CN114044861A - Polyurethane modified acrylate pigment printing adhesive for dacron oxford fabric and preparation method thereof - Google Patents
Polyurethane modified acrylate pigment printing adhesive for dacron oxford fabric and preparation method thereof Download PDFInfo
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- CN114044861A CN114044861A CN202111468233.0A CN202111468233A CN114044861A CN 114044861 A CN114044861 A CN 114044861A CN 202111468233 A CN202111468233 A CN 202111468233A CN 114044861 A CN114044861 A CN 114044861A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
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Abstract
The invention relates to a polyurethane modified acrylate pigment printing adhesive for dacron oxford fabric and a preparation method thereof, wherein the preparation method comprises the following steps of (1) preparing a waterborne polyurethane composite emulsifier by using polyol, polytetrahydrofuran ether glycol, polycaprolactone polyol, hexamethylene diisocyanate, isophorone diisocyanate, 2-dimethylolpropionic acid, hydroxyethyl methacrylate, triethylamine, deionized water and ethylenediamine; (2) preparing an organic silicon prepolymer from an aqueous polyurethane composite emulsifier, ionized water and organic silicon monomers D4 and A-2120; (3) preparing a pre-emulsion from deionized water, butyl acrylate, acrylic acid, styrene, methyl acrylate, itaconic acid, an organic silicon prepolymer and a crosslinking monomer; (4) the polyurethane modified acrylate adhesive is prepared from pre-emulsion, deionized water, APS, residual pre-emulsion, APS aqueous solution and sodium bisulfite aqueous solution, is used for printing polyester fabrics, and has the advantages of high fastness, bright color, washing resistance, soft hand feeling and stain resistance.
Description
Technical Field
The invention relates to a polyurethane modified acrylate pigment printing adhesive and a preparation method thereof, in particular to a pigment printing adhesive for 500D terylene oxford.
Technical Field
The pigment printing is that color paste is prepared by adhesive, pigment, organic auxiliary agent and water, the color paste is transferred to the surface of the fabric by printing process to form flower-shaped patterns, and the patterns are fixed on the surface of the fabric after being dried and formed into films.
The pigment printing method has the advantages of short process flow, simple production, no need of washing after drying the fabric, high production efficiency, energy conservation and no wastewater. The pigment printing has the advantages of complete color spectrum, bright color, clear printing outline, distinct gradation and good light fastness. The color paste can be mixed arbitrarily, the color matching is convenient, the color change can not occur, and the repeatability is good.
The disadvantages of pigment printing are poor rubbing fastness of the pigment adhered to the surface of the fiber, poor wet rubbing fastness, and especially poor fastness when the binder is used in a small amount or when deep-colored patterns are printed. When printing large-block-surface patterns, the hand feeling is hard, and the wearability is affected. The adhesive is easy to generate emulsion breaking, film forming and adhesion, so that the problems of screen plugging, flower cylinder sticking and the like are easy to occur in pigment printing. And the coating suspension is damaged to cause defects such as color points, white spots and the like.
The terylene oxford cloth, particularly the rough style of the 500D terylene oxford cloth, is used for manufacturing bags, camouflage clothes, handbags, outdoor tents and the like, and is well pursued by consumers. The 500D polyester oxford cloth is used for camouflage paint printing, is deeply favored by fashionable people, and has the advantages of simple process, energy conservation, environmental protection and the like, so the oxford camouflage paint printing has very wide development prospect.
The 500D terylene oxford fabric belongs to high-strength filament, high-count and high-density fabrics. The high-strength high-modulus high-tenacity high-impact-resistance, heat-resistance, light-resistance and corrosion-resistance high-tenacity high-heat-tenacity high-corrosion resistance high-tenacity high-heat resistance high-tenacity high-resistance high-tenacity high-moisture-resistance high-resistance, high-resistance high-tenacity high-resistance high-tenacity high-corrosion resistance high-tenacity high-resistance, high-resistance high-tenacity high-resistance high-tenacity high-resistance, high-resistance high-tenacity high-resistance high-. Especially, in the printing process, due to high density, the phenomenon of slurry overflow or fish scale spots is easy to generate because of difficult color paste permeation, so that the defects of uneven color on the surface of the pattern, whitish color, unclear outline and the like are caused.
CN201410330547.8 discloses a modified acrylate printing emulsion, which is obtained by emulsion polymerization of acrylate, methyl methacrylate, vinyl acetate, acrylonitrile, acrylic acid, an organosilicon modified monomer, a crosslinking monomer and a surface active monomer, wherein the organosilicon modified monomer is linear organopolysiloxane containing silicon-bonded alkenyl. According to the preparation method of the modified acrylate printing emulsion, the seed emulsion is prepared from the acrylate, the methyl methacrylate and the surface active monomer, the dosage of the emulsifier is reduced, the polymerization is stable, the gel rate is low, the prepared emulsion has water resistance, resilience, color fastness, washing fastness and soft hand feeling, but the main hard monomer is vinyl acetate, the residual monomer after the reaction is finished has large smell and is smelly, the residual monomer is treated by the vitamin C, the efficiency is low, and the emulsion is easy to turn yellow after being placed for a long time.
CN102108110A discloses a method for preparing an acrylate printing adhesive, which comprises the following steps of (1) weighing a common monomer, a special monomer, an emulsifier, an initiator and deionized water according to a ratio; (2) mixing 40-60% of deionized water, emulsifier and initiator weighed according to the proportion to prepare liquid I; (3) mixing the common monomer and the special monomer weighed according to the proportion with 60-40% of deionized water, an emulsifier and an initiator weighed according to the proportion, stirring and emulsifying to prepare liquid II; (4) dropwise adding the liquid II into the liquid I; (5) after the liquid II is added dropwise, stirring and carrying out heat preservation reaction to obtain an acrylate printing adhesive primary product; (6) and (3) dropwise adding ammonia water into the primary acrylate printing adhesive product to adjust the pH value to 6.5-7.5, and filtering to obtain the acrylate printing adhesive. However, the invention only uses the room temperature self-polymerization of acrylate as the main preparation means of the printing adhesive, and although the release of formaldehyde and the use of an emulsifier containing APEO are limited, the printing adhesive prepared by the invention has the reaction characteristics of hot adhesion, cold brittleness and poor wear resistance.
Disclosure of Invention
The invention provides a polyurethane modified acrylate pigment printing adhesive with high fastness, bright color, washing resistance, soft hand feeling and stain resistance and a preparation method thereof, in particular to a polyurethane modified acrylate pigment printing adhesive used for 500D polyester fabrics.
Preparation method of polyurethane modified acrylate pigment printing adhesive
The raw materials are mixed according to the weight ratio
(1) Preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 20-30 parts of polyester polyol with molecular weight of 2000, 40-60 parts of polytetrahydrofuran ether glycol and 5-10 parts of polycaprolactone polyol into a first reaction kettle, heating to 70-80 ℃, adding 5-15 parts of Hexamethylene Diisocyanate (HDI) and 30-60 parts of isophorone diisocyanate (IPDI) for reaction for 2-3 hours, then adding 5-10 parts of 2, 2-dimethylolpropionic acid (DMPA) for reaction for 1.5-2 hours, cooling to 65-75 ℃, adding 10-30 parts of hydroxyethyl methacrylate (HEMA) for reaction for 1-2 hours, cooling to room temperature, adding 3-8 parts of Triethylamine (TEA) for neutralization, then adding 100 parts of deionized water for high-speed dispersion and homogeneous phase, then adding 1-3 parts of ethylenediamine for chain extension, stirring for 0.5-1 hour, obtaining the waterborne polyurethane composite emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the waterborne polyurethane composite emulsifier obtained in the step (1) and 650-710 parts of deionized water into a second reaction kettle, heating to 40-50 ℃, quickly stirring, adding 310 parts of organosilicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75-80 ℃, and carrying out prepolymerization reaction for 2.5-3h to obtain an organosilicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 900 parts of deionized water, 1100 parts of Butyl Acrylate (BA) 620, 700 parts of Acrylic Acid (AA), 2-5 parts of Acrylic Acid (AA), 30-60 parts of Styrene (ST), 40-80 parts of Methyl Acrylate (MA), 10-20 parts of itaconic acid (ITA), 80-120 parts of the organic silicon prepolymer obtained in the step (2) and 10-40 parts of crosslinking monomer (TAM) into a third reaction kettle, and stirring until complete emulsification is achieved to obtain pre-emulsion;
(4) acrylate polymerization
Adding 300 parts of the pre-emulsion obtained in the step (3) and 150 parts of deionized water 100 into a fourth reaction kettle, stirring and heating to 70-80 ℃, adding 0.5-1 part of APS, then respectively dropwise adding 5-10 parts of the rest pre-emulsion obtained in the step (3), 20 mass percent of APS aqueous solution and 2-6 parts of 20 mass percent of sodium bisulfite aqueous solution at the same time, finishing the dropwise adding for 2.5-3 hours, keeping the temperature for 2-3 hours, cooling to room temperature, adding 20 mass percent of ammonia water to adjust the PH to 8-9, filtering, and discharging to obtain the polyurethane modified acrylate (emulsion) adhesive.
The polyurethane modified acrylate pigment printing adhesive, in particular to the polyurethane modified acrylate pigment printing adhesive used for 500D polyester fabrics, has the advantages of high fastness, bright color, washing resistance, soft hand feeling and stain resistance.
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 to be used as emulsion polymerization. Overcomes the defects that the stability of the synthetic polymer of the conventional emulsifier is poor, the synthetic polymer is easy to lose stability when being stored for a long time, heated and subjected to strong shearing action, the water resistance of the coating is insufficient due to the residual emulsifier, and the like. The polyurethane modified composite emulsifier is polymerized and emulsified with the organosilicon prepolymer, has good steric hindrance and spatial structure, and has good temperature resistance and shear stability when being used for emulsion polymerization to prepare latex particles. Due to the participation of DMPA, 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 reaction temperature is controlled in stages according to the steps, and each reactant and the auxiliary agent are added, so that the molecular activation and the large-amount polymerization are easily caused due to overhigh temperature, and the implosion is caused; the reaction temperature is too low or the reaction time is not enough, so that isocyanate residue is easily caused, and potential safety hazard is caused.
The invention adopts polytetrahydrofuran ether glycol and polycaprolactone polyol as polyurethane emulsifier synthesis monomers, and has the advantages of high reaction activity, narrow relative molecular mass, and low acid value and water content. The Polyurethane (PUDS) composite emulsifier is used for modifying the acrylate emulsion, and the product has better strength, ultraviolet resistance and heat resistance. Compared with adipic acid polyester, polycaprolactone polyol has better hydrolysis resistance and flexibility.
Introducing organosiloxane and a polyurethane group into a polyacrylate printing paste system, wherein the polyurethane group contains a large amount of COOH in DMPA, PU and an acrylate monomer are polymerized to form a waterborne polyurethane modified acrylate (PUA) molecule, the hydrophilic property of the waterborne polyurethane modified acrylate (PUA) molecule is enhanced, the water resistance of the waterborne polyurethane modified acrylate (PUA) molecule is weakened, organosilicon is introduced into a polymer chain segment, and the molecular chain of the organosilicon has Si-O-Si bonds. After the silane coupling agent is added into the acrylate emulsion, the Si-O-Si forms a stable cross-linked network structure, so that the cross-linking density can be improved, and a continuous and compact emulsion film can be formed; meanwhile, the Si-O-Si bond has excellent hydrophobic property, can be enriched on the surface of an adhesive film when forming a film, and blocks the permeation of water molecules to a certain extent, so that the water resistance of the printing paste after forming the film can be obviously improved; the polyurethane is introduced to improve the potential of the emulsion, improve the emulsifying capacity and reduce the gel introduced by the organic silicon monomer; meanwhile, the introduction of the organic silicon can also improve the application performances of the emulsion such as weather resistance, stain resistance, flexibility, elasticity and the like. Other polyurethane monomers have lower active groups and are difficult to couple with organic silicon, and the organic silicon monomer is easy to self-polymerize in the reaction process, so that the gel rate of the reaction is improved, and the performance improvement effect of the organic silicon molecules in emulsion particles is reduced.
During synthesis, 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 acetoacetylated ethylene glycol diester methacrylate (AAEM) is replaced, so that compared with TAM and AAEM, the molecular structure CH3 is more, and the yellowing resistance is stronger.
Example 1
(1) Preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 25 parts of polyester polyol with the molecular weight of 2000, 50 parts of polytetrahydrofuran ether glycol and 5 parts of polycaprolactone polyol into a first reaction kettle, heating to 75 ℃, adding 10 parts of Hexamethylene Diisocyanate (HDI) and 45 parts of isophorone diisocyanate (IPDI) for reaction for 2.5 hours, then adding 5 parts of 2, 2-dimethylolpropionic acid (DMPA) for reaction for 2 hours, cooling to 65 ℃, adding 15 parts of hydroxyethyl methacrylate (HEMA) for reaction for 2 hours, cooling to room temperature, adding 5 parts of Triethylamine (TEA) for neutralization, then adding 100 parts of deionized water for high-speed dispersion, then adding 3 parts of ethylenediamine for chain extension, and stirring for 0.5 hour to obtain the waterborne polyurethane composite emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the composite emulsifier obtained in the step (1) and 650 parts of deionized water into a second reaction kettle, heating to 45 ℃, rapidly stirring, adding 300 parts of organic silicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75 ℃, and carrying out prepolymerization reaction for 2.5 hours to obtain an organic silicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 1000 parts of deionized water, 650 parts of Butyl Acrylate (BA), 4 parts of Acrylic Acid (AA), 50 parts of Styrene (ST), 60 parts of Methyl Acrylate (MA), 15 parts of itaconic acid (ITA), 100 parts of the organic silicon prepolymer obtained in the step (2) and 30 parts of a crosslinking monomer (TAM) into a third reaction kettle, and stirring until complete emulsification is achieved to obtain a pre-emulsion;
(4) acrylate polymerization
And (3) adding 200 parts of the pre-emulsion obtained in the step (3) and 150 parts of deionized water into a fourth reaction kettle, stirring and heating to 75 ℃, adding 1 part of APS, then respectively dropwise adding the rest of the pre-emulsion obtained in the step (3), 5 parts of an APS aqueous solution with the mass percentage of 20% and 4 parts of a sodium bisulfite aqueous solution with the mass percentage of 20%, completing dropwise adding for 2.5 hours, preserving heat for 3 hours, cooling to room temperature, adding 20% ammonia water with the mass percentage to adjust the pH to 8.5, filtering, and discharging to obtain the polyurethane modified acrylate (emulsion) adhesive.
Example 2
(1) Preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 30 parts of polyester polyol with the molecular weight of 2000, 40 parts of polytetrahydrofuran ether glycol and 7 parts of polycaprolactone polyol into a first reaction kettle, heating to 80 ℃, adding 15 parts of Hexamethylene Diisocyanate (HDI) and 50 parts of isophorone diisocyanate (IPDI) for reaction for 2 hours, then adding 10 parts of 2, 2-dimethylolpropionic acid (DMPA) for reaction for 1.5 hours, cooling to 75 ℃, adding 20 parts of hydroxyethyl methacrylate (HEMA) for reaction for 2 hours, cooling to room temperature, adding 7 parts of Triethylamine (TEA) for neutralization, then adding 110 parts of deionized water for high-speed dispersion, then adding 2 parts of ethylenediamine for chain extension, and stirring for 1 hour to obtain the waterborne polyurethane composite emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the composite emulsifier obtained in the step (1) and 700 parts of deionized water into a second reaction kettle, heating to 40 ℃, rapidly stirring, adding 310 parts of organic silicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75 ℃, and carrying out prepolymerization reaction for 2.5 hours to obtain an organic silicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 900 parts of deionized water, 670 parts of Butyl Acrylate (BA), 5 parts of Acrylic Acid (AA), 40 parts of Styrene (ST), 70 parts of Methyl Acrylate (MA), 10 parts of itaconic acid (ITA), 120 parts of the organic silicon prepolymer obtained in the step (2) and 40 parts of a crosslinking monomer (TAM) into a third reaction kettle, and stirring until complete emulsification is achieved to obtain a pre-emulsion;
(4) acrylate polymerization
Adding 250 parts of the pre-emulsion obtained in the step (3) and 150 parts of deionized water into a fourth reaction kettle, stirring and heating to 75 ℃, adding 1 parts of APS, then respectively dropwise adding the rest of the pre-emulsion obtained in the step (3), 10 parts of an APS aqueous solution with the mass percentage of 20% and 6 parts of a sodium bisulfite aqueous solution with the mass percentage of 20% at the same time, finishing the dropwise adding for 2.5 hours, preserving the temperature for 3 hours, cooling to room temperature, adding 20% of ammonia water with the mass percentage to adjust the PH to 8-9, filtering, and discharging to obtain the polyurethane modified acrylate (emulsion) adhesive.
Example 3
(1) Preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 20 parts of polyester polyol with the molecular weight of 2000, 45 parts of polytetrahydrofuran ether glycol and 10 parts of polycaprolactone polyol into a first reaction kettle, heating to 75 ℃, adding 5 parts of Hexamethylene Diisocyanate (HDI) and 50 parts of isophorone diisocyanate (IPDI) for reaction for 2 hours, then adding 10 parts of 2, 2-dimethylolpropionic acid (DMPA) for reaction for 2 hours, cooling to 65 ℃, adding 30 parts of hydroxyethyl methacrylate (HEMA) for reaction for 2 hours, cooling to room temperature, adding 3 parts of Triethylamine (TEA) for neutralization, then adding 120 parts of deionized water for high-speed dispersion and homogenization, then adding 3 parts of ethylenediamine for chain extension, and stirring for 0.5 hour to obtain the waterborne polyurethane composite emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the composite emulsifier obtained in the step (1) and 710 parts of deionized water into a second reaction kettle, heating to 50 ℃, rapidly stirring, adding 300 parts of organic silicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75 ℃, and carrying out prepolymerization reaction for 2.5 hours to obtain an organic silicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 1000 parts of deionized water, 700 parts of Butyl Acrylate (BA), 4 parts of Acrylic Acid (AA), 30 parts of Styrene (ST), 40 parts of Methyl Acrylate (MA), 15 parts of itaconic acid (ITA), 100 parts of the organic silicon prepolymer obtained in the step (2) and 30 parts of a crosslinking monomer (TAM) into a third reaction kettle, and stirring until complete emulsification is achieved to obtain a pre-emulsion;
(4) acrylate polymerization
And (3) adding 270 parts of the pre-emulsion obtained in the step (3) and 120 parts of deionized water into a fourth reaction kettle, stirring and heating to 80 ℃, adding 0.7 part of APS, then respectively dropwise adding the rest of the pre-emulsion obtained in the step (3), 8 parts of an APS aqueous solution with the mass percentage of 20% and 4 parts of a sodium bisulfite aqueous solution with the mass percentage of 20%, completing dropwise adding for 2.5 hours, preserving heat for 3 hours, cooling to room temperature, adding 20% ammonia water with the mass percentage to adjust the pH value to 8-9, filtering, and discharging to obtain the polyurethane modified acrylate (emulsion) adhesive.
Example 4
(1) Preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 20 parts of polyester polyol with the molecular weight of 2000, 40 parts of polytetrahydrofuran ether glycol and 10 parts of polycaprolactone polyol into a first reaction kettle, heating to 80 ℃, adding 5 parts of Hexamethylene Diisocyanate (HDI) and 30 parts of isophorone diisocyanate (IPDI) for reaction for 3 hours, then adding 10 parts of 2, 2-dimethylolpropionic acid (DMPA) for reaction for 2 hours, cooling to 75 ℃, adding 30 parts of hydroxyethyl methacrylate (HEMA) for reaction for 2 hours, cooling to room temperature, adding 8 parts of Triethylamine (TEA) for neutralization, then adding 120 parts of deionized water for high-speed dispersion and homogenization, then adding 3 parts of ethylenediamine for chain extension, and stirring for 0.5 hour to obtain the waterborne polyurethane composite emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the composite emulsifier obtained in the step (1) and 650 parts of deionized water into a second reaction kettle, heating to 45 ℃, rapidly stirring, adding 310 parts of organic silicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75 ℃, and carrying out prepolymerization reaction for 2.5 hours to obtain an organic silicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 900 parts of deionized water, 680 parts of Butyl Acrylate (BA), 5 parts of Acrylic Acid (AA), 50 parts of Styrene (ST), 60 parts of Methyl Acrylate (MA), 20 parts of itaconic acid (ITA), 120 parts of the organic silicon prepolymer obtained in the step (2) and 40 parts of a crosslinking monomer (TAM) into a third reaction kettle, and stirring until complete emulsification is achieved to obtain a pre-emulsion;
(4) acrylate polymerization
And (3) adding 200 parts of the pre-emulsion obtained in the step (3) and 130 parts of deionized water into a fourth reaction kettle, stirring and heating to 75 ℃, adding 1 parts of APS, then respectively dropwise adding the rest of the pre-emulsion obtained in the step (3), 10 parts of an APS aqueous solution with the mass percentage of 20% and 6 parts of a sodium bisulfite aqueous solution with the mass percentage of 20% at the same time, finishing the dropwise adding for 2.5 hours, preserving the temperature for 3 hours, cooling to room temperature, adding 20% of ammonia water with the mass percentage to adjust the PH to 8-9, filtering, and discharging to obtain the polyurethane modified acrylate (emulsion) adhesive.
Example 5
(1) Preparation of waterborne Polyurethane (PUDS) composite emulsifier
Adding 30 parts of polyester polyol with the molecular weight of 2000, 45 parts of polytetrahydrofuran ether glycol and 10 parts of polycaprolactone polyol into a first reaction kettle, heating to 75 ℃, adding 15 parts of Hexamethylene Diisocyanate (HDI) and 45 parts of isophorone diisocyanate (IPDI) for reaction for 2.5 hours, then adding 5 parts of 2, 2-dimethylolpropionic acid (DMPA) for reaction for 2 hours, cooling to 70 ℃, adding 10 parts of hydroxyethyl methacrylate (HEMA) for reaction for 2 hours, cooling to room temperature, adding 7 parts of Triethylamine (TEA) for neutralization, then adding 110 parts of deionized water for high-speed dispersion, then adding 2 parts of ethylenediamine for chain extension, and stirring for 0.5 hour to obtain the waterborne polyurethane composite emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the composite emulsifier obtained in the step (1) and 700 parts of deionized water into a second reaction kettle, heating to 40 ℃, rapidly stirring, adding 300 parts of organic silicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75 ℃, and carrying out prepolymerization reaction for 2.5 hours to obtain an organic silicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 1000 parts of deionized water, 700 parts of Butyl Acrylate (BA), 5 parts of Acrylic Acid (AA), 60 parts of Styrene (ST), 50 parts of Methyl Acrylate (MA), 15 parts of itaconic acid (ITA), 100 parts of the organic silicon prepolymer obtained in the step (2) and 30 parts of a crosslinking monomer (TAM) into a third reaction kettle, and stirring until complete emulsification is achieved to obtain a pre-emulsion;
(4) acrylate polymerization
Adding 250 parts of the pre-emulsion obtained in the step (3) and 150 parts of deionized water into a fourth reaction kettle, stirring and heating to 75 ℃, adding 0.5 part of APS, then respectively dropwise adding the rest of the pre-emulsion obtained in the step (3), 6 parts of an APS aqueous solution with the mass percentage of 20% and 3 parts of a sodium bisulfite aqueous solution with the mass percentage of 20%, completing dropwise adding for 2.5 hours, preserving heat for 3 hours, cooling to room temperature, adding 20% ammonia water with the mass percentage to adjust the pH value to 8-9, filtering, and discharging to obtain the polyurethane modified acrylate (emulsion) adhesive.
And (3) experimental detection:
fabric: 500D oxford
Preparing pigment printing paste: 100 parts of the product of the embodiment 1-5 of the invention, 400 parts of ionized water, 20 parts of GA111 bright red pigment color paste and a proper amount of a thickening agent FS-2000 are respectively mixed and stirred uniformly according to the weight ratio, and the viscosity is 15000-17000 cps (Brookfield VII + viscometer, No. 6 rotor, 12 rpm), so as to prepare the pigment printing paste.
Comparative example
1. Printing paste GZ-101
2. Printing paste NR-101NH
Screen printing is adopted: drying at 160 ℃ and 170 ℃ for 2 minutes.
Test results
Fastness to dry and wet rubbing: according to GB/T3920-1997;
soaping fastness: according to GB/T3921.1-1997;
softness: the first part was determined according to GB/T18318-2001 "textile bending Properties: testing by the inclined plane method;
water resistance of the film: testing according to GB/T1733 + 1993 'determination method for water resistance of paint film';
stain resistance: padding polyester-cotton fabric with synthetic resin, (one-padding one-rolling), drying at 100 ℃, baking at 150 ℃, and drying for 3min, simultaneously immersing the polyester-cotton fabric and the polyester-cotton fabric which are not padded with resin into a 0.02g/L disperse dye bath, treating at 80 ℃ for 5min, washing, drying at 100 ℃, testing a K/S value, and calculating an apparent staining ratio, wherein the smaller the ratio, the better the staining resistance. The apparent staining ratio value = (K/S) A/(K/S) B, wherein (K/S) A is the K/S value of the padded resin fabric; (K/S) B is the K/S value of the non-padded resin web.
High temperature yellowing resistance: printing 500Gg/L resin on clean pure-surface bleaching cloth, drying at 100 ℃, baking at 180 ℃ for 2min, and cooling to test the yellowing index Y = [100 (1.30X-1.15Z) ]/Y of the bleaching cloth, wherein X, Y and Z are tristimulus values of the sample under the condition of a D65/10 light source. The larger the value of Y1, the more yellow the sample is.
And (3) testing the emulsifying capacity: and (3) gradually adding 10g of monomer into 10ml of PU solution with the mass fraction of 10% under stirring, continuing stirring for 5min after the addition is finished, pouring the obtained monomer emulsion into a 25ml measuring cylinder, and standing for 24h to observe the amount of precipitated water.
Water absorption of the coating film: 30mm by 30mm samples were cut from the film. Weighing the mass as M1, soaking in deionized water at room temperature, taking out the adhesive film after 24h, rapidly drying the surface moisture by using test paper, weighing the mass as M2, and calculating the water absorption of the film according to the following formula: water absorption = [ M2-M1)/M1 ] 100%.
And (3) testing mechanical properties: the elongation at break of the film was measured according to GB/T1040-1992, with a tensile rate of 100 mm/min.
Claims (2)
1. The preparation method of the polyurethane modified acrylate pigment printing adhesive for the dacron oxford fabric is characterized by comprising the following steps of:
the raw materials are mixed according to the weight ratio
(1) Preparation of aqueous polyurethane composite emulsifier
Adding 20-30 parts of polyester polyol with the molecular weight of 2000, 40-60 parts of polytetrahydrofuran ether glycol and 5-10 parts of polycaprolactone polyol into a first reaction kettle, heating to 70-80 ℃, adding 5-15 parts of hexamethylene diisocyanate and 30-60 parts of isophorone diisocyanate to react for 2-3 hours, then adding 5-10 parts of 2, 2-dimethylolpropionic acid to react for 1.5-2 hours, cooling to 65-75 ℃, adding 10-30 parts of hydroxyethyl methacrylate to react for 1-2 hours, cooling to room temperature, adding 3-8 parts of triethylamine to neutralize, then adding 120 parts of deionized water to carry out high-speed dispersion and homogeneous phase, then adding 1-3 parts of ethylenediamine, and stirring for 0.5-1 hour to obtain the waterborne polyurethane composite chain extension emulsifier;
(2) preparation of organosilicon prepolymer
Putting 82.5 parts of the waterborne polyurethane composite emulsifier obtained in the step (1) and 650-710 parts of deionized water into a second reaction kettle, heating to 40-50 ℃, quickly stirring, adding 310 parts of organosilicon monomers D4 and A-2120 after the emulsifier is uniformly dispersed, heating to 75-80 ℃, and carrying out prepolymerization reaction for 2.5-3h to obtain an organosilicon prepolymer;
(3) acrylic reactive monomer pre-emulsification
Adding 900 parts of deionized water, 1100 parts of butyl acrylate, 620 parts of butyl acrylate, 700 parts of acrylic acid, 2-5 parts of styrene, 40-80 parts of methyl acrylate, 10-20 parts of itaconic acid, 80-120 parts of the organic silicon prepolymer obtained in the step (2) and 10-40 parts of crosslinking monomer into a third reaction kettle, and stirring until complete emulsification is achieved to obtain pre-emulsion;
(4) acrylate polymerization
Adding 300 parts of the pre-emulsion obtained in the step (3) and 150 parts of deionized water 100 into a fourth reaction kettle, stirring and heating to 70-80 ℃, adding 0.5-1 part of APS, then respectively dropwise adding 5-10 parts of the rest pre-emulsion obtained in the step (3), 20 mass percent of APS aqueous solution and 2-6 parts of 20 mass percent of sodium bisulfite aqueous solution at the same time, finishing the dropwise adding for 2.5-3 hours, keeping the temperature for 2-3 hours, cooling to room temperature, adding 20 mass percent of ammonia water to adjust the PH to 8-9, filtering, and discharging to obtain the polyurethane modified acrylate adhesive.
2. The polyurethane modified acrylate pigment printing adhesive for the dacron oxford fabric obtained by the preparation method of claim 1.
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| CN115094650A (en) * | 2022-08-03 | 2022-09-23 | 浙江迎丰科技股份有限公司 | Digital printing short-process technology suitable for polyester cotton |
| CN115322706A (en) * | 2022-08-31 | 2022-11-11 | 福建华峰新材料有限公司 | Elastic and smooth adhesive and preparation method thereof |
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