CN106752352A - A kind of environment-friendly type aqueous ink - Google Patents
A kind of environment-friendly type aqueous ink Download PDFInfo
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- CN106752352A CN106752352A CN201510832309.1A CN201510832309A CN106752352A CN 106752352 A CN106752352 A CN 106752352A CN 201510832309 A CN201510832309 A CN 201510832309A CN 106752352 A CN106752352 A CN 106752352A
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Abstract
The invention discloses a kind of environment-friendly type aqueous ink, it is obtained by the raw material of following mass fraction：Waterborne acrylic paint 65 ~ 85%, aqueous color paste 15 ~ 25%, deionized water 10 ~ 20%, coalescents 0.2 ~ 0.5%, defoamer 0.2 ~ 0.3%, balance of ammoniacal liquor；Waterborne acrylic paint is obtained by the raw material of following quality proportioning：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 6 parts of oxygen vinethene, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 2 part of DMAE, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.Waterborne acrylic paint as link stuff can be kept a kind of environment-friendly type aqueous ink in the first-class film coloring of PE/PP films and adhesive force by the present invention.
Description
Technical field
The present invention relates to technical field of ink, more particularly, to a kind of environment-friendly type aqueous ink.
Background technology
In the case of environmental protection consciousness is gradually enhanced, especially in food, toy for children and medical package field, water-based ink finally necessarily replaces solvent-based ink.But the aqueous solvent of water-based ink is polar material, it is generally difficult in the Plastic film surface such as PP, PE, OPP, PO wetting of low polarity.Adhesive force on a plastic film is improved, needs emphasis to consider the cohesive force size of link stuff and plastic sheeting when water-based ink is equipped with.Because waterborne acrylic paint has the advantages that color is shallow, transparency is high, good weatherability, it is widely used in field of product packaging.At present, waterborne acrylic paint generally improves the adhesive force of film using high-temperature cross-linking solidification, but easily curling deforms during PE/PP thin film high temperatures, and other performances on PE/PP films can not also meet demand.
The content of the invention
The purpose of the present invention is the defect for overcoming above-mentioned prior art, there is provided a kind of environment-friendly type aqueous ink, can have excellent tinting strength, tinting power, adhesive force, resistance to blocking and resistance to dry friction on PE/PP films.
The purpose of the present invention is achieved through the following technical solutions：
A kind of environment-friendly type aqueous ink, is obtained by the raw material of following mass fraction：Waterborne acrylic paint 65 ~ 85%, aqueous color paste 15 ~ 25%, deionized water 10 ~ 20%, coalescents 0.2 ~ 0.5%, defoamer 0.2 ~ 0.3%, balance of ammoniacal liquor；Waterborne acrylic paint is obtained by the raw material of following quality proportioning：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 6 parts of oxygen vinethene, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 2 part of DMAE, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.
The water solubility of link stuff is not only related to the storage stability of water-based ink and printing applies membrane process, also affects the printing quality of ink.Using waterborne acrylic paint as link stuff, its performance determines the performance of water-based ink to the present invention substantially.The solid content of waterborne acrylic paint is relatively low, and to the good dispersion of dispersible pigment color paste, the coloring on PE/PP films is fabulous, and adhesive force is high, thus can keep the good film coloring on PE/PP films of water-based ink and adhesive force.Water-based ink, due to constantly to grind, stir, can produce a large amount of bubbles unavoidably in preparation process is produced, and can so influence packaging and film performance.Thus the present invention is added micro defoamer, so can effectively alleviate above mentioned problem.Also known as coalescing aid, it can promote the moulding flowing of macromolecular compound and elastic deformation to coalescents, improve coalescence performance.
The water solubility of resin is mainly related to hydrophilic radical and content.According to the drying at room temperature film forming of PE/PP film curing inks, while to reach excellent combination property, waterborne acrylic paint is polymerized from following component：, used as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc. for methyl methacrylate.Butyl acrylate can improve the pliability of glued membrane as soft monomer, increase film adhesive.Acrylic acid and hydroxy-ethyl acrylate, containing hydrophilic groups, hydroxyl etc., can improve the water solubility of polymer, and then cause that resin property is more stablized as hydrophilic monomer.DAAM is used as cross-linking monomer, adipic dihydrazide is used as crosslinking agent, DAAM can introduce the amino low-temperature self-crosslinking of reactive group ketone carbonyl and adipic dihydrazide, allow that resin occurs self-crosslinking reaction in low temperature, the performances such as adhesive force, hardness and the water resistance of film so can be not only improved, can be also applied on PE/PP films.In Raolical polymerizable, polymerization speed depends primarily on the speed of trigger rate, and trigger rate is related to the species of initiator.From azodiisobutyronitrile as initiator, it can react at a lower polymerization temperature, and low viscosity, resin of light color can be obtained.
In solution polymerization process, solvent can be produced a very large impact to polymerisation and polymerizate, and from propylene glycol methyl ether acetate as main solvent, existing ehter bond has carbonyl to the present invention again in its molecular structural formula, and carbonyl yet forms both the structure of ester group, also with alkyl；It is provided simultaneously with non-polar group and polar group, and this two parts group both mutually repelled by restriction, there is respective effect again, therefore, it can dissolve polarity and apolar substance.From dimethylformamide as cosolvent, it can be miscible with water, alcohols and alcohol ethers material.
The glass transition temperature appropriate to obtain resinous polymer, further, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid and the hydroxy-ethyl acrylate is a, the number of the methyl methacrylate is a*55%, and the number of the butyl acrylate is a*30%.Because the construction temperature of water-based ink can not be too high, thus the MFT of water-base resin is controlled on the premise of changing firmness requirements when ensureing to reach resin film forming.Balance by controlling the number of hard monomer and soft monomer to adjust the glass transformation temperature of resin to reach between hardness and MFT of the invention.
To reach good aqueous stability and film performance, further, acrylic acid number is a*9.2%, and the number of the hydroxy-ethyl acrylate is a*5.8%.Acrylic acid is mainly the adhesive force of the aqueous stability and film that improve resin；Hydroxy-ethyl acrylate is primarily introduced into reactive group hydroxyl, improves the aqueous stability of resin, improves the adhesive force and the degree of cross linking of film after reacting.
Further, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid, the hydroxy-ethyl acrylate and DAAM is b, and the number of the azodiisobutyronitrile is b*2%.In polymerisation, the concentration of azodiisobutyronitrile is inversely proportional to the molecular weight of polymer.Specifically, with the increase of dosage of azodiisobutyronitrile, the molecular weight low amplitude of resinous polymer diminishes, and especially when consumption increases to b*2% from b*1%, influences unobvious；And when dosage of azodiisobutyronitrile is too high, reacting the heat for producing is difficult to control, danger can be brought to a large amount of productions.Additionally, azodiisobutyronitrile is relatively costly, storage and transport are also fairly cumbersome, and consumption excessively can also increase product cost.Thus, the present invention is controlled the 2% of the total consumption of monomer the consumption of azodiisobutyronitrile under the conditions of the molecular weight for meeting resin application performance.
Further, the propylene glycol methyl ether acetate and the mass ratio of the dimethylformamide are 2:1.From this mass ratio mixed solvent when, the water-soluble good of synthetic resin, good fluidity, transparency are high.
Further, the adipic dihydrazide and the mass ratio of the azodiisobutyronitrile are 4:5.The adipic dihydrazide can produce influence with the mass ratio of the azodiisobutyronitrile on the film degree of cross linking, water absorption rate and hardness.From the mass ratio, the excellent degree of cross linking and hardness and the water absorption rate compared with ground can be obtained.
The invention has the advantages that：A kind of environment-friendly type aqueous ink can keep good film coloring and adhesive force on PE/PP films as obtained in the present invention.Waterborne acrylic paint is polymerized from following component：From methyl methacrylate as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc..From butyl acrylate as soft monomer, the pliability of glued membrane can be improved, increase film adhesive.From acrylic acid and hydroxy-ethyl acrylate as hydrophilic monomer, containing hydrophilic groups, hydroxyl etc., the water solubility of polymer can be improved, and then cause that resin property is more stablized.From DAAM as cross-linking monomer, adipic dihydrazide is used as crosslinking agent, DAAM can introduce the amino low-temperature self-crosslinking of reactive group ketone carbonyl and adipic dihydrazide, allow that resin occurs self-crosslinking reaction in low temperature, the performances such as adhesive force, hardness and the water resistance of film so can be not only improved, can be also applied on PE/PP films.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
A kind of environment-friendly type aqueous ink, is obtained by the raw material of following mass fraction：Waterborne acrylic paint 65 ~ 85%, aqueous color paste 15 ~ 25%, deionized water 10 ~ 20%, coalescents 0.2 ~ 0.5%, defoamer 0.2 ~ 0.3%, balance of ammoniacal liquor；Waterborne acrylic paint is obtained by the raw material of following quality proportioning：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 6 parts of oxygen vinethene, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 2 part of DMAE, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.
The water solubility of link stuff is not only related to the storage stability of water-based ink and printing applies membrane process, also affects the printing quality of ink.Using waterborne acrylic paint as link stuff, its performance determines the performance of water-based ink to the present invention substantially.The solid content of waterborne acrylic paint is relatively low, and to the good dispersion of dispersible pigment color paste, the coloring on PE/PP films is fabulous, and adhesive force is high, thus can keep the good film coloring on PE/PP films of water-based ink and adhesive force.Water-based ink, due to constantly to grind, stir, can produce a large amount of bubbles unavoidably in preparation process is produced, and can so influence packaging and film performance.Thus the present invention is added micro defoamer, so can effectively alleviate above mentioned problem.Also known as coalescing aid, it can promote the moulding flowing of macromolecular compound and elastic deformation to coalescents, improve coalescence performance.
The water solubility of resin is mainly related to hydrophilic radical and content.According to the drying at room temperature film forming of PE/PP film curing inks, while to reach excellent combination property, waterborne acrylic paint is polymerized from following component：, used as hard monomer, its glass transition temperature is high, can so improve hardness, weatherability and water resistance of polymer etc. for methyl methacrylate.Butyl acrylate can improve the pliability of glued membrane as soft monomer, increase film adhesive.Acrylic acid and hydroxy-ethyl acrylate, containing hydrophilic groups, hydroxyl etc., can improve the water solubility of polymer, and then cause that resin property is more stablized as hydrophilic monomer.DAAM is used as cross-linking monomer, adipic dihydrazide is used as crosslinking agent, DAAM can introduce the amino low-temperature self-crosslinking of reactive group ketone carbonyl and adipic dihydrazide, allow that resin occurs self-crosslinking reaction in low temperature, the performances such as adhesive force, hardness and the water resistance of film so can be not only improved, can be also applied on PE/PP films.In Raolical polymerizable, polymerization speed depends primarily on the speed of trigger rate, and trigger rate is related to the species of initiator.From azodiisobutyronitrile as initiator, it can react at a lower polymerization temperature, and low viscosity, resin of light color can be obtained.
In solution polymerization process, solvent can be produced a very large impact to polymerisation and polymerizate, and from propylene glycol methyl ether acetate as main solvent, existing ehter bond has carbonyl to the present invention again in its molecular structural formula, and carbonyl yet forms both the structure of ester group, also with alkyl；It is provided simultaneously with non-polar group and polar group, and this two parts group both mutually repelled by restriction, there is respective effect again, therefore, it can dissolve polarity and apolar substance.From dimethylformamide as cosolvent, it can be miscible with water, alcohols and alcohol ethers material.
The glass transition temperature appropriate to obtain resinous polymer, preferably, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid and the hydroxy-ethyl acrylate is a, and the number of the methyl methacrylate is a*55%, and the number of the butyl acrylate is a*30%.Because the construction temperature of water-based ink can not be too high, thus the MFT of water-base resin is controlled on the premise of changing firmness requirements when ensureing to reach resin film forming.Balance by controlling the number of hard monomer and soft monomer to adjust the glass transformation temperature of resin to reach between hardness and MFT of the invention.
To reach good aqueous stability and film performance, it is preferable that acrylic acid number is a*9.2%, and the number of the hydroxy-ethyl acrylate is a*5.8%.Acrylic acid is mainly the adhesive force of the aqueous stability and film that improve resin；Hydroxy-ethyl acrylate is primarily introduced into reactive group hydroxyl, improves the aqueous stability of resin, improves the adhesive force and the degree of cross linking of film after reacting.
Preferably, the total number of the methyl methacrylate, the butyl acrylate, the acrylic acid, the hydroxy-ethyl acrylate and DAAM is b, and the number of the azodiisobutyronitrile is b*2%.In polymerisation, the concentration of azodiisobutyronitrile is inversely proportional to the molecular weight of polymer.Specifically, with the increase of dosage of azodiisobutyronitrile, the molecular weight low amplitude of resinous polymer diminishes, and especially when consumption increases to b*2% from b*1%, influences unobvious；And when dosage of azodiisobutyronitrile is too high, reacting the heat for producing is difficult to control, danger can be brought to a large amount of productions.Additionally, azodiisobutyronitrile is relatively costly, storage and transport are also fairly cumbersome, and consumption excessively can also increase product cost.Thus, the present invention is controlled the 2% of the total consumption of monomer the consumption of azodiisobutyronitrile under the conditions of the molecular weight for meeting resin application performance.
Preferably, the propylene glycol methyl ether acetate and the mass ratio of the dimethylformamide are 2:1.From this mass ratio mixed solvent when, the water-soluble good of synthetic resin, good fluidity, transparency are high.
Preferably, the adipic dihydrazide and the mass ratio of the azodiisobutyronitrile are 4:5.The adipic dihydrazide can produce influence with the mass ratio of the azodiisobutyronitrile on the film degree of cross linking, water absorption rate and hardness.From the mass ratio, the excellent degree of cross linking and hardness and the water absorption rate compared with ground can be obtained.
Above content is to combine the further description that specific preferred embodiment is made to the present invention, it is impossible to assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, the other embodiment drawn in the case where technical scheme is not departed from should be included within the scope of the present invention.
Claims (6)
1. a kind of environment-friendly type aqueous ink, it is characterised in that：It is obtained by the raw material of following mass fraction：Waterborne acrylic paint 65 ~ 85%, aqueous color paste 15 ~ 25%, deionized water 10 ~ 20%, coalescents 0.2 ~ 0.5%, defoamer 0.2 ~ 0.3%, balance of ammoniacal liquor；Waterborne acrylic paint is obtained by the raw material of following quality proportioning：12 ~ 18 parts of methyl methacrylate, 12 ~ 18 parts of butyl acrylate, 4 ~ 8 parts of acrylic acid, 1.5 ~ 2.5 parts of hydroxy-ethyl acrylate, 0.5 ~ 1 part of DAAM, 33 ~ 46 parts of propylene glycol methyl ether acetate, 16 ~ 23 parts of dimethylformamide, 3 ~ 6 parts of oxygen vinethene, 1 ~ 3 part of polyoxyethylene glycol Arrcostab, 0.5 ~ 2 part of DMAE, 0.5 ~ 1 part of azodiisobutyronitrile, 0.5 ~ 0.8 part of adipic dihydrazide, 80 ~ 160 parts of distilled water.
2. a kind of environment-friendly type aqueous ink according to claim 1, it is characterised in that：The total number of the methyl methacrylate, the butyl acrylate, the acrylic acid and the hydroxy-ethyl acrylate is a, and the number of the methyl methacrylate is a*55%, and the number of the butyl acrylate is a*30%.
3. a kind of environment-friendly type aqueous ink according to claim 2, it is characterised in that：Acrylic acid number is a*9.2%, and the number of the hydroxy-ethyl acrylate is a*5.8%.
4. a kind of environment-friendly type aqueous ink according to claim 3, it is characterised in that：The total number of the methyl methacrylate, the butyl acrylate, the acrylic acid, the hydroxy-ethyl acrylate and DAAM is b, and the number of the azodiisobutyronitrile is b*2%.
5. a kind of environment-friendly type aqueous ink according to any one in claim 1 ~ 4, it is characterised in that：The propylene glycol methyl ether acetate is 2 with the mass ratio of the dimethylformamide:1.
6. a kind of environment-friendly type aqueous ink according to claim 5, it is characterised in that：The adipic dihydrazide is 4 with the mass ratio of the azodiisobutyronitrile:5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510832309.1A CN106752352A (en) | 2015-11-25 | 2015-11-25 | A kind of environment-friendly type aqueous ink |
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| CN201510832309.1A CN106752352A (en) | 2015-11-25 | 2015-11-25 | A kind of environment-friendly type aqueous ink |
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Application publication date: 20170531 |