KR20110110008A - Precoated aluminum sheet for forming and container-shaped formed article - Google Patents

Abstract

[PROBLEMS] To provide a precoated aluminum sheet for molding having a white appearance or metallic having excellent moldability, heat dissipation and brightness.
[Measures] Molding precoat Al having a first film 3 formed on one side of the aluminum (Al) plate 2 and a second film 6 formed on the other side of the Al plate 2. As the board | substrate 1, the 1st film 3 is a white pigment and the crosslinked polyester resin 4 which cross-reacted the polyester resin whose Tg is 25-100 degreeC with a melamine type hardening | curing agent or an isocyanate type hardening | curing agent, and a white pigment. (5) or an integrated emissivity of infrared rays containing a metallic pigment (5) or containing additive A (5) and having an arithmetic mean roughness Ra of 0.1 to 5 µm, an L * value of 85 or more, and a wavelength of 3 to 30 µm. The crosslinked poly-linked polyether obtained by crosslinking a polyester resin having a Tg of 0 to 80 ° C. with a melamine curing agent or an isocyanate curing agent at a temperature of 25 ° C. of 0.6 or more and a gel fraction of 50% or more. Integral emissivity of the infrared ray which contains the ester resin 7 and the additive 8 or the additive B (8), and whose wavelength is 3-30 micrometers is 25 degreeC This book is more than 50% of 0.6 or higher, the gel fraction.

Description

PRECOATED ALUMINUM SHEET FOR FORMING AND CONTAINER-SHAPED FORMED ARTICLE}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to molding precoat aluminum plates and container-shaped molded articles made of aluminum plates, which are mainly used in industrial electronic devices, consumer electronic devices, automotive electronics, and the like. The present invention relates to a molding precoat aluminum plate and a container-shaped molded article having excellent whiteness, visible light reflectivity, moldability and heat dissipation.

In recent years, as a lighting apparatus with less burden on the environment, LED lighting equipment employing LED has been commercialized one after another. In order to increase the lifetime and the luminous efficiency of the LED, it is necessary to increase the heat dissipation and to efficiently release heat to the outside. In a word, LED lighting devices include LED backlights and bulb-type LED lights used in liquid crystal televisions.

As the LED backlight, a heat sink for improving heat dissipation is used. As shown in Fig. 5 (a), such a heat sink is manufactured mainly by bending a metal plate.

On the other hand, the container produced by die casting is manufactured so that LED lighting may become a shape similar to an incandescent bulb. Such a container may be designed to improve heat dissipation by providing a plurality of fins, irregularities, and the like on the outer peripheral portion to increase the surface area, thereby functioning as a heat sink. In order to spread LED lights side by side with incandescent bulbs and fluorescent lamps, it is necessary to increase productivity. In order to increase productivity, it is preferable to use a press product of a plate rather than die casting. Since the container designed to function as a heat sink is close to a cylinder, it is preferable to draw and manufacture a metal plate as shown in Fig. 5B. On the other hand, since the cover manufactured by drawing processing as shown in FIG. 5 (b) has high sealing property, electromagnetic shielding property is high and it can use suitably also for the consumer electronic device used indoors, such as a home.

As an inexpensive material having good thermal conductivity and having workability that enables drawing processing, there is an aluminum (including aluminum alloy in the present specification. Since the natural oxide film is formed on the surface of the aluminum plate, it is excellent in corrosion resistance. However, in order to impart desired functions such as lubricity, scratch resistance, anti-fingerprint resistance and conductivity, a resin film is formed by an aftercoat method or a precoat method. There are many cases. On the other hand, after-coat method is a method of forming a resin film separately after press-molding an aluminum plate to a predetermined shape, and a precoat method is previously performed before press-molding an aluminum plate to a predetermined shape of an aluminum plate. It is a method of forming a resin film on the surface. On the other hand, when increasing productivity and reducing cost, it is preferable by the precoat method. This is because the precoat method is suitable for mass production because a specific resin film can be formed on the surface of the aluminum plate in advance and a molded article can be produced continuously by a press molding machine.

In the case of an LED lighting container, it is necessary to use the precoat aluminum plate which previously formed the resin film in the surface by the precoat method, in order to raise productivity and reduce cost. In addition, heat dissipation is required as described above as a function of the resin film. In addition, since a drawing process is a process with a large deformation amount, a resin film should not be able to follow this.

As a conventional precoat aluminum plate, there exist some which were described in patent documents 1-4, for example.

In Patent Document 1, a predetermined corrosion resistant film and a predetermined resin film are formed on at least one surface of an aluminum plate having a predetermined arithmetic mean roughness Ra, and other required performances are also improved by defining the surface resistance value. The satisfied precoat aluminum plate is disclosed.

According to the precoat aluminum sheet of Patent Literature 1, it is possible to continuously form in quick-drying press oil which does not require cleaning, and to improve the lubricity and appearance quality to lower the manufacturing cost by eliminating the step of washing the press oil. Since the resin coating provides functions such as scratch resistance and fingerprint resistance, antistatic property, and conductivity to secure earth, it is suitable for, for example, a cover of a slim optical disk drive device mounted in a notebook computer. It is described that it can be used easily.

In addition, Patent Literature 2 discloses a precoat aluminum sheet in which a soft bead of a predetermined hardness is added to a resin film formed by the precoat method to give a cushioning property to the resin film.

According to the precoat aluminum plate of patent document 2, since the counterpart which contacts the said precoat aluminum plate is difficult to be scratched, it is the purpose that it can use suitably as a cover used for the slot-in type optical disk drive apparatus, for example. It is described. That is, it is described that the optical disk can be prevented from being scratched by friction even when the optical disk is in contact with the resin film on the inner surface of the cover.

In addition, in patent document 3, when the value of the gel fraction of a precoat film is compared before and after heat processing of 220 degreeC as an intermolecular crosslinking state of the thermosetting resin formed on the surface of an aluminum plate, the gel after the said heat processing The value of the fraction is continuously reduced from the value of the gel fraction before the heat treatment, and is controlled so that the decrease from the value of the gel fraction before the heat treatment at the time when the heat treatment at 220 ° C. is performed for 10 minutes is less than 10%. Thereby, the precoat aluminum plate which satisfy | filled the high drawing workability is disclosed.

According to the precoat aluminum plate of patent document 3, even if it carries out a deep drawing process or ironing process, since peeling, a crack, and whitening of a film do not occur, it is excellent in moldability, for example, a slim type optical disc It is described that the present invention can be suitably used as a cover for an industrial electronic device such as a drive device, a consumer electronic device, an on-vehicle electronic device, or the like.

And in patent document 4, the precoat aluminum plate which provided the thermoplastic resin film in the one side or both surfaces of an aluminum plate, and provided the thermosetting resin coating layer on this thermoplastic resin film is disclosed.

According to the precoat aluminum plate of patent document 4, since a thermoplastic resin film does not contact a degreasing agent and is protected by the thermosetting resin coating layer which was excellent in chemical-resistance, it is in the state with favorable moldability at the time of drawing or ironing. It is described that the discoloration in the degreasing treatment of the thermoplastic resin film can be prevented, and the printing performance can also be improved. Therefore, it is described that it can use suitably for the case of an electrolytic capacitor, for example.

Japanese Patent Publication No. 2003-313684 Japanese Patent No. 4134237 Japanese Patent Publication No. 2006-305841 Japanese Patent No. 4003915

However, when drawing processing is performed using the precoat aluminum plate of patent documents 1-4, there exists a following problem.

The precoat aluminum plates of patent document 1 and patent document 2 are assumed to be used for the cover of an optical disk drive apparatus, and assume the manufacture of a body by a bending process. Therefore, the deformation | transformation of a resin film cannot follow about processing with a large deformation amount like drawing processing, and it is thought that a crack and peeling generate | occur | produce in a resin film.

In addition, although the precoat aluminum plate of patent document 3 assumes drawing process, the heat dissipation property and visible light reflectivity required for the function as a heat sink of the container of LED lighting are not considered, and it causes the lifetime of LED and the luminous efficiency fall. There is a concern. In addition, since the appearance required as a fresh product is not assumed at all, the appearance is not practical.

Since the precoat aluminum plate of patent document 4 is a film laminate material which laminated the thermoplastic resin film which used the thermoplastic resin as the base resin on the surface of an aluminum plate, there exists a limit in itself about heat resistance.

As a thermoplastic resin, for example, when the polyamide-based resin represented by nylon is used as the base resin, adhesion to the aluminum plate is good and excellent moldability is obtained. However, in a high temperature environment, the base resin discolors due to heat in a relatively short time. Or there is a problem that browning is easy to discolor.

In addition, in the case of using a saturated polyester resin such as PET as the thermoplastic resin as the base resin, the adhesiveness with the aluminum plate is good, the moldability is excellent, and even in a high temperature environment, the base resin does not easily discolor. Although there is a characteristic, the base resin tends to be hydrolyzed, and thus tends to be poor in durability in a high temperature and wet atmosphere.

As the thermoplastic resin, when the polyolefin-based resin represented by polyethylene or polypropylene is used as the base resin, the base resin is composed of only carbon and hydrogen in principle, and does not contain nitrogen or oxygen. Therefore, there is no functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or an amino group, which are the starting points of chemical bonds such as ester bonds, urethane bonds, and amide bonds, and thus poor adhesion to the aluminum plate.

The present invention has been made in view of the above problems, and can be applied to a molded article such as an LED backlight formed of a bending main body, as well as excellent drawing workability (formability) that assumes engraving of a heat sink of an LED bulb. It is an object of the present invention to provide a precoated aluminum sheet for molding having an excellent heat dissipation (infrared radiation) required for increasing the lifespan and luminous efficiency of the LED. Furthermore, it aims at providing the precoat aluminum plate for shaping | molding which combines the white appearance or metallic appearance which has the outstanding brightness | luminance (L * value) and visible light reflectivity which are required as a consumer equipment, especially an illuminating device.

The precoat aluminum sheet for molding according to claim 1 is a precoat aluminum sheet for molding comprising an aluminum plate, a first film formed on one side of the aluminum plate, and a second film formed on the other side of the aluminum plate. As

The first film includes a crosslinked polyester resin obtained by crosslinking and reacting a polyester resin having a glass transition temperature of 25 to 100 ° C. with a melamine curing agent or an isocyanate curing agent, and has an infrared integration of 3 to 30 μm. Emissivity is 0.6 or more at the temperature of 25 ℃, the gel fraction satisfies 50% or more,

The second film contains a crosslinked polyester resin obtained by crosslinking and reacting a polyester resin having a glass transition temperature of 0 to 80 ° C. with a melamine curing agent or an isocyanate curing agent, and having an infrared wavelength of 3 to 30 μm. Emissivity is characterized by satisfying at least 0.6, the gel fraction at least 50% at a temperature of 25 ℃.

According to such a structure, both the 1st film | membrane and the 2nd film | membrane which were formed in the one side and the other side of the aluminum plate, respectively, crosslink reaction of the polyester resin which has a predetermined glass transition temperature with a melamine type hardening | curing agent or an isocyanate type hardening | curing agent. Since it contains the crosslinked polyester resin which was made, it has the outstanding drawing workability (formability). Formability by making the 1st film into the outer surface (namely, the product outer surface) of the container-shaped molded article formed by drawing processing etc., and raising the lower limit of the glass transition temperature of the polyester resin to be used compared with a 2nd film, The scratch resistance (washing durability) which included at the time of washing | cleaning can be made compatible. On the other hand, a 2nd film can be made excellent in moldability by making the upper limit of the glass transition temperature of the polyester resin to be used low compared with a 1st film.

Moreover, since the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more at the temperature of 25 degreeC, a 1st film is excellent in converting and converting heat into infrared rays in the surface. Therefore, LED element becomes hard to become warm, and it becomes possible to raise lifetime and luminous efficiency of LED. On the other hand, since the 2nd film | membrane which becomes an inner surface after a drawing process also contains an additive and the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more at the temperature of 25 degreeC, the heat which generate | occur | produces inside a container is efficient. By absorbing in this, the temperature rise of the LED element can be suppressed.

And since the gel fraction of a resin film is 50% or more in both a 1st film and a 2nd film, the crosslinking density of a resin film becomes high and it can prevent that the additive added in the resin film falls off at the washing | cleaning process. Moreover, chemical resistance, heat resistance, hydrolysis resistance, etc. improve, and also the durability of the film in a washing process improves.

The precoat aluminum sheet for molding according to claim 2, wherein the first coating contains a white pigment, has an L * value of 85 or more, and the second coating contains an additive.

Since the first film contains a white pigment and has an L * value of 85 or more, it can have a bright white surface (white appearance) capable of efficiently reflecting visible light (visible light reflection).

And it can prevent that the white pigment and the additive which were added to the resin film by the 1st film and the 2nd film in a washing process fall off. Moreover, chemical resistance, heat resistance, hydrolysis resistance, etc. are improved, and durability of the film in a washing process is improved.

The precoat aluminum sheet for molding according to claim 3, wherein, in the first film, the white pigment is titanium oxide, and the content rate of titanium oxide is 20 to 70% by mass. With such a configuration, the white appearance of the first film is further excellent, and the visible light reflectivity is further excellent. In addition, moldability becomes good.

The precoat aluminum sheet for molding according to claim 4 is characterized in that, in the first film, the content rate of the titanium oxide is 40 to 60 mass%, and the film thickness is 15 μm or less. With such a configuration, excellent appearance and visible light reflectivity can be obtained in a relatively thin film, which is excellent in economy.

The precoat aluminum sheet for molding according to claim 5, wherein in the second film, the additive contains at least one or more selected from carbon black, graphite, titanium oxide, silica, alumina, and resin beads, and the content thereof is 5 It is -70 mass%, It is characterized by the film thickness of 15 micrometers or less. With such a configuration, the drawing processing inner surface side which is not directly exposed to the naked eye does not require particularly excellent appearance and visible light reflectivity, so that the film can be customized for various purposes such as importance on heat dissipation characteristics, economic importance, and productivity.

The precoat aluminum sheet for molding according to claim 6 may have a bright metallic surface (metallic appearance) capable of efficiently reflecting visible light (visible light reflection) because the first coating includes a metallic pigment. In addition, since the integrated emissivity of infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more at the temperature of 25 degreeC similarly, a 1st film is excellent in converting and converting heat into infrared rays in the surface. Therefore, LED element becomes hard to become warm, and it becomes possible to raise lifetime and luminous efficiency of LED. On the other hand, since the 2nd film | membrane which becomes an inner surface after a drawing process also contains an additive and the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more at the temperature of 25 degreeC, the heat which generate | occur | produces inside a container is efficient. By absorbing in this, the temperature rise of the LED element can be suppressed.

The precoat aluminum sheet for molding according to claim 7, wherein the metallic pigment is an aluminum paste in the first film, and the content rate of the aluminum paste is 3 to 30% by mass. With such a configuration, the metallic outer appearance of the first film is further excellent, and the visible light reflectivity is further excellent. In addition, since the metallic pigment is an aluminum paste having high thermal conductivity, the thermal conductivity of the film is improved, contributing to the heat dissipation effect. Moreover, moldability also becomes favorable.

The precoat aluminum sheet for molding according to claim 8 has a content of 5 to 20% by mass and a film thickness of 15 μm or less in the first film. With such a configuration, excellent appearance and visible light reflectivity can be obtained in a relatively thin film, which is excellent in economy.

The precoat aluminum sheet for molding according to claim 9, wherein, in the second film, the additive contains at least one or more selected from carbon black, graphite, titanium oxide, silica, alumina, resin beads, and aluminum paste, The content is 5 to 70 mass%, and the film thickness is 15 micrometers or less, It is characterized by the above-mentioned. With such a configuration, the drawing processing inner surface side which is not directly exposed to the naked eye does not require particularly excellent appearance and visible light reflectivity, so that the film can be customized for various purposes such as importance on heat dissipation characteristics, economic importance, and productivity.

The precoat aluminum sheet for molding according to claim 10 defines an arithmetic mean roughness Ra of the film surface of the first film, and imparts appropriate roughness to the first film surface. Thereby, the flaw of the film surface becomes inconspicuous and an external appearance quality improves. In addition, if the first film is made to be the outer surface after the drawing process, the first film has the integrated emissivity of infrared rays having a wavelength of 3 to 30 μm satisfying 0.6 or more at a temperature of 25 ° C., thereby converting heat to infrared light on the surface thereof. Excellent for releasing Therefore, LED element becomes hard to become warm, and it becomes possible to raise lifetime and luminous efficiency of LED. On the other hand, since the 2nd film | membrane which becomes an inner surface after drawing processing contains additive B, and the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more at the temperature of 25 degreeC, the heat which generate | occur | produces inside a container By absorbing efficiently, the temperature rise of an LED element can be suppressed.

The precoat aluminum sheet for molding according to claim 11, wherein the additive A included in the first film and the additive B included in the second film are carbon black, graphite, titanium oxide, silica, alumina, resin beads. And at least one or more selected from aluminum pastes, the content ratio is from 3 to 70% by mass, and the film thickness of the first film and the film thickness of the second film together are 15 μm or less. With such a configuration, it is possible to customize the configurations of the first film and the second film in consideration of desired color tone, surface texture, economy, productivity, and the like while ensuring excellent heat dissipation.

The arithmetic mean roughness Ra of the precoat aluminum sheet for shaping | molding of Claim 12 is 0.25 micrometer or more and 5 micrometers or less, It is characterized by the above-mentioned. In such a configuration, since the surface roughness of the first coating film is sufficiently large, the first coating film of the molding precoat aluminum sheet according to the present invention is molded into a molded article that becomes an outer surface, and then the outer surface of the molded article is treated with a boiling chlorine-based cleaner. Even in the case of washing under severe conditions, the phenomenon that the first coating of the molded article sticks to the first coating of another molded article is suppressed.

The container-shaped molded article according to claim 13 is a container-shaped molded article formed by using the precoat aluminum sheet for molding so that the first coating is formed on the outer surface and the second coating is on the inner surface. With such a configuration, since both inner and outer surfaces have excellent moldability, containers of various shapes can be formed, including bending and drawing. Moreover, since heat can be efficiently absorbed on the inner surface side close to the heat source and heat can be efficiently released on the outer surface side, the container has excellent heat dissipation. Moreover, the outer surface side exposed to the naked eye as a product outer surface has a bright and beautiful white appearance, and the container shape molded article suitable for the heat sink of LED bulb which is excellent also in visible light reflection is obtained. In addition, the heat sink of an LED bulb is one of the application uses of the container shape molded article of this invention, and is not limited only to this use. Similarly, the container-shaped molded article is not limited to the one by drawing processing.

According to the invention of Claims 1-12, the 1st film | membrane provided in one side of an aluminum plate and the 2nd film | membrane provided in the other side can obtain the flexibility of a precoat film suitably, and drawing of the precoat aluminum plate for shaping | molding Workability (formability) can be improved. Therefore, it becomes possible to provide a precoat aluminum sheet for molding that can follow molding having a large deformation such as drawing or ironing. In addition, both the first film and the second film have excellent heat dissipation (infrared radiation), and in particular, the first film has a white appearance with excellent brightness and visible light reflecting properties in advance, and the surface function thereof is damaged by press work. Since it is maintained without work, the obtained container-shaped molded article is obtained with the high functional container which has these functions, without performing post-processing after that.

According to the invention according to claim 13, the obtained container-shaped molded article has a white appearance or metallic appearance having excellent brightness (L * value) and visible light reflecting characteristics, which is preferable for a luminaire, or the outer surface of the obtained container-shaped molded article has scratches or the like. It is possible to obtain a container-shaped molded article suitable for the heat sink of an LED bulb, which has an excellent appearance that is hard to be noticeable and has excellent heat dissipation (infrared radiation) as a function. There are many die-cast molded articles having a complicated fin shape in heat sinks of LED bulbs. However, the use of the container of the present invention greatly improves productivity since it can be replaced with a press product of a sheet material. Furthermore, since the surface treatment is also continuously processed on an aluminum plate in advance, it is very excellent in productivity compared with performing a batch treatment such as coating or alumite after molding.

BRIEF DESCRIPTION OF THE DRAWINGS It is a fragmentary sectional view which shows typically the structure of the molding precoat aluminum plate which concerns on this invention.
2 is a perspective view showing an example of a container-shaped molded article according to the present invention.
It is a cross-sectional schematic diagram which shows the process of manufacturing a user cylindrical container by drawing and ironing a test material in an Example.
4 is a perspective view illustrating a simulated LED bulb for temperature measurement.
FIG.5 (a) is a schematic diagram of the box-shaped object (container) by bending process, and FIG.5 (b) is a schematic diagram of the box-shaped body (container) by drawing process.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing the molding precoat aluminum plate and container shape molded article which concerns on this invention suitably with reference to drawings is demonstrated concretely.

<< precoat aluminum plate for the molding >>

As shown in FIG. 1, the molding precoat aluminum plate 1 according to the present invention includes an aluminum plate 2, a first film 3 formed on one side surface of the aluminum plate 2, and an aluminum plate ( It is provided with the 2nd film 6 formed in the other side surface of 2), and can be used for uses, such as drawing processing. Hereinafter, each structure is demonstrated.

<Aluminum plate>

The aluminum plate 2 referred to in the present invention is made of aluminum or an aluminum alloy, and is not particularly limited as the aluminum plate (aluminum plate or aluminum alloy plate) 2 used in the present invention. And the strength required at the time of use. In general, a non-heat treatment type aluminum plate, that is, a 1000 industrial pure aluminum plate, a 3000 Al-Mn alloy plate, and a 5000 Al-Mg alloy plate can be suitably used. In particular, in the case of producing a deep container-shaped ore with ironing, aluminum plates such as A1050, A1100, A3003, A3004, etc. defined in JIS H4000 are recommended. In the case of producing a comparatively shallow container-like ore, when strength is important, aluminum plates such as A5052 and A5182 prescribed in JIS H4000 are recommended. In terms of temper and sheet thickness, various ones can be selected and used depending on the purpose. As described later, the aluminum plate 2 may be subjected to a reactive base treatment, a coating base treatment, an anodizing treatment, an electrolytic etching treatment, a degreasing treatment, or the like.

<The first film>

The 1st film 3 is a crosslinked polyester resin 4 which crosslinked-reacted the polyester resin whose glass transition temperature is 25-100 degreeC with a melamine type hardening | curing agent, or an isocyanate type hardening | curing agent, and this crosslinked polyester resin ( 4) Integral emissivity of an infrared ray having a L * value of 85 or more and having a wavelength of 3 to 30 µm is 0.6 or more and a gel fraction at a temperature of 25 ° C. More than 50% is satisfied.

<The first film>

The 1st film 3 is a crosslinked polyester resin 4 which crosslinked-reacted the polyester resin whose glass transition temperature is 25-100 degreeC with a melamine type hardening | curing agent, or an isocyanate type hardening | curing agent, and this crosslinked polyester resin ( It consists of the metallic resin film containing the metallic pigment 5 disperse | distributed in 4), and the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more and the gel fraction 50% or more at the temperature of 25 degreeC.

[Crosslinked Polyester Resin]

The crosslinked polyester resin 4 becomes a main component (base resin) of the first film 3, and a melamine curing agent or an isocyanate curing agent is used for the polyester resin having a glass transition temperature of 25 to 100 ° C. To crosslinking reaction between molecules.

[Crosslinked Polyester Resin]

The crosslinked polyester resin 4 becomes a main component (base resin) of the first film 3, and a melamine curing agent or an isocyanate curing agent is used for the polyester resin having a glass transition temperature of 25 to 100 ° C. To crosslinking reaction between molecules.

Although there is also a film laminate material using a thermoplastic resin as a base resin without performing intermolecular crosslinking by a thermosetting reaction, as described in the above-mentioned prior art, using a thermoplastic resin as a base resin has various practical problems. However, when the resin which performs intermolecular crosslinking by thermosetting reaction etc. is selected as crosslinked polyester resin 4, since this resin originally has a functional group for intermolecular crosslinking, it is excellent in adhesiveness with the aluminum plate 2. . Moreover, by crosslinking, chemical resistance and heat resistance become high, and it becomes possible to improve also regarding hydrolysis resistance.

On the other hand, as the resin for coating the aluminum plate, epoxy resins, vinylidene fluoride resins, acrylic resins, silicone polyester resins, and the like, are widely known as well as polyester resins. Not suitable for

As the polyester resin, it is preferable to use a saturated polyester resin obtained by condensation polymerization of a polyhydric alcohol and a polybasic acid. Among these, as a polyhydric alcohol, dihydric alcohols, such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 3- butylene glycol, 1, 6- hexanediol, diethylene glycol, glycerin, trimethyl, etc. Trihydric alcohols, such as oleethane and trimethylol propane, Furthermore, tetravalent or more alcohol can be used. As the polybasic acid, for example, dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid and sebacic acid, tribasic acids such as trimellitic anhydride, and more than tetravalent polybasic acids can be used. . These polyhydric alcohols and polybasic acids may be condensation-polymerized using one type or two or more types simultaneously. In addition, by combining these components, the glass transition temperature of the polyester resin can be changed.

The glass transition temperature is one of the transition temperatures of the resin, and in general, the resin at a temperature above the glass transition temperature is soft rubbery, and the resin at a temperature below the glass transition temperature is hard glassy. Therefore, in order to follow the 1st film | membrane 3 to processing with large deformation | transformation, such as a deep drawing process and ironing process, it is theoretically necessary to make glass transition temperature below processing temperature. In practice, however, the polymer material has a wide molecular weight, and thus, the primary structure is not uniform, such as branching structures are formed in the molecule, and even higher order structures, such as the arrangement of molecules, are not uniform. Therefore, glass transition temperature is the representative value to the last, and a transition will gradually generate | occur | produce in the temperature range which has a some width. In addition, even if the polyester resin has a glass phase below the glass transition temperature, the polyester resin has a relatively high elongation except for a part of the state (a state in which crystallization is promoted to a state of a thermoplastic resin that cannot undergo a crosslinking reaction). If it is a range, shaping | molding is possible also as resin which has high glass transition temperature as crosslinked polyester resin (4). On the contrary, when the resin with too low glass transition temperature is made into crosslinked polyester resin 4, the 1st film 3 will become soft too much and a flaw will be easy to produce.

In this invention, the glass transition temperature of the crosslinked polyester resin 4 contained in the 1st film 3 which is supposed to become the outer surface of a container-shaped molded article needs to be the range of 25-100 degreeC. When glass transition temperature is less than 25 degreeC, the 1st film 3 will become soft too much and a flaw will be easy to occur. On the other hand, when it exceeds 100 degreeC, the moldability of the precoat aluminum plate 1 will fall, and the shape which can be formed This will be limited. On the other hand, it is preferable that it is 25-80 degreeC, and, as for glass transition temperature, it is more preferable that it is 25-65 degreeC. In addition, the glass transition temperature here means what was measured by the differential scanning calorimetry (DSC method).

In addition, a crosslinking reaction does not occur only with the said polyester resin. In order to produce the crosslinking reaction required by the present invention, a chemical reaction is used so that a curing agent reacting with a hydroxyl group or a carboxyl group of the polyester resin is added, or a component having a function similar to the curing agent is produced in the polyester resin itself. It is necessary to modify the polyester resin. Examples of functional groups that react with these hydroxyl groups and carboxyl groups include isocyanate groups, amino groups, hydroxyl groups, carboxyl groups, and the like. Crosslinking reactions are easily promoted by adding a substance having three or more of these functional groups as a curing agent. It is possible to. As such a hardening | curing agent, a polyisocyanate compound, a melamine compound, an epoxy compound, an amino compound, a phenol compound, a urea compound, etc. are mentioned. On the other hand, when using polyester resin as a base resin like this invention, it is preferable that the hardening | curing agent is a melamine type hardening | curing agent or an isocyanate type hardening | curing agent. These curing agents are easy to paint, and have advantages such as storage at normal temperature and instant reactivity at baking temperature, and discoloration hardly occurs due to baking.

[White Pigment]

As for the white pigment 5, the 1st coating film 3 is colored white, L * value is 85 or more, and the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers ensures 0.6 or more at the temperature of 25 degreeC. In order to do so, it is made to contain in the crosslinked polyester resin 4 of the 1st film 3. As shown in FIG.

As long as the integrated emissivity of infrared rays having an L * value of 85 or more and a wavelength of 3 to 30 µm is 0.6 or more at a temperature of 25 ° C., the kind, size, form, addition amount, etc. of the white pigment 5 It is not particularly limited.

As a specific example of the white pigment 5 suitable for this purpose, titanium oxide, zinc sulfide, zinc oxide (zincide), barium sulfate, etc. are mentioned.

It is more economical to make the thickness of the first film 3 as thin as possible and to conceal the color tone of the aluminum plate 2. Titanium oxide with strong coloring power is preferable from this viewpoint. Thereby, the integral emissivity of infrared rays whose color tone, L * value, reflectance, and wavelength are 3-30 micrometers is also stabilized.

[Preferable Content of White Pigment: 20 to 70 Mass%]

Although there is no restriction | limiting in particular also about the preferable content rate of the white pigment 5, When the ratio which occupies for the 1st film 3 is less than 20 mass%, the integral emissivity of the infrared rays whose L * value is 85 or more and the wavelength is 3-30 micrometers is 25 The film thickness for satisfying 0.6 or more at a temperature of &lt; RTI ID = 0.0 &gt; On the other hand, when it exceeds 70 mass%, the 1st film 3 will become brittle and moldability will fall. Therefore, as for the content rate of the white pigment 5, 20-70 mass% is preferable. On the other hand, it is more preferable that it is 40-60 mass%.

[Metallic Pigment]

The metallic pigment 5 is for securing the visible light reflectivity by coloring the first film 3 with a metallic color, and the integrated emissivity of infrared rays having a wavelength of 3 to 30 µm with respect to the first film 3 is 25 ° C. In order to ensure 0.6 or more at the temperature of, it is contained in the crosslinked polyester resin (4) of the 1st film (3).

The kind, size, shape, addition amount, etc. of the metallic pigment 5 are not particularly limited as long as the integrated emissivity of infrared rays having a wavelength of 3 to 30 µm is 0.6 or more at a temperature of 25 ° C. .

Specific examples of the metallic pigment 5 suitable for this purpose include aluminum paste, silver paste, various fine particles obtained by treating aluminum or silver by a method such as vapor deposition or plating.

From an economical point of view, an aluminum-based one is preferable, and an aluminum paste is more preferable than various fine particles surface-treated with aluminum from the viewpoint of increasing the thermal conductivity of the first film 3 to assist in heat dissipation. This stabilizes the color tone and the visible light reflection characteristics.

[Preferable Content of Metallic Pigment: 3 to 30 Mass%]

There is no restriction | limiting in particular also about the content rate of the metallic pigment 5, If the ratio which occupies for the 1st film 3 is less than 3 mass%, the force which conceals the aluminum plate 2 which the 1st film 3 is a raw material has Since it will fall, a rolling roll eye will be seen and the appearance will fall. In addition, since the aluminum plate 2 is not concealed similarly, it becomes difficult to secure a condition that the integral emissivity of infrared rays having a wavelength of 3 to 30 µm is 0.6 or more at a temperature of 25 ° C. On the other hand, even when it exceeds 30 mass%, the infrared emission rate of the 1st film 3 will rather fall, and it will become difficult to ensure the conditions that the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers is 0.6 or more at the temperature of 25 degreeC. . This is because when the content rate is too high, the aluminum exposed on the surface of the first film 3 increases, and the aluminum plate 2 serving as the raw material is exposed. That is, in the case of 3-30 mass% which is easy to ensure the state which content of the aluminum paste exposed to the surface of the 1st film 3 concealed, covering up the aluminum plate 2 which is a raw material becomes below a fixed, it is a wavelength. It becomes easy to ensure the conditions that the integral emissivity of this infrared rays of 3-30 micrometers is 0.6 or more at the temperature of 25 degreeC. On the other hand, it is more preferable that content of an aluminum paste is 5-20 mass%.

[Additive A]

Additive A (5) sets the arithmetic mean roughness Ra of the surface prescribed | regulated with respect to the 1st film 3 to 0.1 micrometer or more and 5 micrometers or less, and the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers is 25 degreeC In order to ensure at 0.6 or more, it is made to contain in the crosslinked polyester resin 4 of the 1st film 3. As shown in FIG.

As long as the integrated emissivity of infrared rays having a wavelength of 3 to 30 µm is 0.6 or more at the above conditions, the kind, size, shape, addition amount, etc. of the additive A (5) are particularly limited. no.

Specific examples of the additive A (5) preferred for this purpose include titanium oxide, zinc sulfide, zinc oxide (zinc oxide), barium sulfate, carbon black, graphite, silica, alumina, resin beads, aluminum paste, and the like.

It is more economical to make the thickness of the first film 3 as thin as possible. From this point of view, carbon black, graphite, titanium oxide, silica, alumina and resin beads having high integrated emissivity improving effect of infrared rays having a wavelength of 3 to 30 µm are preferable. Moreover, an aluminum paste is also effective as an additive A from a viewpoint of suppressing reflection from the aluminum plate 2. Thereby, the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers is also stabilized by a high value.

[Preferable Content of Additive A: 3 to 70 Mass%]

The content rate of the additive A (5) is not particularly limited either, but if the proportion of the first film 3 is less than 3% by mass, the integral emissivity of infrared rays having a wavelength of 3 to 30 µm is 0.6 or more at a temperature of 25 ° C. The film thickness for satisfying becomes thick and it is not economical. On the other hand, when it exceeds 70 mass%, the 1st film 3 will become brittle and moldability will fall. Therefore, the blending ratio is preferably 3 to 70% by mass. On the other hand, it is more preferable that it is 5-60 mass%.

[Gel fraction of first coating: 50% or more]

In the present invention, the gel fraction of the first film 3 is made 50% or more. Since the gel fraction is a parameter of the crosslinking reaction degree of the thermosetting resin film, the gel fraction of the crosslinked polyester resin 4 alone should be discussed, but the first film 3 is a crosslinked polyester resin (4). Since the white pigment (5) is included as an essential component in addition to), it is difficult to strictly measure the gel fraction of the base resin of the crosslinked polyester resin (4). Therefore, in this invention, it substitutes by the gel fraction of the 1st membrane | film | coat 3, and is prescribed | regulated by this gel fraction.

When the gel fraction of the first film 3 is 50% or more, the crosslinking density of the crosslinked polyester resin 4 forming the first film 3 is high, and the chemical resistance, heat resistance and water resistance required in the use environment are high. The first film 3 excellent in decomposability can be obtained. On the other hand, in order to improve these effects, the gel fraction is preferably 65% or more. When the gel fraction is 75% or more, the chemical resistance, heat resistance, and hydrolysis resistance are further higher, and therefore, more preferable. On the other hand, since the larger the gel fraction is, the more preferable it is, the upper limit of the gel fraction does not need to be specifically defined. In addition, in order to make a gel fraction 50% or more, it is preferable that the baking temperature at the time of baking a coating film shall be about 150-285 degreeC.

The measurement method of a gel fraction can be performed by the method based on JISK6796 (however, extraction solvent uses 2-butanone (MEK (methyl ethyl ketone) instead of xylene). That is, the test material of the precoat aluminum plate 1 for shaping | molding is immersed for 60 minutes in the boiled 2-butanone, and the mass change of the precoat aluminum plate 1 for shaping | molding before and after immersion is measured. Then, the mass change of only the 1st coating film 3 is calculated by measuring the mass of the aluminum plate 2 which melt | dissolved only the 1st coating film 3 completely, and the component which eluted in 2-butanone is crosslinking-reacting. Based on the assumptions, the ratio is calculated as the gel fraction. In addition, the gel fraction of the 2nd film 6 mentioned later can also be measured similarly.

[L * value of the first film: 85 or more]

In the present invention, the first coating film 3 has an L * value of 85 or more. L * value is the numerical value which shows the brightness, saturation, and brightness in a hue which express the color of a substance, The higher the value, the brighter it is. Since the molding precoat aluminum plate 1 of the present invention assumes application to a lighting device, when the light emitted from the lighting device reaches the surface of the molded article using the precoat aluminum plate 1 for molding, The higher the L * value, the brighter it is. If the L * value is less than 85, the brightness deteriorates when used for a lighting device. Moreover, it is preferable that L * value is 90 or more.

The measurement of the L * value can be measured using a commercially available spectrophotometer, a chromatic color difference meter, or the like that satisfies a specified JIS standard in order to measure the L * value.

[Arithmetic mean roughness Ra of the first film: 0.1 μm or more and 5 μm or less]

In this invention, arithmetic mean roughness Ra of the surface of the 1st film 3 is made into 0.1 micrometer or more and 5 micrometers or less. The precoat aluminum plate 1 for shaping | molding of this invention presupposes that a molded article is produced by drawing processing etc. At this time, when a sliding motion occurs between the tool for processing the precoat aluminum plate 1 for molding and the precoat aluminum plate 1 for molding, and scratches occur on the surface of the precoat aluminum plate 1 for molding. There is. If a noticeable flaw exists in the surface of the 1st film 3 used as the outer surface of a molded article here, the commodity value of a molded article will fall remarkably. If the arithmetic mean roughness Ra of the surface of the 1st film 3 is less than 0.1 micrometer, the external appearance of the surface of the 1st film 3 will be close to a mirror surface, and even a small scratch will be very noticeable, and the scratch resistance will fall. do. For this reason, the arithmetic mean roughness Ra of the 1st film 3 needs to be 0.1 micrometer or more.

On the other hand, it is preferable that the surface of the 1st film 3 becomes 0.25 micrometer or more in arithmetic mean roughness Ra. As mentioned above, although the precoat aluminum plate 1 for shaping | molding of this invention presupposes that it becomes a molded article by drawing processing, in drawing processing with a large deformation amount of the aluminum plate 2, a quick-drying press oil is used. The used washingless technique is not sufficiently established. Therefore, after shaping | molding using high viscosity rustproof oil or emulsion type wax, the method of removing unnecessary press oil and abrasion powder using a washing | cleaning agent is employ | adopted a lot. Here, when it is assumed even the severe washing | cleaning using a boiling chlorine-type cleaner, when surface roughness is less than 0.25 micrometer by arithmetic mean roughness (Ra), when the 1st film | membrane 3 of the molded article opposes in a boiling chlorine-type cleaner, 1st Tackiness begins to form between the coatings 3, and in a severe case, moldings may stick to each other. As for the sticking of the 1st coating films 3 in this washing | cleaning process, the smoothness of the surface of the precoat film 3 is largely involved, and the arithmetic mean roughness Ra of the 1st coating film 3 is 0.25 micrometer. If abnormality arises, micro voids arise between the surfaces of the first coating film 3, which appear to be in contact at first glance, and the surface area which is actually in physical contact becomes small, so that sticking of the molded articles is suppressed. Therefore, as above-mentioned, it is preferable that surface of the 1st film 3 becomes 0.25 micrometer or more in arithmetic mean roughness Ra.

On the other hand, when the arithmetic mean roughness Ra of the surface of the 1st film 3 exceeds 5 micrometers, surface roughness will become large too much and a film surface will become noisy. As a result, since the unevenness | corrugation of the surface of the 1st membrane | film | coat 3 becomes large, contamination, such as sweat, becomes easy to stick to a recessed part. For this reason, as a result of using this molded article, the appearance of the article deteriorates and the surface appearance deteriorates. Moreover, when the arithmetic mean roughness Ra of the surface of the 1st film 3 exceeds 5 micrometers, when the 1st film 3 is stressed by shaping | molding, a stress will be the film thickness of the 1st film 3 The first film 3 tends to be broken at the thin portion, that is, the concave portion of the surface irregularities of the first film 3, and the moldability is lowered. Therefore, center line average roughness Ra of a film surface shall be 5 micrometers or less.

On the other hand, the arithmetic mean roughness Ra of the first film 3 can be controlled by appropriately adjusting the particle diameter, the blending ratio, the film thickness, and the like of the additive A (5) contained in the first film 3. In addition, the measurement of the arithmetic mean roughness Ra of the 1st film 3 can be measured using a commercially available surface roughness measuring instrument.

[Integrated Emissivity of Infrared Rays with a Wavelength of 3 to 30 μm of the First Film: 0.6 or More at a Temperature of 25 ° C.]

In the present invention, the first coating film 3 has an integrated emissivity of infrared rays having a wavelength of 3 to 30 µm at 0.6 or more at a temperature of 25 ° C. Emissivity is a proportional coefficient obtained by dividing infrared radiation on the surface of an object by infrared radiation on the surface of a black body, and is defined for light of a specific wavelength at a specific temperature. The acquired value ranges from 0 (white) to 1 (black), and the larger the number, the greater the infrared radiation. The integral emissivity is what integrates this in the wavelength range of a certain range. According to Planck's radiation, the wavelength of infrared rays which can be generated in the vicinity of room temperature, more specifically in the practical temperature range of 0 to 100 ° C, is within the range of 3 to 30 μm. It is concentrated. In other words, the infrared rays in the wavelength region deviating from the range of this wavelength region can be ignored. For this reason, in this invention, it is limited to the infrared rays of the wavelength range of 3-30 micrometers in 25 degreeC.

If the integrated emissivity of the infrared rays at the wavelength of 3 to 30 µm with respect to the first film 3 is less than 0.6, the ability to emit heat as infrared light on the surface of the first film 3 is lowered, and the ability to cool the product is reduced. Lack. On the other hand, it is preferable that the integral emissivity of said infrared rays is 0.7 or more, and it is more preferable that it is 0.8 or more.

The emissivity of the integrated emissivity of the infrared ray in the wavelength of 3-30 micrometers with respect to the 1st film 3 can be measured using a commercially available simple emissometer, and using a Fourier transform infrared spectrophotometer (FTIR) etc. It can be measured.

[Preferable film thickness of the first film: 15 μm or less]

In the present invention, the film thickness of the first film 3 is preferably 15 μm or less. As described later, in the present invention, the method of forming the first film 3 or the second film 6 is not particularly limited. However, it is preferable to use a roll coater having a uniform coating amount and easy operation. As a general roll coater, the coating thickness that can be coated by one coating is about 1 to 20 μm, but in applications where an excellent appearance is required as in the present invention, in order to secure a stable appearance over a plurality of lots It is desirable to keep the thickness at 15 μm or less. This makes it possible to economically form a film having excellent appearance with one coating.

[Etc]

The 1st film 3 can be made to contain the coloring agent other than a small amount of white, and the additive which provides various functions in the range which exhibits the desired effect of this invention.

For example, in order to further improve moldability, for example, lubricants such as polyethylene wax, canava wax, microcrystaline wax, lanolin, Teflon® wax, silicone wax, graphite lubricant, molybdenum lubricant, It can be contained 1 type or 2 or more types. In addition, as the conductive fine particles for imparting conductivity for the purpose of securing grounding required in electronic devices, etc., for example, metal fine particles including nickel fine particles, metal oxide fine particles, conductive carbon, graphite and the like can be contained. have. On the other hand, when antifouling property is required, a fluorine compound or a silicone compound may be contained. In addition, antimicrobial agents, fungicides, deodorants, antioxidants, ultraviolet absorbers, rust preventive pigments, extender pigments and the like can be contained as long as the desired effects of the present invention are exhibited.

<The second film>

The second film 6 is a crosslinked polyester resin (7) obtained by crosslinking a polyester resin having a glass transition temperature of 0 to 80 ° C with a melamine curing agent or an isocyanate curing agent, and the crosslinking polyester resin ( And 7) the additive 8 dispersed in it. This second film 6 satisfies the integrated emissivity of infrared rays having a wavelength of 3 to 30 µm of 0.6 or more and the gel fraction of 50% or more at a temperature of 25 ° C.

[Crosslinked Polyester Resin]

The crosslinked polyester resin 7 becomes a main component of the second film 6, and the intermolecular crosslinking reaction of the polyester resin having a glass transition temperature of 0 to 80 ° C. using a melamine curing agent or an isocyanate curing agent Let's do it.

The necessity of being a polyester resin, the necessity and advantage of intermolecular crosslinking, examples of the polyhydric alcohol and polybasic acid which can be used as components of the polyester resin, and the description of the glass transition temperature are used in the first film 3. Since it is the same as that of description of the crosslinked polyester resin 4 mentioned above, it abbreviate | omits.

In this invention, the glass transition temperature of the crosslinked polyester resin 7 contained in the 2nd film 6 which is supposed to become an inner surface when it is set as a container-shaped molded article needs to be the range of 0-80 degreeC. Do. Since the 1st film 3 becomes a product outer surface of a container-shaped molded article, when the glass transition temperature is less than 25 degreeC, there existed a subject that the film | membrane became too soft and a flaw was easy, but the 2nd film used as the product inner surface of a container-shaped molded article. Since (6) does not have to consider the scratch resistance to such an extent, it can be used even if it is less than 25 degreeC. However, when it is less than 0 degreeC, since the surface feel becomes strong and it becomes difficult to wind up the precoat aluminum sheet for shaping | molding as a coil, it needs to be 0 degreeC or more. When it exceeds 80 degreeC, the workability of the precoat aluminum plate 1 for shaping | molding falls, and the shape which can be shape | molded will be limited. In particular, since the circuit board etc. adjoin the 2nd film | membrane 6 used as an inner surface of a product, when a processed film | membrane falls out, it will cause a malfunction. In this respect, it is preferable to lower the upper limit of the glass transition temperature than the first film 3 serving as the product outer surface. On the other hand, it is preferable that it is 25-80 degreeC, and, as for glass transition temperature, it is more preferable that it is 25-65 degreeC.

[additive]

The additive 8 is for ensuring an integrated emissivity of infrared rays having a wavelength of 3 to 30 μm with respect to the second film 6 at a temperature of 25 ° C. or higher, and the crosslinked polyester resin of the second film 6 ( 7) to contain.

The kind, size, shape, addition amount, etc. of the additive 8 are not particularly limited as long as the integrated emissivity of infrared rays having a wavelength of 3 to 30 µm is 0.6 or more at a temperature of 25 ° C.

Specific examples of the additive 8 preferred for this purpose include carbon black, graphite, titanium oxide, silica, alumina, resin beads, and the like, and at least one of them can be included.

[Preferable Content of Additives: 5 to 70% by Mass]

There is no restriction | limiting in particular also about the content rate of the additive 8, but when the ratio which occupies for the 2nd film 6 is less than 5 mass%, the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers satisfy | fills 0.6 or more at the temperature of 25 degreeC. In order to make the film thickness thicker, it is not economical. On the other hand, when it exceeds 70 mass%, the 2nd film 6 will be brittle and moldability will fall. Therefore, as for content rate, 5-70 mass% is preferable. On the other hand, it is more preferable that it is 5-60 mass%.

[Gel fraction of second coating: 50% or more]

In the present invention, the gel fraction of the second coating 6 is 50% or more. The reason for limiting the numerical value in this manner is omitted because it is the same as the reason for limiting the gel fraction of the first coating film 3. Since the object of a gel fraction is not made into the crosslinked polyester resin 7 but the 2nd film 6, and the measuring method is the same, it abbreviate | omits.

The gel fraction of the second coating 6 is preferably in the range of 65% or more, and more preferably in the range of 75% or more. Since the larger the gel fraction is, the more preferable it is, the upper limit of the gel fraction does not need to be specifically defined. In addition, in order to make a gel fraction 50% or more, it is preferable to set baking temperature at the time of baking a coating film to about 150-285 degreeC.

[Integrated Emissivity of Infrared Rays with a Wavelength of 3 to 30 μm of the Second Film: 0.6 or More at a Temperature of 25 ° C.]

In the present invention, the second coating film 6 has an integrated emissivity of infrared rays having a wavelength of 3 to 30 µm at 0.6 or more at a temperature of 25 ° C. If the integral emissivity of the infrared rays at the wavelength of 3 to 30 µm of the second coating 6 is less than 0.6, the ability to absorb heat as infrared rays from the surface of the second coating 6 is lowered, and the ability to cool the product is reduced. Lack. On the other hand, it is preferable that the emissivity of this invention is 0.7 or more, and it is more preferable that it is 0.8 or more.

[Preferable film thickness of the second film: 15 μm or less]

In the present invention, the film thickness of the second film 6 is preferably 15 μm or less. Compared with the first film 3, the second film 6 is not severely demanded for its appearance, but in applications where excellent heat dissipation is required as in the present invention, it is possible to secure an integrated emissivity of stable infrared rays over a plurality of lots. In order to achieve this, the film thickness is preferably kept at 15 µm or less. This makes it possible to economically form a film having excellent heat dissipation with one coating.

[Etc]

The 2nd film 6 can be made to contain the coloring agent and the additive which provides various functions in the range which exhibits the desired effect of this invention.

For example, in order to further improve moldability, it is possible to contain a lubricant as described in the first film 3. Moreover, in order to provide the electroconductivity for the purpose of ensuring grounding requested | required by an electronic device, etc., the electroconductive fine particle demonstrated by the 1st film 3 can be contained. In addition, antioxidant, an rust preventive pigment, a extender pigment, etc. can be contained as long as the desired effect of this invention is exhibited.

As mentioned above, although the best embodiment of this invention was described, this invention is not limited to the said embodiment, It can change into the range which does not deviate from the range of this invention.

For example, a ground treatment film (not shown) may be provided on the surface of the aluminum plate 2 by a ground treatment.

<Not processed>

In order that the surface of the aluminum plate 2 may improve adhesiveness with the 1st coating film 3, adhesiveness with the 2nd coating film 6, and corrosion resistance, it is preferable to perform a ground process. As a preferable base treatment, the conventionally well-known reaction type base coating film and coating type base coating film containing Cr, Zr, or Ti can be used. That is, a chromate phosphate film, a chromate chromate film, a zirconium phosphate film, a zirconium oxide film, a titanium phosphate film, a coated chromate film, a coated zirconium film, etc. can be used suitably. An organic-inorganic hybrid type base treatment film in which organic components are combined with these films may be used. On the other hand, in recent years, hexavalent chromium tends to be retarded from the flow of environmental response, and a chromate phosphate coating, zirconium phosphate coating, zirconium oxide coating, titanium phosphate coating, coated zirconium coating, etc., which do not contain hexavalent chromium are used. It is desirable to.

On the other hand, in the present invention, as the film thickness of the undercoat coating, the adhesion amount (calculated in terms of metal Cr, metal Zr or metal Ti) of Cr, Zr or Ti contained in the undercoat coating component to the aluminum plate 2 is, for example, conventionally. Since a known fluorescent X-ray method can be used to measure relatively easily and quantitatively, the quality control of the precoat aluminum sheet 1 for molding can be performed without impairing productivity. On the other hand, it is preferable that it is 10-50 mg / m <^2> in conversion amount of a metal Cr, a metal Zr, or a metal Ti as an adhesion amount of a base treatment film. If the adhesion amount is less than 10 mg / m ² , the entire surface of the aluminum plate 2 cannot be uniformly coated, and the adhesion to the first coating 3 and the second coating 6 and the corrosion resistance are lowered. Moreover, when it exceeds 50 mg / m < ² >, when the precoat aluminum plate 1 for shaping | molding is shape | molded, a crack arises easily in the film | membrane itself of a base process.

In addition, when productivity is not considered, conventionally well-known processes, such as anodizing process and an electrolytic etching process, can also be performed to the surface of the aluminum plate 2. When these processes are performed, fine unevenness | corrugation is formed in the surface of the aluminum plate 2, and the adhesiveness with the 1st film 3 and the adhesiveness with the 2nd film 6 are improved significantly.

In addition, when it is desired to finish by a simple method without requiring such corrosion resistance, the method of only degreasing the surface of the aluminum plate 2 may be sufficient. As the degreasing method, a conventionally known method such as degreasing with an organic drug, degreasing with a surfactant drug, degreasing with an alkali drug, or degreasing with an acid drug can be used. However, in the case of an organic chemical | medical agent or surfactant chemical | medical agent, since the degreasing ability is slightly inferior, the degreasing by an alkali chemical | medical agent or an acidic chemical | medical agent becomes good productivity. The degreasing ability of the alkali chemicals can be controlled by the main component, the concentration, and the treatment temperature of the alkali used. However, when the degreasing ability is strengthened, many smuts are generated. If not, the adhesiveness of the 1st film 3 and the 2nd film 6 may fall rather. In addition, when using the varieties containing much magnesium as an addition element for the aluminum plate 2, as an alkaline chemical | medical agent, magnesium remains on the surface, adhesiveness with the 1st film 3, and 2nd film 6 Adhesiveness with may fall. Therefore, in this case, it is preferable to use or use an acidic chemical | medical agent.

<< container shape molded article >>

As shown in FIG. 2, the container-shaped molded article 10 according to the present invention uses the precoat aluminum plate 1 for molding according to the present invention, and the first coating 3 is the outer surface of the container-shaped molded article 10. And the second film 6 is molded so as to be the inner surface of the container-shaped molded product 10. With such a configuration, since both the inner and outer surfaces have excellent drawing processability (formability) that follows the drawing process, heat can be efficiently absorbed from the inner surface side close to the heat source, and heat can be efficiently released from the outer surface side. The container has excellent heat dissipation. Moreover, the outer surface side exposed to the naked eye as a product outer surface has a bright and beautiful white appearance, and the container shape molded article suitable for the heat sink of LED bulb which is excellent also in visible light reflection is obtained.

The container-shaped molded article 10 according to the present invention has a configuration in which the application to the LED bulb is put into the field of view. Applicable to the application. The work shape may be not only a cylindrical deep drawing shape and a square drawing shape, but also a box-like housing (see Fig. 5 (a)) by bending. In addition, a container is not limited to a user shape, A hole shape may be sufficient.

<< manufacturing method of precoat aluminum sheet for molding >>

Next, an example of the manufacturing method of the precoat aluminum plate 1 for shaping | molding is demonstrated suitably with reference to FIG.

As a manufacturing method of the precoat aluminum plate 1 for shaping | molding, the 1st film 3 is formed in one side surface of the aluminum plate 2, and the 2nd film 6 is provided in the other side surface of the aluminum plate 2. As shown in FIG. What should just be formed is not restrict | limited.

The 1st coating film 3 is a conventionally well-known method of coating material containing the polyester resin used as a raw material of the crosslinked polyester resin 4, a melamine type hardening | curing agent, or an isocyanate type hardening | curing agent, and the white pigment 5. After apply | coating on one side surface of the aluminum plate 2, it can form by carrying out a crosslinking reaction by heating, and similarly, the 2nd film 6 is polyester which becomes a raw material of the crosslinked polyester resin 7 similarly. After coating the coating material containing resin, a melamine type hardening | curing agent, or an isocyanate type hardening | curing agent, and the additive 8 on the other side of the aluminum plate 2 by a conventionally well-known method, and carrying out a crosslinking reaction by heating. It can form by.

The order of applying the paint is not particularly specified, and after applying the paint for the first coat 3 to one side, the paint for the second coat 6 may be applied to the other side, and the second coat 6 After apply | coating a paint for the other side, the paint for the 1st film 3 may be apply | coated to one side, or the paint for the 1st film 3, and the paint for the 2nd film 6, respectively, one side It may be applied to the side and the other side at the same time. Moreover, after apply | coating the heating degree for advancing a crosslinking reaction, the coating material for the 1st film 3, and the coating material for the 2nd film 6, respectively, you may heat one by one, and the coating material for the 1st film 3, agent After coating both the coating materials for 2 films 6, you may heat simultaneously. On the other hand, in order to make the gel fraction of the 1st film 3 and the 2nd film 6 into 50% or more, it is preferable to make the baking temperature at the time of baking a coating material about 150-285 degreeC.

The coating of the paint may be performed by any means such as a brush, a roll coater, a curtain flow coater, a roller curtain coater, an electrostatic spraying machine, a blade coater, a die coater, and the like, and in particular, the coating amount becomes uniform and the work is performed. It is desirable to use a simple roll coater. When apply | coating with a roll coater, control of the film thickness of the 1st membrane | film | coat 3 and the 2nd membrane | film | coat 6 is a conveyance speed of the aluminum plate 2, the rotational direction and rotational speed of a roll, and the pressing pressure between rolls ( Nip pressure) or the like, but in general, the thickness of the first coating 3 and the second coating 6 applied by one coating operation is generally 1 to 20 µm. However, each of the first film 3 and the second film 6 in the present invention is required to have excellent appearance and excellent heat dissipation. In order to ensure performance stably over these lots, it is preferable that the thickness of the 1st film 3 and the 2nd film 6 shall be 15 micrometers upper limit.

Example

Next, the shaping | molding precoat aluminum plate and container shape molded article of this invention are demonstrated concretely in contrast with the Example which satisfy | fills the requirements of this invention, and the comparative example which does not satisfy the requirements of this invention.

[First Embodiment]

In Example 1, the precoat aluminum plate for shaping | molding was examined.

In examination of the precoat aluminum plate for shaping | molding, the aluminum plate used as a raw material used the 0.3-mm-thick material of alloy number A1100-H24. After alkali degreasing with a weak alkali degreasing agent, the phosphate chromate treatment was performed as a base process. The conditions for the phosphoric acid chromate treatment were 20 mg / m ² in terms of chromium adhesion amount. In addition, the mechanical properties of the used aluminum sheet were 130 MPa in tensile strength, 120 MPa in strength, and 8% in elongation.

Next, about the aluminum plate subjected to the phosphate chromate treatment, first, on one side, the coating material of the component described in the first coating film for coating in Table 1 was applied with a bar coater, and then at 100 ° C. at which the crosslinking reaction was not promoted. Temporarily dry for 60 seconds, and then apply the coating material of the component described in the second coating film in Table 1 to the other side with a bar coater, and then change the baking temperature as shown in Table 1 to heat the coating material. By forming a precoat aluminum plate for molding, It was set as the test material according to 1-43. Here, the No. 1 in which the first film thickness and the second film thickness are 25 μm. For 39, since it is difficult to form a film by one coating, the coating is first baked by a 10 μm bar coater, followed by a second coat by coating the remaining 15 μm with a bar coater for one side and the other side. Carried out.

Meanwhile, No. 40 is a test material characterized by the conductivity described in Patent Literature 1, and as a characteristic of the film structure, the white pigment included in the present invention is not included, and silica is included and the film thickness is very thin. No. 41 is a test material which is characterized by the wound prevention property to the optical disc of patent document 2, As a characteristic of a film, the white pigment of this invention is not contained, crosslinked urethane bead is contained, and a base film is an epoxy type There is a point. Also no. 42 is a test material characterized by drawing processability described in Patent Document 3, and the feature of the film structure is that the white pigment and additives included in the present invention are not included. No. 43 is the test material which laminated | stacked the film of patent document 4, As the characteristic, the point which laminated the film which made aromatic nylon the base resin is mentioned.

Meanwhile, No. Since 43 is the test material which laminated | stacked the film which used the aromatic nylon of patent document 4 as a base resin, the film formation method was not the method of coating a coating material like the other example but the method of sticking a film. In addition, the temperature of the reheating quenching treatment for amorphousizing the film instead of the baking temperature is shown in Table 1.

Here, as for the polyester melamine described in the base resin column shown in Table 1, the melamine type hardening | curing agent was mix | blended with polyester type resin, and polyester isocyanate mix | blends isocyanate type hardening | curing agent with polyester type resin Epoxy urea is a compound in which a urea-based curing agent is blended with an epoxy resin, an epoxy phenol is a compound in which a phenol-based curing agent is blended with an epoxy resin, and epoxyacryl is an intramolecular cross-linked acrylic modified epoxy resin. . No. which is a test material laminated the film 43 described the aromatic nylon which is a component of the used film in the base resin column. In addition, the glass transition temperature shown in Table 1 is the glass transition temperature in said each resin, and is measured by the differential scanning calorimetry (DSC method) by a conventional method.

In addition, the additive shown in Table 1 used titanium oxide as a white pigment, carbon black as a black pigment, silica and alumina as inorganic fine particles, crosslinked acrylic beads as crosslinked organic particles, crosslinked urethane beads, etc. as needed.

In addition, the content rate of a white pigment and the content rate of an additive were made into the ratio (mass%) to the mass of the dry resin film which contained the base resin of each film, and the white pigment or an additive.

(Exterior)

About the test material manufactured as mentioned above, first, the external appearance of a 1st film is visually evaluated, and the case where the rolling roll eye of aluminum used as a raw material is not seen is good ((circle)), and the rolling lack of the concealment lack which a rolling roll eye sees is seen. The case was evaluated as defective (×).

After the external appearance evaluation, necessary physical properties in the prepared test material were measured. That is, the L * value of the first film, the integral emissivity of the infrared rays having a wavelength of 3 to 30 µm at 25 ° C, and the gel fraction of the film were measured, and the wavelength at 25 ° C of the second film was 3 to 30 µm. The integral emissivity of phosphorus infrared and the gel fraction of the film were measured.

In addition, L * value and the measuring method and the gel fraction of the integral emissivity of the infrared rays whose wavelengths in 25 degreeC are 3-30 micrometers were measured and evaluated as follows.

(Measurement of L * value)

L * value was measured in the measurement mode (SCI mode) containing a specularly reflected light using the spectrophotometer CM-600d by Konica Minolta. As a light source, D65 called standard light was used by JIS.

It was good that the L * value of a 1st film was 85 or more, and the thing below 85 was evaluated as defect.

(Measurement of Emissivity of Integral Emissivity of Infrared at a Wavelength of 3 to 30 µm)

The emissivity of the integral emissivity of the infrared rays whose wavelength is 3-30 micrometers was measured on 25 degreeC temperature conditions using the commercially available simple emissivity meter (D & S Model AE by D and S company). On the other hand, since the measurement wavelength range of this simple emissometer is 3-30 micrometers, the numerical value displayed becomes an integrated emissivity defined by this invention.

Both the first film and the second film are good that the emissivity (infrared emissivity) of the infrared radiation at a wavelength of 3 to 30 μm (hereinafter simply referred to as “infrared emissivity” in Table 2) is 0.6 or more at a temperature of 25 ° C., and is less than 0.6. Evaluated.

(Measurement of gel fraction)

Since the gel fraction should measure the 1st film and the 2nd film separately, the film formed in the back surface of the surface to be measured using the water resistant abrasive paper was removed. That is, the test material which has a 1st film | membrane grind | polishing-removed the 2nd film | membrane of a test material with water-resistant abrasive paper, and cut out this to 10 cm x 10 cm, and produced it. Similarly, the test material which has a 2nd film grind | polishing-removed the 1st film of a test material, and cut it into 10 cm x 10 cm, and produced it.

After each produced test material was dried for 60 minutes at 80 ° C, the initial mass (a) was measured, and the test material was immersed for 60 minutes in MEK (methyl ethyl ketone) which was then boiled to elute uncrosslinked components, It dried for 60 minutes at 150 degreeC, dried the residual MEK in a film, and measured the mass (b) after extraction. Finally, the film was completely dissolved in the fuming nitric acid, and the mass (c) of only the aluminum plate was measured. Here, since (a)-(c) is the mass of only the original precoat film, and (b)-(c) can be regarded as the mass of the crosslinked film, the gel fraction represented by the following formula, It will show the degree of crosslinking of a film.

Gel fraction (%) = ((b)-(c) / (a)-(c)) × 100

Both the first film and the second film were evaluated to have a good gel fraction of 50% or more and less than 50% of a defective product.

Moreover, about the said test material, the moldability and the durability (wash durability) with respect to the washing | cleaning process after shaping | molding were evaluated. Moldability and washing durability were evaluated as follows.

(Forming)

By the process shown in FIG. 3, the moldability of the test material was investigated.

First, a drawing process was performed after the cylindrical blank punching. Next, by the redrawing process, the cylindrical drawing molded article (middle molded article) of 12 mm (phi) 15 mmL was obtained. Furthermore, ironing was applied to the intermediate molded product so that the plate | board thickness reduction rate of the cylindrical side wall part might be 20%, it was trimmed, it processed into the shape of the cylindrical container of 10 mm diameter x 20 mmL, and the final molded product was obtained. In the process to here, the front and back surface was set so that a 1st film might become an outer surface of a cylindrical container shape, and a 2nd film might be an inner surface. The result of having evaluated the film state in the final molded article obtained at this point was made into the moldability of Table 2. On the other hand, as the press oil, an aqueous emulsion wax containing a fatty acid ester and a surfactant as a main component was used. In addition, processing was performed only at room temperature (35 degreeC).

Evaluation of the film state evaluated the case where there existed no abnormalities, such as peeling of a film, regarding moldability as good ((circle)) and the case where peeling generate | occur | produced as defect (x). This determination was carried out for each of the first film corresponding to the outer surface of the final molded product and the second film corresponding to the inner surface of the final molded product.

(Wash durability)

Trickle was used as a chlorine-type cleaner, and it boiled 1 liter. Twenty said final molded articles were produced for each specimen, and after immersing in boiling tricene for 10 minutes, it was taken out and the external appearance was confirmed. For 20 final molded articles produced for each specimen, cleaning durability was good in cases where surface abnormalities such as dissolution of the coating, peeling of the coating, discoloration of the coating, wounds of the coating, and sticking between the coating films were zero. ), The durability of cleaning was evaluated as the case where there was even one surface abnormality.

Table 1 shows the conditions of the coating material for the first coating film (resin system and glass transition temperature (° C) of the base resin and the kind and content of the white pigment (mass%)) and the conditions of the coating material for the second coating film (resin system and glass of the base resin). Transition temperature (° C.) and the type and content of additives (mass%)), baking temperature (° C.), dry film thickness (μm) of the first film, and dry film thickness (μm) of the second film.

In addition, in Table 2, the first film characteristics (appearance, gel fraction (%), L * value, infrared radiation rate), the second film characteristics (gel fraction (%), infrared radiation rate), the performance of the first film (formation) , Cleaning durability), and performance (forming, cleaning durability) of the second film.

In addition, the underlined part in Table 1 and Table 2 shows that it does not have a requirement or an effect of this invention.

As shown in Table 1 and Table 2, the test material No. 1 (hereinafter, simply referred to as No. 1, etc.) and No. Although 40-43 is a comparative example which does not contain the white pigment which is an essential component in a 1st film, infrared emissivity did not satisfy the requirements of this invention. Moreover, since it did not contain a white pigment, it became a result which a rolling roll eye is seen, and the external appearance of the 1st film became the lack of concealment. On the other hand, No. which is a comparative example of a film laminate material. 43 peeled without melt | dissolving a film in the measurement of a gel fraction.

No. 2, No. 7, No. 8 is a comparative example in which the L * value of the first film did not satisfy the requirements of the present invention, but the hiding power of the first film was insufficient, resulting in an appearance of rolling roll eyes. As a result, the appearance resulted in the lack of concealment. In addition, As for 7, the infrared emissivity also did not satisfy the requirements of the present invention.

No. 10 is a comparative example in which the glass transition temperature of the base resin of the first coating does not satisfy the requirements of the present invention, but in the cleaning durability test, a wound in which molded articles contacted the first coating occurred.

No. 15 is a comparative example in which the gel fractions of the first film and the second film do not satisfy the requirements of the present invention, but both the first film and the second film were dissolved in the cleaning durability test.

No. 19-21 is a comparative example in which the kind of base resin of a 1st film does not satisfy the requirements of this invention, but peeling arose in the 1st film by the moldability test.

No. 42 and No. 43 is a comparative example without the second film itself, but the infrared emissivity of the second film did not satisfy the requirements of the present invention.

No. Although 22 is the comparative example which does not contain the additive which is an essential component in a 2nd film, the infrared emissivity did not satisfy the requirements of this invention.

No. 23 and No. 40 is a comparative example in which the infrared emissivity of the second film does not satisfy the requirements of the present invention.

No. 35 is a comparative example in which the glass transition temperature of the base resin of the second coating does not satisfy the requirements of the present invention, but peeling occurred in the second coating in the moldability test.

No. 36 to 38 and No. Although 41 is a comparative example in which the kind of base resin of a 2nd coating does not satisfy the requirements of this invention, peeling of a 2nd coating occurred in the moldability test.

Test materials other than the above are examples satisfying the requirements of the present invention, but were satisfactory in all results. However, although all the structural requirements of the present invention are satisfied, No. As for 39, since the first film and the second film were difficult to form by one coating, the film thickness is preferably 15 μm or less in consideration of productivity and cost.

Second Embodiment

In Example 2, the container-shaped molded article was examined.

On the examination of the container-shaped molded article, the simulated LED bulb 20 for temperature measurement shown in FIG. 4 was produced. The simulated LED bulb 20 was produced as follows.

First, a commercially available 4.1W LED bulb was purchased and dismantled, and the LED 11, the LED substrate 12, and the circuit 13 were taken out in a state where the LED 11 was lit. The LED 11 is inserted into the cylindrical container 10 formed by molding the first film and the second film having infrared emissivity satisfying the requirements of the present invention so that the outer surface and the circuit 13 lie inside and fixed. The simulated LED bulb 20 for temperature measurement was produced.

Here, in the cylindrical container 10, No.1 in which the 1st film and the 2nd film were provided to the A1100-O of 1 mm of plate | board thickness which performed phosphoric acid chromate treatment after weak alkali degreasing by the method similar to 1st Example. 44 to No. It produced using the precoat aluminum plate for shaping | molding according to 56. Here, the baking temperature was set at 260 ° C. On the other hand, the cylindrical container 10 is No. 44 to No. About each of 56, the cylindrical deep drawing process was implemented so that a 1st film might become an outer surface, and a 2nd film might be an inner surface, and it was set so that it might be set to diameter 55mm (phi) and length 55mmL.

After drilling the hole part 15 of diameter 10mm (phi) and let the power cord 16 pass through the top surface part 14 of a cylindrical container, it filled with the sealing compound and sealed the hole part 15. In addition, the LED substrate 12 is attached to a fixed plate 17 made of aluminum having a diameter of 53 mm phi, so that the circuit 13 of the LED 11 is settled in the cylindrical container 10 (that is, the LED 11 is outside). The opening 18 was fixed by inserting it into the opening 18 of the cylindrical container 10 so as to face the opening.

The temperature measurement was made to light up a light bulb in the state which contacted the front end part of the thermocouple 19 to one surface of four LED 11, observed the temperature change, and measured the highest achieved temperature T1. On the other hand, the tip of the thermocouple 19 is a temperature measuring site, whereby the temperature can be measured.

As a comparative material, a cylindrical container (No. 44) using aluminum platelets not having both the first film and the second film was used as the comparative material temperature measured value T0 when using this. ΔT (ΔT = T1-T0) was defined as the cooling effect. It can be evaluated that the smaller the value of the cooling effect ΔT (that is, the larger the absolute value when ΔT is negative), the better the heat dissipation of the specimen. In Example 2, the case where (DELTA) T was -5 degrees C or less was favorable, and the case where (DELTA) T was higher than -5 degreeC was evaluated as defect.

Table 3 shows the structure of the first film and the second film used for the experiment, the infrared radiation rate, the attainment temperature T1 (° C) and the cooling effect ΔT (° C) of the LED.

In addition, the underlined part in Table 3 shows that it does not have a requirement or an effect of this invention.

Meanwhile, No. 44, No. 45, No. 49 shows that at least one of the first film and the second film is not formed, but for convenience, the infrared emissivity of the outer surface is described in the infrared emissivity column of the first film in Table 3, and the infrared emissivity of the inner surface is indicated in the second in Table 3. It described in the infrared ray emissivity column of a film.

As shown in Table 3, No. 48 and No. 51 to No. 56 is an embodiment of the present invention. In these Examples, it was confirmed that the cooling effect ΔT was a temperature of −5 ° C. or lower, and a favorable effect was obtained.

Meanwhile, No. 45 is a comparative example without the first coating, and No. 46 and No. 47 is a comparative example in which the infrared emissivity of the first film does not satisfy the requirements of the present invention. 49 is a comparative example without the second coating, and No. 50 is a comparative example in which the infrared emissivity of the second film does not satisfy the requirements of the present invention. When either of the 1st film or the 2nd film did not satisfy the requirements of this invention, the cooling effect (DELTA) T became temperature higher than -5 degreeC, and the effect was inadequate.

In this way, it can be seen that when the requirements of the present invention are satisfied, it becomes a molding precoat aluminum plate and a container-shaped molded article excellent in moldability, appearance properties, cleaning durability, and infrared ray emissivity (heat dissipation).

As mentioned above, although the form and Example for inventing the precoat aluminum plate and container shape molded article which concern on this invention were published and demonstrated concretely, the meaning of this invention is not limited to the above content, The technical scope should be construed broadly in accordance with the description of the claims. It is needless to say that the contents of the present invention can be changed, changed, etc. in accordance with the above description.

[Third Embodiment]

In the 3rd Example, the precoat aluminum plate for shaping | molding was examined.

In examination of the precoat aluminum plate for shaping | molding, the aluminum plate used as a raw material used the 0.3-mm-thick material of alloy number A1100-H24. After alkali degreasing with a weak alkali degreasing agent, the phosphate chromate treatment was performed as a base process. The conditions for the phosphoric acid chromate treatment were 20 mg / m ² in terms of chromium adhesion amount. In addition, the mechanical properties of the used aluminum sheet were 130 MPa in tensile strength, 120 MPa in strength, and 8% in elongation.

Next, about the aluminum plate subjected to the phosphate chromate treatment, first, on one side, the coating material of the component described in the first coating film in Table 101 was applied with a bar coater, and then at 100 ° C. to such an extent that the crosslinking reaction did not accelerate. Temporarily dry for 60 seconds, then apply the coating material of the component described in the second coating film in Table 101 to the other side with a bar coater, and then change the baking temperature as shown in Table 101 to heat the coating material. By forming a precoat aluminum plate for molding, It was set as the test material according to 101-144. Here, No. 1 in which the first film thickness and the second film thickness are 25 μm. As for 140, since it is difficult to form a film by one coating, the coating is first performed by a 10 μm bar coater and baked, and then the remaining 15 μm is coated by a bar coater and then baked again on one side and the other side. Carried out.

Meanwhile, No. 141 is a test material with the electroconductivity of patent document 1, As a characteristic of a film structure, the metallic pigment of this invention is not contained, silica is contained, and the film thickness is very thin. No. 142 is a test material with the feature of the wound prevention property to the optical disc of patent document 2, As a characteristic of a film, the metallic pigment of this invention is not contained, a crosslinked urethane bead is contained, and a base film is an epoxy type There is a point. No. 143 is a test material with the feature of drawing processability of patent document 3, As a characteristic of a film structure, the point which does not contain the metallic pigment and additive which are used in this invention is mentioned. No. 144 is a test material which laminated | stacked the film of patent document 4, As the characteristic, the point which laminated the film which made aromatic nylon the base resin is mentioned.

Meanwhile, No. Since 144 is a test material which laminated | stacked the film which used the aromatic nylon of patent document 4 as a base resin, the film formation method was not the method of coating the coating material like the other example but the method of sticking a film. In addition, the temperature of the reheating quenching treatment for amorphousizing the film instead of the baking temperature is shown in Table 101.

Here, as for the polyester melamine described in the base resin column shown in Table 101, the melamine type hardening | curing agent was mix | blended with polyester type resin, and polyester isocyanate mix | blends isocyanate type hardening | curing agent with polyester type resin Epoxy urea is a compound in which a urea-based curing agent is blended with an epoxy resin, an epoxy phenol is a compound in which a phenol-based curing agent is blended with an epoxy resin, and epoxyacryl is an intramolecular cross-linked acrylic modified epoxy resin. . No. which is a test material laminated the film 144 described the aromatic nylon which is a component of the used film in the base resin column. In addition, the glass transition temperature shown in Table 101 is the glass transition temperature in said each resin, and is measured by the differential scanning calorimetry (DSC method) after drying the solvent component of a base resin.

As the additive shown in Table 101, titanium oxide as a white pigment, carbon black as a black pigment, silica and alumina as inorganic fine particles, crosslinked acrylic beads as crosslinked organic particles, crosslinked urethane beads, aluminum paste, and the like were used as necessary.

In addition, the content rate of a metallic pigment and the content rate of an additive were made into the ratio (mass%) to the mass of the dry resin film which contained the base resin of each film, and a metallic pigment or an additive.

(Exterior)

About the test material manufactured as mentioned above, first, the external appearance of a 1st film is visually evaluated, and the case where the rolling roll eye of aluminum used as a raw material is not seen is good ((circle)), and the rolling lack of the concealment lack which a rolling roll eye sees is seen. The case was evaluated as defective (×).

After the external appearance evaluation, necessary physical properties in the prepared test material were measured. That is, the integral emissivity of the infrared rays whose wavelengths at 25 degreeC are 3-30 micrometers, and the gel fraction of a film were measured for both the 1st film and the 2nd film.

In addition, the measuring method and the gel fraction of the integral emissivity of the infrared rays whose wavelengths in 25 degreeC are 3-30 micrometers were measured and evaluated as follows.

(Measurement of Emissivity of Integral Emissivity of Infrared when the Wavelength is 3 to 30 µm)

The emissivity of the integral emissivity of the infrared rays in 3-30 micrometers of wavelengths was measured on 25 degreeC temperature conditions using the commercially available simple emissometer (D & S Model AE by D and S company). On the other hand, since the measurement wavelength range of this simple emissometer is 3-30 micrometers, the numerical value displayed becomes an integrated emissivity defined by this invention.

It is preferable that the emissivity (infrared emissivity) simply described in Table 102) of the integrated emissivity of the infrared rays in the wavelengths of 3 to 30 μm in both the first film and the second film is preferably 0.6 or less at a temperature of 25 ° C., which is less than 0.6. Evaluated as bad.

(Measurement of gel fraction)

Since the gel fraction should measure the 1st film and the 2nd film separately, the film formed in the back surface of the surface to be measured using the water resistant abrasive paper was removed. That is, the test material which has a 1st film | membrane grind | polishing-removed the 2nd film | membrane of a test material with water-resistant abrasive paper, and cut out this to 10 cm x 10 cm, and produced it. Similarly, the test material which has a 2nd film grind | polishing-removed the 1st film of a test material, and cut it into 10 cm x 10 cm, and produced it.

After each produced test material was dried for 60 minutes at 80 ° C, the initial mass (a) was measured, and the test material was immersed for 60 minutes in MEK (methyl ethyl ketone) which was then boiled to elute uncrosslinked components, It dried for 60 minutes at 150 degreeC, dried MEK in a film, and measured the mass (b) after extraction. Finally, the film was completely dissolved in the fuming nitric acid, and the mass (c) of only the aluminum plate was measured. Here, since (a)-(c) is the mass of only the original precoat film, and (b)-(c) can be regarded as the mass of the crosslinked film, the gel fraction represented by the following formula, It will show the degree of crosslinking of a film.

Gel fraction (%) = ((b)-(c) / (a)-(c)) × 100

Both the first film and the second film were evaluated to have a good gel fraction of 50% or more and less than 50% of a defective product.

Moreover, about the said test material, the moldability and the durability (wash durability) with respect to the washing | cleaning process after shaping | molding were evaluated. Moldability and washing durability were evaluated as follows.

(Forming)

By the process shown in FIG. 103, the moldability of the test material was investigated.

First, drawing was performed after cylindrical blank punching. Next, by the redrawing process, the cylindrical drawing molded article (middle molded article) of 12 mm (phi) 15 mmL was obtained. Furthermore, ironing was applied to the intermediate molded product so that the plate | board thickness reduction rate of the cylindrical side wall part might be 20%, it was trimmed, it processed into the shape of the cylindrical container of 10 mm diameter x 20 mmL, and the final molded product was obtained. In the process to here, the front and back surface was set so that a 1st film might become an outer surface of a cylindrical container shape, and a 2nd film might be an inner surface. The result of having evaluated the film state in the final molded article obtained at this point was made into the moldability of Table 2. On the other hand, as the press oil, an aqueous emulsion wax containing a fatty acid ester and a surfactant as a main component was used. In addition, processing was performed only at room temperature (35 degreeC).

Evaluation of the film state evaluated the case where there existed no abnormalities, such as peeling of a film, regarding moldability as good ((circle)) and the case where peeling generate | occur | produced as defect (x). This determination was carried out for each of the first film corresponding to the outer surface of the final molded product and the second film corresponding to the inner surface of the final molded product.

(Wash durability)

Trickle was used as a chlorine-type cleaner, and it boiled 1 liter. Twenty said final molded articles were produced for each specimen, and after immersing in boiling tricene for 10 minutes, it was taken out and the external appearance was confirmed. For 20 final molded articles produced for each specimen, cleaning durability was good in cases where surface abnormalities such as dissolution of the coating, peeling of the coating, discoloration of the coating, wounds of the coating, and sticking between the coating films were zero. ), The durability of cleaning was evaluated as the case where there was even one surface abnormality.

Table 101 shows the conditions of the coating material for the first coating film (resin type and glass transition temperature (° C) of the base resin and the type and content of the metallic pigment (mass%)) and the conditions of the coating material for the second coating film (resin resin and glass of the base resin). Transition temperature (degreeC) and the kind and content rate (mass%) of an additive), baking temperature (degreeC), the dry film thickness (micrometer) of a 1st film, and the dry film thickness (micrometer) of a 2nd film.

Table 102 also shows the first film properties (appearance, gel fraction (%), infrared emissivity), the second film properties (gel fraction (%), infrared emissivity), and the performance of the first film (formability, cleaning durability). And the performance (forming, cleaning durability) of the second film.

In addition, the underlined part in Table 101 and Table 102 shows that it does not have a requirement or an effect of this invention.

As shown in Table 101 and Table 102, Test Material No. 101 (hereinafter, simply referred to as No. 1, etc.) and No. Although 141-144 is the comparative example which does not contain the metallic pigment which is an essential component in a 1st film, infrared emissivity did not satisfy the requirements of this invention. Moreover, since it did not contain a metallic pigment, it became a result which a rolling roll eye is seen, and the external appearance of the 1st film became the lack of concealment. Moreover, No. which is a comparative example of a film laminate material. 144 peeled, without melt | dissolving a film in the measurement of a gel fraction.

No. 102, No. 107, No. 108 is a comparative example in which the infrared emissivity of the first film does not satisfy the requirements of the present invention. They also lacked the hiding power of the 1st film, and became the external appearance which a rolling roll eye sees.

No. Although 110 is a comparative example in which the glass transition temperature of the base resin of a 1st film does not satisfy the requirements of this invention, the wound which the molded articles contacted the 1st film in the cleaning durability test generate | occur | produced.

No. 115 is a comparative example in which the gel fractions of the first film and the second film do not satisfy the requirements of the present invention, but both the first film and the second film were dissolved in the cleaning durability test.

No. Although 119-121 is a comparative example in which the kind of base resin of a 1st film does not satisfy the requirements of this invention, peeling arose in the 1st film in a moldability test.

No. 143 and No. 144 is a comparative example without the second film itself, but the infrared emissivity of the second film did not satisfy the requirements of the present invention.

No. Although 122 is a comparative example which does not contain the additive which is an essential component in a 2nd membrane | film | coat, it came to the result that infrared emissivity does not satisfy the requirements of this invention.

No. 123 and No. 141 is a comparative example in which the infrared emissivity of the second film does not satisfy the requirements of the present invention.

No. 135 is a comparative example in which the glass transition temperature of the base resin of the second coating does not satisfy the requirements of the present invention, but peeling occurred in the second coating in the moldability test.

No. 136 to 138 and no. Although 142 is a comparative example in which the kind of base resin of a 2nd coating does not satisfy the requirements of this invention, peeling of a 2nd coating occurred in a moldability test.

Test materials other than the above are examples satisfying the requirements of the present invention, but were satisfactory in all the results. However, although all the structural requirements of the present invention are satisfied, No. As for 140, since it is difficult to form a film by one coating for both the first film and the second film, the film thickness is preferably 15 µm or less in consideration of productivity and cost.

[Fourth Embodiment]

In Example 4, the container-shaped molded article was examined.

In response to the examination of the container-shaped molded article, a simulated LED bulb 20 for temperature measurement shown in FIG. 104 was produced. The simulated LED bulb 20 was produced as follows.

First, a commercially available 4.1W LED bulb was purchased and dismantled, and the LED 11, the LED substrate 12, and the circuit 13 were taken out in a state where the LED 11 was lit. The LED 11 is inserted into the cylindrical container 10 formed by molding the first film and the second film having an infrared emissivity that satisfies the requirements of the present invention so that the outer surface and the circuit 13 lie in place. The simulated LED bulb 20 for temperature measurement was produced.

Here, in the cylindrical container 10, No.1 in which the 1st film and the 2nd film were provided to the A1100-O of 1 mm of plate | board thickness which performed phosphoric acid chromate treatment after weak alkali degreasing by the method similar to 1st Example. 145-No. It was produced using a precoated aluminum sheet for molding according to 157. Here, the baking temperature was set at 260 ° C. On the other hand, the cylindrical container 10 is No. 145-No. About each of 157, the cylindrical deep drawing process was given so that a 1st film might become an outer surface, and a 2nd film might be an inner surface, and it was set as 55 mm diameter and 55 mmL in length.

After drilling the hole part 15 of diameter 10mm (phi) and let the power cord 16 pass through the top surface part 14 of a cylindrical container, it filled with the sealing compound and sealed the hole part 15. In addition, the LED substrate 12 is attached to a fixed plate 17 made of aluminum having a diameter of 53 mm φ so that the circuit 13 of the LED 11 is settled in the cylindrical container 10 (that is, the LED 11 is outside the outside). The opening 18 was fixed by inserting it into the opening 18 of the cylindrical container 10 so as to face the opening.

The temperature measurement was made to light up a light bulb in the state which contacted the front end part of the thermocouple 19 to one surface of four LED 11, observed the temperature change, and measured the highest achieved temperature T1. On the other hand, the tip of the thermocouple 19 is a temperature measuring site, whereby the temperature can be measured. As a comparative material, the cylindrical container (No. 145) using the aluminum platen which does not have the 1st film and the 2nd film together was used as the comparative material temperature measured value T0 at the time of using this. ΔT (ΔT = T1-T0) was defined as the cooling effect. It can be evaluated that the smaller the value of the cooling effect ΔT (that is, the larger the absolute value when ΔT is negative), the better the heat dissipation of the specimen. In Example 2, the case where (DELTA) T was -5 degrees C or less was favorable, and the case where (DELTA) T was higher than -5 degreeC was evaluated as defect.

Table 103 shows the structure of the first film and the second film used for the experiment, the infrared emissivity, the attainment temperature T1 (° C) and the cooling effect ΔT (° C) of the LED. In addition, the underlined part in Table 103 shows that it does not have a requirement or an effect of this invention.

Meanwhile, No. 145, No. 146, No. At least one of the first film and the second film is not formed at 150, but for convenience, the infrared radiation rate of the outer surface is described in the infrared radiation rate column of the first film in Table 103, and the infrared radiation rate of the inner surface is shown in the second film in Table 103. The infrared ray emissivity column described below.

As shown in Table 103, No. 149 and No. 152-No. 157 is an embodiment of the present invention. In these Examples, it was confirmed that the cooling effect ΔT was a temperature of −5 ° C. or lower, and a favorable effect was obtained.

Meanwhile, No. 146 is a comparative example without the first coating, and No. 147 and No. 148 is a comparative example in which the infrared emissivity of the first film does not satisfy the requirements of the present invention. 150 is a comparative example without the second coating, and No. 151 is a comparative example in which the infrared emissivity of the second film does not satisfy the requirements of the present invention. When either of the infrared or emissivity of the first film or the second film did not satisfy the requirements of the present invention, the cooling effect ΔT was higher than -5 ° C, and the effect was insufficient.

In this way, it can be seen that when the requirements of the present invention are satisfied, it becomes a molding precoat aluminum plate and a container-shaped molded article excellent in moldability, appearance properties, cleaning durability, and infrared ray emissivity (heat dissipation).

As mentioned above, although the form and Example for inventing the precoat aluminum plate and container shape molded article which concern on this invention were published and demonstrated concretely, the meaning of this invention is not limited to the above content, The technical scope should be construed broadly in accordance with the description of the claims. It is needless to say that the contents of the present invention can be changed, changed, etc. in accordance with the above description.

[Fifth Embodiment]

In Example 5, the precoat aluminum sheet for molding was examined.

In examination of the precoat aluminum plate for shaping | molding, the aluminum plate used as a raw material used the 0.3-mm-thick material of alloy number A1100-H24. After alkali degreasing with a weak alkali degreasing agent, the phosphate chromate treatment was performed as a base process. The conditions for the phosphoric acid chromate treatment were 20 mg / m ² in terms of chromium adhesion amount. In addition, the mechanical properties of the used aluminum sheet were 130 MPa in tensile strength, 120 MPa in strength, and 8% in elongation.

Next, about the aluminum plate subjected to the phosphate chromate treatment, first, on one side, the coating material of the component described in the first coating film in Table 201 was coated with a bar coater, and then at 100 ° C. at such a degree that the crosslinking reaction did not accelerate. Temporarily dry for 60 seconds, then apply the coating material of the component described in the second coating film in Table 201 to the other side with a bar coater, and change the baking temperature as shown in Table 201 to heat the coating material. By forming a precoat aluminum plate for molding, It was set as the test material according to 201-249. Here, No. 1 in which the first film thickness and the second film thickness become 25 μm. As for 245, since it is difficult to form a film by one coating, first, 10 μm is coated with a bar coater and baked, and then the remaining 15 μm is coated with a bar coater and then baked again on one side and the other side. Was carried out.

Meanwhile, No. 246 is a test material with features of the conductivity described in Patent Document 1, and the film thickness is very thin as a feature of the film structure. No. 247 is a test material with the feature of the wound prevention property to the optical disk of patent document 2, As a characteristic of a film, a crosslinked urethane bead is contained and the base film is an epoxy type. No. 248 is a test material with the feature of drawing processability of patent document 3, As a characteristic of a film structure, the point which does not contain the additive A and additive B which are used in this invention is mentioned. No. 249 is a test material which laminated the film of patent document 4, As the characteristic, the point which laminated the film which made aromatic nylon the base resin is mentioned.

Meanwhile, No. Since 249 is a test material which laminated | stacked the film which used the aromatic nylon of patent document 4 as a base resin, the film formation method was not the method of coating the coating material like the other example but the method of sticking a film. In addition, the temperature of the reheating quenching treatment for amorphousizing the film instead of the baking temperature is shown in Table 201.

Here, the polyester melamine of the base resin column shown in Table 201 mix | blended the melamine type hardening | curing agent with polyester type resin, and polyester isocyanate mix | blends isocyanate type hardening | curing agent with polyester type resin Epoxy urea is a compound in which a urea-based curing agent is blended with an epoxy resin, an epoxy phenol is a compound in which a phenol-based curing agent is blended with an epoxy resin, and epoxyacryl is an intramolecular cross-linked acrylic modified epoxy resin. . No. which is a test material laminated the film 249 described in the base resin column the aromatic nylon which is a component of the used film. In addition, the glass transition temperature shown in Table 201 is the glass transition temperature in said each resin, and is measured by the differential scanning calorimetry (DSC method) by a conventional method.

In addition, additive A and additive B shown in Table 201 use titanium oxide as a white pigment, carbon black as a black pigment, silica and alumina as inorganic fine particles, crosslinked acrylic beads as organic fine particles, aluminum paste as a metallic pigment, etc. as needed. did. In addition, the content rate was made into the ratio (mass%) of the additive which occupies for the mass of the dry resin film containing a base resin and an additive.

The required physical properties of the test materials produced as described above were measured. That is, while the integral emissivity of the infrared rays whose wavelength at 25 degreeC of a 1st film and a 2nd film is 3-30 micrometers, and the gel fraction of a film were measured, the arithmetic mean roughness Ra was also measured about the 1st film. In addition, the measurement of the integral emissivity, gel fraction, and arithmetic mean roughness Ra of the infrared rays whose wavelength in 25 degreeC is 3-30 micrometers was performed as follows.

(Measurement of Emissivity of Integral Emissivity of Infrared when the Wavelength is 3 to 30 µm)

The emissivity of the integral emissivity of the infrared rays in 3-30 micrometers of wavelengths was measured on 25 degreeC temperature conditions using the commercially available simple emissometer (D & S Model AE by D and S company). On the other hand, since the measurement wavelength range of this simple emissometer is 3-30 micrometers, the numerical value displayed becomes an integrated emissivity defined by this invention.

For both the first and second films, the emissivity (infrared emissivity) simply described in Table 2 of the integrated emissivity of infrared rays at a wavelength of 3 to 30 μm is preferably 0.6 or more at a temperature of 25 ° C., and is less than 0.6. Evaluated as bad.

(Measurement of gel fraction)

Since the gel fraction should measure the 1st film and the 2nd film separately, the film formed in the back surface of the surface to be measured using the water resistant abrasive paper was removed. That is, the test material which has a 1st film | membrane grind | polishing-removed the 2nd film | membrane of a test material with water-resistant abrasive paper, and cut out this to 10 cm x 10 cm, and produced it. Similarly, the test material which has a 2nd film grind | polishing-removed the 1st film of a test material, and cut it into 10 cm x 10 cm, and produced it.

Each produced test material was dried at 80 ° C for 60 minutes, the initial mass (a) was measured, and the test material was immersed for 60 minutes in 2-butanone which was then boiled to elute uncrosslinked components, and then 150 ° C. Was dried for 60 minutes, the remaining 2-butanone in the film was dried, and the mass (b) after extraction was measured. Finally, the film was completely dissolved in fuming nitric acid, and the mass (c) of only the aluminum plate was measured. Here, since (a)-(c) is the mass of only the original precoat film, and (b)-(c) can be regarded as the mass of the crosslinked film, the gel fraction represented by the following formula, It will show the degree of crosslinking of a film.

Gel fraction (%) = ((b)-(c) / (a)-(c)) × 100

Both the first film and the second film were evaluated to have a good gel fraction of 50% or more and less than 50% of a defective product.

(Measurement of arithmetic mean roughness Ra)

The arithmetic mean roughness Ra of the first film was measured by using a surface roughness measuring instrument (Surcoder SE-30D manufactured by Kosaka Research Institute) in a direction perpendicular to the rolling direction with respect to the first film of the specimen ( Iii) and measuring the arithmetic mean roughness Ra described in JIS B0601.

Moreover, about the said test material, the moldability and the durability (wash durability) with respect to the washing | cleaning process after shaping | molding were evaluated. Moldability and washing durability were evaluated as follows.

(Forming)

By the process shown in FIG. 203, the moldability of the test material was investigated.

First, drawing was performed after cylindrical blank punching. Next, by the redrawing process, the cylindrical drawing molded article (middle molded article) of 12 mm (phi) 15 mmL was obtained. Furthermore, ironing was applied to the intermediate molded product so that the plate | board thickness reduction rate of the cylindrical side wall part might be 20%, it was trimmed, it processed into the shape of the cylindrical container of 10 mm diameter x 20 mmL, and the final molded product was obtained. In the process to here, the front and back surface was set so that a 1st film might become an outer surface of a cylindrical container shape, and a 2nd film might be an inner surface. The result of having evaluated the film state in the final molded article obtained at this point was made into the moldability of Table 2. On the other hand, as the press oil, an aqueous emulsion wax containing a fatty acid ester and a surfactant as a main component was used. In addition, processing was performed only at room temperature (35 degreeC).

Evaluation of the film state judged that the case where there was no abnormality, such as film peeling, was good ((circle)) and the case where peeling produced was defective (x) regarding moldability. This determination was carried out for each of the first film corresponding to the outer surface of the final molded product and the second film corresponding to the inner surface of the final molded product.

(Cleaning process durability)

Trickle was used as a chlorine-type cleaner, and it boiled 1 liter. Twenty said final molded articles were produced for each specimen, and after immersing in boiling tricene for 10 minutes, it was taken out and the external appearance was confirmed. For 20 final molded articles produced for each specimen, cleaning durability was good in cases where surface abnormalities such as dissolution of the coating, peeling of the coating, discoloration of the coating, wounds of the coating, and sticking between the coating films were zero. ), The durability of cleaning was evaluated as the case where there was even one surface abnormality.

In Table 201, conditions of the coating material for a 1st coating film (resin system and glass transition temperature (degreeC) of base resin, and kind and content rate (mass%) of additive A), and conditions of the coating material for 2nd coating film (resin system and glass of base resin) The transition temperature (° C.) and the kind and content of the additive B (mass%)), the baking temperature (° C.), the dry film thickness (μm) of the first film, and the dry film thickness (μm) of the second film are shown.

In Table 202, the first film characteristics (gel fraction (%), arithmetic mean roughness Ra (μm), infrared emissivity), the second film characteristics (gel fraction (%), infrared emissivity), the performance of the first film ( Moldability, cleaning durability), and the performance (molding, cleaning durability) of the second film.

In addition, the underlined part in Table 201 and 202 shows that it does not have a requirement or an effect of this invention.

As shown in Tables 201 and 202, Test Material No. 201 (hereinafter, simply referred to as No. 201, etc.) and No. Although 246-249 are the comparative examples which do not contain the additive A which is an essential component in a 1st film, the infrared radiation rate of a 1st film did not satisfy the requirements of this invention. Also no. 201 and No. Regarding 248 and 249, the arithmetic mean roughness did not satisfy the requirements of the present invention. In addition, Regarding the first film of 201, the scratch resistance of the first film was inferior in the test of formability. In addition, 201 and No. As for 248, adhesion (adhesion) of the first films occurs in the cleaning durability test. Also in 249, discoloration occurred in the test of washing durability. On the other hand, No. which is a comparative example of a film laminate material. 249 peeled without melt | dissolving a film in the measurement of a gel fraction.

No. 202, No. 213 did not satisfy the requirements of the present invention for the infrared emissivity of the first film. Among these, No. As for 202, the arithmetic mean roughness of the first film did not satisfy the requirements of the present invention, and the result was that the scratch resistance of the first film was inferior in the test of formability. Furthermore, in the test of cleaning durability, sticking of the first films occurred.

No. Although 215 is a comparative example in which the glass transition temperature of a 1st coating base resin does not satisfy the requirements of this invention, the wound | wound which molded articles contacted the 1st coating by the test of cleaning durability generate | occur | produced.

No. Although 220 is a comparative example in which the gel fractions of the first film and the second film do not satisfy the requirements of the present invention, both of the first film and the second film were dissolved in the test for cleaning durability.

No. 224 is a comparative example in which the kind and glass transition temperature of the first film base resin do not satisfy the requirements of the present invention. Although 225 and 226 are comparative examples in which the kind of 1st film base resin does not satisfy the requirements of this invention, peeling occurred in the film of a 1st film by the test of moldability in all.

No. 248 and No. 249 is a comparative example without the second film itself, but the infrared emissivity of the second film did not satisfy the requirements of the present invention.

No. Although 227 is a comparative example which does not contain the additive B which is an essential component in a 2nd film, it became the result which infrared emissivity does not satisfy the requirements of this invention.

No. 228 and No. 246 is a comparative example in which the infrared emissivity of the second film does not satisfy the present invention.

No. 241 is a comparative example in which the glass transition temperature of the base resin of the second coating does not satisfy the requirements of the present invention, but peeling of the second coating occurred in the moldability test.

No. Although 242-244 is a comparative example in which the kind of base resin of a 2nd coating does not satisfy the requirements of this invention, peeling arose in the film of a 2nd coating in the test of moldability.

Test materials other than the above are examples satisfying the present invention, but were satisfactory in all results. Meanwhile, No. As for 204, in the test of cleaning durability, light tack occurred on the surfaces of the first films, but it was not a problem because it peeled off naturally with drying of the washing liquid tricene. In addition, although all the structural requirements of this invention are satisfied, No. As for 245, since it was difficult to form a film by one coating for both the first film and the second film, the film thickness is preferably 15 µm or less in consideration of productivity and cost.

[Sixth Embodiment]

In Example 6, the container-shaped molded article was examined.

In response to the examination of the container-shaped molded article, a simulated LED bulb 20 for temperature measurement shown in FIG. 204 was produced. The simulated LED bulb 20 was produced as follows.

First, a commercially available 4.1W LED bulb was purchased and dismantled, and the LED 11, the LED substrate 12, and the circuit 13 were taken out in a state where the LED 11 was lit. The LED 11 is inserted into the cylindrical container 10 formed by molding the first film and the second film having infrared emissivity satisfying the requirements of the present invention so that the outer surface and the circuit 13 lie inside and fixed. The simulated LED bulb 20 for temperature measurement was produced.

Here, in the cylindrical container 10, No.1 in which the 1st film and the 2nd film were provided to A1100-O of 1 mm of plate | board thickness which performed phosphoric acid chromate treatment after weak alkali degreasing by the method similar to 1st Example. It produced using the precoat aluminum plate for shaping | molding according to 250-270. Here, the baking temperature was set at 260 ° C. On the other hand, the cylindrical container 10 is No. About each of 250-270, the cylindrical deep drawing process was implemented so that a 1st film might become an outer surface, and a 2nd film might be an inner surface, and it was set as 55 mm diameter and 55 mmL in length.

After drilling the hole part 15 of diameter 10mm (phi) and let the power cord 16 pass through the top surface part 14 of a cylindrical container, it filled with the sealing compound and sealed the hole part 15. In addition, the LED substrate 12 is attached to a fixed plate 17 made of aluminum having a diameter of 53 mm phi, so that the circuit 13 of the LED 11 is settled in the cylindrical container 10 (that is, the LED 11 is outside). The opening 18 was fixed by inserting it into the opening 18 of the cylindrical container 10 so as to face the opening.

The temperature measurement was made to light up a light bulb in the state which contacted the front end part of the thermocouple 19 to one surface of four LED 11, observed the temperature change, and measured the highest achieved temperature T1. On the other hand, the tip of the thermocouple 19 is a temperature measuring site, whereby the temperature can be measured.

As a comparative material, the cylindrical container (No. 50) using the aluminum platen which does not have the 1st film and the 2nd film together was used as the comparative material temperature measured value T0 at the time of using this. ΔT (ΔT = T1-T0) was defined as the cooling effect. It can be evaluated that the smaller the value of the cooling effect ΔT (that is, the larger the absolute value when ΔT is negative), the better the heat dissipation of the specimen. In Example 2, the case where (DELTA) T was -5 degrees C or less was favorable, and the case where (DELTA) T was higher than -5 degreeC was evaluated as defect.

Table 203 shows the structure of the first film and the second film used for the experiment, the infrared ray emissivity, the attainment temperature T1 (° C) and the cooling effect ΔT (° C) of the LED.

In addition, the underlined part in Table 203 shows that it does not have a requirement or an effect of this invention.

Meanwhile, No. 250, no. 251, No. Although 262 is not formed with at least one of a 1st film and a 2nd film, for convenience, the infrared emissivity of an outer surface is described in the infrared emissivity column of the 1st film of Table 203, and the infrared ray emissivity of an inner surface is 2nd in Table 203. It described in the infrared ray emissivity column of a film.

As shown in Table 203, No. 255 to 261 and no. 264 to 270 are embodiments of the present invention. In these Examples, it was confirmed that the cooling effect ΔT was a temperature of −5 ° C. or lower, and a favorable effect was obtained.

Meanwhile, No. 251 is a comparative example without the first coating, and No. 251 was used. 252 and No. 253 and No. 254 is a comparative example in which the infrared radiation rate of the first film does not satisfy the requirements of the present invention. 262 is a comparative example without the second coating, and No. 263 is a comparative example in which the infrared emissivity of the second film does not satisfy the requirements of the present invention. When the infrared emissivity of any of these 1st film or 2nd film does not satisfy the requirements of this invention (it includes the case where at least one of a 1st film and a 2nd film is not formed), And cooling effect (DELTA) T became temperature higher than -5 degreeC, and the effect was insufficient.

In this way, it can be seen that when the requirements of the present invention are satisfied, it becomes a molding precoat aluminum plate and a container-shaped molded article excellent in moldability, cleaning durability, and infrared radiation (heat dissipation).

As mentioned above, although the form and Example for inventing the precoat aluminum plate and container shape molded article which concern on this invention were published and demonstrated concretely, the meaning of this invention is not limited to the above content, The technical scope should be construed broadly in accordance with the description of the claims. It is needless to say that the contents of the present invention can be changed, changed, etc. in accordance with the above description.

1: precoat aluminum sheet for molding
2: aluminum plate
3: first film
4: crosslinked polyester resin
5: white pigment or metallic pigment or additive A
6: second film
7: crosslinked polyester resin
8: additive or additive B
10: container shape molded article

Claims (13)

A molding precoat aluminum plate comprising an aluminum plate, a first film formed on one side of the aluminum plate, and a second film formed on the other side of the aluminum plate,
The first film includes a crosslinked polyester resin obtained by crosslinking and reacting a polyester resin having a glass transition temperature of 25 to 100 ° C. with a melamine curing agent or an isocyanate curing agent, and has an infrared integration of 3 to 30 μm. Emissivity is 0.6 or more at the temperature of 25 ℃, the gel fraction satisfies 50% or more,
The second film includes a crosslinked polyester resin obtained by crosslinking a polyester resin having a glass transition temperature of 0 to 80 ° C. with a melamine curing agent or an isocyanate curing agent, and an additive, and the wavelength is 3 to 30 μm. Integral emissivity of infrared ray satisfies 0.6 or more at 25 ° C and 50% or more gel fraction
A precoat aluminum sheet for molding, characterized in that. The method of claim 1,
The first coating film includes a white pigment, and the L * value is 85 or more. The method of claim 1,
The said 1st membrane | film | coat is a precoat aluminum sheet for shaping | molding of the said white pigment whose titanium oxide and the content rate of this titanium oxide are 20-70 mass%. The method of claim 3, wherein
The said 1st film is a content rate of the said titanium oxide 40-60 mass%, and the film thickness is 15 micrometers or less, The precoat aluminum sheet for shaping | molding. The method according to any one of claims 1 to 4,
The second film is characterized in that the additive contains at least one or more selected from carbon black, graphite, titanium oxide, silica, alumina and resin beads, the content thereof is from 5 to 70 mass%, and the film thickness is 15 μm or less. Molding precoat aluminum sheet. The method of claim 1,
The first coat is a precoat aluminum sheet, characterized in that it comprises a metallic pigment. The method according to claim 6,
The said 1st membrane | film | coat is a precoat aluminum plate for shaping | molding of the said metallic pigment whose aluminum paste is 3-30 mass%. The method of claim 7, wherein
The said 1st film is a content rate of the said aluminum paste 5-20 mass%, and the film thickness is 15 micrometers or less, The precoat aluminum plate for shaping | molding. The method according to claim 6,
The said 2nd membrane | film | coat is the said additive contains at least 1 or more types chosen from carbon black, graphite, titanium oxide, silica, alumina, resin beads, and aluminum paste, The content rate is 5-70 mass%, The film thickness is It is 15 micrometers or less, The molding precoat aluminum plate characterized by the above-mentioned. The method of claim 1,
The said 1st film contains the additive A, the arithmetic mean roughness Ra of the surface is 0.1 micrometer or more and 5 micrometers or less, and the said 2nd film contains the additive B, The shaping | molding precoat aluminum plate characterized by the above-mentioned. The method of claim 10,
The additive A included in the first film and the additive B included in the second film include at least one or more selected from carbon black, graphite, titanium oxide, silica, alumina, resin beads, and aluminum paste. And the content rate is 3-70 mass%, and the film thickness of the said 1st film and the film thickness of the said 2nd film are 15 micrometers or less together, The shaping | molding precoat aluminum plate characterized by the above-mentioned. The method of claim 10,
The arithmetic mean roughness Ra is 0.25 μm or more and 5 μm or less. The molded precoat aluminum plate of Claim 1 was used, and the container-shaped molded article shape | molded so that the said 1st film might become an outer surface, and the said 2nd film would be an inner surface.

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