CN106810647B - Water-based ink resin binder and preparation method thereof - Google Patents
Water-based ink resin binder and preparation method thereof Download PDFInfo
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- CN106810647B CN106810647B CN201611228305.3A CN201611228305A CN106810647B CN 106810647 B CN106810647 B CN 106810647B CN 201611228305 A CN201611228305 A CN 201611228305A CN 106810647 B CN106810647 B CN 106810647B
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
Abstract
The invention provides a water-based ink resin binder, which comprises the following monomers: 10-60% of methyl methacrylate by mass; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 0-40 percent; 1-15% of polyurethane acrylate; 0-40% by mass of methacrylic acid and 20-50% by mass of acrylic acid; and the methyl methacrylate, the butyl acrylate, the isooctyl acrylate, the urethane acrylate, the methacrylic acid and the acrylic acid are polymerized to form the water-based ink resin binder. The invention also provides a preparation method of the water-based ink resin binder. The invention adopts a monomer polymerization method, and endows the binder with different properties by adding monomers with different properties. The water-based ink resin binder which is completely water-soluble, has large adhesion on plastic base materials, can be dried quickly and has low VOC is obtained.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of water-based ink, in particular to a water-based ink resin binder and a preparation method thereof.
[ background of the invention ]
Due to environmental and regulatory pressures, solvent-based inks will gradually come out of the market and are replaced with low VOC (volatile organic compounds) or VOC-free water-soluble inks. The binder of the ink is an important component of the ink, and the properties of the resin binder of the ink largely determine the properties of the ink, such as: water solubility, adhesion, drying speed, etc.
CN105754405A A water-based ink and a preparation method thereof adopt water-based polyurethane as an ink binder, but the characteristics of the water-based polyurethane are not limited, and the influence of the characteristics of the water-based polyurethane on the water-based ink is not mentioned. ZL201310225038.4 an aqueous ink, a method of making the same, and an aqueous binder for use in security articles are a mixture of a styrene-acrylic emulsion and an acrylic emulsion, again without limiting the characteristics of the two emulsions. And the direct synthesis of the binder by the monomer can regulate and control the property of the binder, thereby regulating and controlling the property of the ink. In the preparation method of ZL201010190353.4 integrated plastic gravure alcohol-water composite ink resin, a resin binder is prepared by a monomer polymerization method, but solvents are contained in the preparation and use of the binder and the ink, and the solvents are limited to ethanol and ethyl acetate in the patent. The binder is not aqueous and the VOC of the ink is high. ZL 201410503072.8A water-based ink and its preparation method, binder preparation and use adopt 33% -50% butanol aqueous solution as solvent, so the binder still contains very high VOC.
In addition, although aqueous inks represent a future ink development direction, they also suffer from some important drawbacks, mainly slow drying and poor adhesion on plastic printing substrates.
[ summary of the invention ]
Aiming at the problems, the invention provides a water-based ink resin binder which is completely water-soluble, has low VOC, large adhesive force and quick drying, and a preparation method thereof.
In order to achieve the above object, the present invention provides an aqueous ink resin binder comprising the following monomers: 10-60% of methyl methacrylate by mass; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 0-40 percent; 1-15% of polyurethane acrylate; 0-40% by mass of methacrylic acid and 20-50% by mass of acrylic acid; and the methyl methacrylate, the butyl acrylate, the isooctyl acrylate, the urethane acrylate, the methacrylic acid and the acrylic acid are polymerized to form the water-based ink resin binder.
The invention also provides a preparation method of the water-based ink resin binder, which comprises the following steps:
step 1, preparing monomers according to the following proportions: 10-60% of methyl methacrylate by mass; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 0-40 percent; 1-15% of polyurethane acrylate; 0-40% by mass of methacrylic acid and 20-50% by mass of acrylic acid; then adding an initiator;
step 2, adding a water/alcohol mixed solvent into a reaction kettle, heating the reaction kettle to a preset temperature of 40-90 ℃, starting a cooling reflux device, dropwise adding a monomer, controlling the temperature fluctuation to be 1-2 ℃, and controlling the dropwise adding time to be 1-3 h;
step 3, after the monomer is dripped, keeping the temperature for 0-2 h; raising the temperature to about 5-10 ℃, and keeping the temperature for 1-4 hours;
step 4, stopping the cooling reflux device, starting to distill the azeotrope of the alcohol and the water, and continuously supplementing water;
and 5, cooling, and adding a neutralizing agent to obtain the water-based ink resin binder with a certain concentration.
The invention adopts a monomer polymerization method, and endows the binder with different properties by adding monomers with different properties. The water-based ink resin binder which is completely water-soluble, has large adhesion on plastic base materials, can be dried quickly and has low VOC is obtained.
[ description of the drawings ]
FIG. 1 is a flow chart of a method for preparing a water-based ink resin binder according to the present invention.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantageous effects of the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a water-based ink resin binder, which comprises the following monomers: 10-60% of methyl methacrylate by mass; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 0-40 percent; 1-15% of polyurethane acrylate; 0-40% by mass of methacrylic acid and 20-50% by mass of acrylic acid; and the methyl methacrylate, the butyl acrylate, the isooctyl acrylate, the urethane acrylate, the methacrylic acid and the acrylic acid are polymerized to form the water-based ink resin binder.
The methacrylate endows the binder with hardness, adhesive force and the like, and the content is 10-60%, preferably 20-40%. The butyl acrylate endows the binder with flexibility, quick drying property and the like, and the content is 0-20%, preferably 10-20%. The isooctyl acrylate endows the bonding material with flexibility, improves the adhesive force of a plastic base material, increases the quick drying property of the bonding material and the like, and the content is 0-20%, preferably 10-20%. The polyurethane acrylate can be of a monofunctional type or a bifunctional type and is used for improving the adhesive force of the adhesive, and the content is 1% -15%, preferably 3% -7%. The methacrylic acid endows the binder with water solubility, and the content is 0-40%, preferably 0-20%. The acrylic acid endows the binder with water solubility, and the content is 20-50%, preferably 30-40%.
The above monomers are polymerized by free radicals, and the polymerization initiator is selected from the following components: azo compounds and benzoyl peroxide compounds. For example: azobisisobutyronitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline, benzoyl peroxide, etc. The dosage of the initiator is 1-5% of the total mass of the monomers, and preferably 2-4%.
The invention adopts a solution polymerization method, and the solvent is a water/alcohol mixture. Wherein the alcohol can be methanol, ethanol, propanol, etc., preferably ethanol. The water/alcohol ratio is 1: 1-3.
The polymerization temperature is 40-90 ℃, and preferably 70-85 ℃.
The invention also provides a preparation method of the water-based ink resin binder, which comprises the following steps:
step 1, preparing monomers in proportion and adding an initiator. In the step, the monomers are prepared according to the following proportion: 10-60% of methyl methacrylate by mass; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 0-40 percent; 1-15% of polyurethane acrylate; 0-40% of methacrylic acid and 20-50% of acrylic acid. The initiator is selected from the following components: azo compounds and benzoyl peroxide compounds. For example: azobisisobutyronitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline, benzoyl peroxide, etc. The dosage of the initiator is 1-5% of the total mass of the monomers, and preferably 2-4%.
Step 2, adding a water/alcohol mixed solvent into a reaction kettle, heating the reaction kettle to a preset temperature, and starting a cooling reflux device; then, dropwise adding a monomer, and controlling the temperature fluctuation to be 1-2 ℃; the dripping time is 1-3 h. In the step, the preset temperature of the reaction kettle is 40-90 ℃, and preferably 70-85 ℃.
Step 3, after the monomer is dripped, keeping the temperature for 0-2 h; raising the temperature to about 5-10 ℃, and keeping the temperature for 1-4 hours; in step 3, sodium formaldehyde sulfoxylate may be added as necessary.
And 4, stopping the cooling reflux device, starting to distill the azeotrope of the alcohol and the water, and continuously supplementing water.
And 5, cooling, and adding a neutralizing agent to obtain the water-based ink resin binder with a certain concentration. In the step, the concentration of the water-based ink resin binder is 20-50%, preferably 35-45%.
Wherein the neutralizer in the step 5 is selected from: ammonia, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, N-dimethyl (iso) propanolamine, 2-amino-2-methylpropanol, or the like. The neutralizing agent is added in an amount to adjust the pH of the aqueous ink resin binder to 7.
Example 1
4kg of methyl methacrylate, 1kg of butyl acrylate, 1kg of isooctyl acrylate, 0.3kg of difunctional group urethane acrylate, 4kg of acrylic acid and 0.4kg of benzoyl peroxide are uniformly mixed and added into a charging tank of a reaction kettle. 15kg of ethanol and 7kg of deionized water are added into the reaction kettle. The reaction kettle was heated with stirring and the reflux condenser was turned on. And (3) when the temperature of the reaction kettle rises to 80 ℃, starting to dropwise add the monomer solution, finishing adding the monomer within 2 hours, and keeping the temperature for 2 hours. The temperature of the reaction kettle is raised to 85 ℃, and the constant temperature is kept for 1 hour. The reflux condenser was turned off, distillation was started, and deionized water was continuously added. 16kg of ethanol-water azeotrope is distilled, and 10kg of deionized water is added. Diethanolamine (0.6 kg) was added. Thus, an aqueous ink resin binder A was obtained.
Example 2
4kg of methyl methacrylate, 3kg of isooctyl acrylate, 0.5kg of monofunctional urethane acrylate, 1kg of methacrylic acid, 4kg of acrylic acid and 10kg of ethanol are uniformly mixed and added into a charging tank of a reaction kettle. 6kg of ethanol, 8kg of deionized water and 0.6kg of azobisisobutylamidine hydrochloride were charged into the reaction vessel. The reaction kettle was heated with stirring and the reflux condenser was turned on. When the temperature of the reaction kettle rises to 70 ℃, the monomer solution is dripped, and the monomer is added within 1 hour. The temperature of the reaction kettle is raised to 75 ℃, and the constant temperature is kept for 4 hours. And closing the reflux condenser, raising the temperature, starting distillation, and continuously adding deionized water. 17kg of ethanol-water azeotrope is distilled, and 12kg of deionized water is added. 0.9kg of 2-amino-2-methylpropanol was added. Thus, an aqueous ink resin binder B was obtained.
Example 3
3kg of methyl methacrylate, 2.5kg of isooctyl acrylate, 0.5kg of butyl acrylate, 0.7kg of difunctional poly urethane acrylate, 2kg of methacrylic acid, 4kg of acrylic acid and 0.6kg of benzoyl peroxide are uniformly mixed and added into a charging tank of a reaction kettle. Adding 18kg of ethanol and 10kg of deionized water into the reaction kettle, heating the reaction kettle under stirring, and starting a reflux condenser of the reaction kettle. When the temperature of the reaction kettle rises to 80 ℃, the monomer solution is dripped, the monomer is added within 3 hours, and the temperature is kept for 1 hour. The temperature of the reaction kettle is raised to 85 ℃, the temperature is kept for 2 hours, 0.2kg of formaldehyde sodium sulfoxylate is added, and the temperature is kept for 1 hour. And closing the reflux condenser, raising the temperature, starting distillation, and continuously adding deionized water. 19kg of ethanol-water azeotrope is distilled, and 12kg of deionized water is added. 1kg of N, N-dimethylethanolamine was added. Thus, an aqueous ink resin binder C was obtained.
Example 4
A, B parts of water-based ink resin binder and 40 parts of C, 17 parts of titanium dioxide, 1 part of wetting agent, 1 part of dispersing agent, 0.5-1 part of defoaming agent and 40 parts of deionized water are stirred and mixed uniformly and then are ground for 60min in a sand grinder. Scraping samples on the peritoneal scraping cards respectively. And testing the drying speed and the adhesive force. The results are shown in the following table.
The above results are tested according to the QB/T1046-.
The invention is not limited solely to that described in the specification and embodiments, and additional advantages and modifications will readily occur to those skilled in the art, so that the invention is not limited to the specific details, representative apparatus, and illustrative examples shown and described herein, without departing from the spirit and scope of the general concept as defined by the appended claims and their equivalents.
Claims (8)
1. An aqueous ink resin binder comprising the following monomers: 10-60% of methyl methacrylate; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 10-20 percent; 3-7% of polyurethane acrylate; methacrylic acid with the mass fraction of 0-20 percent and acrylic acid with the mass fraction of 20-50 percent; and the methyl methacrylate, butyl acrylate, isooctyl acrylate, urethane acrylate, methacrylic acid and acrylic acid are polymerized to form the water-based ink resin binder; adopting a solution polymerization method, wherein the solvent is a water/alcohol mixture; wherein the alcohol is methanol, ethanol, propanol; the water/alcohol ratio is 1: 1-3.
2. The aqueous ink resin binder as defined in claim 1, wherein: the content of the methyl methacrylate is preferably 20 to 40 percent; the content of the butyl acrylate is preferably 10-20%; the polyurethane acrylate is of a monofunctional type or a bifunctional type; the content of acrylic acid is preferably 30-40%.
3. The aqueous ink resin binder as defined in claim 1, wherein: the various monomers are polymerized by free radicals, and azo and benzoyl peroxide are selected as polymerization initiators.
4. The aqueous ink resin binder as defined in claim 3, wherein: the initiator is azobisisobutyronitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline and benzoyl peroxide; the dosage of the initiator is 1 to 5 percent of the total mass of the monomers.
5. A preparation method of a water-based ink resin binder comprises the following steps:
step 1, preparing monomers according to the following proportions: 10-60% of methyl methacrylate; butyl acrylate with the mass fraction of 0-40%; isooctyl acrylate with the mass component of 10-20 percent; 3-7% of polyurethane acrylate; methacrylic acid with the mass fraction of 0-20 percent and acrylic acid with the mass fraction of 20-50 percent; then adding an initiator;
step 2, adding a water/alcohol mixed solvent into a reaction kettle, wherein the alcohol is methanol, ethanol or propanol; the water/alcohol ratio is 1: 1-3; heating the reaction kettle to a preset temperature of 40-90 ℃, starting a cooling reflux device, then dropwise adding the monomer, controlling the temperature fluctuation to be 1-2 ℃, and controlling the dropwise adding time to be 1-3 h;
step 3, after the monomer is dripped, keeping the temperature for 0-2 h; raising the temperature to 5-10 ℃, and keeping the temperature for 1-4 h;
step 4, stopping the cooling reflux device, starting to distill the azeotrope of the alcohol and the water, and continuously supplementing water;
and 5, cooling, and adding a neutralizing agent to obtain the water-based ink resin binder with a certain concentration.
6. The method for preparing an aqueous ink resin binder according to claim 5, wherein: step 5, selecting a neutralizer: ammonia, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, N-dimethyl (iso) propanolamine or 2-amino-2-methylpropanol.
7. The method for preparing an aqueous ink resin binder according to claim 5, wherein: in the step 5, the concentration of the aqueous ink resin binder is 20-50%, and the addition amount of the neutralizing agent is used for adjusting the pH value of the aqueous ink resin binder to 7.
8. The method for preparing an aqueous ink resin binder according to claim 5, wherein: the polymerization initiator is selected from azo and benzoyl peroxide.
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| CN105440788A (en) * | 2016-01-06 | 2016-03-30 | 上海墨传新材料科技有限公司 | Water-based ink and preparation method thereof |
| CN105622857A (en) * | 2016-04-01 | 2016-06-01 | 武汉大学 | Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material |
| CN106147672A (en) * | 2015-04-07 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound aqueous polyurethane acrylate binding agent and preparation method thereof |
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| CN106147672A (en) * | 2015-04-07 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound aqueous polyurethane acrylate binding agent and preparation method thereof |
| CN105440788A (en) * | 2016-01-06 | 2016-03-30 | 上海墨传新材料科技有限公司 | Water-based ink and preparation method thereof |
| CN105622857A (en) * | 2016-04-01 | 2016-06-01 | 武汉大学 | Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material |
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Denomination of invention: A water-based ink resin binder and its preparation method Effective date of registration: 20220714 Granted publication date: 20200811 Pledgee: China Co. truction Bank Corp Dongguan branch Pledgor: DONGGUAN HAOCAI INK TECHNOLOGY CO.,LTD. Registration number: Y2022980010511 |