CN104480711A - Modification finishing process of cellulose fibre fabric - Google Patents
Modification finishing process of cellulose fibre fabric Download PDFInfo
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- CN104480711A CN104480711A CN201410763326.XA CN201410763326A CN104480711A CN 104480711 A CN104480711 A CN 104480711A CN 201410763326 A CN201410763326 A CN 201410763326A CN 104480711 A CN104480711 A CN 104480711A
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- 0 C[*+]OI#C[U]*(*)(C(OC)O[Si](N)O*(OC*O)O[Si](*)OC)[U][Si](*)[N+] Chemical compound C[*+]OI#C[U]*(*)(C(OC)O[Si](N)O*(OC*O)O[Si](*)OC)[U][Si](*)[N+] 0.000 description 1
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Abstract
The invention discloses a modification finishing process of a cellulose fibre fabric. The technological process is as follows: by using gamma-aminopropyl triethoxysilane as a raw material, synthesising out poly-gamma-aminopropyl polyhedral oligomeric silsesquioxane POSS-NH2 with a regular octa-amino-group-containing cage structure through acidification catalysis, hydrolysis and condensation, preparing reactive multi-N-methoxyl cage-like silsesquioxane POSS-N(CH2(OH))2 through formylation reaction, and then carrying out padding cross-linking modification finishing, drying and roasting on the mixture solution of the cellulose fibre fabric and the POSS-N(CH2(OH))2, thus the elastic recovery performance of the finished cellulose fibre fabric is effectively improved, and with the increasing of the concentration of the POSS-N(CH2(OH))2, the (warp-directional and weft-directional) wrinkle recovery angles of the finished cellulose fibre fabric are obviously increased, thus improving the shrink-proof and wrinkle-proof performances of the fabric.
Description
Technical field
The present invention relates to the cellulose base fiber fabric modification technical field of Textile Manufacturing Industry, especially relate to textile fabric for cotton, sky silk, model, dyeing cloth and the (POSS-N (CH of viscose and BLENDED FABRIC thereof
2(OH))
2) mixture solution pads, cross-linking modified finishing technique.
Background technology
Along with the development of science and technology, the performance of the mankind to material proposes more higher requirements.Single organic material or inorganic material can not meet industry and the needs of social development, development of new, new material that hydrocarbon organic material and inorganic ceramic material performance can be taken into account, become the focus of current material science research.Silicones is with Si-O-Si for main chain, silicon atom is connected with cross-linking type half inorganic polymer of machine group, and its most outstanding performance is excellent thermo oxidative stability.Silsesquioxane SSQ (Silsesquioxane) refers to that all molecular structures are the special organo-silicon compound of (RSiO3/2) n (in molecule O:Si=3:2), compared with normal silicone, the large percentage of Si-O in its molecule-Si key, the overall performance of material is generally better than silicones.SSQ mainly contains the different molecular structure of general structure, trapezium structure and cage structure three kinds, and what wherein research application was maximum is cage type hexahedron structure.
Cage type hexahedron structure is similar to silicon dioxide structure, and this special stereochemical structure gives the performance of silesquioxane compound uniqueness, as high heat resistance and chemical stability and excellent dielectric properties.In recent years, the developed countries such as the U.S., Germany, Japan have carried out large quantifier elimination to SSQ, achieve gratifying progress, and have formed certain research scale.The research report of China to SSQ is less, but existing relevant report.
At present, overseas utilization cagelike silsesquioxane (English " Polyhedral oligomericsilsequi-oxane ", be called for short POSS) the novel nano reinforcing agent prepared, this nanometer strengthener is that a class had not only been had nanometer cagelike structure but also can have been carried out the new compound of side base functionalization by the method for chemistry.POSS functional monomer is the three-dimensional structure of organic-inorganic hybridized molecule, and have 1-8 reactive organic group, reactive group comprises amido, epoxy radicals, unsaturated double-bond, alkoxyl, hydroxyl, mercapto etc.Most of POSS monomer is single functional, only containing 1 reactive group, multi-functional POSS monomer contains the reactive group of more than 2 or 2, by suitable chemical reaction between reactive group, mutually change, various POSS functional monomer can be formed.Single functional POSS monomer joins in polymer by polymerization, graft reaction, and multi-functional POSS monomer can be used as effective crosslinking agent, thus significantly improves the multiple performances such as the heat of polymer, machinery and gas infiltration.
Cagelike silsesquioxane is the cage modle organic-inorganic hybrid molecule of the important nanoscale of a class, and its molecular formula is (RSiO1.5) n, and size is about 1 ~ 3nm, is considered to " the minimum silicon particle that may exist at present ".Due to the Structure and Properties that it is special, POSS (zero dimension) is considered to and one of nano material of imvite (two dimension), the same most prospect of CNT (one dimension), thus becomes one of focus of material science research.
Cage-type silsesquioxane, its structure and silica similar, be all the tridimensional polyhedral formed by the polynary ring of silica.Wherein a kind of (i.e. n=8) caged silsesquioxane is called T for short usually
8, it belongs to nanoscale structures unit, and its structural formula is as follows.
Cage-type silsesquioxane (POSS) take Si-O as inorganic core, this inorganic kernel gives material excellent mechanical performance, peripheral organic group then improves the compatibility between POSS and polymer, and reactive functionality can realize the chemical bonding effect between silsesquioxane and polymer.Therefore, although cage type POSS nanometer strengthener is similar to SiO
2structure, but it more has the feature being different from general nano particle, and its structure function feature is as follows.
(1) its molecular structure of hybrid structure in molecule: POSS is (RSiO1..5), between silica (SiO
2) and silicones (R
2siO) between, have the hexahedron inorganic framework core of Si-O nanostructured, periphery is surrounded by organic group, and therefore, POSS molecule itself is hybrid systems in the inorganic organic molecule on molecular level.
(2) nanometer size effect: cagelike silsesquioxane (POSS) particle has the large nanometer fine structure of specific area, wherein silicon atom distance (Si-Si) about 0.5nm in hexahedron inorganic framework core, peripheral by organic group spacing (R-R) about 1.5nm, close to polymer segment size.
(3) tailorability of structure: cage modle siloxanes is carried out side base functionalization by the method for chemistry, differential responses functional group or non-reactive functionality is connected at polyhedral summit place, thus oligomeric multiaspect silsesquioxane (POSS) derivatives monomer of obtained various different performance, give it reactive and functional, realize its structural tailoring.
(4) excellent compatibility: POSS has cage type core/shell structure, and its shell is generally 8 organo-functional groups, and wherein 7 functional groups are inertia organic group, and 1 for having the functional group of reactivity.Its organic group can realize the excellent compatibility with organic solvent and polymeric matrix.
(5) highly reactive: the POSS of functionalization not only can pass through blended but also can pass through copolymerization process, and POSS evenly and is stably dispersed in matrix polymer, thus the polymer nanocomposites of processability excellence.Just because of the nanoscale structures of POSS and derivative thereof and reactable and make it be used as novel nano reinforcing agent, to significantly improve and to improve the combination property of material.
The substituting group be positioned on the Si atom on POSS polyhedron summit can be various reactivity or non-reacted group, by changing the kind of the organic group be connected on Si end points, can give POSS reactive or functional, obtaining the R-POSS of desired properties.
Patent CN 101974227 A: " a kind of low-strees epoxy/organosilicon/POSS nano-hybrid material and its preparation method and application ", this invention relates to photoelectricity and chemical technology field, relates to a kind of low-strees epoxy/organosilicon/POSS nano-hybrid material and its preparation method and application.The nano-hybrid material of this invention is mainly used in the fields such as LED encapsulation material, optical protective material, circuit protection coating material, adhesive, coating.
Patent CN201310004033: " multifunctional POSS modified silicon rubber and preparation method thereof ", be characterized in by chemical copolymerization respectively by containing single/bis-/POSS of tri-/tetra-active function groups is incorporated in polysiloxane molecule chain, obtains the POSS modified silicon rubber of POSS as pendant groups, block and crosslinking points.POSS modified silicon rubber prepared by this invention, POSS is dispersed in silicone rubber matrix with real molecular level, there are excellent resistant of high or low temperature, mechanical performance, dielectric properties, can be used for automobile, electronics, building aspect and space material, national defence, space flight and aviation sophisticated technology field.
Patent CN 200910107167: " a kind of fluorin-containing POSS acrylate polymer and preparation method thereof and a kind of coating ", provides the preparation method of fluorin-containing POSS acrylate polymer and the coating containing fluorine POSS acrylate copolymer.Lower-cost POSS acrylate monomer, fluorinated acrylate monomer is adopted in its preparation method, and by controlling the addition sequence of fluorinated acrylate monomer, obtain the fluorin-containing POSS acrylate polymer that fluorinated acrylate construction unit is distributed in copolymer two ends, the coating obtained thus there is low-surface-energy, high antifouling capacity.
Patent CN 201010203753: " a kind of POSS hydridization side acid squarine near-infrared absorption dye and preparation method thereof ", it joins in the mixed system of catalyst, acid binding agent, part and organic solvent by a kind of POSS monomer and halo side's acid cyanines monomer, after 130 DEG C ~ 140 DEG C additions or polymerisation 10 ~ 25h, obtain POSS hydridization side acid cyanines near infrared absorption material.POSS hydridization side acid squarine near-infrared absorption dye has stronger near infrared absorption performance, good heat, light and chemical stability, and resistant to aggregation, material compatibility is good, can be widely used in the fields such as nonlinear optics, photodynamic therapy, optical data storage, laser printing, bioprobe, near-infrared photography and solar cell.
Patent CN200910112356: " epoxy/POSS/ carbon fiber nanometer composite material and preparation method thereof for light sports equipment ", its be by impregnated carbon fiber in the butanone solution of the epoxy resin+curing agent+modification POSS stoichiometrically prepared, obtain the carbon fiber mesh face that epoxy, POSS are coated; The shape of product again this grid surface being curled into design is placed in mould and solidifies, and the demoulding obtains epoxy/POSS/ carbon fiber nanometer composite material.Adding by POSS, the impact resistance of matrix and elastic modelling quantity and hardness, wear-resistant fatigue aging and shock absorption etc. effectively improve.Every mechanical performance index is better than existing carbon fiber in epoxy composite.
In sum, the function of POSS mainly functional POSS monomer joins in polymer by polymerization, graft reaction, and multi-functional POSS monomer as effective crosslinking agent, thus significantly improves the multiple performances such as the heat of polymer, machinery and gas infiltration.
In view of this, the present inventor is according to the achievement of research both at home and abroad, on the basis through a series of research and test, the silsesquioxane nano reinforcing agent of this cage structure and cellulose base fiber fabric are carried out cross-linking modified, the elastic recovery of cellulose base fiber fabric is obtained effectively improve, thus improving shrinkproof, the crease resistance of fabric, this still belongs to the first time at home.
Summary of the invention
The object of the present invention is to provide a kind of cellulose base fiber fabric modification technique, make the cellulose fibre through the present invention's application and BLENDED FABRIC dyeing cloth and (POSS-N (CH
2(OH))
2) mixture solution pads, cross-linking modified arrangement, dry, bakes, after arranging, the elastic recovery of cellulose base fiber fabric obtains and effectively improves, along with (POSS-N (CH
2(OH))
2) increase of concentration, the obvious increase of the creasy recovery angle (warp-wise and broadwise) of cellulose base fiber fabric, thus shrinkproof, the crease resistance that improve fabric.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of cellulose base fiber fabric modification technique, technological process is: take gamma-aminopropyl-triethoxy-silane as raw material, by acidifying catalysis, hydrolysis, condensation, synthesize the poly-γ-aminopropyl silsesquioxane (POSS-NH of compound with regular structure containing the cage structure of eight amino
2), through the obtained reactive many-N methoxyl group cagelike silsesquioxane (POSS-N (CH of formolation reaction
2(OH))
2), then by cellulose base fiber fabric and (POSS-N (CH
2(OH))
2) mixture solution pads cross-linking modified arrangement, dry, bakes, after making arrangement, the elastic recovery of cellulose base fiber fabric obtains and effectively improves.
Described cellulose base fiber fabric is cotton, sky silk, model, the dyeing cloth of viscose and BLENDED FABRIC thereof.
The catalysis of described γ-aminopropyl siloxane, hydrolysis, condensation process is: in there-necked flask, first add raw material gamma-aminopropyl-triethoxy-silane, add the hydrochloric acid solution of mass percent 36.5% as catalyst, hydrochloric acid solution addition is the 0.1-0.5% of material quality, solvent is cyclohexane, cyclohexane and material quality are than being 1:1, deionized water slowly adds with 250ml/min speed and opens stirring, the mass ratio of gamma-aminopropyl-triethoxy-silane and deionized water is 3: 1, after 60 DEG C of reaction 72h, the mixture of the second alcohol and water processed in removal system is carried out with water knockout drum, solvent cyclohexane is removed by rotary evaporation, finally obtain white solid product and gather γ-aminopropyl siloxane POSS-NH
2.
Described reactivity many-N methoxyl groups silsesquioxane POSS-N (CH
2(OH))
2synthesis technique be: thermometer, magnetic agitation and still head are housed in conical flask, add the formalin of 30%W/W mass percent; The pH of formalin is adjusted to 9.3, will gather γ-aminopropyl silsesquioxane POSS-NH
2be dissolved in methyl alcohol MeOH, configuration 175g/L strength solution, progressively instills with 250ml/min speed; Poly-γ-aminopropyl silsesquioxane POSS-NH
2be 1:7.14 with the mass ratio of 30%W/W mass percent formalin, reaction mixture refluxes 16 hours at 90 DEG C; In course of reaction, the pH of reaction mixture remains on 9.3 ± 0.1, regulates with 10%W/W mass percent sodium carbonate liquor; Then mixture fractionation under 1.333kpa vacuum condition, obtains white powder thing; Semifinished product methyl alcohol MeOH is recrystallized, obtained many-N methoxyl group cagelike silsesquioxane POSS-N (CH
2(OH))
2.
Described cellulose base fiber fabric and (POSS-N (CH
2(OH))
2) mixture solution pads, cross-linking modified arrangement, dry, Steaming is: by many for reactivity-N methoxyl group cagelike silsesquioxane (POSS-(NCH
2(OH))
2) to dissolve with pure water and to be diluted to finite concentration (in dyeing and finishing technology, concentration take fabric weight as benchmark, o.w.f 0.8 ~ 15), bath raio 1:15 ~ 1:20, with citric acid (mass percent concentration 0.1%) and MgCl in cross-linking reaction
2(mass percent concentration 1.5%) is catalyst, at room temperature fully stirs mixture; By cellulose base fiber fabric and reactivity many-N methoxyl groups cagelike silsesquioxane (POSS-N (CH
2(OH))
2) mixture solution two soaks two and roll, pick-up 80%, then at 95 DEG C dry 3 minutes; After drying, then bake 1 minute at 165 DEG C.
After adopting such scheme, the silsesquioxane nano reinforcing agent of this cage structure and cellulose base fiber fabric carry out cross-linking modified by the present invention, the elastic recovery of cellulose base fiber fabric is obtained effectively improve, thus improve shrinkproof, the crease resistance of fabric.
Key and the beneficial effect of present invention process are expressed as follows:
One, can with domestic gamma-aminopropyl-triethoxy-silane (as: product of Wu great organosilicon company) for raw material, by acidifying, catalysis, hydrolysis, condensation, synthesize the poly-γ-aminopropyl silsesquioxane (POSS-NH of compound with regular structure containing the cage structure of eight amino
2), through the obtained reactive many-N methoxyl group cagelike silsesquioxane (POSS-N (CH of formolation reaction after it
2(OH))
2); Whole process comprises raw material and synthesis technique can domesticize completely, fundamentally breaks and abroad relies on external import to the blockade of China and POSS raw material;
Two, by cellulose base fiber fabric and (POSS-N (CH
2(OH))
2) mixture solution pads, cross-linking modified arrangement, dry, bake, its process conditions complete voluntarily; After arranging, the elastic recovery of cellulose base fiber fabric obtains and effectively improves, along with (POSS-N (CH
2(OH))
2) increase of concentration, the obvious increase of the creasy recovery angle (warp-wise and broadwise) of cellulose base fiber fabric, this provides new thinking and countermeasure for the shrinkproof, wrinkle resistant of cellulose base fiber fabric.
Detailed description of the invention
A kind of cellulose base fiber fabric modification technique that the present invention discloses, step is as follows:
The first step take gamma-aminopropyl-triethoxy-silane as raw material, by acidifying catalysis, hydrolysis, condensation, synthesizes the poly-γ-aminopropyl silsesquioxane (POSS-NH of compound with regular structure containing the cage structure of eight amino
2).
Hydrolysis, condensation reaction:
When Si-OH and Si-OH collides generation nucleophilic attack, remove hydrone and complete condensation course, form Si-O-Si key, by the process conditions of controlled hydrolysis, condensation, the POSS of compound with regular structure containing eight amino can be synthesized, the poly-γ-aminopropyl silsesquioxane (POSS-NH of cage structure
2) as follows.
Second step will gather γ-aminopropyl silsesquioxane (POSS-NH
2), through the obtained reactive many-N methoxyl group cagelike silsesquioxane (POSS-N (CH of formolation reaction
2(OH))
2), its course of reaction is as follows.
3rd step is by cellulose base fiber fabric and (POSS-N (CH
2(OH))
2) mixture solution pads, cross-linking modified arrangement, dry, bake.After arranging, the elastic recovery of cellulose base fiber fabric obtains and effectively improves, along with (POSS-N (CH
2(OH))
2) increase of concentration, the obvious increase of the creasy recovery angle (warp-wise and broadwise) of cellulose base fiber fabric, thus shrinkproof, the crease resistance that improve fabric.
Reactive many-N methoxyl group cagelike silsesquioxane (POSS-N (CH
2(OH))
2) with the cross-linking reaction of cellulose CSP, as follows:
The present invention is applied particularly to fabric: cotton dyeing cloth (plain cloth), and specification is through 32x32/ latitude 68x68.
1, poly-γ-aminopropyl siloxane (POSS-NH
2) preparation:
Raw material gamma-aminopropyl-triethoxy-silane is first added in there-necked flask, add the hydrochloric acid solution of mass percent 36.5% as catalyst, hydrochloric acid solution addition is the 0.1-0.5% of material quality, solvent is cyclohexane, cyclohexane and material quality are than being 1:1, deionized water slowly adds with 250ml/min speed and opens stirring, the mass ratio of gamma-aminopropyl-triethoxy-silane and deionized water is 3: 1, carry out the mixture of the second alcohol and water processed in removal system with water knockout drum after 60 DEG C of reaction 72h, solvent cyclohexane is removed by rotary evaporation, finally obtain white solid product and gather γ-aminopropyl siloxane (POSS-NH
2).
2, reactive many-N methoxyl group silsesquioxane (POSS-N (CH
2(OH))
2) synthesis:
Thermometer, magnetic agitation and still head are housed in conical flask, add formalin (30%W/W mass percent).The pH of formalin is adjusted to 9.3, will gather γ-aminopropyl silsesquioxane (POSS-NH
2) be dissolved in methyl alcohol (MeOH), configuration 175g/L strength solution, progressively (250ml/min) instillation.Poly-γ-aminopropyl silsesquioxane (POSS-NH
2) be 1:7.14 with the mass ratio of formalin (30%W/W mass percent), reaction mixture refluxes 16 hours at 90 DEG C.In course of reaction, the pH of reaction mixture remains on 9.3 ± 0.1, regulates with 10% (W/W mass percent) sodium carbonate.Then mixture fractionation under 1.333kpa vacuum condition, obtains white powder thing.Semifinished product methyl alcohol (MeOH) recrystallization, so obtained many-N methoxyl group cagelike silsesquioxane (POSS-N (CH
2(OH))
2).
3, cellulose base fiber fabric modification:
By many for reactivity-N methoxyl group cagelike silsesquioxane (POSS-N (CH
2(OH))
2) to dissolve with pure water and rarely respectively to select finite concentration (o.w.f 0.8,1.2,2.0,3.2.), bath raio 1:20, with citric acid (mass percent concentration 0.1%) and MgCl in cross-linking reaction
2(mass percent concentration 1.5%) is catalyst, at room temperature fully stirs mixture.Cotton dyeing cloth (plain cloth) and reactivity many-N methoxyl groups cagelike silsesquioxane (POSS-N (CH2 (OH)) 2) mixture solution two are soaked two and rolled, pick-up 80%, then at 95 DEG C dry 3 minutes.After drying, then bake 1 minute at 165 DEG C.
Reactive many-N methoxyl group cagelike silsesquioxanes (POSS-N (CH2 (OH)) 2) to the effect after cellulose CSP in table 1.
Dry creasing angle (CRA) is undertaken by ASTM method D-1296-98, measures warp, broadwise CRA value.Sample is at 20 DEG C, and relative humidity regulates 24 hours 65% time.
Reactive many-N methoxyl group the Polyhedral oligomeric silsesquioxanes of table 1 are to the modified effect of cellulose fibre
Claims (5)
1. a cellulose base fiber fabric modification technique, it is characterized in that technological process is: take gamma-aminopropyl-triethoxy-silane as raw material, by acidifying catalysis, hydrolysis, condensation, synthesize the poly-γ-aminopropyl silsesquioxane POSS-NH of compound with regular structure containing the cage structure of eight amino
2, through the obtained reactive many-N methoxyl group cagelike silsesquioxane POSS-N (CH of formolation reaction
2(OH))
2, then by cellulose base fiber fabric and POSS-N (CH
2(OH))
2mixture solution pads cross-linking modified arrangement, dry, bakes, completes arrangement.
2. a kind of cellulose base fiber fabric modification technique as claimed in claim 1, is characterized in that: described cellulose base fiber fabric is cotton, sky silk, model, the dyeing cloth of viscose and BLENDED FABRIC thereof.
3. a kind of cellulose base fiber fabric modification technique as claimed in claim 1, it is characterized in that: the catalysis of described γ-aminopropyl siloxane, hydrolysis, condensation process is: in there-necked flask, first add raw material gamma-aminopropyl-triethoxy-silane, add the hydrochloric acid solution of mass percent 36.5% as catalyst, hydrochloric acid solution addition is the 0.1-0.5% of material quality, solvent is cyclohexane, cyclohexane and material quality are than being 1:1, deionized water slowly adds with 250ml/min speed and opens stirring, the mass ratio of gamma-aminopropyl-triethoxy-silane and deionized water is 3: 1, after 60 DEG C of reaction 72h, the mixture of the second alcohol and water processed in removal system is carried out with water knockout drum, solvent cyclohexane is removed by rotary evaporation, finally obtain white solid product and gather γ-aminopropyl siloxane POSS-NH
2.
4. a kind of cellulose base fiber fabric modification technique as claimed in claim 1, is characterized in that: described reactivity many-N methoxyl groups silsesquioxane POSS-N (CH
2(OH))
2synthesis technique be: thermometer, magnetic agitation and still head are housed in conical flask, add the formalin of 30%W/W mass percent; The pH of formalin is adjusted to 9.3, will gather γ-aminopropyl silsesquioxane POSS-NH
2be dissolved in methyl alcohol MeOH, configuration 175g/L strength solution, progressively instills with 250ml/min speed; Poly-γ-aminopropyl silsesquioxane POSS-NH
2be 1:7.14 with the mass ratio of 30%W/W mass percent formalin, reaction mixture refluxes 16 hours at 90 DEG C; In course of reaction, the pH of reaction mixture remains on 9.3 ± 0.1, regulates with 10%W/W mass percent sodium carbonate liquor; Then mixture fractionation under 1.333kpa vacuum condition, obtains white powder thing; Semifinished product methyl alcohol MeOH is recrystallized, obtained many-N methoxyl group cagelike silsesquioxane POSS-N (CH
2(OH))
2.
5. a kind of cellulose base fiber fabric modification technique as claimed in claim 1, is characterized in that: described cellulose base fiber fabric and POSS-N (CH
2(OH))
2mixture solution is padded, cross-linking modified arrangement, and dry, Steaming is: by many for reactivity-N methoxyl group cagelike silsesquioxane POSS-(NCH
2(OH))
2dissolve with pure water and be diluted to finite concentration o.w.f0.8 ~ 15, bath raio 1:15 ~ 1:20, with mass percent concentration 0.1% citric acid and mass percent concentration 1.5%MgCl in cross-linking reaction
2for catalyst, at room temperature fully stir mixture; By cellulose base fiber fabric and reactivity many-N methoxyl groups cagelike silsesquioxane POSS-N (CH
2(OH))
2mixture solution two is soaked two and is rolled, pick-up 80%, then at 95 DEG C dry 3 minutes; After drying, then bake 1 minute at 165 DEG C.
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| CN105603764A (en) * | 2016-01-29 | 2016-05-25 | 辽东学院 | Finishing application of aminophenylsilsesquioxane tussah silk textile and modified finishing textile or fabric |
| CN105648744A (en) * | 2016-01-07 | 2016-06-08 | 江苏天章医用卫生新材料有限公司 | Preparation method of surgical drape with good washing fastness |
| CN107059409A (en) * | 2017-02-06 | 2017-08-18 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN110841566A (en) * | 2019-11-18 | 2020-02-28 | 湖北中烟工业有限责任公司 | High-efficiency anti-seepage water-carrying capsule capable of giving out brittle sound |
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| CN105484027A (en) * | 2016-01-08 | 2016-04-13 | 湖州市千金丝织厂 | Novel formaldehyde-free crease-resist finishing agent and finishing process thereof |
| CN105603764A (en) * | 2016-01-29 | 2016-05-25 | 辽东学院 | Finishing application of aminophenylsilsesquioxane tussah silk textile and modified finishing textile or fabric |
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