CN104610512A - Preparation method of super-soft IPN (interpenetrating polymer network) pigment printing binder - Google Patents
Preparation method of super-soft IPN (interpenetrating polymer network) pigment printing binder Download PDFInfo
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Abstract
The invention provides a preparation method of a super-soft IPN (interpenetrating polymer network) pigment printing binder. The preparation method is characterized in that a first component pre-emulsion is prepared from organosilicon cyclic compounds, a crosslinking monomer, an emulsifier, a catalyst and deionized water, heating, heat preservation, cooling and pH regulation are performed, and a first component network is prepared; a second component pre-emulsion is prepared from a soft monomer, a hard monomer, a crosslinking monomer, a ketone-containing carbonyl monomer, an emulsifier and deionized water; deionized water, an emulsifier and a pH buffer are added; 80-100 parts of the first component network, 14-16 parts of the second component pre-emulsion and 2-2.5 parts of an initiator solution are added, heating is performed until blue light appears, then residual pre-emulsion and initiator solution are added dropwise, heating, heat preservation, cooling and pH regulation are performed, and finally, a hydrazide-based monomer solution is added. The preparation method of the super-soft IPN pigment printing binder has the advantages of simple process, excellent performance and low cost, the pigment printing binder is a formaldehyde-free environment-friendly product and can endow fabric with super-soft handfeel.
Description
Technical field
The present invention relates to pigment printing binding agent technical field, specifically a kind of preparation method of super soft interpenetrating network pigment resin printing adhesive agent.
Background technology
Pigment printing is the printing method be bonded at by finely divided granules of pigments by the effect of tackiness agent on fabric.Pigment printing has that technique is simple, save energy and the little advantage of environmental pollution, and current global pigment printing fabric accounts for more than 70% of tprinted Fabrics ultimate production.In recent years, China's pigment printing there has also been very large development, but product structure is still unreasonable, in, low grade products is in the majority, profit is meagre.And the quality of pigment printing product and class depend on the performance of pigment printing binding agent to a great extent, therefore preparing high performance tackiness agent is the most important measure improving pigment printing technology and quality.
The emulsifying agent used in letex polymerization is mostly containing alkylphenol polyoxyethylene (APEO), and it is a class nonionogenic tenside, is widely used in the industries such as textile printing and dyeing processing, plastics and coating.Such material has been widely studied the potential hazard that environment causes and has proved, some countries of Europe formulated corresponding regulation limitations and have produced and use APEO from 1976, and the APEO limitation that Export Textiles kimonos is loaded onto also clearly defines (≤30mg/kg).The textile and clothing total value that China exports every year, more than 10,000,000,000 dollars, if do not produced in strict accordance with international standard, directly will affect the export trade of textile and clothing.Therefore, seeking novel, efficient, stable and safe tensio-active agent with alternative APEO class tensio-active agent, guarantee product safety environmental protection, is prepare the problem that high-performance coating printing adhesive primarily solves.
In addition, Printing Industry tackiness agent is mostly water polyacrylic acid PA class tackiness agent, but the shortcomings such as pure-acrylic emulsion tackiness agent ubiquity hot sticky cold crisp, wet-milling rubbing fastness and feel are poor, the domestic application performance in order to improve this kind of pigment printing binding agent, especially dry fastness to wet rubbing, the method generally used is exactly participate in copolyreaction with cross-linking monomer N hydroxymethyl acrylamide in the building-up process of PA tackiness agent, but it needs high temperature to bake, and the printing adhesive through baking easily discharges the free formaldehyde be harmful to environment and human body.International Textile ecological Studies association Oko-Tex standard 100 specifies: the burst size of methanal of decorating cloth is lower than 300 × 10
-6, and the burst size of methanal of dress for baby is lower than 20 × 10
-6.Along with people's environmental consciousness and improving constantly product requirement, many environmental regulations have been promulgated in countries in the world, impel environment protection standard to become the primary prerequisite of high-grade paint printing adhesive.Therefore, the pigment printing binding agent obtained using N hydroxymethyl acrylamide as cross-linking monomer, does not meet environmental requirement, is difficult to use in high-grade Printing.
From raising fastness, improve feel and reduce the future developments such as energy consumption, foreign binders mainly experiences four-stage.Forth generation printing adhesive is super soft intercrossed network type tackiness agent.Interpenetrating net polymer (IPN) is a kind of poyblend of uniqueness.It is mutually interted continuously by the network of gained after cross-linked polymer I and each self-crosslinking of cross-linked polymer II.Generally that make second comonomer polymerization in situ and be cross-linked to form polymkeric substance II, such the latter just interts in the network of polymkeric substance I by second comonomer together with in linking agent and the swelling polymkeric substance I entering to be cross-linked of initiator (or activator).In its cross-linker molecules structure, generally there is stronger active group, carrying out crosslinking reaction lower than 100 DEG C with hydroxyl, amino or other group, both can improve the antifriction fastness of film forming, can energy consumption be saved again.China produces tackiness agent compared with same kind of products at abroad, in feel, environmental protection, fastness and stability etc., still have gap.The key addressed these problems is under ensureing that product meets the prerequisite of environmental requirement, finds suitable interpenetrating(polymer)networks and cross-linking system, synthesizes high performance super soft interpenetrating network pigment resin printing adhesive agent.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, and excellent performance, does not use the emulsifying agent containing APEO group, the preparation method of the not super soft interpenetrating network pigment resin printing adhesive agent of release formaldehyde in bake process.
In order to solve the problems of the technologies described above, technical scheme of the present invention is to provide a kind of preparation method of super soft interpenetrating network pigment resin printing adhesive agent, it is characterized in that: the method is made up of following 6 steps:
Step 1: in mass fraction, by methylsiloxane ring body 20 ~ 30 parts, the first component cross-linking monomer 0.2 ~ 0.6 part, emulsifying agent 0.6 ~ 2.0 part, catalyzer 0.5 ~ 3.0 part, deionized water 70 ~ 80 parts of uniform stirrings, be mixed with the first component pre-emulsion, be warming up to 80 ~ 85 DEG C, insulation 4 ~ 6h, cool the temperature to again after below 40 DEG C, adjust ph to 6.5 ~ 7.0, be prepared into the first component network;
Step 2: in mass fraction, by soft monomer 70 ~ 90 parts, hard monomer 10 ~ 30 parts, the second component cross-linking monomer 5 ~ 10 parts, ketocarbonyl-containing monomer 2 ~ 5 parts, emulsifying agent 0.6 ~ 3.0 part, deionized water 50 ~ 70 parts of uniform stirrings, be mixed with the second component pre-emulsion;
Step 3: initiator 0.2 ~ 0.6 part is dissolved in the deionized water of 8 ~ 10 parts, is mixed with initiator solution;
Step 4: in polymerization reaction kettle, adds deionized water 25 ~ 33 parts, emulsifying agent 0.5 ~ 1.0 part and pH buffer reagent 0.2 ~ 0.6 part, stirs;
Step 5: add the first component network 80 ~ 100 parts that step 1 is obtained in the polymerization reaction kettle of step 4, the second component pre-emulsion 14 ~ 16 parts that step 2 is obtained and the initiator solution 2 ~ 2.5 parts that step 3 obtains, be warming up to 78 ~ 82 DEG C, after there is blue light in the emulsion in reactor to be polymerized, initiator solution 6 ~ 8 parts and remaining second component pre-emulsion is dripped again in polymerization reaction kettle, after 2 ~ 3h drips continuously, add remaining initiator solution again, be warmed up to 85 ~ 90 DEG C, insulation 0.5 ~ 1h, cool the temperature to again after below 40 DEG C, adjust ph to 6.5 ~ 7.0,
Step 6: hydrazide group monomer 1 ~ 3 part is dissolved in 4 ~ 5 parts of deionized waters, be made into hydrazide group monomer solution, and add in the polymerization reaction kettle of step 5, stir, obtained low-temperature self-crosslinking polyacrylate pigment printing binding agent, is described super soft interpenetrating network pigment resin printing adhesive agent.
Preferably, in described step 1,
Methylsiloxane ring body is the mixture of any one or two kinds of in hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethyl-ring ten siloxanes;
First component cross-linking monomer is any one in aminopropyl trimethoxysilane, aminopropyl triethoxysilane, vinyltrimethoxy silane and tetraethyl orthosilicate;
Catalyzer is any one in Witco 1298 Soft Acid, sulfuric acid or hydrochloric acid.
Preferably, in described step 2,
Soft monomer is the mixture of any one or two kinds of and butyl acrylate in ethyl propenoate, Isooctyl acrylate monomer, and wherein butyl acrylate accounts for 60% ~ 90% of soft monomer total mass;
Hard monomer is the mixture of any one or two kinds of and methyl methacrylate in vinyl cyanide, vinyl acetate between to for plastic, tertiary ethylene carbonate, vinylbenzene, and wherein methyl methacrylate accounts for 50% ~ 70% of hard monomer total mass;
Second component cross-linking monomer is the mixture of any one and Hydroxyethyl acrylate or Propylene glycol monoacrylate in methacrylic acid and vinylformic acid;
Ketocarbonyl-containing monomer is diacetone-acryloamide(DAA) or AAEM.
Preferably, in described step 3, initiator is ammonium persulphate or Potassium Persulphate.
Preferably, in described step 4, pH buffer reagent is sodium bicarbonate.
Preferably, in described step 6, be adipic dihydrazide containing hydrazide group monomer.
Preferably, in described step 1, step 2, step 4, emulsifying agent is in anionic emulsifier, nonionic emulsifying agent and reactive emulsifier any two kinds or more.
Preferably, described anionic emulsifier is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, succinic acid dihexyl sodium sulfonate or sulfosuccinate surfactant.
Preferably, described nonionic emulsifying agent is fatty alcohol-polyoxyethylene ether.
Preferably, described reactive emulsifier is 3-allyloxy-2-hydroxyl-1-sulfonic acid sodium salt or methacrylic acid hydroxide sodium dimercaptosulphanatein.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention adopts emulsion polymerisation process, compares with other polymerization processs, not only has that viscosity is low, the advantage of easy heat radiation, and has higher polymerization rate, the polymericular weight of gained is high, in addition, take water as medium, production safety, environmental pollution is little, with low cost.
(2) the polysiloxane polyacrylate interpenetrating network printing adhesive that the present invention obtains does not use containing alkylphenol polyoxyethylene class (APEO) emulsifying agent, and product through toasting formaldehydeless release, and not containing organic solvent, belongs to environmentally friendly machine.
(3) polymerization technique of the present invention is simple, polymerization process stable, and workable, facility investment is little, is conducive to large-scale industrial production.
(4) the present invention is without the need to additional crosslink agent, and the mill base stability in storage modulated is good, and low temperature fixation bakes without the need to high temperature, thus significantly save energy.Obtained Printing is soft, with the strong adhesion of fabric, has outstanding dry, wet rubbing fastness and washing fastness, and flower shape clear-cut, lovely luster.
(5) tackiness agent that prepared by the present invention is applicable to cylinder, and the multiple printing technologies such as cylinder, plain net, hand printing have good adaptability to cotton, polyester-cotton blend, acrylic, tricot etc.
(6), after the tackiness agent that prepared by the present invention is used in fabric, fabric can be made to obtain super soft feel.
Embodiment
For making the present invention become apparent, hereby with several preferred embodiment, be described in detail below.
Embodiment 1
By octamethylcyclotetrasiloxane 30.0 parts, emulsifying agent 2.0 parts, catalyzer Witco 1298 Soft Acid 3.0 parts, tetraethyl orthosilicate 0.6 part, deionized water 70 parts, uniform stirring obtains organosilicon pre-emulsion; In polymerization reaction kettle, add above-mentioned organosilicon pre-emulsion, be warming up to 85 DEG C, after insulation 4h, be cooled to 40 DEG C, regulate pH to 6.5, obtained organic silicon emulsion; Butyl acrylate 50.0 parts, Isooctyl acrylate monomer 25.0 parts, methyl methacrylate 13.0 parts, vinyl cyanide 4.0 parts, methacrylic acid 2.0 parts, Propylene glycol monoacrylate 4.0 parts, diacetone-acryloamide(DAA) 2.0 parts, emulsifying agent 2.0 parts, deionized water 70 parts, uniform stirring makes acrylate pre-emulsion; 0.4 part of Potassium Persulphate is dissolved in 8.0 parts of deionized waters, is mixed with initiator solution; In polymerization reaction kettle, add deionized water 33.0 parts, emulsifying agent 0.8 part and sodium bicarbonate 0.6 part, stir; Above-mentioned the macromolecule organic silicon emulsion 100 parts is added in polymerization reaction kettle, acrylate pre-emulsion 14 parts and above-mentioned initiator solution 2 parts, be warming up to 78 DEG C, after blue light appears in emulsion in reactor to be polymerized, then drip remaining pre-emulsion and initiator solution 6 parts continuously in polymerization reaction kettle, after 2h drips continuously, add remaining initiator solution again, be warmed up to 85 DEG C, after insulation 1h, cool the temperature to again after below 40 DEG C, adjust ph to 6.5; Adipic dihydrazide 3.0 parts is dissolved in wiring solution-forming in 5.0 parts of deionized waters, and joins in polymerization reaction kettle, stir, required super soft interpenetrating network pigment resin printing adhesive agent can be obtained.
Wherein, diacetone-acryloamide(DAA) contains 4 functional groups, comprises unsaturated double-bond, amido, carbonyl and end hydrogen base.Unsaturated double-bond participates in addition reaction in the course of the polymerization process, adds adipic dihydrazide after polymerization, post-crosslinking reaction can occur thus the water-wash resistance of raising polymkeric substance and mechanical property under the condition of pH=6.5 ~ 7.Emulsifying agent is made up of succinic acid dihexyl sulfonate surfactants MA-80, fatty alcohol-polyoxyethylene ether AFX-3070, and wherein the weight ratio of MA-80 and AFX-3070 is 1.5: 1.
Gained adhesive agent emulsion performance is shown in Table 1.
Embodiment 2
By octamethylcyclotetrasiloxane 20.0 parts, emulsifying agent 0.6 part, catalyzer Witco 1298 Soft Acid 2.0 parts, aminopropyl trimethoxysilane 0.2 part, deionized water 70 parts, uniform stirring obtains organosilicon pre-emulsion; In polymerization reaction kettle, add above-mentioned organosilicon pre-emulsion, be warming up to 85 DEG C, after insulation 4h, be cooled to 40 DEG C, regulate pH to 7.0, obtained organic silicon emulsion; Butyl acrylate 60.0 parts, Isooctyl acrylate monomer 16.0 parts, methyl methacrylate 10.0 parts, vinyl cyanide 4.0 parts, methacrylic acid 2.0 parts, Propylene glycol monoacrylate 4.0 parts, diacetone-acryloamide(DAA) 2.5 parts, emulsifying agent 0.6 part, deionized water 50 parts, uniform stirring makes acrylate pre-emulsion; 0.3 part of Potassium Persulphate is dissolved in 6.0 parts of deionized waters, is mixed with initiator solution; In polymerization reaction kettle, add deionized water 33.0 parts, emulsifying agent 1.0 parts and sodium bicarbonate 0.6 part, stir; Above-mentioned the macromolecule organic silicon emulsion 80 parts, acrylate pre-emulsion 16 parts and above-mentioned initiator solution 2.5 parts is added in polymerization reaction kettle, be warming up to 82 DEG C, after in reactor to be polymerized there is blue light in emulsion, in polymerization reaction kettle, drip remaining pre-emulsion and initiator solution 8 parts continuously again, after 3h drips continuously, then add remaining initiator solution, be warmed up to 90 DEG C, after insulation 0.5h, then cool the temperature to after below 40 DEG C, adjust ph to 7.0; Adipic dihydrazide 1.0 parts is dissolved in wiring solution-forming in 4.0 parts of deionized waters, and joins in polymerization reaction kettle, stir, required super soft interpenetrating network pigment resin printing adhesive agent can be obtained.
Wherein diacetone-acryloamide(DAA) contains 4 functional groups, comprises unsaturated double-bond, amido, carbonyl and end hydrogen base.Unsaturated double-bond participates in addition reaction in the course of the polymerization process, adds adipic dihydrazide after polymerization, post-crosslinking reaction can occur thus the water-wash resistance of raising polymkeric substance and mechanical property under the condition of pH=6.5 ~ 7.Emulsifying agent is by lauryl sodium sulfate surfactant SDS, and fatty alcohol-polyoxyethylene ether AFX-3070 forms, and wherein the weight ratio of SDS and AFX-3070 is 2: 1.
Gained adhesive agent emulsion performance is shown in Table 1.
Embodiment 3
By pentamethyl-ring ten siloxanes 30.0 parts, emulsifying agent 1.5 parts, aminopropyl triethoxysilane 0.6 part, deionized water 80 parts, uniform stirring obtains organosilicon pre-emulsion; In polymerization reaction kettle, add above-mentioned organosilicon pre-emulsion, be warming up to 85 DEG C, drip catalyst sulfuric acid 0.5 part continuously, after 1h drips, insulation 6h, is cooled to 40 DEG C, regulates pH to 7.0, obtained organic silicon emulsion; Butyl acrylate 68.0 parts, ethyl propenoate 8.0 parts, methyl methacrylate 7.0 parts, vinylbenzene 7.0 parts, methacrylic acid 2.5 parts, Propylene glycol monoacrylate 1.5 parts, diacetone-acryloamide(DAA) 5.0 parts, emulsifying agent 2.5 parts, deionized water 60 parts, uniform stirring makes acrylate pre-emulsion; 0.45 part of Potassium Persulphate is dissolved in 9.0 parts of deionized waters, is mixed with initiator solution; In polymerization reaction kettle, add deionized water 33.0 parts, emulsifying agent 1.0 parts and sodium bicarbonate 0.6 part, stir; Above-mentioned organic silicon emulsion 100 parts, acrylate pre-emulsion 16 parts and above-mentioned initiator solution 2.3 parts is added in polymerization reaction kettle, be warming up to 82 DEG C, after in reactor to be polymerized there is blue light in emulsion, in polymerization reaction kettle, drip remaining pre-emulsion and initiator solution 8 parts continuously again, after 2.5h drips continuously, then add remaining initiator solution, be warmed up to 88 DEG C, after insulation 1h, then cool the temperature to after below 40 DEG C, adjust ph to 6.5; Adipic dihydrazide 1.8 parts is dissolved in wiring solution-forming in 5 parts of deionized waters, and joins in polymerization reaction kettle, stir, required super soft interpenetrating network pigment resin printing adhesive agent can be obtained.
Wherein, diacetone-acryloamide(DAA) contains 4 functional groups, comprises unsaturated double-bond, amido, carbonyl and end hydrogen base.Unsaturated double-bond participates in addition reaction in the course of the polymerization process, adds adipic dihydrazide after polymerization, post-crosslinking reaction can occur thus the water-wash resistance of raising polymkeric substance and mechanical property under the condition of pH=6.5 ~ 7.
Emulsifying agent is by sulfosuccinate surfactant EF-810, and fatty alcohol-polyoxyethylene ether AFX-3070 and 3-allyloxy-2-hydroxyl-1-sulfonic acid sodium salt HAPS forms, and wherein the weight ratio of EF-810, AFX-3070 and HAPS is 1.6: 0.8: 0.6.
Gained adhesive agent emulsion performance is shown in Table 1.
Embodiment 4
By hexamethyl cyclotrisiloxane 25.0 parts, emulsifying agent 0.9 part, catalyzer Witco 1298 Soft Acid 2.5 parts, vinyltrimethoxy silane 0.4 part, deionized water 80 parts, uniform stirring obtains organosilicon pre-emulsion; In polymerization reaction kettle, add above-mentioned organosilicon pre-emulsion, be warming up to 80 DEG C, after insulation 4h, be cooled to 40 DEG C, regulate pH to 7.0, obtained organic silicon emulsion; Butyl acrylate 67.0 parts, ethyl propenoate 9.0 parts, methyl methacrylate 9.0 parts, vinyl acetate between to for plastic 5.0 parts, 2.5 parts, vinylformic acid, Propylene glycol monoacrylate 3.0 parts, AAEM 3.0 parts, emulsifying agent 1.8 parts, deionized water 50 parts, uniform stirring makes acrylate pre-emulsion; 0.35 part of Potassium Persulphate is dissolved in 7.0 parts of deionized waters, is mixed with initiator solution; In polymerization reaction kettle, add deionized water 25.0 parts, emulsifying agent 0.5 part and sodium bicarbonate 0.2 part, stir; Above-mentioned organic silicon emulsion 90 parts, acrylate pre-emulsion 16 parts and above-mentioned initiator solution 2.5 parts is added in polymerization reaction kettle, be warming up to 80 DEG C, after in reactor to be polymerized there is blue light in emulsion, in polymerization reaction kettle, drip remaining pre-emulsion and initiator solution 7 parts continuously again, after 2.5h drips continuously, then add remaining initiator solution, be warmed up to 85 DEG C, after insulation 1h, then cool the temperature to after below 40 DEG C, adjust ph to 7; Adipic dihydrazide 2.5 parts is dissolved in wiring solution-forming in 5 parts of deionized waters, and joins in polymerization reaction kettle, stir, required super soft interpenetrating network pigment resin printing adhesive agent can be obtained.
Wherein, AAEM is a kind of methacrylic acid monomer, can with amine and hydrazine reaction, be the desirable monomer of self-crosslinking, self-vulcanizing ACRYLIC EMULSION.
Emulsifying agent is by sulfosuccinate surfactant EF-810, and fatty alcohol-polyoxyethylene ether AFX-3070 and 3-allyloxy-2-hydroxyl-1-sulfonic acid sodium salt HAPS forms, and wherein the weight ratio of EF-810, AFX-3070 and HAPS is 1.2: 1.0: 0.8.
Gained adhesive agent emulsion performance is shown in Table 1.
Embodiment 5
By hexamethyl cyclotrisiloxane 5 parts, octamethylcyclotetrasiloxane 15 parts, emulsifying agent 2.0 parts, tetraethyl orthosilicate 0.6 part, deionized water 80 parts, uniform stirring obtains organosilicon pre-emulsion; In polymerization reaction kettle, add above-mentioned organosilicon pre-emulsion, be warming up to 85 DEG C, drip hydrochloric 1.5 parts continuously, after 1h drips, insulation 6h, is cooled to 40 DEG C, regulates pH to 6.5, obtained organic silicon emulsion; Butyl acrylate 65.0 parts, ethyl propenoate 11.0 parts, methyl methacrylate 10.0 parts, tertiary ethylene carbonate 4.0 parts, 3.0 parts, vinylformic acid, Propylene glycol monoacrylate 2.5 parts, AAEM 4.0 parts, emulsifying agent 3.0 parts, deionized water 70 parts, uniform stirring makes acrylate pre-emulsion; 0.4 part of ammonium persulphate is dissolved in 8.0 parts of deionized waters, is mixed with initiator solution; In polymerization reaction kettle, add deionized water 25.0 parts, emulsifying agent 0.5 part and sodium bicarbonate 0.2 part, stir; Above-mentioned organic silicon emulsion 80 parts, acrylate pre-emulsion 15 parts and above-mentioned initiator solution 2.0 parts is added in polymerization reaction kettle, be warming up to 78 DEG C, after in reactor to be polymerized there is blue light in emulsion, in polymerization reaction kettle, drip remaining pre-emulsion and initiator solution 8 parts continuously again, after 3h drips continuously, then add remaining initiator solution, be warmed up to 90 DEG C, after insulation 0.5h, then cool the temperature to after below 40 DEG C, adjust ph to 7; Adipic dihydrazide 2.0 parts is dissolved in wiring solution-forming in 5 parts of deionized waters, and joins in polymerization reaction kettle, stir, required super soft interpenetrating network pigment resin printing adhesive agent can be obtained.
Wherein, AAEM is a kind of methacrylic acid monomer, can with amine and hydrazine reaction, be the desirable monomer of self-crosslinking, self-vulcanizing ACRYLIC EMULSION.
Emulsifying agent is made up of succinic acid dihexyl sulfonate surfactants MA-80, fatty alcohol-polyoxyethylene ether AFX-3070, and wherein the weight ratio of MA-80 and AFX-3070 is 1.7: 0.8.
Gained adhesive agent emulsion performance is shown in Table 1.
Contrast experiment
Serial printing adhesive of the present invention is adopted to be mixed with pigment printing and to test it, printing paste formula following (mass percent):
Adopt general printing technology to test described tackiness agent, result is as shown in table 1 below.
Table 1
In table 1, properties detection method is as follows:
(1) formaldehyde test is tested according to GB/T2912.1-1998.
(2) feel test is touched by subjectivity, and 1 is expressed as feel difference, and 2 are expressed as feel generally, and 3 are expressed as feel well, and 4 represent soft comfortable, and 5 represent that feels are extremely excellent.
(3) crock fastness is tested according to GB/T3920-19970, and fastness to washing is tested according to GB/T420-1990.
Can find out from above-mentioned test, the embodiment of the present invention all detects formaldehydeless release, and in self-crosslinking film forming under comparatively cold condition, can belong to environment-friendly and energy-efficient product.Key is to introduce novel effective cross-linking system, and making the pigment printing obtained by the present invention effectively solve the problem of contradiction between feel and crock fastness, washing fastness, is rare high-performance coating printing adhesive on market.
Claims (10)
1. a preparation method for super soft interpenetrating network pigment resin printing adhesive agent, is characterized in that: the method is made up of following 6 steps:
Step 1: in mass fraction, by methylsiloxane ring body 20 ~ 30 parts, the first component cross-linking monomer 0.2 ~ 0.6 part, emulsifying agent 0.6 ~ 2.0 part, catalyzer 0.5 ~ 3.0 part, deionized water 70 ~ 80 parts of uniform stirrings, be mixed with the first component pre-emulsion, be warming up to 80 ~ 85 DEG C, insulation 4 ~ 6h, cool the temperature to again after below 40 DEG C, adjust ph to 6.5 ~ 7.0, be prepared into the first component network;
Step 2: in mass fraction, by soft monomer 70 ~ 90 parts, hard monomer 10 ~ 30 parts, the second component cross-linking monomer 5 ~ 10 parts, ketocarbonyl-containing monomer 2 ~ 5 parts, emulsifying agent 0.6 ~ 3.0 part, deionized water 50 ~ 70 parts of uniform stirrings, be mixed with the second component pre-emulsion;
Step 3: initiator 0.2 ~ 0.6 part is dissolved in the deionized water of 8 ~ 10 parts, is mixed with initiator solution;
Step 4: in polymerization reaction kettle, adds deionized water 25 ~ 33 parts, emulsifying agent 0.5 ~ 1.0 part and pH buffer reagent 0.2 ~ 0.6 part, stirs;
Step 5: add the first component network 80 ~ 100 parts that step 1 is obtained in the polymerization reaction kettle of step 4, the second component pre-emulsion 14 ~ 16 parts that step 2 is obtained and the initiator solution 2 ~ 2.5 parts that step 3 obtains, be warming up to 78 ~ 82 DEG C, after there is blue light in the emulsion in reactor to be polymerized, initiator solution 6 ~ 8 parts and remaining second component pre-emulsion is dripped again in polymerization reaction kettle, after 2 ~ 3h drips continuously, add remaining initiator solution again, be warmed up to 85 ~ 90 DEG C, insulation 0.5 ~ 1h, cool the temperature to again after below 40 DEG C, adjust ph to 6.5 ~ 7.0,
Step 6: hydrazide group monomer 1 ~ 3 part is dissolved in 4 ~ 5 parts of deionized waters, be made into hydrazide group monomer solution, and add in the polymerization reaction kettle of step 5, stir, obtained low-temperature self-crosslinking polyacrylate pigment printing binding agent, is described super soft interpenetrating network pigment resin printing adhesive agent.
2. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 1, is characterized in that: in described step 1,
Methylsiloxane ring body is any one or two kinds of in hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethyl-ring ten siloxanes;
First component cross-linking monomer is any one in aminopropyl trimethoxysilane, aminopropyl triethoxysilane, vinyltrimethoxy silane and tetraethyl orthosilicate;
Catalyzer is any one in Witco 1298 Soft Acid, sulfuric acid or hydrochloric acid.
3. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 1, is characterized in that: in described step 2,
Soft monomer is the mixture of any one or two kinds of and butyl acrylate in ethyl propenoate, Isooctyl acrylate monomer, and wherein butyl acrylate accounts for 60% ~ 90% of soft monomer total mass;
Hard monomer is the mixture of any one or two kinds of and methyl methacrylate in vinyl cyanide, vinyl acetate between to for plastic, tertiary ethylene carbonate, vinylbenzene, and wherein methyl methacrylate accounts for 50% ~ 70% of hard monomer total mass;
Second component cross-linking monomer is the mixture of any one and Hydroxyethyl acrylate or Propylene glycol monoacrylate in methacrylic acid and vinylformic acid;
Ketocarbonyl-containing monomer is diacetone-acryloamide(DAA) or AAEM.
4. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 1, it is characterized in that: in described step 3, initiator is ammonium persulphate or Potassium Persulphate.
5. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 1, it is characterized in that: in described step 4, pH buffer reagent is sodium bicarbonate.
6. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 1, it is characterized in that: in described step 6, is adipic dihydrazide containing hydrazide group monomer.
7. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 1, it is characterized in that: in described step 1, step 2, step 4, emulsifying agent is in anionic emulsifier, nonionic emulsifying agent and reactive emulsifier any two kinds or more.
8. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 7, is characterized in that: described anionic emulsifier is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, succinic acid dihexyl sodium sulfonate or sulfosuccinate surfactant.
9. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 7, is characterized in that: described nonionic emulsifying agent is fatty alcohol-polyoxyethylene ether.
10. the preparation method of a kind of super soft interpenetrating network pigment resin printing adhesive agent as claimed in claim 7, is characterized in that: described reactive emulsifier is 3-allyloxy-2-hydroxyl-1-sulfonic acid sodium salt or methacrylic acid hydroxide sodium dimercaptosulphanatein.
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| CN104910319A (en) * | 2015-06-04 | 2015-09-16 | 东莞长联新材料科技股份有限公司 | Polyacrylate emulsion capable of postponing dye transfer and preparation method thereof |
| CN106988134A (en) * | 2017-04-14 | 2017-07-28 | 厦门安踏体育用品有限公司 | A kind of printing adhesive and preparation method thereof, print paste and clothes |
| CN112281512A (en) * | 2020-10-15 | 2021-01-29 | 西安工程大学 | Polyester fabric printing method |
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| CN112281512A (en) * | 2020-10-15 | 2021-01-29 | 西安工程大学 | Polyester fabric printing method |
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