JPH0673315A - Modifier for coating material - Google Patents
Modifier for coating materialInfo
- Publication number
- JPH0673315A JPH0673315A JP4251869A JP25186992A JPH0673315A JP H0673315 A JPH0673315 A JP H0673315A JP 4251869 A JP4251869 A JP 4251869A JP 25186992 A JP25186992 A JP 25186992A JP H0673315 A JPH0673315 A JP H0673315A
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- Japan
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- paint
- resin
- styrene
- weight
- modifier
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はエポキシ樹脂系塗料用又
はウレタン樹脂系塗料に配合してその特性を改良するた
めの塗料改質材に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint modifier for epoxy resin paints or urethane resin paints to improve its properties.
【０００２】[0002]
【従来の技術】エポキシ樹脂系塗料、ウレタン樹脂系塗
料は防食性が優れ、重防食塗料等として多用されてい
る。そして、このような塗料については、取り扱い作業
性を改善したり、耐水性、耐薬品性、耐候性等を改善し
たりする目的で塗料改質材を使用することが行われてい
る。この種の改質材としてはコ−ルタ−ル、ピッチ、ア
スファルト、ギルソナイト等の瀝青物質の他、石油樹
脂、クマロン樹脂、キシレン樹脂、スチレンオリゴマ−
等が知られている（特開昭６２−５３３８１号公報、特
開昭６２−５３３８１号公報）が、いずれも一長一短が
あるものであった。また、水酸基含有芳香族樹脂を常温
乾燥型塗料に配合することが特開昭５４−１２３１４３
号公報等で知られているが、この塗料はスチレン系共重
合樹脂をバインダ−成分とする常温乾燥型塗料であっ
て、重防食性能の優れたエポキシ樹脂系塗料、ウレタン
樹脂系塗料への適用を教えるものはない。2. Description of the Related Art Epoxy resin-based paints and urethane resin-based paints have excellent anticorrosion properties and are widely used as heavy anticorrosion paints. For such paints, paint modifiers have been used for the purpose of improving handling workability and improving water resistance, chemical resistance, weather resistance and the like. Examples of modifiers of this type include bituminous substances such as coal tar, pitch, asphalt and gilsonite, as well as petroleum resins, coumarone resins, xylene resins and styrene oligomers.
Etc. are known (JP-A-62-53381 and JP-A-62-53381), but both have advantages and disadvantages. Further, it is known to add a hydroxyl group-containing aromatic resin to a room temperature dry type coating composition in JP-A-54-123143.
As is known in Japanese Patent Publication No. JP, etc., this paint is a room-temperature-drying paint that uses a styrene-based copolymer resin as a binder component, and is applied to epoxy resin-based paints and urethane resin-based paints with excellent heavy anticorrosion performance. There is nothing to teach.
【０００３】[0003]
【発明が解決しようとする課題】本発明は防食性能及び
耐水性を改善する塗料改質材を提供することを目的とす
る。SUMMARY OF THE INVENTION It is an object of the present invention to provide a paint modifier which improves anticorrosion performance and water resistance.
【０００４】[0004]
【課題を解決するための手段】本発明は、フェノ−ル類
１重量部に対し、スチレン類４〜１０重量部をカチオン
重合触媒の存在下に反応させて得られる数平均分子量３
００〜１０００、水酸基価２５〜１００のスチレン系樹
脂からなるエポキシ樹脂系塗料用又はウレタン樹脂系塗
料用の塗料改質材である。According to the present invention, the number average molecular weight of 3 is obtained by reacting 4 to 10 parts by weight of styrene with 1 part by weight of phenol in the presence of a cationic polymerization catalyst.
It is a paint modifier for epoxy resin-based paints or urethane resin-based paints, which is composed of styrene-based resin having a hydroxyl value of 0 to 1000 and 25 to 100.
【０００５】本発明の塗料改質材の原料として用いるフ
ェノ−ル類としては、フェノ−ル、クレゾ−ル、キシレ
ノ−ル、エチルフェノ−ル、ｔ−ブチルフェノ−ル等の
１価のフェノ−ル類やビスフェノ−ルＡ、ビスフェノ−
ルＦ、ビフェノ−ル、レゾルシン等の２価のフェノ−ル
類などが挙げられるが、好ましくはｔ−ブチルフェノ−
ル又はビスフェノ−ルＡである。The phenols used as a raw material for the coating material modifying material of the present invention include monovalent phenols such as phenol, cresol, xylenol, ethylphenol and t-butylphenol. Type and bisphenol A, bisphenol
Examples thereof include divalent phenols such as phenol F, biphenol and resorcin, and t-butylphenol is preferable.
Or bisphenol A.
【０００６】もう一つの原料として用いるスチレン類と
しては、スチレンの他にパラメチルスチレンやα−メチ
ルスチレン等のメチルスチレン、エチルスチレン等が挙
げられるが、好ましくはスチレンである。スチレン類は
前記フェノ−ル類１重量部に対して４〜１０重量部、好
ましくは５〜７重量部用いられる。フェノ−ル類が多す
ぎると耐水性が低下するなどの問題を生じ、少なすぎる
とエポキシ樹脂等の塗料用樹脂との相溶性が低下するな
どの問題を生ずる。Examples of styrenes used as the other raw material include methylstyrene such as paramethylstyrene and α-methylstyrene, ethylstyrene and the like in addition to styrene, and styrene is preferable. Styrenes are used in an amount of 4 to 10 parts by weight, preferably 5 to 7 parts by weight, based on 1 part by weight of the above phenols. If the amount of the phenols is too large, the water resistance is lowered, and if the amount is too small, the compatibility with the coating resin such as the epoxy resin is lowered.
【０００７】スチレン類とフェノ−ル類との反応はカチ
オン重合触媒の存在下に行う。ここで使用するカチオン
重合触媒としては、有機スルホン酸、硫酸、しゅう酸、
塩酸等のプロトン酸や塩化アルミニウム、三フッ化ほう
素、これらの錯体等のルイス酸や活性白土、酸性白土、
ゼオライト等の固体酸等が挙げられるが、好ましくは活
性白土である。活性白土は適当な重合度を与えるだけで
なく、反応終了後は静置、濾過等をするだけで分離で
き、アルカリ洗浄等の処理も不用であるという利点があ
る。The reaction between styrenes and phenols is carried out in the presence of a cationic polymerization catalyst. As the cationic polymerization catalyst used here, organic sulfonic acid, sulfuric acid, oxalic acid,
Protic acids such as hydrochloric acid, aluminum chloride, boron trifluoride, Lewis acids such as complexes thereof, activated clay, acid clay,
Solid acids such as zeolite may be mentioned, but activated clay is preferable. The activated clay has an advantage that not only does it give an appropriate degree of polymerization, but it can be separated after completion of the reaction simply by allowing it to stand, filtering, etc., and treatment such as alkali washing is unnecessary.
【０００８】この反応は常温ないし１５０℃で、０．１
ないし１０時間程度で行う。活性白土を触媒として使用
する場合は、１００〜１２０℃程度の反応温度が好まし
く、スチレン類及びフェノ−ル類がほぼ消失するまで、
約０．２〜２時間程度反応を行うことがよい。This reaction is carried out at room temperature to 150 ° C. under 0.1
Or about 10 hours. When using activated clay as a catalyst, a reaction temperature of about 100 to 120 ° C. is preferable, until styrenes and phenols are almost disappeared.
The reaction is preferably performed for about 0.2 to 2 hours.
【０００９】この反応で生成するスチレン系樹脂はスチ
レン類とフェノ−ル類との共重合体からなる樹脂とスチ
レン類のオリゴマ−からなる樹脂の混合物であるが、数
平均分子量が３００〜１０００である必要がある。そし
て、好ましくは４〜６量体を主とするものである。分子
量が大き過ぎると塗料用樹脂との相溶性が低下する。ま
た、水酸基価は２５〜１００の範囲である必要があり、
小さすぎると塗料用樹脂との相溶性が低下し、大きすぎ
ると耐水性を低下させる。The styrene resin produced by this reaction is a mixture of a resin composed of a copolymer of styrenes and phenols and a resin composed of an oligomer of styrenes, and has a number average molecular weight of 300 to 1,000. Need to be And it is preferable that the main component is 4- to 6-mer. If the molecular weight is too large, the compatibility with the coating resin decreases. Further, the hydroxyl value needs to be in the range of 25 to 100,
If it is too small, the compatibility with the coating resin is lowered, and if it is too large, the water resistance is lowered.
【００１０】この反応で生成したスチレン系樹脂につい
て検討したところ、スチレンとフェノ−ル類との共重合
体からなる樹脂は、When the styrene-based resin produced by this reaction was examined, a resin composed of a copolymer of styrene and phenols was found to be
【化１】 で示されるものであることが判明した。また、スチレン
類のオリゴマ−からなる樹脂は、[Chemical 1] It turned out to be what is shown by. Further, a resin composed of a styrene oligomer is
【化２】 なる構造を有する不飽和体型オリゴマ−と[Chemical 2] And an unsaturated oligomer having a structure
【化３】 なる構造を有する飽和体型オリゴマ−とからなるもので
あることが判明した。そして、活性白土を触媒として使
用した場合、共重合体と飽和体型オリゴマ−が主成分で
あり、不飽和体型オリゴマ−は殆ど生成しないことが判
明した。[Chemical 3] It was found to be composed of a saturated oligomer having the following structure. It was also found that when activated clay was used as a catalyst, the copolymer and the saturated oligomer were the main components, and the unsaturated oligomer was hardly generated.
【００１１】この反応の生成物から、触媒、必要により
使用した溶媒等を分離することにより、本発明のスチレ
ン系樹脂を得ることができる。触媒として活性白土を使
用し、溶媒を使用しない場合は、反応終了後、静置、濾
過するだけでスチレン系樹脂を得ることができる。ま
た、トルエン等の溶媒を使用した場合はこれに溶解した
スチレン系樹脂を得ることができるが、塗料にはこのよ
うな溶媒が添加されることが多いので、多くの場合この
溶媒に溶解したままで使用することができる。そして、
このスチレン系樹脂が本発明の塗料改質材となる。The styrene resin of the present invention can be obtained by separating the catalyst, the solvent used, etc., from the product of this reaction. When activated clay is used as a catalyst and a solvent is not used, the styrene resin can be obtained simply by standing and filtering after completion of the reaction. Further, when a solvent such as toluene is used, a styrene resin dissolved in the solvent can be obtained. However, since such a solvent is often added to the paint, in many cases, the styrene resin remains dissolved in the solvent. Can be used in. And
This styrene resin serves as the paint modifier of the present invention.
【００１２】本発明の塗料改質材は、エポキシ樹脂系塗
料、ウレタン樹脂系塗料に配合して改質することが可能
であるが、防食効果を改善する目的からすると常温硬化
二液型のエポキシ樹脂系塗料又はウレタン樹脂系塗料等
の防食塗料に配合することが適当である。特に、重防食
塗料として知られているエポキシ樹脂塗料、ウレタン樹
脂塗料に配合すると、防食効果がより一層向上する。塗
料改質材の配合量は、塗料改質材を含む塗料中の全樹脂
分の１〜７０重量％、好ましくは３０〜６０重量％の範
囲である。また、当然のことであるが塗料にはこの塗料
改質材の他に、顔料、充填材、溶剤等の配合材を配合す
ることができる。The paint modifier of the present invention can be modified by blending it with an epoxy resin-based paint or a urethane resin-based paint. From the viewpoint of improving the anticorrosion effect, a room temperature curing two-component epoxy resin is used. It is suitable to be blended with an anticorrosive paint such as a resin paint or a urethane resin paint. In particular, when it is mixed with an epoxy resin paint or a urethane resin paint known as a heavy anticorrosion paint, the anticorrosion effect is further improved. The compounding amount of the paint modifier is in the range of 1 to 70% by weight, preferably 30 to 60% by weight, of the total resin content in the paint including the paint modifier. Further, as a matter of course, in addition to the paint modifier, the paint may contain a compounding material such as a pigment, a filler, and a solvent.
【００１３】[0013]
実施例１ スチレン８５重量部、パラ−ｔ−ブチルフェノ−ル１５
重量部及びトルエン５０重量部をフラスコに仕込み、１
１５℃に昇温し、活性白土（付着水１２％以下、粉末度
２００メッシュ通過８５％以上、遊離酸価２０ｍｇＫＯ
Ｈ／ｇ以下）１重量部をゆっくり滴下し、１１５℃で１
時間反応を行った。スチレン及びパラ−ｔ−ブチルフェ
ノ−ルは実質的に残存していないことを確認した。これ
を濾過してスチレン系樹脂のトルエンワニスを得た。こ
のワニスを減圧蒸留してトルエンを除去し、スチレン系
樹脂を得た。このスチレン系樹脂の数平均分子量は４８
０であり、水酸基価は５３であった。なお、水酸基価は
無水酢酸でアセチル化したのち、これをＮ／２水酸化ナ
トリウムで滴定することにより測定した。また、このス
チレン系樹脂について、ＩＲ測定及び液体クロマトグラ
フ分析した結果を図１及び図２に示す。Example 1 85 parts by weight of styrene, 15 parts of para-t-butylphenol
1 part by weight and 50 parts by weight of toluene are charged into a flask, and 1
The temperature is raised to 15 ° C., and activated clay (adhered water 12% or less, fineness 200 mesh passing 85% or more, free acid value 20 mg KO
(H / g or less) 1 part by weight is slowly added dropwise at 115 ° C. to 1
The reaction was carried out over time. It was confirmed that styrene and para-t-butylphenol did not substantially remain. This was filtered to obtain a toluene varnish of styrene resin. This varnish was distilled under reduced pressure to remove toluene to obtain a styrene resin. The number average molecular weight of this styrene resin is 48.
It was 0 and the hydroxyl value was 53. The hydroxyl value was measured by acetylating with acetic anhydride and then titrating this with N / 2 sodium hydroxide. The results of IR measurement and liquid chromatographic analysis of this styrene resin are shown in FIGS. 1 and 2.
【００１４】実施例２ パラ−ｔ−ブチルフェノ−ルの代わりにビスフェノ−ル
Ａを使用した他は実施例１と同様にしてスチレン系樹脂
を得た。このスチレン系樹脂の数平均分子量は５７０で
あり、水酸基価７２であった。このスチレン系樹脂につ
いて、ＩＲ測定及び液体クロマトグラフ分析した結果を
図３及び図４に示す。Example 2 A styrenic resin was obtained in the same manner as in Example 1 except that bisphenol A was used in place of para-t-butylphenol. The styrene resin had a number average molecular weight of 570 and a hydroxyl value of 72. The results of IR measurement and liquid chromatographic analysis of this styrene resin are shown in FIGS. 3 and 4.
【００１５】実施例３〜８ パラ−ｔ−ブチルフェノ−ルの代わりに表１に示すフェ
ノ−ル類を使用した他は実施例１と同様にしてスチレン
系樹脂を得た。各実施例の転化率及び得られたスチレン
系樹脂の粘度（Ｐ．Ｓ．７５℃）、色調（ガ−ドナ
−）、相溶性（エポキシアクリレ−トとイソシアネ−ト
から得られるウレタン樹脂に対する）を測定した結果を
表１に示す。 （以下このページ余白）Examples 3 to 8 Styrenic resins were obtained in the same manner as in Example 1 except that the phenols shown in Table 1 were used in place of para-t-butylphenol. The conversion of each example and the viscosity (PS 75 ° C.) of the obtained styrene resin, color tone (gardner), and compatibility (with respect to the urethane resin obtained from epoxy acrylate and isocyanate) ) Is shown in Table 1. (Hereafter, this page margin)
【００１６】[0016]
【表１】 注）Ｃｒはクレゾ−ル、Ｘｙはキシレノ−ル、ＢＰＡは
ビスフェノ−ルＡ、ｔ−ＢＰはｔ−ブチルフェノ−ルを
示す。[Table 1] Note) Cr is cresol, Xy is xylenol, BPA is bisphenol A, and t-BP is t-butylphenol.
【００１７】各実施例で得られたスチレン系樹脂をトル
エンに溶解し８２重量％ワニスとし、これを下記に示す
塗料材料と配合して、２液型塗料とした。The styrene resin obtained in each example was dissolved in toluene to give a 82% by weight varnish, which was blended with the coating material shown below to give a two-pack type coating material.
【００１８】 主剤 エポキシポリオ−ル（６０％エピクロンＨ−２１５、大日本インク (株) 製） ３０．０重量％ 塗料改質剤 スチレン系樹脂（８２重量％ワニス） １６．０重量％ 顔料 タルク ３２．０重量％ 着色顔料 １０．０重量％ 吸水剤 １．０重量％ 揺変剤 １．０重量％ シンナ− （トルエン他） １０．０重量％Main agent Epoxy polyol (60% Epiclon H-215, manufactured by Dainippon Ink and Chemicals, Inc.) 30.0% by weight Paint modifier Styrenic resin (82% by weight varnish) 16.0% by weight Pigment talc 32 0.0% by weight Colored pigment 10.0% by weight Water absorbing agent 1.0% by weight Thixotropic agent 1.0% by weight Thinner (toluene, etc.) 10.0% by weight
【００１９】硬化剤 イソシアネ−ト（７５％タケネ−トＤ−１０３、武田薬
品（株）製） ９０．０重量％ トルエン １０．０重量％ 混合比 主剤／硬化剤＝９０／１０Hardening agent Isocyanate (75% Takenate D-103, manufactured by Takeda Pharmaceutical Co., Ltd.) 90.0% by weight Toluene 10.0% by weight Mixing ratio Main agent / hardening agent = 90/10
【００２０】得られた塗料について、水蒸気透過度（１
００μｍ換算、ｇ／ｍ2 ・ｄａｙ、ｄｒｙ１５０、４０
℃ｘ２日）、鉛筆硬度（ｄｒｙ１５０、２０℃ｘ７
日）、凝集破壊（ｄｒｙ１５０、２０℃ｘ７日、ｋｇ／
ｃｍ2 ）、塩水噴霧試験（３０日間、クロスカット部剥
離巾、ｍｍ）、温度勾配試験（６０−１５℃、合格日
数）を行い、防食性能を測定した。更に、ウェザ−メ−
タ−により耐候性（黄変性ΔＹＩ、光沢、３００ｈｒ
後）の測定を行った。結果を表２に示す。With respect to the obtained paint, the water vapor permeability (1
Converted to 00 μm, g / m 2 · day, dry150, 40
℃ × 2 days), pencil hardness (dry150, 20 ℃ × 7
Day), cohesive failure (dry150, 20 ° C x 7 days, kg /
cm 2 ), salt spray test (30 days, cross-cut part peeling width, mm), and temperature gradient test (60-15 ° C., days passed) to measure the anticorrosion performance. In addition, the weather
Weather resistance (yellowing ΔYI, gloss, 300 hr
After) was measured. The results are shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】実施例９ 実施例２と同様な反応を行い、触媒使用量、反応温度、
反応時間と転化率との関係を調べた。反応条件は下記の
とおりである。また、得られたスチレン系樹脂について
実施例１と同様にして、粘度（トルエン１５％、２５
℃）、色調（ガ−ドナ−）及び相溶性を測定した。結果
を表３に示す。 ビスフェノ−ルＡ／スチレン／トルエン（重量比）＝１
５／８５／５０ 触媒：活性白土 反応時間：触媒添加時間＝３０分、保持時間＝３０〜１
５０分Example 9 The same reaction as in Example 2 was carried out, and the amount of catalyst used, the reaction temperature,
The relationship between reaction time and conversion was investigated. The reaction conditions are as follows. Further, the obtained styrene resin was treated in the same manner as in Example 1 to obtain a viscosity (toluene 15%, 25%
C.), color tone (gardner) and compatibility. The results are shown in Table 3. Bisphenol A / styrene / toluene (weight ratio) = 1
5/85/50 Catalyst: Activated clay Reaction time: Catalyst addition time = 30 minutes, retention time = 30 to 1
50 minutes
【００２３】[0023]
【表３】 [Table 3]
【００２４】実施例１０ 実施例９と同様な反応を行い、触媒種類と転化率、粘度
（２５℃）又は軟化点及び色調（ガ−ドナ−）を測定し
た。結果を表４に示す。なお、反応時間は１５０分と
し、スチレン／パラ−ｔ−ブチルフェノ−ル／トルエン
＝８５／１５／５０とした。Example 10 The same reaction as in Example 9 was carried out, and the catalyst type and conversion, viscosity (25 ° C.) or softening point and color tone (gardner) were measured. The results are shown in Table 4. The reaction time was 150 minutes, and styrene / para-t-butylphenol / toluene = 85/15/50.
【００２５】[0025]
【表４】 得られたスチレン系樹脂について、液体クロマトグラフ
で分析したところ、実験Ｎｏ１及び３は２〜３量体が多
量に存在し、実験Ｎｏ２は４量体以上のものが大部分を
占めていりことが判明した。[Table 4] When the obtained styrene-based resin was analyzed by liquid chromatography, Experiment Nos. 1 and 3 had a large amount of 2-3 trimers, and Experiment No. 2 was mostly tetramers or more. found.
【００２６】[0026]
【発明の効果】本発明の塗料改質材は、これを配合する
ことにより防食性能を高めた塗料とすることができる。
したがって、水中あるいは水気の多い箇所に使用される
材料等の重防食用塗料とすることも可能となる。The paint modifier of the present invention can be made into a paint having improved anticorrosion performance by blending it.
Therefore, it is possible to use a heavy anticorrosion coating material such as a material used in water or a place with a lot of water.
【図１】実施例１の樹脂の液体クロマトグラフ分析のチ
ャ−トFIG. 1 is a chart for liquid chromatographic analysis of the resin of Example 1.
【図２】実施例１の樹脂のＩＲ測定のチャ−トFIG. 2 is a chart for IR measurement of the resin of Example 1.
【図３】実施例２の樹脂の液体クロマトグラフ分析のチ
ャ−トFIG. 3 is a chart for liquid chromatographic analysis of the resin of Example 2.
【図４】実施例１の樹脂のＩＲ測定のチャ−トFIG. 4 is a chart for IR measurement of the resin of Example 1.
Claims (4)
４〜１０重量部をカチオン重合触媒の存在下に反応させ
て得られる数平均分子量３００〜１０００、水酸基価２
５〜１００のスチレン系樹脂からなることを特徴とする
エポキシ樹脂系塗料用又はウレタン樹脂系塗料用の塗料
改質材。1. A number average molecular weight of 300 to 1000 and a hydroxyl value of 2 obtained by reacting 4 to 10 parts by weight of styrene with 1 part by weight of phenol in the presence of a cationic polymerization catalyst.
A paint modifier for an epoxy resin paint or a urethane resin paint, characterized by comprising 5 to 100 styrene resin.
ブチルフェノ−ルであり、スチレン類がスチレンである
請求項１記載の塗料改質材。2. A phenol is bisphenol A or t-.
The paint modifier according to claim 1, which is butylphenol and the styrenes are styrene.
１記載の塗料改質材。3. The paint modifier according to claim 1, wherein the cationic polymerization catalyst is activated clay.
料が二液性反応硬化型塗料である請求項１記載の塗料改
質材。4. The paint modifier according to claim 1, wherein the epoxy resin-based paint or the urethane resin-based paint is a two-component reaction-curable paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25186992A JP3235879B2 (en) | 1992-08-28 | 1992-08-28 | Paint modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25186992A JP3235879B2 (en) | 1992-08-28 | 1992-08-28 | Paint modifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0673315A true JPH0673315A (en) | 1994-03-15 |
| JP3235879B2 JP3235879B2 (en) | 2001-12-04 |
Family
ID=17229146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25186992A Expired - Lifetime JP3235879B2 (en) | 1992-08-28 | 1992-08-28 | Paint modifier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3235879B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006348109A (en) * | 2005-06-14 | 2006-12-28 | Nippon Steel Corp | Coating composition |
| JP2008095036A (en) * | 2006-10-16 | 2008-04-24 | Mitsui Chemicals Inc | Composition |
-
1992
- 1992-08-28 JP JP25186992A patent/JP3235879B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006348109A (en) * | 2005-06-14 | 2006-12-28 | Nippon Steel Corp | Coating composition |
| JP2008095036A (en) * | 2006-10-16 | 2008-04-24 | Mitsui Chemicals Inc | Composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3235879B2 (en) | 2001-12-04 |
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