WO2011034216A1 - Coated metallic material and manufacturing method for same - Google Patents
Coated metallic material and manufacturing method for same Download PDFInfo
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- 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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- titanium oxide
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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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Abstract
Description
まず、本発明の一実施形態に係る塗装金属材の構成について説明する。 <Composition of painted metal material>
First, the structure of the coating metal material which concerns on one Embodiment of this invention is demonstrated.
本実施形態に係る高濃度顔料層は、白色顔料として、ルチル型酸化チタンを固形分体積濃度で35%以上70%以下含有する層であり、上塗り層よりも内層側、すなわち、基材である金属材により近い側に位置する。ただし、被覆層が、下塗り層、高濃度顔料層および上塗り層からなる3層構造である場合には、高濃度顔料層は、下塗り層と上塗り層とに接して挟まれた部分に位置する層とする。また、被覆層が、下塗り層、高濃度顔料層および上塗り層の3層に加えて、他の1以上の層を含む4層以上の複層構造を有する場合には、上塗り層と下塗り層との間に位置し、かつ、ルチル型酸化チタンを固形分体積濃度で35%以上70%以下含有する全ての層を高濃度顔料層とする。更に、被覆層においてルチル型酸化チタンの濃度が連続的に変化し、各層の境界が不明確な場合には、ルチル型酸化チタンの固形分体積濃度が35%以上70%以下の条件を満たす範囲全てを高濃度顔料層とする。 [High concentration pigment layer] (Overview)
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. However, when 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. And When 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.
本実施形態では、高濃度顔料層に含有させる顔料として、ルチル型酸化チタンを使用している。これは、ルチル型酸化チタンの屈折率が、一般的に使用される他の白色顔料よりも高く、バインダとして使用する樹脂や塗膜中の空隙に存在する空気との屈折率差を大きくできることから、顔料と樹脂との界面、および、顔料と空気との界面における全光線反射率をより高めることができるためである。なお、アナターゼ型酸化チタンも比較的高い屈折率を有するが、光触媒性が高く、蛍光灯等の光を受けた際に、バインダ樹脂が分解してしまう可能性があるため好ましくない。 (Rutile titanium oxide)
In this embodiment, 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.
<測定条件>
観察用試料の作製方法:試料を樹脂に埋め込み、試料の垂直断面
を研磨することで試料を作製した。
観察する視野:事前に500倍~1000倍程度の光学顕微鏡もしくは
電子顕微鏡(SEM)にて観察し、高濃度顔料層
に相当する層の任意の場所を選ぶ。
相加平均値を求めるルチル型酸化チタン粒子の選択方法:選んだ視野を電子顕微鏡(SEM)にて10000倍の倍率で観察した画像を撮影する。撮影された画像に映し出せているルチル型酸化チタン全粒子について、粒径を測定する。
個々のルチル型酸化チタン粒子の粒径の測定方法:ルチル型酸化チタン粒の粒径測定においては、各粒の最長径と最短径を測定し、1粒のルチル型酸化チタン粒径=(最長径+最短径)/2とする。
相加平均値の平均(?):上記「観察する視野」を任意に3箇所選択して、それら視野それぞれで得られた「相加平均値」を、更に算術平均する。 In addition, 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. 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.
Measuring method of particle size of individual rutile type titanium oxide particles: In measuring the particle size of rutile type titanium oxide particles, the longest diameter and the shortest diameter of each particle are measured, and one particle size of rutile type titanium oxide = (maximum Longest diameter + shortest diameter) / 2.
Average (?) Of arithmetic mean values: The above “observed visual field” is arbitrarily selected at three locations, and the “arithmetic mean values” obtained in the respective visual fields are further arithmetically averaged.
まず、試料から測定対象となる被覆層を上塗り層、高濃度顔料層、下塗り層のように各層ごとに削り取り、削り取った塗膜の面積A1および質量M1を測定する。次に、削り取った塗膜をるつぼを用いて500℃で1時間加熱し、樹脂成分を分解させる。分解せずに残った部分をルチル型酸化チタンと考えることができるので、その残部の質量M2を測定する。
一般的なルチル型酸化チタン顔料の密度は3800~4200kg・m−3程度であるので、ルチル型酸化チタン顔料の密度を4000kg・m−3と仮定し、また、一般的なポリエステル樹脂の密度は1150~1250kg・m−3程度であるので、ポリエステル樹脂の密度を1200kg・m−3と仮定して、ポリエステル樹脂の体積V1を、V1=(M1−M2)/1200kg・m−3、ルチル型酸化チタンの体積V2を、V2=M2/4000kg・m−3として求める。
このようにして求めたポリエステル樹脂の体積V1、ルチル型酸化チタンの体積V2から、ルチル型酸化チタンの体積濃度C1を、C1=V2/(V1+V2)×100(体積%)として求めることができる。
上記C1の測定を、1つの測定対象(例えば、高濃度顔料層)について、3回測定して、その算術平均を求める。 (Measurement method of solid content volume concentration of rutile titanium oxide)
First, 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. Next, 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.
Since 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, and 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, rutile The volume V2 of titanium oxide is determined as V2 = M2 / 4000 kg · m −3 .
From the volume V1 of the polyester resin thus obtained and the volume V2 of the rutile titanium oxide, the volume concentration C1 of the rutile titanium oxide can be obtained as C1 = V2 / (V1 + V2) × 100 (volume%).
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.
本実施形態に係る高濃度顔料層において、上述したルチル型酸化チタンよりも粒径が大きく、かつ、低い屈折率を有する粒子(以下、「低屈折率粒子」と称する場合がある。)を、ルチル型酸化チタンと併用すると全光線反射率をより効率的に高めることができるため好適である。ルチル型酸化チタンよりも粒径の大きな粒子を更に高濃度顔料層に添加することで、高濃度顔料層中の粒子間の空隙が大きくなり、より多くの空隙を含有させることができ、これにより、全光線反射率を向上させることができる。併せて、ルチル型酸化チタンと併用した粒径の大きな粒子が低屈折率の粒子であることで、この低屈折率粒子とルチル型酸化チタン粒子とが接触した部位の接触界面でも、ルチル型酸化チタン粒子と低屈折率粒子との屈折率差により光を反射させることができ、全光線反射率の向上に寄与することができる。 (Addition of other particles)
In the high-concentration pigment layer according to the present embodiment, 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. By adding 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. In addition, 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.
この低屈折率粒子と、ルチル型酸化チタンの相加平均径の比RL、すなわち、RL=(低屈折率粒子の相加平均径)/(ルチル型酸化チタンの相加平均径)は、1/40以上であることが好ましく、更には1/40~12/40(特に3/40~10/40)であることが好ましい。
なお、本実施形態における低屈折率粒子の平均粒径とは、ルチル型酸化チタンと同様に、塗膜の確認したい部分を電子顕微鏡により10,000倍で観察し、視野中に映し出される低屈折率粒子のうち、粒径の小さい方から数で20%に当たる分と粒径の大きい方から数で5%に当たる分の粒子を除いた残りの低屈折率粒子の粒径の相加平均値である(すなわち、低屈折率粒子の粒径の相加平均値も、上述した「ルチル型酸化チタン」の場合と同様に測定することができる)。 When the particle size of the low refractive index particles is excessively larger than the particle size of the rutile type titanium oxide, voids are efficiently contained in the high concentration pigment layer, and further, the low refractive index particles and It is difficult to achieve the effect of obtaining light reflection at the contact interface with titanium oxide. From such a viewpoint, the average particle diameter of the low refractive index particles is preferably 1 μm or more and 10 μm or less, and more preferably 3 μm or more and 8 μm.
The ratio R L of the low refractive index particles to the rutile titanium oxide, that is, R L = (the arithmetic average diameter of the low refractive index particles) / (the arithmetic average diameter of the rutile titanium oxide) is Is preferably 1/40 or more, more preferably 1/40 to 12/40 (particularly 3/40 to 10/40).
In addition, 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. (In other words, 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”).
高濃度顔料層中の空隙の含有率は、固形分体積量の0.05倍以上0.9倍以下が好ましい。空隙の含有率が固形分体積量の0.05倍未満では、空隙を含有させることによる全光線反射率の向上効果が少なく、空隙の含有率が固形分体積量の0.9倍を超えると、高濃度顔料層が脆くなり(機械的強度が低下し)、加工性および密着性が劣る可能性があるためである。この「空隙の含有率」は、後述する方法で測定することができる。 (Voids in the coating)
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. When 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.
従って、高濃度顔料層中の空隙のサイズは、光の反射率の向上の観点からは可視光波長の約半分である200nm~400nmであることが好ましく、250nm~350nmであることが更に好ましい。ただし、空隙のサイズを制御すること、特に、塗膜中の空隙のサイズを揃えることは困難であるため、上述のような塗膜欠陥等の問題や極端な反射率への影響が無ければ、空隙のサイズについては特に問題とはしない。なお、本実施形態では、空隙のサイズとして、空隙と同一の体積を有する球の直径である等体積球相当径を用いることとする。実際には、高濃度顔料層中の垂直断面の任意の箇所を走行型電子顕微鏡(SEM)にて10000倍の倍率で撮影し、この撮影画像に観察される任意の空隙を選び、この面積と同一の面性を有する円の直径を空隙と同一の体積を有する球の直径と同じであると定義して求めることができる。電子顕微鏡撮影画像に観察される空隙の内、任意の10個の空隙について径を算出し、この算術平均を空隙の径とすることができる。 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.
Therefore, 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. However, it is difficult to control the size of the voids, in particular, to uniform the size of the voids in the coating, so if there are no problems such as the above-mentioned coating film defects or extreme reflectance, The size of the gap is not particularly a problem. In the present embodiment, 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. Actually, an arbitrary portion of the vertical cross section in the high-concentration pigment layer was photographed with a traveling electron microscope (SEM) at a magnification of 10,000 times, and an arbitrary void observed in the photographed image was selected, and this area and It can be determined by defining that the diameter of a circle having the same surface property is the same as the diameter of a sphere having the same volume as the void. Of the voids observed in the electron microscopic image, the diameter can be calculated for any 10 voids, and this arithmetic average can be used as the void diameter.
上記膜厚T1の測定方法は、測定精度の点からは、光学顕微鏡もしくは電子顕微鏡(SEM)を用いた方法によることが好ましい。また、上記した空隙体積は、同一の試料(すなわち、被覆層)について5回測定して、その算術平均を求める。 First, after removing the coating layer to be measured from the sample, 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 **. Similarly to the case of obtaining the volume concentration of rutile type titanium oxide, the area A1 of the shaved coating film, the volume V1 of the binder resin (for example, polyester resin), and the volume V2 of the pigment (for example, rutile type titanium oxide). Ask for. From the obtained A1, V1 and V2, the film thickness T2 of the coating layer when there is no void is obtained as T2 = (V1 + V2) / A1. From the V1, V2, T1 and T2 thus determined, the void volume V3 can be determined from the equation V3 = (V1 + V2) × (T1−T2) / (T1 + T2).
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.
本実施形態に係る高濃度顔料層に使用するバインダ樹脂としては、特に限定されず、一般に使用されているバインダ樹脂、例えば、ポリエステル樹脂、ウレタン樹脂、エポキシ樹脂、アクリル樹脂、シリコーン樹脂、ふっ素樹脂等を用いることができる。ただし、本実施形態に係る高濃度顔料層には、最密充填以上となる量のルチル型酸化チタン粒子を添加するため、塗膜が脆くなりやすいことから、高濃度顔料層に使用するバインダ樹脂としては、加工性や密着性に優れる樹脂を使用することが好ましい。具体的には、バインダ樹脂として、例えば、数平均分子量が19000以上28000以下であるポリエステル樹脂Aを用いることが好ましい。これは、以下のような理由による。 (Binder resin)
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.
本実施形態に係る高濃度顔料層の膜厚は、高い全光線反射率を得るためには、10μm以上であることが好ましく、より高い全光線反射率を求める場合には40μm以上であることが更に好ましい。一方、高濃度顔料層の膜厚が80μmを超えると、塗膜の加工性が低下するおそれがあるため、高濃度顔料層の膜厚は100μm以下であることが好ましく、より高い加工性を求める場合には15μm以下であることが更に好ましい。ここで、本実施形態における高濃度顔料層の膜厚は、以下のようにして測定することができる。すなわち、各塗膜層の被覆面に対して垂直な面で試料をカットし、その断面を光学顕微鏡、電子顕微鏡で観察することにより、塗膜層の膜厚を求めることができる。この「膜厚」測定においては、任意の5箇所について測定した(算術)平均の膜厚とする。
なお、後述する上塗り層及び下塗り層の膜厚も、高濃度顔料層の膜厚と同様にして測定することができる。また、各塗膜層の境界部に混合層が形成された場合については後述する。 (Film thickness)
The film thickness of the high-concentration pigment layer according to the present embodiment is preferably 10 μm or more in order to obtain a high total light reflectance, and 40 μm 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 μm, the processability of the coating film may be lowered. Therefore, the film thickness of the high-concentration pigment layer is preferably 100 μm or less, and higher workability is required. In some cases, it is more preferably 15 μm or less. Here, the film thickness of the high-concentration pigment layer in the present embodiment can be measured as follows. That is, 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. In this “film thickness” measurement, the film thickness is the average (arithmetic) film thickness measured at any five points.
In addition, 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. Moreover, the case where a mixed layer is formed in the boundary part of each coating film layer is mentioned later.
以上、本実施形態に係る高濃度顔料層について詳細に説明したが、続いて、本実施形態に係る上塗り層について説明する。 [Overcoat layer]
Although the high-concentration pigment layer according to this embodiment has been described in detail above, the overcoat layer according to this embodiment will be described next.
本実施形態に係る上塗り層は、上述した高濃度顔料層の表層側、すなわち、基材である金属材からより遠い側に積層された被覆層である。ここで、被覆層が、高濃度顔料層および上塗り層からなる2層構造の場合、これに更に下塗り層を含む3層構造の場合、更には、高濃度顔料層が複数層存在する4層以上の構造の場合には、上塗り層は、最表層に位置することとなる。ただし、上塗り層は、高濃度顔料層の表層側に直接積層されていれば、必ずしも最表層に位置する必要はなく、上塗り層の更に表層側に、別途の被覆層が積層されていてもよい。 (Overview)
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. Here, when 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. However, as long as 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. .
上塗り層のバインダとして用いる樹脂は、特に限定されるものではないが、高濃度顔料層との密着性や、後述する混合層の形成、塗料原料の共通化等の観点から、高濃度顔料層と同一の樹脂を含んで使用することが好ましい。従って、高濃度顔料層のバインダとして、数平均分子量が19000以上28000以下のポリエステル樹脂Aを使用することが好ましいことから、上塗り層においても、バインダとしてポリエステル樹脂Aを使用することが好ましい。上塗り層のバインダとして使用するポリエステル樹脂の数平均分子量が19000未満では、加工性および密着性が低下するおそれがあり、数平均分子量が28000を超えると、塗膜表面が柔らかくなりすぎ、耐疵つき性およびブロッキング性が劣化するおそれがある。 (Binder)
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.
上塗り層は、高濃度顔料層とは異なり、顔料の添加を必須としておらず、用途に応じ顔料添加の有無、添加する顔料の種類、顔料の濃度等を調整することによって、目的に応じた反射特性やその他特性が付与される。 (Pigment)
Unlike the high-concentration pigment layer, 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.
上塗り層には、ルチル型酸化チタン以外に、例えば、つや消し剤を追加で添加してもよい。上塗り層につや消し剤を固形分体積濃度で3%以上15%以下添加することで、つや消し剤を使用しない場合と同程度の全光線反射率のままで、正反射成分のほとんどない反射特性を得ることができる。このような反射特性を有する塗装金属材を、照明器具の反射板として用いた場合、光源との距離、角度に関わらず一定の反射光が得られるので、光源の数が少なかったり、光源間の間隔が広かったりする場合でも、均一な反射光を得ることができる。ただし、つや消し剤の添加によって上塗り層の表面には微細な凹凸が形成されるが、この微細な凹凸には汚れ物質がたまりやすく、また、この汚れ物質は拭き取りによっても除去されにくいため、耐汚染性が低下するおそれがある。従って、つや消し剤の添加量は、反射光の均一性と耐汚染性の低下への影響とを考慮し、適切な量を決定することが望ましい。 (Additional ingredients other than pigments)
In addition to the rutile-type titanium oxide, for example, a matting agent may be additionally added to the topcoat layer. By adding 3% or more and 15% or less of the matting agent in the solid content volume concentration to the overcoat 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. When 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. However, 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.
上塗り層にルチル型酸化チタンを添加する場合には、上塗り層の膜厚が厚いほど、高い加工性、密着性および全光線反射率が得られる。ただし、上塗り層の膜厚が30μmを超えると、塗装時に沸きが発生しやすくなるために塗装性が劣化し、また、塗料コストの面でも好ましくない。一方、上塗り層の膜厚が5μm未満では、上塗り層による加工性、密着性および全光線反射率の向上効果が小さくなるため、上塗り層の膜厚を5μm以上30μm以下とすることが好ましい。安定した加工性、密着性、全光線反射率および塗装性を確保するという観点から、より好ましい上塗り層の膜厚は、10μm以上25μm以下である。 (Film thickness)
When rutile type titanium oxide is added to the topcoat layer, the higher the thickness of the topcoat layer, the higher the workability, adhesion and total light reflectance. However, if the film thickness of the overcoat layer exceeds 30 μm, boiling tends to occur during coating, so that the paintability is deteriorated and the coating cost is not preferable. On the other hand, if the film thickness of the topcoat layer is less than 5 μm, 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 μm or more and 30 μm 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 μm or more and 25 μm or less.
本実施形態に係る塗装金属材では、上述した高濃度顔料層と上塗り層との境界面の中心線平均粗さRaが0.8μm以上であることが必要である。このように、高濃度顔料層と上塗り層との境界面のRaを大きくすることにより、高濃度顔料層と上塗り層との境界面が粗くなるために、拡散反射率を高めることができる。高濃度顔料層と上塗り層との境界面のRaが0.8μm未満であると、上記の密着性の向上効果や反射率を高める効果を充分に得ることができない。0.9μm以上であると反射率がより高まるため、より好適である。2.0μm以上であるとなお良い。
中塗り層と上塗り層との境界面のRaは、各実施例の塗膜を切断して、樹脂に埋め込んだ後に研磨することで、塗膜の表面に垂直な断面を平滑にして、走査型顕微鏡(倍率1000倍)で撮影した写真で評価した。写真の上から、OHPに用いられる透明シートをかぶせて、境界面の凹凸を精密にトレースした後に、図3に示すように、境界面曲線の平均線の方向に基準長さlだけ抜き取り、この抜き取り部分の平均線の方向にX軸を、縦倍率方向にY軸を取り、界面曲線をy=f(x)で表したときに、数1によって求められる値を境界面のRaとした。なお、本願発明では塗膜中の任意の断面5箇所について、前述の方法で測定したRaの平均とする。
[Roughness of the interface between the high-concentration pigment layer and the overcoat layer]
In the coated metal material according to this embodiment, 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 μm or more. Thus, by increasing Ra of the boundary surface between the high-concentration pigment layer and the topcoat layer, the boundary surface between the high-concentration pigment layer and the topcoat layer becomes rough, so that the diffuse reflectance can be increased. When the Ra at the boundary surface between the high-concentration pigment layer and the overcoat layer is less than 0.8 μm, the above-described effects of improving adhesion and increasing the reflectance cannot be sufficiently obtained. Since the reflectance is further increased when the thickness is 0.9 μm or more, it is more preferable. It is more preferable that it is 2.0 μm or more.
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. When the X-axis is taken in the direction of the average line of the extracted portion, the Y-axis is taken in the longitudinal magnification direction, and the interface curve is represented by y = f (x), the value obtained by
高濃度顔料層と上塗り層との境界面のRaは、高濃度顔料層および上塗り層の塗布方法、高濃度顔料層中の顔料(ルチル型酸化チタン)の濃度、高濃度顔料層の顔料種(ルチル型酸化チタン、シリカ等の低屈折率粒子等)、高濃度顔料層および上塗り層形成用の塗料の低シェアでの粘度や表面張力等により、制御することができる。なお、本開発における高濃度顔料層と上塗り層との境界面とは、光学顕微鏡もしくは電子顕微鏡で塗膜の断面を撮影した時に視覚的に見える境界面(境界線)を指す。 (Method for controlling Ra of boundary surface)
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.
更に、分散剤等の添加剤を塗料中に添加することによっても、低シェアでの塗料粘度を調整することができる。 Here, 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. As 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.
Further, the viscosity of the paint with a low share can be adjusted by adding an additive such as a dispersant to the paint.
本実施形態に係る塗装金属材では、高濃度顔料層形成用塗料と上塗り層形成用塗料とをウェットオンウェット法または多層同時塗布法により塗装することで、高濃度顔料層形成用塗料中のルチル型酸化チタンが上塗り相形成用塗料へ各層の界面を超えて拡散していくため、高濃度顔料層と上塗り層との界面付近で、ルチル型酸化チタンの濃度勾配層ができる。本発明では本酸化チタンの濃度勾配層を混合層と呼ぶ。この場合、高濃度顔料層と上塗り層との境界部分に存在する混合層により、高濃度顔料層と上塗り層との間の密着性を向上させることができる。また、プレコート金属材の場合には、塗装後の加工により塗装金属材の全光線反射率が低下する場合があるが、混合層が存在することにより密着性が向上するため、加工後の全光線反射率の低下を抑制することもできる。 [Mixed layer]
In the coated metal material according to the present embodiment, 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. In this case, 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. In the case of a pre-coated metal material, the total light reflectivity of the coated metal material may be reduced by processing after painting. However, the presence of the mixed layer improves the adhesion, so A decrease in reflectance can also be suppressed.
ここで、本実施形態に係る「混合層」とは、高濃度顔料層のルチル型酸化チタンが上塗り塗膜層へ拡散することでルチル型酸化チタンの濃度が傾斜構造になっている層をいう。より具体的には、本実施形態では、ルチル型酸化チタンに着目すれば、高顔料濃度層のTi量をx、上塗り層のTi量をyとしたときに、[x+0.05×(x−y)]~[y−0.05×(x−y)]である部分を混合層とすることとする。各Ti量は後述する、分析方法でもとめることができ、各分析器でTiを測定したときの測定強度を量とみなして計算することができる。 (Definition of mixed layer)
Here, the “mixed layer” according to the present embodiment 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.
本実施形態では、上述した混合層が存在する場合、この混合層は、3μm以上12μm以下の厚みを有することが好ましい。混合層の厚みが3μm未満の場合には、混合層による高濃度顔料層と上塗り層との間の密着性向上効果を安定して得ることができないおそれがある。一方、混合層の厚みが12μmを超えると、必要な機能を分担している高濃度顔料層及び上塗り層の塗膜の厚みを充分に確保することが困難となる。そのため、上塗り層が最表層である場合、最表層の厚み不足による外観不良が起き易くなる等、高濃度顔料層及び上塗り層自体の性能維持が困難となり、実質的に高濃度顔料層形成用塗料と上塗り層形成用塗料とを混合した塗料により形成される塗膜層と同じ性能となってしまうため、必要とする本来の高濃度顔料層及び上塗り層の性能が得られない。なお、混合層の厚みを12μmを超えた厚みに制御するのは実質上困難である。 (Mixed layer thickness)
In the present embodiment, when the above-described mixed layer is present, the mixed layer preferably has a thickness of 3 μm to 12 μm. When the thickness of the mixed layer is less than 3 μm, 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. On the other hand, when the thickness of the mixed layer exceeds 12 μm, it becomes difficult to sufficiently secure the thicknesses of the high-concentration pigment layer and the overcoat layer that share the necessary functions. Therefore, when 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 μm.
混合層の膜厚は、高濃度顔料層または上塗り層のいずれか一方にのみ含まれる成分の膜厚方向の分布状態を分析することによって求めることができる。分析方法としては、公知の分析方法を使用すればよく、例えば、**X線プローブマイクロアナライザ、電子線マイクロアナライザ(EPMA)、X線光電子分光分析(XPS)、オージェ電子分光分析(AES)、グロー放電発光分析(GDS)**等を利用して、塗膜の深さ方向の元素濃度を分析するか、あるいは、塗膜断面における成分分析により、対象となる成分の濃度分布から混合層の膜厚を求めることができる。適用する成分分析の種類や方法は、膜厚、成分量などに応じて適宜選択して行えばよい。EPMA、XPS、AES、GDS以外であっても深さ方向の成分分析が可能な方法であれば適宜選択してもよい。なお、混合層の分析に使用可能な成分としては、Ti以外であってもかまわない。これ分析方法のなかで、GDSは塗膜の表面から不活性のアルゴンイオンで深さ方向にスパッタしながら分析し、測定元素の深さ方向の濃度を精度よく比較できるため、好適である。本願発明での混合層の膜厚は、任意の5箇所について測定した平均の膜厚とする。 (Method for measuring the thickness of the mixed layer)
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. As 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.
混合層の厚みは、主に、塗布方法、焼付け時間によって制御することができる。塗布方法としては、ウェットオンウェット法や多層同時塗布法を採用することにより、混合層が形成しやすくなる。また、焼付け時間を長くすることにより、混合層形成のための時間を充分に長くとることができるため、混合層の厚みを厚くすることができるが、具体的には、焼付け時間を60秒~180秒程度とすることで、混合層の厚みを3μm以上12μm以下とすることができる。 (Control method of mixed layer thickness)
The thickness of the mixed layer can be controlled mainly by the coating method and baking time. As a coating method, a mixed layer can be easily formed by employing a wet-on-wet method or a multilayer simultaneous coating method. In addition, by increasing the baking time, it is possible to sufficiently increase the time for forming the mixed layer, so that the thickness of the mixed layer can be increased. Specifically, 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.
本実施形態に係る塗装金属材では、被覆層の最表面のろ波中心線うねりWCAが2μm以下であることが好ましい。このように、被覆層の最表面のWCAを小さくすることにより、塗装金属材の鮮鋭性を向上させることができるとともに、細かい凹凸の無い滑らかな表面が得られるので、塗装金属材表面に汚染物質がたまりにくくなるため、耐汚染性を向上させることができる。被覆層の最表面のWCAが2μmを超えると、鮮鋭性および耐汚染性が低下するおそれがある。一方、被覆層の最表面のWCAの好適な下限値については、特に規定する必要は無いが、被覆層の最表面のWCAが0.2μm未満のものは実質的に制御が困難であるため、このような観点からは、被覆層の最表面のWCAが0.2μm以下であることが好ましい。なお、本願発明のWCAは任意の5箇所について測定した平均とする。 [Swelling on the outermost surface]
In the coated metal material according to the present embodiment, it is preferable that the filtering center line waviness W CA on the outermost surface of the coating layer is 2 μm or less. Thus, by reducing the WCA on the outermost surface of the coating layer, the sharpness of the coated metal material can be improved and a smooth surface without fine irregularities can be obtained. Since the substance is less likely to accumulate, contamination resistance can be improved. When W CA of the outermost surface of the coating layer is more than 2 [mu] m, sharpness and stain resistance may deteriorate. On the other hand, 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 0.2μm Therefore, from such a viewpoint, it is preferable that the W CA on the outermost surface of the coating layer is 0.2 μm or less. Incidentally, W CA of the present invention is the average determined for any five locations.
被覆層の最表面のWCAは、高濃度顔料層と上塗り層との境界面のRaの影響により変化する。従って、被覆層の最表面のWCAは、主に、塗布方法、低シェアでの塗料粘度によって制御することができる。具体的には、塗布方法をウェットオンウェット法や多層同時塗布法とすることにより、高濃度顔料層から上塗り層へルチル型酸化チタンが拡散するため、高濃度顔料層と上塗り層との境界面のRaが大きくなり、被覆層の最表面のWCAも大きくなる。また、低シェアでの高濃度顔料層形成用の塗料粘度を下げることによって、高濃度顔料層中のルチル型酸化チタンが上塗り層へ拡散しやすくなるため、境界面のRaが大きくなり、被覆層の最表面のWCAも大きくなる。 (Method of controlling the W CA of the outermost surface)
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. In addition, by lowering the viscosity of the paint for forming a high concentration pigment layer with a low share, 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.
また、本実施形態に係る塗装金属材では、金属材上に形成された被覆層のうちの最表層の塗膜層が、シリコーン樹脂またはふっ素樹脂を含有していてもよい。ここで、「最表層の塗膜層」とは、上述した上塗り層が最表層に形成されている場合には当該上塗り層のことであり、上塗り層の表層側に更に塗膜層が積層されている場合には当該塗膜層のことである。本実施形態に係る塗装金属材をプレコート金属板に適用した場合には、加工時における汚れの付着等による全光線反射率の低下が懸念される。これに対して、本実施形態に係る塗装金属材の最表層の塗膜層のバインダの一部または全部として、シリコーン樹脂またはふっ素樹脂を用いることで、塗膜表面に撥油性および撥水性を付与することができる。このように、最表層の塗膜層の表面を撥油性および撥水性とすることで、塗膜表面に汚れが付き難くなり、全光線反射率の低下が抑制されるため、好ましい。 [Give water and oil repellency to the outermost coating film]
Moreover, in the coating metal material which concerns on this embodiment, the coating layer of the outermost layer of the coating layers formed on the metal material may contain silicone resin or fluorine resin. Here, 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. 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. On the other hand, 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. Thus, it is preferable to make the surface of the outermost coating layer oil-repellent and water-repellent, so that the surface of the coating is less likely to become dirty and the decrease in the total light reflectance is suppressed.
また、本実施形態に係る塗装金属材では、金属材上に形成された被覆層のうちの最表層の塗膜層が、塗膜を形成する樹脂骨格中に−Si−O−Si−結合を有していてもよい。ここで、「最表層の塗膜層」とは、上述した上塗り層が最表層に形成されている場合には当該上塗り層のことであり、上塗り層の表層側に更に塗膜層が積層されている場合には当該塗膜層のことである。また、−Si−O−Si−結合におけるSiは、アルコキシシランまたはアルコキシシランの加水分解縮合物に由来するものである。 [Give hydrophilicity to the outermost coating film]
Moreover, in the coating metal material which concerns on this embodiment, 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. You may have. Here, 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.
なお、本実施形態に係る塗装金属材が、上塗り層の表層側に更に最表層の塗膜層(例えば、上述したシリコーン樹脂またはふっ素樹脂を含有する塗膜層や、塗膜を形成する樹脂骨格中に−Si−O−Si−結合を有する塗膜層)を有する場合には、この最表層の塗膜層の膜厚については、上述した撥水性、撥油性、親水性等の特性を得ることができる程度であれば特に限定はされないが、好ましくは最表層の塗膜層の膜厚が1μm以上25μm以下である。上記最表層の塗膜層の膜厚が1μm未満であると、撥水性、撥油性、親水性が不足する可能性があり、25μmを超えると加工性が劣る可能性があり、またコストの面からも、好ましくない。 [Film thickness of outermost coating layer]
In addition, 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) In the case of having a coating layer having a —Si—O—Si— bond, the above-mentioned characteristics such as water repellency, oil repellency and hydrophilicity are obtained for the film thickness of the outermost coating layer. Although it will not specifically limit if it is a grade which can be performed, Preferably the film thickness of the coating layer of the outermost layer is 1 micrometer or more and 25 micrometers or less. If the film thickness of the outermost coating layer is less than 1 μm, water repellency, oil repellency and hydrophilicity may be insufficient, and if it exceeds 25 μm, processability may be inferior, and cost may be reduced. Therefore, it is not preferable.
本実施形態に係る塗装金属材が有する被覆層は、以上説明した高濃度顔料層および上塗り層の他に、下塗り層を含んでいてもよい。この下塗り層は、金属材と高濃度顔料層との間に形成される塗膜層であり、被覆層が、上塗り層、高濃度顔料層および下塗り層の3層からなる場合には、基材となる金属材に最も近い側の塗膜層となる。ただし、この場合、金属材から最も近い側の層であっても、金属材と塗膜との密着性向上や耐食性向上を目的として設ける膜厚1μm未満の被覆層は、本実施形態に係る下塗り層には該当せず、膜厚1μm未満の被覆層よりも表層側の被覆層を下塗り層とする。 [Undercoat] (Overview)
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. However, in this case, even in the layer closest to the metal material, the coating layer having a film thickness of less than 1 μm 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 μm is used as the undercoat layer.
下塗り層のバインダとして用いる樹脂は、特に限定されるものではないが、高濃度顔料層との密着性や、塗料原料の共通化等の観点から、高濃度顔料層と同一の樹脂を含んで使用することが好ましい。従って、高濃度顔料層のバインダとして、数平均分子量が19000以上28000以下のポリエステル樹脂Aを使用することが好ましいことから、下塗り層においても、バインダとしてポリエステル樹脂Aを使用することが好ましい。下塗り層のバインダとして使用するポリエステル樹脂の数平均分子量が19000未満では、加工性および密着性が低下するおそれがあり、数平均分子量が28000を超えると、塗膜表面が柔らかくなりすぎ、耐疵つき性およびブロッキング性が劣化するおそれがある。 (Binder)
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.
下塗り層には、顔料としてルチル型酸化チタンを固形分体積濃度で20%以上35%以下添加すると、より反射率が向上し好適である。下塗り層に添加する顔料としてルチル型酸化チタンが好適である理由は、高濃度顔料層の場合と同様に、ルチル型酸化チタンの屈折率が、他の一般に使用されている顔料よりも高く、バインダとして使用する樹脂および顔料粒子間に存在する空隙部分の空気との屈折率差を大きくでき、これにより、顔料と樹脂との界面、顔料と空気との界面における光反射率を高めることができるためである。 (Pigment)
When 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.
下塗り層の膜厚については、膜厚が厚いほど、高い加工性や密着性が得られ、また、顔料としてルチル型酸化チタンを添加した場合には反射性能についても、膜厚が厚いほど有利であることから、これらの性能面からは、下塗り層の膜厚の上限値を設定する必要はない。しかし、下塗り層の膜厚が30μmを超えると、高濃度顔料層と異なり、塗料中の顔料濃度が低いため、塗装時に沸きが発生しやすく、塗装性が劣化すること、また、塗料コストの観点からも好ましくない。よって、下塗り層の膜厚は30μm以下であることが好ましい。一方、下塗り層の膜厚が5μm未満では、下塗り層による加工性、密着性および反射性能の向上効果が小さくなるため、下塗り層の膜厚は5μm以下であることが好ましい。安定した加工性、密着性、反射特性および塗装性を確保するという観点から、より好ましい下塗り層の膜厚は、10μm以上25μm以下である。 (Film thickness)
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 μm, 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 μm or less. On the other hand, when the film thickness of the undercoat layer is less than 5 μm, 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 μm or less. From the viewpoint of ensuring stable processability, adhesion, reflection characteristics, and paintability, a more preferable thickness of the undercoat layer is 10 μm or more and 25 μm or less.
本実施形態に係る塗装金属材の基材に使用する金属材としては、一般に公知の金属材料または合金材料を用いることができる。具体的には、金属材として、例えば、鋼板、ステンレス鋼板、アルミ板、アルミ合金板、チタン板、銅板等が挙げられる。これらの金属材料または合金材料の表面には、めっきが施されていてもよい。めっきの種類としては、亜鉛めっき、アルミめっき、銅めっき、ニッケルめっき等が挙げられ、これらの合金めっきであってもよい。また、金属材として鋼板を使用する場合には、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、亜鉛−ニッケル合金めっき鋼板、溶融合金化亜鉛めっき鋼板、アルミめっき鋼板、アルミ−亜鉛合金化めっき鋼板等、一般に公知の鋼板およびめっき鋼板を適用できる。 [Base material (metal material)]
As a metal material used for the base material of the coated metal material according to the present embodiment, generally known metal materials or alloy materials can be used. Specifically, examples of 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. Examples of the type of plating include zinc plating, aluminum plating, copper plating, nickel plating, and the like, and may be alloy plating thereof. Moreover, when using a steel plate as the metal material, 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. Generally known steel plates and plated steel plates can be applied.
以上の説明では、本発明を、主に、プレコート金属材に適用した例に基づいて説明しているが、本発明は、プレコート金属材に限られず、ポストコート金属材に適用してもよい。ポストコート金属材の場合には、プレコート金属材とは異なり、必ずしも加工密着性等が要求されるわけではないが、反射板として用いる場合には、高い全光線反射率を有することが必要となる。 [About post-coated metal materials]
In the above description, the present invention is mainly described based on an example in which the present invention is applied to a precoat metal material. However, the present invention is not limited to a precoat metal material, and may be applied to a postcoat metal material. In the case of 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. .
以上、本実施形態に係る塗装金属材の構成について詳細に説明した。続いて、上述したような構成を有する塗装金属材の製造方法について詳細に説明する。 <About the manufacturing method of paint metal material>
The configuration of the painted metal material according to this embodiment has been described in detail above. Then, the manufacturing method of the coating metal material which has the above structure is demonstrated in detail.
まず、塗装金属材がプレコート金属材の場合における本実施形態に係る塗装金属材の製造方法について説明する。本実施形態に係る塗装金属材は、一般的な連続塗装ライン(「CCL」と呼ばれる。)や切板用の塗装ラインにより、適宜必要な処理を選択し、選択した処理を実施することで製造できる。塗装ラインの代表的な製造工程としては、「洗浄」→「乾燥」→「化成処理」→「乾燥」→「塗装」→「乾燥・焼付け」→「冷却」→「乾燥」であるが、本実施形態における塗装金属材の製造工程はこれに限定されるものではない。 [For pre-coated metal materials]
First, the manufacturing method of the coating metal material which concerns on this embodiment in case a coating metal material is a precoat metal material is demonstrated. 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.
次に、塗装金属材がポストコート金属材の場合における本実施形態に係る塗装金属材の製造方法について説明する。 [For post-coated metal]
Next, the manufacturing method of the coating metal material which concerns on this embodiment in case a coating metal material is a postcoat metal material is demonstrated.
以上説明したような本実施形態に係る塗装金属材を使用した電子機器では、この塗装金属材が高い全光線反射率と成形性を高次元で両立しているため、同一光源の場合はこれまでよりも明るくなり、また、これまでより光源の数を少なくしたり、投入電力を少なくしたりしても、これまでと同等の明るさを確保することが可能である。更に、本実施形態に係る塗装金属材は、様々な形状に容易に成形できる、または、より複雑な形状に成形できるといった特性を持つことから、適用可能な電子機器対象の拡大や、適用する部品の生産性向上といった効果も期待できる。 (Summary)
In the electronic device using the painted metal material according to the present embodiment as described above, 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.
まず、本実施例で用いた塗料について詳細に説明する。本実施例では、塗装金属材として、基材となる亜鉛めっき鋼板表面に、当該鋼板側から順に積層された、下塗り層、高濃度顔料層(中塗り層)、上塗り層の3層構造、または、下塗り層、中塗り層、2層の上塗り層の4層構造を有する被覆層が被覆されたプレコート鋼板を用いた。以下、下塗り層用塗料(「下塗り塗料」と称する。)、高濃度顔料層(中塗り層)用塗料(「中塗り塗料」と称する。)、上塗り層用塗料(「上塗り塗料」と称する。)の順に、使用した塗料成分について説明する。 [paint]
First, the paint used in this example will be described in detail. In this example, as 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. Hereinafter, paint for undercoat layer (referred to as “undercoat paint”), paint for high-concentration pigment layer (intercoat layer) (referred to as “intercoat paint”), and paint for topcoat layer (referred to as “overcoat paint”). The paint components used are described in the order of).
下塗り塗料については、下記表1に示すように、バインダとして、東洋紡社製の非晶性ポリエステル樹脂である「バイロン(登録商標)630」(数平均分子量23000,水酸基価5)を使用し、顔料として、平均粒径が280nmのルチル型酸化チタンである石原産業社製「タイペーク(登録商標)CR95」(屈折率:2.5)を使用し、ルチル型酸化チタンの固形分体積濃度が25%となるようにバインダと混合し、下塗り塗料(下塗り−1)を作製した。 (Undercoat paint)
As shown in Table 1 below, for the undercoat paint, “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 a binder. As “Taipaque (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, and the solid content volume concentration of rutile titanium oxide is 25%. The resulting mixture was mixed with a binder so as to prepare an undercoat paint (undercoat-1).
中塗り塗料については、表1に示すように、ベース樹脂として、東洋紡社製の非晶性ポリエステル樹脂である「バイロン(登録商標)」シリーズ、及び住化バイエルウレタン社製の非晶性ポリエステル樹脂である「デスモフェン(登録商標)」シリーズを使用した。例えば、中塗り−1~20では、「バイロン(登録商標)630」(数平均分子量23000、水酸基価5)と住化バイエルウレタン社製の非晶性ポリエステル樹脂である「デスモフェン(登録商標)690」(数平均分子量3500、水酸基価46)とを有機溶剤(ソルベッソ150とシクロヘキサノンとを質量比で1:1に混合したもの)に質量比で1:1で溶解したものを用いた。架橋剤には市販のヘキサ−メトキシ−メチル化メラミンである三井サイテック社製の「サイメル(登録商標)303」をポリエステル樹脂の固形分100質量部に対して15質量部添加し、更に、市販の酸性触媒である三井サイテック社製の「キャタリスト(登録商標)6003B」を0.5質量部添加することで、ポリエステル系クリア塗料を得た。 (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. "(Number average molecular weight 3500, hydroxyl value 46) was dissolved in an organic solvent (a mixture of Solvesso 150 and cyclohexanone in a mass ratio of 1: 1) at a mass ratio of 1: 1". As the cross-linking agent, 15 parts by mass of “Cymel (registered trademark) 303” manufactured by Mitsui Cytec Co., Ltd., which is a commercially available hexa-methoxy-methylated melamine, is added to 100 parts by mass of the polyester resin solid content. A polyester-based clear paint was obtained by adding 0.5 parts by mass of “Catalyst (registered trademark) 6003B” manufactured by Mitsui Cytec, which is an acidic catalyst.
上塗り塗料については、下記表3に示すように、バインダとして、東洋紡社製の非晶性ポリエステル樹脂である「バイロン(登録商標)630」(数平均分子量23000,水酸基価5)を有機溶剤(ソルベッソ150とシクロヘキサノンとを質量比で1:1に混合したもの)に溶解したものを用いた。架橋剤には市販の三井サイテック社製の完全アルキル型メチル化メラミン樹脂(以降、メチル化メラミンと称す)である「サイメル(登録商標)303」をポリエステル樹脂の固形分100質量部に対して15質量部添加し、更に、市販の酸性触媒である三井サイテック社製の「キャタリスト(登録商標)6003B」を0.5質量部添加することで、クリア塗料を得た。このクリア塗料を用いて、顔料として、平均粒径が280nmのルチル型酸化チタンである石原産業社製「タイペーク(登録商標)CR95」(屈折率:2.5)を使用し、ルチル型酸化チタンの固形分体積濃度が25%となるようにバインダと混合し、上塗り塗料(上塗り−1)を作製した。 (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. As the cross-linking agent, “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. Using this clear paint, as a pigment, 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).
次に、本実施例で用いたプレコート金属板について詳細に説明する。 (Pre-coated metal plate)
Next, the precoated metal plate used in this example will be described in detail.
次に、上述したようにして作製したプレコート金属板の評価方法の詳細について説明する。 (Evaluation methods)
Next, the detail of the evaluation method of the precoat metal plate produced as mentioned above is demonstrated.
島津製作所社製の分光光度計「UV265」に、積分球反射付属装置を取り付けたものを用い、基準板としては硫酸バリウム粉末を押し固めたものを用いた。人の目の感度が最も高い波長である555nmにおける全光線反射率を測定し、以下の基準で評価を行った。
◎:全光線反射率が99%以上の場合
◎~○:全光線反射率が97%以上99%未満の場合
○:全光線反射率が95%以上97%未満の場合
○~△:全光線反射率が93%以上95%未満の場合
△:全光線反射率が91%以上93%未満の場合
△~×:全光線反射率が89%以上91%未満の場合
×:全光線反射率が89%未満の場合 1) Measurement of total light reflectance of pre-coated metal plate A spectrophotometer "UV265" manufactured by Shimadzu Corporation is attached with an integrating sphere reflection accessory device, and a barium sulfate powder pressed and used as a reference plate It was. The total light reflectance at 555 nm, which is the wavelength with the highest human eye sensitivity, was measured and evaluated according to the following criteria.
◎: 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% Δ: When the total light reflectance is 91% or more and less than 93% Δ˜ ×: When the total light reflectance is 89% or more and less than 91% ×: Total light reflectance If less than 89%
図1および図2に実験装置の概要を示す。被覆基材を図1および図2に示すような長手方向の両端部が上面側に折り曲げられた形状に成形し、反射板1とした。その中に市販の蛍光灯照明器具2を2本並べて取り付け、その上に、すりガラスで形成されたカバー3を取り付けた。そのカバー3の中央部分(以下、「輝度測定部」という。)4と中央部分4から1.5cm外側にずらした部分(以下、「輝度の均一性比較測定部」という。)5の輝度を、測定点から垂直に50cm離れたところに輝度計6を設置して測定した。蛍光灯照明器具2としては、16形ランプ出力16Wの蛍光灯を用いた。 2) 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
◎:輝度変化率が30%以上の場合
◎~○:輝度変化率が25%以上30%未満の場合
○:輝度変化率が20%以上25%未満の場合
○~△:輝度変化率が15%以上20%未満の場合
△:輝度変化率が10%以上15%未満の場合
×:輝度変化率が10%未満の場合 The luminance was evaluated by measuring the
◎: 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%
◎:輝度の均一度が90%以上の場合
○:輝度の均一度が85%以上90%未満の場合
△:輝度の均一度が70%以上85%未満の場合
×:輝度の均一度が70%未満の場合 The luminance uniformity is evaluated by measuring the luminance at two locations of the luminance uniformity
◎: When the luminance uniformity is 90% or more ○: When the luminance uniformity is 85% or more and less than 90% Δ: When the luminance uniformity is 70% or more and less than 85% ×: The luminance uniformity is 70 Less than%
作製したプレコート金属板を、任意の枚数のサンプルを間に挟んだ状態で180°折り曲げ加工(密着曲げ加工)し、加工部の塗膜を目視で観察し、塗膜の割れの有無を調べた。なお、180°折り曲げを行う際には、プレコート金属板の表面が曲げの外側となるように折り曲げて、密着曲げを行った(一般に、サンプルを挟まない場合は0T曲げ、サンプルを1枚挟む場合は1T曲げとして知られている)。そして、加工部を目視にて観察し、以下の基準で評価を行った。
◎◎:0T曲げで割れや剥離がない
◎: 1T曲げで割れや剥離がない
◎~○: 2T曲げで割れや剥離がない
○: 2T曲げでわずかな割れや剥離があるが、3T曲げで割れや剥離がない
○~△:2T曲げで下塗り塗膜層または原板に達する割れや剥離があるが、3T曲げで割れや剥離がない
△:3T曲げでわずかな割れや剥離があるが、4T曲げで割れや剥離がない
△~×:2T曲げで下塗り塗膜層または原板に達する割れや剥離があるが、3T曲げで割れや剥離がない
×:4T曲げで割れや剥離がある 3) Workability and adhesion 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. When bending 180 °, 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 | standards.
◎: No cracking or peeling with 0T bending ◎: No cracking or peeling with 1T bending ◎ ~ ○: No cracking or peeling with 2T bending ○: Slight cracking or peeling with 2T bending, but 3T bending No cracking or peeling ○ ~ △: There is cracking or peeling reaching the undercoat film layer or the original plate by 2T bending, but there is no cracking or peeling by 3T bending. Δ: There are slight cracking or peeling by 3T bending, but 4T No cracking or peeling by bending △ ~ ×: There is cracking or peeling reaching the undercoat film layer or the original sheet by 2T bending, but there is no cracking or peeling by 3T bending ×: There is cracking or peeling by 4T bending
◎◎:0T曲げで剥離がない
◎: 1T曲げで剥離がない
◎~○: 2T曲げで剥離がない
○: 2T曲げで加工部の全長に対して合計で半分未満の長さで剥離があるが、3T曲げで剥離がない
○~△:2T曲げで加工部の全長に対して合計で半分未満の長さで剥離があるが、3T曲げで剥離がない
△:3T曲げでわずかな割れや剥離があるが、4T曲げで割れや剥離がない
△~×:2T曲げで全長に対して合計で半分以上の長さで剥離があるが、3T曲げで剥離がない
×:4T曲げで剥離がある Furthermore, the process part adhesiveness test which affixes and peels a tape on a process part was also implemented, the adhesiveness after tape peeling was observed visually, and the following references | standards evaluated.
◎: No peeling at 0T bending ◎: No peeling at 1T bending ◎ ~ ○: No peeling at 2T bending ○: There is peeling at less than half the total length of the processed part by 2T bending However, there is no peeling in 3T bending. ○ ~ △: There is peeling in less than half the total length of the processed part in 2T bending, but there is no peeling in 3T bending. There is peeling, but there is no cracking or peeling by 4T bending. △ ~ X: peeling by 2T bending is more than half the total length, but there is no peeling by 3T bending. X: peeling by 4T bending is there
評点を、◎◎の場合に8点、◎の場合に7点、◎~○の場合に6点、○の場合に5点、○~△の場合に4点、△の場合に3点、△~×の場合に2点、×の場合に1点とし、全光線反射率と加工性との評点を加算し、その合計を算出し、以下の基準で評価を行った。
◎:評点の合計が11点以上
○:評点の合計が9点以上11点未満
△:評点の合計が7点以上9点未満
×:評点の合計が7点未満 4) Comprehensive evaluation The score is 8 for ◎◎, 7 for ◎, 6 for ◎ to ○, 5 for ○, 4 for ○ to △, △ 3 points, 2 points in the case of Δ˜ ×, 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
中塗り層と上塗り層との境界面のRaは、各実施例の塗膜を切断して、樹脂に埋め込んだ後に研磨することで、塗膜の表面に垂直な断面を平滑にして、3500倍の走査型顕微鏡で撮影した写真で評価した。写真の上から、OHPに用いられる透明シートをかぶせて、境界面の凹凸を精密にトレースした後に、図3に示すように、境界面曲線の平均線の方向に基準長さlだけ抜き取り、この抜き取り部分の平均線の方向にX軸を、縦倍率方向にY軸を取り、界面曲線をy=f(x)で表したときに、以下の式によって求められる値をマイクロメートル(μm)で示した。なお、測定は任意の5箇所について行い、その平均を求めた。 5) Measurement of boundary surface Ra 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. Was smoothed and evaluated with a photograph taken with a 3500 times scanning microscope. 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. When the X-axis is taken in the direction of the average line of the extracted portion, the Y-axis is taken in the longitudinal magnification direction, and the interface curve is expressed by y = f (x), the value obtained by the following formula is expressed in micrometers (μm). Indicated. In addition, the measurement was performed about arbitrary 5 places and the average was calculated | required.
被覆層の最表面のWCAは、明伸工業社製3次元表面形状測定装置にて計測した。測定時の評価長さ40mm、カットオフ8mmの条件で測定した。詳細はJIS.B0601に準じて測定した。測定は任意の5箇所について行い、その平均を求めた。 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.
中塗り層と上塗り層との境界面付近をGDS(グロー放電発光分光分析装置)により深さ方向のTiの分布を測定した。より具体的には、中塗り層のTi濃度をx、上塗り層のTi濃度をyとしたときに、[x+0.05×(x−y)]~[y−0.05×(x−y)]である部分の厚みを混合層厚みとして測定した。測定は任意の5箇所について行い、その平均を求めた。 7) Measurement of mixed layer thickness In the vicinity of the boundary surface between the intermediate coating layer and the top coating layer, the distribution of Ti in the depth direction was measured by a GDS (glow discharge emission spectroscopy analyzer). More specifically, when the Ti concentration of the intermediate coating layer is x and the Ti concentration of the top coating layer is y, [x + 0.05 × (xy)] to [y−0.05 × (xy). )] Was measured as the mixed layer thickness. The measurement was performed at arbitrary five locations, and the average was obtained.
被覆層の最表面のWCAは、明伸工業社製3次元表面形状測定装置にて計測した。 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.
中塗り層と上塗り層との境界面付近をGDS(グロー放電発光分光分析装置)により深さ方向のTiの分布を測定した。より具体的には、中塗り層のTi濃度をx、上塗り層のTi濃度をyとしたときに、[x+0.05×(x−y)]~[y−0.05×(x−y)]である部分の厚みを、「混合層厚み」として測定した。 7) Measurement of mixed layer thickness In the vicinity of the boundary surface between the intermediate coating layer and the top coating layer, the distribution of Ti in the depth direction was measured by a GDS (glow discharge emission spectroscopy analyzer). More specifically, when the Ti concentration of the intermediate coating layer is x and the Ti concentration of the top coating layer is y, [x + 0.05 × (xy)] to [y−0.05 × (xy). )] Was measured as “mixed layer thickness”.
また、三菱化学社製塗料用カーボン「三菱カーボンMA100」の10%懸濁液を、上述したようにして作製したプレコート金属板の塗膜表面に塗布し、1時間後に日本ウエス社製のクリーニング白メリヤスウエスにて拭き取り、試験前後の色の変化を分光測色計(スガ試験器製、型式MSC−45−2B)によるΔEで求め、以下の基準で評価を行った。
◎:ΔEが0.2未満
◎~○:ΔEが0.2以上0.5未満
○:ΔEが0.5以上1未満
△:ΔEが1以上2未満
×:ΔEが2以上 8) Anti-contamination In addition, a 10% suspension of paint carbon “Mitsubishi Carbon MA100” manufactured by Mitsubishi Chemical Corporation was applied to the surface of the precoated metal sheet prepared as described above, and after 1 hour, Nippon The product was wiped with a cleaning white knitted cloth made by a company, and the change in color before and after the test was determined by ΔE using a spectrocolorimeter (manufactured by Suga Test Instruments Co., Ltd., model MSC-45-2B) and evaluated according to the following criteria.
◎: ΔE is less than 0.2 ◎ ~ ○: ΔE is 0.2 or more and less than 0.5 ○: ΔE is 0.5 or more and less than 1 △: ΔE is 1 or more and less than 2 ×: ΔE is 2 or more
表4~6に、本実施例で作製したプレコート金属板の構成とその評価結果を示す。 (Evaluation results)
Tables 4 to 6 show the configuration of the precoated metal sheet produced in this example and the evaluation results.
2 蛍光灯照明器具
3 カバー
4 輝度測定部
5 輝度の均一性比較測定部
6 輝度計 DESCRIPTION OF
Claims (15)
- 金属材表面の一部または全部に、ルチル型酸化チタンを固形分体積濃度で35%以上70%以下含有する第1の塗膜層と、前記第1の塗膜層の表層側に積層された第2の塗膜層と、を含む少なくとも2層の被覆層を有し、
前記第1の塗膜層と前記第2の塗膜層との境界面の中心線平均粗さRaが0.8μm以上であることを特徴とする、塗装金属材。 A part or all of the metal material surface was laminated on the surface layer side of the first coating layer containing rutile-type titanium oxide in a solid content volume concentration of 35% or more and 70% or less, and the first coating layer. And at least two coating layers including a second coating layer,
A coated metal material, wherein a center line average roughness Ra of a boundary surface between the first coating layer and the second coating layer is 0.8 μm or more. - 前記第1の塗膜層と前記第2の塗膜層との境界部分には、前記第1の塗膜層中の成分と前記第2の塗膜層中の成分とが混在した混合層が存在しており、
前記混合層は、3μm以上12μm以下の厚みを有することを特徴とする、請求項1に記載の塗装金属材。 At the boundary portion between the first coating layer and the second coating layer, there is a mixed layer in which the components in the first coating layer and the components in the second coating layer are mixed. Exists,
The painted metal material according to claim 1, wherein the mixed layer has a thickness of 3 μm to 12 μm. - 前記被覆層の最表面のろ波中心線うねりWCAが2μm以下であることを特徴とする、請求項1または2に記載の塗装金属材。 The coated metal material according to claim 1, wherein a filtered center line waviness W CA of the outermost surface of the coating layer is 2 μm or less.
- 前記被覆層のうちの最表層の塗膜層は、シリコーン樹脂またはふっ素樹脂を含有することを特徴とする、請求項1~3のいずれか1項に記載の塗装金属材。 The coated metal material according to any one of claims 1 to 3, wherein the outermost coating layer of the coating layer contains a silicone resin or a fluorine resin.
- 前記被覆層のうちの最表層の塗膜層は、塗膜を形成する樹脂骨格中に−Si−O−Si−結合を有することを特徴とする、請求項1~3のいずれか1項に記載の塗装金属材。 The outermost coating layer of the coating layer has a -Si-O-Si- bond in a resin skeleton forming the coating film, according to any one of claims 1 to 3. The painted metal material described.
- 前記ルチル型酸化チタンの平均粒径は、200nm以上400nm以下であることを特徴とする、請求項1~5のいずれか1項に記載の塗装金属材。 The coated metal material according to any one of claims 1 to 5, wherein the rutile-type titanium oxide has an average particle diameter of 200 nm or more and 400 nm or less.
- 前記第1の塗膜層は、前記ルチル型酸化チタンよりも粒径が大きく、かつ、前記ルチル型酸化チタンよりも低い屈折率を有する粒子を更に含有することを特徴とする、請求項1~6のいずれか1項に記載の塗装金属材。 The first coating layer further comprises particles having a particle size larger than that of the rutile type titanium oxide and having a refractive index lower than that of the rutile type titanium oxide. 6. The painted metal material according to any one of 6 above.
- 前記第1の塗膜層中には空隙が存在し、
前記空隙の含有率は、前記第1の塗膜層中の固形分体積量の0.05倍以上0.9倍以下であることを特徴とする、請求項1~7のいずれか1項に記載の塗装金属材。 There are voids in the first coating layer,
The content of the voids is 0.05 times or more and 0.9 times or less of a solid content volume in the first coating layer, according to any one of claims 1 to 7. The painted metal material described. - 前記第1の塗膜層の膜厚は、10μm以上80μm以下であることを特徴とする、請求項1~8のいずれか1項に記載の塗装金属材。 The coated metal material according to any one of claims 1 to 8, wherein the thickness of the first coating layer is 10 µm or more and 80 µm or less.
- 前記第2の塗膜層の膜厚は、5μm以上30μm以下であることを特徴とする、請求項1~9のいずれか1項に記載の塗装金属材。 The coated metal material according to any one of claims 1 to 9, wherein the thickness of the second coating layer is 5 µm or more and 30 µm or less.
- 前記被複層は、前記金属材と前記第1の塗膜層との間に積層された第3の塗膜層を更に含むことを特徴とする、請求項1~10のいずれか1項に記載の塗装金属材。 11. The multilayered layer according to claim 1, further comprising a third coating layer laminated between the metal material and the first coating layer. The painted metal material described.
- 前記第3の塗膜層の膜厚は、5μm以上30μm以下であることを特徴とする、請求項11に記載の塗装金属材。 The coated metal material according to claim 11, wherein the film thickness of the third coating layer is 5 μm or more and 30 μm or less.
- 請求項1~12のいずれか1項に記載の塗装金属材の製造方法であって、
前記第1の塗膜層の形成用の塗料と、前記第2の塗膜層の形成用の塗料とを、多層同時塗布またはウェットオンウェット方式により、金属材表面の一部または全部に塗布することを特徴とする、塗装金属材の製造方法。 A method for producing a painted metal material according to any one of claims 1 to 12,
The coating material for forming the first coating layer and the coating material for forming the second coating layer are applied to a part or all of the metal material surface by multilayer simultaneous application or wet-on-wet method. A method for producing a painted metal material. - 請求項1~12のいずれか1項に記載の塗装金属材を照明反射板に使用した、照明器具。 A lighting fixture using the coated metal material according to any one of claims 1 to 12 for an illumination reflector.
- 請求項1~12のいずれか1項に記載の塗装金属材を発光部品の反射板、または、画像表示部の反射板に使用した、電子機器。 An electronic device using the coated metal material according to any one of claims 1 to 12 for a light-emitting component reflector or an image display part reflector.
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JP2016522338A (en) * | 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 | New road markings that support vehicle perception |
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JP2020171874A (en) * | 2019-04-08 | 2020-10-22 | 日鉄鋼板株式会社 | Covering material and inactivation method of germ or virus |
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JP2015516872A (en) * | 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 | Protective coating for low refractive index materials |
JP2016522338A (en) * | 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 | New road markings that support vehicle perception |
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JP2020171874A (en) * | 2019-04-08 | 2020-10-22 | 日鉄鋼板株式会社 | Covering material and inactivation method of germ or virus |
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