CN102465452A - Flame-retardant treatment method for cellulose fabric and flame-retardant cellulose fabric treated by the flame-retardant treatment method - Google Patents
Flame-retardant treatment method for cellulose fabric and flame-retardant cellulose fabric treated by the flame-retardant treatment method Download PDFInfo
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- CN102465452A CN102465452A CN2010105440442A CN201010544044A CN102465452A CN 102465452 A CN102465452 A CN 102465452A CN 2010105440442 A CN2010105440442 A CN 2010105440442A CN 201010544044 A CN201010544044 A CN 201010544044A CN 102465452 A CN102465452 A CN 102465452A
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Abstract
The invention discloses a flame-retardant treatment method for cellulose fabric and flame-retardant cellulose fabric treated by the flame-retardant treatment method. The flame-retardant treatment method is characterized in that at least one suitable cross-linking agent and at least one suitable phosphorus-based fire retardant are applied to cellulose fabric through a two-step method so that the treated cellulose fabric has strong flame retardancy and even still has good flame retardancy after multiple washing processes. In addition, the treated cellulose fabric retains high mechanical strength and has a good handle and a white appearance.
Description
Technical field
The present invention relates generally to the processing method of fabric, more particularly, relates to the flame-retardant finishing method of cellulosic fabric, and the fabric with fire resistance that utilizes this method to obtain.
Background technology
At present, two kinds of representational phosphorus base flame-retardant finishing methods are arranged on the market: " precondensate "/ammonia process and active phosphorus technology, the two is suitable for fabric, and effect is lasting.These two kinds of methods also can obtain having the wearing clothing of good appearance and performance.Yet these two kinds of methods all have the problem of release formaldehyde, and this defective can't let the people accept in many decades from now on, are exposed under the VOC that is disengaged by clothing the influence that possibly produce human body because People more and more is paid close attention to.Therefore, be badly in need of a kind of novel environmental protection and lasting flame-retardant finishing method.
At " precondensate "/NH
3In the technology (trade (brand) name " Proban "), fire retardant is present in the fibrillation of cotton fiber with the form of polymer, and not with cotton fiber in OH group chemical bond.Under the suitable applications step, this technology can give 100% COTTON FABRIC lasting anti-flammability, and the fabric that obtains has good hand feeling and intensity keeps.COTTON FABRIC is used suitable precondensate needs sufficient fiber to prepare humidity control suitable before (fabricpreparation), suitable padding/homogeneous application, suitable phosphorus-containing compound that interpolation is relevant with fibre property, the ammonia cure, control ammonification step guaranteeing enough polymer formation, and the efficient oxidation and the washing of the fabric after the processing.This method is very useful aspect the professional application that involves great expense, and for example fireman or other are exposed to the protective clothing that the staff wore under fire or the overheat condition.This method is not suitable for cotton carpet usually or is sold to the burr surface clothes (raised surfaceapparel) of ordinary consumer.The professional equipment (ammonia cure chamber) that the problem of this method comprises is expensive, need be of little use and twice drying steps of needs (U.S. Pat 4,494,951, US 4,078,101, US 5,238,464, BP GB 2,055, and 919).
The active phosphorus based flameproofing is the compound that reacts with cellulose as the cotton fiber main component (N-methylol dimethyl propyl amido phosphoric acid (N-methylol dimethyl phosphonopropionamide for example; MDPPA), trade (brand) name " Pyrovatex ").These compounds can be used for cotton fiber and the blending cotton fiber that has the low content synthetic fiber.This arrangement is applied to fabric usually after the painted stage, to promote into charcoal (charformation).The durability degree of arrangement makes the fabric of the processing that obtains be suitable for curtain, finishing material, bedding and protective clothing.The active phosphorus based flameproofing typically, in the presence of phosphoric acid catalyst through roll/dry by the fire/the roasting method uses.Arrangement adopts the methylated melamine resin to promote reagent to the combination of fiber/fixing sometimes, thus the enhancing fire resistance.Back cleaning (afterwash) normally needs, and alkali such as sodium carbonate commonly used carry out, and then are further rinsing and drying.The loss that helps to reduce fibre strength is cleaned in the back.The active phosphorus based method has the advantage that need not professional equipments such as ammonia cure unit, and compares with the precondensate method, and is little to the influence of dyestuff.Yet this method is compared with the precondensate method, and it causes more loss of strength.In addition, if in some washing, do not carry out according to chemicals supplier's specification, that may produce the problem of durability, and (DIN: DOS 2,136,407; Light industry science and technology economic information communique, 1975, No.9, pp.75-76).
Summary of the invention
The objective of the invention is to; The release formaldehyde that exists to flame-retardant finishing method in the prior art, the fabric after the arrangement be wash resistant and the serious problem of mechanical strength loss not; A kind of flame-retardant finishing method of cellulosic fabric is provided; The friendly flame-retardant mixture of its environment is to cellulosic fabric, thereby makes fiber have significantly washable fire resistance and less loss of strength.
Another object of the present invention is to, the cellulosic fabric with fire resistance is provided, it has washable fire resistance, and has kept pliable and tough, nonrigid feel, and satisfactory mechanical property has less loss of strength.
For reaching above-mentioned purpose; According to the present invention; A kind of flame-retardant finishing method of cellulosic fabric is provided; Use at least a crosslinking agent and at least a phosphine flame retardant to said cellulosic fabric, so that said crosslinking agent and said phosphine flame retardant form crosslinked polymer in cellulosic fabric through two-step method.
The flame-retardant finishing method of cellulosic fabric of the present invention; Preferably in two-step method; Through padding at least a crosslinking agent and at least a phosphine flame retardant are administered to said cellulosic fabric respectively, so that said crosslinking agent and said phosphine flame retardant form crosslinked polymer in cellulosic fabric with dry.
The flame-retardant finishing method of cellulosic fabric of the present invention, preferably, said pick up of padding cellulosic fabric described in the step is 50～100%.
The flame-retardant finishing method of cellulosic fabric of the present invention; Preferably; Said crosslinking agent is the compound that has at least three active groups, and said active group comprises amido, carbamate groups (urethanegroup), sulfydryl, imido grpup (imine group), imidazole radicals (imidazole group).
The flame-retardant finishing method of cellulosic fabric of the present invention; Preferably; Said phosphine flame retardant is the phosphorio compound that has at least two functional groups, and said functional group comprises undersaturated carbonyl, vinyl, acrylate-based (acrylate group), itrile group.
The flame-retardant finishing method of cellulosic fabric of the present invention; It is characterized in that; Also comprise the step that other auxiliary agent is administered to said cellulosic fabric, said other auxiliary agent comprises other fire retardant, dyestuff, anti wrinkling agent, blowing agent, buffer, pH stabilizing agent, fixative, anti-fouling agent, wetting agent, softener, waterproofing agent, detergent, brightener, emulsifying agent and surfactant.
For reaching above-mentioned purpose, according to the present invention, a kind of cellulosic fabric with fire resistance is provided also, adopt the flame-retardant finishing method of above-mentioned cellulosic fabric and obtain.
Cellulosic fabric with fire resistance of the present invention; Preferably, said cellulosic fabric is made up of following cellulose fibre: cotton, flax, jute, hemp, ramie, Lyocell (Lyocell), regeneration do not replace wood fibre or their blend.
The flame-retardant finishing method of cellulosic fabric of the present invention; Respectively crosslinking agent and phosphine flame retardant are administered to cellulosic fabric through two-step method; The arrangement process does not have formaldehyde; Fabric is after treatment not only repeatedly still keeping effective fire resistance behind the repeated washing, and has kept higher mechanical strength, shows good hand feeling and outward appearance.This two-step method can be fixed to cellulosic fabric with enough phosphorus, makes it repeatedly still have predetermined minimum fire resistance after the washing, thereby is used for different purposes purposes.Also can obtain higher fire resistance though use the phosphorio compound of recruitment, the product that obtains possibly have the rigidity that is difficult to accept.The flame-retardant finishing method of cellulosic fabric of the present invention does not then have the problem of this respect.
The flame-retardant finishing method of cellulosic fabric of the present invention can not produce formaldehyde in whole process, the serious decline of the mechanical performance of the cellulosic fabric after yet can not causing handling.Through padding in the method for using with drying, do not need at high temperature to bake, more energy-conservation.
Cellulosic fabric with fire resistance of the present invention can use separately, perhaps mix cotton with comprise that other commercial fiber of polyester fiber uses with together.Cellulosic fabric can be used for making suitable clothing dress ornament, comprises protective clothing (subduing like foundry work clothes and fire-fighting), child's nightwear, furnishings/finishing material (upholstery), bedding, carpet, curtain/hang from above fabric and tent etc.
The specific embodiment
The method for sorting of cellulosic fabric of the present invention comprises that water solution mixture that will contain crosslinking agent through two-step method and the water solution mixture that contains one or more phosphine flame retardants are administered to cellulosic fabric.In this two-step method, allow compound reaction time enough, and can be warming up to the temperature that is fit to improve reaction rate and removes moisture.
Be meant sense of touch at this used term " acceptable feel " through the cellulosic fabric that obtains after the flame-proof treatment.
Be meant the fabric that comprises cellulose fibre at this used term " cellulosic fabric ", cellulose fibre is the not replacement wood fibre of regeneration such as cotton, jute, flax, hemp, ramie, Lyocell, artificial fibre for example, and their blend.
Be meant the chemicals that is administered on the cellulosic fabric at this used term " fire retardant ".Being administered to " combustibility of reduction " on the fabric, is not that to mean textile material be can not burn.Term " fire retardant effective dose " is meant the effective dose that is used for particular web, so that the flammability test of fabric through requiring after handling.
I. crosslinking agent and phosphine flame retardant
As used at this, crosslinking agent be defined as have can with three of the reaction of this used phosphine flame retardant or any compound of multi-active base group more.For crosslinking agent (micromolecule, oligomer, polymer), the active group of the participation necleophilic reaction that it has is typical nucleophilic reagent, for example amido, carbamate groups, sulfydryl, imido grpup, imidazole radicals etc.
Preferred cross-linking agents is water misciblely maybe can be distributed in the water; And can (for example temperature be lower than 160 ℃ in gentle relatively condition; PH is between about 3～14) following and phosphine flame retardant reaction, and do not contain formaldehyde or known human body or other poisonous material of animal of being exposed to.
Preferably, the crosslinking agent covalent cross-linking of q.s is the phosphine flame retardant of q.s at least, with the sufficient fire resistance of the cellulosic fabric that is used for special-purpose.
As used at this, " phosphine flame retardant " be comprise at least one phosphorus atoms and at least two can with the phosphorio compound of the functional group of crosslinking agent covalent cross-linking, known numerous phosphorio compounds have fire resistance.At this preferred phosphine flame retardant is those phosphorio compounds that contain at least two functional groups, and functional group comprises unsaturated carbonyl, vinyl, acrylate-based, itrile group etc.Suitable phosphorio compound is phosphorus nitrogen acrylic acid ester (phosphonitrilic acrylate), phosphorimidic acid acrylamide (phosphorimidicacrylamide), halogenated alkyl phosphate ester (haloalkyl phosphonate), halogenated alkyl phosphate (haloalkylphosphonate), alkylene phosphonate ester (alkene phosphonate), acrylic acid phosphonate ester (acrylicphosphonate), vinyl phosphonate mercaptan ester, allyl phosphonitrile (allyl triphosphazene) and polymer thereof for example, and their derivative that has hydroxyl, carbonyl, vinyl, itrile group.
In one embodiment, phosphorio compound is connected combination with crosslinking agent through formation C-O, C-N, C-S.Preferably, phosphorio compound does not contain halogen, the noxious material that the cellulosic fabric after handling with minimizing discharges in fire.
For the final use of these fabrics, above-mentioned chemicals can pass through, and for example pads with 50～100% pick up (wet pickup) to be administered to fabric, is preferably 70～90% pick up.Yet, also can use other application technique.
Preferred phosphorio compound is that those can be dissolved or dispersed in the compound in the water.
II. cellulosic fabric
Any cellulosic fabric that contains hydroxyl all can be used above-mentioned chemical treatments.Cotton is preferred cellulose fibre.Other cellulose fibre comprises flax, jute, hemp, Lyocell, ramie, and the not replacement lignocellulose of regeneration, for example artificial fibre.
III. the flame-retardant finishing method of cellulosic fabric
Preferred processing method is for through separating continuous two-step method respectively with containing the solution of crosslinking agent and the solution of phosphorous-containigroups groups fire retardant pads.The first step is to pad the aqueous solution that contains crosslinking agent (micromolecule, oligomer and polymer), heat drying subsequently.In second step, pad the phosphorio compound (phosphine flame retardant) that has functional group, to react and condensation, in the structure of cellulose fibre, form insoluble polymer with aforementioned crosslinking agent.The polymer network that obtains is stable to conventional washing, and the cellulosic fabric that obtains has fire resistance.
Preferably, contain in the solution of solution and phosphorous-containigroups groups fire retardant of crosslinking agent and all do not comprise formaldehyde or other noxious material.Add other composition alternatively in two kinds of above-mentioned solution mixtures; These compositions comprise; But be not limited to other fire retardant, dyestuff, anti wrinkling agent, blowing agent, buffer, pH stabilizing agent, fixative, anti-fouling agent, humidizer, softening agents, waterproofing agent, detergent, brightener, emulsifying agent and surfactant.Other suitable fire retardant includes, but not limited to metal oxide, metal carbonate, halohydrocarbon, phosphine ester (phosphorus ester), phosphamidon, phosphate, aluminum trihydrate (aluminum trihydrate), and nitrogen-containing compound.
Crosslinking agent and phosphine flame retardant through pad use after, cellulosic fabric keeps time enough under enough temperature, so that crosslinking agent and phosphine flame retardant reaction.Cross-linking reaction can take place under the wet condition before redundant moisture is not got rid of, and also can take place under the dried state after redundant moisture is got rid of.
Then, the rinsing fiber cellulose fabric to be removing residue, unreacted chemical article alternatively, and drying.Yet,, also possibly not need this post rinse because used chemicals does not contain scent of or toxicity usually.In addition, any unreacted radical can be used to connect the molecule of other type on the reagent, for example connects through C-N.The example of this quasi-molecule comprises the shitosan that is generally used for giving the fiber antibiotic property.
Crosslinking agent is different with the cellulosic fabric that is processed because of application process with the concentration range of phosphine flame retardant in solution.For example, for burr surface (raised surface) clothes, possibly need more a large amount of retardant solutions to realize sufficient fire resistance.Same reason is adjusted solution concentration to be applied to other cellulosic fabric based on total liquid absorption, for example fibrefill, finishing material, child's nightwear, bedding, batting, protective clothing and curtain.The total amount of adding the flame-retardant mixture (comprising crosslinking agent and phosphine flame retardant) on the cellulosic fabric to depends on multiple factor, comprises the weight and the structure of flammable method of testing, fabric, and multiple mixed-level that maybe fiber in the BLENDED FABRIC.
For protective clothing (foundry work clothes with fire-fighting subdue), child's nightwear, furnishings/finishing material, bedding, carpet, curtain/hang from above fabric and tent etc.; The multiple application technique that can be used to use fire-retardant compound is arranged, and can accomplish through continuous or batch fashion and use.These application techniques comprise immersion (immersion), flood, drip (dripping), come down in torrents (cascading), spread all over fabric liquid circulation, pad, kiss roll, scraper.Flame-retardant mixture of the present invention can be applied to fiber, yarn, fabric or carpet, can prior to, back in or carry out other manufacturing or treatment step simultaneously, for example dye, twine, put in order, wiring, HEAT SETTING, tufting or braiding.Those skilled in the art can confirm the reaction condition reasonable setting in (amount of the phosphine flame retardant of interpolation, suitable temperature and reaction time), to combine crosslinking agent to phosphorio compound.
IV. estimate the method for fire-retardant cellulose fabric
The appropriate level that is used for the flame-retardant mixture of special-purpose depends on the ability of cellulosic fabric through the combustibility test of various criterion after the processing.The test of accepting for the people at present that is used for carpet is pill test (pilltest).Other fabric or final use, for example protective clothing or child's nightwear possibly need vertical flammable test or other flammable test.The testing scheme of these tests is known to those skilled in the art.Utilize these tests, people can confirm easily that different flame-retardant mixtures are used for the validity of a certain special-purpose.At this, preferred test is the strictest vertical flammable test (ASTM D6413-99 standard).Before carrying out vertical flammable test, after all samples drying, place under 20 ℃, the condition of relative humidity 70% and spend the night.
At the washing fastness (AATCC method of testing 61-2003 tests 2A) that has the cellulosic fabric of fire resistance through test after the standard wash repeatedly.
Utilize the TENSILE STRENGTH (according to ISO13934.1:1999 standard) of pulling force equipment I nstron 4411 tests through the cellulosic fabric of flame-proof treatment.
Adopt the CIE whitness index of the SF600 PLUS-CT spectrophotometer measurement of Datacolor Spectraflash, WI (EN ISO 105-J02:1997 (E) standard, AATCC method of testing 110-2005) through the cellulosic fabric of flame-proof treatment.
The present invention can combine following non-limiting example to understand better.
Embodiment 1
Weaving Pure Cotton Khaki Drills cloth fabric pick up with 70% in the aqueous solution of the sericin of mass fraction 10% is padded, then at 110 ℃ of heat dryings.Subsequently, this fabric pads with 70% pick up in the aqueous solution of the ethyl divinyl phosphoric acid (ethyl divinylphosphonate) of mass fraction 15%, then places room temperature (25 ℃) 48h.The fabric that obtains has good hand feeling.
Same fabric also uses Pyrovatex CP New mixture (according to supplier's specification) to handle to contrast.
Handle according to the present invention among table 1: the embodiment 1 and washing after the vertical flammable test result of fabric
Table 2: the tensile test result of fabric: flame-retardant finishing method fabric treated of the present invention among Pyrovatex CP New fabric treated, the embodiment 1 among contrast, the embodiment 1
The reservation of effective and durable fire resistance, good hand feeling and high-tensile strength can be provided for the fabric after handling according to the flame-retardant finishing method of cellulosic fabric of the present invention among conclusion: the embodiment 1.
Embodiment 2
Pure flax plain cloth is at the polyethyene diamine (polyethylenimine) of mass fraction 10% and the NaBH of mass fraction 1%
4Pick up with 60% in the aqueous solution of (brightening agent) is padded, then at 110 ℃ of heat dryings.Subsequently, fabric pads with 60% pick up in water-soluble the dissolving of the phosphorus nitrogen bisacrylamide trimer (phosphonitrilicdiacrylamide trimer) of mass fraction 20%, then 110 ℃ of dryings.
Same fabric also uses Pyrovatex CP New mixture (according to supplier's specification) and Proban method to handle, to be used as contrast.
Handle according to the present invention among table 3: the embodiment 2 and washing after the vertical flammable test result of fabric
Table 4: the whiteness of fabric (CIE) result: contrast, among the embodiment 2 respectively by Pyrovatex CP New, Proban, flame-retardant finishing method fabric treated of the present invention:
Flame-retardant finishing method according to cellulosic fabric of the present invention among conclusion: the embodiment 2 can provide effectively and lasting fire resistance, good surface appearance (acceptable whiteness) for fabric.
Claims (8)
1. the flame-retardant finishing method of a cellulosic fabric; It is characterized in that; Use at least a crosslinking agent and at least a phosphine flame retardant to said cellulosic fabric, so that said crosslinking agent and said phosphine flame retardant form crosslinked polymer in cellulosic fabric through two-step method.
2. the flame-retardant finishing method of cellulosic fabric according to claim 1; It is characterized in that; In the said two-step method; Through padding at least a crosslinking agent and at least a phosphine flame retardant are administered to said cellulosic fabric respectively, so that said crosslinking agent and said phosphine flame retardant form crosslinked polymer in cellulosic fabric with dry.
3. the flame-retardant finishing method of cellulosic fabric according to claim 2 is characterized in that, said pick up of padding cellulosic fabric described in the step is 50～100%.
4. according to the flame-retardant finishing method of each described cellulosic fabric of claim 1～3; It is characterized in that; Said crosslinking agent is the compound that has at least three active groups, and said active group comprises amido, carbamate groups, sulfydryl, imido grpup, imidazole radicals.
5. according to the flame-retardant finishing method of each described cellulosic fabric of claim 1～3; It is characterized in that; Said phosphine flame retardant is the phosphorio compound that has at least two functional groups, and said functional group comprises undersaturated carbonyl, vinyl, acrylate-based, itrile group.
6. the flame-retardant finishing method of cellulosic fabric according to claim 1; It is characterized in that; Also comprise the step that other auxiliary agent is administered to said cellulosic fabric, said other auxiliary agent comprises other fire retardant, dyestuff, anti wrinkling agent, blowing agent, buffer, pH stabilizing agent, fixative, anti-fouling agent, wetting agent, softener, waterproofing agent, detergent, brightener, emulsifying agent and the surfactant outside the said fire retardant.
7. the cellulosic fabric with fire resistance is characterized in that, adopts the flame-retardant finishing method of each described cellulosic fabric of claim 1～6 and obtains.
8. the cellulosic fabric with fire resistance according to claim 7; It is characterized in that said cellulosic fabric is made up of following cellulose fibre: cotton, flax, jute, hemp, ramie, Lyocell, regeneration do not replace wood fibre or their blend.
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Cited By (14)
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| CN102677359A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Curtain fabric |
| CN102677327A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Curtain fabric |
| CN102677291A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Yarn-dyed fabric |
| CN102677350A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Textile fabric |
| CN103334199A (en) * | 2013-06-14 | 2013-10-02 | 山西绿洲纺织有限责任公司 | Cannabis textile fabric and textile technology thereof |
| CN104153196A (en) * | 2014-08-12 | 2014-11-19 | 安徽一隆羽绒有限公司 | Flame retardant cotton finishing process |
| CN105274840A (en) * | 2014-06-26 | 2016-01-27 | 香港理工大学 | Flame retardation finishing agent, fabric flame retardation finishing method and flame retardation fabric |
| WO2016197146A1 (en) * | 2015-06-05 | 2016-12-08 | Cornell University | Modified cellulosic compositions having increased hydrophobicity and processes for their production |
| CN106758229A (en) * | 2016-11-24 | 2017-05-31 | 江苏爱西施科技服务咨询股份有限公司 | A kind of cotton goods fire retarding treating liquid containing modified sericin and preparation method thereof |
| CN108071014A (en) * | 2017-12-08 | 2018-05-25 | 天津工业大学 | A kind of preparation method of novel flame-retardant finishing agent and fire-retardant regenerated cellulose fabric |
| CN108342905A (en) * | 2017-01-24 | 2018-07-31 | 香港理工大学 | A kind of padding finishing method of water-fastness flame-retardant smoke inhibition cellulosic fabric |
| CN108951153A (en) * | 2018-07-18 | 2018-12-07 | 常州雅美特窗饰股份有限公司 | A kind of manufacturing method of light transmission inflaming retarding fabric |
| CN108978206A (en) * | 2018-07-04 | 2018-12-11 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of macromolecular graft modification inflaming retarding fabric |
| CN111648132A (en) * | 2020-06-11 | 2020-09-11 | 周晓珊 | Colorless-change environment-friendly composite flame retardant, and preparation method and application thereof |
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| CN102677359A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Curtain fabric |
| CN102677327A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Curtain fabric |
| CN102677291A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Yarn-dyed fabric |
| CN102677350A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Textile fabric |
| CN103334199A (en) * | 2013-06-14 | 2013-10-02 | 山西绿洲纺织有限责任公司 | Cannabis textile fabric and textile technology thereof |
| CN103334199B (en) * | 2013-06-14 | 2015-03-18 | 山西绿洲纺织有限责任公司 | Cannabis textile fabric and textile technology thereof |
| CN105274840A (en) * | 2014-06-26 | 2016-01-27 | 香港理工大学 | Flame retardation finishing agent, fabric flame retardation finishing method and flame retardation fabric |
| CN104153196A (en) * | 2014-08-12 | 2014-11-19 | 安徽一隆羽绒有限公司 | Flame retardant cotton finishing process |
| WO2016197146A1 (en) * | 2015-06-05 | 2016-12-08 | Cornell University | Modified cellulosic compositions having increased hydrophobicity and processes for their production |
| US11326303B2 (en) | 2015-06-05 | 2022-05-10 | Cornell University | Modified cellulosic compositions having increased hydrophobicity and processes for their production |
| US11913164B2 (en) | 2015-06-05 | 2024-02-27 | Cornell University | Modified cellulosic compositions having increased hydrophobicity and processes for their production |
| CN106758229A (en) * | 2016-11-24 | 2017-05-31 | 江苏爱西施科技服务咨询股份有限公司 | A kind of cotton goods fire retarding treating liquid containing modified sericin and preparation method thereof |
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| CN108071014A (en) * | 2017-12-08 | 2018-05-25 | 天津工业大学 | A kind of preparation method of novel flame-retardant finishing agent and fire-retardant regenerated cellulose fabric |
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Application publication date: 20120523 |