WO2007009325A1 - Resine soluble dans l'alcool et son procede de preparation - Google Patents

Resine soluble dans l'alcool et son procede de preparation Download PDF

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Publication number
WO2007009325A1
WO2007009325A1 PCT/CN2006/000025 CN2006000025W WO2007009325A1 WO 2007009325 A1 WO2007009325 A1 WO 2007009325A1 CN 2006000025 W CN2006000025 W CN 2006000025W WO 2007009325 A1 WO2007009325 A1 WO 2007009325A1
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WO
WIPO (PCT)
Prior art keywords
alcohol
acrylate
methacrylate
vinyl acetate
component
Prior art date
Application number
PCT/CN2006/000025
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English (en)
French (fr)
Other versions
WO2007009325A8 (fr
Inventor
Wenjun Zou
Wenjun Zhong
Mingguo Zou
Guangming Li
Original Assignee
Wenjun Zou
Wenjun Zhong
Mingguo Zou
Guangming Li
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36079987&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2007009325(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Wenjun Zou, Wenjun Zhong, Mingguo Zou, Guangming Li filed Critical Wenjun Zou
Priority to CNB2006800010948A priority Critical patent/CN100480288C/zh
Priority to US11/995,667 priority patent/US8410212B2/en
Priority to JP2008520689A priority patent/JP5149174B2/ja
Priority to EP20060705448 priority patent/EP1932860B1/en
Publication of WO2007009325A1 publication Critical patent/WO2007009325A1/zh
Publication of WO2007009325A8 publication Critical patent/WO2007009325A8/zh

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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
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate

Definitions

  • the present invention relates to an alcohol-soluble copolymer resin, and more particularly to an alcohol-soluble resin as a main raw material in the preparation of an alcohol-soluble fine chemical product such as an alcohol-soluble ink or an alcohol-soluble plastic composite binder, and a preparation method therefor.
  • Resin is the main raw material for the production of fine chemical products such as inks, adhesives and coatings.
  • the resin determines the performance, cost and solvent dilution of these fine chemical products.
  • Currently, most of the resins used in the production of these products are benzene. Classes and ketones are solvent-diluted. These solvents not only seriously pollute the environment, but also because of petroleum refining, the cost increases sharply with the rise of oil prices. Due to cost and environmental pressure, the market uses alcohol as a solvent. The demand for resins is growing.
  • alcohol-soluble resins capable of producing the above-mentioned fine chemical products are: alcohol-soluble polyamide resins, alcohol-soluble polyurethane resins, polyvinyl acetal resins, and these types of resins are more expensive due to raw material costs and production processes. Expensive, the cost of producing the above products is high, so reducing the cost of the alcohol-soluble resin has become an urgent requirement in the market.
  • vinyl acetate is one of the cheapest and non-toxic monomer raw materials on the market, and its polymer is soluble in alcohol, it can be used to produce alcohol-soluble resin as a main raw material, which can greatly reduce the cost, but due to the homopolymer glass of vinyl acetate.
  • the temperature is 28 ° C, the softening point is low, and it is soft and deformed by heat; in addition, it is easy to absorb moisture, and the moisture absorption will seriously affect the performance of the resin. Therefore, at present, no vinyl acetate is used as the main raw material to meet the above products.
  • the reported alcohol-soluble resin is reported.
  • An object of the present invention is to prepare an alcohol-soluble resin which can be used for the production of fine chemical products such as inks; another object of the present invention is to provide a method and use for the preparation of the resin.
  • the alcohol-soluble resin provided by the present invention is obtained by polymerizing a raw material containing 50% to 90% w/w of vinyl acetate with azobisisobutyl bromide and/or benzoyl peroxide as an initiator.
  • the initiator is added in an amount of 0.1 to 1.1% by weight of the raw material, and is polymerized in an ester and/or an alcohol solvent.
  • the preferred raw material ratio is:
  • the reactive functional group compound is acrylic acid, methacrylic acid, butenedioic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, methacrylic acid shrinkage
  • a glyceride a reaction of an unsaturated acid with a diepoxide, one or more of acrylamide, methacrylamide, and methylol acrylamide.
  • the method for preparing an alcohol-soluble resin provided by the present invention comprises the following steps:
  • Component A Vinyl acetate 25_45%
  • An alcohol or ester solvent is added in an amount of 10 to 35% by weight based on the total weight of the above vinyl acetate and acrylate and/or methacrylate.
  • Component B Vinyl acetate 25-45%
  • the total weight of the raw materials is 0. 1 -0. 7% of the initiator
  • Component C Total weight of raw materials 0. 1-0. 4% of the initiator is dissolved by ester and alcohol solvent;
  • the total amount of the above-mentioned initiator is 0.1% of the total weight of the raw materials
  • the component A is added to the reaction vessel, stirred, and heated to reflux temperature;
  • the concentration requirement of the product it is diluted with alcohol and/or ester solvent, and the temperature is lowered while stirring.
  • the temperature of the material in the kettle drops below 50 °C, the alcohol-soluble resin of the desired concentration is obtained.
  • a preferred embodiment of the above-mentioned a step raw material ratio is - a component: vinyl acetate 40-45%
  • Component B Vinyl acetate 40-45%
  • the total weight of the raw materials is 0. 1-0. 7% of the initiator
  • Component C Total weight of the raw materials 0. 1-0. 4% of the initiator is dissolved in the ester and / or alcohol solvent.
  • the invention also provides the use of an alcohol-soluble resin in the preparation of inks, plastic composite adhesives, wood varnishes, paper-printed varnishes and plastic surface decorative lacquers, metal surface protective coatings, and hair colorants.
  • the present invention also provides an ink, a plastic composite adhesive prepared from the above alcohol-soluble resin.
  • the present invention will be further described in detail below by way of specific embodiments, but should not be construed as limiting the scope of the present invention. The modifications, substitutions, and changes made by the ordinary skill in the art All are within the scope of the invention.
  • the equipment required for the present invention is: a reaction kettle equipped with a stirrer, a reflux condenser, a stainless steel drip tank, a heating and a thermostat.
  • the resin prepared in the formulation described in Example 1 is most preferably used for the production of gravure plastic surface printing inks.
  • Component A Vinyl acetate 40 kg
  • Component B Vinyl acetate 33 kg Methyl acrylate 2 kg
  • Component C 0.2 kg of azobisisobutyl phthalate 0.2 kg of each of isopropanol and ethyl acetate was dissolved, and another 20 kg of ethyl acetate and 60 kg of industrial alcohol were used as a diluent.
  • the preparation method was the same as in Example 1, and the solid content was 50 ⁇ 200. 7 ⁇ .
  • Example 2 The resin prepared in the formulation of Example 2 is most preferably used for the production of heat-resistant, retort-resistant gravure plastic composite inks.
  • Example 3 Preparation of Alcohol-Soluble Resin of the Invention
  • Component A Vinyl acetate 45 kg
  • Component B Vinyl acetate 45 kg
  • Component C 0.2 kg of azobisisobutyl phthalate with 5 kg of solvent ethyl acetate dissolved with 20 kg of ethyl acetate and 60 kg of industrial alcohol as a diluent.
  • the preparation method is the same as in Example 1, and the solid content is 50%.
  • Example 4 Preparation of Alcohol-Soluble Resin of the Invention
  • Component A Vinyl acetate 25 kg
  • Component B Vinyl acetate 25 kg
  • Component C 0.2 kg of azobisisobutyl phthalate 0.2 kg of isopropanol and ethyl acetate, 40 kg of ethyl acetate and 40 kg of industrial alcohol were used as diluent.
  • the preparation method was the same as in Example 1, and the solid content was 50 ⁇ 200. 9 ⁇ .
  • the resin prepared in the formulation of Example 4 is a plastic composite adhesive having a solid content of 50%.
  • Example 5 Preparation of the alcohol-soluble ink of the present invention
  • the formulation for producing an alcohol-soluble ink using the resin of the present invention is as follows (weight ratio):
  • Component A Vinyl acetate 30 kg
  • Component B Vinyl acetate 30 kg
  • Component C Benzoyl peroxide 0.3 kg dissolved with 5 kg of ethyl acetate
  • the resin with a solid content of 50% of the resin was obtained.
  • the resin prepared in the formulation described in Example 6 is preferably used as a wood varnish, a paper printing varnish and a plastic surface decorative lacquer.
  • Example 7 Preparation of wood varnish for producing wood of the present invention
  • the formula for producing a wood varnish using the resin of the present invention is as follows (weight ratio):
  • the process for producing the wood varnish of the present invention is as follows:
  • the formulation of the paper printing varnish of this embodiment is as follows (weight ratio):
  • the formula for producing a plastic surface decorative paint using the resin of the present invention is as follows (weight ratio):
  • Component A Vinyl acetate 30 kg
  • Component B Vinyl acetate 30 kg
  • Component C 0.2 kg of azobisisobutyl phthalate with 5 kg of solvent ethyl acetate dissolved with 20 kg of ethyl acetate and 65 kg of industrial alcohol as a diluent.
  • the preparation method is the same as in Example 1, and the solid content is 50%.
  • Example 11 Preparation of Alcohol-Solid Metal Anticorrosive Coating of the Invention
  • the formulation of the metal anticorrosive coating using the resin of the present invention is as follows (weight ratio):
  • Anhydrous ethanol 21 kg The process for producing a metal anticorrosive coating using the resin of the present invention is as follows - the above-mentioned raw materials are placed in a container, stirred at a high speed for 10 minutes to be thoroughly mixed and dispersed uniformly, and then ground to a fineness of less than 15 ⁇ m by a sand mill.
  • Example 12 Preparation of Alcohol-Soluble Resin of the Invention
  • Component B Vinyl acetate 40 kg
  • Component C 0.2 kg of azobisisobutyl phthalate with 5 kg of solvent ethyl acetate dissolved with 20 kg of ethyl acetate and 65 kg of industrial alcohol as a diluent.
  • the preparation method is the same as in Example 1, and the solid content is 50%.
  • Example 13 Preparation of Alcohol-Soluble Hair Colorant of the Invention
  • the formulation of the alcohol-soluble hair colorant using the resin of the present invention is as follows (weight ratio):
  • the results in the table show that the ink prepared by the resin provided by the invention has an adhesion fastness of more than 85%, and has an actual measurement value.
  • the present invention uses a main raw material, vinyl acetate, together with a plurality of monomers to polymerize into a resin having excellent performance and low cost, and the solvent of the resin is used in a wide range, and not only an alcohol solvent but also benzene or an ester may be used if necessary.
  • Ketone solvents provide a new type of resin with excellent properties for many types of fine chemicals such as inks, adhesives and coatings.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Public Health (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Description

一种醇溶性树脂及其制备方法 所属技术领域
本发明涉及一种醇溶性共聚树脂， 具体地说是涉及一种在制备醇溶性油墨、 醇 溶性塑料复合粘合剂等醇溶性精细化工产品时作为主要原料的醇溶性树脂， 及其制 备方法。
技术背景
树脂是生产油墨、 胶粘剂、 涂料等精细化工产品的主要原料， 树脂决定了这些 精细化工产品的性能、 成本以及在使用过程中用何种溶剂稀释； 目前， 大多数生产 上述产品的树脂都以苯类、 酮类作溶剂稀释， 这些溶剂不仅严重污染环境， 且由于 是石油提炼物， 随着石油价格的上涨， 成本大幅升高； 由于成本与环保的压力， 市 场上对以醇类作溶剂的树脂需求越来越大。 迄今为止， 能生产上述精细化工产品的 成熟的醇溶性树脂有： 醇溶性聚酰胺树脂、醇溶性聚氨酯树脂、聚乙烯醇缩醛树脂， 这些类型的树脂由于原材料成本和生产工艺等原因，价格较贵， 用其生产上述产品， 其成本较高， 因此降低醇溶性树脂的成本成了市场的迫切要求。
由于醋酸乙烯是市场上最廉价并且无毒的单体原料之一， 且其聚合物能溶与醇， 用其作主要原料生产醇溶性树脂能大幅降低成本， 但是由于醋酸乙烯的均聚物玻璃 化温度为 28°C， 软化点低， 受热即发软变形； 又加之其容易吸潮， 吸潮后会严重影 响树脂性能， 故目前国内外均未见用醋酸乙烯作主要原料合成满足上述产品要求的 醇溶性树脂的报道。
发明内容
本发明的目的在于制备一种醇溶性树脂， 该树脂可用于制造油墨等精细化工产 品； 本发明的另一目的是提供该树脂的制备方法和用途。
本发明提供的醇溶性树脂， 是由含有 50%— 90%w/w醋酸乙烯的原料， 以偶氮 二异丁晴和 /或过氧化苯甲酰为引发剂聚合而成。
具体地说， 它是由下列重量配比的原料制备而成- 醋酸乙烯 50— 90%
丙烯酸酯和 /或甲基丙烯酸酯 4-35%
活性官能团化合物 6-15%
加入原料总重量 0.1— 1.1 %的引发剂， 在酯类和 /或醇类溶剂中聚合即得。 经筛选比较， 其中优选原材料配比为：
醋酸乙烯 80-90%
丙烯酸酯和 /或甲基丙烯酸酯 4-10 %
1
确 认 本 活性官能团化合物 6-10%
制备时， 需加上述原料总重量的 0.2— 0.9%的偶氮二异丁晴和 /或过氧化苯甲酰 作引发剂， 在酯类和 /或醇类溶剂中聚合得到本发明醇溶性树脂。
所述活性官能团化合物为丙烯酸、 甲基丙烯酸、 丁烯二酸、 丙烯酸羟乙酯、 丙 烯酸羟丙酯、 甲基丙烯酸羟乙酯、 甲基丙烯酸羟丙酯、 丙烯酸缩水甘油酯、 甲基丙 烯酸缩水甘油酯、 不饱和酸与双环氧化合物的反应物、 丙烯酰胺、 甲基丙烯酰胺、 羟甲基丙烯酰胺中的一种或几种。
本发明提供的制备醇溶性树脂的方法， 包括如下步骤：
a、 按下列配比称取原料：
甲组分： 醋酸乙烯 25_45%
丙烯酸酯和 /或甲基丙烯酸酯 1-10%
加入醇类或酯类溶剂，溶剂的量为上述醋酸乙烯和丙烯酸酯和 /或甲基丙烯 酸酯总重量的 10— 35%
乙组分： 醋酸乙烯 25-45%
丙烯酸酯和 /或甲基丙烯酸酯 3— 25%
活性官能团化合物 6— 15%
另加入原料总重量 0. 1 -0. 7%的引发剂
丙组分： 原料总重量 0. 1-0. 4%的引发剂用酯类和醇类溶剂溶解备 用；
上述引发剂总量为原料总重量的 0. 1%；
b、 将甲组分加入反应釜中， 搅拌， 升温至回流温度；
c、 在 1. 5— 4小时内向反应釜中滴加乙组分， 滴加完成后继续反应 1小时； d、 c步骤完成后在 0. 5小时内滴加入丙组分，控制物料温度在 70— 85°C之间继 续反应 2小时；
e、 根据产品的浓度要求加入醇类和 /或酯类溶剂稀释， 边搅拌边降温， 釜内的 物料温度降至 50°C以下时出料， 即得所需浓度的醇溶性树脂。
上述 a步骤原料配比优选的方案是- 甲组分： 醋酸乙烯 40-45%
丙烯酸酯和 /或甲基丙烯酸酯 2-4% 加入醇类或酯类溶剂， 溶剂的量为上述醋酸乙烯和丙烯酸酯和 /或甲基 丙烯酸酯总重量的 10—35%
乙组分： 醋酸乙烯 40-45%
丙烯酸酯和 /或甲基丙烯酸酯 2-6% 活性官能团化合物 6-10%
另加入原料总重量 0. 1-0. 7%的引发剂
丙组分： 原料总重量 0. 1-0. 4%的引发剂在酯类和 /或醇类溶剂溶解备 用。
本发明还提供了醇溶性树脂在制备油墨、 塑料复合粘合剂， 木器上光漆、 纸印 刷上光油和塑料表面装饰漆， 金属表面保护涂料、 毛发着色剂中的用途。
本发明还提供了由上述的醇溶性树脂制备而成的油墨， 塑料复合粘合剂。 下面通过具体实施例的方式对本发明做进一步详述， 但不应理解为是对本发明 保护范围的限制， 凡基于上述技术思想， 利用本领域普通技术知识和惯用手段所做 的修改、 替换、 变更均属于本发明的范围。
具体实施方式
实施例 1 本发明醇溶性树脂的制备
设备： 本发明所需设备为： 反应釜， 反应釜配有搅拌器、 回流冷凝器、 不锈钢 滴加罐、 加热及温控器。
① . 将醋酸乙烯 40公斤、 丙烯酸乙酯 2公斤、 丙烯酸甲酯 1公斤、 甲基丙烯酸 甲酯 3公斤作为甲组分，另加溶剂异丙醇 10公斤和醋酸乙酯 5公斤作为稀释剂一起 加入反应釜中， 升温并搅拌。
② . 将醋酸乙烯 40公斤、 丙烯酸乙酯 3公斤、 丙烯酸甲酯 1公斤、 甲基丙烯酸 甲酯 3公斤、丙烯酸 4公斤、丙烯酸羟丙酯 3公斤、偶氮二异丁晴 0.5公斤作为乙组 分加入滴加罐内。 待釜内物料温度升至回流温度时， 在 2小时内滴入釜内， 之后反 应 1小时。
③ .将偶氮二异丁晴 0.2公斤，加入 2.5公斤异丙醇和 2.5公斤醋酸乙酯溶解后， 在 0.5小时内滴入釜内。
④ . 保温反应 2小时后向釜内加入醋酸乙酯 20公斤、 工业酒精 60公斤， 并冷 却降温后出料， 即得固含量为 50%的树脂 200.7公斤。
实施例 1所述配方制成的树脂最宜用于生产凹版塑料表印油墨。
实施例 2本发明醇溶性树脂的制备
按下列配比称取原料：
甲组分： 醋酸乙烯 40公斤
丙烯酸甲酯 1公斤
甲基丙烯酸甲酯 7公斤
另加 15公斤异丙醇作稀释剂
乙组分： 醋酸乙烯 33公斤 丙烯酸甲酯 2公斤
甲基丙烯酸甲酯 8公斤
甲基丙烯酸 3公斤
丙烯酸羟丙酯 3公斤
丙烯酸缩水甘油酯 3公斤
过氧化苯甲酰 0.5公斤
丙组分： 偶氮二异丁晴 0.2公斤用异丙醇和醋酸乙酯各 2.5公斤溶解 另备醋酸乙酯 20公斤、 工业酒精 60公斤作稀释剂， 制备方法同实施例 1， 得 固含量为 50%的树脂 200. 7公斤。
实施例 2所述配方制成的树脂最宜用作生产耐热、 耐蒸煮凹版塑料复合油墨。 实施例 3本发明醇溶性树脂的制备
按下列配比称取原料：
甲组分： 醋酸乙烯 45公斤
丙烯酸甲酯 1公斤
另加 15公斤无水乙醇作稀释剂
乙组分： 醋酸乙烯 45公斤
丙烯酸甲酯 3公斤
甲基丙烯酸 6公斤
偶氮二异丁晴 0.5公斤
丙组分： 偶氮二异丁晴 0.2公斤用 5公斤溶剂醋酸乙酯溶解 另备醋酸乙酯 20公斤、 工业酒精 60公斤作稀释剂， 制备方法同实施例 1， 得 固含量为 50%的树脂 200. 7公斤。
实施例 3所述配方制成的树脂适宜于用作生产普通凹版塑料复合油墨。 实施例 4本发明醇溶性树脂的制备
按下列配比称取原料：
甲组分： 醋酸乙烯 25公斤
丙烯酸丁酯 20公斤
另加 15公斤异丙醇作稀释剂
乙组分: 醋酸乙烯 25公斤
丙烯酸 5公斤
丙烯酸丁酯 15公斤 丙烯酸羟丙酯 10公斤
偶氮二异丁晴 0.7公斤
丙组分： 偶氮二异丁晴 0.2公斤用异丙醇和醋酸乙酯各 2.5公斤溶解 另备醋酸乙酯 40公斤、 工业酒精 40公斤作稀释剂， 制备方法同实施例 1， 得 固含量为 50%的树脂 200. 9公斤。
实施例 4所述配方制成的树脂就是固含量为 50%的塑料复合胶粘剂。 实施例 5本发明醇溶性油墨的制备
用本发明树脂生产醇溶性油墨的配方如下 （重量比）：
由实施例 1、 2或 3制备的树脂溶液（固含量 50% ) 35公斤
钛百粉 35公斤
帖稀酚树脂 1公斤
醋酸乙酯 6— 9公斤 工业酒精 21— 24公斤 用本发明树脂生产醇溶性油墨的工艺如下：
将上述原料放入容器内， 高速搅拌 20分钟让其充分混合分散均勾， 再经砂磨机 研磨， 研磨时保持物料温度不高于 40 °C， 研磨至细度为 15微米以下即成。 实施例 6本发明醇溶性树脂的制备
按下列配比称取原料：
甲组分: 醋酸乙烯 30公斤
丙烯酸甲酯 2公斤
另加 10公斤异丙醇作稀释剂
乙组分: 醋酸乙烯 30公斤
甲基丙烯酸甲靡 25公斤
甲基丙烯酸 3公斤
丙烯酸甲酯 5公斤
甲基丙烯酸缩水甘油酯 3公斤
顺丁烯二酸 2公斤 （以 5公斤乙醇溶解) 过氧化苯甲酰 0.5公斤
丙组分： 过氧化苯甲酰 0.3公斤用 5公斤醋酸乙酯溶解
另备醋酸乙酯 20公斤、 工业酒精 60公斤作稀释剂， 制备方法同实施例 1， 得 固含量为 50%的树脂 200. 8公斤。 实施例 6所述配方制成的树脂宜作木器上光漆、 纸印刷上光油和塑料表面装饰 漆。 实施例 7本发明生产木器上光漆的制备
用本发明树脂生产木器上光漆的配方如下 （重量比）：
由实施例 6制备的树脂溶液（固含量 50% ) 45公斤
硝化棉醇溶液（70% ) 20公斤
二丁酯 3公斤
醋酸乙酯 12公斤
丁醇 8公斤
无水乙醇 12公斤
用生产本发明木器上光漆的工艺如下：
将上述原料放入容器内， 搅拌 10分钟让其充分混合分散均匀， 再经过滤即成。 实施例 8本发明纸印刷上光油的制备
本实施例生产纸印刷上光油的配方如下（重量比）：
由实施例 6制备的树脂溶液（固含量 50% ) 40公斤
醇溶松香液（固含量 20 % ) 35公斤
气相二氧化硅 3公斤
醋酸乙酯 7公斤
丁醇 2公斤
无水乙醇 13公斤
本实施例工艺如下：
将上述原料放入容器内， 高速搅拌 30分钟让其充分混合分散均匀， 再经过滤即 成。 实施例 9本发明醇溶性塑料表面装饰漆制备
用本发明树脂生产塑料表面装饰漆的配方如下（重量比）：
由实施例 6制备的树脂溶液 (固含量 50% ) 45公斤
颜料 20公斤
流平剂 0.3公斤
防沉剂 1公斤
醋酸乙酯 10公斤 丁醇 2公斤
无水乙醇 21公斤
用本发明树脂生产塑料表面装饰漆的工艺如下：
将上述原料放入容器内， 高速搅拌 10分钟让其充分混合分散均匀，再经过砂磨 机研磨至细度小于 15微米即成。 实施例 10本发明醇溶性树脂的制备
按下列配比称取原料：
甲组分： 醋酸乙烯 30公斤
丙烯酸甲酯 4公斤
另加 10公斤异丙醇稀释
乙组分: 醋酸乙烯 30公斤
甲基丙烯酸甲酯 20公斤
丙烯酸羟丙酯 2公斤
丙烯酸甲酯 4公斤
甲基丙烯酸 5公斤
甲基丙烯酸缩水甘油酯 5公斤
偶氮二异丁晴 0.6公斤
丙组分： 偶氮二异丁晴 0.2公斤用 5公斤溶剂醋酸乙酯溶解 另备醋酸乙酯 20公斤、 工业酒精 65公斤作稀释剂， 制备方法同实施例 1， 得 固含量为 50%的树脂 200. 8公斤。
实施例 5所述配方制成的树脂宜用作生产金属表面保护涂料。 实施例 11本发明醇溶性金属防腐涂料制备
用本发明树脂生产金属防腐涂料的配方如下（重量比）：
由实施例 10制备的树脂溶液（固含量 50% ) 50公斤
钛白或其他原料 15公斤
消泡剂 0.8公斤
流平剂 0.2公斤
防沉剂 1公斤
醋酸乙酯 10公斤
丁醇 2公斤
无水乙醇 21公斤 用本发明树脂生产金属防腐涂料的工艺如下- 将上述原料放入容器内， 高速搅拌 10分钟让其充分混合分散均匀， 再经过砂磨 机研磨至细度小于 15微米即成。 实施例 12本发明醇溶性树脂的制备
按下列配比称取原料- 甲组分： 醋酸乙烯 40公斤
丙烯酸甲酯 4公斤
另加 10公斤异丙醇稀释
乙组分： 醋酸乙烯 40公斤
丙烯酸羟丙酯 2公斤
丙烯酸甲酯 4公斤
甲基丙烯酸 5公斤
甲基丙烯酸缩水甘油酯 5公斤
偶氮二异丁晴 0.6公斤
丙组分： 偶氮二异丁晴 0.2公斤用 5公斤溶剂醋酸乙酯溶解 另备醋酸乙酯 20公斤、 工业酒精 65公斤作稀释剂， 制备方法同实施例 1， 得 固含量为 50%的树脂 200. 8公斤。 实施例 13本发明醇溶性毛发着色剂制备
用本发明树脂生产醇溶性毛发着色剂的配方如下（重量比）：
由实施例 12制备的树脂溶液（固含量 50% ) 40公斤 染料 10公斤
蒸馏水 15公斤
无水乙醇 15公斤
香料 0.05公斤 用本发明树脂生产醇溶性毛发着色剂的工艺如下：
将上述原料放入容器内， 高速搅拌 10分钟让其充分混合分散均匀即成。 将实施例 5制备的醇溶性油墨根据 QB/T2024- 94油墨标准检验， 结果显示 （表 1 ) ; 表 1本发明油墨指标检验结果
(根据 QB/T2024-94油墨标准）
表中结果显示， 本发明提供的树脂制备得到的油墨附着牢度远远大于 85%， 具 实 测 值
检测项目 标准值 实施例 1树脂 实施例 2树脂 实施例 3树脂 测试方法 油 墨 油 墨 油 墨
细度 um ^25 15 15 15 GB/T 13217. 3 粘度 s 25〜70 30 33 37 GB/T 13217. 4 初干性 mm 20〜50 40 32 33 GB/T 13217. 5 附着牢度°/。 ^85 90 94 95 GB/T 13217. 7 溶剂残留
30 12 15 17 气相色谱法 量 Mg/m2
有良好的附着牢度， 且溶剂残留量低， 不留异味。 将制备的油墨经多家印刷厂试用 结果表明， 用本发明树脂生产的油墨在 BOPP、 PE、 PA、 PET薄膜上印刷时， 印刷 适应性好， 即在不同季节、 不同温湿度、 不同设备、 不同承印薄膜的情况下， 印刷 效果相同，对现有的聚酰胺表印油墨体系、 氯化聚丙烯复合油墨体系以及聚氨酯蒸 煮油墨体系均具有良好的配伍套印性和附着力；
总之， 本发明使用主要原料一一醋酸乙烯与多种单体一起聚合成了性能优良、 成本低廉的树脂， 而且树脂的溶剂使用范围宽， 不仅可用醇类溶剂， 必要时也可用 苯、 酯、 酮类溶剂； 为油墨、 粘合剂、 涂料等多类精细化工产品提供了一种性能优 良的新型树脂。

Claims

权利要求书
1、一种醇溶性树脂，其特征在于：它是由含有 50%— 90%w/w醋酸乙烯的原料 制备而成。
2、根据权利要求 1所述的醇溶性树脂， 其特征在于： 它是由下列重量配比的原 料制备而成：
醋酸乙烯 50— 90%
丙烯酸酯和 /或甲基丙烯酸酯 4-35%
活性官能团化合物 6— 15%
加上原料总重量 0.1%— 1.1%的引发剂， 在酯类和 /或醇类溶剂中聚合即得。
3、根据权利要求 2所述的醇溶性树脂， 其特征在于： 它是由下列重量百分比的 原料制备而成：
醋酸乙烯 80-90%
丙烯酸酯和 /或甲基丙烯酸酯 4-10%
活性官能团化合物 6-10%
以上述原料总重量 0.2%—0.9%的偶氮二异丁晴和 /或过氧化苯甲酰作引发剂， 在酯类和 /或醇类溶剂中聚合得到本发明醇溶性树脂。
4、根据权利要求 2或 3所述的醇溶性树脂， 其特征在于： 所述活性官能团化合 物为丙烯酸、 甲基丙烯酸、 丁烯二酸、 丙烯酸羟乙酯、 丙烯酸羟丙酯、 甲基丙烯酸 羟乙酯、 甲基丙烯酸羟丙酯、 丙烯酸缩水甘油酯、 甲基丙烯酸缩水甘油酯、 不饱和 酸与双环氧化合物的反应物、 丙烯酰胺、 甲基丙烯酰胺、 羟甲基丙烯酰胺中的一种 或几种； 所述引发剂为偶氮二异丁晴和 /或过氧化苯甲酰。
5、 制备权利要求 1-4任意一项所述的醇溶性树脂的方法， 其特征在于- a、 按下列配比称取原料：
甲组分： 醋酸乙烯 25—45%
丙烯酸酯和 /或甲基丙烯酸酯 1-10%
加入醇类或酯类溶剂， 溶剂的量为上述醋酸乙烯和丙烯酸酯和 /或甲基丙烯酸 酯总重量的 10— 35% ;
乙组分 : 醋酸乙烯 25-45%
丙烯酸酯和 /或甲基丙烯酸酯 3— 25%
活性官能团化合物 6— 15%
另加入原料总重量 0. 1— 0. 7 %的引发剂
丙组分: 原料总重量 0. 1-0. 4%的引发剂用酯类和 /或醇类溶剂溶解 备用； 上述引发剂总量为原料总重量的 0. 1%-1. 1%；
b、 将甲组分加入反应釜中， 搅拌， 升温至回流温度；
c、 在 1. 5— 4小时内向反应釜中滴加乙组分， 滴加完成后继续反应 1小时； d、 c步骤完成后在 0. 5小时内滴加入丙组分，控制物料温度在 70— 85°C之间继 续反应 2小时；
e、 根据产品的浓度要求加入醇类和 /或酯类溶剂稀释， 边搅拌边降温， 釜内的 物料温度降至 50°C以下时出料， 即得所需浓度的醇溶性油墨树脂。
6、 根据权利要求 5所述的方法， 其特征在于： a步骤所述原料配比为- 甲组分： 醋酸乙烯 40-45%
丙烯酸酯和 /或甲基丙烯酸酯 2 - 4%
加入醇类或酯类溶剂， 溶剂的量为上述醋酸乙烯和丙烯酸酯和 /或甲基丙烯酸 酯总重量的 10— 35% ;
乙组分： 醋酸乙烯 40-45%
丙烯酸酯和 /或甲基丙烯酸酯 2-6%
活性官能团化合物 6-10%
另加入原料总重量 0. 1— 0. 7%的引发剂
丙组分： 原料总重量 0. 1-0. 4%的引发剂在酯类和 /或醇类溶剂溶解 备用。
7、 权利要求 1一 4任一项所述的醇溶性树脂在制备塑料复合粘合剂、 油墨、 纸 印刷上光油、 木器上光漆、 塑料表面装饰涂料、 金属表面保护涂料、 毛发着色剂中 的用途。
8、一种塑料复合粘合剂， 其特征在于： 它是由权利要求 1一 4任一项所述的醇 溶性树脂制备而成。
9、 一种油墨， 其特征在于： 它是由权利要求 1一 4任一项所述的醇溶性树脂， 加上颜料、 溶剂和助剂组成。
PCT/CN2006/000025 2005-07-15 2006-01-09 Resine soluble dans l'alcool et son procede de preparation WO2007009325A1 (fr)

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CN101899236A (zh) * 2009-06-01 2010-12-01 钟文军 一种耐高温蒸煮油墨及其制备方法

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CN1737021A (zh) 2006-02-22
EP1932860B1 (en) 2012-10-03
CN101090917A (zh) 2007-12-19
US20090149615A1 (en) 2009-06-11
EP1932860A4 (en) 2010-02-17
JP5149174B2 (ja) 2013-02-20
WO2007009325A8 (fr) 2007-05-24
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EP1932860A1 (en) 2008-06-18
US8410212B2 (en) 2013-04-02

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