WO2012122722A1 - 一种涂料油墨用氟碳抗缩孔流平剂 - Google Patents

一种涂料油墨用氟碳抗缩孔流平剂 Download PDF

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WO2012122722A1
WO2012122722A1 PCT/CN2011/072271 CN2011072271W WO2012122722A1 WO 2012122722 A1 WO2012122722 A1 WO 2012122722A1 CN 2011072271 W CN2011072271 W CN 2011072271W WO 2012122722 A1 WO2012122722 A1 WO 2012122722A1
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acrylate
weight
butyl acetate
solvent
cratering
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陈永康
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Priority to US13/696,305 priority Critical patent/US20140094579A1/en
Priority to EP11860762.1A priority patent/EP2684901A4/en
Publication of WO2012122722A1 publication Critical patent/WO2012122722A1/zh
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/22—Esters containing halogen

Definitions

  • the invention relates to a fluorocarbon anti-cratering leveling agent (fluorine surfactant) for coating ink and a manufacturing method thereof, and belongs to the technical field of coating additives.
  • fluorocarbon anti-cratering leveling agent fluorine surfactant
  • non-silicone and fluorine-containing leveling agents used in solvent-based industrial coatings have the disadvantages of poor resistance to shrinkage and porosity; and silicone-based leveling agents with excellent anti-cratering ability have high temperature resistance and poor recoatability. Disadvantages.
  • An object of the present invention is to provide a fluorocarbon anti-cratering fluid leveling agent (fluorine surfactant) for coating inks which can reduce the surface tension of a coating system and has excellent anti-cratering ability.
  • fluorocarbon anti-cratering fluid leveling agent fluorine surfactant
  • a fluorocarbon anti-cratering leveling agent for paint inks also known as: fluorosurfactant
  • fluorosurfactant characterized by: surface tension: 21-24 dyne, number average molecular weight is 1500 ⁇ 4500, the weight average molecular weight is 3000 ⁇ 15000, and the polydispersity is 1.5 ⁇ 2.8.
  • the fluorocarbon anti-cratering leveling agent (fluorine surfactant) for a coating ink is made of the following raw materials by weight:
  • the solvent is xylene, butyl acetate, propylene glycol methyl ether or propylene glycol methyl ether acetate;
  • the fluorine-containing acrylate monomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, Hexafluorobutyl acrylate, dodecafluoroheptyl acrylate or dodecafluoroheptyl methacrylate;
  • the initiator is azobisisobutyronitrile, benzoyl peroxide, t-amyl peroxyacetate ( TAPA), di-tert-amyl peroxide (DTAP).
  • Preparation method in a four-necked flask with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 30-40% of butyl acetate was added. Parts by weight, and stir the stirrer; when the temperature rises to 118 °C, after the solvent butyl acetate is refluxed in the condenser, 30-40% by weight of butyl acetate and trifluoroethyl acrylate are added dropwise.
  • the product of the invention has excellent working performance and simple production method.
  • figure 1 It is a schematic diagram of the surface tension values of the fluorocarbon surfactant for the solvent-based coating of the present invention, the fluorine-containing acrylate leveling agent, the pure acrylate leveling agent and the acrylic varnish stock solution.
  • the leveling agent can effectively reduce the surface tension of the coating system.
  • the number average molecular weight and the weight average molecular weight are both in this range, the long wave leveling property of the paint is excellent.
  • the amount of each component is:
  • Fluorinated acrylate monomer 5 ⁇ 90% (example 90%, 50%, 5%)
  • the solvent is xylene, butyl acetate, propylene glycol methyl ether or propylene glycol methyl ether acetate;
  • the fluorine-containing acrylate monomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, Hexafluorobutyl acrylate, dodecafluoroheptyl acrylate or dodecafluoroheptyl methacrylate;
  • the initiator is azobisisobutyronitrile, benzoyl peroxide, t-amyl peroxyacetate ( TAPA), di-tert-amyl peroxide (DTAP).
  • the surface tension value of the fluorosurfactant is at 22.992.
  • Dyne reduces the surface tension of the coating system more than polyacrylate leveling agents and fluorine-containing grades.
  • the varnish has excellent anti-cratering ability, substrate wettability and leveling speed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

一种涂料油墨用氟碳抗缩孔流平剂
技术领域
本发明涉及一种涂料油墨用氟碳抗缩孔流平剂（氟素表面活性剂）及制造方法，属于涂料助剂技术领域。
背景技术
目前用于溶剂型工业涂料中的非硅类和含氟类流平剂存在抗缩孔能力差的缺点；而抗缩孔能力优的有机硅类流平剂存在不耐高温和重涂性差等缺点。
发明内容
本发明的目的在于提供一种能降低涂料体系表面张力、具有抗缩孔能力强的涂料油墨用氟碳抗缩孔流平剂（氟素表面活性剂）。
本发明的技术解决方案是：
一种涂料油墨用氟碳抗缩孔流平剂（又称：氟素表面活性剂），其特征是：表面张力： 21-24 达因，数均分子量为 1500~4500 ，重均分子量为 3000~15000 ，多分散性 1.5~2.8 。
所述的一种涂料油墨用氟碳抗缩孔流平剂（氟素表面活性剂），由下列重量百分比的原料制成：
溶剂 5~90%
含氟丙烯酸酯单体 5~90%
引发剂 0.1~10%
其中所述溶剂为二甲苯、醋酸丁酯、丙二醇甲醚或丙二醇甲醚醋酸酯；含氟丙烯酸酯单体为丙烯酸三氟乙酯、甲基丙烯酸三氟乙酯、丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸十二氟庚酯或甲基丙烯酸十二氟庚酯；引发剂为偶氮二异丁腈、过氧化苯甲酰、过氧化醋酸叔戊酯（ TAPA ）、过氧化二叔戊基（ DTAP ）。
制备方法：在带有回流冷凝管、温度计、搅拌器以及滴液漏斗的四口烧瓶中，加入醋酸丁酯中的 30~40% 重量份，并开动搅拌器搅拌；当温度升至 118 ℃ ，等溶剂醋酸丁酯在冷凝管中回流后，开始滴加由 醋酸丁酯中的 30~40% 重量份、丙烯酸三氟乙酯 ，偶氮二异丁腈中70 ~ 90% 重量份，3h后完成滴加，然后保持温度在118℃继续搅拌2h；再补滴加余量的醋酸丁酯和余量的偶氮二异丁腈的混合物10分钟，然后保持温度在118℃继续搅拌2h。保温结束后 减压蒸馏掉溶剂或将固含调至 50% ， 取出产物。
本发明产品工作性能优异，生产方法简便。
下面结合附图和实施例对本发明作进一步说明。
图 1 是本发明溶剂型涂料用氟素表面活性剂与含氟类丙烯酸酯流平剂、纯丙烯酸酯流平剂和丙烯酸清漆原液的表面张力值示意图。
图 2 是 纯丙烯酸酯流平剂、含氟类丙烯酸酯流平剂与本发明 涂料油墨用氟碳抗缩孔流平剂 在丙烯酸清漆中表面张力值比较图。
具体实施方式
实施例 1 ：
在带有回流冷凝管、温度计、搅拌器以及滴液漏斗的四口烧瓶中，加入 50 克醋酸丁酯并开动搅拌器搅拌。当温度升至 118 ℃，等溶剂醋酸丁酯在冷凝管中回流后，开始滴加由 15 克醋酸丁酯、 210 丙烯酸三氟丁酯，5.74克偶氮二异丁腈，3h后完成滴加，然后保持温度在118℃继续搅拌2h；再补滴加5克醋酸丁酯和1.19克偶氮二异丁腈的混合物10分钟，然后保持温度在118℃继续搅拌2h。保温结束后 减压蒸馏掉溶剂或将固含调至 50% ， 取出产物。封罐包装。
  1. 1. 产品性能：外观：微黄色透明液体；固含：50%或100%；表面张力 21-24 达因，数均分子量为 1500~4500 ，重均分子量为 3000~15000 ，多分散性 1.5~2.8 。
表面张力在21-24达因时，流平剂能有效降低 涂料体系表面张力。 数均分子量和重均分子量，多分散性都在这个区间内时，油漆的长波流平性优。
实施例2：
各组分的用量为：
溶剂 5~90% （例 5% 、 50% 、 90% ）
含氟丙烯酸酯单体 5~90% （例 90% 、 50% 、 5% ）
引发剂 0.1~10% （例 10% 、 5% 、 0.1% ）；
其中所述溶剂为二甲苯、醋酸丁酯、丙二醇甲醚或丙二醇甲醚醋酸酯；含氟丙烯酸酯单体为丙烯酸三氟乙酯、甲基丙烯酸三氟乙酯、丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸十二氟庚酯或甲基丙烯酸十二氟庚酯；引发剂为偶氮二异丁腈、过氧化苯甲酰、过氧化醋酸叔戊酯（ TAPA ）、过氧化二叔戊基（ DTAP ）。
上述同一种组分的分步使用比例同实施例 1 。其余同实施例 1 。
  1. 2. 所得流平剂 表面张力 21-24 达因，数均分子量为 1500~4500 ，重均分子量为 3000~15000 ，多分散性 1.5~2.8 。
举例说明： 1 、溶剂型涂料用氟素表面活性剂、含氟类丙烯酸酯流平剂，纯丙烯酸酯流平剂和丙烯酸清漆原液的表面张力值，见图 1 。
2 、若在丙烯酸清漆中分别添加含氟类流平剂和纯丙烯酸酯流平剂 0.1% ， 0.3% ， 0.5% ， 0.8% ，丙烯酸清漆的表面张力下降趋势图，见图 2 。
以上说明氟素表面活性剂的表面张力值在 22.992 达因时，比聚丙烯酸酯流平剂和含氟类更能降低涂料体系的表面张力。又因为清漆的表面张力值降低了，所以该清漆具有很好的抗缩孔能力、底材润湿性和流平速度。

Claims (1)

1. 一种涂料油墨用氟碳抗缩孔流平剂，其特征是：表面张力： 21-24 达因，数均分子量为 1500~4500 ，重均分子量为 3000~15000 ，多分散性 1.5~2.8 。
2. 根据权利要求 1 所述的一种涂料油墨用氟碳抗缩孔流平剂，其特征是：由下列重量百分比的原料制成：
溶剂 5~90%
含氟丙烯酸酯单体 5~90%
引发剂 0.1~10%
其中所述溶剂为二甲苯、醋酸丁酯、丙二醇甲醚或丙二醇甲醚醋酸酯；含氟丙烯酸酯单体为丙烯酸三氟乙酯、甲基丙烯酸三氟乙酯、丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸十二氟庚酯或甲基丙烯酸十二氟庚酯；引发剂为偶氮二异丁腈、过氧化苯甲酰、过氧化醋酸叔戊酯、过氧化二叔戊基；
制备方法：在带有回流冷凝管、温度计、搅拌器以及滴液漏斗的四口烧瓶中，加入醋酸丁酯中的 30~40% 重量份，并开动搅拌器搅拌；当温度升至 118 ℃ ，等溶剂醋酸丁酯在冷凝管中回流后，开始滴加由 醋酸丁酯中的 30~40% 重量份、丙烯酸三氟乙酯 ，偶氮二异丁腈中70 ~ 90% 重量份，3h后完成滴加，然后保持温度在118℃继续搅拌2h；再补滴加余量的醋酸丁酯和余量的偶氮二异丁腈的混合物10分钟，然后保持温度在118℃继续搅拌2h，保温结束后 减压蒸馏掉溶剂或将固含调至 50% ， 取出产物。
PCT/CN2011/072271 2011-03-11 2011-03-29 一种涂料油墨用氟碳抗缩孔流平剂 Ceased WO2012122722A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/696,305 US20140094579A1 (en) 2011-03-11 2011-03-29 Fluorocarbon anti-shrinkage leveling agent for coating and ink
EP11860762.1A EP2684901A4 (en) 2011-03-11 2011-03-29 FLUOROCARBON EQUALIZATION AGENT ANTI-FORMATION OF CRATERS FOR COATING AND INK

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CN201110058889.5 2011-03-11
CN2011100588895A CN102153902B (zh) 2011-03-11 2011-03-11 一种涂料油墨用氟碳抗缩孔流平剂

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CN103694765A (zh) * 2013-12-31 2014-04-02 张锦碧 一种改性烤漆流平剂
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EP2684901A1 (en) 2014-01-15
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EP2684901A4 (en) 2014-10-22
CN102153902A (zh) 2011-08-17

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