JP2009298114A - Precoated metal - Google Patents

Precoated metal Download PDF

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JP2009298114A
JP2009298114A JP2008158111A JP2008158111A JP2009298114A JP 2009298114 A JP2009298114 A JP 2009298114A JP 2008158111 A JP2008158111 A JP 2008158111A JP 2008158111 A JP2008158111 A JP 2008158111A JP 2009298114 A JP2009298114 A JP 2009298114A
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foaming agent
metal plate
coating film
metal
layer
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Takahiro Shimizu
孝浩 清水
Eiichiro Yoshikawa
英一郎 吉川
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Kobe Steel Ltd
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Kobe Steel Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a precoated metal which has metal plate surfaces coated with a coating containing a foaming agent, and an excellent deformation processability, and in which the metal plate is easily separated from the rest of the layers in recovering the metal plates by separating it from the rest of the layers, when a laminate comprising the metal plate and other layers laminated on it becomes unsed. <P>SOLUTION: (1) The precoated metal has metal plate surfaces coated with a coating containing a foaming agent. The foaming agent has an average particle size of ≤2 μm and is contained in the coating in an amount of 25-200 mass% of the resin solid. The coating is 4-20 μm tick. (2) The precoated metal is the one as is described above and contains a foaming agent with an average particle size of ≤1.2 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、プレコートメタルに関する技術分野に属するものである。   The present invention belongs to the technical field related to pre-coated metal.

金属板表面にプラスチックや木質板等を積層した積層体は、自動車部品や建築用部材等として用いられている。これらの積層体は、使用時は金属板と他層とが強く接着されていることが必要である。使用された後、換言すれば、不用となったとき、金属板を金属資源としてリサイクル(再利用)するため、金属板を他層から分離して回収するに際し、金属板を他層から容易に分離し得ることが望まれる。   A laminated body in which a plastic or a wooden board is laminated on a metal plate surface is used as an automobile part, a building member, or the like. In these laminates, it is necessary that the metal plate and the other layer are strongly bonded when used. In other words, in order to recycle (reuse) the metal plate as a metal resource when it is no longer needed after being used, the metal plate can be easily removed from the other layer when recovered from the other layer. It is desirable to be able to separate.

このような積層体として、特開2001−212900号公報に記載された積層体がある。この公報に記載された積層体は、例えば、金属板に、発泡剤を含有する架橋性ポリマー層(以下、発泡剤含有ポリマー層という)、架橋性ポリマー層、プラスチック層を順次積層してなる積層体である。この積層体は、使用時は金属板と他層とが強く接着されているが、不用となったとき、エネルギーを照射すること(加熱等)により発泡剤含有ポリマー層中の発泡剤が発泡して(ガスを発生して)金属板と他層とが剥離し易くなり、ひいては、小さな力で容易に金属板と他層を剥離させて分離し得るというものである。
特開2001−212900号公報
As such a laminated body, there exists a laminated body described in Unexamined-Japanese-Patent No. 2001-212900. The laminate described in this publication is, for example, a laminate obtained by sequentially laminating a crosslinkable polymer layer containing a foaming agent (hereinafter referred to as a foaming agent-containing polymer layer), a crosslinkable polymer layer, and a plastic layer on a metal plate. Is the body. In this laminate, the metal plate and other layers are strongly bonded during use, but when it is no longer needed, the foaming agent in the foaming agent-containing polymer layer foams by irradiating energy (heating, etc.). Therefore, the metal plate and the other layer can be easily separated (by generating gas), and as a result, the metal plate and the other layer can be easily separated and separated by a small force.
JP 2001-212900 A

特開2001−212900号公報に記載された積層体での発泡剤含有ポリマー層の厚みについては、特に規定されておらず、実施例ではいずれの場合も300μmである。   The thickness of the foaming agent-containing polymer layer in the laminate described in Japanese Patent Application Laid-Open No. 2001-212900 is not particularly specified, and is 300 μm in any case in the examples.

このように発泡剤含有ポリマー層の厚みが300μmと厚いと、曲げ加工性や成型加工性(以下、変形加工性という)が問題となる場合がある。即ち、金属板を曲げ加工や成型加工(以下、変形加工という)した後、この金属板に発泡剤含有ポリマー層、架橋性ポリマー層、プラスチック層を順次積層する場合には、金属板の変形加工性さえよければ問題とならないが、金属板に発泡剤含有ポリマー層を積層した後、これを変形加工する場合には、その際に発泡剤含有ポリマー層に割れや亀裂が生じたり、発泡剤含有ポリマー層が剥がれたりするという問題がある。このように発泡剤含有ポリマー層に割れや亀裂が生じたり、発泡剤含有ポリマー層が剥がれたりした場合、この発泡剤含有ポリマー層上に他層を積層して得られる積層体は使用時の機能が低下して不充分なものとなる。   Thus, when the thickness of the foaming agent-containing polymer layer is as thick as 300 μm, bending workability and molding processability (hereinafter referred to as deformation processability) may become a problem. That is, when a metal plate is bent or molded (hereinafter referred to as deformation processing) and then a foaming agent-containing polymer layer, a crosslinkable polymer layer, and a plastic layer are sequentially laminated on the metal plate, the metal plate is deformed. However, if it is deformed after laminating a foaming agent-containing polymer layer on a metal plate, the foaming agent-containing polymer layer may be cracked or cracked at that time. There is a problem that the polymer layer peels off. In this way, when the foaming agent-containing polymer layer is cracked or cracked or the foaming agent-containing polymer layer is peeled off, the laminate obtained by laminating other layers on this foaming agent-containing polymer layer is a function in use. Decreases and becomes insufficient.

このような問題を解決する手段として、発泡剤含有ポリマー層の厚みを薄くすることが考えられる。しかしながら、単に発泡剤含有ポリマー層の厚みを薄くすると、発泡剤含有ポリマー層中の発泡剤の量(質量、即ち、グラム数)が少なくなるため、積層体が不用となったときにエネルギー照射により発泡剤含有ポリマー層中の発泡剤を発泡させても、金属板と他層とが剥離し易くなる程度が低下して不充分となり、ひいては、小さな力で容易に金属板と他層を剥離させて分離することはできなくなる。従って、単に発泡剤含有ポリマー層の厚みを薄くするのでは駄目である。   As means for solving such a problem, it is conceivable to reduce the thickness of the foaming agent-containing polymer layer. However, simply reducing the thickness of the foaming agent-containing polymer layer decreases the amount of foaming agent in the foaming agent-containing polymer layer (mass, that is, the number of grams). Even if the foaming agent in the foaming agent-containing polymer layer is foamed, the degree to which the metal plate and other layers are easily peeled is reduced and insufficient, and as a result, the metal plate and other layers are easily peeled off with a small force. Cannot be separated. Therefore, it is not possible to simply reduce the thickness of the foaming agent-containing polymer layer.

本発明はこのような事情に鑑みてなされたものであって、その目的は、発泡剤を含有する塗膜を金属板表面にコートしたプレコートメタルであって、変形加工性に優れており、また、他層が積層されて積層体として使用後に不用となったときに金属板を他層から分離して回収するに際し、金属板を他層から容易に分離し得るプレコートメタルを提供しようとするものである。   The present invention has been made in view of such circumstances, and its purpose is a pre-coated metal in which a metal plate surface is coated with a coating film containing a foaming agent, and is excellent in deformation processability. To provide a pre-coated metal that can easily separate the metal plate from the other layer when the metal plate is separated from the other layer and recovered when the other layer is laminated and is no longer used as a laminate. It is.

本発明者らは、上記目的を達成するため、鋭意検討した結果、本発明を完成するに至った。本発明によれば上記目的を達成することができる。   As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. According to the present invention, the above object can be achieved.

このようにして完成され上記目的を達成することができた本発明は、プレコートメタルに係わり、請求項1〜2記載のプレコートメタル(第1〜2発明に係るプレコートメタル)であり、それは次のような構成としたものである。   The present invention thus completed and capable of achieving the above object relates to a pre-coated metal, and is the pre-coated metal according to claim 1 or 2 (the pre-coated metal according to the first or second invention). The configuration is as follows.

即ち、請求項1記載のプレコートメタルは、発泡剤を含有する塗膜を金属板表面にコートしたプレコートメタルであって、前記発泡剤の平均粒径が2μm以下であり、前記発泡剤の含有量が前記塗膜中の樹脂固形分に対して25〜200質量%であると共に、前記塗膜の厚みが4〜20μmであることを特徴とするプレコートメタルである〔第1発明〕。   That is, the precoat metal according to claim 1 is a precoat metal obtained by coating a metal plate surface with a coating film containing a foaming agent, wherein the foaming agent has an average particle size of 2 μm or less, and the content of the foaming agent Is a pre-coated metal characterized in that the thickness of the coating film is 4 to 20 μm with respect to the resin solid content in the coating film [first invention].

請求項2記載のプレコートメタルは、前記発泡剤の平均粒径が1.2μm以下である請求項1記載のプレコートメタルである〔第2発明〕。   The precoated metal according to claim 2 is the precoated metal according to claim 1, wherein the foaming agent has an average particle diameter of 1.2 μm or less [second invention].

本発明に係るプレコートメタルによれば、変形加工性に優れており、また、他層が積層されて積層体として使用後に不用となったときに金属板を他層から分離して回収するに際し、金属板を他層から容易に分離し得る。   According to the pre-coated metal according to the present invention, it is excellent in deformation workability, and when separating and recovering the metal plate from the other layer when the other layer is laminated and becomes unnecessary after use as a laminate, The metal plate can be easily separated from the other layers.

本発明者らは、前述の目的を達成すべく、鋭意研究を重ねた。その結果、下記のような知見を得た。   The inventors of the present invention have made extensive studies in order to achieve the above-described object. As a result, the following knowledge was obtained.

発泡剤を含有する塗膜を金属板表面にコートしたプレコートメタルにおいて、発泡剤の平均粒径が大きい場合には、塗膜の厚みを薄くすると、塗膜中の発泡剤の量(質量、即ち、グラム数)が少なくなるため、他層が積層されて積層体として使用後に不用となったときにエネルギー照射(加熱等)により塗膜中の発泡剤を発泡させても、金属板と他層とが剥離し易くなる程度が小さく、このため、容易に金属板と他層を剥離させて分離することはできなくなる。   In the pre-coated metal in which the metal plate surface is coated with a coating film containing a foaming agent, when the average particle size of the foaming agent is large, the amount of foaming agent in the coating film (mass, ie, , The number of grams) is reduced, and when the other layer is laminated and becomes unnecessary after use as a laminate, the metal plate and the other layer can be foamed even if the foaming agent in the coating film is foamed by energy irradiation (heating, etc.) Is less likely to be peeled off. For this reason, the metal plate and the other layer cannot be easily separated from each other.

これに対し、発泡剤の平均粒径が2μm以下と小さい場合には、塗膜の厚みを薄くしても、このような問題はない。即ち、発泡剤の平均粒径が2μm以下と小さい場合には、塗膜の厚みを薄くすると、確かに塗膜中の発泡剤の量(質量、即ち、グラム数)は少なくなるものの、他層が積層されて積層体として使用後に不用となったときにエネルギー照射により塗膜中の発泡剤を発泡させる(ガスを発生させる)と、金属板と他層とが剥離し易くなり、このため、容易に金属板と他層を剥離させて分離し得ることがわかった。   On the other hand, when the average particle diameter of the foaming agent is as small as 2 μm or less, there is no such problem even if the thickness of the coating film is reduced. That is, when the average particle size of the foaming agent is as small as 2 μm or less, reducing the thickness of the coating film will certainly reduce the amount of foaming agent in the coating film (mass, that is, the number of grams). When the foaming agent in the coating film is foamed by energy irradiation when gas is laminated and becomes unnecessary after use as a laminate (generating gas), the metal plate and the other layer easily peel off, It was found that the metal plate and other layers can be easily separated and separated.

このように発泡剤の平均粒径が2μm以下と小さい場合には、塗膜の厚みを薄くしても、エネルギー照射により塗膜中の発泡剤を発泡させると、金属板と他層とが剥離し易くなる理由については、次のように考えられる。   In this way, when the average particle size of the foaming agent is as small as 2 μm or less, the metal plate and the other layer are separated when the foaming agent in the coating film is foamed by energy irradiation even if the thickness of the coating film is reduced. The reason why it is easy to do is considered as follows.

発泡剤の平均粒径が2μm以下と小さい場合には、発泡剤の平均粒径が大きい場合よりも、塗膜中の発泡剤の分散性が向上し、発泡剤がより均一に分布するようになるため、塗膜の一断面(金属板に平行な断面)当たりの発泡剤の占有面積、即ち、金属板に垂直な方向(金属板を水平に置いたときは上方)から見たときの発泡剤の円面積の総和が大きくなり、このため、エネルギー照射した際、金属板と他層の剥離に有効に働く発泡剤の割合が高く、発泡剤の発泡の程度が全体的に大きくなる。従って、塗膜の厚みを薄くすることにより塗膜中の発泡剤の量(質量、即ち、グラム数)が少なくなっても、エネルギー照射した際、金属板と他層の剥離に有効に働く発泡剤の割合が高く、発泡剤の発泡の程度が全体的に充分な水準にあり、よって、金属板と他層とが剥離し易くなる。このため、発泡剤の平均粒径が2μm以下と小さい場合には、塗膜の厚みを薄くしても、エネルギー照射により塗膜中の発泡剤を発泡させると、金属板と他層とが剥離し易くなる。   When the average particle size of the foaming agent is as small as 2 μm or less, the dispersibility of the foaming agent in the coating is improved and the foaming agent is more uniformly distributed than when the average particle size of the foaming agent is large. Therefore, the area occupied by the foaming agent per cross section (cross section parallel to the metal plate) of the coating film, that is, foaming when viewed from the direction perpendicular to the metal plate (above when the metal plate is placed horizontally) The sum total of the circular area of the agent increases, and for this reason, when the energy is irradiated, the ratio of the foaming agent that effectively works to peel off the metal plate and the other layer is high, and the degree of foaming of the foaming agent is increased overall. Therefore, even if the amount of foaming agent in the coating film (mass, ie number of grams) is reduced by reducing the thickness of the coating film, foaming that effectively works to peel off the metal plate and other layers when irradiated with energy. The ratio of the agent is high, and the degree of foaming of the foaming agent is at a sufficient level as a whole. Therefore, the metal plate and the other layer are easily separated. For this reason, when the average particle size of the foaming agent is as small as 2 μm or less, the metal plate and the other layer peel off when the foaming agent in the coating film is foamed by energy irradiation even if the coating film thickness is reduced. It becomes easy to do.

本発明は、上記のような知見に基づき完成されたものであり、それはプレコートメタルに係わるものである。このようにして完成された本発明に係るプレコートメタルは、発泡剤を含有する塗膜を金属板表面にコートしたプレコートメタルであって、前記発泡剤の平均粒径が2μm以下であり、前記発泡剤の含有量が前記塗膜中の樹脂固形分に対して25〜200質量%であると共に、前記塗膜の厚みが4〜20μmであることを特徴とするプレコートメタルである〔第1発明〕。   The present invention has been completed based on the above findings, and it relates to pre-coated metal. The pre-coated metal according to the present invention thus completed is a pre-coated metal obtained by coating a metal plate surface with a coating film containing a foaming agent, and the foaming agent has an average particle size of 2 μm or less, The precoat metal is characterized in that the content of the agent is 25 to 200% by mass with respect to the resin solid content in the coating film, and the thickness of the coating film is 4 to 20 μm [first invention]. .

本発明に係るプレコートメタルは、塗膜の厚みが4〜20μmと薄いので、変形加工性に優れている。このように塗膜の厚みは薄くても、発泡剤の平均粒径が2μm以下と小さいので、上記知見からわかるように、他層が積層されて積層体として使用後に不用となったときにエネルギー照射により塗膜中の発泡剤を発泡させると、金属板と他層とが剥離し易く、容易に金属板と他層を剥離させて分離し得る。従って、本発明に係るプレコートメタルによれば、変形加工性に優れており、また、他層が積層されて積層体として使用後に不用となったときに金属板を他層から分離して回収するに際し、金属板を他層から容易に分離し得る。   The precoat metal according to the present invention is excellent in deformation workability because the thickness of the coating film is as thin as 4 to 20 μm. Thus, even if the thickness of the coating film is thin, the average particle diameter of the foaming agent is as small as 2 μm or less, and as can be seen from the above knowledge, when the other layers are laminated and become unnecessary after use as a laminate, energy When the foaming agent in the coating film is foamed by irradiation, the metal plate and the other layer are easily separated, and the metal plate and the other layer can be easily separated and separated. Therefore, according to the pre-coated metal according to the present invention, the deformability is excellent, and when the other layer is laminated and becomes unnecessary after use as a laminate, the metal plate is separated from the other layer and collected. At this time, the metal plate can be easily separated from the other layers.

本発明に係るプレコートメタルでの数値限定理由について、以下説明する。   The reason for the numerical limitation in the precoated metal according to the present invention will be described below.

塗膜の厚み:4〜20μmとしているのは、塗膜の厚み:20μm以下の場合には、変形加工性が良いが、塗膜の厚み:20μm超の場合には、変形加工性が低下して不充分となり、一方、塗膜の厚み:4μm未満の場合には、塗膜中の発泡剤の量(質量、即ち、グラム数)が少なくなり過ぎるため、他層が積層されて積層体として使用後に不用となったときにエネルギー照射により塗膜中の発泡剤を発泡させても、金属板と他層とが剥離し易くなる程度が小さくなり、このため、容易に金属板と他層を剥離させて分離することはできなくなるからである。   The coating thickness: 4 to 20 μm is good when the coating thickness is 20 μm or less, but the deformability is good, but when the coating thickness is more than 20 μm, the deformability decreases. On the other hand, when the thickness of the coating film is less than 4 μm, the amount of foaming agent in the coating film (mass, that is, the number of grams) becomes too small, and other layers are laminated to form a laminate. Even if the foaming agent in the coating film is foamed by energy irradiation when it becomes unnecessary after use, the degree to which the metal plate and the other layer are easily peeled is reduced. This is because they cannot be separated by separation.

発泡剤の平均粒径:2μm以下としているのは、発泡剤の平均粒径:2μm超の場合には、塗膜の厚み:4〜20μmの条件下において、他層が積層されて積層体として使用後に不用となったときにエネルギー照射により塗膜中の発泡剤を発泡させても、金属板と他層とが剥離し易くなる程度が小さくなり、このため、容易に金属板と他層を剥離させて分離することはできなくなるからである。換言すれば、発泡剤の平均粒径:2μm超の場合には、上記の金属板と他層を容易に剥離させて分離する点から塗膜の厚み:4〜20μmとすることができず、ひいては変形加工性が低下して不充分となるからである。   The average particle diameter of the foaming agent is 2 μm or less. When the average particle diameter of the foaming agent is more than 2 μm, the thickness of the coating film is 4 to 20 μm. Even if the foaming agent in the coating film is foamed by energy irradiation when it becomes unnecessary after use, the degree to which the metal plate and the other layer are easily peeled is reduced. This is because they cannot be separated by separation. In other words, when the average particle diameter of the foaming agent is more than 2 μm, the thickness of the coating film cannot be made 4 to 20 μm from the point that the metal plate and the other layer are easily separated and separated, As a result, deformation workability is lowered and becomes insufficient.

発泡剤の含有量を塗膜中樹脂固形分に対して25〜200質量%としている理由は次の通りである。即ち、25質量%未満とした場合には、塗膜中の発泡剤の量(質量、即ちグラム数)が少なくなり過ぎるため、他層が積層されて積層体として使用後に不用となったときにエネルギー照射により塗膜中の発泡剤を発泡させても、金属板と他層とが剥離し易くなる程度が小さくなり、このため、容易に金属板と他層を剥離させて分離することはできなくなる。一方、200質量%超とした場合には、正常な塗膜を有するものとならない。即ち、発泡剤を含有する塗料を金属板表面に塗布してプレコートメタルを作製するに際し、発泡剤が多すぎるため、そもそも塗料にならず、たとえ塗料として金属板表面に塗布したとしても円滑に塗布することができず、また、乾燥後形成される塗膜は表面が粗雑であり、金属板表面との密着性も悪いものとなる。   The reason why the content of the foaming agent is 25 to 200% by mass with respect to the resin solid content in the coating film is as follows. That is, when the amount is less than 25% by mass, the amount of foaming agent in the coating film (mass, that is, the number of grams) is too small, and when other layers are laminated and become unnecessary after use as a laminate. Even if the foaming agent in the coating film is foamed by energy irradiation, the degree to which the metal plate and the other layer are easily peeled is reduced. Therefore, the metal plate and the other layer can be easily separated and separated. Disappear. On the other hand, when it exceeds 200 mass%, it does not have a normal coating film. That is, when a coating containing a foaming agent is applied to the surface of a metal plate to produce a pre-coated metal, there is too much foaming agent, so it does not become a coating in the first place, even if it is applied as a coating on the surface of a metal plate. In addition, the coating film formed after drying has a rough surface and poor adhesion to the metal plate surface.

本発明に係るプレコートメタルにおいて発泡剤の平均粒径は1.2μm以下であることが望ましい〔第2発明〕。発泡剤の平均粒径:1.2μm以下の場合は、発泡剤の平均粒径:1.2μm超2μm以下の場合に比較し、他層が積層されて積層体として使用後に不用となったときにエネルギー照射により塗膜中の発泡剤を発泡させて金属板と他層とを剥離し易くするに際し、その程度を高くする(金属板と他層とをより剥離し易くする)ことができる。   In the precoated metal according to the present invention, the average particle size of the foaming agent is desirably 1.2 μm or less [second invention]. When the average particle size of the foaming agent is 1.2 μm or less, when the average particle size of the foaming agent is more than 1.2 μm and 2 μm or less, the other layers are laminated and become unnecessary after use as a laminate. When the foaming agent in the coating film is foamed by energy irradiation to easily peel the metal plate and the other layer, the degree can be increased (the metal plate and the other layer can be more easily peeled).

本発明に係るプレコートメタルにおいて、発泡剤(加熱等のエネルギー照射によりガスを発生するもの)としては特には限定されず、種々のものを用いることができ、例えば、無機発泡剤、有機発泡剤、熱膨張性中空球体を用いることができる。上記無機発泡剤としては、例えば、重炭酸ナトリウム、炭酸ナトリウム、重炭酸アンモニウム、亜硝酸アンモニウム、アジド化合物、ホウ水素化ナトリウム、軽金属等を用いることができる。上記有機発泡剤としては、例えば、アゾジカルボンアミド、アゾビスイソブチロニトリル等のアゾ系化合物、p-トルエンスルホニルヒドラジン、p,p'- オキシビス(ベンゼンスルホヒドラジド)等のヒドラジン誘導体、N,N'- ジニトロソペンタメチレンテトラミン等のN,N'- ジニトロソ化合物、1-H-テトラゾール、5-フェニルテトラゾール、1-メチル-5- メルカプトテトラゾール、1-フェニル-5- メルカプトテトラゾール、1,5'- ビステトラゾール・グアニジン塩、5,5'- ビステトラゾール・2 アンモニウム塩、5,5'- ビステトラゾール・2 アミノグアニジン塩、5,5'- ビステトラゾール・ピペラジン塩、5,5'- アゾビステトラゾール・ジアミノグアニジン塩、5,5'- アゾビステトラゾール・2 グアニジン塩、5,5'- アゾビステトラゾール・2 アミノグアニジン塩等のテトラゾール誘導体等を用いることができる。上記熱膨張性中空球体としては、例えば、塩化ビニリデンとアクリロニトリルの共重合体等からなる殻部分の内部にエタン等の低沸点炭化水素を含有させたもの等を用いることができる。これらのなかでも、発泡時に高圧ガスを生成する5,5'- ビステトラゾール・2 アンモニウム塩は特に好ましい。   In the pre-coated metal according to the present invention, the foaming agent (that generates gas by energy irradiation such as heating) is not particularly limited, and various materials can be used, for example, an inorganic foaming agent, an organic foaming agent, Thermally expandable hollow spheres can be used. As said inorganic foaming agent, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium nitrite, an azide compound, sodium borohydride, a light metal etc. can be used, for example. Examples of the organic foaming agent include azo compounds such as azodicarbonamide and azobisisobutyronitrile, hydrazine derivatives such as p-toluenesulfonylhydrazine and p, p'-oxybis (benzenesulfohydrazide), N, N N, N'-dinitroso compounds such as '-dinitrosopentamethylenetetramine, 1-H-tetrazole, 5-phenyltetrazole, 1-methyl-5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 1,5' -Bistetrazole and guanidine salts, 5,5'- Bistetrazole and 2 ammonium salts, 5,5'- Bistetrazole and 2 aminoguanidine salts, 5,5'- Bistetrazole and piperazine salts, 5,5'-Azobis Tetrazole / diaminoguanidine salt, 5,5'-azobistetrazole / 2 guanidine salt, 5,5'-azobistetrazole / 2 aminoguanidine salt, etc. A sol derivative or the like can be used. As the above-mentioned thermally expandable hollow sphere, for example, a material in which a low-boiling hydrocarbon such as ethane is contained inside a shell portion made of a copolymer of vinylidene chloride and acrylonitrile or the like can be used. Among these, 5,5′-bistetrazole · diammonium salt that generates a high-pressure gas during foaming is particularly preferable.

塗膜の樹脂としては特には限定されず、種々のものを用いることができる。発泡剤を含有する塗膜は、塗料(樹脂と溶媒とを混合したもの)に発泡剤を混合したものを金属板表面に塗布し、乾燥し、硬化させて形成する。この塗料の樹脂としては特には限定されず、種々のものを用いることができ、例えば、ポリエステル樹脂を用いることができる。   It does not specifically limit as resin of a coating film, A various thing can be used. The coating film containing a foaming agent is formed by applying a mixture of a paint (a mixture of a resin and a solvent) and a foaming agent to the surface of the metal plate, drying and curing. The resin for the paint is not particularly limited, and various types of resins can be used. For example, a polyester resin can be used.

塗膜中の樹脂固形分とは、塗膜中の樹脂成分(溶媒は含まない)のことである。即ち、完全に乾燥した後の塗膜中の樹脂のことである。   The resin solid content in the coating film is a resin component (not including a solvent) in the coating film. That is, it is the resin in the coating after it has been completely dried.

本発明の実施例および比較例を以下説明する。なお、本発明はこの実施例に限定されるものではなく、本発明の趣旨に適合し得る範囲で適当に変更を加えて実施することも可能であり、それらはいずれも本発明の技術的範囲に含まれる。   Examples of the present invention and comparative examples will be described below. The present invention is not limited to this embodiment, and can be implemented with appropriate modifications within a range that can be adapted to the gist of the present invention, all of which are within the technical scope of the present invention. include.

5,5'- ビステトラゾール・2 アンモニウム塩(以下、BHT-2NH3という)をキシレン中で解砕処理した。このとき、分散剤を用い、分散剤濃度:1.6質量%とし、BHT-2NH3濃度:10質量%とした。 5,5′-bistetrazole · 2 ammonium salt (hereinafter referred to as BHT-2NH 3 ) was crushed in xylene. At this time, the dispersant was used, the dispersant concentration was 1.6% by mass, and the BHT-2NH 3 concentration was 10% by mass.

この解砕処理前後のBHT-2NH3の粒径分布を図1に示す。解砕処理前のBHT-2NH3の平均粒径は22.80μmであり、解砕処理後のBHT-2NH3の平均粒径は1.15μmである。この解砕処理後のBHT-2NH3を発泡剤として用いた。 The particle size distribution of BHT-2NH 3 before and after this crushing treatment is shown in FIG. The average particle size of BHT-2NH 3 before the crushing treatment is 22.80 μm, and the average particle size of BHT-2NH 3 after the crushing treatment is 1.15 μm. BHT-2NH 3 after this pulverization treatment was used as a foaming agent.

ポリエステル樹脂と上記解砕処理されたBHT-2NH3(平均粒径:1.15μm)を含む溶液を混合して塗料として用いた。この塗料を、厚み0.8mm、幅60mm、長さ130mmの鋼板に、バーコーターを用いて塗布した後、210℃で1分間の焼き付けを行って塗膜を形成した。   A solution containing the polyester resin and the crushed BHT-2NH3 (average particle size: 1.15 μm) was mixed and used as a paint. This paint was applied to a steel plate having a thickness of 0.8 mm, a width of 60 mm, and a length of 130 mm using a bar coater, followed by baking at 210 ° C. for 1 minute to form a coating film.

なお、上記の例では、発泡剤として平均粒径:1.15μmのBHT-2NH3を用いたが、これに代えて、これと異なる平均粒径のBHT-2NH3も用いた。 In the above example, the average particle diameter as a foaming agent: was used BHT-2NH 3 of 1.15 .mu.m, instead of this, which was used as well BHT-2NH 3 different average particle size.

このようにして鋼板表面に塗膜が形成されたもの(プレコートメタル)の上に、市販接着剤(ホットメルトタイプ、商品名「アドマーQE60」、シート状)を置き、L字形状の鋼片(厚み0.8mm×幅25mm×長さ150mmの鋼板の一部を曲げ、厚み0.8mm×幅25mm×100mm/50mmのL字形状にしたもの)2と上記プレコートメタル(塗膜面側)1とを接着させた。この接着に際し、220℃で1分間加熱した。この接着状態を図2に示す。なお、このL字形状の鋼片接着後のものは積層体(試験片)に相当する。   A commercially available adhesive (hot melt type, trade name “Admer QE60”, sheet shape) is placed on the surface (precoated metal) on which the coating film is formed on the steel plate surface in this way, and an L-shaped steel piece ( Bending part of a steel plate with a thickness of 0.8 mm × width 25 mm × length 150 mm to make a L-shape of thickness 0.8 mm × width 25 mm × 100 mm / 50 mm) 2 and the pre-coated metal (coating surface side) 1 And were adhered. During the bonding, the film was heated at 220 ° C. for 1 minute. This adhesion state is shown in FIG. In addition, the thing after this L-shaped steel piece adhesion | attachment is corresponded to a laminated body (test piece).

このL字形状の鋼片接着後のもの(試験片)を、330℃で1.5分間加熱し、塗膜中の発泡剤(BHT-2NH3)を発泡させた。 This L-shaped steel piece after bonding (test piece) was heated at 330 ° C. for 1.5 minutes to foam the foaming agent (BHT-2NH 3 ) in the coating film.

上記発泡後(加熱→冷却後)の試験片のプレコートメタル部1を押さえて固定し、L字形状の鋼片2の上部(非接着部)3を引っ張り、金属板と他層(接着剤層、L字形状の鋼片)との剥離のし易さ(剥離性)を評価した。   The precoated metal part 1 of the test piece after foaming (after heating → cooling) is pressed and fixed, the upper part (non-adhesive part) 3 of the L-shaped steel piece 2 is pulled, and the metal plate and the other layer (adhesive layer) The ease of peeling (peelability) with an L-shaped steel piece was evaluated.

このとき、金属板と他層が剥離し、L字形状の鋼片(接着していた部分)の変形無しの場合は、剥離性:◎(極めて良好)とし、金属板と他層が剥離し、L字形状の鋼片(接着していた部分)の変形は小さい場合は、剥離性:○(良好)とし、金属板と他層が剥離しなかった場合は、剥離性:×(不良)とした。   At this time, the metal plate and the other layer peel off, and when there is no deformation of the L-shaped steel piece (bonded part), the peelability is ◎ (very good), and the metal plate and the other layer peel off. When the deformation of the L-shaped steel piece (adhered part) is small, the peelability is ○ (good), and when the metal plate and other layers are not peeled, the peelability is × (defect). It was.

上記試験の結果を表1に示す。No.1〜2 、6 〜7 の場合は、プレコートメタルとして比較例に係るものを用いており、剥離性:×(不良)であった。これに対し、No.3〜4 の場合は、プレコートメタルとして本発明例に係るものを用いており、剥離性:◎(極めて良好)、または、剥離性:○(良好)であった。   The results of the above test are shown in Table 1. In the case of No. 1-2 and 6-7, the thing concerning a comparative example was used as a precoat metal, and it was peelability: x (defect). On the other hand, in the case of No. 3-4, the thing based on the example of this invention was used as a precoat metal, and it was peelability: (double-circle) (very good) or peelability: (circle) (good).

No.5の場合は、発泡剤の含有量が200質量%を大幅に超えて多すぎるため、正常な塗膜を形成できるような塗料にならず、このため、鋼板への塗布をしなかった。   In the case of No.5, the content of the foaming agent greatly exceeded 200% by mass, so that the coating film could not form a normal coating film, and therefore it was not applied to the steel sheet. .

Figure 2009298114
Figure 2009298114

本発明に係るプレコートメタルは、変形加工性に優れており、また、他層が積層されて積層体として使用後に不用となったときに金属板を他層から分離して回収するに際し、金属板を他層から容易に分離し得て有用である。   The pre-coated metal according to the present invention is excellent in deformation workability, and when the other layer is laminated and used as a laminate after use, the metal plate is separated from the other layer and collected. Can be easily separated from other layers.

実施例に係る解砕処理前後のBHT-2NH3の粒径分布を示す図である。It shows the particle size distribution of BHT-2NH 3 before and after cracking treatment according to the embodiment. 実施例に係るプレコートメタルとL字形状の鋼片との接着状態を示す図である。It is a figure which shows the adhesion state of the precoat metal which concerns on an Example, and an L-shaped steel piece.

符号の説明Explanation of symbols

1--プレコートメタル、 2--L字形状の鋼片、
3--L字形状の鋼片2の上部(非接着部)。
1--Pre-coated metal, 2--L-shaped steel slab,
3—The upper part of the L-shaped steel piece 2 (non-bonded part).

Claims (2)

発泡剤を含有する塗膜を金属板表面にコートしたプレコートメタルであって、前記発泡剤の平均粒径が2μm以下であり、前記発泡剤の含有量が前記塗膜中の樹脂固形分に対して25〜200質量%であると共に、前記塗膜の厚みが4〜20μmであることを特徴とするプレコートメタル。   A pre-coated metal in which a metal plate surface is coated with a coating film containing a foaming agent, the average particle size of the foaming agent is 2 μm or less, and the content of the foaming agent is based on the resin solid content in the coating film And a thickness of the coating film of 4 to 20 μm. 前記発泡剤の平均粒径が1.2μm以下である請求項1記載のプレコートメタル。   The precoated metal according to claim 1, wherein the foaming agent has an average particle size of 1.2 μm or less.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06246226A (en) * 1993-02-24 1994-09-06 Nippon Paint Co Ltd Raw material body with easily peelable coating film
JPH0761458A (en) * 1993-08-19 1995-03-07 Nitto Denko Corp Adhesive sheet
JPH07251477A (en) * 1994-03-16 1995-10-03 Nippon Zeon Co Ltd Foamed metal structure and its manufacture
JPH07256808A (en) * 1994-03-23 1995-10-09 Zeon Kasei Co Ltd Damping structure, and structural body using said structure
JP2001212900A (en) * 1999-11-22 2001-08-07 Sumitomo Chem Co Ltd Easily releasable laminate
JP2003238721A (en) * 2002-02-14 2003-08-27 Sumitomo Chem Co Ltd Modified silicone resin composition and adhesive having the resin composition as effective component
JP2003246154A (en) * 2002-02-26 2003-09-02 Fuji Photo Film Co Ltd Transfer sheet, method for forming image, and method for preparing ceramic material with image
JP2007168443A (en) * 2000-10-13 2007-07-05 Sumitomo Chemical Co Ltd Laminate made of bonding resin composition and adherend
JP2008126425A (en) * 2006-11-16 2008-06-05 Kobe Steel Ltd Metal plate having easily decomposable coating film and separation method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06246226A (en) * 1993-02-24 1994-09-06 Nippon Paint Co Ltd Raw material body with easily peelable coating film
JPH0761458A (en) * 1993-08-19 1995-03-07 Nitto Denko Corp Adhesive sheet
JPH07251477A (en) * 1994-03-16 1995-10-03 Nippon Zeon Co Ltd Foamed metal structure and its manufacture
JPH07256808A (en) * 1994-03-23 1995-10-09 Zeon Kasei Co Ltd Damping structure, and structural body using said structure
JP2001212900A (en) * 1999-11-22 2001-08-07 Sumitomo Chem Co Ltd Easily releasable laminate
JP2007168443A (en) * 2000-10-13 2007-07-05 Sumitomo Chemical Co Ltd Laminate made of bonding resin composition and adherend
JP2003238721A (en) * 2002-02-14 2003-08-27 Sumitomo Chem Co Ltd Modified silicone resin composition and adhesive having the resin composition as effective component
JP2003246154A (en) * 2002-02-26 2003-09-02 Fuji Photo Film Co Ltd Transfer sheet, method for forming image, and method for preparing ceramic material with image
JP2008126425A (en) * 2006-11-16 2008-06-05 Kobe Steel Ltd Metal plate having easily decomposable coating film and separation method

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