【発明の詳細な説明】[Detailed description of the invention]
［技術分野］
本発明は、チタン板と発泡樹脂とを複合した複
合パネルに関するものである。
［背景技術］
鉄、アルミニウムに続く第３の金属として注目
されているチタンを建築材料として使用する動き
が近年急速に高まつてきている。チタンは比重
4.51と鉄の60％しかなくて軽く、強度も高くて熱
膨張率も低く、そのうえ半永久的に錆びない特徴
を持ち、航空機や重化学工業のプラントなどに多
く使用されるようになつてきたが、価格がステン
レス鋼板の10倍もするために、建築分野では従来
よりあまり使用されていなかつた。しかしながら
例えば塩害の激しい海岸地帯におては建築物の外
装材にチタンを使用すると極めて耐食性がよいた
めにチタンを用いた建築材料の開発が急速に進ん
できたのである。一方、金属板を建材に使用する
場合、断熱性を向上させ結露を防止するために硬
質ポリウレタンフオームやイソシアヌレートフオ
ーム、フエノールフオームなどの発泡樹脂を金属
板の裏打ち材として設けたり、あるいはこれらの
発泡樹脂を金属板間にサンドイツチしたりして、
金属サンデイングやサンドイツチパネルなどとし
た複合パネルとして用いることが普及してきてい
る。この金属板と発泡樹脂との複合パネルは、金
属板に発泡樹脂とその発泡の際の自己接着性によ
つて接着させることで形成されているが、金属板
としてチタン板を用いた複合パネルの場合、チタ
ン鋼板は耐食性が優れるために却つて発泡樹脂と
の接着性を高めるうえで不利になる。
すなわち発泡樹脂との接着性を高めるために、
例えばチタン板の表面処理を通常の燐酸塩やクロ
ム酸などの化成処理液で処理したり、あるいはさ
らにその上に塗料を塗装したりすることがなされ
るが、チタン板はその優れた耐食性のためにこれ
らの化成処理液では十分に化成処理されず、チタ
ン板への発泡樹脂の十分な接着性を得ることがで
きないのである。そこで、チタン板の表面をダル
加工ロールで荒らしたり、スコツチブライトロー
ルやワイヤーブラシロールで研摩したりして、チ
タン板の表面を粗面化し、発泡樹脂との接着性を
向上させたり、さらにはこのように粗面化してか
らクロム酸処理とすると共に塗料を塗装して発泡
樹脂との接着性を向上させる試みもなされている
が、これらにおいてもチタン板と発泡の際の自己
接着性による発泡樹脂との間の接着力は１Kg／cm2
以下と低く、さらに経時的に接着力が低下し易く
温度変化の激しい場合には膨張収縮の繰り返しで
剥離が発生する危険性がある。
［発明の目的］
本発明は、上記の点に鑑みて為されたものであ
り、チタン板と発泡樹脂との接着性に優れ複合強
度が高い複合パネルを提供することを目的とする
ものである。
［発明の開示］
しかして本発明に係る複合パネルは、クロム酸
と珪酸塩及び燐酸を含有する化成処理液で表面処
理されたチタン板の表面に、樹脂塗料の塗膜を介
して発泡樹脂の層がその発泡の際の自己接着性に
よつて接着されて成ることを特徴とするものであ
り、以下本発明を詳細に説明する。
チタン板をまず脱脂処理したのちに、次いで表
面を化成処理液で化成処理する。化成処理液とし
てはクロム酸（CrO3）と珪酸塩（SiO2）と燐酸
（H3PO4）とを混合したものを用いるものであ
り、この化成処理液においてクロム酸と珪酸塩と
燐酸の割合の重量比率は、燐酸を１とするとクロ
ム酸を１〜３、珪酸塩を１〜３に設定するのが好
ましく、配合比率がこれから外れるとチタン板へ
の塗膜の密着性の向上の効果を十分に得ることが
できない。化成処理液をチタン板の表面にロール
コーターやフローコーターなどの塗布装置によつ
て塗布して乾燥することによつて、化成処理をお
こなうことができる。化成処理液の塗布量は乾燥
状態で片面10〜500mg／m2の範囲に、乾燥温度は
60〜120℃の範囲に設定されるのが好ましいが、
勿論これらに限定されるものではない。
このようにチタン板の表面をクロム酸と珪酸塩
及び燐酸を含む化成処理液で化成処理したのち、
チタン板の表面にポリエステル樹脂系塗料、アク
リル樹脂系塗料、エポキシ樹脂系塗料、ウレタン
樹脂系塗料、アルキツドメラミン樹脂塗料、エポ
キシウレタン樹脂系塗料など後述の発泡樹脂と密
着性の良い樹脂塗料を塗布する。塗布は乾燥塗膜
厚さで２〜30μとなるようにおこなうのがよく、
焼き付け硬化温度を160〜240℃に、焼き付け時間
を20〜60秒程度にそれぞれ設定して乾燥させ、発
泡樹脂との密着性が良好な樹脂塗膜を形成させ
る。
発泡樹脂としては硬質ポリウレタンフオームや
イソシアヌレートフオーム、フエノールフオーム
などを用いることができ、この発泡樹脂の原液を
チタン板の上記樹脂塗膜を形成させた面に注入し
て発泡硬化させ、この発泡硬化時の自己接着性に
よつて発泡樹脂をチタン板に接着させ、チタン板
を金属外皮材とし発泡樹脂の層が複合された複合
パネルを得ることができる。この複合パネルにあ
つて、チタン板の表面はクロム酸と珪酸塩及び燐
酸を含む化成処理液で化成処理されているために
チタン板と樹脂塗膜との接着性が高く、塗膜を介
して発泡樹脂の層を強固に接着させることができ
る。ちなみに、チタン板と発泡樹脂との接着強度
は、発泡樹脂が硬質ウレタンフオームの場合は
1.8〜2.5Kg／cm2程度、イソシアヌレートフオーム
の場合は0.9〜1.2Kg／cm2程度にそれぞれ高めるこ
とができ、しかも発泡樹脂が凝集破壊されるまで
チタン板と発泡樹脂との間での界面剥離は生じな
い。これに対してチタン板の表面粗度を調整して
粗面化したものにおいては、発泡樹脂が硬質ウレ
タンフオームの場合で1.0〜1.2Kg／cm2程度、イソ
シアヌレートフオームの場合で0.6〜0.8Kg／cm2程
度と低く、しかも剥離はチタン板と発泡樹脂との
間で界面剥離として生じるものであり、さらにチ
タン板の表面粗度を調整してクロム酸による化成
処理をし、そして塗膜を形成させるようにしたも
のにおいても、発泡樹脂が硬質ウレタンフオーム
の場合で1.2〜1.4Kg／cm3程度、イソシアヌレート
フオームの場合で0.7〜0.9Kg／cm2程度と高いもの
が得られず、しかも剥離はチタン板と発泡樹脂と
の間での界面剥離及び発泡樹脂の凝集破壊とが混
在して生じる。
ここで複合パネルを製造するにあたつて、バツ
チ方式の製造と連続方式の製造とのいずれの方法
も採用することができる。バツチ方法の場合は例
えば、一対の金属外皮材としてチタン板を用い、
あるいは一対の金属外皮材として一方をチタン
板、他方を塗装鋼板や塗装アルミニウム板を用
い、この一対の金属外皮材に嵌合部やリブをロー
ル成形機やプレスベンダーなどで加工し、次いで
一対の金属外皮材の周辺嵌合部を硬質ポリ塩化ビ
ニルなどの樹脂型押し枠で囲い、これを水平型あ
るいは長尺の生産に適した縦型の多段プレスに10
〜20組セツトし、枠の１〜２箇所の孔から各金属
外皮材間に発泡樹脂の原液を注入し、一定時間発
泡させて硬化させ、一対の金属外皮材間の発泡樹
脂の層をサンドイツチさせた複合パネルを製造す
ることができる。このようにして例えば第１図に
示すような内面にクロム酸と珪酸塩及び燐酸を含
む化成処理液で化成処理皮膜１が形成された一対
の金属外皮材３，３間に樹脂塗膜２，２を介して
発泡樹脂の層４が接着されたサンドイツチ構造の
複合パネルを得ることができる。また連続方式の
場合は例えば、コイル状のチタン板を巻き戻して
ロール成形機で製品形状に応じた形状に端部の成
形やリブの成形をおこなうと共にチタン板の全体
形状を断面凹型に成形し、このチタン板を連続し
て送りつつ凹部に発泡樹脂の原液をノズルから注
入散布し、発泡樹脂原液を発泡させつつこれをダ
ブルコンベアーに導入して所定の15〜25mm程度の
間隔で挟持して搬送する間に発泡硬化させ、チタ
ン板に発泡樹脂の層を裏打ち積層させた複合パネ
ルを製造することができる。このとき、アルミニ
ウム箔やスチール箔、アルミニウム蒸着クラフト
紙、石綿紙、不織布などの軟質コイルを繰り出し
てダブルコンベアーの入側から導入し、発泡樹脂
のチタン板と反対側の面に装着させて覆わせるよ
うにする。このようにして第２図ａのようにチタ
ン板の金属外皮材１の内面側に発泡樹脂の層４が
化成処理皮膜と樹脂塗膜（いずれも図示は省略）
を介して積層接着され、さらに発泡樹脂の層４の
裏面に軟質コイル５が接着された金属サイジング
構造の複合パネルを得ることができる。さらに連
続方式でサンドイツチ構造の複合パネルを製造す
る場合には、一対の金属外皮材としてチタン板を
用い、あるいは一対の金属外皮材として一方をチ
タン板、他方を塗装鋼板や塗装アルミニウム板を
用い、ロール成形機でこの一対の金属外皮材の両
側端の嵌合部やリブ波の成形をおこない、次いで
この一対の金属外皮材を上下に対向させてこの間
に発泡樹脂の原液を注入散布し、発泡樹脂原液を
発泡させつつこれをダブルコンベアーに導入して
所定の22〜200mm程度の間隔で挟持して搬送する
間に発泡硬化させることによつて、金属外皮材間
に発泡樹脂の層をサンドイツチさせた複合パネル
を製造することができ、これをダブルコンベアー
の出側に設けた走間切断機で自由な寸法に切断す
る。このようにして例えば第２図ｂに示すような
一対の金属外皮材３，３の内面側に発泡樹脂の層
４が化成処理皮膜と樹脂塗膜（いずれも図示は省
略）を介して積層接着されたサンドイツチ構造の
複合パネルを得ることができる。第２図ｂ中６は
アルミニウム箔、７はEPTなどのゴムパツキン
であり、またこのサンドイツチ構造の複合パネル
の断面構造は第１図のものと同じである。
次ぎに本発明を実施例によつて例証する。
実施例 １
板厚が0.5mmJIS Ｈ 46001種のチタン板をアル
カリ脱脂剤（日本パーカライジング株式会社製フ
アインクリーナーFC4336）によつて70℃、15秒
間の条件で脱脂したのち湯洗した。次にCr6+が
6000ppm、Cr3+が4000ppm、PO4が10000ppm、
SiO2が20000ppmで、PHが１〜２のクロム酸、珪
酸塩、燐酸混合の塗型化成処理液を、濃度50％、
Cr6+濃度30±２ポイント、温度18℃の条件でロー
ルコーターにて上記チタン板に片面の乾燥重量が
120mg／m2となる塗布量で塗布し、90℃で30秒間
乾燥することによつて化成処理をおこなつた。次
いでこのチタン板の化成処理表面にオイルフリー
ポリエステル系塗料（日本ペイント株式会社製
「Ｒ−50」；ポリエステル66％、アルキツド34％）
を乾燥塗膜10μ厚になるように塗布し、板温200
℃、焼き付け時間60秒の条件で乾燥することによ
つて、チタン板の片面に樹脂塗膜を形成させた。
次ぎにこの一対のチタン板を樹脂塗膜が対向する
ように上下に対向配置し、硬質ウレタンフオーム
原液（ポリウレタン化成株式会社製；MDI、ポ
リオール、フロンＲ−11、アクチベーター配合）
をチタン板間に注入て発泡させることによつて、
フオーム密度が50Kg／m3の発泡樹脂の層をその自
己接着性がチタン板の樹脂塗膜面に接着させた。
このようにして厚み35mmの発泡樹脂層が一対のチ
タン板にサンドイツチされた第２図ｂの構造の複
合パネルを連続式工法で得た。
実施例 ２
発泡樹脂の原液として難燃型のイソシアヌレー
トフオーム原液（ポリウレタン化成株式会社製；
特殊MDI、特殊ポリオール、フロンＲ−11、ア
クチベーター配合（を用い、フオーム密度が45
Kg／m3になるように発泡させるようにした他は、
実施例１と同様にして厚み35mmの発泡樹脂層が一
対のチタン板にサンドイツチされた第２図ｂの構
造の複合パネルを連続式工法で得た。
比較例 １
板厚0.5mmのJIS Ｈ 4600 １種のチタン板をア
ルカリ脱脂剤（日本パーカライジング株式会社製
フアインクリーナFC4336）によつて70℃、15秒
間の条件で脱脂したのち湯洗した。次いでスコツ
チブライトロールにてこのチタン板の表面を研摩
することによつて、表面粗度を平均Ra＝0.16μと
し、化成処理をすることなくこの研摩面を対向さ
せて一対のチタン板を上下に対向配置し、あとは
実施例１と同様にして硬質ウレタンフオーム原液
をチタン板間に注入して発泡させることによつ
て、フオーム密度が50Kg／m3の発泡樹脂の層をそ
の自己接着性でチタン板の研摩面に接着させた。
このようにして厚み35mmの発泡樹脂層が一対のチ
タン板にサンドイツチされた第２図ｂの構造の複
合パネルを連続式工法で得た。
比較例 ２
発泡樹脂の原液として実施例２と同じイソシア
ヌレートフオーム原液を用い、フオーム密度が45
Kg／m3になるよう発泡させるようにした他は、比
較例１と同様にして厚み35mmの発泡樹脂層が一対
のチタン板にサンドイツチされた第２図ｂの構造
の複合パネルを連続式工法で得た。
比較例 ３
比較例１と同様にしてチタン板の表面を研摩処
理したのち、化成処理することなくチタン板の研
摩表面に実施例１と同様にしてポリエステル系塗
料（「Ｒ−50」）の10μ厚の樹脂塗膜を形成させ、
次いでこの一対のチタン板を樹脂塗膜が対向する
ように上下に対向配置し、実施例１と同様にして
硬質ウレタンフオーム原液をチタン板間に注入し
て発泡させることによつて、フオーム密度が50
Kg／m3で厚み35mmの発泡樹脂層が一対のチタン板
にサンドイツチされた第２図ｂの構造の複合パネ
ルを連続式工法で得た。
比較例 ４
発泡樹脂の原液として実施例２と同じイソシア
ヌレートフオーム原液を用い、フオーム密度が45
Kg／m3になるよう発泡させぬようにした他は、比
較例３と同様にして厚み35mmの発泡樹脂層が一対
のチタン板にサンドイツチされた第２図ｂの構造
の複合パネルを連続式工法で得た。
比較例 ５
チタン板を比較例１と同様にして研摩処理した
のちに実施例１と同様にしてクロム酸、珪酸塩、
燐酸混合の塗布型化成処理液で化成処理し、塗装
をすることなくこの一対のチタン板を化成処理面
が対向するように上下に対向配置し、実施例１と
同様にして硬質ウレタンフオーム原液をチタン板
間に注入して発泡させることによつて、フオーム
密度が50Kg／m3で厚み35mmの発泡樹脂層が一対の
チタン板にサンドイツチされた第２図ｂの構造の
複合パネルを連続式工法で得た。
比較例 ６
発泡樹脂の原液として実施例２と同じイソシア
ヌレートフオーム原液を用い、フオーム密度が45
Kg／m3になるよう発泡させるようにした他は、比
較例５と同様にして厚み35mmの発泡樹脂層が一対
のチタン板にサンドイツチされた第２図ｂの構造
の複合パネルを連続式工法で得た。
比較例 ７
比較例１と同様にしてチタン板の表面を研摩処
理し、次ぎにクロム酸（CrO3）12.5重量％と珪
酸塩（SiO2）12.5重量％の計25重量％の混合液の
化成処理液（関西ペイント株式会社製）を、ロー
ルコーターによつて上記チタン板の研摩面に片面
の乾燥重量が120mg／m2となるように塗布し、80
℃で30秒間乾燥して化成処理をした。次ぎにチタ
ン板の研摩表面に実施例１と同様にしてポリエス
テル系塗料「（Ｒ−50」）の10μ厚の樹脂塗膜を形
成させ、次いでこの一対のチタン板を軸脂塗膜が
対向するように上下に対向配置し、実施例１と同
様にして硬質ウレタンフオーム原液をチタン板間
に注入して発泡させることによつて、フオーム密
度が50Kg／m3で厚み35mmの発泡樹脂層が一対のチ
タン板にサンドイツチされた第２図ｂの構造の複
合パネルを連続式工法で得た。
比較例 ８
発泡樹脂の原液として実施例２と同じイソシア
ヌレートフオーム原液を用い、フオーム密度が45
Kg／m3になるよう発泡させるようにした他は、比
較例７と同様にして厚み35mmの発泡樹脂層が一対
のチタン板にサンドイツチされた第２図ｂの構造
の複合パネルを連続式工法で得た。
上記実施例１、２及び比較例１乃至８における
研摩処理の有無、化成処理の種類、塗装の有無、
発泡樹脂の種類を第１表に整理して示す。
[Technical Field] The present invention relates to a composite panel made of a titanium plate and a foamed resin. [Background Art] In recent years, there has been a rapid increase in the use of titanium, which is attracting attention as the third metal after iron and aluminum, as a building material. Titanium has a specific gravity
4.51, which is only 60% of iron, it is light, has high strength, has a low coefficient of thermal expansion, and has the characteristics of semi-permanently rust-free, so it has come to be widely used in aircraft and heavy chemical industry plants. Because it is 10 times more expensive than stainless steel sheets, it has not been used much in the construction field. However, for example, in coastal areas where salt damage is severe, when titanium is used as an exterior material for buildings, it has extremely good corrosion resistance, so the development of building materials using titanium has progressed rapidly. On the other hand, when metal plates are used as building materials, foamed resins such as rigid polyurethane foam, isocyanurate foam, or phenol foam are provided as a backing material for the metal plates to improve heat insulation and prevent condensation. By sandwiching the resin between metal plates,
It is becoming popular to use it as a composite panel such as metal sanding or sanderch panels. This composite panel of a metal plate and foamed resin is formed by adhering the foamed resin to the metal plate using the self-adhesive properties of the foamed resin, but a composite panel using a titanium plate as the metal plate is In this case, since the titanium steel plate has excellent corrosion resistance, it becomes disadvantageous in terms of improving adhesiveness with the foamed resin. In other words, in order to improve the adhesion with the foamed resin,
For example, the surface of a titanium plate is treated with a chemical conversion treatment solution such as phosphate or chromic acid, or is coated with paint, but titanium plates have excellent corrosion resistance. However, these chemical conversion treatment liquids do not provide sufficient chemical conversion treatment, and it is not possible to obtain sufficient adhesion of the foamed resin to the titanium plate. Therefore, we roughened the surface of the titanium plate with a dull roll or polished it with a Scotch Bright roll or wire brush roll to roughen the surface of the titanium plate and improve its adhesion with the foamed resin. Attempts have also been made to roughen the surface in this way and then treat it with chromic acid, as well as painting it with paint to improve the adhesion to the foamed resin, but these methods also have problems due to the self-adhesion of the titanium plate and the foaming process. Adhesive strength between foamed resin is 1Kg/cm 2
If the adhesive strength is as low as below, and furthermore, the adhesive strength tends to decrease over time and there are severe temperature changes, there is a risk that peeling will occur due to repeated expansion and contraction. [Object of the invention] The present invention has been made in view of the above points, and an object thereof is to provide a composite panel with excellent adhesiveness between a titanium plate and a foamed resin and high composite strength. . [Disclosure of the Invention] The composite panel according to the present invention is a titanium plate whose surface has been treated with a chemical conversion treatment solution containing chromic acid, silicate, and phosphoric acid. The present invention is characterized in that the layers are adhered by self-adhesive properties during foaming, and the present invention will be described in detail below. After the titanium plate is first degreased, the surface is then chemically treated with a chemical conversion treatment liquid. The chemical conversion treatment liquid used is a mixture of chromic acid (CrO 3 ), silicate (SiO 2 ), and phosphoric acid (H 3 PO 4 ). It is preferable to set the weight ratio of phosphoric acid to 1, chromic acid to 1 to 3, and silicate to 1 to 3. If the blending ratio deviates from this, the effect of improving the adhesion of the coating film to the titanium plate will increase. I can't get enough of it. Chemical conversion treatment can be performed by applying a chemical conversion treatment liquid onto the surface of a titanium plate using a coating device such as a roll coater or a flow coater and drying it. The amount of chemical conversion treatment liquid applied is in the range of 10 to 500 mg/ m2 per side in dry condition, and the drying temperature is
It is preferable to set the temperature in the range of 60 to 120℃,
Of course, it is not limited to these. After chemically treating the surface of the titanium plate with a chemical conversion treatment solution containing chromic acid, silicate, and phosphoric acid,
Apply a resin paint with good adhesion to the foamed resin described below, such as polyester resin paint, acrylic resin paint, epoxy resin paint, urethane resin paint, alkyd melamine resin paint, or epoxy urethane resin paint, on the surface of the titanium plate. do. It is best to apply to a dry film thickness of 2 to 30μ.
The baking curing temperature is set to 160 to 240°C and the baking time is set to about 20 to 60 seconds, respectively, and dried to form a resin coating film with good adhesion to the foamed resin. As the foamed resin, hard polyurethane foam, isocyanurate foam, phenol foam, etc. can be used. A stock solution of this foamed resin is injected onto the surface of the titanium plate on which the resin coating is formed, and the resin is foamed and hardened. By adhering the foamed resin to the titanium plate due to its self-adhesive properties, it is possible to obtain a composite panel in which the titanium plate is used as a metal outer material and a layer of the foamed resin is combined. In this composite panel, the surface of the titanium plate is chemically treated with a chemical conversion treatment solution containing chromic acid, silicate, and phosphoric acid, so the adhesion between the titanium plate and the resin coating is high, and the adhesiveness between the titanium plate and the resin coating is high. The foamed resin layer can be firmly bonded. By the way, the adhesive strength between the titanium plate and the foamed resin is as follows if the foamed resin is a hard urethane foam.
It can be increased to about 1.8 to 2.5Kg/ cm2 , and to about 0.9 to 1.2Kg/ cm2 for isocyanurate foam, and the interface between the titanium plate and the foamed resin can be increased until the foamed resin undergoes cohesive failure. No peeling occurs. On the other hand, when the surface roughness of a titanium plate is roughened by adjusting the surface roughness, the foamed resin is about 1.0 to 1.2 Kg/ cm2 when it is a hard urethane foam, and 0.6 to 0.8 Kg when it is an isocyanurate foam. / cm2 , and the peeling occurs as interfacial peeling between the titanium plate and the foamed resin.Furthermore, the surface roughness of the titanium plate is adjusted, chemical conversion treatment is performed using chromic acid, and the coating film is removed. Even in the case where the foamed resin is made of hard urethane foam, it is about 1.2 to 1.4 Kg/cm 3 , and when it is isocyanurate foam, it is about 0.7 to 0.9 Kg/cm 2 . Peeling occurs as a mixture of interfacial peeling between the titanium plate and the foamed resin and cohesive failure of the foamed resin. In manufacturing the composite panel, either a batch manufacturing method or a continuous manufacturing method can be employed. In the case of the batch method, for example, a titanium plate is used as a pair of metal shell materials,
Alternatively, use a titanium plate on one side and a painted steel plate or painted aluminum plate as a pair of metal skin materials, process the fitting parts and ribs on the pair of metal skin materials with a roll forming machine, press bender, etc. The peripheral fitting part of the metal shell material is surrounded by a resin-embossed frame made of hard polyvinyl chloride, etc., and this is placed in a horizontal or vertical multi-stage press suitable for long length production.
Set up ~20 sets, inject foamed resin stock solution between each metal sheathing material through one or two holes in the frame, allow it to foam for a certain period of time and harden, and sandwich the foamed resin layer between the pair of metal sheathing materials. It is possible to produce composite panels with In this way, for example, as shown in FIG. 1, a resin coating film 2 is formed between a pair of metal outer coating materials 3, 3 on which a chemical conversion coating 1 is formed on the inner surface with a chemical conversion treatment solution containing chromic acid, silicate, and phosphoric acid. It is possible to obtain a composite panel with a sandwich structure in which a layer 4 of foamed resin is adhered via 2. In the case of the continuous method, for example, a coiled titanium plate is unwound and a roll forming machine is used to form the ends and ribs into a shape according to the product shape, as well as to form the overall shape of the titanium plate into a concave cross section. While continuously feeding this titanium plate, a foamed resin stock solution is injected and sprayed into the recesses from a nozzle, and while the foamed resin stock solution is being foamed, it is introduced into a double conveyor and held at a predetermined interval of about 15 to 25 mm. It is possible to produce a composite panel in which the titanium plate is backed and laminated with a layer of foamed resin by foaming and curing during transportation. At this time, a soft coil made of aluminum foil, steel foil, aluminum-deposited kraft paper, asbestos paper, non-woven fabric, etc. is unrolled and introduced from the entrance side of the double conveyor, and is attached to the opposite side of the foam resin titanium plate to cover it. do it like this. In this way, as shown in Fig. 2a, a layer 4 of foamed resin is formed on the inner surface of the metal outer sheath material 1 of the titanium plate with a chemical conversion coating and a resin coating (both illustrations are omitted).
It is possible to obtain a composite panel having a metal sizing structure in which the soft coil 5 is bonded to the back surface of the foamed resin layer 4. Furthermore, when manufacturing a composite panel with a sandwich structure using a continuous method, a titanium plate is used as a pair of metal skin materials, or a titanium plate is used as one of the pair of metal skin materials, and a painted steel plate or a painted aluminum plate is used as the other metal skin material. A roll forming machine is used to form the fitting portions and rib waves on both sides of the pair of metal sheathing materials, and then the pair of metal sheathing materials are placed vertically facing each other, and a stock solution of foamed resin is injected and dispersed between them to form foam. By foaming the resin stock solution, introducing it into a double conveyor, and curing it while sandwiching and conveying it at a predetermined interval of about 22 to 200 mm, a layer of foamed resin is sandwiched between the metal shell materials. A composite panel can be produced, which is cut into arbitrary dimensions using a running cutting machine installed on the exit side of the double conveyor. In this way, a foamed resin layer 4 is laminated and bonded to the inner surface of a pair of metal outer skin materials 3, 3 through a chemical conversion coating and a resin coating (both not shown) as shown in FIG. 2b. It is possible to obtain composite panels of sanderch structure. In FIG. 2b, 6 is an aluminum foil, and 7 is a rubber seal such as EPT, and the cross-sectional structure of this composite panel with a sandwich structure is the same as that in FIG. 1. The invention will now be illustrated by examples. Example 1 A JIS H 46001 type titanium plate having a thickness of 0.5 mm was degreased with an alkaline degreaser (Fine Cleaner FC4336 manufactured by Nippon Parkerizing Co., Ltd.) at 70°C for 15 seconds, and then washed with hot water. Then Cr 6+
6000ppm, Cr 3+ 4000ppm, PO 4 10000ppm,
A coating mold chemical treatment solution containing 20,000 ppm of SiO 2 and a mixture of chromic acid, silicate, and phosphoric acid with a pH of 1 to 2 was applied at a concentration of 50%.
The dry weight of one side was coated on the above titanium plate using a roll coater at a Cr 6+ concentration of 30±2 points and a temperature of 18℃.
The chemical conversion treatment was carried out by coating at a coating amount of 120 mg/m 2 and drying at 90° C. for 30 seconds. Next, an oil-free polyester paint ("R-50" manufactured by Nippon Paint Co., Ltd.; 66% polyester, 34% alkyd) is applied to the chemically treated surface of the titanium plate.
Apply to a dry coating thickness of 10μ, and heat the plate to 200℃.
A resin coating film was formed on one side of the titanium plate by drying at ℃ and baking time of 60 seconds.
Next, the pair of titanium plates were arranged vertically so that the resin coatings faced each other, and a hard urethane foam stock solution (manufactured by Polyurethane Kasei Co., Ltd.; containing MDI, polyol, Freon R-11, and activator) was applied.
By injecting between titanium plates and foaming,
A layer of foamed resin with a foam density of 50 Kg/m 3 was adhered to the resin coated surface of the titanium plate due to its self-adhesive properties.
In this way, a composite panel having the structure shown in Fig. 2b, in which a foamed resin layer with a thickness of 35 mm was sandwiched between a pair of titanium plates, was obtained by a continuous construction method. Example 2 A flame-retardant isocyanurate foam stock solution (manufactured by Polyurethane Kasei Co., Ltd.;
Using special MDI, special polyol, Freon R-11, and activator combination, the foam density is 45
Other than foaming to achieve kg/ m3 ,
In the same manner as in Example 1, a composite panel having the structure shown in FIG. 2b, in which a foamed resin layer with a thickness of 35 mm was sandwiched between a pair of titanium plates, was obtained by a continuous construction method. Comparative Example 1 A JIS H 4600 type 1 titanium plate having a thickness of 0.5 mm was degreased with an alkaline degreaser (Fine Cleaner FC4336 manufactured by Nippon Parkerizing Co., Ltd.) at 70°C for 15 seconds, and then washed with hot water. Next, the surface of this titanium plate was polished with a Scotch bright roll to give an average surface roughness of Ra = 0.16μ, and the pair of titanium plates were placed one above the other with the polished surfaces facing each other without chemical conversion treatment. Then, in the same manner as in Example 1, a hard urethane foam stock solution was injected between the titanium plates and foamed, thereby forming a layer of foamed resin with a foam density of 50 kg/m 3 with its self-adhesive properties. It was then glued to the polished surface of the titanium plate.
In this way, a composite panel having the structure shown in Fig. 2b, in which a foamed resin layer with a thickness of 35 mm was sandwiched between a pair of titanium plates, was obtained by a continuous construction method. Comparative Example 2 The same isocyanurate foam stock solution as in Example 2 was used as the foamed resin stock solution, and the foam density was 45.
A composite panel with the structure shown in Figure 2b , in which a foamed resin layer with a thickness of 35 mm is sandwiched between a pair of titanium plates, was constructed using the continuous construction method in the same manner as in Comparative Example 1, except that the foam was foamed to a thickness of Kg/m3. I got it from Comparative Example 3 After polishing the surface of a titanium plate in the same manner as in Comparative Example 1, 10μ of polyester paint (“R-50”) was applied to the polished surface of the titanium plate in the same manner as in Example 1 without chemical conversion treatment. Forms a thick resin coating,
Next, the pair of titanium plates were arranged vertically so that the resin coatings faced each other, and in the same manner as in Example 1, the hard urethane foam stock solution was injected between the titanium plates and foamed, thereby increasing the foam density. 50
A composite panel having the structure shown in Fig. 2b, in which a foamed resin layer with a thickness of 35 mm and a weight of Kg/m 3 was sandwiched between a pair of titanium plates, was obtained by a continuous construction method. Comparative Example 4 The same isocyanurate foam stock solution as in Example 2 was used as the foamed resin stock solution, and the foam density was 45.
A composite panel with the structure shown in Fig. 2b , in which a foamed resin layer with a thickness of 35 mm is sandwiched between a pair of titanium plates, was fabricated in a continuous manner in the same manner as in Comparative Example 3, except that the foaming was not carried out so as to maintain Obtained by construction method. Comparative Example 5 A titanium plate was polished in the same manner as in Comparative Example 1, and then treated with chromic acid, silicate,
A hard urethane foam stock solution was applied in the same manner as in Example 1 by chemically treating the titanium plates with a coating-type chemical conversion treatment solution containing phosphoric acid, and placing the pair of titanium plates vertically so that the chemically treated surfaces faced each other without painting. A composite panel with the structure shown in Figure 2b, in which a foamed resin layer with a foam density of 50 kg/m 3 and a thickness of 35 mm is sandwiched between a pair of titanium plates, is constructed using a continuous construction method by injecting foam between the titanium plates. I got it from Comparative Example 6 The same isocyanurate foam stock solution as in Example 2 was used as the foamed resin stock solution, and the foam density was 45.
A composite panel with the structure shown in Figure 2b , in which a foamed resin layer with a thickness of 35 mm is sandwiched between a pair of titanium plates, was constructed using the continuous construction method in the same manner as in Comparative Example 5, except that the foam was foamed to a thickness of Kg/m3. I got it from Comparative Example 7 The surface of a titanium plate was polished in the same manner as in Comparative Example 1, and then a mixture of 12.5% by weight of chromic acid (CrO 3 ) and 12.5% by weight of silicate (SiO 2 ) was chemically converted to a total of 25% by weight. A treatment solution (manufactured by Kansai Paint Co., Ltd.) was applied to the polished surface of the titanium plate using a roll coater so that the dry weight of one side was 120 mg/m 2 .
It was dried at ℃ for 30 seconds and subjected to chemical conversion treatment. Next, a 10μ thick resin coating film of polyester paint "(R-50") is formed on the polished surface of the titanium plate in the same manner as in Example 1, and then the pair of titanium plates are coated with the shaft fat coating film facing each other. A pair of foamed resin layers with a foam density of 50 kg/m 3 and a thickness of 35 mm were obtained by injecting and foaming a hard urethane foam stock solution between the titanium plates in the same manner as in Example 1. A composite panel with the structure shown in Fig. 2b, which was sandwiched onto a titanium plate, was obtained using a continuous construction method. Comparative Example 8 The same isocyanurate foam stock solution as in Example 2 was used as the foamed resin stock solution, and the foam density was 45.
A composite panel with the structure shown in Figure 2b , in which a foamed resin layer with a thickness of 35 mm is sandwiched between a pair of titanium plates, was fabricated using the continuous construction method in the same manner as Comparative Example 7, except that the foam was foamed to a thickness of Kg/m3. I got it from The presence or absence of polishing treatment, the type of chemical conversion treatment, the presence or absence of painting in Examples 1 and 2 and Comparative Examples 1 to 8,
The types of foamed resins are summarized in Table 1.
【表】
また実施例１、２及び比較例１乃至８で得た複
合パネルについてチタン板と発泡樹脂層との接着
性の評価をおこなつた。結果を第２表に示す。第
２表の「密着性評価」の「強制剥離」の試験は、
厚さ35mmの複合パネル100mm角に切断してこれを
引張試験機によつて引つ張つて強制剥離させるこ
とによつておこない、この強制剥離させたときの
数値をKg／cm2で表示した。また「密着性評価」の
「ひつかき評価」は、この強制剥離させたときの
剥離面を観察することによつて試験をおこない、
チタン板と発泡樹脂層との界面で剥離が発生して
いるときは「×」、界面剥離と発泡樹脂の凝集破
壊とが混在するときは「△」、界面剥離がなく発
泡樹脂の凝集破壊のみのときは「〇」で表示し、
また発泡樹脂が凝集破壊したときでも、さらに厚
さ1.2mm、幅30mm、長さ300mmの鋼製物差の端部を
試験片の端部30mmの箇所において発泡樹脂の破壊
部分に斜め45度で当てて押すことでひつかき、こ
のひつかきによつて界面剥離が生じたときには
「×」で表示した。また「湿潤密着性評価」は、
湿潤試験JIS Ｚ 0236に基づいて1000時間処理し
たものを上記「密着性評価」と同様に試験して評
価したものである。さらに「総合評価」は、発泡
樹脂が硬質ポリウレタンフオームの場合、強制剥
離1.2Kg／cm2以上、ひつかき評価「〇」のものを
「◎」、強制剥離1.2Kg／cm2以上、ひつかき評価
「△」以上のものを「△」、強制剥離1.2Kg／cm2以
下、ひつかき評価「×」のものを「×」で示し、
また発泡樹脂がイソシアヌレートフオームの場
合、強制剥離0.9Kg／cm2以上、ひつかき評価「〇」
のものを「〇」、強制剥離0.7Kg／cm2以上、ひつか
き評価「△」以上のものを「△」、強制剥離0.7
Kg／cm2以下、ひつかき評価「×」のものを「×」
で示した。[Table] Furthermore, the adhesion between the titanium plate and the foamed resin layer was evaluated for the composite panels obtained in Examples 1 and 2 and Comparative Examples 1 to 8. The results are shown in Table 2. The "forced peeling" test in "adhesion evaluation" in Table 2 is as follows:
Composite panels with a thickness of 35 mm were cut into 100 mm square pieces and forcedly peeled off by being pulled using a tensile tester. The value obtained when this forced peeling was performed was expressed in kg/cm 2 . In addition, the "pull evaluation" of the "adhesion evaluation" is performed by observing the peeled surface when this forced peeling is performed.
"×" indicates that peeling occurs at the interface between the titanium plate and the foamed resin layer; "△" indicates that there is a mixture of interfacial detachment and cohesive failure of the foamed resin; there is no interfacial peeling and only cohesive failure of the foamed resin. When , it is displayed as “〇”,
In addition, even when the foamed resin undergoes cohesive failure, the edge of a steel bar with a thickness of 1.2 mm, width of 30 mm, and length of 300 mm is placed 30 mm from the end of the test piece at a 45-degree angle to the fractured portion of the foamed resin. When the material is applied and pressed, it causes a strain, and when interfacial peeling occurs due to this strain, it is indicated by an "x". In addition, "wet adhesion evaluation"
The samples were treated for 1000 hours based on the wet test JIS Z 0236 and evaluated in the same manner as in the above "adhesion evaluation". Furthermore, in the "overall evaluation", if the foamed resin is a rigid polyurethane foam, those with forced peeling of 1.2 kg/cm 2 or more and a hardness rating of "○" are "◎", and those with forced peeling of 1.2kg/ cm2 or more and hardness rating of "○". Those with a rating of "△" or higher are marked with a "△", those with forced peeling of 1.2Kg/ cm2 or less, and those with a pressure rating of "x" are marked with a "x".
In addition, if the foamed resin is isocyanurate foam, forced peeling is 0.9Kg/cm 2 or more, and the force rating is "〇".
``〇'' for those with forced peeling of 0.7Kg/cm2 or more, ``△'' for those with a hardness rating of ``△'' or higher, forced peeling of 0.7
Kg/cm 2 or less, those with a hit rating of “×” are marked “×”
It was shown in
【表】
第２表の結果、チタン板と発泡樹脂層との接着
性を十分に高めるには、実施例１、２のようにチ
タン板の表面をクロム酸と珪酸塩及び燐酸を含有
する化成処理液で表面処理すると共にこの化成処
理膜の表面に樹脂塗料の塗膜を形成することが必
要であり、チタン板を研摩処理するだけの場合
（比較例１、２）や、チタン板を研摩処理して樹
脂塗料の塗膜を形成させる場合（比較例３、４）、
チタン板を研摩処理してクロム酸と珪酸塩及び燐
酸を含有する化成処理液で表面処理する場合（比
較例５、６）、チタン板を研摩処理してクロム酸
と珪酸塩を含有する化成処理液で表面処理すると
共に樹脂塗料の塗膜を形成させる場合（比較例
７、８）のいずれのものにあつてもチタン板と発
泡樹脂層との十分な接着性を得ることはできない
ことが確認される。
［発明の効果］
クロム酸と珪酸塩及び燐酸を含有する化成処理
液で表面処理されたチタン板の表面に、樹脂塗料
の塗膜を介して発泡樹脂の層をその発泡の際の自
己接着性によつて接着させるようにしてあるの
で、樹脂塗料の塗膜はクロム酸と珪酸塩及び燐酸
を含有する化成処理液による化成処理膜によつて
密着性高くチタン板に接着されており、この結果
樹脂塗料の塗膜を介して発泡樹脂の層を強固にチ
タン板に接着させることができ、チタン板から発
泡樹脂の層が剥離するようなことを防止すること
ができるものである。[Table] As shown in Table 2, in order to sufficiently improve the adhesion between the titanium plate and the foamed resin layer, the surface of the titanium plate should be coated with a chemical compound containing chromic acid, silicate, and phosphoric acid as in Examples 1 and 2. It is necessary to treat the surface with a treatment liquid and to form a coating film of resin paint on the surface of this chemical conversion treatment film. When processing to form a resin paint film (Comparative Examples 3 and 4),
When a titanium plate is polished and surface treated with a chemical conversion treatment containing chromic acid, silicate, and phosphoric acid (Comparative Examples 5 and 6), a titanium plate is polished and surface treated with a chemical conversion treatment containing chromic acid and silicate. It was confirmed that sufficient adhesion between the titanium plate and the foamed resin layer could not be obtained in either case of surface treatment with liquid and formation of a resin paint film (Comparative Examples 7 and 8). be done. [Effects of the invention] A layer of foamed resin is applied to the surface of a titanium plate that has been surface-treated with a chemical conversion treatment solution containing chromic acid, silicate, and phosphoric acid through a coating film of resin paint to improve self-adhesion during foaming. The coating film of the resin paint is adhered to the titanium plate with high adhesion by the chemical conversion treatment film made of the chemical conversion treatment solution containing chromic acid, silicate, and phosphoric acid. The foamed resin layer can be firmly adhered to the titanium plate through the resin paint film, and the foamed resin layer can be prevented from peeling off from the titanium plate.
【図面の簡単な説明】[Brief explanation of the drawing]
第１図は本発明の一実施例の一部の断面図、第
２図ａ，ｂはそれぞれ本発明の他の実施例の断面
図である。
１は化成処理皮膜、２は塗膜、３はチタン板等
の金属外皮材、４は発泡樹脂の層である。
FIG. 1 is a sectional view of a part of one embodiment of the invention, and FIGS. 2a and 2b are sectional views of other embodiments of the invention, respectively. 1 is a chemical conversion film, 2 is a coating film, 3 is a metal outer covering material such as a titanium plate, and 4 is a foamed resin layer.