CN113956403A - Preparation method of polyurethane modified acrylate thick plate printing adhesive - Google Patents
Preparation method of polyurethane modified acrylate thick plate printing adhesive Download PDFInfo
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- CN113956403A CN113956403A CN202111371921.5A CN202111371921A CN113956403A CN 113956403 A CN113956403 A CN 113956403A CN 202111371921 A CN202111371921 A CN 202111371921A CN 113956403 A CN113956403 A CN 113956403A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 238000007639 printing Methods 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 42
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 42
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000839 emulsion Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004945 emulsification Methods 0.000 claims abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 9
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 239000003755 preservative agent Substances 0.000 claims description 9
- 230000002335 preservative effect Effects 0.000 claims description 9
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 9
- 239000004320 sodium erythorbate Substances 0.000 claims description 9
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- -1 methyl propylene hydroxyethyl ester Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 16
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005108 dry cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a polyurethane modified acrylate thick plate printing adhesive, and particularly relates to the field of special printing. The preparation method comprises the steps of preparation of the waterborne polyurethane composite emulsifier, acrylic monomer pre-emulsification, seed emulsion preparation, emulsion polymerization and compound emulsion. The invention adopts the cohesion promoter SA510, is based on a special acrylate high-molecular emulsion product, is applied to a water-based acrylate system, can interact with an acrylic acid high-molecular chain for a butyl acrylate system, and improves the cohesion of the emulsion by using a small addition amount, thereby improving the strength and the heat resistance of the emulsion.
Description
Technical Field
The invention relates to the field of special printing, in particular to a preparation method of a polyurethane modified acrylate thick plate printing adhesive.
Background
The printing adhesive cement in the clothing field can be printed with any light color on dark clothes due to good coverage, has certain glossiness and stereoscopic impression, enables ready-made clothes to look more high-grade, and is rapidly popularized and can be used on almost every printing T-shirt.
The thick plate printing refers to repeatedly printing on the surface of the fabric for many times, and finally forming a special printing with a certain thickness and a certain 3D stereoscopic effect on the surface of the fabric. The process is relatively complex, firstly a thick plate needs to be manufactured, the thickness of the thick plate photosensitive emulsion is 0.5mm, and common printing needs to be printed for 6-10 times. The thick plate printing is also because the thick plate printing is easier to layer on the fabric, the added filler is more, the content of the binder is less, so the fastness on the fabric is relatively low, and the fastness of the thick plate printing adhesive cement on the fabric is poorer due to the non-wetting property of the waterproof fabric and the coating fabric to water substances, so the problem needs to be improved on the binder.
The acrylate adhesive has good coloring performance, strong binding power with textile fabrics and good film forming performance, and a formed film is transparent, flexible and elastic, so the acrylate adhesive becomes the first choice for preparing thick plate printing paste. However, the acrylate polymer structure is generally a chain linear structure, so that the acrylate polymer is extremely sensitive to temperature and gradually becomes soft and sticky with the rise of temperature; when the temperature is reduced to a certain limit, the thick plate printing paste prepared by the acrylate adhesive can not change in winter and summer because the thick plate printing paste gradually becomes brittle, namely the phenomenon of hot sticking and cold brittleness. In addition, the film formed by the acrylate adhesive can swell under the action of an organic solvent, so that the film falls off.
Therefore, the thick plate printing paste which has good friction resistance and washing resistance and is suitable for temperature change and has no influence on printing effect is developed.
Disclosure of Invention
Therefore, the invention provides a preparation method of a polyurethane modified acrylate thick plate printing adhesive, which aims to solve the problems of poor friction resistance, hot sticking and cold brittleness, solvent intolerance and the like of the existing adhesive.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to the invention, the preparation method of the polyurethane modified acrylate thick plate printing adhesive comprises the following steps:
step one, preparation of waterborne polyurethane composite emulsifier
Adding polyether glycol into the reaction kettle A, heating to 65-70 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and keeping the temperature for 2-3 h; then adding 2, 2-dimethylolpropionic acid to react for 1.5-2h, adding methyl propylene hydroxyethyl ester to react for 0.5-1h, cooling to room temperature, adding triethylamine to neutralize, then adding deionized water to disperse the homogeneous phase at a high speed, finally adding ethylenediamine to chain extend, and stirring for 0.5-1h to obtain a composite emulsifier A;
step two, acrylic monomer pre-emulsification
Adding the emulsifier A, deionized water, butyl acrylate, isooctyl acrylate, acrylonitrile, methyl methacrylate, acrylic acid and acetoacetylated modified acrylic acid self-crosslinking monomer into a reaction kettle B, and dispersing and mixing at a high speed of 1000r/min for 20-40min to prepare a pre-emulsion B;
step three, preparing seed emulsion
Adding deionized water, part of the pre-emulsion B and ammonium persulfate into the reaction kettle C, heating to 80-85 ℃, stirring at the speed of 200r/min for heat preservation reaction until the solution presents blue light;
step four, emulsion polymerization
Controlling the temperature of the reaction kettle C to be 80-85 ℃, simultaneously dropwise adding an ammonium persulfate aqueous solution and the rest of the pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the rest of the pre-emulsion B at the same time, wherein the dropwise adding time is 2-3h, after the dropwise adding is completed, heating to 85-90 ℃, preserving the heat for 1-2 h, then cooling to 65-70 ℃, adding tert-butyl hydroperoxide and sodium erythorbate, and preserving the heat for 0.5-1 h;
step five, compounding the emulsion
Adjusting the pH value to 7-8, adding an associative thickener, uniformly stirring to obtain the polyurethane modified acrylate, cooling a reaction kettle C to room temperature, and adding a cohesion accelerator SA510, a preservative MV and a water-based defoamer to obtain the product polyurethane modified acrylate adhesive.
Further, in the step one, the addition amount of each component is as follows: 20-30 parts of polyether glycol, 10-15 parts of isophorone diisocyanate, 0.2-0.5 part of dibutyltin dilaurate, 5-10 parts of 2, 2-dimethylolpropionic acid, 10-15 parts of methyl propylene hydroxyethyl ester, 1-3 parts of triethylamine, 100 parts of deionized water, 120 parts of organic solvent and 1-3 parts of ethylenediamine.
Further, in the second step, the addition amount of each component is as follows: 5-10 parts of emulsifier A, 100-120 parts of deionized water, 60-80 parts of butyl acrylate, 20-30 parts of isooctyl acrylate, 10-20 parts of acrylonitrile, 20-30 parts of methyl methacrylate, 2-5 parts of acrylic acid and 2-5 parts of acetoacetylated modified acrylic acid self-crosslinking monomer.
Furthermore, in the third step, the adding amount of each component is 80-100 parts of deionized water, 10-15 parts of pre-emulsion B and 0.2-0.4 part of ammonium persulfate.
Further, in the fourth step, the ammonium persulfate aqueous solution is prepared by dissolving 1 part of ammonium persulfate in 20 parts of deionized water.
Further, in the fourth step, the dropping amount of the aqueous solution of ammonium persulfate is 10-15 parts.
Furthermore, the adding amount of each component in the fourth step is 0.2 to 0.5 part of tert-butyl hydroperoxide and 0.2 to 0.5 part of sodium erythorbate.
Furthermore, in the fifth step, the addition amount of each component is 0.5-1 part of cohesive force promoter SA 5100.1-0.2 part of preservative MV, 0.5-1 part of associative thickener and 0.1-0.2 part of aqueous defoamer.
The invention has the following advantages:
the invention adopts reactive waterborne polyurethane containing hydrophilic groups and double bond end capping as an emulsifier to replace the conventionally used lauryl sodium sulfate and the like as emulsion polymerization. The stability of the emulsion is enhanced, and the average particle size is reduced because DMPA participates in the emulsion so that the emulsion contains-COOH, the potential is higher, and the emulsifying capacity is better; the emulsion has high potential, the surface tension is reduced, the double electric layer effect formed on the interface is enhanced, the particles are not easy to aggregate, and the emulsion stability is enhanced; the elongation at break of the urethane-modified acrylate emulsion shows an upward tendency because the soft segment of urethane contains a large number of ether bonds, which is advantageous for the free movement of the segment and the extension of the molecular chain.
The polyurethane macromolecular chain is provided with a hydrophilic chain segment and a hydrophobic chain segment, the structure of the polyurethane macromolecular chain is similar to that of a macromolecular emulsifier, under the action of high-speed emulsification, a particle structure with a hydrophilic group facing outwards and a hydrophobic chain segment facing inwards is formed, and a PU particle structure is finally formed.
The two ends of a hydroxyethyl methacrylate (2HEMA) molecule respectively contain hydroxyl and carbon-carbon double bonds, the hydroxyl can react with free-NCO groups at the two ends of a polyurethane prepolymer macromolecular chain, the double bonds do not participate in any reaction in polyurethane synthesis, a double-bond-terminated polyurethane macromolecular chain is finally formed, the double bonds at the two ends of the polyurethane molecular chain and the double bonds in an acrylate monomer are subjected to polymerization reaction when the PUA core-shell emulsion is synthesized, a bridge is built between shell layer polyurethane and core layer acrylate, so that the polyurethane modified acrylate thick plate printing adhesive has the advantages of good acrylate flexibility and the like in the interior, and has the advantages of excellent performances such as polyurethane wear resistance, water washing resistance and the like in the exterior.
During synthesis, the acetoacetylated modified acrylic acid self-crosslinking monomer (TAM) is used for replacing N-hydroxymethyl acrylamide (NMA) as a crosslinking agent, the problem of continuous release of formaldehyde in the use process is solved, and the acetoacetylated ethylene glycol diester methacrylate (AAEM) is replaced, so that compared with TAM and AAEM, the molecular structure-CH 3 is more, and the yellowing resistance is stronger.
The invention adopts the cohesion promoter SA510, is based on a special acrylate high-molecular emulsion product, is applied to a water-based acrylate system, can interact with an acrylic acid high-molecular chain for a butyl acrylate system, and improves the cohesion of the emulsion by using a small addition amount, thereby improving the strength and the heat resistance of the emulsion.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
SA510 produced by Dalianjindingxiang chemical Co., Ltd as cohesion accelerator;
the acetoacetylated modified acrylic acid self-crosslinking monomer TAM is cured at room temperature by Beijing Baiyuan chemical Co., Ltd;
BY-706 manufactured BY antifoaming agent Beijing Baiyuan chemical Co., Ltd;
FS-300H is produced by Liaoning sidereal fine chemical Co.Ltd as thickener;
example 1 preparation method of polyurethane modified acrylate thick plate printing adhesive
The preparation method of the polyurethane modified acrylate thick plate printing adhesive provided by the embodiment comprises the following steps:
step 1, preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 20kg of polyether glycol (N210) into a reaction kettle A, heating to 70 ℃, adding 10kg of isophorone diisocyanate (IPDI) and 0.2kg of dibutyltin dilaurate (DBTDL), and keeping the temperature for 2 hours at the temperature; then adding 10kg of 2, 2-dimethylolpropionic acid (DMPA), reacting for 1.5h, adding 10kg of hydroxyethyl methacrylate (HEMA), reacting for 0.5 h, cooling to room temperature, adding 1kg of Triethylamine (TEA) for neutralization, then adding 100kg of deionized water for high-speed dispersion and homogeneous phase, then adding 2kg of ethylenediamine for chain extension, and stirring for 0.5 h to obtain 153.2kg of composite emulsifier A;
step 2, acrylic monomer Pre-emulsification
Adding the emulsifier A10kg, 120kg of deionized water, 70kg of butyl acrylate, 30kg of isooctyl acrylate, 15kg of acrylonitrile, 25kg of methyl methacrylate, 4kg of acrylic acid and 2kg of acetoacetylated modified acrylic acid self-crosslinking monomer into a reaction kettle B, and dispersing and mixing at a high speed of 800r/min for 30min to obtain 276kg of pre-emulsion B;
step 3, seed emulsion preparation
Adding 80kg of deionized water, 10kg of pre-emulsion B10kg and 0.2kg of ammonium persulfate into a reaction kettle C, heating to 85 ℃, stirring at 180r/min, and carrying out heat preservation reaction until the solution presents blue light;
step 4, emulsion polymerization
Controlling the temperature of the reaction kettle C to be 80 ℃, simultaneously dropwise adding 10kg of ammonium persulfate aqueous solution and the residual pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the pre-emulsion B simultaneously, wherein the dropwise adding time is 3 hours, after the dropwise adding is completed, heating to 85 ℃, keeping the temperature for 1 hour, then cooling to 70 ℃, adding 0.5kg of tert-butyl hydroperoxide and 0.5kg of sodium erythorbate, and keeping the temperature for 0.5 hour;
step 5, compounding the emulsion
Adjusting the pH value to 7-8, adding 0.5kg of associative thickener, uniformly stirring to obtain the polyurethane modified acrylate reaction kettle C, cooling to room temperature, adding 0.5kg of cohesive force promoter SA5100.5kg, 0.1kg of preservative MV0.1kg and 0.2kg of water-based defoamer, and obtaining the product polyurethane modified acrylate adhesive.
Example 2 preparation method of polyurethane modified acrylate thick plate printing adhesive
The preparation method of the polyurethane modified acrylate thick plate printing adhesive provided by the embodiment comprises the following steps:
step 1, preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 25kg of polyether glycol (N210) into a reaction kettle A, heating to 65 ℃, adding 15kg of isophorone diisocyanate (IPDI) and 0.2kg of dibutyltin dilaurate (DBTDL), and keeping the temperature for 2.5 hours at the temperature; then adding 5kg of 2, 2-dimethylolpropionic acid (DMPA), reacting for 2h, adding 15kg of hydroxyethyl methacrylate (HEMA), reacting for 0.5 h, cooling to room temperature, adding 2kg of Triethylamine (TEA) for neutralization, then adding 120kg of deionized water for high-speed dispersion and homogeneous phase, then adding 1kg of ethylenediamine for chain extension, and stirring for 0.5 h to obtain 183.2kg of composite emulsifier A;
step 2, acrylic monomer Pre-emulsification
Adding the emulsifier A10kg, 100kg of deionized water, 80kg of butyl acrylate, 20kg of isooctyl acrylate, 10kg of acrylonitrile, 30kg of methyl methacrylate, 2kg of acrylic acid and 3kg of acetoacetylated modified acrylic acid self-crosslinking monomer into a reaction kettle B, and dispersing and mixing at a high speed of 800r/min for 40min to obtain 255kg of pre-emulsion B;
step 3, seed emulsion preparation
Adding 100kg of deionized water, 15kg of pre-emulsion B and 0.3kg of ammonium persulfate into a reaction kettle C, heating to 85 ℃, stirring at 150r/min, and carrying out heat preservation reaction until the solution presents blue light;
step 4, emulsion polymerization
Controlling the temperature of the reaction kettle C to be 85 ℃, simultaneously dropwise adding 12kg of ammonium persulfate aqueous solution and the residual pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the pre-emulsion B at the same time, wherein the dropwise adding time is 2.5 hours, after the dropwise adding is completed, heating to 90 ℃, preserving the heat for 1 hour, then cooling to 70 ℃, adding 0.5kg of tert-butyl hydroperoxide and 0.5kg of sodium erythorbate, and preserving the heat for 0.5 hour;
step 5, compounding the emulsion
Adjusting the pH value to 7-8, adding 0.7kg of associative thickener, uniformly stirring to obtain the polyurethane modified acrylate reaction kettle C, cooling to room temperature, adding 0.5kg of cohesive force promoter SA5100.5kg, 0.2kg of preservative MV0.2kg and 0.2kg of water-based defoamer, and obtaining the product polyurethane modified acrylate adhesive.
Example 3 preparation method of polyurethane modified acrylate thick plate printing adhesive
The preparation method of the polyurethane modified acrylate thick plate printing adhesive provided by the embodiment comprises the following steps:
step 1, preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 25kg of polyether glycol (N210) into a reaction kettle A, heating to 70 ℃, adding 10kg of isophorone diisocyanate (IPDI) and 0.3kg of dibutyltin dilaurate (DBTDL), and keeping the temperature for 2 hours at the temperature; then adding 5kg of 2, 2-dimethylolpropionic acid (DMPA), reacting for 1.5h, adding 15kg of hydroxyethyl methacrylate (HEMA), reacting for 1h, cooling to room temperature, adding 2kg of Triethylamine (TEA) for neutralization, then adding 110kg of deionized water for high-speed dispersion and homogeneous phase, then adding 2kg of ethylenediamine for chain extension, and stirring for 0.5 h to obtain 169.3kg of composite emulsifier A;
step 2, acrylic monomer Pre-emulsification
Adding 7kg of the emulsifier A, 110kg of deionized water, 80kg of butyl acrylate, 20kg of isooctyl acrylate, 20kg of acrylonitrile, 20kg of methyl methacrylate, 3kg of acrylic acid and 3kg of acetoacetylated modified acrylic acid self-crosslinking monomer into a reaction kettle B, and dispersing and mixing at a high speed of 1000r/min for 30min to obtain 263kg of pre-emulsion B;
step 3, seed emulsion preparation
Adding 100kg of deionized water, 15kg of pre-emulsion B and 0.2kg of ammonium persulfate into a reaction kettle C, heating to 80 ℃, stirring at 180r/min, and carrying out heat preservation reaction until the solution presents blue light;
step 4, emulsion polymerization
Controlling the temperature of a reaction kettle C to be 80 ℃, simultaneously dropwise adding 11kg of ammonium persulfate aqueous solution and the residual pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the pre-emulsion B at the same time, wherein the dropwise adding time is 2 hours, after the dropwise adding is completed, heating to 85 ℃, preserving heat for 2 hours, then cooling to 65 ℃, adding 0.3kg of tert-butyl hydroperoxide and 0.3kg of sodium erythorbate, and preserving heat for 1 hour;
step 5, compounding the emulsion
Adjusting the pH value to 7-8, adding 0.7kg of associative thickener, uniformly stirring to obtain the polyurethane modified acrylate reaction kettle C, cooling to room temperature, adding 0.8kg of cohesive force promoter SA5100.8kg, 0.2kg of preservative MV0.2kg and 0.1kg of water-based defoamer to obtain the product polyurethane modified acrylate adhesive.
Example 4 preparation method of polyurethane modified acrylate thick plate printing adhesive
The preparation method of the polyurethane modified acrylate thick plate printing adhesive provided by the embodiment comprises the following steps:
step 1, preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 25kg of polyether glycol (N210) into a reaction kettle A, heating to 70 ℃, adding 15kg of isophorone diisocyanate (IPDI) and 0.2kg of dibutyltin dilaurate (DBTDL), and keeping the temperature for 2 hours at the temperature; then adding 5kg of 2, 2-dimethylolpropionic acid (DMPA), reacting for 1.5h, adding 15kg of hydroxyethyl methacrylate (HEMA), reacting for 0.5 h, cooling to room temperature, adding 3kg of Triethylamine (TEA) for neutralization, then adding 120kg of deionized water for high-speed dispersion and homogeneous phase, then adding 2kg of ethylenediamine for chain extension, and stirring for 0.5 h to obtain 185.2kg of composite emulsifier A;
step 2, acrylic monomer Pre-emulsification
Adding the emulsifier A10kg, deionized water 110kg, butyl acrylate 60kg, isooctyl acrylate 30kg, acrylonitrile 10kg, methyl methacrylate 20kg, acrylic acid 2kg, and acetoacetylated modified acrylic acid self-crosslinking monomer 2kg into a reaction kettle B, and dispersing and mixing at a high speed of 1000r/min for 30min to obtain 244kg of pre-emulsion B;
step 3, seed emulsion preparation
Adding 100kg of deionized water, 15kg of pre-emulsion B and 0.4kg of ammonium persulfate into a reaction kettle C, heating to 85 ℃, stirring at 180r/min, and carrying out heat preservation reaction until the solution presents blue light;
step 4, emulsion polymerization
Controlling the temperature of the reaction kettle C to be 85 ℃, simultaneously dropwise adding 12kg of ammonium persulfate aqueous solution and the residual pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the pre-emulsion B at the same time, wherein the dropwise adding time is 2.5 hours, after the dropwise adding is completed, heating to 85 ℃, keeping the temperature for 1 hour, then cooling to 65 ℃, adding 0.3kg of tert-butyl hydroperoxide and 0.3kg of sodium erythorbate, and keeping the temperature for 1 hour;
step 5, compounding the emulsion
Adjusting the pH value to 7-8, adding 0.5kg of associative thickener, uniformly stirring to obtain the polyurethane modified acrylate reaction kettle C, cooling to room temperature, adding 0.5kg of cohesive force promoter SA5100.5kg, 0.2kg of preservative MV0.2kg and 0.2kg of water-based defoamer, and obtaining the product polyurethane modified acrylate adhesive.
Example 5 preparation method of polyurethane modified acrylate thick plate printing adhesive
The preparation method of the polyurethane modified acrylate thick plate printing adhesive provided by the embodiment comprises the following steps:
step 1, preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 30kg of polyether glycol (N210) into a reaction kettle A, heating to 70 ℃, adding 15kg of isophorone diisocyanate (IPDI) and 0.4kg of dibutyltin dilaurate (DBTDL), and keeping the temperature for 2 hours at the temperature; then adding 5kg of 2, 2-dimethylolpropionic acid (DMPA), reacting for 1.5h, adding 10kg of hydroxyethyl methacrylate (HEMA), reacting for 0.5 h, cooling to room temperature, adding 2kg of Triethylamine (TEA), neutralizing, adding 100kg of deionized water, dispersing at high speed to form homogeneous phases, adding 1kg of ethylenediamine for chain extension, and stirring for 0.5 h to obtain 163.4kg of composite emulsifier A;
step 2, acrylic monomer Pre-emulsification
Adding the emulsifier A10kg, 100kg of deionized water, 80kg of butyl acrylate, 20kg of isooctyl acrylate, 10kg of acrylonitrile, 30kg of methyl methacrylate, 2kg of acrylic acid and 4kg of acetoacetylated modified acrylic acid self-crosslinking monomer into a reaction kettle B, and dispersing and mixing at a high speed of 800r/min for 40min to prepare 256kg of pre-emulsion B;
step 3, seed emulsion preparation
Adding 90kg of deionized water, 15kg of pre-emulsion B15kg and 0.4kg of ammonium persulfate into a reaction kettle C, heating to 80 ℃, stirring at 200r/min, and carrying out heat preservation reaction until the solution presents blue light;
step 4, emulsion polymerization
Controlling the temperature of a reaction kettle C to be 80 ℃, simultaneously dropwise adding 14kg of ammonium persulfate aqueous solution and the residual pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the pre-emulsion B at the same time, wherein the dropwise adding time is 2 hours, after the dropwise adding is completed, heating to 90 ℃, preserving heat for 1 hour, then cooling to 65 ℃, adding 0.3kg of tert-butyl hydroperoxide and 0.3kg of sodium erythorbate, and preserving heat for 1 hour;
step 5, compounding the emulsion
Adjusting the pH value to 7-8, adding 0.8kg of associative thickener, uniformly stirring to obtain the polyurethane modified acrylate reaction kettle C, cooling to room temperature, adding 0.8kg of cohesive force promoter SA5100.8kg, 0.2kg of preservative MV0.2kg and 0.2kg of water-based defoamer to obtain the product polyurethane modified acrylate adhesive.
Test example
The polyurethane modified acrylate thick plate printing adhesives of the examples 1-5 and the commercial samples were formulated according to the following formulations for comparison.
Supplementing the above components to 100 parts by deionized water, dispersing at a high speed of 1000r/min, uniformly stirring, filtering by using 200-mesh filter cloth, and uniformly grinding by using a three-roll grinder to obtain the printing paste for testing the thick plate.
The printing process comprises the following steps:
the knitted pure cotton cloth is selected as printing sample cloth, and the silk screen printing plate is made of 120-mesh gauze.
The thick plate produced by Liaoning sidereal fine chemical Co., Ltd is printed for 3 times by using SC-511 bottom coating, each time is 3 times, each time is blown to the surface dry by electric blowing and then the next printing is carried out, the thick plate printing paste is printed for 5 times by using test thick plate printing paste, each time is 3 times, each time is blown to the surface dry by electric blowing and then the next printing is carried out.
Drying at 130 ℃ for 2 minutes after printing is finished to obtain a test sample
1. Low temperature resistance test
After printing, the sample is placed in a refrigerator, the temperature is controlled to be-20 ℃, the sample is placed for 48 hours, and the sample is taken out to test whether the sample loses elasticity.
2. High temperature resistance test
And (3) placing the sample in an oven, controlling the temperature to be 50 ℃, placing for 24 hours, and taking out the sample to test whether the sample is sticky.
3. Fastness to rubbing
Testing according to GB/T3920-1997.
4. Stiffness of the sheet
Taking the printed fabric, cutting the printed fabric into a sample strip of 15 multiplied by 2cm, and measuring the stiffness of the fabric by using an electronic stiffness meter with the model number of LLY-01.
5. Dry cleaning resistant
The fabric was washed with a standard dry cleaner for 45 minutes and the fabric prints were tested for dry cleaning resistance.
Table 1 table comparing indexes of examples and comparative examples
In conclusion, compared with the common commercial thick plate printing adhesive, the thick plate printing adhesive provided by the embodiments 1-5 of the invention obviously enhances the mechanical property of the thick plate printing product and solves the problems of 'hot sticking and cold brittleness', solvent dry cleaning intolerance and the like of the commercial product.
All the technical features of the above embodiments can be combined arbitrarily, and for simplicity of description, all possible combinations of the technical features of the above embodiments are not described; these examples, which are not explicitly described, should be considered to be within the scope of the present description.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. The preparation method of the polyurethane modified acrylate thick plate printing adhesive is characterized by comprising the following steps:
step one, preparation of waterborne polyurethane composite emulsifier
Adding polyether glycol into the reaction kettle A, heating to 65-70 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, and keeping the temperature for 2-3 h; then adding 2, 2-dimethylolpropionic acid to react for 1.5-2h, adding methyl propylene hydroxyethyl ester to react for 0.5-1h, cooling to room temperature, adding triethylamine to neutralize, then adding deionized water to disperse the homogeneous phase at a high speed, finally adding ethylenediamine to chain extend, and stirring for 0.5-1h to obtain a composite emulsifier A;
step two, acrylic monomer pre-emulsification
Adding a composite emulsifier A, deionized water, butyl acrylate, isooctyl acrylate, acrylonitrile, methyl methacrylate, acrylic acid and an acetoacetylated modified acrylic acid self-crosslinking monomer into a reaction kettle B, and dispersing and mixing at a high speed of 1000r/min for 20-40min to prepare a pre-emulsion B;
step three, preparing seed emulsion
Adding deionized water, part of the pre-emulsion B and ammonium persulfate into the reaction kettle C, heating to 80-85 ℃, stirring at the speed of 200r/min for heat preservation reaction until the solution presents blue light;
step four, emulsion polymerization
Controlling the temperature of the reaction kettle C to be 80-85 ℃, simultaneously dropwise adding an ammonium persulfate aqueous solution and the rest of the pre-emulsion B in the step 2 into the reaction kettle C, completing the dropwise adding of the ammonium persulfate aqueous solution and the rest of the pre-emulsion B at the same time, wherein the dropwise adding time is 2-3h, after the dropwise adding is completed, heating to 85-90 ℃, preserving the heat for 1-2 h, then cooling to 65-70 ℃, adding tert-butyl hydroperoxide and sodium erythorbate, and preserving the heat for 0.5-1 h;
step five, compounding the emulsion
Adjusting the pH value to 7-8, adding an associative thickener, uniformly stirring to obtain the polyurethane modified acrylate, cooling a reaction kettle C to room temperature, and adding a cohesion accelerator SA510, a preservative MV and a water-based defoamer to obtain the product polyurethane modified acrylate adhesive.
2. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein in the first step, the addition amount of each component is as follows: 20-30 parts of polyether glycol, 10-15 parts of isophorone diisocyanate, 0.2-0.5 part of dibutyltin dilaurate, 5-10 parts of 2, 2-dimethylolpropionic acid, 10-15 parts of methyl propylene hydroxyethyl ester, 1-3 parts of triethylamine, 100 parts of deionized water, 120 parts of organic solvent and 1-3 parts of ethylenediamine.
3. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein in the second step, the addition amount of each component is as follows: 5-10 parts of a composite emulsifier A, 100-120 parts of deionized water, 60-80 parts of butyl acrylate, 20-30 parts of isooctyl acrylate, 10-20 parts of acrylonitrile, 20-30 parts of methyl methacrylate, 2-5 parts of acrylic acid and 2-5 parts of an acetoacetylated modified acrylic acid self-crosslinking monomer.
4. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein in the third step, the addition amount of each component is 80-100 parts of deionized water, 80-15 parts of pre-emulsion B10 and 0.2-0.4 part of ammonium persulfate.
5. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein in the fourth step, the ammonium persulfate aqueous solution is prepared by dissolving 1 part of ammonium persulfate in 20 parts of deionized water.
6. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein in the fourth step, the dropping amount of the aqueous solution of ammonium persulfate is 10-15 parts.
7. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein the amount of each component added in the fourth step is 0.2-0.5 part of tert-butyl hydroperoxide and 0.2-0.5 part of sodium erythorbate.
8. The method for preparing the polyurethane modified acrylate thick plate printing adhesive according to claim 1, wherein the five components are added in the amount of 0.5-1 part of cohesion accelerator SA 5100.1-0.2 part of preservative MV 0.5-1 part of associative thickener and 0.1-0.2 part of aqueous defoaming agent.
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