CN111138612A - Printing thickener and preparation method thereof - Google Patents
Printing thickener and preparation method thereof Download PDFInfo
- Publication number
- CN111138612A CN111138612A CN202010027340.9A CN202010027340A CN111138612A CN 111138612 A CN111138612 A CN 111138612A CN 202010027340 A CN202010027340 A CN 202010027340A CN 111138612 A CN111138612 A CN 111138612A
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- printing
- monomer
- thickener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
Abstract
The invention relates to the field of printing and dyeing, and discloses a printing thickener which comprises the following components in parts by weight: 50-60 parts of acrylic monomers, 10-15 parts of water-soluble stabilizers, 50-75 parts of pH regulators, 0.5-1.5 parts of polyoxyethylene ether acrylate functional monomers, 0.2-0.5 part of cationic monomers, 0.2-0.5 part of cross-linking agents, 40-50 parts of oil phase solvents, 4-5 parts of emulsifiers, 20-25 parts of initiators and 7-9 parts of reverse phase emulsifiers. The thickening agent has strong thickening capability and electrolyte resistance capability and good color yield; the preparation method of the thickening agent comprises the following steps: stirring water, acrylic monomers and a water-soluble stabilizer; adjusting the pH value to 5.5-6.5; adding a cationic monomer, a cross-linking agent and an oxidant, and stirring to obtain an aqueous phase solution; stirring and emulsifying an oil phase solvent, an emulsifier, an acrylic monomer and a polyoxyethylene ether acrylate functional monomer to obtain an oil phase solution; adding the water phase solution into the oil phase solution for emulsification, and heating; adding a reducing agent and a reverse-phase emulsifier, and stirring to obtain the printing thickener.
Description
Technical Field
The invention relates to the technical field of printing and dyeing, and particularly relates to a printing thickener and a preparation method thereof.
Background
The thickener is a rheological additive and plays a decisive role in controlling the rheological property of the system. Pigment printing is a printing method in which a film is formed on a fabric by using a high molecular compound and a pigment is fixed on the fabric. The thickening agent is added into the printing paste to increase the viscosity of the printing paste and reduce the fluidity of the printing paste, so that the printing paste has pseudoplasticity. The viscosity is reduced under the action of shearing force, the printing and dyeing fabric is easy to leak from meshes of the printing and dyeing screen, and the viscosity is increased after the shearing force is lost, so that the printing and dyeing fabric can be kept in place and cannot permeate to other parts of the fabric. Secondly, the printing paste is distributed on the surface of the fabric, and yarns in the fabric cannot be bonded, so that the printing paste is beneficial to hand feeling. The rheological characteristics of the paste enable the binder to be self-crosslinking or externally crosslinking to tightly bond the coating particles to each other, and can improve the rubbing resistance and washing fastness. The nature of the thickener therefore determines the printing properties of the printing pastes and also directly influences the quality of the printed products.
At present, the main research directions of various circles are color yield, thickening capacity, printing uniformity and the like in the synthesis of acrylic acid active thickening agents. Patent CN106589207B discloses an electrolyte-resistant pigment printing thickener, which is an acrylic acid active thickener synthesized from an acrylic acid monomer, a pH regulator, an oil phase solvent, a cross-linking agent, an initiator, an emulsifier, a reverse phase emulsifier and a comonomer, but has the defects of low solid content, hard hand feeling, high VOC content and poor color yield.
Disclosure of Invention
The first purpose of the invention is to provide a printing thickener which has strong thickening capability, high solid content, low VOC content and good color yield.
The second purpose of the invention is to provide a preparation method of the printing thickener, which is simple and easy to implement, has strong operability and is beneficial to improving the polymerization stability and the storage stability of products.
The embodiment of the invention is realized by the following steps:
a printing thickener comprises the following components in parts by weight:
50-60 parts of acrylic monomers, 10-15 parts of water-soluble stabilizers, 50-75 parts of pH regulators, 0.5-1.5 parts of polyoxyethylene ether acrylate functional monomers, 0.2-0.5 part of cationic monomers, 0.2-0.5 part of cross-linking agents, 35-50 parts of oil phase solvents, 4-5 parts of emulsifiers, 7-9 parts of reverse phase emulsifiers, 20-25 parts of oxidants and 0.1-0.25 part of reducing agents; the oil phase solvent comprises 20-25 parts by weight of a first continuous phase and 15-25 parts by weight of a second continuous phase.
Further, the acrylic monomer is one or more of methacrylic acid, ethyl methacrylate, bis-methacrylic acid, acrylamide sulfonate, butyl acrylate and the like.
Further, the water-soluble stabilizer is an acrylic polymer.
Further, the polyoxyethylene ether acrylate functional monomer is one or more of octadecyl polyoxyethylene methacrylate, eicosyl polyoxyethylene methacrylate and docosyl polyoxyethylene methacrylate.
Further, the cationic monomer is one or more of MAPTAC, DAPMAC and DMC ammonium salt.
Further, the cross-linking agent is one or more of dipropylamine and tetraene ammonium chloride.
Further, the first continuous phase is one or more of D40, D60, and D70; the second continuous phase is one or more of 15# white oil, 68# white oil, 100# white oil and 150# white oil.
Further, the oxidant is one or more of potassium persulfate and ammonium persulfate; the reducing agent is sodium bisulfite.
Further, the emulsifier is one or more of Span-80, Span-60 and 1599A; the reverse emulsifier is one or more of Tween-80 and Tween-60.
A preparation method of a printing thickener comprises the following steps:
(1) adding 15-20 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer, and stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 5.5-6.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 15-20 minutes, and heating to 50-60 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 20-30 minutes, then slowly dropwise adding the aqueous solution of the reducing agent, controlling the dropwise adding time to be 1.5-2 hours, controlling the temperature to be 75-80 ℃, and continuing to keep the temperature for 1-2 hours after the dropwise adding of the aqueous solution of the reducing agent is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
The invention has the beneficial effects that:
1. the acrylic monomer in the invention takes acrylic acid as a main monomer, and methacrylic acid, ethyl methacrylate, bis-methacrylic acid, butyl acrylate, acrylamide sulfonate and the like are introduced into an acrylic acid molecular chain, so that methyl, ethyl, amide or amide sulfonate and other groups exist on the acrylic acid molecular chain, the polarity of the molecular chain is improved, the thickening effect on water is increased, the affinity on dye and fiber is increased, the transfer efficiency of the dye in the sizing agent is improved, and the effect on improving the color yield is remarkable.
2. According to the printing thickener, the acrylic polymer is used as a water-soluble stabilizer, an oily solvent (wherein the oily solvent adopts continuous phases with different processes) and an emulsification system are matched, the stabilizer contains a group with strong hydrophobicity, when the water amount reaches a certain degree, molecules of the thickener extend, the thickening effect on water is increased, high-concentration polymerization and low-concentration polymerization are realized, and the printing thickener meeting the requirements is finally prepared.
3. According to the invention, on the premise of ensuring the thickening capability of the thickener, by adding polyoxyethylene ether acrylate functional monomers (such as octadecyl polyoxyethylene methacrylate, eicosyl polyoxyethylene methacrylate and docosyl polyoxyethylene methacrylate), long-chain alkyl groups of carbon 18 or carbon 20 or carbon 22 are introduced into an acrylic acid molecular chain, so that the steric hindrance capability of the long-chain alkyl groups is strong, when an acrylate macromolecular chain swells and expands, different thixotropy can be provided due to the steric hindrance effect, the adjustment of different rheological properties of the thickener can be realized through the optimization of the carbon length and the introduction amount of the functional monomers, and the requirements of various printing on thixotropy can be met after the adjustment of different rheological properties, so that the problems of screen-tight printing, unclear printing and the like are solved.
4. The cationic monomer is introduced to enable molecular chains to have positive charges, so that the cationic monomer has an effect of removing electrolytes, and the electrolyte resistance of the thickener is further improved.
5. The cross-linking agent greatly improves the cross-linking density and the cross-linking efficiency, and has the structural characteristic of association cross-linking by cooperating with the polyoxyethylene acrylate functional monomer.
6. According to the preparation method, the oxidizing agent and the reducing agent are added step by step in the preparation process, so that the components of the thickening agent are polymerized at a lower temperature, the reaction is stable and mild, the molecular weight of the prepared thickening agent is increased, and the thickening effect is improved; and finally, the thickening agent is prepared by a polymerization method of adding the reverse-phase emulsifier, which is beneficial to improving the polymerization stability and the storage stability of the product.
7. The printing paste thickened by the thickener has the advantages of low VOC content, high system solid content, strong thickening capability and electrolysis resistance, good stability, soft hand feeling, good color yield and good storage stability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The printing thickener and the preparation method thereof provided by the embodiment of the invention are specifically described below.
A printing thickener comprises the following components in parts by weight:
50-60 parts of acrylic monomers, 10-15 parts of water-soluble stabilizers, 50-75 parts of pH regulators, 0.5-1.5 parts of polyoxyethylene ether acrylate functional monomers, 0.2-0.5 part of cationic monomers, 0.2-0.5 part of cross-linking agents, 35-50 parts of oil phase solvents, 4-5 parts of emulsifiers, 7-9 parts of reverse phase emulsifiers, 20-25 parts of oxidants and 0.1-0.25 part of reducing agents; the oil phase solvent comprises 20-25 parts by weight of a first continuous phase and 15-25 parts by weight of a second continuous phase.
In the embodiment, considering that the problems of high thickening capacity, light and dark color yield, printing screen-impermeable and pulp-impermeable printing, unclear printing outline, low chemical resistance, difficulty in aqueous de-pasting or hard hand feeling after printing, low solid content, high using amount and the like in acrylic acid thickening, in the embodiment, acrylic acid is used as a main monomer for the acrylic acid monomer, and methacrylic acid, ethyl methacrylate, bis-methacrylic acid, butyl acrylate, acrylamide sulfonate and the like are introduced to an acrylic acid molecular chain, so that methyl, ethyl ester, amide or amide sulfonate and other groups exist on the acrylic acid molecular chain to improve the polarity of the molecular chain, thereby not only increasing the thickening effect on water, but also increasing the affinity to dyes and fibers, improving the transfer efficiency of the dyes in the pulp and having a remarkable effect on improving the color yield.
Considering that the conventional acrylic thickener has low solid content and large using amount, and brings negative benefits to use, transportation, fabric hand feeling and the like, in this embodiment, the inventor creatively uses an acrylic polymer as a water-soluble stabilizer, and matches with the exploration of an oily solvent (wherein the oily solvent adopts continuous phases with different processes) and an emulsification system, the stabilizer contains a group with strong hydrophobicity, when the water amount reaches a certain degree, the molecules of the thickener extend, the thickening effect on water is increased, high-concentration polymerization and low-concentration polymerization are realized, and finally the printing thickener meeting the requirements is prepared.
In this embodiment, the polyoxyethylene ether acrylate functional monomer is one or more of octadecyl polyoxyethylene methacrylate, eicosyl polyoxyethylene methacrylate, and docosyl polyoxyethylene methacrylate. On the premise of ensuring the thickening capacity of the thickener, in the embodiment, the inventor discovers that long-chain alkyl groups of carbon 18-22 exist on a molecular chain after the introduction of functional monomers by researching the influence of the functional monomers such as carbon 18, carbon 20, carbon 22 alkyl polyoxyethylene methacrylate and the like on the rheological property of the thickener, so that the steric hindrance capacity of the long-chain alkyl groups is high, when an acrylate macromolecular chain swells and expands, different thixotropy can be provided due to the steric hindrance effect, the adjustment of different rheological properties of the thickener can be realized through the optimization of the carbon length and the introduction amount of the functional monomers, and the requirements of various printing on thixotropy can be met after the adjustment of different rheological properties, so that the problems of screen-tight printing, unclear printing and the like are solved.
In this embodiment, the cationic monomer is one or more of MAPTAC, DAPMAC and DMC ammonium salt, and the introduction of the cationic monomer makes the molecular chain have positive charges, which has an effect of removing electrolytes, thereby further increasing the electrolyte resistance of the thickener.
In this embodiment, the crosslinking agent is one or more of dipropylamine and tetraene ammonium chloride. Because a plurality of auxiliaries such as dye, urea, anti-dyeing salt and the like are often added into the printing paste, the auxiliaries contain a positive ion group, so that the extension of acrylate carboxyl is hindered, the thickening of the thickener to the paste is greatly reduced, in order to solve the problems, the characteristics of the traditional dipropylamine crosslinking system are absorbed in the embodiment, and meanwhile, the tetraalkyene ammonium chloride crosslinking monomer is added, so that the crosslinking density and the crosslinking efficiency are greatly improved, and the associative crosslinking structural characteristics are formed by the synergistic effect of the alkyl polyoxyethylene methacrylate functional monomer.
In the present embodiment, the first continuous phase is one or more of D40, D60 and D70; the second continuous phase is one or more of 15# white oil, 68# white oil, 100# white oil and 150# white oil. The viscosity of the thickener increases with the amount of white oil, since the molecular chain increases when the amount of white oil is small, and the thickening effect is the best when the molecular weight is large, therefore, the second continuous phase is controlled within the range of 15-25 parts.
In this embodiment, the oxidant is one or more of potassium persulfate and ammonium persulfate; the reducing agent is sodium bisulfite.
In the embodiment, the emulsifier is one or more of Span-80, Span-60 and 1599A; the reverse emulsifier is one or more of Tween-80 and Tween-60.
A preparation method of a printing thickener comprises the following steps:
(1) adding 15-20 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer, and stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 5.5-6.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 15-20 minutes, and heating to 50-60 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 20-30 minutes, then slowly dropwise adding the aqueous solution of the reducing agent, controlling the dropwise adding time to be 1.5-2 hours, controlling the temperature to be 75-80 ℃, and continuing to keep the temperature for 1-2 hours after the dropwise adding of the aqueous solution of the reducing agent is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
In the process of preparing the thickening agent, firstly, an acrylic acid high-molecular water-soluble stabilizer is synthesized by free radical polymerization, and then, an acrylate thickening agent is synthesized by inverse emulsion polymerization, so that on one hand, the phenomenon of sudden polymerization in the polymerization process can be avoided; on the other hand, the acrylic acid modified polyester can be subjected to good random copolymerization with acrylic monomers in a water phase at an initiator and a certain temperature, so that methyl, ethyl ester, 2-ethylhexyl ester, amide, sulfonic acid groups and the like exist on an acrylic acid molecular chain, the polarity of the molecular chain is improved, the thickening effect on water is increased, the affinity to dye and fiber is increased, the transfer efficiency of the dye in the slurry is improved, the effect of improving the color yield is remarkable, and the electrolyte resistance of the thickener is effectively improved; in the preparation process, the oxidizing agent and the reducing agent are added step by step, so that the components of the thickening agent are polymerized at a lower temperature, the reaction is stable and mild, the molecular weight of the prepared thickening agent is increased, and the thickening effect is improved; and finally, the thickening agent is prepared by adding the reverse-phase emulsifier through a polymerization method, so that the polymerization stability and the product storage stability are improved, and the product stability can be further improved due to the moderate proportion of the polymerized oil phase and the polymerized water phase.
The invention adopts a redox initiation system, utilizes the redox reaction between an oxidant and a reducing agent to generate free radicals capable of initiating polymerization, and after the reducing agent is added into the oxidant, the mechanism of generating the free radicals is changed, so that the reaction activation energy is greatly reduced, and the polymerization reaction can reach high conversion rate at lower temperature.
Example 1
The embodiment provides a printing thickener which comprises the following components in parts by weight: 50 parts of methacrylic acid, 10 parts of acrylic polymer, 50 parts of pH regulator, 0.5 part of octadecyl polyoxyethylene methacrylate, 0.2 part of DMC ammonium salt, 0.2 part of tetraene ammonium chloride, 0 part of D4020 part, 15 parts of 15# white oil, 4 parts of Span-80 emulsifier, 20 parts of potassium persulfate, 0.1 part of sodium bisulfite and 7 parts of Tween-80 emulsifier.
The embodiment also provides a preparation method of the printing thickener, which comprises the following steps: (1) adding 15 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer into the reactor, and starting stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 5.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 15 minutes, and heating to 50 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 20 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 1.5 hours, controlling the temperature to be 75 ℃, and continuing to keep the temperature for 1 hour after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (3) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding 7 parts of reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Example 2
The embodiment provides a printing thickener which comprises the following components in parts by weight: 60 parts of methacrylic acid, 15 parts of acrylic polymer, 75 parts of pH regulator, 1.5 parts of octadecyl polyoxyethylene methacrylate, 0.5 part of DMC ammonium salt, 0.5 part of tetraene ammonium chloride, 5 parts of D4025 parts of 15# white oil, 5 parts of Span-80 emulsifier, 25 parts of potassium persulfate, 0.25 part of sodium bisulfite and 9 parts of Tween-80 emulsifier.
The embodiment also provides a preparation method of the printing thickener, which comprises the following steps: (1) adding 20 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer into the reactor, and starting stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 6.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 20 minutes, and heating to 60 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 30 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 80 ℃, and continuing to keep the temperature for 2 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Example 3
The embodiment provides a printing thickener which comprises the following components in parts by weight: 55 parts of methacrylic acid, 12 parts of acrylic polymer, 60 parts of pH regulator, 1 part of octadecyl polyoxyethylene methacrylate, 0.4 part of DMC ammonium salt, 0.4 part of tetraene ammonium chloride, 2 parts of D4022 parts, 20 parts of 15# white oil, 4 parts of Span-80 emulsifier, 22 parts of potassium persulfate, 0.2 part of sodium bisulfite and 8 parts of Tween-80 emulsifier.
The embodiment also provides a preparation method of the printing thickener, which comprises the following steps: (1) adding 18 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer into the reactor, and starting stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a PH regulator into the step (1) until the PH reaches 6;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 18 minutes, and heating to 55 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 25 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 73 ℃, and continuing to keep the temperature for 1.5 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Example 4
The embodiment provides a printing thickener which comprises the following components in parts by weight: 50 parts of acrylamide, 10 parts of acrylic polymer, 50 parts of pH regulator, 0.5 part of eicosyl polyoxyethylene methacrylate, 0.2 part of DMC ammonium salt, 0.2 part of tetraene ammonium chloride, D6020 part, 15 parts of 68# white oil, 4 parts of Span-60 emulsifier, 20 parts of ammonium persulfate, 0.1 part of sodium bisulfite and 7 parts of Tween-60 emulsifier.
The embodiment also provides a preparation method of the printing thickener, which comprises the following steps: (1) adding 15 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer into the reactor, and starting stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 5.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 15 minutes, and heating to 50 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 20 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 1.5 hours, controlling the temperature to be 75 ℃, and continuing to keep the temperature for 1 hour after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Example 5
The embodiment provides a printing thickener which comprises the following components in parts by weight: 60 parts of acrylamide, 15 parts of acrylic polymer, 75 parts of pH regulator, 1.5 parts of eicosyl polyoxyethylene methacrylate, 0.5 part of DMC ammonium salt, 0.5 part of tetraene ammonium chloride, D6025 parts, 25 parts of 68# white oil, 5 parts of Span-60 emulsifier, 25 parts of ammonium persulfate, 0.25 part of sodium bisulfite and 9 parts of Tween-60 emulsifier.
The embodiment also provides a preparation method of the printing thickener, which comprises the following steps: (1) adding 20 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer into the reactor, and starting stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 6.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 20 minutes, and heating to 60 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 30 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 80 ℃, and continuing to keep the temperature for 2 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Example 6
The embodiment provides a printing thickener which comprises the following components in parts by weight: 55 parts of acrylamide, 13 parts of acrylic polymer, 60 parts of pH regulator, 1 part of eicosyl polyoxyethylene methacrylate, 0.4 part of DMC ammonium salt, 0.4 part of tetraene ammonium chloride, D6022 parts, 20 parts of 68# white oil, 4 parts of Span-60 emulsifier, 22 parts of ammonium persulfate, 0.2 part of sodium bisulfite and 8 parts of Tween-60 emulsifier.
The embodiment also provides a preparation method of the printing thickener, which comprises the following steps: (1) adding 20 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer into the reactor, and starting stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a PH regulator into the step (1) until the PH reaches 6;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 20 minutes, and heating to 55 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 25 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 80 ℃, and continuing to keep the temperature for 1.5 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Comparative example 1
The comparative example provides a printing thickener comprising the following components in parts by weight: 55 parts of methacrylic acid, 12 parts of acrylic polymer, 60 parts of pH regulator, 0.4 part of DMC ammonium salt, 2 parts of D4022, 20 parts of 15# white oil, 4 parts of Span-80 emulsifier, 22 parts of potassium persulfate, 0.2 part of sodium bisulfite and 8 parts of Tween-80 emulsifier.
The comparative example also provides a method for preparing a printing thickener, comprising the following steps: (1) adding 18 parts of water into a reactor, adding an acrylic monomer and a water-soluble stabilizer into the reactor in a water-adding manner, and starting stirring until the acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a PH regulator into the step (1) until the PH reaches 6;
(3) adding a cationic monomer and an oxidant into the acrylate solution neutralized in the step (2), and continuously stirring until the cationic monomer and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier and the oil-soluble acrylic monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 18 minutes, and heating to 55 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 25 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 73 ℃, and continuing to keep the temperature for 1.5 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Comparative example 2
The comparative example provides a printing thickener comprising the following components in parts by weight: 55 parts of methacrylic acid, 12 parts of acrylic polymer, 60 parts of pH regulator, 1 part of octadecyl polyoxyethylene methacrylate, 0.4 part of tetraene ammonium chloride, 2 parts of D4022, 20 parts of 15# white oil, 4 parts of Span-80 emulsifier, 22 parts of potassium persulfate, 0.2 part of sodium bisulfite and 8 parts of Tween-80 emulsifier.
The comparative example also provides a method for preparing a printing thickener, comprising the following steps: (1) adding 18 parts of water into a reactor, adding an acrylic monomer and a water-soluble stabilizer into the reactor in a water-adding manner, and starting stirring until the acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a PH regulator into the step (1) until the PH reaches 6;
(3) adding a cross-linking agent and an oxidant into the acrylate solution neutralized in the step (2), and continuously stirring until the acrylate solution is completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 18 minutes, and heating to 55 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 25 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 73 ℃, and continuing to keep the temperature for 1.5 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Comparative example 3
The comparative example provides a printing thickener comprising the following components in parts by weight: 55 parts of methacrylic acid, 12 parts of acrylic polymer, 60 parts of pH regulator, 0.4 part of DMC ammonium salt, 0.4 part of tetraene ammonium chloride, 2 parts of D4022 parts, 20 parts of 15# white oil, 4 parts of Span-80 emulsifier, 22 parts of potassium persulfate, 0.2 part of sodium bisulfite and 8 parts of Tween-80 emulsifier.
The comparative example also provides a method for preparing a printing thickener, comprising the following steps: (1) adding 18 parts of water into a reactor, adding an acrylic monomer and a water-soluble stabilizer into the reactor in a water-adding manner, and starting stirring until the acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a PH regulator into the step (1) until the PH reaches 6;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier and the oil-soluble acrylic monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 18 minutes, and heating to 55 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 25 minutes, then slowly dropwise adding the reducing agent aqueous solution, controlling the dropwise adding time to be 2 hours, controlling the temperature to be 73 ℃, and continuing to keep the temperature for 1.5 hours after the dropwise adding of the reducing agent aqueous solution is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Experimental example 1
The experimental method comprises the following steps: setting the examples 1-6 and the comparative example 1 as experimental groups 1-7, and respectively testing the thickening capability of the thickening agent provided by the experimental groups 1-7 on the printing paste, wherein the printing pastes in the experimental groups 1-7 are added with the same printing paste auxiliary agent, the same thickening agent is used for thickening the paste, and meanwhile, different amounts of the thickening agent are tested. The printing paste additive comprises the following components in parts by weight: 5 percent of reactive dye, 3 percent of baking soda, 1 percent of dye-resistant salt and 20 percent of urea, and the same method for preparing the color paste is adopted, a DV 2-type rotational viscosity instrument, a 6# rotor and a 10r/min rotating speed are adopted for testing, the viscosity is represented by Cpa.s, and the thickening effect is better when the Cpa.s data is larger.
The data in the table show that, under the condition of a small amount of thickener in the printing paste, the thickening capacity of the printing thickener provided by the experimental groups 1-6 to the printing paste is better than that of the printing thickener provided by the experimental group 7, the cross-linking agent in the invention is not added in the experimental group 7, and compared with the experimental groups 1-6 and the experimental group 7, the combination of the components provided by the embodiment of the invention can generate specific correlation which cannot be replaced by other substances.
Experimental example 2
The experimental method comprises the following steps: examples 1 to 6 and comparative example 2 were set as experimental groups 1 to 6 and 8, and the electrolyte resistance of the thickeners provided in experimental groups 1 to 6 and 8 were tested, respectively, wherein white slurry was prepared under the same consumption of the thickener, 100g/L of anhydrous sodium sulfate was added thereto, and the viscosity retention rate was examined, and the higher the retention rate, the better the effect. The test was carried out using a rotational viscosity apparatus model DV 2-type, rotor # 6, at a speed of 10r/min, and the test data are shown in Table 2:
the data in the table show that, under the condition of a small amount of the thickener in the printing paste, the thickening capacity of the printing thickener provided by the experimental groups 1-6 to the printing paste is better than that of the printing thickener provided by the experimental group 8, the cationic monomer in the invention is not added in the experimental group 8, and the comparison of the experimental groups 1-6 and the experimental group 8 shows that the combination of the components provided by the embodiment of the invention can generate specific correlation which cannot be replaced by other substances.
Experimental example 3
The experimental method comprises the following steps: examples 1 to 6 and comparative example 3 were set as experimental groups 1 to 6 and experimental group 9, and the color yield depth properties of the thickeners provided in experimental groups 1 to 6 and experimental group 9 were respectively tested,
the printing pastes in the experiment groups 1-6 are added with the same printing paste auxiliaries, the same thickening agent (4.5% of the amount) is used for thickening the printing pastes, the experiment groups 1-6 and the experiment group 9 are prepared into the printing pastes with the same viscosity, the printing pastes are printed by a flat screen platform printing machine, and the prepared cloth samples are subjected to printing-drying-steaming-washing-soaping-washing-drying process flows, wherein the L value of each cloth sample is detected by a precise color difference instrument, and the smaller the L value is, the darker the color depth is represented. The printing paste additive comprises the following components in parts by weight: 5 percent of reactive dye, 3 percent of baking soda, 1 percent of dye-resistant salt and 20 percent of urea, and the same method for preparing the color paste is adopted, a DV 2-type rotational viscosity instrument and a No. 6 rotor are adopted, the rotating speed of 10r/min is adopted to detect the viscosity value, and the test data is shown in a table 3:
| group number | Viscosity (Cpa.s) | Value of L |
| Experimental group 1 | 20500 | 50.16 |
| Experimental group 2 | 20600 | 49.96 |
| Experimental group 3 | 21000 | 50.25 |
| Experimental group 4 | 20500 | 50.16 |
| Experimental group 5 | 21500 | 50.21 |
| Experimental group 6 | 20500 | 50.05 |
| Experimental group 9 | 20000 | 52.85 |
As can be seen from the data in the table above, the dye yield of the printing paste by the printing thickener provided by the experimental groups 1-6 is better than that of the printing thickener provided by the experimental group 9 under the condition of smaller consumption of the thickener in the printing paste, the polyoxyethylene ether acrylate functional monomer provided by the invention is not added in the experimental group 9, and the comparison of the experimental groups 1-6 and the experimental group 9 shows that the combination of the components provided by the embodiment of the invention can generate specific correlation which cannot be replaced by other substances, on the premise of ensuring the thickening capability of the thickener, the inventor discovers that the molecular chain has long-chain alkyl groups of carbon 18-22 after the functional monomers are introduced to ensure that the steric hindrance capability of the long-chain alkyl groups is strong by researching the influence of the functional monomers such as carbon 18, carbon 20, carbon 22 alkyl polyoxyethylene methacrylate and the like on the rheological property of the thickener, when the macromolecular chains of the acrylate are swelled and expanded, different thixotropy can be provided due to steric hindrance, adjustment of different rheological properties of the thickener can be realized through optimization of the carbon length and the introduction amount of the functional monomer, and requirements of various printing on thixotropy can be met after adjustment of different rheological properties, so that the problems of screen-tight printing, paste-tight printing, unclear printing and the like are solved.
According to the invention, acrylic acid is taken as a main monomer, and methacrylic acid, ethyl methacrylate, bis-methacrylic acid, butyl acrylate, acrylamide sulfonate and the like are introduced into an acrylic acid molecular chain, so that methyl, ethyl, amide or amide sulfonate and other groups exist on the acrylic acid molecular chain, the polarity of the molecular chain is improved, the thickening effect on water is increased, the affinity on dye and fiber is increased, the transfer efficiency of the dye in the sizing agent is improved, and the effect of improving the color yield is remarkable.
In conclusion, the thickener prepared by the formula and the proportion range of the components provided by the embodiment of the invention has high solid content, strong thickening capability and electrolytic resistance, good stability and soft hand feeling; the prepared printing paste has good color yield and good storage stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The printing thickener is characterized by comprising the following components in parts by weight:
50-60 parts of acrylic monomers, 10-15 parts of water-soluble stabilizers, 50-75 parts of pH regulators, 0.5-1.5 parts of polyoxyethylene ether acrylate functional monomers, 0.2-0.5 part of cationic monomers, 0.2-0.5 part of cross-linking agents, 35-50 parts of oil phase solvents, 4-5 parts of emulsifiers, 7-9 parts of reverse phase emulsifiers, 20-25 parts of oxidants and 0.1-0.25 part of reducing agents; the oil phase solvent comprises 20-25 parts by weight of a first continuous phase and 15-25 parts by weight of a second continuous phase.
2. The printing thickener of claim 1, wherein the acrylic monomer is one or more of methacrylic acid, ethyl methacrylate, bis-methacrylic acid, acrylamide sulfonate, butyl acrylate.
3. Printing thickener according to claim 1, wherein the water soluble stabilizer is an acrylic polymer.
4. The printing thickener of claim 1, wherein the polyoxyethylene ether acrylate functional monomer is one or more of octadecyl polyoxyethylene methacrylate, eicosyl polyoxyethylene methacrylate, and docosyl polyoxyethylene methacrylate.
5. The printing thickener of claim 1 wherein the cationic monomer is one or more of MAPTAC, DAPMAC and DMC ammonium salt.
6. The printing thickener of claim 1, wherein the cross-linking agent is one or more of bisacrylamide and tetraalkenylammonium chloride.
7. The printing thickener of claim 1, wherein the first continuous phase is one or more of D40, D60, and D70; the second continuous phase is one or more of 15# white oil, 68# white oil, 100# white oil and 150# white oil.
8. The printing thickener of claim 1, wherein the oxidant is one or more of potassium persulfate and ammonium persulfate; the reducing agent is sodium bisulfite.
9. The printing thickener of claim 1, wherein the emulsifier is one or more of Span-80, Span-60, 1599A; the reverse emulsifier is one or more of Tween-80 and Tween-60.
10. A method for preparing a printing thickener according to any of claims 1 to 9, comprising the steps of:
(1) adding 15-20 parts of water into a reactor, adding a water-based acrylic monomer and a water-soluble stabilizer, and stirring until the water-based acrylic monomer and the water-soluble stabilizer are completely dissolved;
(2) dropwise adding a pH regulator into the solution obtained in the step (1) until the pH value reaches 5.5-6.5;
(3) adding a cationic monomer, a cross-linking agent and an oxidant into the neutralized acrylate solution in the step (2), and continuously stirring until the cationic monomer, the cross-linking agent and the oxidant are completely dissolved to obtain an aqueous phase solution;
(4) uniformly stirring the first continuous phase, the second continuous phase, the emulsifier, the oil-soluble acrylic monomer and the polyoxyethylene ether acrylate functional monomer, and emulsifying at a high speed to obtain an oil phase solution; slowly adding the water phase solution in the step (3) into the oil phase solution, continuing to emulsify at high speed for 15-20 minutes, and heating to 50-60 ℃ after emulsification is finished;
(5) introducing nitrogen into the mixture obtained in the step (4) for 20-30 minutes, then slowly dropwise adding the aqueous solution of the reducing agent, controlling the dropwise adding time to be 1.5-2 hours, controlling the temperature to be 75-80 ℃, and continuing to keep the temperature for 1-2 hours after the dropwise adding of the aqueous solution of the reducing agent is finished;
(6) and (4) filtering the material obtained in the step (5) by using a 200-mesh filter screen, adding a reverse phase emulsifier, and uniformly stirring to obtain the printing thickener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010027340.9A CN111138612A (en) | 2020-01-10 | 2020-01-10 | Printing thickener and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010027340.9A CN111138612A (en) | 2020-01-10 | 2020-01-10 | Printing thickener and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111138612A true CN111138612A (en) | 2020-05-12 |
Family
ID=70524406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010027340.9A Pending CN111138612A (en) | 2020-01-10 | 2020-01-10 | Printing thickener and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111138612A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112252057A (en) * | 2020-07-29 | 2021-01-22 | 爱森（中国）絮凝剂有限公司 | Preparation method of composite anionic polyacrylamide printing and dyeing thickener |
| CN113185650A (en) * | 2021-05-26 | 2021-07-30 | 成都德美精英化工有限公司 | Powder printing thickener and preparation method thereof |
| CN114134732A (en) * | 2021-11-24 | 2022-03-04 | 杭州传化精细化工有限公司 | Compound thickener and preparation method thereof |
| CN114921966A (en) * | 2022-06-15 | 2022-08-19 | 广东蓝德堡新材料有限公司 | Multifunctional cationic emulsion for non-woven fabric base wall cloth coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1997838A2 (en) * | 1992-07-01 | 2008-12-03 | Coatex S.A.S. | Acrylic copolymer partially or fully water-soluble, cross-linked or not and use thereof |
| CN102766233A (en) * | 2012-07-31 | 2012-11-07 | 浙江传化股份有限公司 | Disperse printing thickener and preparation method thereof |
| CN106589207A (en) * | 2016-12-06 | 2017-04-26 | 湖北达雅生物科技股份有限公司 | Electrolyte-resistant pigment printing thickener |
-
2020
- 2020-01-10 CN CN202010027340.9A patent/CN111138612A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1997838A2 (en) * | 1992-07-01 | 2008-12-03 | Coatex S.A.S. | Acrylic copolymer partially or fully water-soluble, cross-linked or not and use thereof |
| CN102766233A (en) * | 2012-07-31 | 2012-11-07 | 浙江传化股份有限公司 | Disperse printing thickener and preparation method thereof |
| CN106589207A (en) * | 2016-12-06 | 2017-04-26 | 湖北达雅生物科技股份有限公司 | Electrolyte-resistant pigment printing thickener |
Non-Patent Citations (1)
| Title |
|---|
| 夏宇正等: "《精细高分子化工及应用》", 30 September 2000 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112252057A (en) * | 2020-07-29 | 2021-01-22 | 爱森（中国）絮凝剂有限公司 | Preparation method of composite anionic polyacrylamide printing and dyeing thickener |
| CN112252057B (en) * | 2020-07-29 | 2022-04-26 | 爱森（中国）絮凝剂有限公司 | Preparation method of composite anionic polyacrylamide printing and dyeing thickener |
| CN113185650A (en) * | 2021-05-26 | 2021-07-30 | 成都德美精英化工有限公司 | Powder printing thickener and preparation method thereof |
| CN114134732A (en) * | 2021-11-24 | 2022-03-04 | 杭州传化精细化工有限公司 | Compound thickener and preparation method thereof |
| CN114921966A (en) * | 2022-06-15 | 2022-08-19 | 广东蓝德堡新材料有限公司 | Multifunctional cationic emulsion for non-woven fabric base wall cloth coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111138612A (en) | Printing thickener and preparation method thereof | |
| KR910008315B1 (en) | Improved water thicakening agents | |
| CN110483687B (en) | Fracturing fluid thickening agent and preparation method thereof | |
| CN110591018B (en) | V-type polydimethylsiloxane hydrophobic association emulsion polymerization printing thickener, preparation method and application | |
| CN101775099B (en) | Paint thickener for printing and preparation method thereof | |
| CN108641048B (en) | Preparation method of salt-tolerant attapulgite composite thickener | |
| CN102675558B (en) | Salt-resistive thickening agent as well as preparation method and application thereof | |
| Ragab et al. | Synthetic Thickener in Textile Printing | |
| CN104358125A (en) | Environment-friendly type self-crosslinking water and oil repellent textile finishing agent and preparation method thereof | |
| CN1939946B (en) | Production of modified paste and dye printing paste | |
| DE2806646A1 (en) | TERPOLYMER EMULSIONS FOR THICKENING BUTADIEN / STYROL-LATICES | |
| CN113152120B (en) | Washing-free disperse printing thickener and preparation method thereof | |
| CN111978458B (en) | Polyacrylic acid thickening agent modified by nonionic side chain and side group and preparation method thereof | |
| CN101736608B (en) | Pigment printing thickener and method for preparing same | |
| CN111303344A (en) | Preparation method of modified sodium alginate/polyacrylic acid composite thickening agent | |
| CN113355942B (en) | Color paste for internal coloring of paper pulp and preparation method thereof | |
| CN113930984A (en) | Preparation method of modified attapulgite-polyacrylic acid salt-resistant thickening agent | |
| CN108368674B (en) | Thickening composition for textile printing pastes | |
| CN108822244B (en) | Preparation method of salt-tolerant thickening agent | |
| CN106749863B (en) | A kind of imitative reactive coating printing adhesive and preparation method thereof, application method | |
| CN117188185A (en) | High-color-yield low-waste-gas environment-friendly thickener and application thereof in printing technology | |
| CN109134770B (en) | High-molecular method of active brilliant red dye K-2BP | |
| CN113529444A (en) | White-bottom anti-staining soaping agent for nylon and preparation method thereof | |
| CN112252057A (en) | Preparation method of composite anionic polyacrylamide printing and dyeing thickener | |
| CN111944086A (en) | Nonionic and alkaline structure modified polyacrylic acid thickening agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200512 |