CN112280377A - Corrosion-resistant environment-friendly ink and preparation method thereof - Google Patents

Corrosion-resistant environment-friendly ink and preparation method thereof Download PDF

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CN112280377A
CN112280377A CN202011263736.XA CN202011263736A CN112280377A CN 112280377 A CN112280377 A CN 112280377A CN 202011263736 A CN202011263736 A CN 202011263736A CN 112280377 A CN112280377 A CN 112280377A
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corrosion
weight
resistant environment
antioxidant
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CN112280377B (en
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梁雄佳
谢家福
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Jiecheng Industrial Shenzhen Co ltd
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Jiecheng Industrial Shenzhen Co ltd
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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
    • 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
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon 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
    • 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
    • C09D11/14—Printing inks based on carbohydrates

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention relates to the technical field of printing ink, in particular to corrosion-resistant environment-friendly printing ink and a preparation method thereof. The corrosion-resistant environment-friendly ink comprises the following raw materials in parts by weight: 40-50 parts of acrylic emulsion, 4-6 parts of PVDF resin, 6-10 parts of modified epoxy resin, 5-9 parts of composite auxiliary agent microspheres, 2-4 parts of hydroxyethyl cellulose, 3-5 parts of silane coupling agent, 1.5-3.5 parts of dimethyl silicone oil, 2-5 parts of photosensitizer, 2-4 parts of polyethylene wax, 0.5-1 part of antioxidant and 5-10 parts of deionized water. The environment-friendly printing ink has good weather resistance and corrosion resistance, has the characteristics of good adhesive force, good colorability, good appearance effect and low VOC (volatile organic compounds) emission, is not easy to fall off and fade, can reduce the pollution to the environment, is suitable for large-scale production and application, and the preparation method of the corrosion-resistant environment-friendly printing ink is simple and convenient to operate, easy to control, good in stability and beneficial to industrial mass production.

Description

Corrosion-resistant environment-friendly ink and preparation method thereof
Technical Field
The invention relates to the technical field of printing ink, in particular to corrosion-resistant environment-friendly printing ink and a preparation method thereof.
Background
With the development of economy and the increasing awareness of environmental protection, people increasingly pay attention to the environmental protection of ink printed on various articles, such as medical packaging, food packaging, toys for children and the like, and the influence of the ink on the environment and the body is more of great concern. However, most of the existing printing inks have high pollution discharge amount of Volatile Organic Compounds (VOC), seriously pollute the atmospheric environment and harm the health of people. Meanwhile, the existing printing ink has the problems of poor weather resistance, corrosion resistance, wear resistance, poor adhesive force and the like, and cannot meet the market demand and the environmental protection requirement, so that the novel corrosion-resistant environmental protection printing ink which has good corrosion resistance and weather resistance and is not easy to separate from and fade has very important significance.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the corrosion-resistant environment-friendly ink which has the characteristics of good weather resistance and corrosion resistance, good adhesive force, good colorability, good appearance effect, low VOC (volatile organic compound) emission, good printing adaptability, good texture of formed patterns, difficult shedding and fading and capability of reducing pollution to the environment.
The invention also aims to provide a preparation method of the corrosion-resistant environment-friendly ink, the preparation method is simple and convenient to operate and easy to control, and the prepared corrosion-resistant environment-friendly ink is easy to print, good in adaptability and stability and beneficial to industrial mass production.
The purpose of the invention is realized by the following technical scheme: the corrosion-resistant environment-friendly printing ink comprises the following raw materials in parts by weight: 40-50 parts of acrylic emulsion, 4-6 parts of PVDF resin, 6-10 parts of modified epoxy resin, 5-9 parts of composite auxiliary agent microspheres, 2-4 parts of hydroxyethyl cellulose, 3-5 parts of silane coupling agent, 1.5-3.5 parts of dimethyl silicone oil, 2-5 parts of photosensitizer, 2-4 parts of polyethylene wax, 0.5-1 part of antioxidant and 5-10 parts of deionized water.
The corrosion-resistant environment-friendly ink is prepared by compounding acrylic emulsion, modified epoxy resin and PVDF resin, and is matched with composite auxiliary agent microspheres, hydroxyethyl cellulose, a silane coupling agent, an antioxidant, dimethyl silicon oil and the like, and the raw materials have good compatibility and are mutually beneficial, so that the prepared corrosion-resistant environment-friendly ink has excellent weather resistance, corrosion resistance, wear resistance and mechanical property, has the advantages of good adhesive force, good colorability, good appearance effect and good printing adaptability, patterns are not easy to fade, the ink is water-based ink, the use of an organic solvent can be reduced, the characteristic of low VOC (volatile organic compound) emission is realized, the pollution to the environment can be reduced, the preparation method is simple and efficient, the operation and control are convenient, the industrial production is facilitated, and the product performance is stable.
Further, the preparation method of each part of the acrylic emulsion comprises the following steps:
s1, uniformly mixing 1-2 parts by weight of emulsifier and 20-25 parts by weight of deionized water, adding 16-20 parts by weight of first monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion A;
s2, uniformly mixing 1-2 parts by weight of emulsifier and 20-25 parts by weight of deionized water, adding 16-20 parts by weight of second monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion B;
s3, uniformly mixing 1-2 parts of emulsifier, 18-22 parts of deionized water and 1.5-2.5 parts of sodium bicarbonate, heating to 85-95 ℃, simultaneously dropwise adding 15-20 parts of pre-emulsion A and 3-6 parts of initiator solution, stirring for 50-70min, simultaneously dropwise adding the rest of pre-emulsion A, 4-7 parts of initiator solution and pre-emulsion B, reacting at constant temperature for 45-60min after dropwise adding, adding 3-6 parts of methyltriethoxysilane, 2-4 parts of maleic anhydride grafted ethylene-octene copolymer and 4-7 parts of nano silicon dioxide, performing ultrasonic treatment, cooling, and adding an alkaline regulator until the pH value reaches 7-8 to obtain the acrylic emulsion. The alkaline regulator is ammonia water. The initiator solution consists of an initiator and deionized water according to the weight ratio of 1: 4-6.
According to the invention, different acrylic monomers are adopted for polymerization, and are matched with the maleic anhydride grafted ethylene-octene copolymer, the nano silicon dioxide and the propenyl trimethoxy silane to prepare the cross-linked acrylic emulsion, the formed acrylic polymer has a net structure, high mechanical strength, good flexibility and low film forming temperature, the corrosion resistance, the weather resistance and the wear resistance of the environment-friendly ink are improved, and the adhesive force is strong. The maleic anhydride grafted ethylene-octene copolymer is preferably, but not limited to, a maleic anhydride grafted ethylene-octene copolymer elastomer PC-28.
Further, in the step S1, each part of the first monomer composition includes 6 to 10 parts of methyl methacrylate, 2 to 4 parts of isooctyl acrylate, and 1 to 2 parts of hydroxyethyl acrylate. In the step S2, each part of the second monomer composition includes 20 to 25 parts of butyl acrylate, 4 to 7 parts of cyclohexyl methacrylate, and 3 to 5 parts of glycidyl methacrylate.
According to the invention, the acrylic acid emulsion prepared by matching the acrylic acid monomers has a hard core and soft shell structure, so that the corrosion resistance, abrasion resistance and mechanical property of the acrylic acid emulsion are improved, and the adhesive force of the corrosion-resistant environment-friendly ink is enhanced.
Further, the emulsifier is composed of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyl sulfate according to the weight ratio of 1: 1-1.5. The emulsifier of the invention can improve the interface density and the interface efficiency of the emulsifier by adopting the matching of the emulsifiers, can improve the stability of the acrylic emulsion by the space stabilizing effect, has good dispersibility in the environment-friendly ink, and has good compatibility with other raw materials and stable and uniform ink quality.
Further, the initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate. The initiator can promote the stable crosslinking of the acrylic monomer and improve the stability of the acrylic emulsion.
Further, the silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane. By adopting the silane coupling agent, the compatibility of all raw materials is improved, the adhesive force of the silane coupling agent on a plastic base material is improved, and the weather resistance, the corrosion resistance and the mechanical property of the ink after curing are improved.
Further, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant DNP and antioxidant 703. By adopting the antioxidant, the antioxidant performance of the environment-friendly ink can be improved, and the ink is not easy to fall off and fade.
Further, the preparation method of each part of the modified epoxy resin comprises the following steps: taking 45-52 parts of epoxy resin, 6-10 parts of gamma-methacryloxypropyltrimethoxysilane, 1-3 parts of poly hexamethylene diamine adipate, 2-4 parts of polyethylene glycol and 0.5-1 part of nano silicon carbide according to parts by weight, and performing ultrasonic dispersion treatment to obtain a mixed material; and then continuously stirring at the temperature of 90-110 ℃ under the condition of introducing nitrogen, and reacting for 4-6h to obtain the modified epoxy resin. The stirring speed of the mixed materials is 600-800 RPM.
According to the invention, the preparation method is used for modifying the epoxy resin, and the process steps and process parameters are strictly controlled, so that the modified epoxy resin with stable performance is prepared; the gamma-methacryloxypropyl trimethoxysilane contains Si-O bonds, the polyhexamethylene adipate has excellent weather resistance, self-lubrication and mechanical strength, and the gamma-methacryloxypropyl trimethoxysilane, the polyhexamethylene adipate and the polyethylene glycol are matched to improve the toughness of the environment-friendly ink, the corrosion resistance, the weather resistance and the heat resistance of the environment-friendly ink, adjust the viscosity of a system and improve the compatibility of various raw materials, so that the prepared modified epoxy resin is uniformly dispersed in the system, endows the ink with good toughness, avoids the problems of edge lifting, cracking and the like, and has good appearance effect.
Further, the epoxy resin is bisphenol A type epoxy resin, preferably but not limited to bisphenol A type epoxy resin E-42 (634). The polyethylene glycol is preferably, but not limited to, polyethylene glycol 400. The PVDF resin is preferably but not limited to Kynar PVDF 2850.
Furthermore, each part of the photosensitizer consists of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone and trimethylolpropane tertiary acrylated tertiary amine according to the weight ratio of 1:1-2: 1-1.5. By adopting the photosensitizer, the invention has good fusion promoting effect and initiation efficiency, can accelerate the photocuring speed, weaken or avoid the internal shrinkage of an ink system, ensures that the environment-friendly ink has good corrosion resistance, weather resistance and adhesive force after being cured and formed, forms a stable ink layer, has good pattern texture and is not easy to fall off.
Further, the preparation method of each part of the composite auxiliary agent microsphere comprises the following steps: (1) taking 30-35 parts by weight of N, N-dimethylformamide, heating to 60-80 ℃, and adding 3-5 parts by weight of hydroxymethyl cellulose and 4-6 parts by weight of polyacrylamide to form a mixed material A; (2) adding 3-5 parts of nano titanium dioxide and 2-4 parts of nano aluminum oxide into the mixed material A obtained in the step (1), and stirring and homogenizing to form a suspension; (3) and adding 10-15 parts of absolute ethyl alcohol into the suspension, cooling to room temperature, and then sequentially standing, filtering, washing and drying to obtain the composite auxiliary agent microspheres.
According to the invention, polyacrylamide and hydroxymethyl cellulose are used as carriers of nano titanium dioxide and nano alumina, and the compatibility of the polyacrylamide and the hydroxymethyl cellulose with acrylic emulsion and modified epoxy resin is good, so that the problems that the nano titanium dioxide and the nano alumina are easy to agglomerate and difficult to disperse in an ink system, the compatibility with the acrylic emulsion and the modified epoxy resin is not good and the like can be effectively solved, the ink printing has good pattern texture, all raw materials are uniformly dispersed, the glossiness is high, and the corrosion resistance, the weather resistance, the self-cleaning performance and the stain resistance of the ink layer are improved; in addition, the polyacrylamide and the hydroxymethyl cellulose can be matched with other resins, so that the adhesion and the flexibility of the corrosion-resistant ink after curing are improved.
The other purpose of the invention is realized by the following technical scheme: the preparation method of the corrosion-resistant environment-friendly ink comprises the following steps:
step A, uniformly mixing acrylic emulsion, PVDF resin, a photosensitizer, composite auxiliary agent microspheres and deionized water according to parts by weight, and stirring at the temperature of 60-70 ℃ for 30-45min to obtain a mixture A;
and step B, adding the modified epoxy resin, the hydroxyethyl cellulose, the silane coupling agent, the dimethyl silicone oil, the polyethylene wax and the antioxidant into the mixture A prepared in the step A according to parts by weight, stirring at the temperature of 55-65 ℃ for 40-50min, grinding until the fineness is less than 20 mu m, and filtering to obtain the corrosion-resistant environment-friendly ink.
The preparation method of the corrosion-resistant environment-friendly ink is simple and convenient to operate and easy to control, and by controlling the proportion of the raw materials and the specific steps and process parameters, the prepared corrosion-resistant environment-friendly ink has good adhesive force with a base material, scratch resistance, good pattern texture after printing, good corrosion resistance and weather resistance, stable product quality and contribution to industrial mass production.
The invention has the beneficial effects that: the corrosion-resistant environment-friendly ink disclosed by the invention has good weather resistance and corrosion resistance, has the characteristics of good adhesion, good colorability, good appearance effect and low VOC (volatile organic compounds) emission, is good in printing adaptability, and can be used for reducing the pollution to the environment, and the formed patterns are good in texture and not easy to fall off and fade, and are suitable for large-scale production and application. The preparation method of the corrosion-resistant environment-friendly ink is simple and convenient to operate and easy to control, and the prepared corrosion-resistant environment-friendly ink is good in printing adaptability and stability and beneficial to industrial mass production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The corrosion-resistant environment-friendly printing ink comprises the following raw materials in parts by weight: 45 parts of acrylic emulsion, 5 parts of PVDF resin, 7 parts of modified epoxy resin, 6 parts of composite auxiliary agent microspheres, 3 parts of hydroxyethyl cellulose, 4 parts of silane coupling agent, 2 parts of dimethyl silicone oil, 3 parts of photosensitizer, 3 parts of polyethylene wax, 0.8 part of antioxidant and 5-10 parts of deionized water.
Further, the preparation method of each part of the acrylic emulsion comprises the following steps:
s1, uniformly mixing 1.5 parts by weight of emulsifier and 24 parts by weight of deionized water, adding 18 parts by weight of first monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion A;
s2, uniformly mixing 1.5 parts by weight of emulsifier and 24 parts by weight of deionized water, adding 17 parts by weight of second monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion B;
s3, uniformly mixing 1.5 parts of emulsifier, 20 parts of deionized water and 2 parts of sodium bicarbonate, heating to 90 ℃, simultaneously dripping 18 parts of pre-emulsion A and 4 parts of initiator solution, stirring for 60min, then simultaneously dripping the rest of pre-emulsion A, 5 parts of initiator solution and pre-emulsion B, reacting at a constant temperature for 50min after dripping, adding 4 parts of methyltriethoxysilane, 3 parts of maleic anhydride grafted ethylene-octene copolymer and 5 parts of nano silicon dioxide, performing ultrasonic treatment, cooling, and adding an alkaline regulator until the pH value reaches 7.5 to obtain the acrylic emulsion. The alkaline regulator is ammonia water. The maleic anhydride grafted ethylene-octene copolymer is preferably, but not limited to, a maleic anhydride grafted ethylene-octene copolymer elastomer PC-28. The initiator solution consists of an initiator and deionized water according to the weight ratio of 1: 5.
Further, in the step S1, each part of the first monomer composition includes 8 parts of methyl methacrylate, 3 parts of isooctyl acrylate, and 1.5 parts of hydroxyethyl acrylate. In the step S2, each part of the second monomer composition includes 22 parts of butyl acrylate, 5 parts of cyclohexyl methacrylate, and 4 parts of glycidyl methacrylate.
Further, the emulsifier is composed of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyl sulfate according to the weight ratio of 1:1. The initiator is potassium persulfate.
Further, the silane coupling agent is composed of vinyltriethoxysilane and vinyltris (beta-methoxyethoxy) silane according to the weight ratio of 1: 2. The antioxidant is antioxidant 1010 and antioxidant DNP, and the weight ratio of the antioxidant to the antioxidant is 1: 0.8.
Further, the preparation method of each part of the modified epoxy resin comprises the following steps: according to the parts by weight, 48 parts of epoxy resin, 8 parts of gamma-methacryloxypropyltrimethoxysilane, 2 parts of polyhexamethylene diamine adipate, 3 parts of polyethylene glycol and 0.8 part of nano silicon carbide are subjected to ultrasonic dispersion treatment to obtain a mixed material; and then continuously stirring at the temperature of 100 ℃ under the condition of introducing nitrogen, and reacting for 5 hours to obtain the modified epoxy resin. The mixing speed of the mixture was 700 RPM.
Further, the epoxy resin is bisphenol A type epoxy resin, preferably but not limited to bisphenol A type epoxy resin E-42 (634). The polyethylene glycol is preferably, but not limited to, polyethylene glycol 400. The PVDF resin is preferably but not limited to Kynar PVDF 2850.
Further, each part of the photosensitizer consists of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone and trimethylolpropane tertiary acrylated tertiary amine according to the weight ratio of 1:1.5: 1.2.
Further, the preparation method of each part of the composite auxiliary agent microsphere comprises the following steps: (1) taking 32 parts by weight of N, N-dimethylformamide, heating to 70 ℃, and adding 4 parts by weight of hydroxymethyl cellulose and 5 parts by weight of polyacrylamide to form a mixed material A; (2) adding 4 parts of nano titanium dioxide and 3 parts of nano aluminum oxide into the mixed material A obtained in the step (1), and stirring and homogenizing to form a suspension; (3) and adding 12 parts of absolute ethyl alcohol into the suspension, cooling to room temperature, and then sequentially standing, filtering, washing and drying to obtain the composite auxiliary agent microspheres.
The preparation method of the corrosion-resistant environment-friendly ink comprises the following steps:
step A, uniformly mixing acrylic emulsion, PVDF resin, a photosensitizer, composite auxiliary agent microspheres and deionized water according to parts by weight, and stirring at the temperature of 60-70 ℃ for 30-45min to obtain a mixture A;
and step B, adding the modified epoxy resin, the hydroxyethyl cellulose, the silane coupling agent, the dimethyl silicone oil, the polyethylene wax and the antioxidant into the mixture A prepared in the step A according to parts by weight, stirring for 45min at the temperature of 60 ℃, grinding until the fineness is less than 20 mu m, and filtering to obtain the corrosion-resistant environment-friendly ink.
Example 2
The corrosion-resistant environment-friendly printing ink comprises the following raw materials in parts by weight: 40 parts of acrylic emulsion, 4 parts of PVDF resin, 6 parts of modified epoxy resin, 5 parts of composite auxiliary agent microspheres, 2 parts of hydroxyethyl cellulose, 3 parts of silane coupling agent, 1.5 parts of dimethyl silicone oil, 2 parts of photosensitizer, 2 parts of polyethylene wax, 0.5 part of antioxidant and 5 parts of deionized water.
Further, the preparation method of each part of the acrylic emulsion comprises the following steps:
s1, uniformly mixing 1 part of emulsifier and 20 parts of deionized water in parts by weight, adding 16 parts of the first monomer composition, and performing ultrasonic dispersion treatment to obtain a pre-emulsion A;
s2, uniformly mixing 1 part of emulsifier and 20 parts of deionized water in parts by weight, adding 16 parts of second monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion B;
s3, uniformly mixing 1 part of emulsifier, 18 parts of deionized water and 1.5 parts of sodium bicarbonate, heating to 85 ℃, simultaneously dripping 15 parts of pre-emulsion A and 3 parts of initiator solution, stirring for 70min, then simultaneously dripping the rest of pre-emulsion A, 4 parts of initiator solution and pre-emulsion B, reacting at constant temperature for 45min after dripping, adding 4 parts of methyltriethoxysilane, 3 parts of maleic anhydride grafted ethylene-octene copolymer and 5 parts of nano silicon dioxide, performing ultrasonic treatment, cooling, and adding an alkaline regulator until the pH value reaches 7 to obtain the acrylic emulsion. The initiator solution consists of an initiator and deionized water according to the weight ratio of 1: 4.
Further, in the step S1, each part of the first monomer composition includes 6 parts of methyl methacrylate, 2 parts of isooctyl acrylate, and 1 part of hydroxyethyl acrylate. In the step S2, each part of the second monomer composition includes 20 parts of butyl acrylate, 4 parts of cyclohexyl methacrylate and 3 parts of glycidyl methacrylate.
Further, the emulsifier is composed of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyl sulfate according to the weight ratio of 1:1. The initiator is sodium persulfate and ammonium persulfate according to the weight ratio of 1: 0.5.
Further, the silane coupling agent is vinyl triethoxysilane and vinyl tri (beta-methoxyethoxy) silane in a weight ratio of 1: 2. The antioxidant is prepared from the following components in parts by weight of 1: 1.5.
Further, the preparation method of each part of the modified epoxy resin comprises the following steps: according to the parts by weight, 45 parts of epoxy resin, 6 parts of gamma-methacryloxypropyltrimethoxysilane, 1 part of polyhexamethylene diamine adipate, 2 parts of polyethylene glycol and 0.5 part of nano silicon carbide are subjected to ultrasonic dispersion treatment to obtain a mixed material; and then continuously stirring at the temperature of 90 ℃ under the condition of introducing nitrogen, and reacting for 6 hours to obtain the modified epoxy resin. The mixing speed of the mixture was 600 RPM.
Further, each part of the photosensitizer consists of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone and trimethylolpropane tertiary acrylated tertiary amine according to the weight ratio of 1:1: 1.5.
Further, the preparation method of each part of the composite auxiliary agent microsphere comprises the following steps: (1) taking 30 parts by weight of N, N-dimethylformamide, heating to 60 ℃, and adding 3 parts by weight of hydroxymethyl cellulose and 4 parts by weight of polyacrylamide to form a mixed material A; (2) adding 3 parts of nano titanium dioxide and 2 parts of nano aluminum oxide into the mixed material A obtained in the step (1), and stirring and homogenizing to form a suspension; (3) and adding 10 parts of absolute ethyl alcohol into the suspension, cooling to room temperature, and then sequentially standing, filtering, washing and drying to obtain the composite auxiliary agent microspheres.
The preparation method of the corrosion-resistant environment-friendly ink comprises the following steps:
step A, uniformly mixing acrylic emulsion, PVDF resin, a photosensitizer, composite auxiliary agent microspheres and deionized water according to parts by weight, and stirring at the temperature of 60 ℃ for 45min to obtain a mixture A;
and step B, adding the rest raw materials, namely the modified epoxy resin, the hydroxyethyl cellulose, the silane coupling agent, the dimethyl silicone oil, the polyethylene wax and the antioxidant into the mixture A prepared in the step A according to parts by weight, stirring for 50min at the temperature of 55 ℃, grinding until the fineness is less than 20 mu m, and filtering to obtain the corrosion-resistant environment-friendly ink.
The rest of this embodiment is the same as embodiment 1, and is not described herein again.
Example 3
The corrosion-resistant environment-friendly printing ink comprises the following raw materials in parts by weight: 50 parts of acrylic emulsion, 6 parts of PVDF resin, 10 parts of modified epoxy resin, 9 parts of composite auxiliary agent microspheres, 4 parts of hydroxyethyl cellulose, 5 parts of silane coupling agent, 3.5 parts of dimethyl silicone oil, 5 parts of photosensitizer, 4 parts of polyethylene wax, 1 part of antioxidant and 10 parts of deionized water.
Further, the preparation method of each part of the acrylic emulsion comprises the following steps:
s1, uniformly mixing 2 parts by weight of emulsifier and 25 parts by weight of deionized water, adding 20 parts by weight of first monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion A;
s2, uniformly mixing 2 parts by weight of emulsifier and 25 parts by weight of deionized water, adding 20 parts by weight of second monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion B;
s3, uniformly mixing 2 parts of emulsifier, 22 parts of deionized water and 2.5 parts of sodium bicarbonate, heating to 95 ℃, simultaneously dripping 20 parts of pre-emulsion A and 6 parts of initiator solution, stirring for 70min, then simultaneously dripping the rest of pre-emulsion A, 7 parts of initiator solution and pre-emulsion B, reacting at constant temperature for 45min after dripping, adding 6 parts of methyltriethoxysilane, 4 parts of maleic anhydride grafted ethylene-octene copolymer and 7 parts of nano silicon dioxide, performing ultrasonic treatment, cooling, and adding an alkaline regulator until the pH value reaches 8 to obtain the acrylic emulsion.
Further, in the step S1, each part of the first monomer composition includes 10 parts of methyl methacrylate, 4 parts of isooctyl acrylate, and 2 parts of hydroxyethyl acrylate. In the step S2, each part of the second monomer composition includes 25 parts of butyl acrylate, 7 parts of cyclohexyl methacrylate and 5 parts of glycidyl methacrylate.
Further, the emulsifier is composed of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyl sulfate according to the weight ratio of 1: 1.5. The initiator is potassium persulfate.
Further, the silane coupling agent is composed of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane according to the weight ratio of 1:2: 1. The antioxidant is composed of an antioxidant 1010 and an antioxidant 703 according to the weight ratio of 1:2: 2.
Further, the preparation method of each part of the modified epoxy resin comprises the following steps: according to the parts by weight, 52 parts of epoxy resin, 10 parts of gamma-methacryloxypropyltrimethoxysilane, 3 parts of polyhexamethylene diamine adipate, 4 parts of polyethylene glycol and 1 part of nano silicon carbide are taken and subjected to ultrasonic dispersion treatment to obtain a mixed material; and then continuously stirring at the temperature of 110 ℃ under the condition of introducing nitrogen, and reacting for 6 hours to obtain the modified epoxy resin. The mixing speed of the mixture was 800 RPM.
Further, each part of the photosensitizer consists of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-acetone and trimethylolpropane tertiary acrylated tertiary amine according to the weight ratio of 1:2: 1.
Further, the preparation method of each part of the composite auxiliary agent microsphere comprises the following steps: (1) taking 35 parts by weight of N, N-dimethylformamide, heating to 80 ℃, and adding 5 parts by weight of hydroxymethyl cellulose and 6 parts by weight of polyacrylamide to form a mixed material A; (2) adding 5 parts of nano titanium dioxide and 4 parts of nano aluminum oxide into the mixed material A obtained in the step (1), and stirring and homogenizing to form a suspension; (3) and adding 15 parts of absolute ethyl alcohol into the suspension, cooling the suspension to room temperature, and then sequentially standing, filtering, washing and drying to obtain the composite auxiliary agent microspheres.
The preparation method of the corrosion-resistant environment-friendly ink comprises the following steps:
step A, uniformly mixing acrylic emulsion, PVDF resin, a photosensitizer, composite auxiliary agent microspheres and deionized water according to parts by weight, and stirring at the temperature of 70 ℃ for 30min to obtain a mixture A;
and step B, adding the modified epoxy resin, the hydroxyethyl cellulose, the silane coupling agent, the dimethyl silicone oil, the polyethylene wax and the antioxidant into the mixture A prepared in the step A according to parts by weight, stirring at the temperature of 65 ℃ for 40min, grinding, sieving by a 500-mesh sieve, and filtering to obtain the corrosion-resistant environment-friendly ink.
The rest of this embodiment is the same as embodiment 1, and is not described herein again.
Example 4
The corrosion-resistant environment-friendly printing ink comprises the following raw materials in parts by weight: 42 parts of acrylic emulsion, 4.5 parts of PVDF resin, 7 parts of modified epoxy resin, 6 parts of composite auxiliary agent microspheres, 2.5 parts of hydroxyethyl cellulose, 3.5 parts of silane coupling agent, 2.5 parts of dimethyl silicone oil, 3 parts of photosensitizer, 2.5 parts of polyethylene wax, 0.8 part of antioxidant and 7 parts of deionized water.
Further, the preparation method of each part of the acrylic emulsion comprises the following steps:
s1, uniformly mixing 1.8 parts by weight of emulsifier and 22 parts by weight of deionized water, adding 17 parts by weight of first monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion A;
s2, uniformly mixing 1.8 parts by weight of emulsifier and 22 parts by weight of deionized water, adding 17 parts by weight of second monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion B;
s3, uniformly mixing 1.5 parts of emulsifier, 19 parts of deionized water and 2 parts of sodium bicarbonate, heating to 88 ℃, simultaneously dripping 16 parts of pre-emulsion A and 4 parts of initiator solution, stirring for 65min, then simultaneously dripping the rest of pre-emulsion A, 6 parts of initiator solution and pre-emulsion B, reacting at a constant temperature for 50min after dripping, adding 5 parts of methyltriethoxysilane, 2.5 parts of maleic anhydride grafted ethylene-octene copolymer and 5 parts of nano silicon dioxide, performing ultrasonic treatment, cooling, and adding an alkaline regulator until the pH value reaches 7.8 to obtain the acrylic emulsion.
Further, in the step S1, each part of the first monomer composition includes 7 parts of methyl methacrylate, 2.5 parts of isooctyl acrylate, and 1.5 parts of hydroxyethyl acrylate. In the step S2, each part of the second monomer composition includes 23 parts of butyl acrylate, 5 parts of cyclohexyl methacrylate and 4 parts of glycidyl methacrylate.
Further, the preparation method of each part of the modified epoxy resin comprises the following steps: according to the parts by weight, 48 parts of epoxy resin, 7 parts of gamma-methacryloxypropyltrimethoxysilane, 2 parts of polyhexamethylene diamine adipate, 3 parts of polyethylene glycol and 0.8 part of nano silicon carbide are subjected to ultrasonic dispersion treatment to obtain a mixed material; and then continuously stirring at 105 ℃ under the condition of introducing nitrogen, and reacting for 5.5 hours to obtain the modified epoxy resin. The mixing speed of the mixture was 750 RPM.
Further, the preparation method of each part of the composite auxiliary agent microsphere comprises the following steps: (1) taking 33 parts by weight of N, N-dimethylformamide, heating to 75 ℃, and adding 3.5 parts by weight of hydroxymethyl cellulose and 4.5 parts by weight of polyacrylamide to form a mixed material A; (2) adding 3.5 parts of nano titanium dioxide and 2.5 parts of nano aluminum oxide into the mixed material A obtained in the step (1), and stirring and homogenizing to form a suspension; (3) and adding 12 parts of absolute ethyl alcohol into the suspension, cooling to room temperature, and then sequentially standing, filtering, washing and drying to obtain the composite auxiliary agent microspheres.
The preparation method of the corrosion-resistant environment-friendly ink comprises the following steps:
step A, uniformly mixing acrylic emulsion, PVDF resin, a photosensitizer, composite auxiliary agent microspheres and deionized water according to parts by weight, and stirring at the temperature of 65 ℃ for 40min to obtain a mixture A;
and step B, adding the modified epoxy resin, the hydroxyethyl cellulose, the silane coupling agent, the dimethyl silicone oil, the polyethylene wax and the antioxidant into the mixture A prepared in the step A according to parts by weight, stirring for 45min at the temperature of 60 ℃, grinding until the fineness is less than 20 mu m, and filtering to obtain the corrosion-resistant environment-friendly ink.
The rest of this embodiment is the same as embodiment 1, and is not described herein again.
Comparative example 1
This comparative example differs from example 1 above in that: the acrylic emulsion of this comparative example was a badrich RS-916F acrylic emulsion. Replacing the composite auxiliary agent microspheres described in example 1 with a composite auxiliary agent: the preparation method of each part of the composite auxiliary agent microsphere comprises the following steps: according to the weight parts, 32 parts of N, N-dimethylformamide, 9 parts of RS-916F acrylic emulsion, 4 parts of nano titanium dioxide and 3 parts of nano aluminum oxide are mixed and then are subjected to standing, filtering, washing and drying treatment in sequence to obtain the composite auxiliary agent.
Comparative example 2
This comparative example differs from example 1 above in that: the modified epoxy resin of this comparative example was replaced with bisphenol A type epoxy resin E-42 (634); the comparative example does not contain PVDF resin and polyethylene wax.
6 wt% of pigment is added into the ink prepared in the examples 1-4 and the comparative examples 1-2, deionized water is added for dilution, the weight ratio of the added deionized water to the ink after the pigment is added is 2:3, the PET film used for the surface of the jigsaw puzzle is printed, and the performance test is carried out after the ink layers formed after the printing of the examples 1-4 and the comparative examples 1-2 are placed for 24H at room temperature, and the test results are shown in the following table:
Figure BDA0002775455080000141
the prints obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to xenon lamp weathering test for weather resistance:
the xenon lamp aging test specifically comprises the steps of placing a prepared printed matter in a xenon lamp aging test box, adjusting the working temperature and humidity in the xenon lamp aging test box to be 70 ℃ and 60%, placing for 72 hours, and observing the fading and yellowing phenomena. The inks obtained in examples 1 to 4 of the present invention had viscosities of 31 to 35 pas.
Figure BDA0002775455080000142
The inventive examples 1-4 and comparative examples 1-2 were tested for alcohol resistance and abrasion resistance by pushing cotton cloth with 500 gram force of viscose alcohol (99.7%) back and forth 600 times, with no bottom exposure in examples 1-4 and slight bottom exposure in comparative examples 1-2. The rubber is horizontally pushed back and forth 600 times by using a common rubber loaded with 500 grams of force, the bottom of the rubber is not exposed in examples 1-4 and comparative example 2, and the slight exposure of the bottom of the rubber in comparative example 1 is generated.
Tinting strength, adhesion and peel strength, maximum limits of volatile organic compounds and maximum limits of soluble harmful elements were determined according to GB/T26394-. It was determined that the maximum limits of volatile organic compounds and the maximum limits of soluble harmful elements were satisfactory for examples 1-4 and comparative example 1. Examples 1-4 both the volatile organic compound and soluble harmful element content were significantly below the maximum limit criteria of this standard. The inks of examples 1-4 were used for lithographic and silk screening, and the prints were clear in pattern, clear in dot, high in color saturation and density, and had good gloss.
The corrosion-resistant environment-friendly ink disclosed by the invention has the characteristics of good weather resistance, corrosion resistance and wear resistance, good adhesion, good colorability, good appearance effect, low VOC (volatile organic compounds) emission, good printing adaptability, good texture of formed patterns, difficulty in falling and fading, capability of reducing pollution to the environment and suitability for large-scale production and application. The preparation method of the corrosion-resistant environment-friendly ink is simple and convenient to operate and easy to control, and the prepared corrosion-resistant environment-friendly ink is good in printing adaptability and stability and beneficial to industrial mass production.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (10)

1. The corrosion-resistant environment-friendly printing ink is characterized in that: the feed comprises the following raw materials in parts by weight: 40-50 parts of acrylic emulsion, 4-6 parts of PVDF resin, 6-10 parts of modified epoxy resin, 5-9 parts of composite auxiliary agent microspheres, 2-4 parts of hydroxyethyl cellulose, 3-5 parts of silane coupling agent, 1.5-3.5 parts of dimethyl silicone oil, 2-5 parts of photosensitizer, 2-4 parts of polyethylene wax, 0.5-1 part of antioxidant and 5-10 parts of deionized water.
2. The corrosion-resistant environment-friendly ink as claimed in claim 1, wherein: the preparation method of each part of the acrylic emulsion comprises the following steps:
s1, uniformly mixing 1-2 parts by weight of emulsifier and 20-25 parts by weight of deionized water, adding 16-20 parts by weight of first monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion A;
s2, uniformly mixing 1-2 parts by weight of emulsifier and 20-25 parts by weight of deionized water, adding 16-20 parts by weight of second monomer composition, and performing ultrasonic dispersion treatment to obtain pre-emulsion B;
s3, uniformly mixing 1-2 parts of emulsifier, 18-22 parts of deionized water and 1.5-2.5 parts of sodium bicarbonate, heating to 85-95 ℃, simultaneously dropwise adding 15-20 parts of pre-emulsion A and 3-6 parts of initiator solution, stirring for 50-70min, simultaneously dropwise adding the rest of pre-emulsion A, 4-7 parts of initiator solution and pre-emulsion B, reacting at constant temperature for 45-60min after dropwise adding, adding 3-6 parts of methyltriethoxysilane, 2-4 parts of maleic anhydride grafted ethylene-octene copolymer and 4-7 parts of nano silicon dioxide, performing ultrasonic treatment, cooling, and adding an alkaline regulator until the pH value reaches 7-8 to obtain the acrylic emulsion.
3. The corrosion-resistant environment-friendly ink as claimed in claim 2, wherein: in the step S1, each part of the first monomer composition includes 6 to 10 parts of methyl methacrylate, 2 to 4 parts of isooctyl acrylate, and 1 to 2 parts of hydroxyethyl acrylate.
4. The corrosion-resistant environment-friendly ink as claimed in claim 2, wherein: in the step S2, each part of the second monomer composition includes 20 to 25 parts of butyl acrylate, 4 to 7 parts of cyclohexyl methacrylate, and 3 to 5 parts of glycidyl methacrylate.
5. The corrosion-resistant environment-friendly ink as claimed in claim 2, wherein: the emulsifier is composed of nonylphenol polyoxyethylene ether ammonium sulfate and sodium dodecyl sulfate according to the weight ratio of 1: 1-1.5.
6. The corrosion-resistant environment-friendly ink as claimed in claim 2, wherein: the initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
7. The corrosion-resistant environment-friendly ink as claimed in claim 1, wherein: the preparation method of each part of the modified epoxy resin comprises the following steps: taking 45-52 parts of epoxy resin, 6-10 parts of gamma-methacryloxypropyltrimethoxysilane, 1-3 parts of poly hexamethylene diamine adipate, 2-4 parts of polyethylene glycol and 0.5-1 part of nano silicon carbide according to parts by weight, and performing ultrasonic dispersion treatment to obtain a mixed material; and then continuously stirring at the temperature of 90-110 ℃ under the condition of introducing nitrogen, and reacting for 4-6h to obtain the modified epoxy resin.
8. The corrosion-resistant environment-friendly ink as claimed in claim 7, wherein: the stirring speed of the mixed materials is 600-800 RPM.
9. The corrosion-resistant environment-friendly ink as claimed in claim 1, wherein: the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant DNP and antioxidant 703.
10. A method for preparing the corrosion-resistant environment-friendly ink according to any one of claims 1 to 9, wherein the method comprises the following steps: the method comprises the following steps:
step A, uniformly mixing acrylic emulsion, PVDF resin, a photosensitizer, composite auxiliary agent microspheres and deionized water according to parts by weight, and stirring at the temperature of 60-70 ℃ for 30-45min to obtain a mixture A;
and step B, adding the modified epoxy resin, the hydroxyethyl cellulose, the silane coupling agent, the dimethyl silicone oil, the polyethylene wax and the antioxidant into the mixture A prepared in the step A according to parts by weight, stirring at the temperature of 55-65 ℃ for 40-50min, grinding, and filtering to obtain the corrosion-resistant environment-friendly ink.
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