WO1998009809A1 - Tole d'acier inox revetue d'une couche protectrice alcalino-soluble - Google Patents

Tole d'acier inox revetue d'une couche protectrice alcalino-soluble Download PDF

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Publication number
WO1998009809A1
WO1998009809A1 PCT/JP1996/002533 JP9602533W WO9809809A1 WO 1998009809 A1 WO1998009809 A1 WO 1998009809A1 JP 9602533 W JP9602533 W JP 9602533W WO 9809809 A1 WO9809809 A1 WO 9809809A1
Authority
WO
WIPO (PCT)
Prior art keywords
stainless steel
acrylic resin
steel sheet
film
epoxy
Prior art date
Application number
PCT/JP1996/002533
Other languages
English (en)
Japanese (ja)
Inventor
Yukio Uchida
Keiji Izumi
Hirohumi Taketsu
Masaya Yamamoto
Tsuyoshi Masuda
Original Assignee
Nisshin Steel Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to JP62082528A priority Critical patent/JPS63247503A/ja
Priority to JP08465195A priority patent/JP3305913B2/ja
Application filed by Nisshin Steel Co., Ltd. filed Critical Nisshin Steel Co., Ltd.
Priority to CA002236006A priority patent/CA2236006A1/fr
Priority to DE69635454T priority patent/DE69635454T2/de
Priority to KR10-1998-0703338A priority patent/KR100429651B1/ko
Priority to EP96929542A priority patent/EP0862993B1/fr
Priority to AU68900/96A priority patent/AU721321B2/en
Priority to ES96929542T priority patent/ES2252757T3/es
Priority to PCT/JP1996/002533 priority patent/WO1998009809A1/fr
Priority to CN96199480A priority patent/CN1102499C/zh
Publication of WO1998009809A1 publication Critical patent/WO1998009809A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

  • the present invention relates to a stainless steel sheet coated with a protective film, which has an excellent anti-galling property at the time of press working and which can remove the protective film with a solution after press working.
  • Stainless steel sheets are excellent in corrosion resistance and appearance, and as such are found in kitchen equipment and building materials, for many applications, the skin unique to stainless steel sheets is used as it is.
  • stainless steel sheets have the drawback that they are extremely noticeable even on a part of the surface where the surface condition changes. For this reason, when manufacturing a member that uses the surface of a stainless steel plate as it is by pressing, a protective film of polyvinyl chloride resin should be attached to prevent galling of the steel plate surface due to the mold. I was In addition, since the protective film of vinyl chloride resin has insufficient lubricity and workability, it is processed by applying press oil on the protective film and then peeling off the protective film by hand, like trichloroethane. The surface of the processed product was cleaned with a chlorinated solvent or an aqueous solution.
  • the protective film made of vinyl chloride resin has insufficient lubricating properties, partial film breakage may occur during pressing of stainless steel sheets, causing galling on the steel sheet surface.
  • removing the protective film by hand requires a lot of labor, time and cost, and the part that has been ironed by the application is firmly adhered to the stainless steel plate, so that the film may be peeled off at the time of peeling. Torn or left without peeling There was a part. Therefore, in order to prevent the film from breaking during peeling as much as possible, the protective film was conventionally thickened.However, since the protective film must be thicker even on a machine that manufactures components that are not severely pressed. The material costs were getting higher. In addition, the application and removal of press oil will worsen the working environment.
  • an aqueous solution or aqueous dispersion of an alkaline soluble resin composition containing an acrylic resin as a main component is made of stainless steel sheet.
  • a method has been proposed in which an acrylic resin is applied to form a protective film of an acrylic resin. Since the stainless steel plate on which the protective film is formed by this method is processed into a member and then treated with an alkaline solution to dissolve and remove the protective film, there is no need to remove the protective film. For this reason, the protective film can be firmly adhered to the stainless steel plate so that peeling does not occur during press working, and galling does not occur. Also, since the entire protective film is dissolved with an alkaline solution, there is no residual protective film.
  • This soluble composition is prepared by adjusting the acid value of an acrylic resin to make it soluble.However, the adhesion to a protected object is controlled by a glass transition temperature.
  • a method of denaturing with another resin oligomer or prepolymer is known.
  • an acid value of 40 to 400 on the surface of the stainless steel sheet and a glass transition temperature of 110 ° C The lower film of acrylic resin with a temperature of 30 ° C is 1 to 60, and the acrylic resin with an acid value of 4 () to 400 and a glass transition temperature of 40 to 80 ° C.
  • An upper layer film of 3 to 60 m is sequentially formed, and the total thickness of the upper and lower layer films is 5 to: L 0 0 ⁇ (refer to Japanese Patent Application Laid-Open No. Hei 8-1556177). Gazette).
  • This protective film increases adhesion and alkali solubility in a single film, increasing the adhesiveness of the film, creating a base on which stainless steel steel sheets are stacked, blocking, and the resistance during press working. Since the galling property is also insufficient, the glass transition temperature of the lower layer coating was made lower than that of the upper layer coating in a state where the lower and upper layer coatings were made soluble in alkali, thereby improving the adhesion to the stainless steel sheet. However, due to insufficient adhesion and strength of the coating, there was a platform where galling occurred if pressing was severe. In addition, since the protective film is a disposable material that is removed after pressing, it is economically preferable to reduce the film thickness. However, since the film strength is weak, it has been difficult to reduce the thickness to less than 5 m.
  • composition in which an acrylic resin is modified with an oligomer or prepolymer of another resin to improve the adhesion at least one active compound in the molecule with the acrylic resin is used.
  • a prepolymer having a polyisocyanate group and a block dosocyanate group After reacting a prepolymer having a polyisocyanate group and a block dosocyanate group to obtain a block isocyanate-containing acrylic resin, water is added, and then an amino group-containing compound is added.
  • Acryl-urethane resins reacted with block isocyanate-containing acrylic resins are known (refer to Japanese Patent Application Laid-Open No. Hei 4-328173).
  • Another object of the present invention is to provide a stainless steel sheet coated with an Al-soluble type protective coating, which does not generate a grit on the stainless steel sheet even if the film thickness is reduced.
  • Still another object of the present invention is to provide an alkali-soluble protective coating-coated stainless steel sheet having a uniform thickness even when the thickness is 3 m or less.
  • the protective coating-coated stainless steel sheet of the present invention is obtained by adding an acrylic resin having an acid value of 40 to 300 and a glass transition temperature of 0 ° C to 2 CTC to the surface of the stainless steel sheet with a molecular weight of 500 to An epoxy-modified acrylic resin underlayer film modified with 3 to 20% by mass of epoxy () epoxy resin, an acid value of 40 to 300, and a glass transition temperature of 40 ° C to 80 ° C.
  • An upper layer of acrylic resin at a temperature of ° C is sequentially formed, and the total thickness of the upper and lower layers is 1 to 20 / m.
  • the protective film In order to impart film adhesion and alkali solubility to the protective film, it is preferable to form the protective film into a two-layer structure as described in Japanese Patent Application Laid-Open No. 8-156.177. Therefore, as a result of various studies to improve the galling resistance during press working, it was found that the galling resin was modified with epoxy to improve the galling resistance.
  • Table 1 shows that the acid value and the glass transition temperature are 100 and 100 ° C, respectively, obtained by copolymerizing various components of methyl methacrylate, butyl acrylate, and methacrylic acid.
  • Epoxy-modified acrylic resin obtained by reacting epoxy resin with different molecular weights to the acrylic resin is applied to the surface of stainless steel plate, dried, and the solubility of the film in the aqueous alkali solution, film adhesion, Force and molecular weight of 500 to 200,000
  • the use of an epoxy-modified acrylic resin modified with an epoxy oligomer improves the galling resistance.
  • the test method and evaluation method of the film physical properties in Table 1 were based on the method described in Example 1 described later.
  • Epoxy polyol is modified by mass%.
  • the acid value of The lower layer should be an epoxy-modified acrylic resin film with a low glass transition temperature, with an epoxy-modified amount of 3 to 20% by mass, and the upper layer should be a high acrylic resin film. This harmonized the aqueous solution solubility, galling resistance and blocking resistance of the coating.
  • the underlayer coating of the present invention has an acid value of 40 to 300 and a glass transition temperature of 0 to 20.
  • the C-acrylic resin is converted to an epoxy-modified acrylic resin film in which the epoxy resin is modified by 3 to 20% by mass with an epoxy oligomer, but the acid value of 40 to 300 is less than 40. If so, it is difficult to dissolve and remove with an aqueous alkali solution, and if it exceeds 300, the strength of the film decreases, and the film may be scraped off during processing.
  • the acid value is preferably in the range of 100 to 300.
  • the acid value refers to the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of acrylic resin. Further, the reason why the glass transition temperature is set to 0 to 20 nC is that if the temperature is lower than 0 ° C, the film hardness at room temperature becomes insufficient and the galling resistance is reduced. This is because high adhesion cannot be obtained, and when the temperature is 10 to 20 ° C., the anti-blocking property is further improved.
  • the reason why the molecular weight of the epoxy oligomer of the acrylic resin-modified ffl is set to 500 to 200 is that if the molecular weight is less than 500, the galling resistance is insufficient and exceeds 200. This is because alkali solubility is impaired.
  • the reason why the epoxy modification amount is set to 3 to 20% by mass is that if it is less than 3% by mass, sufficient anti-galling property cannot be obtained, and if it exceeds 20% by mass, alkali solubility is impaired. Because. In order to balance galling resistance and dissolution resistance, the molecular weight of the epoxy oligomer should be 800 to 1200, the amount of modification Is preferably 3 to 10% by mass.
  • an epoxy oligomer having a molecular weight of 500 to 2000 There are various methods to perform the reaction, but a typical method is to first synthesize an acrylic resin having an acid value of 40 to 300 and a glass transition temperature of 0 to 20 ° C, and then to obtain a molecular weight. Is added to the epoxy resin of 5 () 0 to 2000, heated to around 100 ° C after addition of the amine, and reacted with the epoxy resin of the epoxy resin.
  • the polymerization is carried out while dropping the acrylic monomer. There is a method of mounting.
  • a carboxylic acid compound having an unsaturated bond for example, acrylic acid, methacrylic acid, maleic anhydride or unsaturated fatty acid
  • the upper film has an acid value of 40 to 300 and a glass transition temperature of 40 ° C to 80 °.
  • the acrylic resin of C is used.
  • the acid value of 40 to 300 is the same as that for the underlayer coating.
  • the glass transition temperature is 40. C ⁇ 80.
  • the reason for setting the temperature to C is that if the temperature is lower than 40 ° C, the temperature in the factory will rise to nearly 40 ° C in summer, and if the temperature increases, the film will become sticky. (If it is higher than TC, the film becomes brittle and there is a base where cracking and peeling occur during film formation.
  • the thickness of the lower layer coating and the upper layer coating is less than l; tm, it will not be possible to prevent stiffness on the surface of the steel plate during pressing, and if it exceeds 20 / m, it will be scraped off by the mold. Significant increases in the amount of coating require frequent maintenance of the mold, reducing productivity. For this reason, it is desirable that the thickness be 1 to 20 ⁇ m, preferably 1 to 5 ⁇ m. When the glass transition temperature of the lower film is low, the upper film is more than half of the lower film. When the thickness is set to, the blocking resistance becomes good.
  • FIG. 1 is a cross-sectional view of a mold for a draw bead test used in Example 1 for a galling resistance test of a film.
  • the acrylic resin for the lower and upper coatings may include acrylic acid and / or methacrylic acid polymerization or copolymers or acrylates and methacrylates as required for these monomers.
  • a polymer obtained by copolymerizing the above compounds and adjusting the acid value and the glass transition temperature according to the amount of polymerization, the component of the copolymer, etc. may be used.
  • the (meth) acrylic acid ester includes methyl (meth) acrylate and ethyl (meta) acrylate.
  • the copolymerizable monomer may further include a monomer copolymerizable with (meth) acrylic acid ester, for example, styrene, acrylonitrile, acrylamide, butadiene, vinyl acetate, and the like. .
  • the lubricating property is improved, processing can be performed without oiling, the oiling and degreasing steps can be omitted, and the galling resistance is also reduced. improves.
  • the addition amount of the fat powder is less than 1% by mass, the lubricating property is inferior to that when the press oil is applied,
  • the addition amount is preferably set to 1 to 25% by mass, and more preferably 1 to 10% by mass in consideration of the long-term stability of the processing solution.
  • the average particle size of the resin powder is less than 0.1 m, the friction coefficient of the coating film becomes small, but the lubricating property is not sufficiently obtained. Resin powder falls off during processing and does not exhibit lubricity. For this reason, the average grain size should be 0.1 to 10 m.
  • the resin powder is not particularly limited, and examples thereof include powders of fluororesin, polyethylene resin, polyester resin, and the like. These resin powders may be used alone or in combination, or may be melt-blended. In order to enhance the lubricity of the skin, it is preferable to use a mixture of a fluororesin powder having excellent lubricity and a polyethylene resin powder which is difficult to deform under high surface pressure.
  • the lower and upper coatings on Jii are formed by coating epoxy-modified acrylic resin emulsion with a coating method such as a roll coater to obtain a uniform coating, and then drying. after, an acid value of 4 0-3 0 0, the glass transition temperature of 4 0 P Celsius to 8 0.
  • An emulsion of acrylic resin, which is C, may be similarly applied and dried.
  • an emulsion treatment solution of acryl resin having different acid value and glass transition temperature can be obtained.
  • those having a low glass transition temperature were reacted with bisphenol A-type epoxy resin to carry out epoxy modification.
  • this epoxy-modified acrylic resin emulsion was applied to the surface of a stainless steel plate (steel type: SUS304, finish: BA, plate thickness: 0.6 mm) using a barco oven, and the oven was used. After drying, an underlayer film was formed.
  • the test piece was subjected to a DuPont impact test (weight drop height: 500 mm, weight of the weight: 500 g), and a taping test was conducted in which the cellophane tape was stuck on the protruding portion and then peeled off. ()% Or more symbol ⁇ , 60 to less than 80% symbol ⁇ , 40 to less than 60% symbol ⁇ , 20 to less than 40% symbol x, less than 20% The evaluation was made with the symbol XX.
  • Example 6 300 20 1200 5 10
  • Methyl methacrylate, butyl acrylate, acrylic acid, and methacrylic acid are copolymerized to synthesize an acrylic resin with an acid value of 100 and a glass transition temperature of 10 ° C.
  • Bisphenol with a molecular weight of 100 An A-type epoxy resin was reacted to obtain an epoxy-modified acrylic resin having a modification amount of 10% by mass. Then, an emulsion treatment liquid of this resin was applied to the same stainless steel plate surface as in Example 1 with a bar coater, and dried by oven to form a lower layer film having a thickness of 5 zxm.
  • an acrylic resin having an acid value of 100 and a glass transition temperature of 40 ° C is synthesized by copolymerizing methyl methacrylate, butyl acrylate, and methacrylic acid, and the emulsion is obtained.
  • a polyethylene resin powder and / or a fluorine resin powder were added to the cleaning solution, sealed in a glass container, and left in a 40 ° C atmosphere 121 for 10 E! LfM] or 20 hours. Then, the treatment liquid after standing was applied on the lower film by the same method as described above, and dried to form an upper film.
  • Table 5 shows the results of the following tests performed on the emulsion treatment solution for the upper layer coating and the obtained acrylic resin coating coated stainless steel sheet.
  • Resin powder A is a mixture of polyethylene resin powder
  • B is a mixture of fluororesin powder

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Feeding And Controlling Fuel (AREA)
  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
  • Control Of Steam Boilers And Waste-Gas Boilers (AREA)

Abstract

L'invention porte sur une tôle d'acier inox revêtue d'un revêtement protecteur alcalino-soluble en protégeant la surface devant être soumise à un usinage à la presse. Ledit revêtement protecteur comprend une couche inférieure de résine acrylique modifiée à l'époxyde présentant un indice d'acidité compris entre 40 et 300 et une température de transition vitreuse comprise entre 40 et 20 °C, et comportant de 3 à 20 % en masse d'un oligomère époxyde d'un poids moléculaire compris entre 40 et 300 et d'une température de transition vitreuse comprise entre 40 et 80 °C. Ces revêtements sont formés de couches successives déposées à la surface de la tôle et dont l'épaisseur total peut atteindre entre 1 et 20 νm.
PCT/JP1996/002533 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble WO1998009809A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
JP62082528A JPS63247503A (ja) 1987-04-03 1987-04-03 円錐型二重管貫流ボイラ
JP08465195A JP3305913B2 (ja) 1995-03-16 1995-03-16 耐カジリ性に優れたアルカリ可溶型保護皮膜被覆ステンレス鋼板
CA002236006A CA2236006A1 (fr) 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble
DE69635454T DE69635454T2 (de) 1987-04-03 1996-09-06 Mit basisch löslicher schutzschicht bedecktes rostfreies stahlblech
KR10-1998-0703338A KR100429651B1 (ko) 1996-09-06 1996-09-06 알칼리 가용성 보호 피막 피복 스테인리스 강판
EP96929542A EP0862993B1 (fr) 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble
AU68900/96A AU721321B2 (en) 1987-04-03 1996-09-06 Alkali-soluble protective-film coated stainless steel sheet
ES96929542T ES2252757T3 (es) 1987-04-03 1996-09-06 Chapa de acero inoxidable cubierta con un revestimiento protector soluble en alcalis.
PCT/JP1996/002533 WO1998009809A1 (fr) 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble
CN96199480A CN1102499C (zh) 1987-04-03 1996-09-06 碱可溶型保护皮膜被覆不锈钢板

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP62082528A JPS63247503A (ja) 1987-04-03 1987-04-03 円錐型二重管貫流ボイラ
CA002236006A CA2236006A1 (fr) 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble
PCT/JP1996/002533 WO1998009809A1 (fr) 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble
CN96199480A CN1102499C (zh) 1987-04-03 1996-09-06 碱可溶型保护皮膜被覆不锈钢板

Publications (1)

Publication Number Publication Date
WO1998009809A1 true WO1998009809A1 (fr) 1998-03-12

Family

ID=27427434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/002533 WO1998009809A1 (fr) 1987-04-03 1996-09-06 Tole d'acier inox revetue d'une couche protectrice alcalino-soluble

Country Status (8)

Country Link
EP (1) EP0862993B1 (fr)
JP (1) JPS63247503A (fr)
CN (1) CN1102499C (fr)
AU (1) AU721321B2 (fr)
CA (1) CA2236006A1 (fr)
DE (1) DE69635454T2 (fr)
ES (1) ES2252757T3 (fr)
WO (1) WO1998009809A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103640281A (zh) * 2013-11-27 2014-03-19 合肥美的电冰箱有限公司 用于冰箱的复合板及其制备方法和具有其的冰箱

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2740790B2 (ja) * 1990-09-29 1998-04-15 株式会社日阪製作所 食品用ピュアースチーム発生器
CN100443559C (zh) * 2006-09-20 2008-12-17 赵鹏 一种水性带锈防腐涂料

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5644768A (en) * 1979-09-19 1981-04-24 Dainippon Toryo Co Ltd Preparation of metal plated body
JPH08252887A (ja) * 1995-03-16 1996-10-01 Nisshin Steel Co Ltd 耐カジリ性に優れたアルカリ可溶型保護皮膜被覆ステンレス鋼板

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3378393B2 (ja) * 1994-12-05 2003-02-17 日新製鋼株式会社 アルカリ可溶型高密着性保護皮膜被覆ステンレス鋼板

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5644768A (en) * 1979-09-19 1981-04-24 Dainippon Toryo Co Ltd Preparation of metal plated body
JPH08252887A (ja) * 1995-03-16 1996-10-01 Nisshin Steel Co Ltd 耐カジリ性に優れたアルカリ可溶型保護皮膜被覆ステンレス鋼板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0862993A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103640281A (zh) * 2013-11-27 2014-03-19 合肥美的电冰箱有限公司 用于冰箱的复合板及其制备方法和具有其的冰箱

Also Published As

Publication number Publication date
EP0862993A1 (fr) 1998-09-09
EP0862993B1 (fr) 2005-11-16
CN1102499C (zh) 2003-03-05
CA2236006A1 (fr) 1998-03-12
ES2252757T3 (es) 2006-05-16
AU6890096A (en) 1998-03-26
EP0862993A4 (fr) 2003-07-02
CN1207069A (zh) 1999-02-03
JPS63247503A (ja) 1988-10-14
DE69635454D1 (de) 2005-12-22
AU721321B2 (en) 2000-06-29
DE69635454T2 (de) 2006-08-03

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