JPH02196876A - Coating of excellent processability and coated steel plate using same - Google Patents
Coating of excellent processability and coated steel plate using sameInfo
- Publication number
- JPH02196876A JPH02196876A JP1719589A JP1719589A JPH02196876A JP H02196876 A JPH02196876 A JP H02196876A JP 1719589 A JP1719589 A JP 1719589A JP 1719589 A JP1719589 A JP 1719589A JP H02196876 A JPH02196876 A JP H02196876A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- coating
- paint
- solvent
- crosslinking agent
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 44
- 239000010959 steel Substances 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title abstract description 55
- 239000011248 coating agent Substances 0.000 title abstract description 46
- 229920001225 polyester resin Polymers 0.000 claims abstract description 46
- 239000004645 polyester resin Substances 0.000 claims abstract description 46
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 239000003973 paint Substances 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 43
- 229920000728 polyester Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 5
- 239000010960 cold rolled steel Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000003449 preventive effect Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 239000012948 isocyanate Substances 0.000 abstract description 7
- 150000002513 isocyanates Chemical class 0.000 abstract description 7
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 239000008240 homogeneous mixture Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 description 7
- 239000008397 galvanized steel Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高加工性、高硬度および高鮮映性が要求され
る用途に使用される塗装鋼板およびそのための塗料に関
する０本発明の塗装鋼板は、例えば、家電および建材用
に好適であり、将来的には自動車用にも使用可能性があ
る。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to coated steel sheets and paints therefor used in applications requiring high workability, high hardness, and high sharpness. Steel plates are suitable for, for example, home appliances and building materials, and may also be used for automobiles in the future.
（従来の技術）
塗装鋼板（プレコート鋼板）は、ユーザーにより打ち抜
き、折り曲げ、絞りなどの加工が行われた後、そのまま
製品の外面となるため、高度の加工性および加工時の耐
傷つき性（高硬度）が要求される。(Conventional technology) Painted steel sheets (pre-painted steel sheets) are processed by the user by punching, bending, drawing, etc., and then become the outer surface of the product. hardness) is required.
しかし、塗装鋼板の製造に従来から使用されてきた溶剤
型塗料の場合、加工性と硬度は一般に両立せず、加工性
に優れた塗装鋼板は被膜が軟らかいため傷つきやすく、
硬度の高いものは加工性が劣るという傾向を示す０例え
ば、アクリル系塗料のＰＩ！膜は高硬度であるが加工性
が悪く、高分子量ポリエステル系塗料の塗膜は、加工性
は良好であるが、硬度が低いといった具合である。However, in the case of solvent-based paints traditionally used to manufacture painted steel sheets, workability and hardness are generally not compatible, and painted steel sheets with excellent workability are easily damaged due to their soft coatings.
0 For example, acrylic paint PI! The film has high hardness but poor processability, and the coating film of high molecular weight polyester paint has good processability but low hardness.
一方、近年、粉体塗料を用いた塗装鋼板（粉体プレコー
ト鋼板）も市場に出回りつつある。粉体プレコート鋼板
は、従来の溶剤型塗料を用いた塗装鋼板と比べて、硬度
と加工性とがバランス良く両立するという優れた塗膜物
性を有している。On the other hand, in recent years, coated steel sheets using powder coatings (powder pre-coated steel sheets) are also becoming available on the market. Powder pre-coated steel sheets have superior coating film properties that provide a good balance of hardness and workability, compared to steel sheets coated with conventional solvent-based paints.
第１図は、各種の代表的な塗料から得られた塗装鋼板の
鉛筆硬度と加工性（塗膜の亀裂を生じないで１８０°曲
げ可能な最少板ばさみ枚数、Ｔ＝鋼板厚み）との関係を
示す、溶剤型塗料の場合、上記のように硬度と加工性は
両立せず、アクリル系塗料では高強度、低加工性、高分
子量ポリエステル系塗料ではその逆、一般ポリエステル
系塗料（不飽和ポリエステル系塗料）では両者の中間と
いうように、硬度が高くなると加工性は低下する。Figure 1 shows the relationship between the pencil hardness and workability (minimum number of sheets that can be bent 180 degrees without cracking the coating, T = steel sheet thickness) of painted steel sheets obtained from various typical paints. As mentioned above, in the case of solvent-based paints, hardness and workability are not compatible; acrylic paints have high strength and low workability, high molecular weight polyester paints have the opposite, and general polyester paints (unsaturated polyester For paints), the higher the hardness, the lower the workability, which is somewhere between the two.
これに対し、粉体型塗料は加工性が最もよく、しかも硬
度も一般ポリエステル系塗料と同程度（鉛筆硬度的と高
く、加工性と硬度がバランスよく高水準にある。On the other hand, powder type paints have the best workability, and their hardness is on the same level as general polyester paints (as high as pencil hardness), and has a well-balanced and high level of workability and hardness.
しかし、粉体塗装によると塗膜表面の凹凸（いわゆる、
ゆず肌）が避けられないため、粉体プレコート鋼板は鏡
面に近い高鮮映性が要求される用途には使用できない。However, with powder coating, the unevenness of the coating surface (so-called
Powder-precoated steel sheets cannot be used in applications that require high image clarity close to a mirror surface because of the unavoidable appearance of citrus skin.
また、粉体プレコート鋼板の生産速度は、工業化されて
いるラインスピードで通常２０ ＋＊／ｗｉｎ以下であ
り、溶剤型塗料での生産速度６０〜８０ ｍ／ｗｉｎと
比べて生産性がはるかに劣る。粉体塗装のラインスピー
ドはわ〕体吐出ガン数や乾燥機の能力に依存するが、粉
体塗装では色替え作業に多大な時間を要するため、通常
二つの塗装ユニットを用意しなければならず、ラインス
ピードを上げるには多大な初期設備投資が必要となる。In addition, the production speed of powder pre-coated steel sheets is usually less than 20 m/win at industrial line speeds, which is far inferior to the production speed of 60 to 80 m/win for solvent-based paints. . The line speed for powder coating depends on the number of discharge guns and the capacity of the dryer, but in powder coating it takes a lot of time to change colors, so usually two coating units must be prepared. , large initial capital investment is required to increase line speed.
そのため、工業化塗装ラインではラインスピードを２０
＋ｓ／ｓｉｎ以上に上げることは困難である。Therefore, in industrial painting lines, the line speed should be increased to 20
It is difficult to increase it above +s/sin.
（発明が解決しようとする課題）
溶剤型ポリエステル系塗料の場合、基体樹脂であるポリ
エステルが溶剤に熔解しなければならないという制約が
あるため、フタル酸を酸成分として合成した溶解性の高
い（結晶性の低い）ポリエステル樹脂を使用している。(Problem to be solved by the invention) In the case of solvent-based polyester paints, there is a restriction that the base resin polyester must be dissolved in the solvent. (polyester resin with low properties) is used.
加工性と硬度とのバランスという物性面からは、分子構
造の対称性が高いテレフタル酸を酸成分として合成した
、結晶性の商いポリエステル樹脂を使用することが望ま
しい、しかし、結晶性の高いポリエステル樹脂は溶剤へ
の溶解性が著しく低いため、粉体塗料として塗料化せざ
るを得ない。しかし、粉体塗料を使用して製造された塗
装鋼板は、前記のように、ゆず肌が多く、鮮映性が悪い
上、生産性が低（、生産コストが大きいという欠点を有
している。From the viewpoint of physical properties such as the balance between processability and hardness, it is desirable to use a crystalline polyester resin synthesized from terephthalic acid, which has a highly symmetrical molecular structure, as an acid component. Because it has extremely low solubility in solvents, it has no choice but to be made into a powder coating. However, as mentioned above, coated steel sheets manufactured using powder coatings have the disadvantages of having a lot of orange skin, poor image clarity, low productivity (and high production costs). .
本発明の目的は、高加工性、高硬度で、しかも高鮮映性
の塗装鋼板を提供することである。An object of the present invention is to provide a coated steel sheet with high workability, high hardness, and high sharpness.
本発明の別の目的は、従来粉体塗料化していたようなポ
リエステル樹脂を使用して、加工性に優れた溶剤型塗料
を提供することである。Another object of the present invention is to provide a solvent-based coating material with excellent processability using a polyester resin that has conventionally been made into a powder coating material.
（課題を解決するための手段）
前述したように、テレフタル酸等の対称性の高い分子構
造を有する化合物を酸成分として合成されたポリエステ
ル樹脂は、結晶性が高く、物性が良好であるが、一般有
機溶剤にＨ？容性であるため粉体塗料化されていた。本
発明者らは、これを溶剤型塗料とするべ（、検討を重ね
た。(Means for Solving the Problems) As mentioned above, polyester resins synthesized using a compound with a highly symmetrical molecular structure such as terephthalic acid as an acid component have high crystallinity and good physical properties; H in general organic solvents? Due to its compatibility, it was made into a powder coating. The inventors of the present invention have repeatedly investigated whether this should be made into a solvent-based paint.
従来のポリエステル系粉体塗料は、結晶性の高いポリエ
ステル樹脂を架橋剤と加熱熔融し、得られた混合物を粉
末化することにより製造されている０本発明者らは、こ
の加熱溶融時に、一般有機溶剤には難溶性の粉体塗料用
ポリエステル樹脂がブロックトイソシアネートなどの架
橋剤とはよく溶解しあい、均質に相溶した溶融／８液が
得られることに着目してさらに検討を進めた結果、この
ように架橋剤と相溶した粉体塗料用ポリエステル樹脂は
、常温付近の温度で一般有機溶剤に溶解することができ
、この樹脂から溶剤型塗料を製造することができること
を見出した。Conventional polyester powder coatings are manufactured by heating and melting a highly crystalline polyester resin with a crosslinking agent and powdering the resulting mixture. As a result of further investigation, we focused on the fact that the polyester resin for powder coatings, which is poorly soluble in organic solvents, dissolves well in crosslinking agents such as blocked isocyanates, resulting in a homogeneously compatible molten/8 liquid. It has been discovered that a polyester resin for powder coatings that is compatible with a crosslinking agent in this manner can be dissolved in a general organic solvent at a temperature around room temperature, and that a solvent-based coating material can be produced from this resin.
一方、粉体塗料の塗膜表面にゆず肌が発生する原因は、
塗料粉体が加熱熔融時に凝集するためであると推定され
、実際に塗料粉体の粒径が小さい程、ゆず肌の凹凸は小
さく目立たなくなった。すなわち、基体樹脂を完全に溶
解させて分子オーダ−の大きさで存在させれば、ゆず肌
の防止には最も有効である。On the other hand, the cause of the appearance of orange skin on the surface of the powder paint film is as follows.
It is presumed that this is because the paint powder aggregates during heating and melting, and in fact, the smaller the particle size of the paint powder, the smaller and less noticeable the unevenness of the orange skin. That is, it is most effective for preventing orange skin if the base resin is completely dissolved and present in a molecular order size.
このようにして、従来は粉体塗料化していた高結晶性ポ
リエステル樹脂を溶剤型塗料として使用することにより
、物性が良好で、しかも高鮮映性の塗装鋼板を得ること
ができる。In this way, by using a highly crystalline polyester resin, which has conventionally been made into a powder coating, as a solvent-based coating, a coated steel sheet with good physical properties and high image clarity can be obtained.
ここに、本発明の要旨は、一般有機溶剤に難溶性のポリ
エステル樹脂を架橋剤と共に加熱熔融してポリエステル
樹脂と架橋剤とが均質に相溶した混合物とし、得られた
混合物を有機溶剤に溶解させることにより電溶性ポリエ
ステル樹脂を可溶化したことを特徴とする、難溶性ポリ
エステル樹脂を１０重量％以上の濃度で含有する加工性
に優れた溶剤型ポリエステル樹脂塗料にある。Here, the gist of the present invention is to heat and melt a polyester resin that is poorly soluble in general organic solvents together with a crosslinking agent to form a mixture in which the polyester resin and the crosslinking agent are homogeneously miscible with each other, and to dissolve the resulting mixture in an organic solvent. The present invention provides a solvent-type polyester resin paint with excellent processability, which contains a sparingly soluble polyester resin at a concentration of 10% by weight or more, and is characterized by solubilizing an electrolytic polyester resin by solubilizing the electrolytic polyester resin.
この塗料は、冷延鋼板もしくは亜鉛系めっき鋼板にリン
酸化成処理もしくはクロメート処理を施した後、塗布さ
れる。必要に応じて、この塗料の塗装置ｉｌに適当なフ
”ライマーを塗布してもよい。This paint is applied to a cold-rolled steel sheet or a zinc-plated steel sheet after being subjected to phosphorylation treatment or chromate treatment. If necessary, a suitable primer may be applied to the coating area of this paint.
（作用）
本発明の塗料に使用するポリエステル樹脂は、−１有ｉ
溶剤に難溶性のもの、すなわち高結晶性ポリエステル樹
脂である。(Function) The polyester resin used in the paint of the present invention is -1
It is a highly crystalline polyester resin that is poorly soluble in solvents.
本明細書において、一般有機溶剤とは、溶解度パラメー
タが７．５〜１１．５の範囲内のものを意味する。この
ような溶剤の例には、トルボン、キソレン、酢酸セロソ
ルブ、酢酸ブチル、シクロヘキサノン、メチルエチルケ
トン、イソホロン（ソルヘソソ：登録商標）等の塗料用
シンナーとして使用されている溶剤がある。In this specification, a general organic solvent means one having a solubility parameter within the range of 7.5 to 11.5. Examples of such solvents include solvents used as paint thinners such as Torbone, xolene, cellosolve acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and isophorone (Solhesoso®).
また、難溶性とは、室温付近（１０〜３５℃）の温度で
溶剤中での溶解度が１０重量％未満であることを意味す
る。基体樹脂が室温付近で溶剤にＩＯ重景気以上の濃度
で熔解する場合には、溶剤に直接熔解することにより溶
剤型塗料を製造でき、本発明の方法を採用する必要がな
い。また、このような可溶性のポリエステル樹脂は、上
述したように硬度と加工性のバランスが悪い。Moreover, poorly soluble means that the solubility in a solvent is less than 10% by weight at a temperature around room temperature (10 to 35°C). If the base resin is dissolved in a solvent at a concentration higher than IO at around room temperature, a solvent-based paint can be produced by directly dissolving it in a solvent, and there is no need to employ the method of the present invention. Furthermore, such soluble polyester resins have a poor balance between hardness and processability, as described above.
本発明で使用するのに通した難溶性のポリエステル樹脂
は、上述したように粉体塗料に使用されるポリエステル
樹脂であり、これは、例えば酸成分としてテレフタル酸
、アジピン酸、セバシン酸など、グリコール成分として
エチレングリコール、ジエチレングリコール、ネオペン
チルグリコールなどを原料として合成された、分子量が
約３０００〜２０．０００のポリエステル樹脂である。The poorly soluble polyester resin used in the present invention is a polyester resin used in powder coatings as described above, and includes glycols such as terephthalic acid, adipic acid, and sebacic acid as acid components. It is a polyester resin with a molecular weight of about 3000 to 20,000, synthesized using ethylene glycol, diethylene glycol, neopentyl glycol, etc. as raw materials.
本発明においては、このＫｌ ？ｔｊ性ポリエステル樹
脂を架橋剤と加熱溶融することにより、ポリエステル樹
脂と架橋剤とが互いに均質に相溶した７８融？容液を得
る。In the present invention, this Kl? By heating and melting the TJ polyester resin and the crosslinking agent, the polyester resin and the crosslinking agent are homogeneously compatible with each other. Obtain the liquid.
架橋剤としては、熱硬化型ポリエステル系粉体塗料の製
造に利用されている架橋剤を使用できる。As the crosslinking agent, a crosslinking agent used in the production of thermosetting polyester powder coatings can be used.
好適な架橋剤の例は、ε−カプロラクタム、フェノール
等でブロックされたブロックトイソシアネート；ならび
にメチルアルコール、ブチルアルコール等で変性された
メラミンなどである。Examples of suitable crosslinking agents include blocked isocyanates blocked with ε-caprolactam, phenol, etc.; and melamine modified with methyl alcohol, butyl alcohol, etc.
ポリエステル樹脂と架橋剤との混合割合は特に限定され
ないが、顎外ｌ容融後にポリエステル樹脂を溶解でき、
かつ溶剤に溶解した時に常温付近でポリエステル樹脂が
１０重項九以上の濃度で溶解するような量で架橋剤を使
用する必要がある。また、架橋剤が多くなりすぎると、
ポリエステル樹脂の可溶化は容易となるが、得られた塗
料の硬度が高くなりすぎ、加工性が低下することがある
。適当な架橋剤の使用輩は、基体樹脂、架橋剤および溶
剤の種類より異なり、実験により適宜決定することがで
きるが、通電はポリエステル樹脂１００重量部に対して
架橋剤１０〜４０重量部、好ましくは２０〜３０重量部
の範囲内である。The mixing ratio of the polyester resin and the crosslinking agent is not particularly limited, but it is possible to dissolve the polyester resin after melting the jaw.
Further, it is necessary to use the crosslinking agent in an amount such that when dissolved in a solvent, the polyester resin dissolves at a concentration of 10 doublets or more at around room temperature. Also, if there is too much crosslinking agent,
Although the polyester resin can be easily solubilized, the hardness of the resulting coating material may become too high and processability may be reduced. The appropriate amount of crosslinking agent to be used varies depending on the type of base resin, crosslinking agent, and solvent, and can be appropriately determined by experiment, but the current is preferably 10 to 40 parts by weight of the crosslinking agent per 100 parts by weight of the polyester resin. is within the range of 20 to 30 parts by weight.
ポリエステル樹脂と架橋剤の加熱）８融は、ポリエステ
ルの融点以上で、かつ使用する架橋剤の架橋開始温度以
下、例えば、ブロックトイソシアネートの解離温度以下
あるいはメラミン樹脂の自己縮合開始温度以下の温度で
行う。加熱は、ポリエステル樹脂と架橋剤とが溶解しあ
い、均質な溶融溶液状の混合物が得られるまで続ける。Heating of polyester resin and crosslinking agent) 8) Melting is at a temperature above the melting point of the polyester and below the crosslinking initiation temperature of the crosslinking agent used, for example, below the dissociation temperature of blocked isocyanate or below the self-condensation initiation temperature of melamine resin. conduct. Heating is continued until the polyester resin and crosslinking agent dissolve into each other and a homogeneous molten solution mixture is obtained.
こうして得られた溶融溶液を冷却し、固化した混合物を
、好ましくは溶剤に溶解しやすい大きさにわ）砕後、上
述したような１種もしくは２種以上の一般有機溶剤に溶
解すると、本発明の溶剤型塗ｔ４が得られる。必要によ
り、顔料、消泡剤、レベリング剤、分散剤などの慣用の
塗料添加剤を添加する。これらの添加剤は、溶剤に添加
するのではなく、例えば、ポリエステル樹脂と架橋剤と
の加熱溶融前に一方の成分に混合しておくこともできる
。The molten solution obtained in this manner is cooled, the solidified mixture is crushed (preferably into a size that is easily soluble in a solvent), and then dissolved in one or more general organic solvents as described above. A solvent-based coating t4 is obtained. If necessary, conventional paint additives such as pigments, defoamers, leveling agents, dispersants, etc. are added. Rather than being added to the solvent, these additives may be mixed into one of the components, for example, before the polyester resin and the crosslinking agent are heated and melted.
なお、市販の熱硬化型ポリエステル系粉体塗料は、−ｇ
に高結晶性で難溶性のポリエステル樹脂とブロックトイ
ソシアネートもしくは変性メラミンなどの架橋剤に、場
合により顔料を加えて加熱溶融させた後、粉砕して粉末
化したものであるので、このような粉体塗料を溶剤と混
合し、樹脂および架橋剤を溶剤に溶解させることによっ
ても、本発明の溶剤型塗料を得ることができる。In addition, commercially available thermosetting polyester powder coatings are -g
This type of powder is made by adding a pigment to a highly crystalline and poorly soluble polyester resin and a crosslinking agent such as blocked isocyanate or modified melamine, heating and melting the mixture, and then pulverizing it into a powder. The solvent-based paint of the present invention can also be obtained by mixing the body paint with a solvent and dissolving the resin and crosslinking agent in the solvent.
溶剤の使用量は、ポリエステル樹脂を完全に熔解でき、
しかもポリエステル樹脂の濃度が１０重量％以上となる
ような量とする。ポリエステルの重量濃度が１０％未満
であると、得られた溶剤型塗料をロールコートした場合
に、有用な膜厚１０μｍ以上の塗膜を形成させることは
通常困難である。これは、基体樹脂濃度がこのように低
いと、未乾燥膜厚が大きくなりすぎて、乾燥時にオーブ
ン内の熱風によりさざ波を生じ、塗装外観が著しく低下
してしまうためである。The amount of solvent used is such that the polyester resin can be completely melted.
Moreover, the amount is such that the concentration of the polyester resin is 10% by weight or more. When the weight concentration of polyester is less than 10%, it is usually difficult to form a useful coating film with a thickness of 10 μm or more when the resulting solvent-based coating material is roll coated. This is because if the base resin concentration is so low, the undried film thickness becomes too large, causing ripples due to the hot air in the oven during drying, which significantly deteriorates the painted appearance.
本発明の溶剤型塗料は、従来は粉体塗料化されていた物
性の良好な高結晶性の１ｌＫＦ性ポリエステルを基体樹
脂として含有するため、従来の各種の溶剤型塗料と比べ
て硬度と加工性とのバランスが良好であり、しかも溶剤
型であるため粉体塗装の欠点である生産性の悪さや塗膜
表面のゆず肌発生を改善できるものである。The solvent-based paint of the present invention contains high-crystalline 11KF polyester with good physical properties, which was conventionally made into powder paint, as a base resin, so it has better hardness and processability than various conventional solvent-based paints. Moreover, since it is a solvent-based coating, it can improve the disadvantages of powder coating, such as poor productivity and the appearance of orange skin on the coating surface.
本発明によれば、この塗料を冷延鋼板もしくは亜鉛系メ
ッキ鋼板に塗布し、塗膜を加熱硬化させることにより、
高加工性、高硬度、かつ高鮮映性の塗装鋼板を得ること
力１できる。According to the present invention, by applying this paint to a cold-rolled steel plate or a zinc-plated steel plate and curing the coating film by heating,
It is possible to obtain coated steel sheets with high workability, high hardness, and high sharpness.
亜鉛系メッキ鋼板としては、電気メッキもしくは溶融メ
ッキにより得られた純亜鉛メッキ鋼板および亜鉛合金メ
ッキ鋼板、さらには合金化溶融亜鉛メッキ鋼板が含まれ
る。Examples of zinc-based plated steel sheets include pure galvanized steel sheets and zinc alloy plated steel sheets obtained by electroplating or hot-dip plating, as well as alloyed hot-dip galvanized steel sheets.
本発明の塗料を塗布する前に、母材鋼板を慣用のリン酸
塩化成処理およびクロメート処理の少なくとも一方によ
り下地処理することが好ましい。Before applying the coating material of the present invention, it is preferable to subject the base steel plate to a base treatment by at least one of conventional phosphate chemical treatment and chromate treatment.
この下地処理をしないと、良好な塗膜密着性が得られな
いことがある。If this base treatment is not performed, good coating film adhesion may not be obtained.
また、特に高い耐食性が要求される場合には、前記下地
処理の後、防錆顔料が添加されたプライマーを塗布する
こともできる。このようなブライマーとしては、エポキ
シ系またはポリエステル系のものが適している。Furthermore, if particularly high corrosion resistance is required, a primer containing a rust-preventing pigment may be applied after the above-mentioned surface treatment. Epoxy-based or polyester-based brimers are suitable as such brimers.
本発明の塗料は、ロールコート、スプレーなど通常の方
法で塗布できる。塗布後、オープンなどの加熱手段によ
り塗膜を焼付け、樹脂を架橋させて硬化塗膜を得る。こ
の加熱は、通常は温度１８０〜２５０℃で約１〜３分行
う０本発明の塗装鋼板は、このようにして形成した膜厚
１〇−以上、通常は１０〜２５／Ｊ６の硬化塗膜を有す
る。The paint of the present invention can be applied by a conventional method such as roll coating or spraying. After coating, the coating film is baked by a heating means such as an open oven, and the resin is crosslinked to obtain a cured coating film. This heating is normally carried out at a temperature of 180 to 250°C for about 1 to 3 minutes. has.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
なお、％および部は、特に指定しない限り、重量％およ
び重量部を意味する。Note that % and parts mean % by weight and parts by weight unless otherwise specified.
大嵐拠土
溶剤難溶性ポリエステル樹脂（東洋紡製パイロンＧＭ９
００、融点８０〜９０℃、主としてエチレングリコール
とテレフタル酸とのポリエステル）のベレフ）１００部
に二酸化チタン顔料（石原産業製Ｒ８２０） ４０部を
添加し、この混合物を１００〜１２０℃に加熱して樹脂
を溶融させ、約１５〜３０分間混練する。その後、架橋
剤としてブロックトイソシアネート （大日本インキ製
バーノックＴｌ−５５０、オキムによりブロック）を２
０部添加した後、さらに同じ温度で約１５〜３０分間混
練して、樹脂と架橋剤が均質に相溶した溶融溶液を得た
。Dairan Soil Solvent Slightly Soluble Polyester Resin (Toyobo Pylon GM9
40 parts of titanium dioxide pigment (R820 manufactured by Ishihara Sangyo Co., Ltd.) was added to 100 parts of Beref (polyester with a melting point of 80-90°C, mainly ethylene glycol and terephthalic acid), and the mixture was heated to 100-120°C. Melt the resin and knead for about 15-30 minutes. Then, blocked isocyanate (Dainippon Ink Co., Ltd. Burnock Tl-550, blocked by Okim) was added as a crosslinking agent.
After adding 0 part, the mixture was further kneaded at the same temperature for about 15 to 30 minutes to obtain a molten solution in which the resin and the crosslinking agent were homogeneously dissolved.
この溶融溶液を室温に冷却した後、得られた混合物を溶
剤に溶解しやすいように約５００−に粉砕し、シクロへ
キサノン／ツルペッツ１５０の容量比で１／１の混合溶
媒に溶解し、固形分濃度５０％の溶剤型塗料Ａを作成し
た。その際の溶解性は良好であった。なお、この塗料Ａ
のポリエステル樹脂濃度は３１％である。After cooling this molten solution to room temperature, the resulting mixture was pulverized to about 500 ml to make it easy to dissolve in the solvent, and dissolved in a mixed solvent of cyclohexanone/Tsurupez 150 in a volume ratio of 1/1 to form a solid. A solvent-based paint A with a concentration of 50% was prepared. The solubility at that time was good. Furthermore, this paint A
The polyester resin concentration of is 31%.
溶融亜鉛メッキ鋼板（０，５ｍｍ厚、片面当たり付着量
６０ ｇ／ｍ”）に、リン酸亜鉛系下地処理を施した基
材の上に、上記塗料Ａをロールコートしく乾燥膜厚１５
ｓ） 、温度２５０℃で２分間の焼付により塗膜を硬化
させ、塗装鋼板試料（ア）を得た。The above paint A was roll coated onto a hot-dip galvanized steel sheet (0.5 mm thick, coating amount per side 60 g/m") with a zinc phosphate base treatment to a dry film thickness of 15.
s) The coating film was cured by baking at a temperature of 250° C. for 2 minutes to obtain a coated steel plate sample (A).
また、上記と同様に溶融亜鉛メッキ鋼板の上にリン酸亜
鉛系下地処理を施した後、市販の溶剤型エポキシ変性ポ
リエステル樹脂塗料（日本ペイント製フレキコート１１
０）を使用して、乾燥膜厚８声のプライマー皮膜を形成
させた後、塗料Ａを試験片（ア） と同様の条件で塗装
し、塗装鋼板試料（イ）を得た。In addition, after applying a zinc phosphate base treatment to a hot-dip galvanized steel sheet in the same manner as above, a commercially available solvent-based epoxy-modified polyester resin paint (Flexicoat 11 manufactured by Nippon Paint Co., Ltd.) was applied.
0) to form a primer film with a dry film thickness of 8 tones, paint A was applied under the same conditions as the test piece (A) to obtain a coated steel plate sample (B).
裏隻涯ｌ
市販の粉体塗料Ｂ（日本油脂型コナンク１６００Ｇ）を
シクロヘキサノン／ツルペッツ１５０（容量比で１／１
）の混合溶媒に溶解し、固形分濃度５０％の溶剤型塗料
Ｂ°を得た。この場合も溶解性は良好であった。実施例
１と同様に下地処理した溶融亜鉛メッキ鋼板上に塗料Ｂ
°を２０−ずつ２回ロールコートし、初回は２３０℃、
２回目は２５０℃でそれぞれ２分づつ焼付けを行って、
膜厚４０−の！！！装鋼板試料（つ）を得た。On the other hand, commercially available powder paint B (NOF type Conanc 1600G) was mixed with cyclohexanone/Tsurupez 150 (volume ratio 1/1).
) to obtain a solvent-based paint B° with a solid content concentration of 50%. In this case as well, solubility was good. Paint B was applied on a hot-dip galvanized steel sheet that had been prepared in the same manner as in Example 1.
Roll coated twice at 20 °C, first time at 230 °C,
The second time, bake at 250℃ for 2 minutes each time.
Film thickness 40-mm! ! ! A steel plate sample (one) was obtained.
ｌ較■上
市販の粉体塗料Ｂを実施例１と同様に下地処理した溶融
亜鉛メッキ鋼板上に静電粉体塗装し、膜厚約４０／Ｊｌ
の塗装鋼板試料（１）を得た。焼付は２５０℃で２分間
行った。Comparison ■ Commercially available powder coating B was electrostatically powder coated on a hot-dip galvanized steel sheet that had been prepared in the same manner as in Example 1, and the film thickness was approximately 40/Jl.
A coated steel plate sample (1) was obtained. Baking was performed at 250°C for 2 minutes.
ル較■１
実施例１の試料（イ）の作製と同様に溶融亜鉛メッキ鋼
板を下地処理し、次いで市販のエポキシ変性ポリエステ
ル塗料から乾燥膜厚８−のプライマー皮膜を設けた。そ
の上に溶剤型高分子量ポリエステル塗料Ｃ（日本ペイン
ト製フレキコート２００）の乾燥膜厚１５−の塗膜をロ
ールコートによりにより形成させて（ｆｉＮ膜乾燥：２
３０℃で７０秒間）、塗装鋼板試料（オ）を得た。Comparison 1 A hot-dip galvanized steel sheet was subjected to surface treatment in the same manner as in the preparation of sample (a) of Example 1, and then a primer film with a dry film thickness of 8 mm was applied from a commercially available epoxy-modified polyester paint. On top of that, a coating film of solvent-based high molecular weight polyester paint C (Flexicoat 200 manufactured by Nippon Paint Co., Ltd.) with a dry film thickness of 15 mm was formed by roll coating (fiN film drying: 2
(at 30° C. for 70 seconds) to obtain a coated steel plate sample (E).
得られた各塗装鋼板の加工性、硬度、および表面仕上が
りについて調べた。加工性は、同じ塗装鋼板の試験片２
枚の間に同じ厚み（０，５ｅｕ＋）の鋼板をはさんで１
８０度に折り曲げ、亀裂の生じない最少の板ばさみ枚数
にて評価した。鉛筆硬度はキズの付かない最高硬さを表
示した０表面仕上がりは目視により評価した。結果を第
１表に示す。The workability, hardness, and surface finish of each coated steel plate obtained were investigated. Workability was measured using test piece 2 of the same painted steel plate.
A steel plate of the same thickness (0.5eu+) is sandwiched between the sheets.
The board was bent at an angle of 80 degrees and evaluated using the minimum number of board scissors that would not cause cracks. The pencil hardness was 0, which indicated the maximum hardness without scratches.Surface finish was evaluated visually. The results are shown in Table 1.
第１表
第１表より、本発明のポリエステル系塗料（すなわち、
粉体塗料用のポリエステル樹脂を溶剤型塗料としたもの
）により得られた塗装鋼板は、加工性、硬度、表面仕上
がりのすべてに関して良い結果が得られた。これに対し
、粉体塗料のままでは、塗膜表面がゆず肌となり、一方
市販の溶剤型ポリエステル樹脂では、物性が加工性およ
び硬度のいずれも低かった。Table 1 From Table 1, the polyester paint of the present invention (i.e.
The coated steel sheet obtained by using a polyester resin for powder coating as a solvent-based coating showed good results in terms of workability, hardness, and surface finish. On the other hand, when the powder coating was used as it was, the coating surface had an orange-like texture, while when using a commercially available solvent-based polyester resin, the physical properties were low in both processability and hardness.
（発明の効果）
本発明によると、物性がよいにもかかわらず常温付近で
一般有機溶剤にｌｄｌ溶性であったため粉体塗料化され
ていた高結晶性法リエステル樹脂を、架橋剤とともに溶
融することで溶剤に可溶化させて、溶剤型塗料として使
用することが可能となる。(Effects of the Invention) According to the present invention, a highly crystalline polyester resin, which had been made into a powder coating because it was ldl-soluble in general organic solvents at around room temperature despite its good physical properties, can be melted together with a crosslinking agent. It can be solubilized in a solvent and used as a solvent-based paint.
そのため、本発明の塗料は従来の溶剤型塗料と同様に取
扱いが容易で、これを母材鋼板に塗布すると、ゆず肌が
なく、しかも高加工性で高硬度の塗装鋼板を得ることが
できる。Therefore, the paint of the present invention is easy to handle in the same way as conventional solvent-based paints, and when applied to a base steel plate, it is possible to obtain a coated steel plate with no orange peel, high workability, and high hardness.
また、本発明の塗装鋼板は、粉体塗装による塗装鋼板に
比べて、高い生産速度で製造でき、したがって生産コス
トの低減が可能となる。Moreover, the coated steel sheet of the present invention can be manufactured at a higher production rate than a coated steel sheet using powder coating, and therefore production costs can be reduced.
第１図は、各種塗料から得られた塗装鋼板の鉛筆硬度と
加工性の関係を示す図である。FIG. 1 is a diagram showing the relationship between pencil hardness and workability of coated steel plates obtained from various paints.
Claims (3)
剤と共に加熱溶融してポリエステル樹脂と架橋剤とが均
質に相溶した混合物とし、得られた混合物を有機溶剤に
溶解させることにより難溶性ポリエステル樹脂を可溶化
したことを特徴とする、難溶性ポリエステル樹脂を１０
重量％以上の濃度で含有する加工性に優れた溶剤型ポリ
エステル樹脂塗料。(1) A polyester resin that is poorly soluble in general organic solvents is heated and melted together with a crosslinking agent to form a mixture in which the polyester resin and the crosslinking agent are homogeneously miscible with each other, and the resulting mixture is dissolved in an organic solvent to produce a poorly soluble polyester resin. 10 slightly soluble polyester resins characterized by solubilized resins.
A solvent-based polyester resin paint with excellent processability containing a concentration of % by weight or more.
酸塩処理およびクロメート処理の少なくとも一方により
形成された下地化成皮膜と、請求項１記載の塗料から形
成された硬化塗膜とを有する、加工性に優れた塗装鋼板
。(2) A base chemical conversion film formed by at least one of phosphate treatment and chromate treatment on the surface of a cold-rolled steel sheet or a zinc-based plated steel sheet, and a cured paint film formed from the paint according to claim 1. , painted steel plate with excellent workability.
するエポキシ系もしくはポリエステル系のプライマーか
ら形成された皮膜を有する、請求項２記載の塗装鋼板。(3) The coated steel sheet according to claim 2, further comprising a film formed from an epoxy or polyester primer containing a rust preventive pigment between the base chemical conversion film and the paint film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1719589A JPH02196876A (en) | 1989-01-26 | 1989-01-26 | Coating of excellent processability and coated steel plate using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1719589A JPH02196876A (en) | 1989-01-26 | 1989-01-26 | Coating of excellent processability and coated steel plate using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02196876A true JPH02196876A (en) | 1990-08-03 |
Family
ID=11937151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1719589A Pending JPH02196876A (en) | 1989-01-26 | 1989-01-26 | Coating of excellent processability and coated steel plate using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02196876A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745709A (en) * | 2020-01-13 | 2021-05-04 | 万辉(广州)高新材料有限公司 | Art powder coating with snakeskin effect and preparation method thereof |
-
1989
- 1989-01-26 JP JP1719589A patent/JPH02196876A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745709A (en) * | 2020-01-13 | 2021-05-04 | 万辉(广州)高新材料有限公司 | Art powder coating with snakeskin effect and preparation method thereof |
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