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WO2012048602A1 - Solvant mélangé, composition de revêtement de bobine et procédé pour la préparation de matériau de bobine - Google Patents

Solvant mélangé, composition de revêtement de bobine et procédé pour la préparation de matériau de bobine Download PDF

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Publication number
WO2012048602A1
WO2012048602A1 PCT/CN2011/078155 CN2011078155W WO2012048602A1 WO 2012048602 A1 WO2012048602 A1 WO 2012048602A1 CN 2011078155 W CN2011078155 W CN 2011078155W WO 2012048602 A1 WO2012048602 A1 WO 2012048602A1
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WO
WIPO (PCT)
Prior art keywords
weight
coating composition
resin
solvent
average molecular
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.)
Ceased
Application number
PCT/CN2011/078155
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English (en)
Chinese (zh)
Inventor
施建刚
李季
杨俊峰
贾桂兰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Feixiang New Material R & D (suzhou) Institute Co Ltd
HEBEI CASDA BIOMATERIALS CO Ltd
Original Assignee
Feixiang New Material R & D (suzhou) Institute Co Ltd
HEBEI CASDA BIOMATERIALS 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
Application filed by Feixiang New Material R & D (suzhou) Institute Co Ltd, HEBEI CASDA BIOMATERIALS CO Ltd filed Critical Feixiang New Material R & D (suzhou) Institute Co Ltd
Publication of WO2012048602A1 publication Critical patent/WO2012048602A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids

Definitions

  • the present invention relates to a mixed solvent and a coil coating composition containing the mixed solvent and a method of producing a coiled steel material to which the coil coating composition is applied.
  • Coil coating is a special coating suitable for metal coil coating process. Due to the requirements of the coating process and the increasing use of coil steel, the requirements for coil coatings are increasing. For example, the coating process uses a roll coater to continuously coat the strip, which requires the coil coating to dry quickly at high temperatures. At the same time, during the drying process, the temperature of the steel sheet is as high as 220-260 ° C. In the furnace, the ambient temperature is as high as 400 degrees. Therefore, the heat resistance of the coil coating becomes extremely important. In addition, when the coil coating is applied to the surface of household appliances, it is often in contact with household chemicals or detergents. , must also consider its chemical resistance, low toxicity, and so on. In addition, coil coatings must also have some basic properties of the coating, such as gloss, leveling and adhesion.
  • a mixed solvent such as a solvent composition composed of propylene glycol alkyl ether and alkyl 3-alkoxypropionate
  • JP-A-7-146562 A composition of a solvent composed of propylene glycol alkyl ether acetate and propylene glycol alkyl ether (U.S. Patent No. 4,983,490).
  • the above composition has an operator's dissatisfaction and resentment due to malodor, and there is a concern that it is toxic and damages health.
  • the conventional mixed solvent has problems in solubility, volatility, toxicity, and the like;
  • the dimethyl dimethyl carbonate mixture (DBE) is a by-product of the production of adipic acid, and the ratio of the components of the mixture produced by each manufacturer is large, the solvent The performance is difficult to stabilize and the amount is large. It is also limited to use in some fields (CN 101402814A).
  • the aromatic solvent oil solvent is harmful to the health of workers and family members in construction and decoration, and also pollutes the environment. Summary of the invention
  • An object of the present invention is to provide a mixed solvent capable of overcoming the above disadvantages, and a coil coating composition containing the mixed solvent and a method for producing a coiled steel material using the coil coating composition.
  • the present invention provides a mixed solvent, characterized in that the solvent contains sec-octyl acetate and a cosolvent,
  • the co-solvent is an organic solvent which is completely miscible with sec-octyl acetate, wherein the weight ratio of sec-octyl acetate to the co-solvent is 1: 0.1-30.
  • the present invention provides a coil coating composition characterized in that the composition comprises: based on the total amount of the composition:
  • the host resin being at least one of a polyurethane resin, a polyacryl resin, a polyester resin, an alkyd resin, and an epoxy resin;
  • the present invention provides a method for preparing a coiled steel material, the method comprising applying a coating composition to a surface of a coiled steel substrate and curing the coating composition, wherein the coating composition is the above-mentioned coil coating composition Things.
  • the coil coating composition obtained by using the mixed solvent provided by the invention as a solvent that is, the coil coating composition provided by the invention has good fluidity, high solid content, strong stability, no benzene poison, and the formed paint film is clear and transparent, Good leveling, can avoid the tailing of the steel plate interface.
  • the coil steel material obtained by the preparation method of the coil steel material provided by the invention has a flat surface, high gloss and good adhesion of the coating material. detailed description
  • the present invention provides a mixed solvent, characterized in that the solvent contains sec-octyl acetate and a co-solvent, and the co-solvent is an organic solvent which is completely miscible with sec-octyl acetate, wherein sec-octyl acetate and The cosolvent weight ratio is 1: 0.1-30.
  • the coil coating composition obtained by using the mixed solvent provided by the invention as a solvent that is, the coil coating composition provided by the invention has good fluidity, high solid content, high stability, no benzene toxicity, and the coil compounded by the composition Steel coating, the film formed is clear and transparent, with good leveling, can avoid the tailing of the steel plate interface. This may be because, for solvents in solvent-based coil coatings, important factors that determine their performance are compatibility, viscosity, and volatility.
  • Compatibility means that the solvent used needs to have good miscibility with a variety of resins, so as to act as a diluent, so that the sprayed film will be clear and transparent.
  • Viscosity is an important parameter of the solvent's ability to dissolve the resin. Different solvents have different viscosities due to the difference in the properties of the dissolved resin. When the nozzle is sprayed, if the viscosity is too high, the ejection pressure becomes high, thereby increasing the amount of unnecessary solvent used, which increases the cost. On the other hand, if the viscosity is too low, the resin cannot be concentratedly sprayed on the interface of the coiled steel sheet.
  • Volatility is an important factor concerning whether the solvent evaporates quickly and does not remain on the surface of the substrate.
  • volatility When the volatility is too low, it not only causes the solvent to remain non-volatile, but also causes a tailing phenomenon at the interface of the coiled steel sheet, and in the subsequent process, There are problems such as a decrease in the production efficiency of the processing step.
  • volatility when the volatility is too high, the coiled steel plate is rapidly cooled and sprayed. The coated resin is not completely dissolved and adhered, so that it is liable to cause defects caused by blasting and over-baking of the paint film.
  • 2-octyl acetate (20A) the molecular formula is C 1Q H 2Q 0 2 , is a colorless transparent liquid, slightly aromatic, and low toxicity.
  • sec-octyl acetate As a solvent in detergents and perfumes has been reported, but there is no research on its application in coil coatings.
  • sec-octyl acetate has excellent solubility, and is excellent in compatibility with polyurethane resin, polyester resin, alkyd resin, epoxy resin, etc. Meanwhile, sec-octyl acetate has a high boiling point and is not easy to be used. Volatile, but as the temperature increases, it volatilizes faster than other solvents; in addition, sec-octyl acetate is slightly aromatic and very toxic. Due to the various properties of sec-octyl acetate, it is a mixed solvent with other solvents and used in coil coatings, and very good results can be obtained.
  • the weight ratio of sec-octyl acetate to the co-solvent is 1:0.5-20.
  • the co-solvent may be a cyclic ketone, an alkyl acetate having a total carbon number of 3-8, an aromatic hydrocarbon solvent oil, a compound having a structure represented by the formula (1), and having the structure represented by the formula (2). At least one of a compound having a structure represented by the formula (3) and a compound having a structure represented by the formula (4),
  • R4 and each independently are a C 2 -C 5 alkylene group
  • R 2 , R 3 , R 5 , R 7 , R 8 and R 9 are each independently a dC 5 alkyl group.
  • the co-solvent satisfying the above conditions may, for example, be an S-1000 aromatic solvent oil, an S-1500 aromatic solvent oil, an S-800 aromatic solvent oil, an S-200 aromatic solvent oil, or an ethylene glycol.
  • the co-solvent is S-1000 type aromatic hydrocarbon solvent oil, S-1500 type aromatic hydrocarbon solvent oil, S-200 type aromatic hydrocarbon solvent oil, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol single Methyl ether acetate, ethoxymethyl acrylate, propylene glycol monomethyl ether acetate, cyclohexanone and methyl isobutyl ketone.
  • the present invention provides a coil coating composition characterized in that the composition comprises: based on the total amount of the composition:
  • the host resin being at least one of a polyurethane resin, an acrylic resin, a polyester resin, an alkyd resin, and an epoxy resin;
  • the content of the mixed solvent is 5-30% by weight based on the total amount of the composition; the content of the host resin is 30-55 wt%; and the content of the titanium dioxide is 20-40 wt%;
  • the fumed silica is contained in an amount of 0.2 to 0.5% by weight.
  • the mixed solvent is the mixed solvent. Therefore, the type of the cosolvent in the mixed solvent, the ratio of the octyl acetate to the cosolvent, and the like are also the same as described above, and will not be described herein.
  • the various host resins are not particularly required, and may be various resins conventional in the art.
  • the polyurethane resin has a weight average molecular weight of 1000-8000, more preferably 6000-8000;
  • the acrylic resin has a weight average molecular weight of from 1,000 to 8,000, more preferably from 2,000 to 5,000;
  • the polyester resin has a weight average molecular weight of from 1,000 to 8,000, further preferably from 3,000 to 6,000; and the alkyd resin has a weight average molecular weight of from 1,000 to 8,000.
  • the polyester resin may be Dynapol LH 818-05 polyester resin and/or Dynapol LH 826-05 polyester resin; the polyurethane resin may be Hw 180Pc polyurethane resin; the acrylic resin may be HB-225 type acrylic resin; It is epoxy resin 601 and/or shell epoxy 834.
  • the titanium dioxide and the fumed silica are not particularly limited, and may be titanium dioxide and fumed silica which are conventional in the art.
  • the titanium dioxide is titanium dioxide
  • the particle diameter of the titanium dioxide may be The particle diameter of the fumed silica may be from 10 to 100 ⁇ m, preferably from 10 to 50 nm, and more preferably from 10 to 30 nm, in the range of 0.2 to 0.6 ⁇ m, preferably 0.2 to 0.4 ⁇ m.
  • the preparation method of the composition may be a conventional method, preferably comprising a mixing and grinding step, which is preferably carried out by stirring, and the stirring may be carried out at a rate of 300 to 10,000 rpm. It is further preferably from 1,000 to 5,000 rpm; the time may be from 10 to 50 minutes.
  • the manner of grinding includes sanding and ball milling, preferably, grinding using sanding. The purpose of the grinding is to lower the fineness of the mixture. Preferably, the grinding is such that the fineness of the composition is from 10 to 50 ⁇ m, more preferably from 10 to 15 ⁇ m.
  • the present invention provides a method for preparing a coiled steel material, the method comprising applying a coating composition to a surface of a coiled steel substrate and curing the coating composition, wherein the coating composition is the above-mentioned coil coating composition Things.
  • the coating amount of the coating composition may be various coating amounts conventionally used, for example, 200 to 1000 g, per square meter of the steel coil substrate. More preferably, it is 300-800 grams.
  • the curing conditions may be curing conditions well known in the art, including a curing temperature of 200 to 260 ° C, preferably 200 to 235 ° C, and a curing time of 15 - 85 seconds, preferably 25-65 seconds.
  • Example 1 The method for producing a coiled steel material according to the present invention, the method such that the prepared coiled steel material has a thickness of 10 to 20 ⁇ m, more preferably 13 to 17 ⁇ m.
  • the contents of the present invention will be further described by way of examples.
  • Dynapol LH 818-05 polyester resin weight average molecular weight of 6000
  • Aerosil 200 fumed silica particle diameter of 12 nm
  • RCL 310 titanium dioxide particle diameter 0.28 ⁇ m
  • S-200 aromatic solvent oil 8.3 parts by weight of sec-octyl acetate mixed, stirred at high speed (2000 rpm) for 40 min, and then dispersed by sanding to a fineness of 10-15 ⁇ m. , a coil coating composition P1 is obtained.
  • the coil coating composition PI is applied to the coiled steel substrate (Baogang hot-dip galvanized sheet, model DC51D+Z) by spraying at a dosage of 500 grams per square meter, and dried at 230 ° C for 50 seconds. It was allowed to cure to obtain a coil material C1 having a thickness of 15 ⁇ m. Comparative example 1
  • a coil coating composition was prepared according to the method of Example 1, except that 4.2 parts by weight of S-200 aromatic hydrocarbon solvent oil and 8.3 parts by weight of sec-octyl acetate were provided by 2.3 parts by weight of propylene glycol monomethyl ether and 10.5 parts by weight. Instead of ethyl 3-methoxypropionate, a coil coating composition DP1 was obtained.
  • Example 2 Using the above materials, a coil material DC1 was prepared in accordance with the method of Example 1.
  • Example 2 Using the above materials, a coil material DC1 was prepared in accordance with the method of Example 1.
  • Example 2 Using the above materials, a coil material DC1 was prepared in accordance with the method of Example 1.
  • CABOT M-5 fumed silica (particle diameter 12 nm), 24 parts by weight of R 706 titanium dioxide (0.26 ⁇ m), 10 parts by weight of ethylene glycol monobutyl ether, 5.7 parts by weight of sec-octyl acetate mixed, The mixture was stirred at a high speed (3000 rpm) for 30 minutes, and then dispersed by sanding to a fineness of 10-15 ⁇ m to obtain a coil coating composition ⁇ 2.
  • the coil coating composition ⁇ 2 was applied to the coiled steel substrate (Ma Steel, model SGCC) by spraying at a rate of 800 g per square meter, and dried at 200 ° C for 65 seconds to obtain a solidified coating. Coil material C2 with a thickness of 16 microns.
  • Example 3
  • Hw 180Pc polyurethane resin 45 parts by weight of Hw 180Pc polyurethane resin, 0.2 parts by weight of Aerosil 202 fumed silica (particle diameter 14 nm), 30 parts by weight of R 960 titanium dioxide (0.35 ⁇ m), 0.5 part by weight of propylene glycol monomethyl ether acetate
  • the ester was mixed with 7.5 parts by weight of sec-octyl acetate, stirred at a high speed (4000 rpm) for 20 minutes, and then dispersed by sanding to a fineness of 10-15 ⁇ m to obtain a coil coating composition ⁇ 3.
  • the coil coating composition ⁇ 3 was applied by spraying onto a coiled steel substrate (Baosteel, model DX52D+Z) at a rate of 300 grams per square meter, and dried at 210 ° C for 25 seconds to cure.
  • a coiled steel material C3 having a thickness of 14 ⁇ m was obtained.
  • Example 5 It was applied according to the method described in Example 1 and dried at 230 ° C for 50 seconds to obtain a coiled steel material C4 having a thickness of 15 ⁇ m.
  • Example 5 It was applied according to the method described in Example 1 and dried at 230 ° C for 50 seconds to obtain a coiled steel material C4 having a thickness of 15 ⁇ m.
  • Example 6 The coating was carried out according to the method described in Example 1, and dried at 240 ° C for 25 seconds to obtain a coiled steel material C5 having a thickness of 13 ⁇ m.
  • Example 6 The coating was carried out according to the method described in Example 1, and dried at 240 ° C for 25 seconds to obtain a coiled steel material C5 having a thickness of 13 ⁇ m.
  • Shell epoxy resin 834 50.0 parts by weight of Shell epoxy resin 834, 0.2 parts by weight of Aerasil 202 fumed silica, 27.5 parts by weight of RCL 310 titanium dioxide, 8.6 parts by weight of cyclohexanone and 4.9 parts by weight of sec-octyl acetate were mixed.
  • the mixture was stirred at a high speed (1000 rpm) for 50 minutes, and then dispersed by sanding to a fineness of 10-15 ⁇ m to obtain a coil coating composition ⁇ 6.
  • Example 1 It was applied according to the method described in Example 1 and baked at 230 ° C for 50 seconds to be solidified to obtain a coiled steel material C6 having a thickness of 17 ⁇ m.
  • Test example 1 It was applied according to the method described in Example 1 and baked at 230 ° C for 50 seconds to be solidified to obtain a coiled steel material C6 having a thickness of 17 ⁇ m.
  • the coil coating compositions Pl-P6, DPI and coiled steel materials Cl-C6, DC1 were tested by the following methods. Appearance visual inspection: including liquid form of coil coating composition P1-P6 and DPI, whether C1-C6 and DC1 have tailing phenomenon; Viscosity test: Determination by coating 4-cup viscometer NDJ-5; Adhesion test: Film cross-cut test; Leveling test: Using a knife coating test; Gloss: Determined by a gloss meter; Fineness: Determined by a squeegee fineness meter.
  • the coil coating composition of the present invention is clear and transparent and has a high solid content as compared with Comparative Example 1, indicating that the mixed solvent of the present invention has excellent dissolving power.
  • the coil coating composition of the invention has moderate viscosity; no abnormal change in storage at 5-30 ° C for 1 year, indicating that the coil coating composition of the invention has good stability, and the VOC of the coil coating composition of the invention The value is lower than that of Comparative Example 1, indicating that the coil coating composition of the present invention has low toxicity and good environmental friendliness.
  • the formed paint film After the coiled steel coating prepared according to the present invention is applied to a coiled steel substrate, the formed paint film has excellent fineness and adhesion, and has better retention while maintaining fineness and adhesion than the comparative example. Good leveling and gloss.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention porte sur un solvant mélangé comprenant de l'acétate de sec-octyle et un cosolvant. L'invention porte également sur une composition de revêtement de bobine, comprenant, sur la base du poids de la composition : (1) 1-50 % en poids du solvant ; (2) 10-70 % en poids d'une résine en tant qu'ingrédient principal ; (3) 1-40 % en poids de dioxyde de titane ; et (4) 0,1-1 % en poids de silice sublimée. L'invention porte également sur un procédé pour la préparation d'un matériau de bobine comprenant l'application de la composition de revêtement sur la surface d'un substrat de bobine. La composition de revêtement de bobine obtenue à l'aide du solvant mélangé de la présente invention présente les avantages suivants, à savoir qu'elle a une bonne fluidité, une teneur en matières solides élevée et une stabilité élevée, qu'elle est exempte de toxicité due au benzène et que le film de peinture formé de cette manière est limpide et transparent et a de bonnes propriétés de nivellement.
PCT/CN2011/078155 2010-10-12 2011-08-09 Solvant mélangé, composition de revêtement de bobine et procédé pour la préparation de matériau de bobine Ceased WO2012048602A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010508794.4 2010-10-12
CN201010508794.4A CN102443344B (zh) 2010-10-12 2010-10-12 一种混合溶剂及卷钢涂料组合物和卷钢材料的制备方法

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Publication Number Publication Date
WO2012048602A1 true WO2012048602A1 (fr) 2012-04-19

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CN (1) CN102443344B (fr)
WO (1) WO2012048602A1 (fr)

Cited By (1)

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CN110423543A (zh) * 2019-08-14 2019-11-08 程浩源 一种基于有机硅改性醇酸树脂的卷材涂料及其制备方法

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CN103253018B (zh) * 2013-05-21 2016-01-20 辽宁超烁图码科技板业有限公司 印花金属板的生产方法及采用该方法生产的印花金属板
CN107417895B (zh) * 2017-05-19 2019-10-25 江苏三木化工股份有限公司 一种成本低的卷钢底漆用醇酸树脂及制备方法
CN116660099B (zh) * 2023-07-24 2023-10-31 绵阳新启科技有限公司 一种水性涂料流动性检测系统及方法

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