JP3172318B2 - Water repellent anticorrosion layer and anticorrosion treated material - Google Patents
Water repellent anticorrosion layer and anticorrosion treated materialInfo
- Publication number
- JP3172318B2 JP3172318B2 JP07096793A JP7096793A JP3172318B2 JP 3172318 B2 JP3172318 B2 JP 3172318B2 JP 07096793 A JP07096793 A JP 07096793A JP 7096793 A JP7096793 A JP 7096793A JP 3172318 B2 JP3172318 B2 JP 3172318B2
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- Prior art keywords
- coating
- group
- anticorrosion
- liquid
- cross
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、室温で簡便に密着性よ
く施工できて金属の腐食防止処理に好適な撥水性防食層
及びその防食処理材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent anticorrosive layer which can be easily applied at room temperature with good adhesion and is suitable for metal corrosion prevention treatment, and a material for the anticorrosion treatment.
【０００２】[0002]
【従来の技術】従来、生産ラインによる加熱塗覆方式で
金属表面に熱溶融ポリエチレンやエポキシ樹脂をライニ
ングしてなる防食層が知られていた。しかしながら、ラ
イニングに煩雑な処理操作と大量の熱量が要求されるう
えに保管時や運搬時に形成防食層が外的要因で損傷しや
すく、防食部品の接続部、例えばパイプラインの接続部
へのライニング処理が困難な問題点があった。2. Description of the Related Art Heretofore, there has been known an anticorrosion layer formed by lining hot-melt polyethylene or epoxy resin on a metal surface by a heating coating method using a production line. However, lining requires a complicated processing operation and a large amount of heat, and the anticorrosion layer formed during storage and transportation is easily damaged by external factors, and lining to the connection part of anticorrosion parts, for example, the connection part of the pipeline There was a problem that processing was difficult.
【０００３】一方、大量の熱量を要しない冷工法で形成
できて現場施工に有利な防食層としては、金属表面にウ
レタン樹脂やエポキシ樹脂を塗布してなる重合硬化皮膜
が知られていた。しかしながら、塗膜厚がバラツキやす
くて均一な防食層を形成しにくく、二液タイプの塗布液
の場合には混合比のバラツキで皮膜の物性が不均一とな
り均質な防食層を形成しにくい問題点があった。On the other hand, as a corrosion protection layer which can be formed by a cooling method which does not require a large amount of heat and which is advantageous for on-site construction, a polymerized cured film formed by applying a urethane resin or an epoxy resin to a metal surface has been known. However, it is difficult to form a uniform anticorrosion layer because the coating thickness tends to fluctuate, and in the case of a two-pack type coating liquid, the physical properties of the film are uneven due to the variation in the mixing ratio, making it difficult to form a uniform anticorrosion layer. was there.
【０００４】他方、厚さや均質さの良好な防食層として
は、フィルム等の防食基材に感圧接着層を設けた防食テ
ープを金属表面に巻回ないし接着したものが知られてい
た。しかしながら、外気温や外圧で防食テープが変形し
やすくて防食層にシワや浮きが発生しやすく、またゴミ
や埃等が付着して汚染されやすい問題点があった。On the other hand, as an anticorrosion layer having good thickness and homogeneity, there has been known an anticorrosion tape in which a pressure-sensitive adhesive layer provided on an anticorrosion substrate such as a film is wound or adhered to a metal surface. However, there has been a problem that the anticorrosion tape is easily deformed due to an external temperature or an external pressure, wrinkles and floating are easily generated in the anticorrosion layer, and there is a problem that dirt, dust and the like are easily attached and contaminated.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、ライニング
処理の如く煩雑な処理操作や大量の熱量を要することな
く作業現場でも簡便に室温等の低温で施工できて防食部
品の接続部の処理も容易であり、形成防食層が厚さや物
性の均一性に優れると共に外的要因で損傷や変形を起こ
しにくい強靱さを有してシワや浮きが発生しにくくゴミ
や埃等で汚染されにくい撥水性防食層を得ることを課題
とする。SUMMARY OF THE INVENTION The present invention can be easily carried out at a low temperature such as room temperature even at a work site without requiring complicated processing operations such as a lining process and a large amount of heat, and can also process a joint portion of an anticorrosion component. It is easy, and the formed anticorrosive layer has excellent uniformity of thickness and physical properties, and has a toughness that is not easily damaged or deformed by external factors, and it is hard to be wrinkled or lifted up. The task is to obtain an anticorrosion layer.
【０００６】[0006]
【課題を解決するための手段】本発明は、未架橋液状シ
リコーンゴムを主成分とし硬化剤又は硬化触媒の一方を
含有する液状混和物を多孔性基材に含浸させてなる室温
架橋型被覆材を金属表面又は防食欠陥部に被覆施与して
被覆層を形成し、その被覆層を、未架橋液状シリコーン
ゴム及び／又はシリコーンオイルを主成分とし前記の硬
化剤又は硬化触媒の他方を含有する架橋用塗液で架橋さ
せたことを特徴とする撥水性防食層、及び前記の室温架
橋型被覆材と架橋用塗液とからなることを特徴とする撥
水性防食処理材を提供するものである。SUMMARY OF THE INVENTION The present invention relates to a room temperature cross-linkable coating material obtained by impregnating a porous base material with a liquid mixture containing an uncrosslinked liquid silicone rubber as a main component and one of a curing agent and a curing catalyst. Is applied to a metal surface or an anticorrosion defect to form a coating layer, and the coating layer contains an uncrosslinked liquid silicone rubber and / or silicone oil as a main component and the other of the above-mentioned curing agent or curing catalyst. A water-repellent anticorrosion layer characterized by being cross-linked with a cross-linking coating liquid, and a water-repellent anticorrosion treated material comprising the room-temperature cross-linkable coating material and a cross-linking coating liquid. .
【０００７】[0007]
【作用】上記構成の室温架橋型被覆材は、含有の液状混
和物を介して金属表面等の被覆面に対し粗面や曲面であ
る場合にも充分な濡れ性や変形性を示して良好に密着す
る。また硬化剤と硬化触媒の分離で安定した長期保存が
可能となると共に、架橋用塗液の施与でそれが室温架橋
型被覆材の被覆層中に浸透し前記液状混和物中の未架橋
液状シリコーンゴムと硬化剤とが硬化触媒の作用の下に
反応して室温等で架橋し、金属等に強固に接着しつつ多
孔性基材と共に強靱な撥水性の防食層を形成する。The room temperature cross-linking type coating material having the above-mentioned structure shows satisfactory wettability and deformability even when the coated surface such as a metal surface is rough or curved through the contained liquid admixture. In close contact. In addition, the separation of the curing agent and the curing catalyst enables stable long-term storage, and the application of the coating liquid for crosslinking allows the liquid to penetrate into the coating layer of the room-temperature crosslinking type coating material and uncrosslinked liquid in the liquid mixture. The silicone rubber and the curing agent react under the action of a curing catalyst to crosslink at room temperature or the like, and form a tough water-repellent anticorrosion layer together with the porous substrate while firmly adhering to a metal or the like.
【０００８】前記の結果、厚さや物性の均一性に優れる
防食層を作業現場でも簡便に低温施工で形成でき、パイ
プライン等の接続部も容易に処理できる。また液状シリ
コーンゴムの架橋反応を利用した硬化機構であるので防
食層形成時に有害な有機溶剤等の関与を回避でき、数時
間程度の短時間でタックフリーな状態に硬化してゴミや
埃等で汚染されにくいうえに表面張力も小さくて水垢等
も付着しにくく光沢のある美観に優れる状態を持続す
る。さらに形成される防食層は外的要因で損傷や変形を
起こしにくくシワや浮きが発生しにくくて撥水性の防食
効果を長期に持続する。As a result, an anticorrosive layer having excellent uniformity in thickness and physical properties can be easily formed at a work site by low-temperature construction, and a connection portion such as a pipeline can be easily processed. In addition, since it is a curing mechanism using the crosslinking reaction of liquid silicone rubber, it is possible to avoid the involvement of harmful organic solvents etc. when forming the anticorrosion layer, and it cures to a tack-free state in a short time of about several hours, In addition to being less contaminated, the surface tension is small, and scales and the like are less likely to adhere, and a state of excellent glossy beauty is maintained. Further, the formed anticorrosion layer is less likely to be damaged or deformed by external factors, and is less likely to generate wrinkles and floating, thereby maintaining a water-repellent anticorrosion effect for a long time.
【０００９】[0009]
【実施例】本発明において用いる室温架橋型被覆材は、
未架橋液状シリコーンゴムを主成分とし硬化剤又は硬化
触媒の一方を含有する液状混和物を柔軟な多孔性基材に
含浸させたものである。また架橋用塗液は、未架橋液状
シリコーンゴム及び／又はシリコーンオイルを主成分と
し前記の硬化剤又は硬化触媒の他方を含有させたもので
ある。The room temperature crosslinking type coating material used in the present invention is as follows.
A flexible porous substrate is impregnated with a liquid mixture containing an uncrosslinked liquid silicone rubber as a main component and one of a curing agent and a curing catalyst. Further, the coating liquid for crosslinking contains uncrosslinked liquid silicone rubber and / or silicone oil as a main component and contains the other of the above-mentioned curing agents or curing catalysts.
【００１０】液状混和物は、未架橋液状シリコーンゴム
すなわち液状ポリオルガノシロキサンを主成分とし、硬
化剤又は硬化触媒を含有して縮合反応型又は付加反応型
などの硬化機構で硬化してゴム状の硬化物となるもので
ある。The liquid admixture contains an uncrosslinked liquid silicone rubber, ie, a liquid polyorganosiloxane as a main component, and contains a curing agent or a curing catalyst and is cured by a curing mechanism such as a condensation reaction type or an addition reaction type to form a rubbery mixture. It becomes a cured product.
【００１１】前記の未架橋液状シリコーンゴムとして
は、一般単位式：ＲaＳiＯ(4-a)/2（式中、Ｒは置換も
しくは非置換の１価の炭化水素基又は水酸基、ａは１〜
３の整数である。）で表される構成単位からなる単一重
合体、もしくは共重合体、又はこれらの混合物を用いる
ことができる。The uncrosslinked liquid silicone rubber has a general formula: R a SiO (4-a) / 2 (wherein R is a substituted or unsubstituted monovalent hydrocarbon or hydroxyl group, and a is 1 ~
It is an integer of 3. ), A homopolymer or a copolymer composed of the structural units represented by formula (1), or a mixture thereof.
【００１２】上記の式中、基Ｒの置換もしくは非置換の
１価の炭化水素基は、同一であってもよいし、異なって
いてもよく、例えばメチル基、エチル基、プロピル基、
ブチル基、ヘキシル基、ドデシル基等のアルキル基、ビ
ニル基、アリル基等のアルケニル基、フェニル基、トリ
ル基等のアリール基、ベンジル基、β−フェニルエチル
基、β−フェニルプロピル基等のアラルキル基、３，
３，３−トリフルオロプロピル基、クロロメチル基等の
１価の置換炭化水素基等をあげることができ、これらは
未架橋液状シリコーンゴム（液状ポリオルガノシロキサ
ン）の合成の容易さやその硬化機構及び組成物の流動
性、さらには組成物の硬化物の例えば耐熱性等の物理的
性質に応じて適宜選択することができる。In the above formula, the substituted or unsubstituted monovalent hydrocarbon group of the group R may be the same or different, for example, a methyl group, an ethyl group, a propyl group,
Alkyl groups such as butyl group, hexyl group and dodecyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group, β-phenylethyl group and β-phenylpropyl group. Group, 3,
And monovalent substituted hydrocarbon groups such as a 3,3-trifluoropropyl group and a chloromethyl group. These compounds can be used to easily synthesize an uncrosslinked liquid silicone rubber (liquid polyorganosiloxane), its curing mechanism, and the like. It can be appropriately selected according to the fluidity of the composition and the physical properties such as heat resistance of the cured product of the composition.
【００１３】用いる未架橋液状シリコーンゴムは、常温
で液状であればその分子構造は特に限定されず、直鎖
状、分岐状、網状もしくは僅かに三次元網状構造を有す
るもの、又はこれらが混在した状態のものであっても何
ら差し支えないが、２５℃における粘度が１００〜１０
０，０００ｃＳｔのものが好ましく、１，０００〜５
０，０００ｃＳｔのものがさらに好ましい。The molecular structure of the uncrosslinked liquid silicone rubber to be used is not particularly limited as long as it is liquid at room temperature, and it has a linear, branched, network or slightly three-dimensional network structure, or a mixture of these. It may be in any state, but the viscosity at 25 ° C. is 100 to 10
It is preferable to use the one of 000 cSt,
The one with 000 cSt is more preferred.
【００１４】前記の粘度が１００ｃＳｔ未満では、組成
物の硬化物に優れた機械的性質を付与することが困難で
あり、また１００，０００ｃＳｔを超える場合は、組成
物に適度な流動性を付与することができない。When the viscosity is less than 100 cSt, it is difficult to impart excellent mechanical properties to a cured product of the composition. When the viscosity exceeds 100,000 cSt, the composition has appropriate fluidity. Can not do.
【００１５】液状混和物の調製は、未架橋液状シリコー
ンゴムと硬化剤又は硬化触媒の一方を混合することによ
り行うことができる。硬化剤は、硬化触媒の存在下に室
温等の低温で未架橋液状シリコーンゴムや架橋用塗液の
主成分であるシリコーンオイルと反応して未架橋液状シ
リコーンゴムや架橋用塗液のシリコーンオイルと架橋す
るものである。The preparation of the liquid mixture can be carried out by mixing an uncrosslinked liquid silicone rubber with one of a curing agent and a curing catalyst. The curing agent reacts with the uncrosslinked liquid silicone rubber or the silicone oil which is the main component of the crosslinking coating liquid at a low temperature such as room temperature in the presence of a curing catalyst to react with the uncrosslinked liquid silicone rubber or the silicone oil of the crosslinking coating liquid. It crosslinks.
【００１６】未架橋液状シリコーンゴムや硬化剤又は硬
化触媒としては、室温等の低温で硬化するように、その
縮合反応型や付加反応型などの硬化機構に応じて適宜な
組合せで用いることができる。The uncrosslinked liquid silicone rubber, curing agent or curing catalyst can be used in an appropriate combination depending on the curing mechanism such as condensation reaction type or addition reaction type so as to cure at a low temperature such as room temperature. .
【００１７】ちなみに縮合反応型の液状混和物の場合
は、未架橋液状シリコーンゴムとして（ａ）分子鎖末端
がシラノール基又はアルコキシ基で封鎖されたポリオル
ガノシロキサンを用い、硬化剤として（ｂ）ケイ素原子
に結合した加水分解性基を一分子中に少なくとも３個有
する有機ケイ素化合物、又は硬化触媒を配合する。In the case of the condensation reaction type liquid mixture, (a) a polyorganosiloxane whose molecular chain ends are blocked with a silanol group or an alkoxy group is used as an uncrosslinked liquid silicone rubber, and (b) silicon is used as a curing agent. An organosilicon compound having at least three hydrolyzable groups bonded to an atom in one molecule or a curing catalyst is blended.
【００１８】（ａ）成分のポリオルガノシロキサン中の
ケイ素原子に結合する置換又は非置換の１価の炭化水素
基の中でも、合成の容易さからメチル基、ビニル基もし
くはフェニル基が好ましい。さらにはケイ素原子に結合
する炭化水素基がメチル基である場合が、他の炭化水素
基の場合と比較して原料中間体の合成が容易であり、得
られる重合体の重合度の高さに比べて粘度が最も低く、
また硬化物である弾性体の物性のバランスに好影響を与
えるため最も好ましい。Among the substituted or unsubstituted monovalent hydrocarbon groups bonded to silicon atoms in the polyorganosiloxane (a), a methyl group, a vinyl group or a phenyl group is preferred from the viewpoint of ease of synthesis. Furthermore, when the hydrocarbon group bonded to the silicon atom is a methyl group, the synthesis of the raw material intermediate is easier than in the case of other hydrocarbon groups, and the degree of polymerization of the obtained polymer is high. The lowest viscosity compared to
It is most preferable because it has a favorable effect on the balance of physical properties of the elastic body which is a cured product.
【００１９】従って、実質的に全てがメチル基であるこ
とが最も好ましいが、硬化物に耐熱性が要求される場合
はケイ素原子に結合する炭化水素基のうち、一部がフェ
ニル基であることが好ましい。このようにメチル基以外
の炭化水素基を含有する場合においても上述した理由か
ら、重合体中の全炭化水素基数の８５％以上がメチル基
であることが好ましい。Therefore, it is most preferable that substantially all of the group is a methyl group. However, when heat resistance is required for the cured product, a part of the hydrocarbon group bonded to the silicon atom is a phenyl group. Is preferred. As described above, even when a hydrocarbon group other than a methyl group is contained, it is preferable that 85% or more of the total number of hydrocarbon groups in the polymer is a methyl group.
【００２０】（ｂ）成分の有機ケイ素化合物としては、
ケイ素原子に結合した加水分解性基を一分子中に少なく
とも３個有するものであれば如何なるものであってもよ
く、例えばシラン化合物もしくはその部分加水分解縮合
物、直鎖状ポリオルガノシロキサン又は環状ポリオルガ
ノシロキサンを用いることができる。As the organosilicon compound of the component (b),
Any compound having at least three hydrolyzable groups bonded to a silicon atom in one molecule may be used, for example, a silane compound or a partially hydrolyzed condensate thereof, a linear polyorganosiloxane, or a cyclic polyorganosiloxane. Organosiloxanes can be used.
【００２１】有機ケイ素化合物中のケイ素原子に結合す
る加水分解性基としては、アルコキシ基、アシロキシ
基、Ｎ，Ｎ−ジアルキルアミノ基、Ｎ−アルキルアミド
基、Ｎ，Ｎ−ジアルキルアミノキシ基、ケトオキシム
基、アルケノキシ基などをあげることができる。Examples of the hydrolyzable group bonded to a silicon atom in the organosilicon compound include an alkoxy group, an acyloxy group, an N, N-dialkylamino group, an N-alkylamide group, an N, N-dialkylaminoxy group, and a ketoxime. And alkenoxy groups.
【００２２】また有機ケイ素化合物においてケイ素原子
には、上記した加水分解性基以外に例えばメチル基、エ
チル基、プロピル基、ブチル基等のアルキル基、ビニル
基、アリル基等のアルケニル基、フェニル基等のアリー
ル基、３，３，３−トリフルオロプロピル基、クロロメ
チル基等のハロアルキル基などの置換又は非置換の１価
の炭化水素基が結合していてもよい。In the organosilicon compound, the silicon atom may be, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as a vinyl group or an allyl group, or a phenyl group in addition to the above-mentioned hydrolyzable group. Or a substituted or unsubstituted monovalent hydrocarbon group such as an aryl group such as a haloalkyl group such as a 3,3,3-trifluoropropyl group or a chloromethyl group.
【００２３】かかる（ｂ）成分は、ケイ素原子に結合し
た加水分解性基が（ａ）成分中のシラノール基又はアル
コキシ基の当量以上になるように配合することが好まし
い。（ｂ）成分の配合量が過少では（ａ）成分の縮合反
応が充分に進行しない。The component (b) is preferably blended so that the hydrolyzable group bonded to the silicon atom is at least equivalent to the silanol group or the alkoxy group in the component (a). If the amount of the component (b) is too small, the condensation reaction of the component (a) does not proceed sufficiently.
【００２４】一方、縮合反応を促進するための硬化触媒
としては、有機カルボン酸の金属塩、例えば酢酸、オク
タン酸、ラウリン酸、ステアリン酸、オレイン酸、ナフ
テン酸、安息香酸等のカルボン酸と、スズ、亜鉛、鉛、
鉄、アンチモン、バリウム、チタン、マンガン等の金属
との塩などをあげることができる。On the other hand, as a curing catalyst for accelerating the condensation reaction, metal salts of organic carboxylic acids, for example, carboxylic acids such as acetic acid, octanoic acid, lauric acid, stearic acid, oleic acid, naphthenic acid and benzoic acid; Tin, zinc, lead,
Examples thereof include salts with metals such as iron, antimony, barium, titanium, and manganese.
【００２５】また前記以外にも例えば、ジブチルスズジ
アセテート、ジブチルスズジオクトエート、ジブチルス
ズジラウレート、水酸化ジメチルスズオレエート、ジブ
チルスズオレエート、ジフェニルスズジアセテート、酸
化ジブチルスズ、ジブチルスズジメトキシド等の有機ス
ズ化合物、テトラプロピルチタネート、テトラブチルチ
タネート、テトラオクチルチタネート等の有機チタン酸
エステル、ジイソプロポキシ（アセチルアセトナト）チ
タン、ジイソプロピルビス（エチルアセトアセタト）チ
タン、１，３−プロピレンジオキシビス（アセチルアセ
トナト）チタン、１，３−プロピレンジオキシビス（エ
チルアセトアセタト）チタン等のチタンキレート化合物
等の有機金属化合物などもあげることができる。Other than the above, for example, organotin compounds such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dimethyltin oleate hydroxide, dibutyltin oleate, diphenyltin diacetate, dibutyltin oxide and dibutyltin dimethoxide; Organic titanates such as propyl titanate, tetrabutyl titanate, tetraoctyl titanate, diisopropoxy (acetylacetonato) titanium, diisopropyl bis (ethyl acetoacetato) titanium, 1,3-propylene dioxybis (acetyl acetonate) Organic metal compounds such as titanium chelate compounds such as titanium and 1,3-propylenedioxybis (ethylacetoacetato) titanium can also be mentioned.
【００２６】このような縮合反応型の液状混和物の場
合、未架橋液状シリコーンゴムは、硬化剤及び硬化触媒
（場合により不要のこともある。）の存在下、空気中等
の湿気に触れることで加水分解され、架橋反応が進行し
てゴム状に硬化する。In the case of such a condensation reaction type liquid mixture, the uncrosslinked liquid silicone rubber is exposed to moisture in the air or the like in the presence of a curing agent and a curing catalyst (sometimes unnecessary). It is hydrolyzed and undergoes a cross-linking reaction to be cured into a rubbery state.
【００２７】一方、付加反応型の液状混和物の場合は、
未架橋液状シリコーンゴムとして（ｃ）ケイ素原子に結
合したアルケニル基を一分子中に少なくとも２個有する
ポリオルガノシロキサンを用い、硬化剤として（ｄ）オ
ルガノハイドロジェンシラン又はポリオルガノハイドロ
ジェンシロキサン、又は付加反応用の硬化触媒を配合す
る。また硬化してゲル状物になるものを得ようとする場
合には、（ｃ）成分としてケイ素原子に結合したアルケ
ニル基を一分子中に１個有するポリオルガノシロキサン
を併用することもできる。On the other hand, in the case of an addition reaction type liquid mixture,
As an uncrosslinked liquid silicone rubber, (c) a polyorganosiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule is used, and (d) an organohydrogensilane or a polyorganohydrosiloxane is used as a curing agent. A curing catalyst for the reaction is blended. When it is desired to obtain a gelled product by curing, a polyorganosiloxane having one alkenyl group bonded to a silicon atom in one molecule can be used as the component (c).
【００２８】（ｃ）成分のポリオルガノシロキサンに含
有されているアルケニル基としては、例えばビニル基、
アリル基、１−ブテニル基、１−ヘキセニル基などをあ
げることができ、合成の容易さからビニル基が好まし
い。The alkenyl group contained in the polyorganosiloxane of the component (c) includes, for example, a vinyl group,
Examples thereof include an allyl group, a 1-butenyl group, and a 1-hexenyl group, and a vinyl group is preferable because of ease of synthesis.
【００２９】またアルケニル基以外に結合可能な置換又
は非置換の１価の炭化水素基については、上記したとお
りであるが合成の容易さ、組成物の流動性、組成物から
得られる硬化物が良好な物理的性質を保持しうる程度の
重合が可能であることなどからメチル基であることが最
も好ましい。The substituted or unsubstituted monovalent hydrocarbon group which can be bonded other than the alkenyl group is as described above, but the ease of synthesis, the fluidity of the composition and the cured product obtained from the composition are Most preferably, it is a methyl group because polymerization is possible to the extent that good physical properties can be maintained.
【００３０】（ｄ）成分のオルガノハイドロジェンシラ
ン又はポリオルガノハイドロジェンシロキサンにおける
ケイ素原子に結合可能な有機機としては、上記の置換又
は非置換の１価の炭化水素基と同様のものをあげること
ができるが、合成の容易さからメチル基が好ましい。The organic group capable of bonding to a silicon atom in the organohydrogensilane or polyorganohydrogensiloxane of the component (d) is the same as the above-mentioned substituted or unsubstituted monovalent hydrocarbon group. However, a methyl group is preferred because of ease of synthesis.
【００３１】かかる（ｄ）成分としては、ケイ素原子に
結合した水素原子を一分子中に平均２個を超える数を有
するポリオルガノハイドロジェンシロキサンが好まし
い。このポリオルガノハイドロジェンシロキサンとして
は、直鎖状、分岐状、環状等の何れを用いてもよく、ま
たこれらの混合物を用いてもよいが硬化後の組成物自体
に良好な物理的性質を付与するという点で、以下のイ〜
ハで示す化合物又はそれらの混合物を用いることが好ま
しい。As the component (d), a polyorganohydrogensiloxane having an average of more than two hydrogen atoms bonded to silicon atoms in one molecule is preferable. As the polyorganohydrogensiloxane, any of linear, branched, cyclic and the like may be used, and a mixture of these may be used, but it imparts good physical properties to the cured composition itself. In terms of doing, the following a ~
It is preferable to use a compound represented by C or a mixture thereof.
【００３２】イ．（ＣＨ3）2ＨＳiＯ1/2とＳiＯ1/2単位
からなり、ケイ素原子に結合した水素原子の含有量が分
子量の０．３〜１．２重量％である分岐状ポリオルガノ
ハイドロジェンシロキサン。A. A branched polyorganohydrogensiloxane comprising (CH 3 ) 2 HSiO 1/2 and SiO 1/2 units, wherein the content of hydrogen atoms bonded to silicon atoms is 0.3 to 1.2% by weight of the molecular weight.
【００３３】ロ．次式： （ただし、ｐは２〜１００、ｑは０〜１００の整数であ
る。）で表され、ケイ素原子に結合した水素原子の含有
量が分子量の０．５〜１．６重量％である直鎖状ポリオ
ルガノハイドロジェンシロキサン。B. The following formula: (Where p is an integer of 2 to 100 and q is an integer of 0 to 100), wherein the content of the hydrogen atom bonded to the silicon atom is 0.5 to 1.6% by weight of the molecular weight. Polyorganohydrogensiloxane.
【００３４】ハ．次式： （ただし、ｐは１〜１００、ｑは０〜１００の整数であ
る。）で表され、ケイ素原子に結合した水素原子の含有
量が分子量の０．５〜１．６重量％である直鎖状ポリオ
ルガノハイドロジェンシロキサン。C. The following formula: (Where p is an integer of 1 to 100 and q is an integer of 0 to 100), wherein the content of the hydrogen atom bonded to the silicon atom is 0.5 to 1.6% by weight of the molecular weight. Polyorganohydrogensiloxane.
【００３５】（ｄ）成分の配合量は、（ｃ）成分中のア
ルケニル基１個に対し、（ｃ）成分中のケイ素原子に結
合した水素原子の数が０．５〜４．０個、好ましくは
１．０〜３．０個となるような量である。水素原子の数
が０．５個未満では組成物の硬化が充分に進行せず、組
成物の硬化物の硬度が低くなり、４．０個を超えると組
成物の硬化物の物理的性質が低下する。The amount of component (d) is such that the number of hydrogen atoms bonded to silicon atoms in component (c) is 0.5 to 4.0 per alkenyl group in component (c), Preferably, the amount is 1.0 to 3.0. If the number of hydrogen atoms is less than 0.5, curing of the composition will not proceed sufficiently, and the hardness of the cured product of the composition will be low. If it exceeds 4.0, the physical properties of the cured product of the composition will be low. descend.
【００３６】一方、付加反応用の硬化触媒としては、
（ｃ）成分のアルケニル基と（ｄ）成分のヒドロシリル
基との間の付加反応を促進するものが用いられ、その例
としては白金系、ロジウム系、パラジウム系の触媒など
があげられる。就中、白金系触媒が好ましく用いられ、
その例としては白金の単体、塩化白金酸、白金−オレフ
ィン錯体、白金−アルコール錯体、白金配位化合物など
をあげることができる。On the other hand, as a curing catalyst for the addition reaction,
A catalyst that promotes an addition reaction between the alkenyl group of the component (c) and the hydrosilyl group of the component (d) is used, and examples thereof include platinum-based, rhodium-based, and palladium-based catalysts. In particular, platinum-based catalysts are preferably used,
Examples thereof include simple platinum, chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex, and a platinum coordination compound.
【００３７】このような付加反応型の液状混和物の場
合、未架橋液状シリコーンゴムは、硬化剤及び硬化触媒
の存在下、ヒドロシリル化反応が起こり、これが架橋反
応となってゴム状に硬化する。In the case of such an addition-reaction-type liquid mixture, the uncrosslinked liquid silicone rubber undergoes a hydrosilylation reaction in the presence of a curing agent and a curing catalyst, which is crosslinked to cure into a rubbery state.
【００３８】他方、架橋用塗液の調製は、未架橋液状シ
リコーンゴム及び／又はシリコーンオイル、及び硬化剤
と硬化触媒のうち液状混和物に配合しなかった方を混合
することにより行うことができる。架橋用塗液調製用の
未架橋液状シリコーンゴムとしては、液状混和物に準じ
たものを用いることができる。On the other hand, the coating liquid for crosslinking can be prepared by mixing an uncrosslinked liquid silicone rubber and / or silicone oil, and a curing agent and a curing catalyst which are not blended with the liquid mixture. . As the uncrosslinked liquid silicone rubber for preparing the coating liquid for crosslinking, those based on the liquid mixture can be used.
【００３９】シリコーンオイルとしては、硬化触媒の存
在下に室温等の低温で硬化剤と反応する官能基を有する
ものや、官能基を有しない液状ポリオルガノシロキサン
などが用いられる。官能基を有しない液状ポリオルガノ
シロキサンからなるシリコーンオイルとしては、トリメ
チルシロキシ基で末端封鎖されたポリジメチルシロキサ
ン又はポリメチルフェニルシロキサンなどが例示され
る。As the silicone oil, those having a functional group which reacts with the curing agent at a low temperature such as room temperature in the presence of a curing catalyst, and liquid polyorganosiloxanes having no functional group are used. Examples of the silicone oil composed of a liquid polyorganosiloxane having no functional group include polydimethylsiloxane or polymethylphenylsiloxane end-blocked by a trimethylsiloxy group.
【００４０】従って架橋用塗液の調製に用いる未架橋液
状シリコーンゴムやシリコーンオイル、硬化剤や硬化触
媒としては、室温等の低温で硬化するように、縮合反応
型や付加反応型等の液状混和物の硬化機構に対応させて
適宜な組合せで選択することができる。Accordingly, as the uncrosslinked liquid silicone rubber or silicone oil, a curing agent or a curing catalyst used for preparing the crosslinkable coating liquid, a liquid admixture such as a condensation reaction type or an addition reaction type is used so as to be cured at a low temperature such as room temperature. An appropriate combination can be selected according to the curing mechanism of the product.
【００４１】硬化剤の使用量は、未架橋液状シリコーン
ゴム（及び／又はシリコーンオイル）１００重量部あた
り０．０１〜２０重量部、就中０．１〜１０重量部が一
般的である。硬化触媒の使用量は、未架橋液状シリコー
ンゴム（及び／又はシリコーンオイル）１００重量部あ
たり０．０１〜１０重量部が一般的である。防食層の表
面の美観を維持する点よりは、表面張力が３５dyn／cm
以下の防食層が形成されるようにすることが好ましい。The amount of the curing agent used is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the uncrosslinked liquid silicone rubber (and / or silicone oil). The amount of the curing catalyst used is generally 0.01 to 10 parts by weight per 100 parts by weight of the uncrosslinked liquid silicone rubber (and / or silicone oil). Rather than maintaining the appearance of the surface of the anticorrosion layer, the surface tension is 35 dyn / cm.
It is preferable to form the following anticorrosion layer.
【００４２】液状混和物、架橋用塗液の調製に際して
は、例えば充填剤、可塑剤、老化防止剤、防錆剤、防カ
ビ剤、酸化防止剤、紫外線吸収剤、オゾン劣化防止剤、
チキソロープ剤、顔料ないし着色剤などの増粘剤ないし
配合剤を必要に応じて適宜に配合することができる。そ
の配合量は、調製物の１〜９０重量％が一般的である。In preparing the liquid mixture and the coating liquid for crosslinking, for example, a filler, a plasticizer, an antioxidant, a rust inhibitor, a fungicide, an antioxidant, an ultraviolet absorber, an ozone deterioration inhibitor,
Thickening agents or compounding agents such as thixotropic agents, pigments or coloring agents can be appropriately compounded as needed. The compounding amount is generally 1 to 90% by weight of the preparation.
【００４３】調製する液状混和物は、多孔性基材に含浸
させた場合に滴下しない程度の粘度を有するものが好ま
しい。架橋用塗液では、塗布性や室温架橋型被覆材への
浸透性などの点より０．０１〜１０００ポイズ程度の粘
度（２５℃）とすることが好ましい。また架橋用塗液の
施与量を可及的に一定にして均質な防食層を形成する点
よりは、架橋用塗液に顔料ないし着色剤を配合してその
色により施与量を判別できるようにすることが好まし
い。The liquid mixture to be prepared preferably has such a viscosity that it does not drip when impregnated into a porous substrate. The viscosity of the cross-linking coating liquid is preferably about 0.01 to 1000 poise (25 ° C.) from the viewpoints of applicability and permeability to the room temperature cross-linkable coating material. Further, rather than forming a uniform anticorrosive layer with the applied amount of the cross-linking coating liquid as constant as possible, the applied amount can be determined by blending a pigment or colorant into the cross-linking coating liquid and by its color. It is preferable to do so.
【００４４】室温架橋型被覆材は、多孔性基材に液状混
和物を含浸させることにより得ることができる。多孔性
基材は、液状混和物の保持材、室温架橋型被覆材を巻回
又は接着する際の作業時における補助材、防食層の厚さ
の調節材や均一化材、衝撃緩和や損傷防止、光遮断によ
る劣化防止等の防食層保護材などとして機能するもので
ある。従って多孔性基材としては、種々の繊維からなる
例えば織布、不織布、フェルトなどの適宜なものを用い
うる。室温架橋型被覆材は、テープ、シート、切片など
の適宜な形態に形成することができる。The room temperature crosslinking type coating material can be obtained by impregnating a porous base material with a liquid mixture. The porous base material is a holding material for the liquid mixture, an auxiliary material for winding or bonding the room temperature cross-linkable coating material, a material for adjusting the thickness of the anticorrosion layer and a uniform material, and for alleviating impact and preventing damage. It functions as an anticorrosion layer protective material for preventing deterioration due to light blocking. Therefore, as the porous substrate, an appropriate material such as a woven fabric, a nonwoven fabric, or a felt made of various fibers can be used. The room temperature crosslinking type coating material can be formed into an appropriate form such as a tape, a sheet, a section, or the like.
【００４５】本発明の撥水性防食層の形成は、金属表面
又は防食層欠損部等の防食欠陥部に室温架橋型被覆材を
巻回方式や貼付方式等の適宜な方式で被覆施与し、その
被覆層を架橋用塗液で架橋させることにより行うことが
できる。その架橋は、室温架橋型被覆材と架橋用塗液を
合体させることにより室温等の低温で進行させることが
できる。The water-repellent anticorrosion layer of the present invention is formed by coating a room temperature crosslinkable coating material on a metal surface or an anticorrosion defect portion such as a defect portion of the anticorrosion layer by an appropriate method such as a winding method or a sticking method. The coating can be carried out by crosslinking the coating layer with a coating liquid for crosslinking. The crosslinking can proceed at a low temperature such as room temperature by combining the room temperature crosslinking type coating material and the coating liquid for crosslinking.
【００４６】従って前記の架橋は、予め架橋用塗液を金
属表面等に塗布しその上に室温架橋型被覆材を施与する
方式、室温架橋型被覆材に架橋用塗液を塗布しそれを金
属表面等に被覆施与する方式、室温架橋型被覆材を金属
表面等に被覆施与しその被覆層に架橋用塗液を塗布する
方式、それらの組合せ方式などの適宜な方式で進行させ
ることができる。表面の平滑性、室温架橋型被覆材の被
覆施与時間の自由性などの点よりは、室温架橋型被覆材
を金属表面等に被覆施与した後に架橋用塗液を塗布する
方式が好ましい。なお架橋に際しては、室温架橋型被覆
材の被覆層をバーナーなどで加熱することにより架橋速
度を速めることができる。Therefore, the above-mentioned crosslinking is carried out by applying a coating liquid for crosslinking in advance on a metal surface or the like and then applying a room temperature crosslinking coating material thereon. Proceed with appropriate methods, such as a method of applying a coating on a metal surface, a method of applying a room temperature cross-linkable coating material to a metal surface and applying a coating solution for cross-linking to the coating layer, or a combination thereof. Can be. From the viewpoints of surface smoothness and freedom of coating application time of the room temperature cross-linkable coating material, it is preferable to apply a cross-linking coating solution after coating the room temperature cross-linkable coating material on a metal surface or the like. At the time of crosslinking, the rate of crosslinking can be increased by heating the coating layer of the room temperature crosslinking type coating material with a burner or the like.
【００４７】実施例１ 未架橋液状シリコーンゴム１００部（重量部、以下同
じ）、ホワイトカーボン（補強剤）１００部、テトラエ
トキシシラン（硬化剤）５部をプラネタリーミキサで混
練し、それをポリエステル不織布（目付１００ｇ／
ｍ2）に含浸させ、それをロール状に巻取って１００mm
幅に切断し坪量１kg／ｍ2の室温架橋型被覆材を得た。Example 1 100 parts (parts by weight, hereinafter the same) of uncrosslinked liquid silicone rubber, 100 parts of white carbon (reinforcing agent), and 5 parts of tetraethoxysilane (curing agent) were kneaded with a planetary mixer, and the resulting mixture was polyester. Non-woven fabric (100 g / weight)
m 2 ), roll it up into a roll
It was cut into a width to obtain a room temperature crosslinked type coating material having a basis weight of 1 kg / m 2 .
【００４８】一方、未架橋液状シリコーンゴム１００
部、ホワイトカーボン３０部、アルミニウム粉（着色
剤）１０部、ジブチル錫ジラウレート（硬化触媒）５部
をプラネタリーミキサで混練し、着色型架橋用塗液を得
た。On the other hand, uncrosslinked liquid silicone rubber 100
Parts, 30 parts of white carbon, 10 parts of aluminum powder (colorant), and 5 parts of dibutyltin dilaurate (curing catalyst) were kneaded with a planetary mixer to obtain a coloring type crosslinking coating liquid.
【００４９】次に、前記の室温架橋型被覆材より長さ１
５０mmのサンプルを切取り、それを幅１００mm、長さ１
５０mm、厚さ２mmの鋼板面に接着し、その上に前記の着
色型架橋用塗液を１００ｇ／ｍ2の割合で塗布し、２３
℃で２４時間保持して室温硬化させ撥水性防食層を形成
した。前記の撥水性防食層に碁盤目状の切れ目を入れ、
ＪＩＳ Ｋ ５４００に準拠してテストしたところ評価
点数（１０点満点）は１０点であった。Next, the length of the above-mentioned room temperature crosslinking type coating material is 1
Cut a 50mm sample and cut it into a 100mm width and 1 length
50 mm and a thickness of 2 mm were adhered to a steel plate surface, and the above-mentioned coloring type crosslinking coating liquid was applied thereon at a rate of 100 g / m 2 ,
C. for 24 hours to cure at room temperature to form a water-repellent anticorrosive layer. Make a grid-like cut in the water-repellent anticorrosion layer,
When the test was performed in accordance with JIS K 5400, the evaluation score (out of 10 points) was 10.
【００５０】他方、上記の室温架橋型被覆材を幅５０mm
で切断してテープを形成し、それを直径１００mmの鋼管
にラップ代５５％で巻回したのちその上に上記の着色型
架橋用塗液を１００ｇ／ｍ2の割合で塗布し、２３℃で
２４時間保持して室温硬化させ撥水性防食層を形成し
た。その際、着色型架橋用塗液の塗布後４時間（２３
℃）で表面がタックフリーとなり、タックフリー時にお
ける表面張力は２７dyn／cm（ＪＩＳ Ｋ ６７６８）
であった。On the other hand, the above room temperature crosslinking type coating material is
To form a tape, which is wound on a steel pipe having a diameter of 100 mm at a wrapping rate of 55%, and then the above-mentioned coating solution for color-type crosslinking is applied thereon at a rate of 100 g / m 2 , and at 23 ° C. It was kept at room temperature for 24 hours to form a water-repellent anticorrosive layer. At that time, 4 hours (23 hours) after the application of the coloring type crosslinking coating liquid.
C), the surface becomes tack-free, and the surface tension during tack-free is 27 dyn / cm (JIS K 6768).
Met.
【００５１】前記の撥水性防食層について水密性を評価
したところ良好な結果が得られると共に、鋼管上の撥水
性防食層に切れ目を入れて無理に剥がして重ね合せ部を
観察したところ、重ね合せ部の段差部分も確実に充填さ
れており、水路となる孔部は全く形成されていなかっ
た。The water-repellent anticorrosive layer was evaluated for watertightness, and good results were obtained. The water-repellent anticorrosive layer on the steel pipe was cut and forcibly peeled off, and the superposed portion was observed. The step portion of the portion was also securely filled, and the hole serving as the water channel was not formed at all.
【００５２】実施例２ 未架橋液状シリコーンゴム１００部、ホワイトカーボン
１００部、ジブチル錫ジラウレート５部をプラネタリー
ミキサで混練し、それをポリエステル不織布（目付１０
０ｇ／ｍ2）に含浸させ、それをロール状に巻取って１
００mm幅に切断し坪量１kg／ｍ2の室温架橋型被覆材を
得た。Example 2 100 parts of uncrosslinked liquid silicone rubber, 100 parts of white carbon and 5 parts of dibutyltin dilaurate were kneaded with a planetary mixer, and the mixture was kneaded with a polyester nonwoven fabric (having a basis weight of 10%).
0 g / m 2 ), and it is wound into a roll and
The sheet was cut to a width of 00 mm to obtain a room temperature crosslinking type coating material having a basis weight of 1 kg / m 2 .
【００５３】一方、シリコーンオイル１００部、ホワイ
トカーボン３０部、アルミニウム粉（着色剤）１０部、
テトラエトキシシラン５部をプラネタリーミキサで混練
し、着色型架橋用塗液を得た。On the other hand, 100 parts of silicone oil, 30 parts of white carbon, 10 parts of aluminum powder (colorant),
Five parts of tetraethoxysilane were kneaded with a planetary mixer to obtain a coloring type crosslinking coating liquid.
【００５４】前記の室温架橋型被覆材と着色型架橋用塗
液を用いて実施例１に準じ撥水性防食層を形成しその特
性を調べたところ、碁盤目試験において１０点が得られ
ると共に、着色型架橋用塗液の塗布後６時間（２３℃）
で表面がタックフリーとなり、タックフリー時における
表面張力は２６dyn／cmであった。さらに水密性も良好
で、水路となる孔部は全く形成されていなかった。A water-repellent anticorrosion layer was formed using the room temperature cross-linkable coating material and the colored cross-linking coating solution according to Example 1, and the characteristics thereof were examined. As a result, 10 points were obtained in a grid test, and 6 hours (23 ° C) after application of the coating solution for colored crosslinking
The surface became tack-free, and the surface tension during tack-free was 26 dyn / cm. Further, the watertightness was good, and no holes serving as water channels were formed.
【００５５】[0055]
【発明の効果】本発明によれば、有機溶剤の関与なく基
材で補強されたシリコーン系の強靱で、撥水性、防食
性、耐熱性、厚さや物性の均一性、密着性に優れる防食
層を作業現場でも簡便に能率よく低温施工で形成するこ
とができる。また形成防食層は、汚染、損傷、シワや浮
きが生じにくく防食効果の長期持続性に優れている。According to the present invention, a corrosion-resistant layer excellent in water repellency, corrosion resistance, heat resistance, uniformity of thickness and physical properties, and adhesion is provided. Can be easily and efficiently formed at a work site by low-temperature construction. Further, the formed anticorrosion layer is less likely to cause contamination, damage, wrinkles and floating, and is excellent in long-term durability of the anticorrosion effect.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ３２Ｂ 25/20 Ｂ３２Ｂ 25/20 Ｃ２３Ｆ 11/00 Ｃ２３Ｆ 11/00 Ｂ Ｆ１６Ｌ 58/10 Ｆ１６Ｌ 58/10 (72)発明者 三輪 直樹 大阪府茨木市下穂積１丁目１番２号 日 東電工株式会社内 (72)発明者 藤本 哲夫 東京都港区六本木６丁目２番31号 東芝 シリコーン株式会社内 (72)発明者 千葉 修二 東京都港区六本木６丁目２番31号 東芝 シリコーン株式会社内 (56)参考文献 特開 平２−48939（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 B05D 7/24 302 C23F 11/00 F16L 58/10 Continued on the front page (51) Int.Cl. 7 Identification symbol FI B32B 25/20 B32B 25/20 C23F 11/00 C23F 11/00 B F16L 58/10 F16L 58/10 (72) Inventor Naoki Miwa Ibaraki, Osaka 1-1-2 Shimohozumi, Nichito Nitto Denko Corporation (72) Inventor Tetsuo Fujimoto 6-2-31 Roppongi, Minato-ku, Tokyo Toshiba Silicone Co., Ltd. (72) Inventor Shuji Chiba Roppongi, Minato-ku, Tokyo 6-2-3-1 Toshiba Silicone Co., Ltd. (56) References JP-A-2-48939 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B32B 1/00-35 / 00 B05D 7/24 302 C23F 11/00 F16L 58/10
Claims (5)
硬化剤又は硬化触媒の一方を含有する液状混和物を多孔
性基材に含浸させてなる室温架橋型被覆材を金属表面又
は防食欠陥部に被覆施与して被覆層を形成し、その被覆
層を、未架橋液状シリコーンゴム及び／又はシリコーン
オイルを主成分とし前記の硬化剤又は硬化触媒の他方を
含有する架橋用塗液で架橋させたことを特徴とする撥水
性防食層。1. A room temperature cross-linkable coating material obtained by impregnating a porous base material with a liquid mixture containing an uncrosslinked liquid silicone rubber as a main component and one of a curing agent and a curing catalyst on a metal surface or an anticorrosion defect. The coating was applied to form a coating layer, and the coating layer was cross-linked with a cross-linking coating liquid containing uncrosslinked liquid silicone rubber and / or silicone oil as a main component and containing the other of the above-mentioned curing agents or curing catalysts. A water repellent and anticorrosive layer characterized by the following.
項１に記載の撥水性防食層。2. The water-repellent anticorrosive layer according to claim 1, wherein the surface tension is 35 dyn / cm or less.
着色剤を添加した架橋用塗液で架橋してなる着色された
請求項１に記載の撥水性防食層。3. The water-repellent anticorrosion layer according to claim 1, which is formed by crosslinking a coating layer comprising a room-temperature crosslinking type coating material with a crosslinking coating solution containing a coloring agent.
硬化剤又は硬化触媒の一方を含有する液状混和物を多孔
性基材に含浸させてなる室温架橋型被覆材と、未架橋液
状シリコーンゴム及び／又はシリコーンオイルを主成分
とし前記の硬化剤又は硬化触媒の他方を含有する架橋用
塗液とからなることを特徴とする撥水性防食処理材。4. A room temperature cross-linkable coating material obtained by impregnating a porous base material with a liquid mixture containing an uncrosslinked liquid silicone rubber as a main component and one of a curing agent and a curing catalyst; And / or a cross-linking coating liquid containing silicone oil as a main component and the other of the above-mentioned curing agent or curing catalyst.
に記載の撥水性防食処理材。5. The cross-linking coating solution contains a colorant.
The water repellent and anticorrosion treated material according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07096793A JP3172318B2 (en) | 1993-03-04 | 1993-03-04 | Water repellent anticorrosion layer and anticorrosion treated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07096793A JP3172318B2 (en) | 1993-03-04 | 1993-03-04 | Water repellent anticorrosion layer and anticorrosion treated material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256975A JPH06256975A (en) | 1994-09-13 |
| JP3172318B2 true JP3172318B2 (en) | 2001-06-04 |
Family
ID=13446811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07096793A Expired - Lifetime JP3172318B2 (en) | 1993-03-04 | 1993-03-04 | Water repellent anticorrosion layer and anticorrosion treated material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3172318B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3442160B2 (en) * | 1994-09-30 | 2003-09-02 | 東燃ゼネラル石油株式会社 | Method of forming SiO2 ceramic coating |
| JP3571838B2 (en) * | 1996-03-05 | 2004-09-29 | 積水化学工業株式会社 | Blood test container |
| JP3273593B2 (en) * | 1997-06-09 | 2002-04-08 | 日東電工株式会社 | Painted protective structure |
| JP6876246B2 (en) * | 2017-02-14 | 2021-05-26 | 日産自動車株式会社 | Transparent coating, manufacturing method of transparent coating and antifouling parts for automobiles |
| JP2019072856A (en) * | 2017-10-12 | 2019-05-16 | 日東シンコー株式会社 | Protective sheet set |
| JP7042370B1 (en) * | 2021-01-21 | 2022-03-25 | 日東電工株式会社 | Anti-corrosion tape and anti-corrosion structure |
| JP7381996B2 (en) * | 2021-10-22 | 2023-11-16 | 日産化学株式会社 | Membrane forming composition and gas separation membrane |
-
1993
- 1993-03-04 JP JP07096793A patent/JP3172318B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06256975A (en) | 1994-09-13 |
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