Fabric manufacturing process for printing through polystyrene foam

Abstract

The invention is applicable to the technical field of textile, and provides a fabric manufacturing process for printing through polystyrene foam, which comprises the following steps: S1, glue selection and blending; s2, pattern design and printing: designing a pattern by using computer design software, and coating glue on the cloth according to the shape and size of the pattern through electrostatic auxiliary printing equipment; s3, curing treatment; according to the cloth printing technology, fine patterns can be formed on the cloth, meanwhile, the back face of the cloth is kept flat and smooth, and the attractiveness and comfort of a product are improved; mechanical printing equipment is adopted, the processing efficiency is high, and compared with traditional embroidery printing, the production period can be remarkably shortened, and the production cost is reduced; by means of accurate printing equipment and a glue blending technology, a complex and fine pattern effect can be achieved, and the pattern presenting capacity is high; the used glue meets the environment-friendly requirement, a large number of needles, threads and dyes are not needed, and the method has certain advantages in the aspect of reducing waste and energy consumption.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of textiles, and particularly relates to a fabric manufacturing process through foaming glue printing. BACKGROUND

[0002] In the field of fabric printing, traditional processes such as embroidery and printing can present rich patterns and colors, but often have problems such as low processing efficiency and uneven back, especially the embroidery process, although the pattern is fine, but it needs to be operated on the fabric with needle and thread, which is time-consuming and laborious, and easy to form protrusions on the back of the fabric, affecting the overall appearance and comfort.

[0003] In order to overcome these defects, the industry has been exploring new printing processes, among which the method of printing by glue has gradually attracted attention. This method uses the adhesion and plasticity of glue to form patterns on the fabric, not only high processing efficiency, but also can keep the back of the fabric smooth and flat. However, the existing glue printing process still needs to be improved in terms of pattern fineness and level. SUMMARY

[0004] The present application provides a fabric manufacturing process through foaming glue printing, which aims to solve the above problems.

[0005] The present application is implemented as follows: a fabric manufacturing process through foaming glue printing, comprising the following steps: S1. Glue selection and preparation: 50-65wt% of water-based polyurethane-acrylate copolymer emulsion, 8-12wt% of modified nano-silica, 5-10wt% of modified cellulose nanowhisker, 0.5-2wt% of foaming agent (such as azodicarbonamide), 0.1-0.5wt% of foam stabilizer (such as sodium dodecyl sulfate), 1-3wt% of photoinitiator (such as TPO photoinitiator), 8-12wt% of pigment (phthalocyanine blue / titanium dioxide, etc.), the rest is deionized water and auxiliary agent (leveling agent, etc.), after mixing, first stir at 800-1000rpm for 30-40min to disperse uniformly, then mechanically foam at 2000-3000rpm for 3-5min, the mechanical foaming introduces air through high-speed shear force, forming a closed-cell structure with a pore size of 50-200μm, the expansion rate is controlled by the concentration of foaming agent and stirring speed; The nano-SiO2 is grafted with acrylate chains by silane coupling agent KH-570, and free radical copolymerization occurs with polyurethane-acrylate copolymer in the curing stage to form a three-dimensional network structure in the cell wall, thereby improving the mechanical strength. The hydroxyl groups (-OH) on the surface are hydrolyzed and condensed with the methoxyl groups of KH-570 to form Si-O-Si bonds, thereby reducing the inter-particle van der Waals force, preventing cell merging, improving the uniformity of cell wall thickness, and improving the cell compression strength. The modified cellulose nanowhiskers are used to stabilize the cells together: SiO2 provides rigid support, and cellulose whiskers impart heat-responsive shrinkage.

[0006] S2. Pattern design and printing: design the pattern using computer design software, and coat the glue on the fabric according to the shape and size of the pattern by electrostatic auxiliary printing equipment. The electrostatic auxiliary printing equipment uses a high-voltage electrostatic field to make the atomized glue droplets deposit in a targeted manner (such as an Epson nozzle modification system). S3. Curing treatment: S3.1 UV pre-curing: wavelength 365 nm, intensity 80-100 mW / cm², irradiation time 3-5 s; TPO decomposition radicals are initiated by UV to make the acrylate double bonds polymerize rapidly, forming a cross-linked shell layer on the cell surface layer, inhibiting the flow of glue, preventing pattern edge diffusion, and improving line precision. S3.2 Gradient temperature heating curing: 60°C→80°C→100°C.

[0007] Preferably, the preparation method of the modified nano-silica is as follows: Disperse nano-silica (30-50 nm) in an ethanol / water (1:1) solution, add silane coupling agent KH-570 (addition amount is 15-20% of the mass of nano-silica), and react at 55-65°C for 2h, then centrifuge and dry. The modified nano-silica is added in a gradient in the polymerization of the acrylic emulsion, and the final emulsion solid content is 40±1%, and the SiO2 dispersion degree is >95%.

[0008] Preferably, the modified cellulose nanowhisker is a cellulose nanowhisker grafted with poly-N-isopropyl acrylamide, and the grafting rate is 30–50wt%.

[0009] Preferably, the preparation method of the modified cellulose nanowhisker (CNW) is as follows: (a) Carboxyl modification of cellulose nanocrystals (CNW) surface (TEMPO oxidation method) Take 200 parts of cellulose nanowhisker aqueous dispersion (1.5-2.5wt%) by weight, and add 0.01-0.02 parts of TEMPO and 0.1 parts of NaBr. Stirring at 0-5°C, slowly add 10 portions of NaClO solution (effective chlorine 12%), control pH=10.5 (add 0.5M sodium hydroxide to maintain); After 2h reaction, add 5 portions of ethanol to terminate; Centrifuge (7500-8500rpm, 10-20min) to collect the precipitate, wash with deionized water for 3 times; Dialysis (3500 Da bag) for 48h to remove small molecular impurities, obtain carboxylated CNW (COOH-CNW) aqueous dispersion; (b) Introduce RAFT chain transfer agent on CNW surface Take 100 portions of carboxylated CNW aqueous dispersion (solid content 1-2wt%), add 1.5 portions of GMA, adjust pH=9 (sodium hydroxide solution).

[0010] Stirring at 55-65°C for 12h to make GMA epoxy group react with carboxyl group of COOH-CNW, introduce double bond; Add 0.2-0.4 portions of CPADB (RAFT agent), deoxygenate for 30-40min under nitrogen; Add 0.01 portions of AIBN (initiator), react for 24h under nitrogen protection at 65-75°C; Centrifuge the reaction solution (10000rpm, 20min), wash the precipitate with ethanol and water for 3 times respectively, dialysis for 72h to remove unreacted substances, freeze-drying to obtain RAFT-CNW solid powder; (c) RAFT polymerization to graft PNIPAM Dissolve 1 portion of RAFT-CNW and 4-6 portions of NIPAM monomer in 50 portions of anhydrous ethanol / water mixed solvent (volume ratio 1:1); Deoxygenate for 30-40min under nitrogen, add 0.2-0.4 portions of AIBN; Stirring at 65-75°C for 24h under nitrogen protection; Pour the reaction solution into ice ethyl ether to precipitate.

[0011] Centrifuge (8000rpm, 15-20min) to collect the precipitate, wash with acetone for 3 times to remove homopolymer; Dialysis (3500 Da bag, ethanol / water mixture) for 72h, freeze-drying.

[0012] Thermal response shrinkage: the grafted poly N-isopropyl acrylamide undergoes hydrophilic-hydrophobic phase transition at 32-35°C, the molecular chain shrinks and drives the cellulose skeleton to fold when heated, resulting in micro-volume shrinkage and forming a controllable concave structure with a depth of 5-20μm; Thixotropic thickening: rigid nanowhiskers form a network structure under low shear (colloid standing) (viscosity > 1000 cP), effectively inhibiting colloid flow, and dissociate under high shear (print head spraying) (viscosity < 200 cP), resulting in a sudden drop in viscosity (< 200 cP) and achieving high-precision line coating without halo.

[0013] Preferably, the electrostatic printing has a print head voltage of -3.0 ± 0.3 kV, a print head to fabric distance of 5-8 mm, the fabric is grounded to form an electric field, the electric field strength is 0.4-0.8 kV / mm, the ambient humidity is controlled at 30-50% RH, and the glue atomization particle size is 15-25 μm.

[0014] Preferably, the gradient temperature is specifically 60°C for 30 s, 80°C for 30 s, and 100°C for 60 s, with a heating rate of 2°C / s, and infrared radiation heating can be used; the gradient temperature avoids the instant collapse of the bubble, stabilizes the bubble structure at 60°C, and avoids rapid shrinkage; 80°C triggers the contraction of PNIPAM to form a three-dimensional recess, enhancing the stereoscopic effect of the pattern; 100°C completely polymerizes the acrylate, and the nanometer SiO2 and cellulose whiskers form an interpenetrating network; UV curing of the surface layer + infrared gradient curing of the deep layer realizes external shaping and internal shaping.

[0015] Preferably, the glue further contains 0.3-0.5 wt% of an ionic liquid (such as 1-ethyl-3-methylimidazolium tetrafluoroborate), which is pre-dissolved in ethanol (1:1 by volume) before being added to the glue, and the glue is stirred at 800-1000 rpm for 30-40 min; the ionic liquid reduces the electrical resistance of the glue, improves the efficiency of electrostatic atomization, is compatible with nanometer SiO2, and the cations are adsorbed on the surface of the nanometer SiO2, reducing the surface tension of the glue, the atomization voltage, and avoiding bubble rupture.

[0016] Preferably, the process further includes a post-processing step of washing the fabric and softening or waterproofing the fabric as needed.

[0017] Compared with the prior art, the embodiments of the present application have the following beneficial effects: Smooth back: due to the use of glue printing, the process can form fine patterns on the fabric while keeping the back smooth, improving the appearance and comfort of the product.

[0018] High processing efficiency: the process uses mechanized printing equipment, greatly improving the processing efficiency, and significantly shortening the production cycle and reducing the production cost compared with traditional embroidery printing.

[0019] Strong pattern rendering capability: through precise printing equipment and glue blending technology, the process can achieve complex and delicate pattern effects, providing more creative space for designers and making the product more personalized and creative.

[0020] Environmental protection: the glue used in this process meets the environmental protection requirements and will not pollute the environment. At the same time, since a large number of needles and dyes do not need to be used, this process also has certain advantages in reducing waste and energy consumption. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a flow chart of a fabric manufacturing process by foaming glue printing provided by the present application. DETAILED DESCRIPTION

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the description and claims of this application as well as the above-mentioned drawing figures are not to be limited in scope so as to encompass any subsequent alteration, modification, combination or equivalence in the feeds that may come to be known or used in this art having regard to the teachings of the present application. The terms "comprising", "having", "including", and "containing" used herein are meant to encompass the items listed thereafter as well as other items. The terms "first", "second", and the like used in the description and in the claims of this application signify the different instances of an embodiment and do not require or imply any actual order or sequence of steps.

[0023] Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are they necessarily mutually exclusive of other embodiments. It is expressly understood that the embodiments described herein are merely examples from a whole class of comparable embodiments which those skilled in the art will readily identify. The term "comprising" is intended to mean that the process or composition include the recited steps or components, and that additional steps or components can also be present.

[0024] The present application provides a fabric manufacturing process by foaming glue printing, as shown in Figure 1 , comprising the following steps: S1. Glue selection and preparation: 50-65wt% of water-based polyurethane-acrylate copolymer emulsion, 8wt% of modified nanosilica, 5wt% of modified cellulose nanowhisker, 0.5wt% of foaming agent (azobisformamide), 0.1wt% of foam stabilizer (sodium dodecyl sulfate), 1wt% of photoinitiator (TPO photoinitiator), 8wt% of pigment (titanium dioxide), 0.3wt% of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, pre-dissolved in ethanol (1:1 volume ratio) before adding to the glue), and the balance of deionized water and additives (BYK-349), after mixing, first stir at 800rpm for 30min to uniformly disperse, then mechanically foam at 2000rpm for 3min; S2. Pattern design and printing: design the pattern by using computer design software, and coat the glue on the fabric (polyester blended fabric, 100g / m2 in this embodiment) according to the shape and size of the pattern by using electrostatic auxiliary printing equipment; In the electrostatic printing, the voltage of the nozzle is -2.7kV, the distance between the nozzle and the fabric is 8mm, the fabric is grounded to form an electric field, the electric field strength is 0.34kV / mm, the environmental humidity is controlled at 30%RH, and the particle size of the glue mist is 15-25μm; S3. Solidification treatment: S3.1 UV pre-curing: wavelength 365nm, intensity 80mW / cm2 irradiation for 3s; S3.2 Gradient temperature heating and curing: 60℃ for 30s→80℃ for 30s→100℃ for 60s, the heating rate is 2℃ / s, and infrared radiation heating can be used.

[0025] S4. Post-treatment: washing the fabric, and softening or waterproofing the fabric according to the needs (softening treatment uses 5% amino silicone oil emulsion padding; waterproofing treatment uses fluorine-containing resin coating).

[0026] The preparation method of the modified nanosilica comprises the following steps: The nanosilica (30-50nm) is dispersed in an ethanol / water (1:1) solution, the silane coupling agent KH-570 is added (the addition amount is 15% of the mass of the nanosilica), and the reaction is carried out at 55℃ for 2h, and then centrifugal drying is performed. The modified nanosilica is gradiently added in the polymerization of the acrylic emulsion, and the final emulsion solid content is 40±1%, and the SiO2 dispersion degree is >95%.

[0027] Further, the modified cellulose nanowhisker is a cellulose nanowhisker grafted with poly-N-isopropyl acrylamide, and the grafting rate is 30–50wt%.

[0028] Still further, the preparation method of the modified cellulose nanowhisker (CNW) comprises the following steps: (a) Carboxyl modification on the surface of cellulose nanocrystals (TEMPO oxidation method) According to weight parts, 200 parts of cellulose nanowhisker aqueous dispersion (1.5wt%) is taken, 0.01 parts of TEMPO and 0.1 parts of NaBr are added; Stir at 0℃, slowly add 10 parts of NaClO solution (effective chlorine 12%), and control the pH value at 10.5 (add 0.5M sodium hydroxide to maintain); After the reaction is carried out for 2h, 5 parts of ethanol are added to terminate the reaction; Centrifugal (7500rpm, 10min) to collect the precipitate, and wash with deionized water for 3 times; Dialysis (3500 Da bag) for 48 h to remove small molecule impurities to obtain a carboxylated CNW (COOH-CNW) aqueous dispersion; (b) Introducing a RAFT chain transfer agent onto the surface of CNW Take 100 parts of the carboxylated CNW aqueous dispersion (solid content 1-2 wt%) and add 1.5 parts of GMA, and adjust the pH to 9 (NaOH solution).

[0029] Stir the reaction at 55°C for 12 h to allow the GMA epoxy group to react with the carboxyl group of COOH-CNW to introduce a double bond; Add 0.2 parts of CPADB (RAFT reagent) and deoxygenate for 30 min under nitrogen; Add 0.01 parts of AIBN (initiator) and react at 65°C under nitrogen for 24 h; Centrifuge the reaction solution (10000 rpm, 20 min), wash the precipitate with ethanol and water three times, dialyze for 72 h to remove unreacted substances, and freeze-dry to obtain a RAFT-CNW solid powder; (c) RAFT polymerization of grafted PNIPAM Dissolve 1 part of RAFT-CNW and 4 parts of NIPAM monomer in 50 parts of anhydrous ethanol / water mixed solvent (volume ratio 1:1); Deoxygenate for 30 min under nitrogen and add 0.2 parts of AIBN; Stir the reaction at 65°C under nitrogen for 24 h; Pour the reaction solution into ice ether to precipitate.

[0030] Centrifuge (8000 rpm, 15 min) to collect the precipitate and wash with acetone three times to remove homopolymer; Dialyze (3500 Da bag, ethanol / water mixture) for 72 h and freeze-dry.

[0031] Example 2 The present application provides a fabric manufacturing process by foaming offset printing, as shown in Figure 1 The process comprises the following steps: S1. Glue selection and preparation: 53wt% of water-based polyurethane-acrylate copolymer emulsion, 9wt% of modified nano-silica, 6wt% of modified cellulose nanowhisker, 1wt% of foaming agent (azodicarbonamide), 0.2wt% of foam stabilizer (sodium dodecyl sulfate), 1.5wt% of photoinitiator (TPO photoinitiator), 9wt% of pigment (titanium dioxide), 0.35wt% of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, pre-dissolved in ethanol (1:1 volume ratio) before adding to the glue), and the rest is deionized water and additives (BYK-349). After mixing, first stir at 850 rpm for 32 min to uniformly disperse, then mechanically foam at 2250 rpm for 3 min; S2. Pattern design and printing: use computer design software to design patterns, and use electrostatic auxiliary printing equipment to coat the glue on the fabric (polyester blended fabric, 100g / m² in this embodiment) according to the shape and size of the pattern; The nozzle voltage in the electrostatic printing is -2.7kV, the nozzle-fabric distance is 8mm, the fabric is grounded to form an electric field, the electric field strength is 0.34kV / mm, the environmental humidity is controlled at 30%RH, and the glue atomization particle size is 15-25μm; S3. Curing treatment: S3.1 UV pre-curing: wavelength 365nm, intensity 80mW / cm² irradiation for 3s; S3.2 Gradient temperature heating and curing: 60℃ for 30s→80℃ for 30s→100℃ for 60s, heating rate 2℃ / s, infrared radiation heating can be used.

[0032] S4. Post-treatment: wash the fabric, and perform softening treatment or waterproof treatment on the fabric as needed (softening treatment uses 5% amino silicone oil emulsion padding; waterproof treatment uses fluorine-containing resin coating).

[0033] The preparation method of the modified nano-silica is as follows: Disperse nano-silica (30-50nm) in an ethanol / water (1:1) solution, add silane coupling agent KH-570 (addition amount is 15-% of the mass of nano-silica), react at 55℃ for 2h, and centrifuge and dry; The modified nano-silica is added in gradient in the polymerization of the acrylic emulsion, and the final emulsion solid content is 40±1%, and the SiO2 dispersion degree is >95%.

[0034] Further, the modified cellulose nanowhisker is cellulose nanowhisker grafted with poly N-isopropyl acrylamide, and the grafting rate is 30–50wt%.

[0035] Further, the preparation method of the modified cellulose nanowhisker (CNW) is as follows: (a) Carboxylated modification of cellulose nanocrystal (CNW) surface (TEMPO oxidation method) Take 200 parts of cellulose nanowhisker aqueous dispersion (1.5 wt%) by weight, add 0.01 parts of TEMPO, 0.1 parts of NaBr; Stir at 0°C, slowly add 10 parts of NaClO solution (effective chlorine 12%), control pH = 10.5 (add 0.5M sodium hydroxide to maintain); After 2h of reaction, add 5 parts of ethanol to terminate; Centrifuge (7500rpm, 10min) to collect the precipitate, and wash with deionized water for 3 times; Dialysis (3500 Da bag) for 48h to remove small molecular impurities, and obtain carboxylated CNW (COOH-CNW) aqueous dispersion; (b) Introducing RAFT chain transfer agent to CNW surface Take 100 parts of carboxylated CNW aqueous dispersion (solid content 1-2 wt%), add 1.5 parts of GMA, and adjust pH = 9 (NaOH solution).

[0036] Stir at 55°C for 12h to make GMA epoxy group react with the carboxyl group of COOH-CNW, and introduce double bond; Add 0.2 parts of CPADB (RAFT reagent), and deoxygenate for 30min under nitrogen; Add 0.01 parts of AIBN (initiator), and react for 24h at 65°C under nitrogen protection; Centrifuge the reaction solution (10000rpm, 20min), wash the precipitate with ethanol and water for 3 times respectively, dialyze for 72h to remove unreacted substances, and freeze-dry to obtain RAFT-CNW solid powder; (c) RAFT polymerization to graft PNIPAM Dissolve 1 part of RAFT-CNW and 4 parts of NIPAM monomer in 50 parts of anhydrous ethanol / water mixed solvent (volume ratio 1:1); Deoxygenate for 30min under nitrogen, and add 0.2 parts of AIBN; Stir and react for 24h at 65°C under nitrogen protection; Pour the reaction solution into ice ethyl ether to precipitate.

[0037] Centrifuge (8000rpm, 15min) to collect the precipitate, and wash with acetone for 3 times to remove homopolymer; Dialyze (3500 Da bag, ethanol / water mixture) for 72h, and freeze-dry.

[0038] Example 3 The embodiment of the application provides a fabric manufacturing process through foaming offset printing, like Figure 1As shown, comprising the following steps: S1. Glue selection and preparation: 57.5wt% of water-based polyurethane-acrylate copolymer emulsion, 10wt% of modified nanosilica, 7.5wt% of modified cellulose nanowhisker, 1.25wt% of foaming agent (azodicarbonamide), 0.3wt% of foam stabilizer (sodium dodecyl sulfate), 2wt% of photoinitiator (TPO photoinitiator), 10wt% of pigment (titanium dioxide), 0.4wt% of ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, pre-dissolved in ethanol (1:1 by volume) before adding to the glue), and the rest is deionized water and additives (BYK-349). After mixing, first stir at 900 rpm for 35 min to uniformly disperse, then mechanically foam at 2500 rpm for 4 min; S2. Pattern design and printing: use computer design software to design patterns, and use electrostatic auxiliary printing equipment to coat the glue on the fabric (polyester blended fabric, 100g / m² in this embodiment) according to the shape and size of the pattern; The voltage of the electrostatic printing nozzle is -3.0kV, the nozzle to fabric distance is 6mm, the fabric is grounded to form an electric field, the electric field strength is 0.5kV / mm, the environmental humidity is controlled at 40%RH, and the glue atomization particle size is 15-25μm; S3. Curing treatment: S3.1 UV pre-curing: wavelength 365nm, intensity 90mW / cm² irradiation for 4s; S3.2 Gradient temperature heating and curing: 60℃ for 30s→80℃ for 30s→100℃ for 60s, heating rate 2℃ / s, infrared radiation heating can be used.

[0039] S4. Post-processing: wash the fabric, and perform softening treatment or waterproof treatment on the fabric as needed (softening treatment uses 5% amino silicone oil emulsion padding; waterproof treatment uses fluorine-containing resin coating).

[0040] The preparation method of the modified nanosilica is as follows: Disperse nanosilica (30-50nm) in an ethanol / water (1:1) solution, add silane coupling agent KH-570 (addition amount is 17.5% of the mass of nanosilica), react at 60℃ for 2h, and centrifuge and dry; The modified nanosilica is added in gradient in the polymerization of the acrylic emulsion, and the final emulsion solid content is 40±1%, and the SiO2 dispersion degree is >95%.

[0041] Further, the modified cellulose nanowhisker is cellulose nanowhisker grafted with poly N-isopropyl acrylamide, and the grafting rate is 30–50wt%.

[0042] Further, the preparation method of the modified cellulose nanowhisker (CNW) is as follows: (a) Carboxyl modification on the surface of cellulose nanocrystal (CNW) (TEMPO oxidation method) Take 200 parts of cellulose nanowhisker water dispersion (2wt%) by weight, and add 0.015 parts of TEMPO, 0.1 parts of NaBr; Stir at 2°C, slowly add 10 parts of NaClO solution (effective chlorine 12%), control pH=10.5 (add 0.5M sodium hydroxide to maintain); After 2h of reaction, add 5 parts of ethanol to terminate; Centrifuge (8000rpm, 15min) to collect the precipitate, and wash with deionized water for 3 times; Dialysis (3500 Da bag) for 48h to remove small molecular impurities, and obtain carboxylated CNW (COOH-CNW) water dispersion; (b) Introducing RAFT chain transfer agent on the surface of CNW Take 100 parts of carboxylated CNW water dispersion (solid content 1-2wt%), add 1.5 parts of GMA, and adjust pH=9 (NaOH solution).

[0043] Stir at 55-65°C for 12h to make the GMA epoxy group react with the carboxyl group of COOH-CNW, and introduce double bond; Add 0.3 parts of CPADB (RAFT reagent), and deoxygenate for 35min under nitrogen; Add 0.01 parts of AIBN (initiator), and react for 24h at 70°C under nitrogen protection; Centrifuge the reaction solution (10000rpm, 20min), wash the precipitate with ethanol and water for 3 times respectively, dialyze for 72h to remove unreacted substances, and freeze-dry to obtain RAFT-CNW solid powder; (c) RAFT polymerization grafting PNIPAM Dissolve 1 part of RAFT-CNW and 5 parts of NIPAM monomer in 50 parts of anhydrous ethanol / water mixed solvent (volume ratio 1:1); Deoxygenate for 35min under nitrogen, and add 0.3 parts of AIBN; Stir and react for 24h at 70°C under nitrogen protection; Pour the reaction solution into ice ethyl ether to precipitate.

[0044] Centrifuge (8000rpm, 17.5min) to collect the precipitate, and wash with acetone for 3 times to remove homopolymer; Dialyze (3500 Da bag, ethanol / water mixture) for 72h, and freeze-dry.

[0045] Example 4 This invention provides a fabric manufacturing process using foam printing, such as... Figure 1 As shown, it includes the following steps: S1. Adhesive selection and formulation: 60wt% waterborne polyurethane-acrylate copolymer emulsion, 11wt% modified nano silica, 9wt% modified cellulose nano whiskers, 1.5wt% foaming agent (azodicarbonamide), 0.4wt% foam stabilizer (sodium dodecyl sulfate), 2.5wt% photoinitiator (TPO photoinitiator), 11wt% pigment (titanium dioxide), 0.4wt% ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, pre-dissolved in ethanol (1:1 volume ratio) before adding the colloid), the balance being deionized water and additives (BYK-349). After mixing, stir at 950 rpm for 38 min until uniformly dispersed, then mechanically foam at 2750 rpm for 5 min. S2. Pattern design and printing: The pattern is designed using computer design software, and the glue is applied to the fabric (in this embodiment, a polyester blended fabric with a weight of 100g / m²) according to the shape and size of the pattern using electrostatic assisted printing equipment. In the electrostatic printing process, the printhead voltage is -3.3kV, the distance between the printhead and the fabric is 5mm, the fabric is grounded to form an electric field with an electric field strength of 0.66kV / mm, the ambient humidity is controlled at 50%RH, and the adhesive atomization particle size is 15-25μm. S3. Curing process: S3.1 UV pre-curing: irradiation for 5 seconds at a wavelength of 365nm and an intensity of 100mW / cm²; S3.2 Gradient temperature rise thermosetting: 60℃ for 30s → 80℃ for 30s → 100℃ for 60s, heating rate 2℃ / s, infrared radiation heating can be used.

[0046] S4. Post-treatment: Clean the fabric and, if necessary, perform a softening or waterproofing treatment (softening treatment uses 5% amino silicone oil emulsion impregnation; waterproofing treatment uses fluorinated resin coating).

[0047] The preparation method of the modified nano-silica includes the following steps: Nano-silica (30-50nm) was dispersed in an ethanol / water (1:1) solution, and silane coupling agent KH-570 (20% of the mass of nano-silica) was added. The mixture was reacted at 65℃ for 2 hours and then centrifuged and dried. The modified nano-silica was added dropwise in the acrylic emulsion polymerization process, resulting in an emulsion with a solid content of 40±1% and a SiO2 dispersion of >95%.

[0048] Furthermore, the modified cellulose nanocrystals are cellulose nanocrystals grafted with poly(N-isopropylacrylamide) at a grafting rate of 30–50 wt%.

[0049] Further, the preparation method of the modified cellulose nanowhisker (CNW) is as follows: (a) Carboxyl modification on the surface of cellulose nanocrystal (CNW) (TEMPO oxidation method) Take 200 parts of cellulose nanowhisker water dispersion liquid (2.5wt%) by weight, add 0.02 parts of TEMPO, and 0.1 parts of NaBr; Stir at 5°C, slowly add 10 parts of NaClO solution (effective chlorine 12%), control pH=10.5 (add 0.5M sodium hydroxide to maintain); After 2h of reaction, add 5 parts of ethanol to terminate; Centrifuge (8500rpm, 20min) to collect the precipitate, and wash with deionized water for 3 times; Dialysis (3500 Da bag) for 48h to remove small molecular impurities, and obtain carboxylated CNW (COOH-CNW) water dispersion liquid; (b) Introducing RAFT chain transfer agent on the surface of CNW Take 100 parts of carboxylated CNW water dispersion liquid (solid content 1-2wt%), add 1.5 parts of GMA, and adjust pH=9 (NaOH solution).

[0050] Stir at 65°C for 12h to make the GMA epoxy group react with the carboxyl group of COOH-CNW, and introduce double bond; Add 0.4 parts of CPADB (RAFT reagent), and deoxygenate for 40min under nitrogen; Add 0.01 parts of AIBN (initiator), and react for 24h at 75°C under nitrogen protection; Centrifuge the reaction liquid (10000rpm, 20min), wash the precipitate with ethanol and water for 3 times respectively, dialyze for 72h to remove unreacted substances, and freeze-dry to obtain RAFT-CNW solid powder; (c) RAFT polymerization grafting PNIPAM Dissolve 1 part of RAFT-CNW and 6 parts of NIPAM monomer in 50 parts of anhydrous ethanol / water mixed solvent (volume ratio 1:1); Deoxygenate for 40min under nitrogen, and add 0.4 parts of AIBN; Stir and react for 24h at 75°C under nitrogen protection; Pour the reaction liquid into ice ethyl ether to precipitate.

[0051] Centrifuge (8000rpm, 20min) to collect the precipitate, and wash with acetone for 3 times to remove homopolymer; Dialyze (3500 Da bag, ethanol / water mixture) for 72h, and freeze-dry.

[0052] Example 5 This invention provides a fabric manufacturing process using foam printing, such as... Figure 1 As shown, it includes the following steps: S1. Adhesive selection and formulation: 65wt% waterborne polyurethane-acrylate copolymer emulsion, 12wt% modified nano silica, 10wt% modified cellulose nano whiskers, 2wt% foaming agent (azodicarbonamide), 0.5wt% foam stabilizer (sodium dodecyl sulfate), 3wt% photoinitiator (TPO photoinitiator), 12wt% pigment (titanium dioxide), 0.5wt% ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, pre-dissolved in ethanol (1:1 volume ratio) before adding the colloid), the balance being deionized water and additives (BYK-349). After mixing, stir at 1000rpm for 40min until uniformly dispersed, then mechanically foam at 3000rpm for 5min. S2. Pattern design and printing: The pattern is designed using computer design software, and the glue is applied to the fabric (in this embodiment, a polyester blended fabric with a weight of 100g / m²) according to the shape and size of the pattern using electrostatic assisted printing equipment. In the electrostatic printing process, the printhead voltage is -3.3kV, the distance between the printhead and the fabric is 5mm, the fabric is grounded to form an electric field with an electric field strength of 0.66kV / mm, the ambient humidity is controlled at 50%RH, and the adhesive atomization particle size is 15-25μm. S3. Curing process: S3.1 UV pre-curing: irradiation for 5 seconds at a wavelength of 365nm and an intensity of 100mW / cm²; S3.2 Gradient temperature rise thermosetting: 60℃ for 30s → 80℃ for 30s → 100℃ for 60s, heating rate 2℃ / s, infrared radiation heating can be used.

[0053] S4. Post-treatment: Clean the fabric and apply a softening or waterproofing treatment as needed (softening treatment uses 5% amino silicone oil emulsion impregnation; waterproofing treatment uses fluorinated resin coating).

[0054] The preparation method of the modified nano-silica includes the following steps: Nano-silica (30-50nm) was dispersed in an ethanol / water (1:1) solution, and silane coupling agent KH-570 (20% of the mass of nano-silica) was added. The mixture was reacted at 65℃ for 2 hours and then centrifuged and dried. The modified nano-silica was added dropwise in the acrylic emulsion polymerization process, resulting in an emulsion with a solid content of 40±1% and a SiO2 dispersion of >95%.

[0055] Further, the modified cellulose nanowhisker is a cellulose nanowhisker grafted with poly-N-isopropyl acrylamide, and the grafting rate is 30-50 wt%.

[0056] Still further, the preparation method of the modified cellulose nanowhisker (CNW) is as follows: (a) Carboxyl modification on the surface of cellulose nanowhisker (TEMPO oxidation method) Take 200 parts of cellulose nanowhisker water dispersion (2.5 wt%) by weight, and add 0.02 parts of TEMPO and 0.1 parts of NaBr; Stir at 5°C, slowly add 10 parts of NaClO solution (effective chlorine 12%), and control pH=10.5 (add 0.5M sodium hydroxide to maintain); After reacting for 2h, add 5 parts of ethanol to terminate; Centrifuge (8500rpm, 20min) to collect the precipitate, and wash with deionized water for 3 times; Dialysis (3500 Da bag) for 48h to remove small molecular impurities, and obtain carboxylated CNW (COOH-CNW) water dispersion; (b) Introducing RAFT chain transfer agent on the surface of CNW Take 100 parts of carboxylated CNW water dispersion (solid content 1-2 wt%), and add 1.5 parts of GMA, and adjust pH=9 (NaOH solution).

[0057] Stir at 65°C for 12h to make the epoxy group of GMA react with the carboxyl group of COOH-CNW, and introduce double bond; Add 0.4 parts of CPADB (RAFT reagent), and deoxygenate for 40min under nitrogen; Add 0.01 parts of AIBN (initiator), and react for 24h at 75°C under nitrogen protection; Centrifuge the reaction solution (10000rpm, 20min), wash the precipitate with ethanol and water for 3 times respectively, dialyze for 72h to remove unreacted substances, and freeze-dry to obtain RAFT-CNW solid powder; (c) RAFT polymerization grafting PNIPAM Dissolve 1 part of RAFT-CNW and 6 parts of NIPAM monomer in 50 parts of anhydrous ethanol / water mixed solvent (volume ratio 1:1); Deoxygenate for 40min under nitrogen, and add 0.4 parts of AIBN; Stir and react for 24h at 75°C under nitrogen protection; Pour the reaction solution into ice ethyl ether to precipitate.

[0058] Centrifuge (8000rpm, 20min) to collect the precipitate, and wash with acetone for 3 times to remove homopolymer; Dialysis (3500 Da bag, ethanol / water mixture) 72 h, freeze-drying.

[0059] Comparative Example 1: Different from Example 3 is that the modified nanosilica is replaced by ordinary nanosilica.

[0060] Comparative Example 2: Different from Example 3 is that the modified cellulose nanowhisker is not added, and an equivalent amount of deionized water is added.

[0061] Comparative Example 3: Different from Example 3 is that the ionic liquid is not added, and an equivalent amount of deionized water is added.

[0062] Comparative Example 4: Different from Example 3 is that there is no gradient temperature curing (100°C constant temperature curing).

[0063] Comparative Example 5: Different from Example 3 is that there is no mechanical foaming (direct liquid coating printing).

[0064] Performance Test Test Items and Methods Pattern Fineness Test Method: Optical microscope measures the minimum printable line width (average of 10 measurements) Standard: Line edge definition (edge diffusion <5 μm is qualified).

[0065] Stereoscopic Height Difference Test Method: Laser confocal microscope scans the pattern cross-section Standard: Vertical distance between the highest protrusion and the lowest depression.

[0066] Cell Stability Test Method: SEM electron microscope observes cell structure integrity Standard: Cell integrity rate = number of unbroken cells / total number of cells x 100%.

[0067] Wear Resistance Test Method: Martin's abrasion tester (ASTM D4157-2013) Standard: Number of rubs when the pattern completely falls off.

[0068] Air Permeability Test Method: Fabric air permeability tester (GB / T 5453-1997) Standard: Air permeability per unit area (L / m² / s).

[0069] The test results are shown in Table 1 below: Table 1

[0070] From the above results, the application realizes the unification of high precision (≤0.1mm) and high stereoscopic effect (≥35μm) through the synergistic effect of modified nano-SiO2, cellulose whisker thermal response shrinkage and gradient curing process, and the bubble structure is stable, and the wear resistance is significantly better than that of the traditional process.

[0071] It should be noted that for the foregoing embodiments, in order to simply describe, they are all expressed as a series of action combinations, but those skilled in the art should know that the application is not limited by the order of the described actions, because according to the application, certain steps can be performed in other order or simultaneously. Secondly, those skilled in the art should know that the embodiments described in the specification all belong to preferred embodiments, and the actions and modules involved are not necessarily necessary for the application.

[0072] The above examples are only used to illustrate the technical solutions of the present application, and not to limit the protection scope of the application. Obviously, the described examples are only some of the embodiments of the present application, not all the embodiments. Based on these examples, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of the application to be protected.

Claims

1. A process for making a fabric printed with a foamed paste, characterized in that, The method comprises the following steps: S1. Glue selection and preparation: 50-65 wt% of water-based polyurethane-acrylate copolymer, 8-12 wt% of modified nano-silica, 5-10 wt% of modified cellulose nanowhisker, 0.5-2 wt% of foaming agent, 0.1-0.5 wt% of foam stabilizer, 1-3 wt% of photoinitiator, 8-12 wt% of pigment, and the balance of deionized water and auxiliary agents are mixed and uniformly dispersed, and then mechanically foamed; S2. Pattern design and printing: a pattern is designed by using computer design software, and the glue is coated on the fabric according to the shape and size of the pattern by using electrostatic auxiliary printing equipment; S3. Curing treatment: S3.1 UV pre-curing: irradiation for 3-5 s at a wavelength of 365 nm and an intensity of 80-100 mW / cm²; S3.2 Gradient temperature rising heat curing: 60°C→80°C→100°C.

2. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, The preparation method of the modified nano-silica comprises the following steps: The nano-SiO2 is dispersed in an ethanol / water solution, the silane coupling agent KH-570 is added, and reaction is carried out at 55-65°C for 2 h, and then centrifugal drying is performed; The modified nano-silica is gradiently added in acrylic emulsion polymerization, and the final emulsion solid content is 40±1%, and the SiO2 dispersity is >95%.

3. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, The modified cellulose nanowhisker is a cellulose nanowhisker grafted with poly-N-isopropyl acrylamide, and the grafting rate is 30-50 wt%.

4. The process for making a fabric printed with foamed glue as claimed in claim 3, wherein, The preparation method of the modified cellulose nanowhisker comprises the following steps: (a) TEMPO oxidation method is used to prepare carboxylated cellulose nanowhisker; (b) GMA ring-opening reaction is used to introduce double bonds on the surface of the carboxylated cellulose nanowhisker; (c) CPADB is used as a RAFT reagent to graft PNIPAM, and the reaction molar ratio is CNW:NIPAM:AIBN=1:4-6:0.2-0.

4.

5. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, In the electrostatic printing, the voltage of the nozzle is -3.0±0.3 kV, the distance between the nozzle and the fabric is 5-8 mm, the fabric is grounded to form an electric field, the environmental humidity is controlled to be 30-50% RH, and the glue atomization particle size is 15-25 μm.

6. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, The gradient temperature rising is specifically as follows: 60°C for 30 s, 80°C for 30 s, and 100°C for 60 s, the temperature rising rate is 2°C / s, and infrared radiation heating is adopted.

7. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, The foaming glue has a cell diameter of 50-200 μm, the cell wall contains a nano-SiO2 crosslinked network, and the wall thickness is 1-3 μm.

8. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, The glue further comprises 0.3-0.5 wt% of ionic liquid, the ionic liquid is pre-dissolved in ethanol before being added, and then the glue is added.

9. The process for making a fabric printed with foamed glue as claimed in claim 1, wherein, The method further comprises a post-treatment step: the fabric is washed, and the fabric is subjected to softening treatment or waterproof treatment as needed.

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