WO2016197260A1 - Aqueous plastic gravure printing surface printing/composite ink, binder and preparation methods therefor - Google Patents

Aqueous plastic gravure printing surface printing/composite ink, binder and preparation methods therefor Download PDF

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Publication number
WO2016197260A1
WO2016197260A1 PCT/CN2015/000396 CN2015000396W WO2016197260A1 WO 2016197260 A1 WO2016197260 A1 WO 2016197260A1 CN 2015000396 W CN2015000396 W CN 2015000396W WO 2016197260 A1 WO2016197260 A1 WO 2016197260A1
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Prior art keywords
parts
binder
water
monomer
composite ink
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PCT/CN2015/000396
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French (fr)
Chinese (zh)
Inventor
孟宪平
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孟宪平
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Priority to CN201580002486.5A priority Critical patent/CN106488960B/en
Priority to PCT/CN2015/000396 priority patent/WO2016197260A1/en
Publication of WO2016197260A1 publication Critical patent/WO2016197260A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • 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
    • C09D11/023—Emulsion inks
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/08—Printing inks based on natural 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
    • 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
    • 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
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the invention relates to the field of plastic printing inks, in particular to a method for preparing water-based gravure plastic printing surface printing/composite inks and connecting materials.
  • solvent-based ink printing In order to meet the requirements of drying speed and quality of printing products, toxic solvents such as toluene, xylene and ethyl acetate are widely used.
  • solvent based inks In solvent based inks.
  • the solvent-based ink is made of a chlorinated polymer with a strong solvent such as benzene, and is used as a diluent in the use of benzene, lipids, and alcohols.
  • the object of the present invention is to overcome the deficiencies in the above background art, and to provide a method for preparing a water-based gravure plastic printing surface/composite ink and a binder, which solves the problem that the water-based plastic printing ink has a slow drying speed, poor color development, and water resistance. Problems such as poor heat and humidity resistance.
  • a water-based gravure plastic printing surface/composite ink the technical solution adopted is:
  • a water-based gravure plastic printing surface printing/composite ink which is prepared by the following components in parts by weight: 68-88 parts of the connecting material, 10-30 parts of the organic pigment, 0.1-0.15 parts of the adhesion promoter, and the drying agent 1 ⁇ 1.5 parts, defoaming agent 0.2 to 0.5 parts.
  • the following steps are carried out: mixing the binder resin, organic pigment, adhesion promoter, dry aid and antifoaming agent; dispersing and grinding to fine particles through a high-speed dispersing machine; packaging.
  • the binder is prepared by the following components in parts by weight: 1-8 parts of modified rosin, 1.5-4.5 parts of methacrylic monomer or acrylic monomer, 4-25 parts of acrylate monomer, methacrylate 20 to 28 parts of the monomer, 0.8 to 2 parts of azobisisobutyronitrile, 28 to 30 parts of anhydrous ethanol, 4 to 7 parts of amine or ammonia, 0.5 to 3 parts of a cosolvent, and 30 to 32 parts of distilled water.
  • the acrylic monomer or methacrylic acid monomer, the acrylate monomer, the methacrylate monomer, the azobisisobutyronitrile are mixed into the raw materials in the proportion by weight, and are put into the high-level tank of the raw material of the reaction kettle. Stir well;
  • the anhydrous ethanol is put into the reaction vessel with the condenser and the nitrogen introduction tube, the cooling tube in the kettle is closed, the modified rosin is added under stirring, the nitrogen pipe is opened, the nitrogen gas is introduced, the air in the reaction kettle is replaced, and the temperature is heated to the same time.
  • the modified rosin is melted at 80 ° C to 82 ° C;
  • the temperature in the reaction vessel is raised to 82 ° C to 85 ° C, and the temperature is maintained for more than 4 hours to obtain a copolymer solution; the obtained copolymer
  • the mass ratio of the resin in the solution is 58-62%; the glass transition temperature of the obtained copolymer ranges from 15 to 38 ° C;
  • the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, amine or ammonia is added, the pH of the copolymer is adjusted to 8.5-9.0, and the co-solvent and distilled water are simultaneously added to adjust the solidity of the resin.
  • the content of mass ratio is 38% to 42%, that is, a water-soluble acrylic resin binder is obtained.
  • the above water-based gravure plastic printing surface printing/composite ink and binder preparation has the following advantages: using modified rosin instead of (n-)-tert-dodecyl mercaptan as a molecular weight modifier in acrylic resin polymerization, effective The molecular weight and viscosity of the acrylic resin are lowered, the content of the resin in the ink is increased, the cohesive force of the resin is adjusted, the solvent is easily released, and the fluidity of the ink is good, thereby achieving rapid drying and smoothness of the ink film.
  • the modified rosin is used as an emulsifier of the acrylic resin, so that the ink body is less likely to generate bubbles, improve the gloss, reduce the amount of the (meth)acrylic monomer in the polymerization, improve the water resistance of the ink film, and make the printing product completely
  • the printing effect of the solvent-based ink is achieved, the gloss is high, and the water resistance and the moist heat resistance are excellent.
  • the modified rosin is used as a modifier of the acrylic resin, which effectively improves the bonding strength and color development of the acrylic resin and the pigment particles, and the ink body does not cause pigment precipitation during long-term storage and use, and the printed product is colored and beautiful.
  • the adhesion promoter is a polyethyleneimine or titanate coupling agent.
  • the dry aid is light calcium carbonate.
  • the antifoaming agent is a mixture of non-silicone amides and hydrocarbons.
  • the organic pigments include: stable phthalocyanine blue, phthalocyanine green, benzidine yellow, Lisol red, titanium white powder.
  • the particle size is ⁇ 15 microns.
  • the preferred solution for the binder for inks is:
  • the cosolvent is a propylene glycol ether
  • the amine added after the polymerization is triethylamine; the ammonia is ammonia water.
  • drying speed is fast, (50 ⁇ 60 ° C hot air) dry speed of 110 ⁇ 150 meters per minute, strong adhesion (printing substrate needs to be treated by electric spark), high gloss, good transparency, strong scratch resistance, water resistance, heat and humidity resistance, and application Wide range, suitable for printing on a variety of plastic substrates, the prospects are considerable.
  • the temperature in the autoclave was raised to 82 ° C and kept for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the resulting copolymer had a glass transition temperature in the range of 35 to 36 ° C.
  • the cooling device in the reaction vessel was opened, the temperature was lowered to 65 ° C, 52 kg of triethylamine was added, the pH of the copolymer was adjusted to 8.5 to 9.0, and 5 kg of propylene glycol methyl ether and 277 kg of distilled water were simultaneously added to adjust the resin mass ratio.
  • the solid content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
  • Example 1 a water-soluble acrylic resin binder obtained in Example 1 was mixed, and a method of preparing a surface/composite ink was prepared.
  • the temperature in the autoclave was raised to 82 ° C and kept for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the obtained copolymer glass had a vitrification range of 32 to 33 ° C.
  • the condensation device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, 53 kg of triethylamine is added, the pH of the copolymer is adjusted to 8.5-9.0, and 3 kg of propylene glycol methyl ether and 275 kg of distilled water are simultaneously added to adjust the solid.
  • the content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
  • Example 3 a water-soluble acrylic resin binder obtained in Example 3 was mixed, and a method of preparing a surface/composite ink was prepared.
  • the temperature in the reactor was raised to 82 ° C and held for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the obtained copolymer had a vitrification range of 32 to 33 ° C.
  • the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, 54.8 kg of triethylamine is added, the pH of the copolymer is adjusted to 8.5-9.0, and 5 kg of propylene glycol diethyl ether and 274 kg of distilled water are simultaneously added to adjust the solid.
  • the content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
  • Example 5 a water-soluble acrylic resin binder obtained in Example 5 was mixed, and a method of preparing a surface/composite ink was prepared.
  • the dispersing machine is dispersed and ground to a particle size of ⁇ 15 ⁇ m, and packaged; that is, a water-soluble gravure plastic printing surface/composite ink is obtained.
  • nitrile 16 kg of acrylic monomer, 204 kg of isobutyl methacrylate monomer, 32 kg of 2-hydroxyethyl methacrylate monomer, 104 kg of n-butyl acrylate monomer, 20 kg of ethyl acrylate monomer, 9 kg of azobisisobutyl
  • the nitrile is mixed into a stock preparation, and is put into a high-position tank which is connected to the upper part of the reaction vessel and has a flow agent, and is uniformly stirred.
  • the temperature in the reaction vessel was raised to 82 ° C and kept for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the obtained copolymer had a glass transition temperature of 19 to 20 ° C.
  • the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, 55 kg of triethylamine is added, the pH of the copolymer is adjusted to 8.5-9.0, and 4 kg of propylene glycol ether and 274.5 kg of distilled water are simultaneously added to adjust the solid.
  • the content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
  • Example 7 a water-soluble acrylic resin binder obtained in Example 7 was mixed, and a method of preparing a surface/composite ink was prepared.
  • the isobutyronitrile is mixed into a raw material, and is put into a high-position tank which is connected to the upper part of the reaction vessel and has a flow agent, and is uniformly stirred.
  • the temperature in the reaction vessel was raised to 82 ° C and held for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the copolymer glass transition temperature was 32 to 33 ° C.
  • the cooling device in the reactor is opened, the temperature is lowered to 60-65 ° C, 38 kg of ammonia water is added, the pH of the copolymer is adjusted to 8.5-9.0, and 5 kg of propylene glycol methyl ether and 289 kg of distilled water are simultaneously added to adjust the solid content to 40%, that is, a water-soluble acrylic resin binder was obtained.
  • a water-soluble acrylic resin binder obtained in Example 9 is mixed, and a method of preparing a surface/composite ink is prepared.

Abstract

An aqueous plastic gravure printing surface printing/composite ink, a binder and preparation methods therefor. The ink is formulated from the following components: 68-88 parts of a binder, 10-30 parts of an organic pigment, 0.1-0.15 part of an adhesion promoter, 1-1.5 parts of a drying aid, and 0.2-0.5 part of a defoaming agent. The binder is prepared from the following components: 1-8 parts of a modified rosin, 1.5-4.5 parts of a methacrylic acid monomer or an acrylic acid monomer, 4-25 parts of an acrylate monomer, 20-28 parts of a methacrylate monomer, 0.8-2 parts of azobisisobutyronitrile, 28-30 parts of anhydrous ethanol, 4-7 parts of an amine or ammonia, 0.5-3 parts of a cosolvent and 30-32 parts of distilled water. The modified rosin is used for decreasing the molecular weight and viscosity of an acrylic acid resin, improving the content of the resin in the ink, and adjusting the cohesion of the resin so that the solvent can be easily released, and the fluidity of the ink is good, so as to achieve fast drying and the smoothness of the ink film.

Description

水性凹版塑料印刷表印/复合油墨及连接料的制备方法Water-based gravure plastic printing surface printing/composite ink and preparation method of connecting material 技术领域Technical field
本发明涉及塑料印刷油墨领域，特别是一种水性凹版塑料印刷表印/复合油墨及连接料的制备方法。The invention relates to the field of plastic printing inks, in particular to a method for preparing water-based gravure plastic printing surface printing/composite inks and connecting materials.
背景技术Background technique
目前，我国仍有90％以上的塑料印刷企业采用溶剂型的油墨印刷，为了达到干燥速度和印品质量的要求，甲苯、二甲苯、醋酸乙酯等挥发性极强的有毒溶剂，被广泛应用在溶剂型油墨中。溶剂型油墨是以氯化聚合物配以强溶剂苯等芳香族类制成，使用时用苯类、脂类、醇类作为稀释剂，在油墨的生产和使用过程中会挥发大量的有毒(溶剂)气体，严重的破坏大气的臭氧层，造成极大的环境污染，对人们的身体健康造成了极大的伤害，尤其是直接危害操作人员的身体健康，并且由于溶剂大量挥发造成操作车间溶剂存留超标(尤其是冬季)形成了极大的火灾安全隐患。另外，由于苯极易残留在干燥的油墨微膜中，二甲苯更容易加大苯残留量，印刷完的食品软包装安全性也很差，直接影响了人们的身体、身心健康，尤其对儿童的危害更为巨大。At present, more than 90% of plastic printing enterprises in China use solvent-based ink printing. In order to meet the requirements of drying speed and quality of printing products, toxic solvents such as toluene, xylene and ethyl acetate are widely used. In solvent based inks. The solvent-based ink is made of a chlorinated polymer with a strong solvent such as benzene, and is used as a diluent in the use of benzene, lipids, and alcohols. It will volatilize a large amount of toxic during the production and use of the ink ( Solvent) gas, which seriously damages the ozone layer of the atmosphere, causes great environmental pollution, and causes great harm to people's health, especially directly damaging the health of the operator, and the solvent in the operation workshop is caused by the large amount of solvent volatilization. Excessive standards (especially in winter) have created significant fire safety hazards. In addition, since benzene is easily left in the dry ink microfilm, xylene is more likely to increase the amount of benzene residues, and the printed food soft packaging is also less safe, directly affecting people's physical and mental health, especially for children. The harm is even greater.
对于市场上出现的醇溶性油墨，虽然较为环保，但一些塑料印刷企业为降低成本多采用价格低廉的甲醇代替价格稍高的乙醇作为稀释剂，甲醇挥发出的气体依然对环境产生污染，长期使用直接影响操作人员的身体健康，尤其是眼睛，而且甲醇挥发性强的特点，容易造成火灾安全隐患。For the alcohol-soluble inks appearing on the market, although it is more environmentally friendly, some plastic printing companies use low-cost methanol instead of the slightly higher-priced ethanol as a diluent to reduce costs. The gas volatilized by methanol still pollutes the environment and is used for a long time. It directly affects the health of the operator, especially the eyes, and the strong volatility of methanol is likely to cause fire safety hazards.
还有市场上出现的水性塑料印刷油墨，由于干燥速度慢，展色力差，附着牢度差，耐水性耐湿热性差，光泽度不良，且墨膜强度不好，存放中易产生颜料沉淀，不防冻等缺点，达不到现有塑料印刷中，印刷速度快，印品质量高的要求；国外采用增长印刷机烘道来解决干燥问题，却增加了印刷成本，因此均没有被广大印刷企业认可和推广应用。There are also water-based plastic printing inks appearing on the market. Due to the slow drying speed, poor color development, poor adhesion, poor water and moisture resistance, poor gloss, and poor ink film strength, pigment precipitation is likely to occur during storage. Not anti-freezing and other shortcomings, can not meet the requirements of the existing plastic printing, printing speed, high quality of printed products; foreign use of the printing press drying tunnel to solve the drying problem, but increased the printing cost, so they are not by the majority of printing companies Recognize and promote the application.
发明内容Summary of the invention
本发明的目的为了克服上述背景技术中的不足，而提供一种水性凹版塑料印刷表印/复合油墨及连接料的制备方法，以解决水性塑料印刷油墨干燥速度慢，展色力差，耐水性耐湿热性差等问题。The object of the present invention is to overcome the deficiencies in the above background art, and to provide a method for preparing a water-based gravure plastic printing surface/composite ink and a binder, which solves the problem that the water-based plastic printing ink has a slow drying speed, poor color development, and water resistance. Problems such as poor heat and humidity resistance.
为达到上述目的，本发明采用以下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种水性凹版塑料印刷表印/复合油墨，所采用的技术方案是：A water-based gravure plastic printing surface/composite ink, the technical solution adopted is:
一种水性凹版塑料印刷表印/复合油墨，按重量份数由以下组份配制：连接料68～88份，有机颜料10～30份，附着力促进剂0.1～0.15份，助干剂1～1.5份，消泡剂0.2～0.5份。A water-based gravure plastic printing surface printing/composite ink, which is prepared by the following components in parts by weight: 68-88 parts of the connecting material, 10-30 parts of the organic pigment, 0.1-0.15 parts of the adhesion promoter, and the drying agent 1~ 1.5 parts, defoaming agent 0.2 to 0.5 parts.
前述水性凹版塑料印刷表印/复合油墨的制备方法采用如下技术方案：The preparation method of the foregoing water-based gravure plastic printing surface/composite ink adopts the following technical solutions:
按以下步骤进行：将连接料树脂，有机颜料，附着力促进剂，助干剂和消泡剂混合；经高速分散机，分散研磨至微小颗粒；包装。The following steps are carried out: mixing the binder resin, organic pigment, adhesion promoter, dry aid and antifoaming agent; dispersing and grinding to fine particles through a high-speed dispersing machine; packaging.
前述连接料所采用的技术方案是：The technical solution adopted by the foregoing connecting materials is:
连接料，按重量份数由以下组份配制：改性松香1～8份，甲基丙烯酸单体或丙烯酸单体1.5～4.5份，丙烯酸酯类单体4～25份，甲基丙烯酸酯类单体20～28份，偶氮二异丁腈0.8～2份，无水乙醇28～30份，胺或氨类4～7份，助溶剂0.5～3份，蒸馏水30～32份。The binder is prepared by the following components in parts by weight: 1-8 parts of modified rosin, 1.5-4.5 parts of methacrylic monomer or acrylic monomer, 4-25 parts of acrylate monomer, methacrylate 20 to 28 parts of the monomer, 0.8 to 2 parts of azobisisobutyronitrile, 28 to 30 parts of anhydrous ethanol, 4 to 7 parts of amine or ammonia, 0.5 to 3 parts of a cosolvent, and 30 to 32 parts of distilled water.
连接料的制备所采用的技术方案：The technical solution adopted for the preparation of the binder:
将丙烯酸单体或甲基丙烯酸单体，丙烯酸酯类单体，甲基丙烯酸酯类单体，偶氮二异丁腈按重量份数配比混合成备料，投入到反应釜的原料高位槽内，搅拌均匀；The acrylic monomer or methacrylic acid monomer, the acrylate monomer, the methacrylate monomer, the azobisisobutyronitrile are mixed into the raw materials in the proportion by weight, and are put into the high-level tank of the raw material of the reaction kettle. Stir well;
将无水乙醇投入到带有冷凝器、氮气导入管的反应釜中，关闭釜内冷却管，在搅拌下加入改性松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃～82℃，将改性松香融化；The anhydrous ethanol is put into the reaction vessel with the condenser and the nitrogen introduction tube, the cooling tube in the kettle is closed, the modified rosin is added under stirring, the nitrogen pipe is opened, the nitrogen gas is introduced, the air in the reaction kettle is replaced, and the temperature is heated to the same time. The modified rosin is melted at 80 ° C to 82 ° C;
打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时，将原料高位槽内备料滴加完全；Turn on the flowmeter and add the prepared material to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The drip acceleration is controlled for 2 to 3 hours, and the preparation in the high-level tank of the raw material is completely added;
将反应釜内温度升至82℃～85℃，保温4小时以上，制得共聚物溶液；所制得的共聚物 溶液中树脂的质量比固含量为58～62％；所得共聚物的玻璃化温度范围在15～38℃；The temperature in the reaction vessel is raised to 82 ° C to 85 ° C, and the temperature is maintained for more than 4 hours to obtain a copolymer solution; the obtained copolymer The mass ratio of the resin in the solution is 58-62%; the glass transition temperature of the obtained copolymer ranges from 15 to 38 ° C;
聚合完全后，打开反应釜内冷却装置，将温度降到60～65℃，加入胺类或氨类，调整共聚物的pH值到8.5～9.0，并且同时加入助溶剂、蒸馏水，调整树脂的固含量质量比至38％～42％，即制得水溶性丙烯酸树脂连接料。After the polymerization is completed, the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, amine or ammonia is added, the pH of the copolymer is adjusted to 8.5-9.0, and the co-solvent and distilled water are simultaneously added to adjust the solidity of the resin. The content of mass ratio is 38% to 42%, that is, a water-soluble acrylic resin binder is obtained.
以上水性凹版塑料印刷表印/复合油墨及连接料配制与现有技术相比，具有：采用改性松香代替(正)叔十二烷基硫醇作为丙烯酸树脂聚合中的分子量调节剂，有效的降低了丙烯酸树脂的分子量和粘度，提高了墨体中树脂的含量，调整了树脂的内聚力，使溶剂很容易被释放，且墨体的流动性好，从而达到快速干燥和墨膜的平滑性。Compared with the prior art, the above water-based gravure plastic printing surface printing/composite ink and binder preparation has the following advantages: using modified rosin instead of (n-)-tert-dodecyl mercaptan as a molecular weight modifier in acrylic resin polymerization, effective The molecular weight and viscosity of the acrylic resin are lowered, the content of the resin in the ink is increased, the cohesive force of the resin is adjusted, the solvent is easily released, and the fluidity of the ink is good, thereby achieving rapid drying and smoothness of the ink film.
采用改性松香作为丙烯酸树脂的乳化剂，使墨体不易产生气泡，提高光泽度，同时减少了(甲基)丙烯酸单体在聚合中的用量，提高了墨膜的耐水性，使印品完全达到了溶剂型油墨的印刷效果，光泽度高，耐水性耐湿热性优异。The modified rosin is used as an emulsifier of the acrylic resin, so that the ink body is less likely to generate bubbles, improve the gloss, reduce the amount of the (meth)acrylic monomer in the polymerization, improve the water resistance of the ink film, and make the printing product completely The printing effect of the solvent-based ink is achieved, the gloss is high, and the water resistance and the moist heat resistance are excellent.
采用改性松香作为丙烯酸树脂的改性剂，有效的提高了丙烯酸树脂与颜料粒子的结合强度及展色力，墨体在长期存放和使用过程中不产生颜料沉淀，且印品着色艳丽。The modified rosin is used as a modifier of the acrylic resin, which effectively improves the bonding strength and color development of the acrylic resin and the pigment particles, and the ink body does not cause pigment precipitation during long-term storage and use, and the printed product is colored and beautiful.
水性凹版塑料印刷表印/复合油墨所采用的优选方案是：The preferred solution for water-based gravure plastic printing/composite inks is:
所述附着力促进剂为聚乙烯亚胺或钛酸酯偶联剂。The adhesion promoter is a polyethyleneimine or titanate coupling agent.
助干剂为轻质碳酸钙。The dry aid is light calcium carbonate.
所述消泡剂为非有机硅的酰胺类与碳氢化合物的混合物。The antifoaming agent is a mixture of non-silicone amides and hydrocarbons.
有机颜料包括：稳定酞菁蓝、酞菁绿、联苯胺黄、立索尔宝红、钛白粉。The organic pigments include: stable phthalocyanine blue, phthalocyanine green, benzidine yellow, Lisol red, titanium white powder.
凹版塑料印刷表印/复合油墨的制备方法所采用的优选方案是：The preferred solution for the preparation of gravure plastic printing/composite inks is:
所述颗粒粒径≤15微米。The particle size is < 15 microns.
油墨用连接料所采用的优选方案是：The preferred solution for the binder for inks is:
所述助溶剂为丙二醇醚类，The cosolvent is a propylene glycol ether,
聚合后加入的胺类是三乙胺；氨类是氨水。The amine added after the polymerization is triethylamine; the ammonia is ammonia water.
所述保温4小时后，所制得的共聚物溶液中树脂的固含量质量比为60％。After the incubation for 4 hours, the solid content ratio of the resin in the obtained copolymer solution was 60%.
使用时用无污染的水或蒸馏水作为稀释剂，缓解了石油产品的压力，极大地降低了印刷成本，印品无溶剂残留，达到了溶剂型油墨印刷的效果；干燥速度快，(有50～60℃热风)干速达110～150米每分钟，附着牢度强(印刷基材需要经过电火花处理)，光泽度高，透明度好，抗划伤性强，耐水性耐湿热性优异，且应用面广，可适合各种塑料基材印刷，前景可观。When used, it uses non-polluting water or distilled water as a diluent to relieve the pressure of petroleum products, greatly reducing the printing cost, printing solvent-free residue, and achieving the effect of solvent-based ink printing; drying speed is fast, (50~ 60 ° C hot air) dry speed of 110 ~ 150 meters per minute, strong adhesion (printing substrate needs to be treated by electric spark), high gloss, good transparency, strong scratch resistance, water resistance, heat and humidity resistance, and application Wide range, suitable for printing on a variety of plastic substrates, the prospects are considerable.
具体实施方式detailed description
下面结合实施例详述本发明：The invention will be described in detail below with reference to examples:
实施例1Example 1
本实施例中连接料的制备方法按如下步骤进行：The preparation method of the binder in this embodiment is carried out as follows:
将28kg甲基丙烯酸单体、224kg甲基丙烯酸正丁酯单体、64kg甲基丙烯酯甲酯单体、56kg丙烯酸丁酯单体、8kg偶氮二异丁腈混合成备料，投入到连接在反应釜上部带有流量剂的原料高位槽内，搅拌均匀。28 kg of methacrylic acid monomer, 224 kg of n-butyl methacrylate monomer, 64 kg of methacrylic ester methyl ester monomer, 56 kg of butyl acrylate monomer, and 8 kg of azobisisobutyronitrile were mixed into a preparation, and the mixture was put into connection. The upper part of the reaction vessel is filled with a flow agent in a high-position tank and stirred uniformly.
将258kg无水乙醇投入到带有冷凝器、氮气导入管且釜内设有过水冷却装置的反应釜中，关闭釜内冷却管，在搅拌下加入28kg氢化松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃，将氢化松香融化。258 kg of absolute ethanol was placed in a reaction vessel equipped with a condenser, a nitrogen gas introduction tube and a water-cooling device in the kettle, the inner cooling tube was closed, 28 kg of hydrogenated rosin was added under stirring, and a nitrogen gas valve was opened to introduce nitrogen gas. The air in the reaction vessel was replaced while heating to 80 ° C, and the hydrogenated rosin was melted.
打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时将原料高位槽内备料滴加完全。Turn on the flowmeter and add the preparation to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The drip acceleration is controlled to increase the preparation in the high-level tank of the raw material by 2 to 3 hours.
将反应釜内温度升至82℃，保温4小时，即制得固含量质量为60％的共聚物溶液；所得共聚物的玻璃化温度范围在35～36℃。The temperature in the autoclave was raised to 82 ° C and kept for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the resulting copolymer had a glass transition temperature in the range of 35 to 36 ° C.
聚合完全后，打开反应釜内冷却装置，将温度降到65℃，加入52kg三乙胺，调整共聚物的pH值到8.5～9.0，并且同时加入5kg丙二醇甲醚、277kg蒸馏水，调整树脂质量比固含量到40％，即制得水溶性丙烯酸树脂连接料。 After the polymerization was completed, the cooling device in the reaction vessel was opened, the temperature was lowered to 65 ° C, 52 kg of triethylamine was added, the pH of the copolymer was adjusted to 8.5 to 9.0, and 5 kg of propylene glycol methyl ether and 277 kg of distilled water were simultaneously added to adjust the resin mass ratio. The solid content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
实施例2Example 2
本实施例中是由实施例1得到的水溶性丙烯酸树脂连接料进行混合，并制备表印/复合油墨的方法。In this embodiment, a water-soluble acrylic resin binder obtained in Example 1 was mixed, and a method of preparing a surface/composite ink was prepared.
将68.7质量份的水溶性丙烯酸树脂连接料、30质量份的钛白粉、0.1质量份的钛酸酯偶联剂、1质量份的轻质碳酸钙(颗粒较细较均匀的碳酸钙)和0.2质量份的消泡剂(采用台湾德谦公司生产的080消泡剂)混合，经高速分散机，分散研磨至颗粒粒径≤15微米，包装；即制得(有50～60℃热风)干燥速度达到110～150米每分钟，附着牢度强，光泽度高，透明度好，抗划伤性强，耐水性耐湿热性优异的速干型水溶性凹版塑料印刷表印/复合油墨。68.7 parts by mass of the water-soluble acrylic resin binder, 30 parts by mass of titanium dioxide, 0.1 part by mass of a titanate coupling agent, 1 part by mass of light calcium carbonate (finer and more uniform calcium carbonate) and 0.2 The mass of defoamer (using 080 defoamer produced by Taiwan Deqian Company) is mixed and dispersed by a high-speed disperser to a particle size of ≤15 μm, packaged; that is, dried (with 50-60 ° C hot air) Fast-drying water-soluble gravure plastic printing surface/composite ink with speed up to 110-150 meters per minute, strong adhesion, high gloss, good transparency, strong scratch resistance, water resistance and moist heat resistance.
实施例3Example 3
本实施例中连接料的制备方法按如下步骤进行：The preparation method of the binder in this embodiment is carried out as follows:
将27kg丙烯酸单体、95kg丙烯酸乙酯单体、58kg甲基丙烯酸正丁酯单体、125kg甲基丙烯酸甲酯单体、57kg丙烯酸正丁酯单体、10kg偶氮二异丁腈混合成备料，投入到连接在反应釜上部带有流量剂的原料高位槽内，搅拌均匀。Mixing 27 kg of acrylic monomer, 95 kg of ethyl acrylate monomer, 58 kg of n-butyl methacrylate monomer, 125 kg of methyl methacrylate monomer, 57 kg of n-butyl acrylate monomer, and 10 kg of azobisisobutyronitrile It is put into the high-position tank of the raw material which is connected to the upper part of the reaction vessel with a flow agent, and is stirred evenly.
将256.5kg无水乙醇投入到带有冷凝器、氮气导入管且釜内设有过水冷却装置的反应釜中，关闭釜内冷却管，在搅拌下加入38kg聚合松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃，将聚合松香融化。256.5kg of absolute ethanol was put into a reaction vessel equipped with a condenser, a nitrogen introduction tube and a water-cooling device in the kettle, the inner cooling tube was closed, 38 kg of polymerized rosin was added under stirring, and a nitrogen tube valve was opened to introduce nitrogen gas. The air in the reaction vessel was replaced while heating to 80 ° C to melt the polymerized rosin.
打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时将原料高位槽内备料滴加完全。Turn on the flowmeter and add the preparation to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The drip acceleration is controlled to increase the preparation in the high-level tank of the raw material by 2 to 3 hours.
将反应釜内温度升至82℃，保温4小时，即制得固含量质量比为60％的共聚物溶液；所得到的共聚物玻璃的玻璃化范围在32～33℃。The temperature in the autoclave was raised to 82 ° C and kept for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the obtained copolymer glass had a vitrification range of 32 to 33 ° C.
聚合完全后，打开反应釜内冷凝装置，将温度降到60～65℃，加入53kg三乙胺，调整共聚物的pH值到8.5～9.0，并且同时加入3kg丙二醇甲醚、275kg蒸馏水，调整固含量到40％，即制得水溶性丙烯酸树脂连接料。After the polymerization is completed, the condensation device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, 53 kg of triethylamine is added, the pH of the copolymer is adjusted to 8.5-9.0, and 3 kg of propylene glycol methyl ether and 275 kg of distilled water are simultaneously added to adjust the solid. The content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
实施例4Example 4
本实施例中是由实施例3得到的水溶性丙烯酸树脂连接料进行混合，并制备表印/复合油墨的方法。In this embodiment, a water-soluble acrylic resin binder obtained in Example 3 was mixed, and a method of preparing a surface/composite ink was prepared.
将88质量份的水溶性丙烯酸树脂连接料、10质量份的酞菁蓝BGS、0.15质量份的聚乙烯亚胺、1.5质量份的轻质碳酸钙和0.5质量份的消泡剂(采用台湾德谦公司生产的080消泡剂)混合，经高速分散机，分散研磨至颗粒粒径≤15微米，包装；即制得水溶性凹版塑料印刷表印/复合油墨。88 parts by mass of the water-soluble acrylic resin binder, 10 parts by mass of phthalocyanine blue BGS, 0.15 parts by mass of polyethyleneimine, 1.5 parts by mass of light calcium carbonate, and 0.5 parts by mass of antifoaming agent (using Taiwan De The 080 defoamer produced by Qian Company is mixed and dispersed by a high-speed disperser to a particle size of ≤15 μm, and packaged; that is, a water-soluble gravure plastic printing surface/composite ink is prepared.
实施例5Example 5
本实施例中连接料的制备方法按如下步骤进行：The preparation method of the binder in this embodiment is carried out as follows:
将27kg丙烯酸单体、103kg甲基丙烯酸甲酯单体、112kg甲基丙烯酸正丁酯单体、101kg丙烯酸乙酯单体、29kg丙烯酸正丁酯单体、9.5kg偶氮二异丁腈混合成备料，投入到连接在反应釜上部带有流量剂的原料高位槽内，搅拌均匀。27kg of acrylic monomer, 103kg of methyl methacrylate monomer, 112kg of n-butyl methacrylate monomer, 101kg of ethyl acrylate monomer, 29kg of n-butyl acrylate monomer, 9.5kg of azobisisobutyronitrile Prepare the material and put it into the high-level tank of the raw material with the flow agent attached to the upper part of the reactor, and stir it evenly.
将256.5kg无水乙醇投入到带有冷凝器、氮气导入管且釜内设有过水冷却装置的反应釜中，关闭釜内冷却管，在搅拌下加入28kg聚合松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃，将聚合松香融化。256.5kg of absolute ethanol was put into a reaction vessel equipped with a condenser, a nitrogen introduction tube and a water-cooling device in the kettle, the inner cooling tube was closed, 28 kg of polymerized rosin was added under stirring, and a nitrogen tube valve was opened to introduce nitrogen gas. The air in the reaction vessel was replaced while heating to 80 ° C to melt the polymerized rosin.
打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时将原料高位槽内备料滴加完全。Turn on the flowmeter and add the preparation to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The drip acceleration is controlled to increase the preparation in the high-level tank of the raw material by 2 to 3 hours.
将反应釜内温度升至82℃，保温4小时，即制得固含量质量比为60％的共聚物溶液；所得到的共聚物的玻璃化范围在32～33℃。The temperature in the reactor was raised to 82 ° C and held for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the obtained copolymer had a vitrification range of 32 to 33 ° C.
聚合完全后，打开反应釜内冷却装置，将温度降到60～65℃，加入54.8kg三乙胺，调整共聚物的pH值到8.5～9.0，并且同时加入5kg丙二醇***、274kg蒸馏水，调整固含量到40％，即制得水溶性丙烯酸树脂连接料。After the polymerization is completed, the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, 54.8 kg of triethylamine is added, the pH of the copolymer is adjusted to 8.5-9.0, and 5 kg of propylene glycol diethyl ether and 274 kg of distilled water are simultaneously added to adjust the solid. The content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
实施例6 Example 6
本实施例中是由实施例5得到的水溶性丙烯酸树脂连接料进行混合，并制备表印/复合油墨的方法。In this embodiment, a water-soluble acrylic resin binder obtained in Example 5 was mixed, and a method of preparing a surface/composite ink was prepared.
将86.7质量份的水溶性丙烯酸树脂连接料、12质量份的酞菁绿G、0.12质量份的聚乙烯亚胺、1.2质量份的轻质碳酸钙和0.3质量份的消泡剂混合，经高速分散机，分散研磨至颗粒粒径≤15微米，包装；即制得水溶性凹版塑料印刷表印/复合油墨。86.7 parts by mass of the water-soluble acrylic resin binder, 12 parts by mass of phthalocyanine green G, 0.12 parts by mass of polyethyleneimine, 1.2 parts by mass of light calcium carbonate, and 0.3 parts by mass of an antifoaming agent are mixed at a high speed. The dispersing machine is dispersed and ground to a particle size of ≤15 μm, and packaged; that is, a water-soluble gravure plastic printing surface/composite ink is obtained.
实施例7Example 7
本实施例中连接料的制备方法按如下步骤进行：The preparation method of the binder in this embodiment is carried out as follows:
将16kg丙烯酸单体、204kg甲基丙烯酸异丁酯单体、32kg甲基丙烯酸-2-羟乙酯单体、104kg丙烯酸正丁酯单体、20kg丙烯酸乙酯单体、9kg偶氮二异丁腈混合成备料，投入到连接在反应釜上部带有流量剂的原料高位槽内，搅拌均匀。16 kg of acrylic monomer, 204 kg of isobutyl methacrylate monomer, 32 kg of 2-hydroxyethyl methacrylate monomer, 104 kg of n-butyl acrylate monomer, 20 kg of ethyl acrylate monomer, 9 kg of azobisisobutyl The nitrile is mixed into a stock preparation, and is put into a high-position tank which is connected to the upper part of the reaction vessel and has a flow agent, and is uniformly stirred.
将256.5kg无水乙醇投入到带有冷凝器、氮气导入管且釜内设有过水冷却装置的反应釜中，关闭釜内冷却管，在搅拌下加入24kg歧化松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃，将歧化松香融化。256.5kg of absolute ethanol was put into a reaction vessel equipped with a condenser, a nitrogen gas introduction tube and a water-cooling device in the kettle, the inner cooling tube was closed, 24 kg of disproportionated rosin was added under stirring, and a nitrogen tube valve was opened to introduce nitrogen gas. The air in the reaction vessel was replaced while heating to 80 ° C to melt the disproportionated rosin.
打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时将高位槽内备料滴加完全。Turn on the flowmeter and add the prepared material to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The dropping acceleration is controlled to increase the preparation in the high-level tank completely within 2 to 3 hours.
将反应釜内温度升至82℃，保温4小时，即制得固含量质量比为60％的共聚物溶液；所得到的共聚物玻璃化温度19～20℃。The temperature in the reaction vessel was raised to 82 ° C and kept for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the obtained copolymer had a glass transition temperature of 19 to 20 ° C.
聚合完全后，打开反应釜内冷却装置，将温度降到60～65℃，加入55kg三乙胺，调整共聚物的pH值到8.5～9.0，并且同时加入4kg丙二醇***、274.5kg蒸馏水，调整固含量到40％，即制得水溶性丙烯酸树脂连接料。After the polymerization is completed, the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, 55 kg of triethylamine is added, the pH of the copolymer is adjusted to 8.5-9.0, and 4 kg of propylene glycol ether and 274.5 kg of distilled water are simultaneously added to adjust the solid. The content is up to 40%, that is, a water-soluble acrylic resin binder is obtained.
实施例8Example 8
本实施例中是由实施例7得到的水溶性丙烯酸树脂连接料进行混合，并制备表印/复合油墨的方法。In this embodiment, a water-soluble acrylic resin binder obtained in Example 7 was mixed, and a method of preparing a surface/composite ink was prepared.
将88.66质量份的水溶性丙烯酸树脂连接料、10质量份的联苯胺黄G、0.14质量份的钛酸酯偶联剂、1.3质量份的轻质碳酸钙和0.4质量份的消泡剂(采用台湾德谦公司生产的080消泡剂)混合，经高速分散机，分散研磨至颗粒粒径≤15微米，包装；即制得水溶性凹版塑料印刷表印/复合油墨。88.66 parts by mass of a water-soluble acrylic resin binder, 10 parts by mass of benzidine yellow G, 0.14 parts by mass of a titanate coupling agent, 1.3 parts by mass of light calcium carbonate, and 0.4 parts by mass of an antifoaming agent (using The 080 defoamer produced by Taiwan Deqian Company is mixed and dispersed by a high-speed dispersing machine to a particle size of ≤15 μm, and packaged; that is, a water-soluble gravure plastic printing surface/composite ink is obtained.
实施例9Example 9
本实施例中连接料的制备方法按如下步骤进行：The preparation method of the binder in this embodiment is carried out as follows:
将24kg丙烯酸单体、20kg甲基丙烯酸-2-羟丙酯单体、92kg甲基丙烯酸甲酯单体、124kg甲基丙烯酸正丁酯单体、116kg丙烯酸乙酯单体、9.5kg偶氮二异丁腈混合成备料，投入到连接在反应釜上部带有流量剂的原料高位槽内，搅拌均匀。24 kg of acrylic monomer, 20 kg of 2-hydroxypropyl methacrylate monomer, 92 kg of methyl methacrylate monomer, 124 kg of n-butyl methacrylate monomer, 116 kg of ethyl acrylate monomer, 9.5 kg of azodi The isobutyronitrile is mixed into a raw material, and is put into a high-position tank which is connected to the upper part of the reaction vessel and has a flow agent, and is uniformly stirred.
将256.5kg的无水乙醇投入到带有冷凝器、氮气导入管且釜内设有过水冷却装置的反应釜中，关闭釜内冷却管，在搅拌下加入24kg氢化松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃，将氢化松香融化。256.5kg of absolute ethanol was put into a reaction vessel equipped with a condenser, a nitrogen introduction tube and a water-cooling device in the kettle, and the inside of the kettle was closed, and 24 kg of hydrogenated rosin was added under stirring to open the nitrogen tube valve. Nitrogen gas was used to displace the air in the reaction vessel while heating to 80 ° C to melt the hydrogenated rosin.
打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时将高位加料槽内备料滴加完全。Turn on the flowmeter and add the preparation to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The drip acceleration is controlled to increase the preparation in the high feed tank completely in 2 to 3 hours.
将反应釜内温度升至82℃，保温4小时，即制得固含量质量比为60％的共聚物溶液；共聚物玻璃化温度32～33℃。The temperature in the reaction vessel was raised to 82 ° C and held for 4 hours to obtain a copolymer solution having a solid content of 60% by mass; the copolymer glass transition temperature was 32 to 33 ° C.
聚合完全后，打开反应釜内冷却装置，将温度降到60～65℃，加入38kg氨水，调整共聚物的pH值到8.5～9.0，并且同时加入5kg丙二醇甲醚、289kg蒸馏水，调整固含量到40％，即制得水溶性丙烯酸树脂连接料。After the polymerization is completed, the cooling device in the reactor is opened, the temperature is lowered to 60-65 ° C, 38 kg of ammonia water is added, the pH of the copolymer is adjusted to 8.5-9.0, and 5 kg of propylene glycol methyl ether and 289 kg of distilled water are simultaneously added to adjust the solid content to 40%, that is, a water-soluble acrylic resin binder was obtained.
实施例10Example 10
本实施例中是由实施例9得到的水溶性丙烯酸树脂连接料进行混合，并制备表印/复合油墨的方法。In this embodiment, a water-soluble acrylic resin binder obtained in Example 9 is mixed, and a method of preparing a surface/composite ink is prepared.
将86质量份的水溶性丙烯酸树脂连接料、12质量份的立索尔宝红BK、0.13质量份的聚 乙烯亚胺、1.1质量份的轻质碳酸钙和0.2质量份的消泡剂混合，经高速分散机，分散研磨至颗粒粒径≤15微米，包装；即制得水溶性凹版塑料印刷表印/复合油墨。86 parts by mass of the water-soluble acrylic resin binder, 12 parts by mass of Lisol Baohong BK, and 0.13 parts by mass of poly Ethyleneimine, 1.1 parts by mass of light calcium carbonate and 0.2 parts by mass of antifoaming agent are mixed, dispersed and ground to a particle size of ≤15 μm by a high-speed disperser, and packaged; that is, a water-soluble gravure plastic printing surface is produced/ Composite ink.
以上实施例是对本发明中进行了具体说明，但本发明创造并不限于所述的实施例，熟悉本领域的技术人员在不违背本发明创造精神的前提下还可以作出种种的等同配方和制备方法的等同变换，这些等同变换均包含在本申请权利要求所限定的范围内。 The above embodiments are specifically described in the present invention, but the present invention is not limited to the embodiments described above, and various equivalent formulations and preparations can be made by those skilled in the art without departing from the inventive spirit of the present invention. Equivalent transformations of the methods, which are included within the scope of the claims of the present application.

Claims (12)

  1. 一种水性凹版塑料印刷表印/复合油墨，按重量份数由以下组份配制：连接料68～88份，有机颜料10～30份，附着力促进剂0.1～0.15份，助干剂1～1.5份，消泡剂0.2～0.5份。A water-based gravure plastic printing surface printing/composite ink, which is prepared by the following components in parts by weight: 68-88 parts of the connecting material, 10-30 parts of the organic pigment, 0.1-0.15 parts of the adhesion promoter, and the drying agent 1~ 1.5 parts, defoaming agent 0.2 to 0.5 parts.
  2. 根据权利要求1所述的凹版塑料印刷表印/复合油墨，其特征在于，所述附着力促进剂为聚乙烯亚胺或钛酸酯偶联剂。The gravure plastic printing surface/composite ink according to claim 1, wherein the adhesion promoter is a polyethyleneimine or a titanate coupling agent.
  3. 根据权利要求1所述的的水性凹版塑料印刷表印/复合油墨，其特征在于：助干剂为轻质碳酸钙。The aqueous gravure plastic printing/composite ink according to claim 1, wherein the dry aid is light calcium carbonate.
  4. 根据权利要求1所述的水性凹版塑料印刷表印/复合油墨，其特征在于，所述消泡剂为非有机硅的酰胺类与碳氢化合物的混合物。The aqueous gravure plastic printing/composite ink according to claim 1, wherein the antifoaming agent is a mixture of a non-silicone amide and a hydrocarbon.
  5. 根据权利要求1所述的水性凹版塑料印刷表印/复合油墨，其特征在于，有机颜料包括：稳定酞菁蓝、酞菁绿、联苯胺黄、立索尔宝红、钛白粉。The aqueous gravure plastic printing surface/composite ink according to claim 1, wherein the organic pigment comprises: stable phthalocyanine blue, phthalocyanine green, benzidine yellow, lissole red, titanium white powder.
  6. 一种用于前述权利要求1至5任意一项所述的油墨用连接料，按重量份数由以下组份配制：改性松香1～8份，甲基丙烯酸单体或丙烯酸单体1.5～4.5份，丙烯酸酯类单体4～25份，甲基丙烯酸酯类单体20～28份，偶氮二异丁腈0.8～2份，无水乙醇28～30份，胺或氨类4～7份，助溶剂0.5～3份，蒸馏水30～32份。A binder for ink according to any one of claims 1 to 5, which is prepared in parts by weight from the following components: 1 to 8 parts of modified rosin, methacrylic acid monomer or acrylic monomer 1.5 to 4.5 parts, 4 to 25 parts of acrylate monomer, 20 to 28 parts of methacrylate monomer, 0.8 to 2 parts of azobisisobutyronitrile, 28 to 30 parts of anhydrous ethanol, amine or ammonia 4~ 7 parts, 0.5 to 3 parts of a cosolvent, and 30 to 32 parts of distilled water.
  7. 根据权利要求6所述的水性凹版塑料印刷用表印/复合油墨用连接料，其特征在于，所述改性松香为氢化松香、聚合松香或歧化松香中的一种。The binder for printing/composite ink for water-based gravure printing according to claim 6, wherein the modified rosin is one of hydrogenated rosin, polymerized rosin or disproportionated rosin.
  8. 一种基于权利要求1中所述的水性凹版塑料印刷表印/复合油墨的制备方法，按以下步骤进行：将连接料树脂，有机颜料，附着力促进剂，助干剂和消泡剂混合；经高速分散机，分散研磨至≤15微米的微小颗粒粒径；包装。A method for preparing a water-based gravure plastic printing surface/composite ink according to claim 1, which is carried out by mixing a binder resin, an organic pigment, an adhesion promoter, a dry aid and an antifoaming agent; Dispersed and ground to a particle size of ≤15 microns by a high-speed disperser; packaging.
  9. 一种基于权利要求6中所述的连接料的制备方法，按如下步骤进行：A method for preparing a binder according to claim 6, which is carried out as follows:
    将丙烯酸单体或甲基丙烯酸单体，丙烯酸酯类单体，甲基丙烯酸酯类单体，偶氮二异丁腈按重量份数配比混合成备料，投入到反应釜的原料高位槽内，搅拌均匀；The acrylic monomer or methacrylic acid monomer, the acrylate monomer, the methacrylate monomer, the azobisisobutyronitrile are mixed into the raw materials in the proportion by weight, and are put into the high-level tank of the raw material of the reaction kettle. Stir well;
    将无水乙醇投入到带有冷凝器、氮气导入管的反应釜中，关闭釜内冷却管，在搅拌下加入改性松香，打开氮气管阀门导入氮气，置换反应釜内空气，同时加温到80℃～82℃，将改性松香融化；The anhydrous ethanol is put into the reaction vessel with the condenser and the nitrogen introduction tube, the cooling tube in the kettle is closed, the modified rosin is added under stirring, the nitrogen pipe is opened, the nitrogen gas is introduced, the air in the reaction kettle is replaced, and the temperature is heated to the same time. The modified rosin is melted at 80 ° C to 82 ° C;
    打开流量计将备料匀速的滴加到反应釜中，同时打开冷凝器，回收气体，且要边滴加边搅拌，滴加速度控制在2～3小时，将原料高位槽内备料滴加完全：Turn on the flowmeter and add the preparation to the reaction kettle at a constant rate. At the same time, turn on the condenser, recover the gas, and stir while adding dropwise. The dropping acceleration is controlled for 2 to 3 hours, and the preparation in the high-level tank of the raw material is completely added:
    将反应釜内温度升至82℃～85℃，保温4小时以上，制得共聚物溶液；所制得的共聚物溶液中树脂的固含量质量比为58～62％；所得到的共聚物玻璃化温度范围在15～38℃；The temperature in the reaction vessel is raised to 82 ° C to 85 ° C, and the temperature is maintained for 4 hours or more to obtain a copolymer solution; the solid content ratio of the resin in the obtained copolymer solution is 58 to 62%; the obtained copolymer glass The temperature range is from 15 to 38 ° C;
    聚合完全后，打开反应釜内冷却装置，将温度降到60～65℃，加入胺类或氨类，调整共聚物的pH值到8.5～9.0，并且同时加入助溶剂、蒸馏水，调整树脂的固含量质量比至38％～42％，即制得水溶性丙烯酸树脂连接料。After the polymerization is completed, the cooling device in the reaction vessel is opened, the temperature is lowered to 60-65 ° C, amine or ammonia is added, the pH of the copolymer is adjusted to 8.5-9.0, and the co-solvent and distilled water are simultaneously added to adjust the solidity of the resin. The content of mass ratio is 38% to 42%, that is, a water-soluble acrylic resin binder is obtained.
  10. 根据权利要求9所述的连接料的制备方法，其特征在于，所述助溶剂为丙二醇醚类，The method for preparing a binder according to claim 9, wherein the auxiliary solvent is a propylene glycol ether.
  11. 根据权利要求9所述的连接料的制备方法，其特征在于：聚合后加入的胺类是三乙胺：氨类是氨水。The method for preparing a binder according to claim 9, wherein the amine added after the polymerization is triethylamine: the ammonia is ammonia.
  12. 根据权利要求9所述的连接料的制备方法，其特征在于：所述保温4小时后，所制得的共聚物溶液中树脂的固含量质量比为60％。 The method for preparing a binder according to claim 9, wherein the solid content ratio of the resin in the copolymer solution obtained after the heat retention for 4 hours is 60%.
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CN116515429A (en) * 2023-07-05 2023-08-01 山东泰宝信息科技集团有限公司 Acrylic pressure-sensitive adhesive for screen printing
CN116515429B (en) * 2023-07-05 2023-08-22 山东泰宝信息科技集团有限公司 Acrylic pressure-sensitive adhesive for screen printing

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