CN103233375B - Stereo printing paste for suede and preparation method thereof - Google Patents
Stereo printing paste for suede and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a stereo printing paste for suede and a preparation method thereof. The stereo printing paste for suede is characterized in that the polyurethane modified acrylic resin printing paste is prepared from methoxy polyethylene glycol acrylate, butyl acrylate, ethyl acrylate, polyoxyallyl ether glycol, polyoxyethylene ether glycol, trimethylolpropane, dimethylolpropionic acid or dimethylolbutanoic acid, polyisocyanates, a chain extender, a catalyst, methyl ethyl ketoxime, triethylamine, hydroxyethyl methylacrylate or hydroxypropyl methacrylate, crylic acid, glycidyl methacrylate, N-hydroxymethyl acrylamide, acetoacetic acid ethyl methacrylate, an initiator, sodium hydrogen sulfite, zinc oxide, a thickener and deionized water by the steps of prepolymerizing, sealing, neutralized emulsifying, emulsion polymerizing and thickening. The prepared polyurethane modified acrylic resin printing paste has excellent permeability, adhesive force, ageing resistance, water resistance and dry friction resistance. The stereo printing on the suede is carried out in a flat screen printing manner; and the stereo printing paste has obvious concave-convex feeling and sculpture feeling.
Description
Technical field
What the present invention relates to is a kind of fabric panel printing paste, particularly a kind of stereoscopic printing slurry for flock suede fabric and preparation method thereof and application.
Concentrator of the present invention is a kind of at 150～170 ℃ of polyurethane modified acrylic resin slurries that carry out cross-linking reaction.
Background technology
Traditional flock suede stereoscopic printing, to process by bronze designs or patterns on fans, wooden furniture, etc., high-temperature high-pressure flower process, bronze designs or patterns on fans, wooden furniture, etc. and high temperature embossing are easy to damage fabric intensity, and the equipment of bronze designs or patterns on fans, wooden furniture, etc., high temperature embossing, at least tens thousand of units, at most hundreds thousand of units, and the steel rider of stamp and steel plate price are also high, on steel rider and steel plate, texturing difficulty is larger, so flexibility and polytropy are limited.Along with people are to fashion-orientation, personalization, the pursuit of characterization, traditional embossing, bronze designs or patterns on fans, wooden furniture, etc. technique, cannot meet people's demand.
Open there are no the technology of stereoscopic printing slurry for flock suede fabric and preparation method thereof at present.
Summary of the invention
The present invention, in order to meet people's growing personalization, the demand of characterization, provides a kind of polyurethane modified acrylic resin concentrator for flock suede fabric and preparation method thereof.
This concentrator can adopt common PLATE SCREAM PRINTING and manual platen printing technology to carry out stamp, the diversity third dimension stamp of realization to flock suede, there is obvious concave-convex sense, engraving sense, the style of high temperature embossing, bronze designs or patterns on fans, wooden furniture, etc., and there is not network blocking, baking temperature carries out cross-linking reaction at 150～170 ℃, has excellent permeability, high-strength adhesion strength, ageing-resistant performance, water-fastness, resistance to dry friction performance.
The present invention starches preparation method for the stereoscopic printing of flock suede:
raw material mass mixture ratio:
10 ~ 30 parts of methoxy polyethylene glycol acrylates
100 ~ 300 parts of butyl acrylates
100 ~ 300 parts of ethyl acrylates
50～100 parts of polypropylene oxide ether dihydroxylic alcohols (number-average molecular weight 1000～3000)
50～100 parts of polyethylene glycol oxide ether dihydroxylic alcohols (number-average molecular weight 1000～3000)
1～5 part of trimethylolpropane
7～18 parts of dihydromethyl propionic acid or dimethylolpropionic acids
30～160 parts of polyisocyanates
3～10 parts of chain extenders
0.02～0.06 part of catalyst
7～18 parts of methyl ethyl ketoximes
5～13 parts of triethylamines
1 ~ 9 part of hydroxyethyl methylacrylate or hydroxy propyl methacrylate
1 ~ 6 part, acrylic acid
1 ~ 6 part of glycidyl methacrylate
1 ~ 6 part of N hydroxymethyl acrylamide
1 ~ 5 part of AAEM (AAEM)
0.5 ~ 2.0 part of initator
0.1 ~ 0.5 part of sodium hydrogensulfite
0.1 ~ 0.5 part of zinc chloride
9 ~ 29 parts of thickener FS-200E
580 ~ 1820 parts of deionized waters;
Methoxy polyethylene glycol acrylate: structural formula CH3O(CH2CH2O) nOCCH=CH2, n=8～33;
Initator: for ammonium persulfate or potassium peroxydisulfate or sodium peroxydisulfate one of them;
Chain extender: be selected from 1,2-butanediol, BDO, neopentyl glycol, 1,3-PD one of them or two kinds and be combined with;
Polyisocyanates: be selected from toluene di-isocyanate(TDI) (TDI), 1.6-hexylidene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate (H
12mDI) one of them or two kinds are combined with;
Catalyst: be selected from dibutyl tin laurate or acetic acid dibutyl tin one of them;
Thickener FS-200E is the product F S-200E of Liaoning Sunichem Co., Ltd.;
preparation method:
(1) press above-mentioned raw materials quality proportioning by methoxy polyethylene glycol acrylate, butyl acrylate, ethyl acrylate
,polypropylene oxide ether dihydroxylic alcohols, polyethylene glycol oxide ether dihydroxylic alcohols, trimethylolpropane, dihydromethyl propionic acid or dimethylolpropionic acid, polyisocyanates, chain extender, catalyst are added in reactor, stir and heat up, 60～80 ℃ of reactions 6～8 hours, make base polyurethane prepolymer for use as;
(2) then add the methyl ethyl ketoxime of above-mentioned raw materials quality proportioning, 60～80 ℃ of reactions 2～4 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of above-mentioned methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 20～40 ℃, after adding the triethylamine of above-mentioned raw materials quality proportioning to stir, rapid stirring, add 510 ~ 1500 parts of deionized waters, carry out emulsification, make closure polyaminoester emulsion;
(4) while stirring toward the acrylic acid, glycidyl methacrylate, N hydroxymethyl acrylamide, the AAEM (AAEM) that add above-mentioned raw materials quality proportioning in emulsifying kettle, and add hydroxyethyl methylacrylate or hydroxy propyl methacrylate, make pre-polymerization emulsion;
(5) get 1/4th of above-mentioned pre-polymerization quality of the emulsion, join in resin polymerization still;
(6) the above-mentioned pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) initator of above-mentioned raw materials quality proportioning and 30 ~ 120 parts of stirring and dissolving of deionized water is even, make initiator solution;
(8) sodium hydrogensulfite of above-mentioned raw materials quality proportioning and 20 ~ 100 parts of stirring and dissolving of deionized water is even, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is stirred and is warmed up to 75～80 ℃, then add the above-mentioned initiator solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 75～80 ℃, then at 75～80 ℃, slowly add remaining pre-polymerization emulsion and remaining initiator solution and the remaining sodium hydrogensulfite reductant aqueous solution, in 2 ~ 3 hours, add, be then warming up to 80～85 ℃ of reactions 2 ~ 3 hours;
(10) then cool to 20-40 ℃, add the zinc chloride of above-mentioned raw materials quality proportioning and the solder(ing)acid that 20 ~ 100 parts of stirring and dissolving of deionized water are evenly made, then the thickener FS-200E that adds above-mentioned raw materials quality proportioning, stir 30 ~ 60 minutes, then filter blowing, obtain product polyurethane modified acrylic resin printing paste.
Product of the present invention is a kind of polyurethane modified acrylic resin, in its structure, both had polyurethane segment, and had again acrylic resin segment, polyurethane resin function base is in main chain, give polyurethane resin cohesive energy large, intensity is large, resistance to solvent, the performances such as rub resistance, but function base is easily attacked and is decomposed by oxygen, hydrone, its loss of properties on aging.The function base of acrylic resin is on side chain, and the decomposition of its function base can not affect the performance of acrylic resin substantially, and its ageing-resistant performance is excellent.The segment of acrylic resin is received in polyurethane resin structure functional group that can shielding protection polyurethane resin; avoid oxygen and hydrone to attack; make its polyurethane modified acrylic resin both there is the intensity of polyurethane resin large; cohesive force waits by force excellent properties, has again the ageing-resistant performance of acrylic resin.In addition, because this product is the polyurethane modified acrylic resin of methyl ethyl ketoxime sealing, be heat reactivity product, so the feature such as film forming not under room temperature condition has good penetrability, and cohesive force is strong, not network blocking.
Flock suede stereoscopic printing slurry of the present invention is heat reactivity product, during use, need not add other auxiliary agents such as crosslinking agent, thickener again, can be directly used in PLATE SCREAM PRINTING or the manual table printing of flock suede, and technological operation is simple.
Adopt printing paste of the present invention, with common PLATE SCREAM PRINTING or manual table printing, just can on flock suede, print out and there is concave-convex sense, embossment sense, the colored type that third dimension is strong, the Printing with embossing and bronze designs or patterns on fans, wooden furniture, etc. style, the stereoscopic printing of flock suede, graceful fashion, new and original, solitary characteristic, and, PLATE SCREAM PRINTING and manual table printing, cost is low, flexible and changeable, can make new advances fast, meet the demand of people to the stereoscopic printing of different flock suedes, flock suede third dimension Printing is applicable to case and bag, sofa, clothes, automotive trim, high-grade packaging material etc.
Accompanying drawing explanation
Fig. 1 is the test example 1 of the present invention flock suede stereoscopic printing cloth specimen that table printing is printed by hand.
Fig. 2 is the flock suede stereoscopic printing cloth specimen that test example 3 use PLATE SCREAM PRINTING of the present invention are printed.
The specific embodiment
Embodiment 1:
(1) by methoxy polyethylene glycol acrylate, structural formula: CH3O(CH2CH2O) nOCCH=CH2 (n=20) is 20 grams,
200 grams of butyl acrylates,
150 grams of ethyl acrylates,
80 grams of polypropylene oxide ether dihydroxylic alcohols (number-average molecular weight 2000),
60 grams of polyethylene glycol oxide ether dihydroxylic alcohols (number-average molecular weight 2000),
4.5 grams of BDOs,
2 grams of trimethylolpropanes,
10 grams of dihydromethyl propionic acids,
51.4 grams of toluene di-isocyanate(TDI)s (TDI),
0.03 gram of dibutyl tin laurate,
Join in reactor, stir and heat up, at 76 ± 2 ℃, react 7 hours, make base polyurethane prepolymer for use as;
(2) then add 10.9 grams of methyl ethyl ketoximes, at 75 ± 2 ℃, react 3 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 30 ± 2 ℃, after adding 7.5 grams of triethylamines to stir, rapid stirring, adds 800 grams of deionized waters, carries out emulsification, makes closure polyaminoester emulsion;
(4) then in emulsifying kettle, add 6 grams of hydroxy propyl methacrylates while stirring, 3.5 grams, acrylic acid, 3 grams of glycidyl methacrylate, 3 grams of N hydroxymethyl acrylamides, 3 grams of AAEMs (AAEM), emulsification is even, makes pre-polymerization emulsion;
(5) get the above-mentioned pre-polymerization emulsion of 1/4th quality, join in resin polymerization still;
(6) the above-mentioned pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) 1 gram of ammonium persulfate is even with 50 grams of stirring and dissolving of deionized water, make the initiator ammonium persulfate aqueous solution;
(8) 0.3 gram of sodium hydrogensulfite is even with 30 grams of stirring and dissolving of deionized water, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is heated to 77 ± 2 ℃ while stirring, then add the above-mentioned initiator ammonium persulfate aqueous solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 78 ± 2 ℃, then at 78 ± 2 ℃, slowly add remaining pre-polymerization emulsion and the remaining initiator ammonium persulfate aqueous solution and remaining reductant aqueous solution of sodium bisulfite, at 2.5 hours, add 83 ± 2 ℃ of insulation reaction that then heat up 2.5 hours;
(10) then cool to 25 ± 2 ℃, add 0.2 gram of solder(ing)acid of evenly making with 50 grams of stirring and dissolving of deionized water of zinc chloride, then add 11 grams of thickener FS-200E, at 25 ± 2 ℃, stir 40 minutes, then filter blowing, obtain product polyurethane modified acrylic resin flock suede stereoscopic printing slurry.
Embodiment 2:
(1) by methoxy polyethylene glycol acrylate, structural formula: CH3O(CH2CH2O) nOCCH=CH2 (n=30) is 26 grams,
180 grams of butyl acrylates,
160 grams of ethyl acrylates,
60 grams of polypropylene oxide ether dihydroxylic alcohols (number-average molecular weight 1800),
80 grams of polyethylene glycol oxide ether dihydroxylic alcohols (number-average molecular weight 1800),
5 grams of neopentyl glycols,
3 grams of trimethylolpropanes,
11 grams of dimethylolpropionic acids,
30 grams of toluene di-isocyanate(TDI)s (TDI),
25.1 grams of 1.6-hexylidene diisocyanates (HDI),
0.04 gram of acetic acid dibutyl tin,
Join in reactor, stir and heat up, at 76 ± 2 ℃, react 7 hours, make base polyurethane prepolymer for use as;
(2) then add 12.5 grams of methyl ethyl ketoximes, at 70 ± 2 ℃, react 3 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 30 ± 2 ℃, after adding 7.5 grams of triethylamines to stir, rapid stirring, adds 810 grams of deionized waters, carries out emulsification, makes closure polyaminoester emulsion;
(4) then in emulsifying kettle, add 6 grams of hydroxyethyl methylacrylates while stirring, 4 grams, acrylic acid, 4 grams of glycidyl methacrylate, 3 grams of N hydroxymethyl acrylamides, 3 grams of AAEMs (AAEM), emulsification is even, makes pre-polymerization emulsion;
(5) get the above-mentioned pre-polymerization emulsion of 1/4th quality, join in resin polymerization still;
(6) the pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) 1 gram of potassium peroxydisulfate and 50 grams of stirring and dissolving of deionized water is even, make the initiator potassium persulfate aqueous solution;
(8) 0.3 gram of sodium hydrogensulfite and 50 grams of stirring and dissolving of deionized water is even, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is heated to 77 ± 2 ℃ while stirring, then add the above-mentioned initiator potassium persulfate aqueous solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 78 ± 2 ℃, then at 78 ± 2 ℃, slowly add residue pre-polymerization emulsion and the remaining initiator potassium persulfate aqueous solution and remaining reductant aqueous solution of sodium bisulfite, at 2.5 hours, add 83 ± 2 ℃ of insulation reaction that then heat up 2.5 hours;
(10) then cool to 30 ± 2 ℃, add 0.2 gram of solder(ing)acid of evenly making with 50 grams of stirring and dissolving of deionized water of zinc chloride, then add 10 grams of thickener FS-200E, at 30 ± 2 ℃, stir 50 minutes, then filter blowing, obtain product polyurethane modified acrylic resin flock suede stereoscopic printing slurry.
Embodiment 3:
(1) by methoxy polyethylene glycol acrylate, structural formula: CH3O(CH2CH2O) nOCCH=CH2 (n=16) is 20 grams,
150 grams of butyl acrylates,
150 grams of ethyl acrylates,
80 grams of polypropylene oxide ether dihydroxylic alcohols (number-average molecular weight 2000),
80 grams of polyethylene glycol oxide ether dihydroxylic alcohols (number-average molecular weight 2000),
2.5 grams of BDOs,
2.5 grams of neopentyl glycols,
1.5 grams of trimethylolpropanes,
13.4 grams of dihydromethyl propionic acids,
75 grams of isophorone diisocyanate (IPDI),
0.04 gram of dibutyl tin laurate,
Join in reactor, stir and heat up, at 77 ± 2 ℃, react 7 hours, make base polyurethane prepolymer for use as;
(2) then add 12 grams of methyl ethyl ketoximes, at 75 ± 2 ℃, react 3 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 30 ± 2 ℃, after adding 10.1 grams of triethylamines to stir, rapid stirring, adds 900 grams of deionized waters, carries out emulsification, makes closure polyaminoester emulsion;
(4) then in emulsifying kettle, add 6 grams of hydroxyethyl methylacrylates while stirring, 2.5 grams, acrylic acid, 4 grams of glycidyl methacrylate, 3.5 grams of N hydroxymethyl acrylamides, 4 grams of AAEMs (AAEM), emulsification is even, makes pre-polymerization emulsion;
(5) get the above-mentioned pre-polymerization emulsion of 1/4th quality, join in resin polymerization still;
(6) the pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) 1.2 grams of sodium peroxydisulfates and 60 grams of stirring and dissolving of deionized water is even, make initator sodium persulfate aqueous solution;
(8) 0.4 gram of sodium hydrogensulfite and 40 grams of stirring and dissolving of deionized water is even, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is heated to 77 ± 2 ℃ while stirring, then add the above-mentioned initator sodium persulfate aqueous solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 78 ± 2 ℃, then at 78 ± 2 ℃, slowly add remaining pre-polymerization emulsion and remaining initator sodium persulfate aqueous solution and remaining reductant aqueous solution of sodium bisulfite, at 2.5 hours, add 83 ± 2 ℃ of insulation reaction that then heat up 2.5 hours;
(10) then cool to 25 ± 2 ℃, add 0.3 gram of solder(ing)acid of evenly making with 60 grams of stirring and dissolving of deionized water of zinc chloride, then add 15 grams of thickener FS-200E, at 25 ± 2 ℃, stir 50 minutes, then filter blowing, obtain product polyurethane modified acrylic resin flock suede stereoscopic printing slurry.
Embodiment 4:
(1) by methoxy polyethylene glycol acrylate, structural formula: CH3O(CH2CH2O) nOCCH=CH2 (n=20) is 20 grams,
200 grams of butyl acrylates,
200 grams of ethyl acrylates,
60 grams of polypropylene oxide ether dihydroxylic alcohols (number-average molecular weight 1500),
80 grams of polyethylene glycol oxide ether dihydroxylic alcohols (number-average molecular weight 1500),
4 grams of 1,3-PDs,
2 grams of trimethylolpropanes,
12 grams of dimethylolpropionic acids,
Dicyclohexyl methyl hydride diisocyanate (H
12mDI) 82 grams,
0.03 gram of acetic acid dibutyl tin,
Join in reactor, stir and heat up, at 75 ± 2 ℃, react 7 hours, make base polyurethane prepolymer for use as;
(2) then add 11.9 grams of methyl ethyl ketoximes, at 72 ± 2 ℃, react 3 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 30 ± 2 ℃, after adding 8.2 grams of triethylamines to stir, rapid stirring, adds 1000 grams of deionized waters, carries out emulsification, makes closure polyaminoester emulsion;
(4) then in emulsifying kettle, add 6 grams of hydroxyethyl methylacrylates while stirring, 2.3 grams, acrylic acid, 2.6 grams of glycidyl methacrylate, 3 grams of N hydroxymethyl acrylamides, 3 grams of AAEMs (AAEM), emulsification is even, makes pre-polymerization emulsion;
(5) get the above-mentioned pre-polymerization emulsion of 1/4th quality, join in resin polymerization still;
(6) the pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) 1.1 grams of ammonium persulfates and 55 grams of stirring and dissolving of deionized water is even, make the initiator ammonium persulfate aqueous solution;
(8) 0.3 gram of sodium hydrogensulfite and 30 grams of stirring and dissolving of deionized water is even, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is heated to 77 ± 2 ℃ while stirring, then add the above-mentioned initiator ammonium persulfate aqueous solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 78 ± 2 ℃, then at 78 ± 2 ℃, slowly add remaining pre-polymerization emulsion and the remaining initiator ammonium persulfate aqueous solution and remaining reductant aqueous solution of sodium bisulfite, at 2.5 hours, add 83 ± 2 ℃ of insulation reaction that then heat up 2.5 hours;
(10) then cool to 30 ± 2 ℃, add 0.2 gram of solder(ing)acid of evenly making with 50 grams of stirring and dissolving of deionized water of zinc chloride, then add 16 grams of thickener FS-200E, at 30 ± 2 ℃, stir 50 minutes, then filter blowing, obtain product polyurethane modified acrylic resin flock suede stereoscopic printing slurry.
Embodiment 5
(1) by methoxy polyethylene glycol acrylate, structural formula: CH3O(CH2CH2O) nOCCH=CH2 (n=25) is 20 grams,
100 grams of butyl acrylates,
200 grams of ethyl acrylates,
80 grams of polypropylene oxide ether dihydroxylic alcohols (number-average molecular weight 2000),
80 grams of polyethylene glycol oxide ether dihydroxylic alcohols (number-average molecular weight 2000),
2.5 grams of 1,2-butanediols,
2.5 grams of BDOs,
3 grams of trimethylolpropanes,
11 grams of dihydromethyl propionic acids,
30.5 grams of 1.6-hexylidene diisocyanates (HDI),
35.6 grams of isophorone diisocyanate (IPDI),
0.04 gram of dibutyl tin laurate,
Join in reactor, stir and heat up, at 76 ± 2 ℃, react 7.5 hours, make base polyurethane prepolymer for use as;
(2) then add 12 grams of methyl ethyl ketoximes, at 72 ± 2 ℃, react 3 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 30 ± 2 ℃, after adding 8.3 grams of triethylamines to stir, rapid stirring, adds 950 grams of deionized waters, carries out emulsification, makes closure polyaminoester emulsion;
(4) then in emulsifying kettle, add 8 grams of hydroxyethyl methylacrylates while stirring, 1.3 grams, acrylic acid, 2 grams of glycidyl methacrylate, 2 grams of N hydroxymethyl acrylamides, 3 grams of AAEMs (AAEM), emulsification is even, makes pre-polymerization emulsion;
(5) get the above-mentioned pre-polymerization emulsion of 1/4th quality, join in resin polymerization still;
(6) the pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) 1 gram of potassium peroxydisulfate and 50 grams of stirring and dissolving of deionized water is even, make the initiator potassium persulfate aqueous solution;
(8) 0.3 gram of sodium hydrogensulfite and 30 grams of stirring and dissolving of deionized water is even, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is heated to 77 ± 2 ℃ while stirring, then add the above-mentioned initiator potassium persulfate aqueous solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 78 ± 2 ℃, then at 78 ± 2 ℃, slowly add remaining pre-polymerization emulsion and the remaining initiator potassium persulfate aqueous solution and remaining reductant aqueous solution of sodium bisulfite, at 2.5 hours, add 83 ± 2 ℃ of insulation reaction that then heat up 2.5 hours;
(10) then cool to 30 ± 2 ℃, add 0.2 gram of solder(ing)acid of evenly making with 50 grams of stirring and dissolving of deionized water of zinc chloride, then add 14 grams of thickener FS-200E, at 30 ± 2 ℃, stir 50 minutes, then filter blowing, obtain product polyurethane modified acrylic resin flock suede stereoscopic printing slurry.
The technique for applying of flock suede stereoscopic printing slurry of the present invention:
Flock suede PLATE SCREAM PRINTING or manual table printing → oven dry (100 ~ 110 ℃, 3 ~ 5 minutes) → bake (150 ~ 170 ℃, 2 ~ 3 minutes).
The application test example of flock suede stereoscopic printing slurry of the present invention:
experimental example 1:
The printing paste making with embodiment 1, platen is to flock suede stamp by hand, 105 ℃ of bake out temperatures, drying time 3.5 minutes, 160 ℃ of baking temperatures, bake 2.5 minutes time.Obtain flock suede stereoscopic printing cloth specimen and see accompanying drawing 1.
experimental example 2:
The printing paste making with embodiment 2, platen is to flock suede stamp by hand, 100 ℃ of bake out temperatures, drying time 4 minutes, 160 ℃ of baking temperatures, bake 3 minutes time.
experimental example 3:
The printing paste making with embodiment 3, by PLATE SCREAM PRINTING to flock suede stamp, 104 ℃ of bake out temperatures, drying time 3.4 minutes, 165 ℃ of baking temperatures, bake 2.5 minutes time.Obtain flock suede stereoscopic printing cloth specimen and see accompanying drawing 2.
experimental example 4
The printing paste making with embodiment 4, by PLATE SCREAM PRINTING to flock suede stamp, 103 ℃ of bake out temperatures, drying time 3.5 minutes, 166 ℃ of baking temperatures, bake 2.5 minutes time.
experimental example 5
The printing paste making with embodiment 5, by PLATE SCREAM PRINTING to flock suede stamp, 101 ℃ of bake out temperatures, drying time 4 minutes, 161 ℃ of baking temperatures, bake 3 minutes time.
The flock suede that above-mentioned all test examples adopt is that grey 105D is through compiling sea island filament suede nap.
Sampling detects the indices of above-mentioned test example flock suede stereoscopic printing fabric, and testing result data are as routine table 1
Example table 1
Note: washing fastness detects: press ISO 6330 6A standards;
Dry fastness detects: press GB5711-5718-85 standard.
From detection architecture, can find out, the present invention is for flock suede stereoscopic printing slurry, and platen or PLATE SCREAM PRINTING are to flock suede stamp by hand, the colored type third dimension of printing off is obvious, and has excellent wash durability, and repeatedly washing flower type is unchanged, and soft, resistance to dry fastness can reach 5 grades.
Claims (2)
1. for a stereoscopic printing slurry preparation method for flock suede, it is characterized in that:
Raw material mass mixture ratio:
10 ~ 30 parts of methoxy polyethylene glycol acrylates,
100 ~ 300 parts of butyl acrylates,
100 ~ 300 parts of ethyl acrylates,
50～100 parts of polypropylene oxide ether dihydroxylic alcohols,
50～100 parts of polyethylene glycol oxide ether dihydroxylic alcohols,
1～5 part of trimethylolpropane,
7～18 parts of dihydromethyl propionic acid or dimethylolpropionic acids,
30～160 parts of polyisocyanates,
3～10 parts of chain extenders,
0.02～0.06 part of catalyst,
7～18 parts of methyl ethyl ketoximes,
5～13 parts of triethylamines,
1 ~ 9 part of hydroxyethyl methylacrylate or hydroxy propyl methacrylate,
1 ~ 6 part, acrylic acid,
1 ~ 6 part of glycidyl methacrylate,
1 ~ 6 part of N hydroxymethyl acrylamide,
1 ~ 5 part of AAEM (AAEM),
0.5 ~ 2.0 part of initator,
0.1 ~ 0.5 part of sodium hydrogensulfite,
0.1 ~ 0.5 part of zinc chloride,
9 ~ 29 parts of thickener FS-200E,
580 ~ 1820 parts of deionized waters;
Wherein: methoxy polyethylene glycol acrylate: structural formula CH
3o(CH
2cH
2o)
noCCH=CH
2, n=8～33;
The number-average molecular weight of polypropylene oxide ether dihydroxylic alcohols is 1000～3000;
The number-average molecular weight of polyethylene glycol oxide ether dihydroxylic alcohols is 1000～3000;
Initator: for ammonium persulfate or potassium peroxydisulfate or sodium peroxydisulfate one of them;
Chain extender: be selected from 1,2-butanediol, BDO, neopentyl glycol, 1,3-PD one of them or two kinds and be combined with;
Polyisocyanates: be selected from toluene di-isocyanate(TDI), 1,6-hexylidene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate one of them or two kinds are combined with;
Catalyst: be selected from dibutyl tin laurate or acetic acid dibutyl tin one of them;
Thickener FS-200E is the product F S-200E of Liaoning Sunichem Co., Ltd.;
preparation method:
(1) press above-mentioned raw materials quality proportioning by methoxy polyethylene glycol acrylate, butyl acrylate, ethyl acrylate
,polypropylene oxide ether dihydroxylic alcohols, polyethylene glycol oxide ether dihydroxylic alcohols, trimethylolpropane, dihydromethyl propionic acid or dimethylolpropionic acid, polyisocyanates, chain extender, catalyst are added in reactor, stir and heat up, 60～80 ℃ of reactions 6～8 hours, make base polyurethane prepolymer for use as;
(2) then add the methyl ethyl ketoxime of above-mentioned raw materials quality proportioning, 60～80 ℃ of reactions 2～4 hours, make methyl ethyl ketoxime sealing base polyurethane prepolymer for use as;
(3) base polyurethane prepolymer for use as of above-mentioned methyl ethyl ketoxime sealing is put in emulsifying kettle, cools to 20～40 ℃, after adding the triethylamine of above-mentioned raw materials quality proportioning to stir, rapid stirring, add 510 ~ 1500 parts of deionized waters, carry out emulsification, make closure polyaminoester emulsion;
(4) while stirring toward the acrylic acid, glycidyl methacrylate, N hydroxymethyl acrylamide, the AAEM (AAEM) that add above-mentioned raw materials quality proportioning in emulsifying kettle, and add hydroxyethyl methylacrylate or hydroxy propyl methacrylate, make pre-polymerization emulsion;
(5) get 1/4th of above-mentioned pre-polymerization quality of the emulsion, join in resin polymerization still;
(6) the above-mentioned pre-polymerization emulsion of all the other 3/4ths quality, joins in pre-newborn still;
(7) initator of above-mentioned raw materials quality proportioning and 30 ~ 120 parts of stirring and dissolving of deionized water is even, make initiator solution;
(8) sodium hydrogensulfite of above-mentioned raw materials quality proportioning and 20 ~ 100 parts of stirring and dissolving of deionized water is even, make the sodium hydrogensulfite reductant aqueous solution;
(9) resin polymerization still is stirred and is warmed up to 75～80 ℃, then add the above-mentioned initiator solution of 1/4th quality and the above-mentioned sodium hydrogensulfite reductant aqueous solution of 1/5th quality, carry out initiation reaction, reaction temperature is controlled at 75～80 ℃, then at 75～80 ℃, slowly add remaining pre-polymerization emulsion and remaining initiator solution and the remaining sodium hydrogensulfite reductant aqueous solution, in 2 ~ 3 hours, add, be then warming up to 80～85 ℃ of reactions 2 ~ 3 hours;
(10) then cool to 20-40 ℃, add the zinc chloride of above-mentioned raw materials quality proportioning and the solder(ing)acid that 20 ~ 100 parts of stirring and dissolving of deionized water are evenly made, then the thickener FS-200E that adds above-mentioned raw materials quality proportioning, stir 30 ~ 60 minutes, then filter blowing, obtain product polyurethane modified acrylic resin printing paste.
2. the stereoscopic printing slurry of the flock suede that claim 1 method obtains.
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| CN103526583A (en) * | 2013-10-23 | 2014-01-22 | 合肥聚合辐化技术有限公司 | Hot-water-endurance printing binding agent and preparation method thereof |
| CN103526581A (en) * | 2013-10-23 | 2014-01-22 | 合肥聚合辐化技术有限公司 | Environment-friendly printing adhesive as well as preparation method thereof |
| CN103526596A (en) * | 2013-10-23 | 2014-01-22 | 合肥聚合辐化技术有限公司 | Environment-friendly low-temperature setting print adhesive and preparation method thereof |
| CN104746363B (en) * | 2013-12-30 | 2016-11-23 | 辽宁恒星精细化工有限公司 | A kind of leather pattern-printing slurry and preparation method thereof |
| CN104141243B (en) * | 2014-07-28 | 2016-08-24 | 绍兴彩色橼纺织科技有限公司 | Stereoscopic printing is starched |
| CN104264515A (en) * | 2014-09-24 | 2015-01-07 | 无锡市东北塘宏良染色厂 | Printing paste |
| CN107001553B (en) * | 2014-09-26 | 2020-10-27 | 科慕埃弗西有限公司 | Sulfonated fluorinated, non-fluorinated or partially fluorinated carbamates |
| CN104452307B (en) * | 2014-12-15 | 2016-06-22 | 辽宁恒星精细化工有限公司 | A kind of ventilative, uvioresistant, antistatic polyurethane resin coating adhesive and preparation method thereof |
| CN105348455B (en) * | 2015-12-11 | 2018-01-23 | 六安科瑞达新型材料有限公司 | The epoxy radicals acrylic matting resin and preparation method of a kind of modification |
| CN106638042B (en) * | 2016-10-03 | 2018-11-02 | 辽宁恒星精细化工有限公司 | Dyed fabric increases deep finishing agent and preparation method |
| CN112144305A (en) * | 2019-09-16 | 2020-12-29 | 滨州亚光家纺有限公司 | Carving three-dimensional printing method for towel |
| CN115386061B (en) * | 2022-08-04 | 2024-03-08 | 辽宁恒星精细化工有限公司 | Thermal reactive aqueous polyurethane resin and preparation method and application thereof |
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| CN100419152C (en) * | 2006-09-13 | 2008-09-17 | 合肥安大天辐新材料有限公司 | Environment-protection coating printing adhesive and its preparing method |
| CN102619106B (en) * | 2012-04-16 | 2013-06-19 | 辽宁恒星精细化工有限公司 | Real leather suede leather stereoscopic printing paste and preparation method |
| CN102899927B (en) * | 2012-10-24 | 2014-05-21 | 绍兴中纺院江南分院有限公司 | Digital printing binding agent, preparation method and applications of digital printing binding agent |
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