amount of binder resin and pigment.
  • a coating material (top coating-3) to which 0.5 part by mass of BYK-340, which is a fluorine-based additive of BYK, was added was also prepared.
  • "Super Becamine (registered trademark) J830” which is a butylated melamine resin manufactured by Chemical Industry Co., Ltd. and "Cymel (registered trademark) 303” which is a methylated melamine manufactured by Mitsui Cytec Co., Ltd. were mixed at a mass ratio of 1: 1. A thing was used.
  • top coat-4 a clear paint
  • top coat-5 a top coat (top coat-5).
  • top coats-8 and 9 prepared in the same manner as top coats 4 and 5 except that “ZX-001”, which is a silicone / fluorine copolymer resin manufactured by Fuji Kogyo Co., Ltd., was used as the base resin for the binder. did.
  • top coating-10 which added 20 mass parts of tetraethoxysilane with respect to 100 mass parts of total amounts of binder resin and a pigment was also produced using the same binder resin and pigment as the said top coating-1.
  • the prepared original plate is spray-degreased with a 2% by weight, 50 ° C. aqueous solution of an alkaline degreasing solution “FC-4336” manufactured by Nihon Parkerizing Co., Ltd., washed with water, dried, and then chromate-free formed by Nihon Parkerizing Co., Ltd.
  • the treatment “CT-E300N” was applied with a roll coater and dried in a hot air oven. The drying conditions in the hot air oven were 60 ° C. at the ultimate plate temperature of the steel plate.
  • the coating amount of the chromate-free treatment was applied so that the total solid content was 200 g / m 2 .
  • the prepared undercoat paint is applied to one surface of the metal plate subjected to chemical conversion treatment with a roll coater so that the film thickness after drying is 20 ⁇ m, and the other surface is manufactured by Nippon Fine Coatings Co., Ltd.
  • water was wiped with a spray to the painted metal plate, and water-cooled.
  • a pre-coated metal plate having a three-layer coating layer was also prepared by coating one layer of top coating and baking in the manner described above (the coating method in this procedure is referred to as “coating method (ii)”).
  • an intermediate coating and a top coating, and then a top coating on top of the undercoat coating layer are simultaneously laminated using a slide hopper type curtain coater, and hot air is blown into the induction.
  • the laminated coating film was simultaneously dried, baked and cured in a heating furnace under the condition that the ultimate plate temperature of the metal plate was 220 ° C.
  • a pre-coated metal plate having a four-layer coating layer was prepared by wiping water on the coated metal plate with a spray and water cooling (hereinafter, the coating method in this procedure is referred to as “ It is referred to as “painting method (iii)”).
  • ⁇ When the total light reflectance is 99% or more ⁇ ⁇ ⁇ : When the total light reflectance is 97% or more and less than 99% ⁇ : When the total light reflectance is 95% or more and less than 97% ⁇ ⁇ ⁇ : Total light When the reflectance is 93% or more and less than 95% ⁇ : When the total light reflectance is 91% or more and less than 93% ⁇ ⁇ ⁇ : When the total light reflectance is 89% or more and less than 91% ⁇ : Total light reflectance If less than 89%
  • Luminance measurement of lighting equipment Fig. 1 and Fig. 2 show an outline of the experimental apparatus.
  • the coated substrate was formed into a shape in which both end portions in the longitudinal direction were bent on the upper surface side as shown in FIGS.
  • Two commercially available fluorescent lamp luminaires 2 were mounted side by side, and a cover 3 formed of ground glass was mounted thereon.
  • the brightness of the central part (hereinafter referred to as “brightness measuring part”) 4 of the cover 3 and the part 5 (hereinafter referred to as “brightness uniformity comparison measuring part”) 5 shifted from the central part 4 to the outside by 1.5 cm.
  • the luminance meter 6 was installed at a distance of 50 cm vertically from the measurement point.
  • the fluorescent lamp illuminator 2 a fluorescent lamp with a 16-type lamp output of 16 W was used.
  • ⁇ When the luminance change rate is 30% or more ⁇ to ⁇ : When the luminance change rate is 25% or more and less than 30% ⁇ : When the luminance change rate is 20% or more and less than 25% ⁇ ⁇ ⁇ : The luminance change rate is 15 %: When the luminance change rate is 10% or more and less than 15% X: When the luminance change rate is less than 10%
  • the reference reflector was prepared by applying a white paint having a high reflectance, which is a means for increasing the reflectance of the conventional reflector surface.
  • the paint shown in Table 4 was applied by a method similar to the production of the primer-coated plate so that the film thickness after drying was 10 ⁇ m, and was dried and cured. On top of that, the coating materials shown in Table 4 are again applied with a roll coater so that the film thickness after drying is 20 ⁇ m, and the ultimate temperature of the metal plate becomes 230 ° C. in an induction heating furnace in which hot air is blown. Dry and cured under conditions. And after dry baking, water was wiped with a spray to the painted metal plate, and water-cooled.
  • ⁇ When the luminance uniformity is 90% or more
  • ⁇ When the luminance uniformity is 85% or more and less than 90%
  • ⁇ When the luminance uniformity is 70% or more and less than 85% ⁇ :
  • the luminance uniformity is 70 Less than%
  • the prepared pre-coated metal plate is bent 180 ° (adhesion bending) with an arbitrary number of samples sandwiched between them, and the coating film in the processed part is visually observed. The presence or absence of cracks was examined.
  • the pre-coated metal plate was bent so that the surface of the pre-coated metal plate was outside the bend, and was tightly bent (generally, 0T bend when no sample was sandwiched, and one sample was sandwiched) Is known as 1T bending). And the process part was observed visually and evaluated by the following references
  • the score is 8 for ⁇ , 7 for ⁇ , 6 for ⁇ to ⁇ , 5 for ⁇ , 4 for ⁇ to ⁇ , ⁇ 3 points, 2 points in the case of ⁇ ⁇ ⁇ , 1 point in the case of ⁇ , the scores of total light reflectivity and workability were added, the total was calculated, and the evaluation was performed according to the following criteria.
  • ⁇ Total score is 11 points or more
  • Total score is 9 points or more and less than 11 points
  • ⁇ Total score is 7 points or more and less than 9 points
  • Total score is less than 7 points
  • the boundary surface Ra between the intermediate coating layer and the top coating layer is a cross section perpendicular to the surface of the coating film by cutting the coating film of each example, embedding it in resin, and polishing it.
  • outermost surface W CA of the outermost surface of the measuring coating layer 6) outermost surface W CA was measured by Akinobu Kogyo three-dimensional surface shape measurement apparatus. Measurement was performed under the conditions of an evaluation length of 40 mm and a cutoff of 8 mm. For details, see JIS. It measured according to B0601. The measurement was performed at arbitrary five locations, and the average was obtained.
  • outermost surface W CA of the outermost surface of the measuring coating layer 6) outermost surface W CA was measured by Akinobu Kogyo three-dimensional surface shape measurement apparatus.
  • ⁇ E is less than 0.2 ⁇ ⁇ ⁇ : ⁇ E is 0.2 or more and less than 0.5 ⁇ : ⁇ E is 0.5 or more and less than 1 ⁇ : ⁇ E is 1 or more and less than 2 ⁇ : ⁇ E is 2 or more
  • Tables 4 to 6 show the configuration of the precoated metal sheet produced in this example and the evaluation results.
  • the precoated metal plates (NO. 1-42 and 48-62) according to the examples of the present invention had good results in all of the total light reflectance, luminance, coating film processability, and contamination resistance.
  • the Ra of the boundary surface between the intermediate coating layer and the top coating layer is 0.8 ⁇ m or more.
  • the area that can contribute to reflection increases, it can be seen that a high total light reflectance can be obtained. It can also be seen that excellent adhesion can be obtained because the contact area between the intermediate coating layer and the top coating layer increases.
  • a pigment that is not titanium oxide (NO. 43, 44) is not suitable because the total light reflectance is inferior.
  • a rutile-type titanium oxide having a volume concentration of less than 35% (NO. 45) in the intermediate coating layer is not suitable because the total light reflectance is inferior.
  • a rutile-type titanium oxide having a solid content volume concentration exceeding 70% (NO. 46) in the intermediate coating layer is not suitable because it has poor workability and adhesion.
  • a material having an Ra of less than 0.8 ⁇ m (NO. 47) at the boundary surface between the intermediate coating layer and the top coating layer is unsuitable because workability and adhesion are poor.
  • Ra is added to the intermediate coating layer together with the rutile titanium oxide and a low refractive index pigment having a particle size larger than that of the rutile titanium oxide, thereby improving the Ra of the boundary surface between the intermediate coating layer and the top coating layer. It can be seen that higher total light reflectivity and better adhesion can be obtained.
  • Ra of the boundary surface between the intermediate coating layer and the top coating layer can be improved by lowering the viscosity at a low share of the intermediate coating material, resulting in higher total light reflectance and better adhesion. It can be seen that However, too low a viscosity at low shear of the intermediate coating, the W CA of the outermost surface becomes 4 [mu] m (NO.16), stain resistance tended slightly inferior. Therefore, it can be seen that the outermost surface W CA is more preferably 2 ⁇ m or less.
  • the mixed layer present at the boundary between the intermediate coating layer and the top coating layer becomes thick, and higher total light reflectance and better adhesion can be obtained. Recognize. It can be seen that the thickness of the mixed layer present at the boundary between the intermediate coating layer and the top coating layer is more preferably 3 ⁇ m or more.
  • a precoating metal plate according to an embodiment of the present invention contains a silicone resin or a fluorine resin in the top coat layer or the outermost layer binder (NO. 58 to 62, 64 to 80), contamination resistance is obtained. It can be seen that the property is improved and more suitable.
  • the contamination resistance is improved, and it is more preferable. I know that there is.
  • the NO. No. 81 is particularly excellent in total light reflectance and luminance, and the intermediate coating layer has a thin film thickness of NO. It can also be seen that No. 82 is particularly excellent in workability and adhesion.

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JP2015516872A (ja) * 2012-03-30 2015-06-18 スリーエム イノベイティブ プロパティズ カンパニー 低屈折率材料のための保護コーティング
JP2016522338A (ja) * 2013-04-08 2016-07-28 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ 車両の周囲知覚をサポートする新規の路面標示物
WO2017090775A1 (ja) * 2015-11-26 2017-06-01 新日鐵住金株式会社 被覆金属板
JP2020171874A (ja) * 2019-04-08 2020-10-22 日鉄鋼板株式会社 被覆材及び菌又はウイルスの不活化方法

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JP2020142477A (ja) * 2019-03-08 2020-09-10 富士ゼロックス株式会社 塗装品、粉体塗料セット、及び、塗装品の製造方法

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WO2006062214A1 (ja) * 2004-12-08 2006-06-15 Nippon Steel Corporation プレコート金属板およびプレコート金属板の製造方法
WO2007013232A1 (ja) * 2005-07-28 2007-02-01 Nippon Steel Corporation プレコート金属板及びその製造方法
WO2010064725A1 (ja) * 2008-12-03 2010-06-10 新日本製鐵株式会社 塗装金属材及びその製造方法

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WO2006062214A1 (ja) * 2004-12-08 2006-06-15 Nippon Steel Corporation プレコート金属板およびプレコート金属板の製造方法
WO2007013232A1 (ja) * 2005-07-28 2007-02-01 Nippon Steel Corporation プレコート金属板及びその製造方法
WO2010064725A1 (ja) * 2008-12-03 2010-06-10 新日本製鐵株式会社 塗装金属材及びその製造方法

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Publication number Priority date Publication date Assignee Title
JP2015516872A (ja) * 2012-03-30 2015-06-18 スリーエム イノベイティブ プロパティズ カンパニー 低屈折率材料のための保護コーティング
JP2016522338A (ja) * 2013-04-08 2016-07-28 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ 車両の周囲知覚をサポートする新規の路面標示物
WO2017090775A1 (ja) * 2015-11-26 2017-06-01 新日鐵住金株式会社 被覆金属板
JPWO2017090775A1 (ja) * 2015-11-26 2018-10-11 新日鐵住金株式会社 被覆金属板
JP2020171874A (ja) * 2019-04-08 2020-10-22 日鉄鋼板株式会社 被覆材及び菌又はウイルスの不活化方法
JP7374605B2 (ja) 2019-04-08 2023-11-07 日鉄鋼板株式会社 被覆材及び菌又はウイルスの不活化方法

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