JPS62174276A - Crepe finish - Google Patents
Crepe finishInfo
- Publication number
- JPS62174276A JPS62174276A JP1608686A JP1608686A JPS62174276A JP S62174276 A JPS62174276 A JP S62174276A JP 1608686 A JP1608686 A JP 1608686A JP 1608686 A JP1608686 A JP 1608686A JP S62174276 A JPS62174276 A JP S62174276A
- Authority
- JP
- Japan
- Prior art keywords
- paint
- sulfonic acid
- tertiary amine
- shrinking
- polyester resin
- 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.)
- Granted
Links
- 229920001225 polyester resin Polymers 0.000 claims abstract description 30
- 239000004645 polyester resin Substances 0.000 claims abstract description 30
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 21
- 150000007974 melamines Chemical class 0.000 claims abstract description 21
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 19
- 239000004640 Melamine resin Substances 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims description 44
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical group CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 19
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 claims description 2
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 2
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 claims 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 150000003839 salts Chemical group 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 31
- 239000002987 primer (paints) Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229920003270 Cymel® Polymers 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002320 enamel (paints) Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- -1 organic acid salts Chemical class 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ちぢみ模様仕上げを行うことのできるちぢみ
塗料、特にプレコートメタル用として好ましいちぢみ塗
料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a shrinking paint capable of producing a shrinking pattern finish, and particularly to a shrinking paint suitable for use on pre-coated metal.
ちぢみ模様を形成するちぢみ塗料として、桐油などの共
役二重結合をもつ長油系の乾性油を使用したアルキド樹
脂ワニスを樹脂成分とし、乾燥剤に多址のコバルトやマ
ンガンなどの有機酸塩°を配合した塗料が一般的に使用
されている。通常この塗料をスプレー塗装し、６０〜１
００℃で約２０分間加熱焼付けを行うとちぢみ模様を形
成するが、これをさらに１：１ｌＯ−１５０℃で約２０
分間焼付けて硬化させ、ちぢみ模様を有する塗膜を得て
いる。これらの塗料は一般に素材を加工後塗装す、るボ
ストコート用塗料として使用されている。As a shrinking paint that forms a shrinking pattern, the resin component is an alkyd resin varnish that uses a long drying oil with conjugated double bonds such as tung oil, and a large amount of organic acid salts such as cobalt and manganese as a drying agent. Paints containing these are commonly used. Usually, this paint is spray painted and 60-1
A shrinking pattern is formed by baking at 00°C for about 20 minutes, and this is further baked at 1:1O-150°C for about 20 minutes.
The coating was baked for a minute to harden, resulting in a coating with a wrinkled pattern. These paints are generally used as bottom coat paints, which are applied after processing the material.
しかし、このような従来のちぢみ塗料は、塗装後の加工
性が悪く、かつ焼付に長時間を要するため、塗装後の加
工が必要で、しかも短時間に焼付けるプレコートメタル
用塗料としては使用することができないという問題点が
あった。However, such conventional shrinking paints have poor workability after painting and require a long time to bake, so they require processing after painting and are not used as paints for pre-coated metals that are baked in a short time. The problem was that it could not be done.
本発明はこのような問題点を解決するためのもので、短
時間で硬化して優れたちぢみ模様仕上げを行うことがで
き、加工性、付着性および耐食性が良好で、プレニ−１
−メタル用に使用可能なちぢみ塗料を提供することを目
的としている。The present invention is intended to solve these problems. It can be cured in a short time to give an excellent wrinkled pattern finish, has good workability, adhesion and corrosion resistance, and is suitable for plenylon 1.
- The aim is to provide a shrinking paint that can be used on metal.
本発明者らは、プレコートメタル用塗料について鋭意研
究した結果、水酸基を有するポリエステル樹脂と反応性
の高いメチル化メラミン樹脂に、沸点８０〜１５０℃の
３級アミンでブロックしたスルホン酸を加えることによ
り、熱硬化時に表面に近い塗膜中からブロックした３級
アミンが遊雛して揮発し、これにより表面層だけ速く硬
化反応を起こし、その結果ちぢみ塗膜を形成することを
見い出し本発明にいたった。As a result of intensive research into paints for pre-coated metals, the present inventors found that by adding sulfonic acid blocked with a tertiary amine with a boiling point of 80 to 150°C to a methylated melamine resin that is highly reactive with polyester resins having hydroxyl groups. They discovered that during thermal curing, the blocked tertiary amines in the paint film near the surface float and volatilize, causing a faster curing reaction only in the surface layer, resulting in the formation of a shrinking paint film, leading to the present invention. Ta.
本発明は、（Ａ）水酸基を有するポリエステル樹脂６０
〜９５重量部と、
（Ｂ）メチル化メラミン樹脂５〜４０重量部と、（Ｃ）
沸点８０〜１５０℃の３級アミンでブロックしたスルホ
ン酸０．２〜３重量部と
を含有することを特徴とするちぢみ塗料である。The present invention provides (A) polyester resin 60 having hydroxyl groups.
~95 parts by weight, (B) 5 to 40 parts by weight of methylated melamine resin, and (C)
This is a shrinking paint characterized by containing 0.2 to 3 parts by weight of sulfonic acid blocked with a tertiary amine having a boiling point of 80 to 150°C.
本発明に用いる（Ａ）成分のポリエステル樹脂は、（Ｂ
）成分のメチル化メラミン樹脂のメトキシ基と反応する
官能基としての水酸基を有するポリエステル樹脂であり
、一般に塗料用として使用されるポリエステル樹脂が使
用できる。プレコートメタル用のちぢみ塗料とする場合
は、通常プレコートメタルに使用される可撓性を有する
ポリエステル樹脂が好ましい。このようなポリエステル
樹脂としては、たとえば油変性ポリエステル樹脂、オイ
ルフリーポリエステル樹脂、シリコン変性ポリエステル
樹脂などがあげられ、いずれも市販品が使用できる。油
変性ポリエステル樹脂としては、たとえば、大日本イン
キ化学工業（株）製のベラコライＩ−Ｍ−６６０１−［
１Ｏ−５（商標）があげられる。オイルフリーポリエス
テル樹脂としては、たとえば、大日本インキ化学工業（
株）ｙ５のベッコライトト６６０２−６０−５、ベラコ
ライトＭ−６４０１−５０、ベラコライト阿−６４０２
−５０、ベッコライトト６００３−ＧＯ、ベラフライト
Ｍ−（ｉ００５−６０．ベラコライＩ−Ｍ−（ｉ００？
−６０，ベラコライト４８−３１２．ベラコライト４９
−３７６、ベラフライト４６−ＩＧ［−３、ベラコライ
ｈＭ−６２０１−４０−ＩＭ、ベラコライ１− Ｍ−６
２０４−５０−３、ベラコライ１−Ｍ−６２０４−５０
−５、三井東圧（株）製のアルマテックスＰ−０４５，
アルマテックスＩ）−６４（ｉ、アルマテックスＩ）−
６４７１３Ｃ、アルマテックスｌＩＭＰ１５．アルマテ
ックスＩＩＭＰ２Ｓ、アルマテックスＩＩ Ｍ １１３
４、ダイナミートノーベル社製のダイナボール８２９、
ダイナポールＬＩ＋７９０．ダイナポールＬｌ１８１２
、ダイナポールＬ１１８２１．ディニスエムレジン社製
ノシンレサイＩ〜Ｗ８３６０ＳＬ、シンレサイトＷ３６
２７０Ｆ、シンレサイトＷ８６３５５ＳＦ、 シンＬ／
サイトＷ８６４６０ＳＫＫ。The polyester resin of component (A) used in the present invention is (B
) is a polyester resin having a hydroxyl group as a functional group that reacts with the methoxy group of the methylated melamine resin of component (2), and polyester resins commonly used for paints can be used. In the case of a shrinking paint for pre-coated metal, a flexible polyester resin that is normally used for pre-coated metal is preferred. Examples of such polyester resins include oil-modified polyester resins, oil-free polyester resins, and silicone-modified polyester resins, all of which can be commercially available. As the oil-modified polyester resin, for example, Belakolai I-M-6601-[ manufactured by Dainippon Ink and Chemicals Co., Ltd.
1O-5 (trademark). As an oil-free polyester resin, for example, Dainippon Ink and Chemicals (
Y5 Co., Ltd. Beccolite 6602-60-5, Belacolaite M-6401-50, Belacolaite A-6402
-50, Bekkoraito 6003-GO, Bekkoraito M-(i005-60. Bekkorai I-M-(i00?
-60, Bellacolite 48-312. Belacolite 49
-376, Bellacorai 46-IG [-3, Bellacorai hM-6201-40-IM, Bellacorai 1-M-6
204-50-3, Belakolai 1-M-6204-50
-5, Almatex P-045 manufactured by Mitsui Toatsu Co., Ltd.
Almatex I)-64 (i, Almatex I)-
64713C, Almatex lIMP15. Almatex II MP2S, Almatex II M 113
4. Dynaball 829 manufactured by Dynamite Nobel,
Dynapol LI+790. Dynapol Ll1812
, Dynapol L11821. Noshinresai I~W8360SL manufactured by Dinis M Resin, Shinresai W36
270F, Shinresite W86355SF, Shin L/
Site W86460SKK.
ウララック１０ｇ−１（Ａ８−５（１，ウララック１０
ｇ−ＲＡ８Ａ１−５０（いずれも商標）等があげられる
。シリコン変性ポリエステル樹脂としては、たとえば、
日蝕アロー化学（株）製のアロプラック１フ１０．フ０
プラツツ１７１１．７０プラッツ７３２３．ディニスエ
ムレジン社製ノシンレサイトＤ−９９６０Ｗ、シンネト
−／Ｌ／Ｌ５Ｌ５ＵＦ。Ularac 10g-1 (A8-5 (1, Ularac 10
Examples include g-RA8A1-50 (all trademarks). Examples of silicon-modified polyester resins include:
Alloplak 1F manufactured by Solar Eclipse Arrow Chemical Co., Ltd. 10. F0
Platz 1711.70 Platz 7323. Noshinrecite D-9960W, Shinneto/L/L5L5UF manufactured by Dinis M Resin.
ウララック５２６５５−Ａｔ−６０（いずれも商標）等
があげられる。Examples include Uralac 52655-At-60 (all trademarks).
これらのポリエステル樹脂は１種単独または２種以上の
混合使用が可能である。ポリエステル樹脂の配合量は樹
脂分（固形分）として６０〜９５重景部、重量しくは６
０〜９０重量部である。These polyester resins can be used singly or in combination of two or more. The amount of polyester resin blended is 60 to 95 parts as resin content (solid content), and 6 parts by weight.
It is 0 to 90 parts by weight.
本発明に用いるＣＢ）成分のメチル化メラミン樹脂は、
メチル化によるメトキシ基を有するメラミン樹脂であり
、メトキシ基を３個以上含むもの。The methylated melamine resin of component CB used in the present invention is:
A melamine resin that has methoxy groups due to methylation, and contains three or more methoxy groups.
特にヘキサメトキシメチロールメラミンが好ましいが、
一般に市叛されているメチル化メラミン樹脂が使用でき
る。通常市販されているブチル化メラミン松脂では、水
酸基を有するポリエステル樹脂との反応が遅く、ちぢみ
模様を与えない。Particularly preferred is hexamethoxymethylolmelamine,
Methylated melamine resins, which are commonly used in the market, can be used. Commercially available butylated melamine pine resin reacts slowly with polyester resins having hydroxyl groups and does not give a shriveled pattern.
このようなメチル化メラミン樹脂としては、たとえば、
三井東圧（株）製のサイメル３００、サイメル３０１、
サイメル３０３、サイメル１１３０−２６６Ｊ、三相ケ
ミカル（株）製の二カラツクＭＷ−３０Ｍ、二カラツク
ＭＷ−３０、二カラツクＭＸ−４０、二カラツクＮＸ−
４８５、二カラツクＭＷ−２２、住友化学（株）製のス
ミマールＮ−１００Ｃ，スミマールＭ−５５、スミマー
ルＭ−４０５，モンサンド（株）製のレジミン７４５、
レジミン７４７、レジミン７５３、レジミン７５５（い
ずれも商標）等があげられる。Examples of such methylated melamine resins include:
Cymel 300, Cymel 301 manufactured by Mitsui Toatsu Co., Ltd.
Cymel 303, Cymel 1130-266J, Nikaratsu MW-30M, Nikaratsu MW-30, Nikaratsu MX-40, Nikaratsu NX- manufactured by Sanso Chemical Co., Ltd.
485, Nikaratsuku MW-22, Sumimaru N-100C manufactured by Sumitomo Chemical Co., Ltd., Sumimaru M-55, Sumimaru M-405, Regimin 745 manufactured by Monsando Co., Ltd.
Examples include RESIMIN 747, RESIMIN 753, and RESIMIN 755 (all trademarks).
これらのメチル化メラミン樹脂は１種単独または２種以
上の混合使用が可能である。メチル化メラミン樹脂の配
合量は樹脂分（固形分）とじで５〜４０重量部、好まし
くは１０〜３０重量部である。These methylated melamine resins can be used alone or in combination of two or more. The blending amount of the methylated melamine resin is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on the resin content (solid content).
ポリエステル樹脂／メチル化メラミン樹脂の重量比が９
５７５より大きい場合は、十分な硬化塗膜が得られず、
塗膜の加工性、付着性および耐食性が劣り、６０／４０
より小さい場合には、塗膜の加工性および耐食性が劣る
。The weight ratio of polyester resin/methylated melamine resin is 9
If it is larger than 575, a sufficiently cured coating film cannot be obtained,
Poor workability, adhesion and corrosion resistance of coating film, 60/40
If it is smaller, the processability and corrosion resistance of the coating film will be poor.
本発明に用いる（Ｃ）成分の沸点８０〜１５０℃の３級
アミンでブロックしたスルホン酸は、スルホン酸を上記
３級アミンの塩とすることにより、スルホン酸の触媒と
しての作用を一時的にブロックしたものである。すなわ
ちスルホン酸は（Ａ）成分と（［３）成分の反応触媒で
あって、反応時間を短縮し、塗膜の表面硬化と内部硬化
との差を大きくして、ちぢみ模様を良好にするものであ
るが、３級アミンの塩とすることにより、この触媒作用
は一時的にブロックされろ。The sulfonic acid blocked with a tertiary amine having a boiling point of 80 to 150°C, which is component (C) used in the present invention, can temporarily inhibit the catalytic action of the sulfonic acid by converting the sulfonic acid into a salt of the tertiary amine. It is blocked. In other words, sulfonic acid is a reaction catalyst for component (A) and component ([3), which shortens the reaction time, increases the difference between surface hardening and internal hardening of the coating film, and improves the wrinkle pattern. However, this catalytic action can be temporarily blocked by using a tertiary amine salt.
スルホン酸としては、たとえば、パラトルエンスルホン
酸、ドデシルベンゼンスルホン酸、ジノニルナフタレン
ジスルホン酸、メタンスルホン酸、ジノニルナフタレン
スルホン酸などがあげられ。Examples of the sulfonic acid include paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, methanesulfonic acid, and dinonylnaphthalenesulfonic acid.
これらは１種単独または２種以上の混合使用が可能であ
る。These can be used singly or in combination of two or more.
沸点８０〜１５０℃の３級アミンとしては、たとえばＮ
−メチルモルホリン、Ｎ、Ｎ−ジメチルアリルアミン、
Ｎ−メチルジアリルアミン、トリアリルアミン、Ｎ。Examples of tertiary amines with a boiling point of 80 to 150°C include N
-methylmorpholine, N,N-dimethylallylamine,
N-methyldiallylamine, triallylamine, N.
Ｎ、Ｎ′，Ｎ′−テ１−ラメチルー１，２−ジアミノエ
タン、Ｎ、Ｎ。N,N',N'-tera-1-ramethyl-1,2-diaminoethane, N,N.
Ｎ′，Ｎ′−テ１〜ラメチルー１，３−ジアミノプロパ
ン、Ｎ−メチルピペリジン、ピリジン等があげられ、こ
れらは１種ｉ１を独または２種以上の混合使用が可能で
ある。Examples include N',N'-te1-ramethyl-1,3-diaminopropane, N-methylpiperidine, and pyridine, and these can be used singly or in combination of two or more.
３級アミンでブロックしたスルホン酸は次のようにして
製造される。すなわち過剰の３級アミンとスルホン酸を
計量後容器に仕込み、２０〜３０℃で１０〜２０分間か
きまぜて未反応のスルホン酸基を完全に塩の形にする。The tertiary amine-blocked sulfonic acid is produced as follows. That is, excess tertiary amine and sulfonic acid are weighed and charged into a container, and stirred at 20 to 30°C for 10 to 20 minutes to completely convert unreacted sulfonic acid groups into salt form.
塩の形にした３級アミンでブロックしたスルホン酸を（
Ａ）、（Ｂ）成分と混合してちぢみ塗料を製造する。Sulfonic acid blocked with tertiary amine in salt form (
A shrinking paint is produced by mixing with components A) and (B).
（ｃ） 成分の３級アミンでブロックしたスルホン酸は
ちぢみ模様の形成に必要であり、樹脂合計量１００重量
部に対して０．２〜３重量部、好ましくは０．２〜２．
８重量部用いる。３級アミンでブロックしたスルホン酸
の量が樹脂合計量１００重量部に対して０．２重量部未
満では良好なちぢみ模様が得られず、３重量部を越える
場合はト分な耐食性を得ることができない。The tertiary amine-blocked sulfonic acid component (c) is necessary for forming a shriveled pattern, and is present in an amount of 0.2 to 3 parts by weight, preferably 0.2 to 2.0 parts by weight, based on 100 parts by weight of the total amount of resin.
Use 8 parts by weight. If the amount of sulfonic acid blocked with tertiary amine is less than 0.2 parts by weight based on 100 parts by weight of the total amount of resin, a good wrinkle pattern cannot be obtained, and if it exceeds 3 parts by weight, adequate corrosion resistance cannot be obtained. I can't.
本発明のちぢみ塗料は、上記必須成分のほかに必要に応
じて、二酸化チタン、カーボンブラック、酸化鉄、黄鉛
などの無機顔料；シアニングリーン、シアニンブルーな
どの有機顔料７アルミニウム粉、銅粉などの全屈粉末；
硫酸バリウム、タルク、マイカなどの体質顔料；顔料分
散剤、レベリング剤、沈降防止剤、破泡剤などの添加剤
および溶剤を含んでいてもよい。In addition to the above-mentioned essential ingredients, the shrinking paint of the present invention may optionally contain inorganic pigments such as titanium dioxide, carbon black, iron oxide, and yellow lead; organic pigments such as cyanine green and cyanine blue; 7 aluminum powder, copper powder, etc. Total bending powder;
It may contain extender pigments such as barium sulfate, talc, and mica; additives such as pigment dispersants, leveling agents, antisettling agents, and foam-breaking agents; and solvents.
本発明のちぢみ塗料は上記各成分を混合して製造される
。塗装方法は必要によりキジロール等の溶剤で塗装粘度
に希釈して塗装を行い、２００〜３００℃の高温度で４
０〜１２０秒間焼付を行うことにより、ちぢみ模様を有
する塗膜を形成することができろ。The shrinking paint of the present invention is produced by mixing the above-mentioned components. The coating method is to dilute the coating to a coating viscosity with a solvent such as Kijiroll if necessary, and then apply the coating at a high temperature of 200 to 300℃.
By performing baking for 0 to 120 seconds, it is possible to form a coating film having a wrinkled pattern.
得られる塗膜は加工性が良好であり、短時間で焼付でき
るためプレコートメタル用の塗料に適しているが、これ
に限定されず、ポストコート用の塗料としても使用でき
る。The resulting coating film has good processability and can be baked in a short time, making it suitable as a paint for pre-coating metals, but it can also be used as a paint for post-coating.
本発明のちぢみ塗料をクリヤーまたはカラークリヤー塗
料として用いる場合には、鉄、亜鉛鉄板、ステンレス鋼
、アルミニウムなどの素材の上に直接塗装してもよく、
プライマーを塗装した素材に塗装してもよく、また通常
のプレコートメタル鋼板上に塗装してもよい。本発明の
ちぢみ塗料をエナメル塗料として用いる場合には、通常
のエナメル塗料と同様に用いればよい。When the shrinking paint of the present invention is used as a clear or color clear paint, it may be applied directly onto materials such as iron, galvanized iron, stainless steel, and aluminum.
It may be applied to a primer-coated material, or it may be applied to an ordinary pre-coated metal steel plate. When the shrinking paint of the present invention is used as an enamel paint, it may be used in the same manner as a normal enamel paint.
本発明のちぢみ塗料はバーコーター、フローコーター、
ロールコータ−、ロールフローコーター、スプレーガン
などを用いて塗装することができる。The shrinking paint of the present invention can be applied to bar coaters, flow coaters,
Coating can be performed using a roll coater, roll flow coater, spray gun, etc.
また意匠性を高めるためにエンボス鋼板として使用する
こともできる。It can also be used as an embossed steel plate to enhance the design.
本発明のちぢみ塗料は、触媒となるスルホン酸が沸点８
０〜１５０℃の３級アミンでブロックされた状態で塗料
に含まれるため、触媒としての作用が一時抑えられ、貯
蔵安定性が良い。そして塗装後２００〜３００℃の高温
度で焼付を行うと、表面に近い塗膜中からブロックした
３級アミンが遊離して揮発し、同時に遊離したスルホン
酸が触媒作用を回復して１表面磨だけ速く硬化反応を起
こし、その結果ちぢみ模様を有する塗膜が得られ、４０
〜１２０秒の短時間で加熱硬化が終了する。In the shrinking paint of the present invention, the sulfonic acid serving as the catalyst has a boiling point of 8.
Since it is contained in the paint in a blocked state with a tertiary amine at 0 to 150°C, its catalytic action is temporarily suppressed and its storage stability is good. Then, when baking is performed at a high temperature of 200 to 300℃ after painting, the blocked tertiary amine is liberated from the coating near the surface and volatilized, and at the same time, the liberated sulfonic acid restores the catalytic action and polishes the surface. The curing reaction occurs as quickly as possible, resulting in a coating film with a wrinkled pattern.
Heat curing is completed in a short time of ~120 seconds.
生成する塗膜はちりめん模様状の微細な凹凸を２次元的
に不特定の方向に有し、凹凸の大きさ、形状等はちぢみ
塗料の組成、塗装条件、焼付条件等により変化し、これ
らを調整することにより任意のちぢみ模様を有する塗膜
が得られる。また得られる塗膜は加工性、付着性、耐食
性等が優れており、塗膜形成後に加工を行っても、塗膜
の外観。The resulting paint film has two-dimensional crepe-like minute irregularities in unspecified directions, and the size and shape of the irregularities vary depending on the composition of the crepe paint, coating conditions, baking conditions, etc. By adjusting, a coating film having an arbitrary crimp pattern can be obtained. In addition, the resulting coating film has excellent processability, adhesion, corrosion resistance, etc., and the appearance of the coating film remains unchanged even if processing is performed after the coating film is formed.
加工性、付着性、耐食性等は変化しない。Workability, adhesion, corrosion resistance, etc. do not change.
以上の通り１本発明によれば、水酸基を有するポリエス
テル樹脂、メチル化メラミン樹脂および沸点８０〜１５
０℃の３級アミンでブロックしたスルホン酸を特定の割
合で含有することにより、貯蔵安定性が良く、短時間で
加熱硬化して優れたちぢみ模様仕上げを行うことができ
、加工性、付着性、耐食性等が良好で、プレコートメタ
ル用として使用可能である。As described above, according to the present invention, a polyester resin having a hydroxyl group, a methylated melamine resin and a boiling point of 80 to 15
By containing a specific proportion of sulfonic acid blocked with tertiary amine at 0°C, it has good storage stability, can be heated and cured in a short time to create an excellent wrinkle pattern finish, and has good workability and adhesion. It has good corrosion resistance and can be used for pre-coated metal.
次に実施例および比較例により本発明をさらに詳細に説
明する。各例中、部は重量部を示す。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In each example, parts indicate parts by weight.
実施例１
第１表に示した配合に基づき、オイルフリーポリエステ
ル松脂として大日本インキ化学工業（株）製のベツコラ
イトト６００３−（ｉｏ（商標、不揮発分６０％）１５
０部と、メチル化メラミン樹脂として三井東圧化学（株
）製のサイメル３０３（商標）１０部と、沸点８０〜１
５０℃の３級アミンでブロックしたスルホン酸としてＮ
−メチルモルホリンでブロックしたパラ１〜ルエンスル
ホン酸０．５部とを混合し、ディシルバーにて３０分間
分散してクリヤー塗料を得た。得られた塗料をキジロー
ルを用いて塗装粘度まで希釈した。希釈粘度は、フォー
ドカップＮｕ ４を用いて２５℃で１２０秒であった。Example 1 Based on the formulation shown in Table 1, Betsucolite 6003-(io (trademark, non-volatile content 60%) 15 manufactured by Dainippon Ink and Chemicals Co., Ltd.) was used as an oil-free polyester resin.
0 parts, 10 parts of Cymel 303 (trademark) manufactured by Mitsui Toatsu Chemical Co., Ltd. as a methylated melamine resin, and a boiling point of 80 to 1
N as sulfonic acid blocked with tertiary amine at 50°C
- 0.5 part of para-1 to luenesulfonic acid blocked with methylmorpholine was mixed and dispersed for 30 minutes using a Disilver to obtain a clear paint. The resulting paint was diluted to coating viscosity using Kijiroll. Dilution viscosity was 120 seconds at 25°C using a Ford Cup Nu 4.
一方、化成処理した０ 、 ６ｍｍ Ｘ １００ｍｍ
Ｘ ２００ｍｍの亜エイ；メッキ鋼板に、プライマーと
してダイナミートノーベル社製のダイナポールＬ−２０
５（商標）をバーコーターで塗装し、２５０℃で６０秒
間力“Ｌ付けて乾燥塗膜厚５μｍのプライマー塗膜を↑
：？た。このプライマー塗装した鋼板に、上記の希釈し
たクリヤー塗料をバーコーターを用いて塗装し、２６０
℃で９０秒間焼付けて乾燥塗膜厚３５μｍを得た。On the other hand, chemically treated 0.6mm x 100mm
X 200mm sub-ray; Dynapol L-20 manufactured by Dynamite Nobel Co., Ltd. as a primer on the plated steel plate
5 (trademark) with a bar coater, apply force "L" at 250℃ for 60 seconds, and apply a primer coating with a dry coating thickness of 5μm↑
:? Ta. The above-mentioned diluted clear paint was applied to this primer-coated steel plate using a bar coater.
It was baked for 90 seconds at .degree. C. to obtain a dry film thickness of 35 .mu.m.
得られた硬化塗膜の性能を第１表に示した。The performance of the obtained cured coating film is shown in Table 1.
実施例２〜９
第１表に示した配合に基づき、実施例２〜７では、実施
例１と同様にディシルバーにて３０分間分散してクリヤ
ー塗料を得た。実施例８〜９では、オイルフリーポリエ
ステル樹脂と顔料とをペイントコンディショナーを用い
て５時間分散させた後、メチル化メラミン樹脂とＮ−メ
チルモルホリンでブロックしたスルホン酸を加え、ディ
シルバーにて３０分間分散してエナメル塗料を得た。Examples 2 to 9 Based on the formulations shown in Table 1, in Examples 2 to 7, clear paints were obtained by dispersing in a disilver for 30 minutes in the same manner as in Example 1. In Examples 8 and 9, oil-free polyester resin and pigment were dispersed using a paint conditioner for 5 hours, then methylated melamine resin and sulfonic acid blocked with N-methylmorpholine were added, and the mixture was dispersed in a dissilver for 30 minutes. Enamel paint was obtained by dispersion.
得られた塗料を実施例１と同様にキジロールを用いて実
施例１と同様の塗料粘度まで希釈し、実施例１と同様の
プライマーを亜鉛メッキ鋼板に塗装し、２５０℃で６０
秒間焼付けて乾燥塗膜厚５μｍのプライマー塗膜を得た
。このプライマー塗装した鋼板に、希釈した上記のクリ
ヤー塗料をバーコーターを用いて塗装し、２６０℃で９
０秒間焼付けて乾燥塗膜厚３５μｍを得た。The obtained paint was diluted to the same paint viscosity as in Example 1 using a kiji roll in the same manner as in Example 1, and the same primer as in Example 1 was applied to a galvanized steel plate and heated at 250°C for 60°C.
A primer coating film with a dry coating thickness of 5 μm was obtained by baking for seconds. The above-mentioned diluted clear paint was applied to this primer-coated steel plate using a bar coater, and the temperature was 90°C at 260°C.
It was baked for 0 seconds to obtain a dry coating thickness of 35 μm.
得られた硬化塗膜の性能を第１表に示した。The performance of the obtained cured coating film is shown in Table 1.
比較例１〜５
第１表に示した配合に基づき、実施例１と同様にしてク
リヤー塗料を得た。Comparative Examples 1 to 5 Clear paints were obtained in the same manner as in Example 1 based on the formulations shown in Table 1.
得られた塗料を実施例１と同様にキジロールで希釈し、
実施例１と同様のプライマーを塗装した亜鉛メッキ鋼板
上（乾燥塗膜厚５μｍ）にバーコーターで塗装した後、
２６０℃で９０秒間焼付けて乾燥塗膜厚３５μ口を得た
。The obtained paint was diluted with Kijiroll in the same manner as in Example 1,
After coating with a bar coater on a galvanized steel plate coated with the same primer as in Example 1 (dry coating thickness 5 μm),
It was baked at 260°C for 90 seconds to obtain a dry coating thickness of 35μ.
得られた硬化塗膜の性能を第１表に示した。The performance of the obtained cured coating film is shown in Table 1.
第１表において、実施例１〜３はオイルフリーポリエス
テル樹脂とメチル化メラミン樹脂との比率を変えた例で
あり、実施例４〜５はＮ−メチルモルホリンでブロック
したスルホン酸の量を変えた例である。実施例６は油変
性ポリエステル樹脂を。In Table 1, Examples 1 to 3 are examples in which the ratio of oil-free polyester resin and methylated melamine resin was changed, and Examples 4 to 5 were examples in which the amount of sulfonic acid blocked with N-methylmorpholine was changed. This is an example. Example 6 uses oil-modified polyester resin.
実施例７はシリコン変性ポリエステル樹脂を用いた例で
ある。実施例８〜９はエナメル塗料の例である。Example 7 is an example using silicone modified polyester resin. Examples 8-9 are examples of enamel paints.
第１表から明らかなように、実施例１〜９は良好なちぢ
み模様と、プレコート鋼板に必要な良好な加工性、付着
性および耐食性が得られることがわかる。As is clear from Table 1, Examples 1 to 9 provide a good crimp pattern and good workability, adhesion, and corrosion resistance required for precoated steel sheets.
それに対してメチル化メラミン樹脂が５重量部未満の比
較例１は、加工性、付着性および耐食性が劣る。またメ
チル化メラミン樹脂が４０重基部を越える比較例２は、
加工性および耐食性が劣る。On the other hand, Comparative Example 1 containing less than 5 parts by weight of methylated melamine resin has poor processability, adhesion, and corrosion resistance. Comparative Example 2, in which the methylated melamine resin exceeds 40 bases,
Poor workability and corrosion resistance.
Ｎ−メチルモルホリンでブロックしたスルホン酸の量が
０．２重量部未満の比較例３は、良好なちぢみ模様が得
られず、３重量部を越える比較例４は、耐食性が劣る。In Comparative Example 3, in which the amount of sulfonic acid blocked with N-methylmorpholine was less than 0.2 parts by weight, a good crimp pattern could not be obtained, and in Comparative Example 4, in which the amount of sulfonic acid blocked with N-methylmorpholine exceeded 3 parts by weight, corrosion resistance was poor.
そしてブチル化メラミン樹脂を用いた比較例５は、良好
なちぢみ模様が得られないことがわかる。It can be seen that in Comparative Example 5 using a butylated melamine resin, a good crimp pattern cannot be obtained.
Claims (5)
５重量部と、 （Ｂ）メチル化メラミン樹脂５〜４０重量部と、（Ｃ）
沸点８０〜１５０℃の３級アミンでブロックしたスルホ
ン酸０．２〜３重量部と を含有することを特徴とするちぢみ塗料。(1) (A) Polyester resin with hydroxyl group 60-9
5 parts by weight, (B) 5 to 40 parts by weight of methylated melamine resin, and (C)
A shrinking paint characterized by containing 0.2 to 3 parts by weight of sulfonic acid blocked with a tertiary amine having a boiling point of 80 to 150°C.
ステル樹脂、オイルフリーポリエステル樹脂またはシリ
コン変性ポリエステル樹脂である特許請求の範囲第１項
記載のちぢみ塗料。(2) The shrinking paint according to claim 1, wherein the polyester resin having hydroxyl groups is an oil-modified polyester resin, an oil-free polyester resin, or a silicone-modified polyester resin.
むものである特許請求の範囲第１項または第２項記載の
ちぢみ塗料。(3) The shrinking paint according to claim 1 or 2, wherein the methylated melamine resin contains three or more methoxy groups.
ベンゼンスルホン酸、ジノニルナフタレンジスルホン酸
、メタンスルホン酸またはジノニルナフタレンスルホン
酸である特許請求の範囲第１項ないし第３項のいずれか
に記載のちぢみ塗料。(4) The sulfonic acid according to any one of claims 1 to 3, wherein the sulfonic acid is p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, methanesulfonic acid, or dinonylnaphthalenesulfonic acid. Shrinking paint.
メチルアリルアミン、Ｎ−メチルジアリルアミン、トリ
アリルアミン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチル−１
，２−ジアミノエタン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメ
チル−１，３−ジアミノプロパン、Ｎ−メチルピペリジ
ン、またはピリジンである特許請求の範囲第１項ないし
第４項のいずれかに記載のちぢみ塗料。(5) Tertiary amine is N-methylmorpholine, N,N-dimethylallylamine, N-methyldiallylamine, triallylamine, N,N,N',N'-tetramethyl-1
, 2-diaminoethane, N,N,N',N'-tetramethyl-1,3-diaminopropane, N-methylpiperidine, or pyridine. Shrinking paint as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61016086A JPH0611879B2 (en) | 1986-01-28 | 1986-01-28 | Chijimi paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61016086A JPH0611879B2 (en) | 1986-01-28 | 1986-01-28 | Chijimi paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174276A true JPS62174276A (en) | 1987-07-31 |
| JPH0611879B2 JPH0611879B2 (en) | 1994-02-16 |
Family
ID=11906726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61016086A Expired - Fee Related JPH0611879B2 (en) | 1986-01-28 | 1986-01-28 | Chijimi paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611879B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254776A (en) * | 1988-04-04 | 1989-10-11 | Nippon Paint Co Ltd | Resin composition for coating |
| JPH02269168A (en) * | 1988-12-26 | 1990-11-02 | Nippon Steel Corp | Coating composition for coating metal plates |
| JPH0971750A (en) * | 1995-09-06 | 1997-03-18 | Kansai Paint Co Ltd | Coating composition and coated metal sheet prepared using the same |
| US6649734B2 (en) | 2001-04-23 | 2003-11-18 | Basf Corporation | Curable coating compositions having improved compatibility and scratch and mar resistance, cured coated substrates made therewith and methods for obtaining the same |
| JP2007122035A (en) * | 2005-09-28 | 2007-05-17 | Fujifilm Corp | Antireflection film, and polarizing plate and image display apparatus using same |
| US8007878B2 (en) | 2005-08-03 | 2011-08-30 | Fujifilm Corporation | Antireflection film, polarizing plate, and image display device |
| US8017242B2 (en) | 2005-09-28 | 2011-09-13 | Fujifilm Corporation | Antireflection film, polarizing plate and image display |
| WO2017186714A1 (en) | 2016-04-28 | 2017-11-02 | Akzo Nobel Coatings International B.V. | Method of forming wrinkle finish coating on a metal substrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52127927A (en) * | 1976-04-21 | 1977-10-27 | Kansai Paint Co Ltd | Thermosetting coating compositions |
| JPS58108259A (en) * | 1981-12-22 | 1983-06-28 | Nippon Kagaku Toryo Kk | High solid paint composition |
| JPS6096660A (en) * | 1983-10-31 | 1985-05-30 | Aisin Chem Co Ltd | Thick coating paint composition |
-
1986
- 1986-01-28 JP JP61016086A patent/JPH0611879B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52127927A (en) * | 1976-04-21 | 1977-10-27 | Kansai Paint Co Ltd | Thermosetting coating compositions |
| JPS58108259A (en) * | 1981-12-22 | 1983-06-28 | Nippon Kagaku Toryo Kk | High solid paint composition |
| JPS6096660A (en) * | 1983-10-31 | 1985-05-30 | Aisin Chem Co Ltd | Thick coating paint composition |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254776A (en) * | 1988-04-04 | 1989-10-11 | Nippon Paint Co Ltd | Resin composition for coating |
| JPH02269168A (en) * | 1988-12-26 | 1990-11-02 | Nippon Steel Corp | Coating composition for coating metal plates |
| JPH068400B2 (en) * | 1988-12-26 | 1994-02-02 | 新日本製鐵株式会社 | Paint composition for painted metal plates |
| JPH0971750A (en) * | 1995-09-06 | 1997-03-18 | Kansai Paint Co Ltd | Coating composition and coated metal sheet prepared using the same |
| US6649734B2 (en) | 2001-04-23 | 2003-11-18 | Basf Corporation | Curable coating compositions having improved compatibility and scratch and mar resistance, cured coated substrates made therewith and methods for obtaining the same |
| US8007878B2 (en) | 2005-08-03 | 2011-08-30 | Fujifilm Corporation | Antireflection film, polarizing plate, and image display device |
| JP2007122035A (en) * | 2005-09-28 | 2007-05-17 | Fujifilm Corp | Antireflection film, and polarizing plate and image display apparatus using same |
| US8017242B2 (en) | 2005-09-28 | 2011-09-13 | Fujifilm Corporation | Antireflection film, polarizing plate and image display |
| WO2017186714A1 (en) | 2016-04-28 | 2017-11-02 | Akzo Nobel Coatings International B.V. | Method of forming wrinkle finish coating on a metal substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0611879B2 (en) | 1994-02-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |