CN111575903B - High-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth and preparation method thereof - Google Patents
High-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth and preparation method thereof Download PDFInfo
- Publication number
- CN111575903B CN111575903B CN202010412916.3A CN202010412916A CN111575903B CN 111575903 B CN111575903 B CN 111575903B CN 202010412916 A CN202010412916 A CN 202010412916A CN 111575903 B CN111575903 B CN 111575903B
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- China
- Prior art keywords
- triethylene tetramine
- ethyl acrylate
- carboxymethyl cellulose
- copolymer
- reaction
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- 239000000835 fiber Substances 0.000 title claims abstract description 177
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 135
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 135
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 135
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 135
- 239000004744 fabric Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229960001124 trientine Drugs 0.000 claims abstract description 177
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 171
- 229920001577 copolymer Polymers 0.000 claims abstract description 149
- XTGPPGSXLLAPIH-UHFFFAOYSA-N C(C=C)(=O)OCC.C=C.C=C.C=C Chemical group C(C=C)(=O)OCC.C=C.C=C.C=C XTGPPGSXLLAPIH-UHFFFAOYSA-N 0.000 claims abstract description 124
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 90
- 230000003020 moisturizing effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 63
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 238000005886 esterification reaction Methods 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 34
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 32
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006068 polycondensation reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 25
- 238000007142 ring opening reaction Methods 0.000 claims description 25
- NCAVPEPBIJTYSO-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.OCCCCOC(=O)C=C NCAVPEPBIJTYSO-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- 239000007795 chemical reaction product Substances 0.000 claims description 22
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 claims description 21
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 claims description 21
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 claims description 21
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims description 21
- 229940074393 chlorogenic acid Drugs 0.000 claims description 21
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 claims description 21
- 235000001368 chlorogenic acid Nutrition 0.000 claims description 21
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 claims description 21
- 238000007259 addition reaction Methods 0.000 claims description 19
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 19
- 230000001965 increasing effect Effects 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 230000002787 reinforcement Effects 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 239000011686 zinc sulphate Substances 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 37
- 230000003712 anti-aging effect Effects 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000003110 anti-inflammatory effect Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 35
- 238000012360 testing method Methods 0.000 description 33
- 238000005303 weighing Methods 0.000 description 33
- 238000005452 bending Methods 0.000 description 28
- 238000012512 characterization method Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000004132 cross linking Methods 0.000 description 17
- 125000003700 epoxy group Chemical group 0.000 description 13
- 238000002791 soaking Methods 0.000 description 13
- 238000005520 cutting process Methods 0.000 description 11
- 125000004185 ester group Chemical group 0.000 description 11
- 238000000691 measurement method Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- 230000001815 facial effect Effects 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 239000000648 calcium alginate Substances 0.000 description 6
- 235000010410 calcium alginate Nutrition 0.000 description 6
- 229960002681 calcium alginate Drugs 0.000 description 6
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- CYCBPQPFMHUATH-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound OCCCCOCC1CO1 CYCBPQPFMHUATH-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000661 sodium alginate Substances 0.000 description 3
- 235000010413 sodium alginate Nutrition 0.000 description 3
- 229940005550 sodium alginate Drugs 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
- D04H1/4258—Regenerated cellulose series
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/492—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
- D06M2101/08—Esters or ethers of cellulose
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of masks, and discloses a high-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth and a preparation method thereof. The mask base cloth comprises the following raw materials in parts by weight: 88-92 parts of carboxymethyl cellulose fiber and 8-12 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer. The carboxymethyl cellulose fiber mask base cloth has high wet strength and softness, good hygroscopicity and moisture retention, is not easy to deform and damage after being soaked in wet water or essence, is easy to attach to the skin, and has good moisturizing function on the skin; in addition, the product has good antibacterial, anti-inflammatory and anti-aging effects.
Description
Technical Field
The invention relates to the technical field of masks, in particular to a high-flexibility high-moisture-retention carboxymethyl cellulose fiber mask base cloth and a preparation method thereof.
Background
The spunlace nonwoven fabric is a common mask base fabric in the current market, and the fibers which can be used for producing the spunlace nonwoven mask base fabric comprise tencel fibers, viscose fibers, cotton fibers, silk fibers, cuprammonium fibers and the like. The carboxymethyl cellulose fiber is cellulose ether prepared by carboxymethylation of viscose fiber, has good air permeability, biodegradability, biocompatibility, metal ion adsorption and the like, and is very suitable for manufacturing base cloth of the beauty mask. However, the mask base cloth made of carboxymethyl cellulose fiber has the problems of low wet strength and poor moisture absorption and retention.
Chinese patent publication No. CN201811489908.8 discloses an alginate fiber mask base cloth and a preparation method thereof. The mask base cloth consists of carboxymethyl cellulose fiber, calcium alginate fiber and sodium alginate, and the preparation method comprises the following steps: (1) opening the carboxymethyl cellulose fiber and the calcium alginate fiber respectively; (2) mixing the carboxymethyl cellulose fiber and the calcium alginate fiber which are opened in the step (1), and opening the mixture after mixing; (3) carding the mixed fibers obtained in the step (2) into a web, and then carrying out spunlace processing by using a spunlace machine; (4) and (4) soaking the mixed fiber prepared in the step (3) in a sodium alginate aqueous solution, and drying to obtain the sodium alginate fiber. The mask base cloth utilizes the characteristic that calcium alginate fibers contain a large number of hydrophilic groups, improves the water absorption capacity and the water retention capacity of the mask base cloth, but does not improve the wet strength, and the calcium alginate fibers are brittle and hard and have small strength, so that the flexibility of the carboxymethyl cellulose fiber mask base cloth can be influenced by blending the calcium alginate fibers with the carboxymethyl cellulose fibers.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth and a preparation method thereof. The mask base cloth has high wet strength, high softness, high hygroscopicity and high moisture retention.
The specific technical scheme of the invention is as follows:
the high-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth comprises the following raw materials in parts by weight: 88-92 parts of carboxymethyl cellulose fiber and 8-12 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer.
In the prior art, fibers in the carboxymethyl cellulose fiber facial mask base cloth are interwoven together through mutual entanglement and intermolecular hydrogen bonds, when the facial mask base cloth is wetted, the intermolecular hydrogen bonds are broken, and water molecules enter between the fibers entangled with each other, so that the fibers are loosely arranged, and the strength of the facial mask is reduced and the facial mask is easy to deform after being soaked in wet water or essence.
The invention adopts hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer to improve the wet strength of the mask base cloth, and the mechanism is as follows: the ethyl acrylate-triethylene tetramine copolymer participates in the crosslinking between carboxymethyl cellulose fibers through the esterification reaction between hydroxyl grafted on the molecular chain of the ethyl acrylate-triethylene tetramine copolymer and carboxyl in the carboxymethyl cellulose; in the absence of a catalyst, the hydrolysis rate of ester bonds is very low and almost negligible, so that the cross-linking between carboxymethyl cellulose fibers cannot be influenced by soaking in wet water or essence, and the mask base cloth has high wet strength.
While improving the wet strength, the ethyl acrylate-triethylene tetramine copolymer can endow the mask base cloth with better softness, hygroscopicity and moisture retention: because the molecular chain of the ethyl acrylate-triethylene tetramine copolymer is endowed with larger flexibility due to a large amount of-C-N-structures in the ethyl acrylate-triethylene tetramine copolymer, compared with the direct crosslinking among carboxymethyl cellulose fibers, the softness of the mask base cloth can be improved through the crosslinking of the ethyl acrylate-triethylene tetramine copolymer, so that the mask base cloth can be attached to the face skin more easily; in addition, a large amount of-CONH-and-NH-in the ethyl acrylate-triethylene tetramine copolymer can endow the copolymer with better hydrophilicity, so that the mask base cloth has better hygroscopicity and moisture retention.
Preferably, the preparation method of the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer comprises the following steps:
(a) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine to perform addition reaction, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1-1.5; removing methanol by reduced pressure distillation, and then carrying out polycondensation reaction;
(b) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to a molar ratio of 1: 7-8, and continuing to perform polycondensation until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(c) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether and the ethyl acrylate-triethylene tetramine copolymer obtained in the step (b) in N, N-dimethylformamide according to the mass ratio of 15-20: 1, and adding a ring-opening reaction catalyst to perform a ring-opening reaction; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; and after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer.
In the step (a), the reaction is divided into two stages of an addition reaction and a polycondensation reaction. And (3) an addition reaction stage, wherein the main reaction comprises the following two steps: (1) the carbon-carbon double bond in the ethyl acrylate and one amino group in the triethylene tetramine are subjected to addition reaction, and-NH-is connected to a carbon atom positioned at the tail end of an ethyl acrylate chain in the carbon-carbon double bond; (2) the carbon-carbon double bond in the ethyl acrylate and one imino group in the triethylene tetramine are subjected to addition reaction, and the-N-is connected to a carbon atom positioned at the tail end of an ethyl acrylate chain in the carbon-carbon double bond. And in the condensation polymerization stage, an amide bond is generated through the reaction of an ester group and an amino group, and the two reactants and two main products generated through the addition reaction are condensed to form the ethyl acrylate-triethylene tetramine copolymer.
In the step (a), the ratio of the ethyl acrylate to the triethylene tetramine needs to be controlled within a suitable range because: if the relative dosage of the ethyl acrylate is too large, more imino groups in the triethylene tetramine can be consumed, so that the content of imino groups in the synthesized ethyl acrylate-triethylene tetramine copolymer is low, the number of hydroxyl groups capable of being grafted is limited, and the combination between the copolymer and the carboxymethyl cellulose is influenced, so that the wet strength of the mask base cloth is low; if the relative dosage of the triethylene tetramine is too large, the branching degree of the ethyl acrylate-triethylene tetramine copolymer is low, the crosslinking degree of carboxymethyl cellulose fibers in the mask base cloth is low, the wet strength is low, intermolecular hydrogen bonds are formed among molecular chain entanglement and-CONH & lt- & gt of the ethyl acrylate-triethylene tetramine copolymer, the hydrophilicity of the copolymer is influenced, and the hygroscopicity and the moisture retention of the mask base cloth are poor. According to the invention, a large number of experiments are researched, the molar ratio of the ethyl acrylate to the triethylene tetramine is set to be 1: 1-1.5, and the mask base cloth can be ensured to have high wet strength, hygroscopicity and moisture retention.
In the step (b), carboxyl in the n-butyric acid and amino in the triethylene tetramine are subjected to condensation reaction to play a role of a blocking agent, so that the terminal amino in the ethyl acrylate-triethylene tetramine copolymer is prevented from continuously reacting with an ester group, the molecular chain of the copolymer is prevented from being further extended, the molecular chain of the copolymer is prevented from being entangled and cannot form effective crosslinking with carboxymethyl cellulose fiber, and the effect of the ethyl acrylate-triethylene tetramine copolymer on enhancing the softness and the wet strength of the mask base cloth is ensured. The n-butyric acid molecular chain has larger flexibility and smaller length, and cannot influence the softness of the mask when used as an end-capping agent.
In the step (c), the purpose of carrying out hydroxyl grafting modification on the ethyl acrylate-triethylene tetramine copolymer is as follows: the ethyl acrylate-triethylene tetramine copolymer is connected with the carboxymethyl cellulose through the esterification reaction between hydroxyl and carboxyl on the carboxymethyl cellulose, and further participates in the crosslinking between the carboxymethyl cellulose fibers. The principle is as follows: the 4-hydroxybutyl acrylate glycidyl ether contains both an ester group and an epoxy group, and the ester group is grafted to a copolymer molecular chain by the ring-opening reaction of the epoxy group and an imino group in an ethyl acrylate-triethylene tetramine copolymer; then the ester group is hydrolyzed to remove methacrylic acid, and the hydroxyl is left on the molecular chain of the copolymer.
The invention adopts 4-hydroxy butyl acrylate glycidyl ether as a grafting modifier for the following two reasons: (1) in the process of ring-opening reaction of epoxy group and imino group, secondary hydroxyl group is formed, but the present invention does not utilize the secondary hydroxyl group to link ethyl acrylate-triethylene tetramine copolymer with carboxymethyl cellulose, i.e. modifier containing epoxy group but not containing ester group is not used, because: after the compound with the epoxy group is grafted to the nitrogen atom in the ethyl acrylate-triethylene tetramine copolymer through the ring-opening reaction, the hydroxyl group formed by the ring-opening reaction is too close to the nitrogen atom, and after the hydroxyl group and carboxymethyl cellulose form a network, the chain length between adjacent branch points in the network is short, so that the softness of the mask base cloth is adversely affected. The 4-hydroxybutyl acrylate glycidyl ether contains both epoxy groups and ester groups, the distance between the ester groups and the epoxy groups is moderate, and when the hydroxyl groups and the carboxyl groups on the carboxymethyl cellulose are subjected to esterification reaction, the reactivity of the primary hydroxyl groups is higher than that of the secondary hydroxyl groups, so that the chain length between adjacent branch points in a formed network structure is moderate, the wet strength cannot be influenced due to the overlong chain length between the adjacent branch points, and the flexibility cannot be influenced due to the overlong chain length between the adjacent branch points. (2) According to the invention, a modifier containing hydroxyl and epoxy groups is not adopted for direct grafting, because under the ring-opening reaction condition of imino and epoxy groups, hydroxyl can also perform ring-opening reaction with epoxy groups, so that the modifier molecules react to cause consumption of the modifier, the grafting rate is reduced, the combination between the copolymer and carboxymethyl cellulose is further influenced, and the wet strength of the mask base cloth is lower.
In the step (c), it is necessary to control the ratio of 4-hydroxybutylacrylate glycidyl ether to the ethyl acrylate-triethylenetetramine copolymer within a suitable range for the following reasons: in the process of hydroxyl grafting modified ethyl acrylate-triethylene tetramine copolymer, the grafting rate is too low, so that the number of hydroxyl groups capable of forming ester groups on the copolymer and carboxymethyl cellulose fibers is too small, the crosslinking degree of the carboxymethyl cellulose fibers is low, and the wet strength of the mask base cloth is influenced; too high grafting ratio can result in too high crosslinking degree of the carboxymethyl cellulose fiber, and the softness and air permeability of the mask base cloth are affected. By controlling the mass ratio of the 4-hydroxybutyl acrylate glycidyl ether to the ethyl acrylate-triethylene tetramine copolymer to be 15-20: 1, the grafting ratio can be controlled within a proper range, so that the mask base cloth has high wet strength and good softness and air permeability.
Preferably, in the step (a), the temperature of the addition reaction is 18-23 ℃ and the time is 2.5-3 h.
Preferably, in the step (a), the temperature of the polycondensation reaction is 140-145 ℃, the pressure is 0.08-0.1 kPa, and the time is 2-2.5 h.
Preferably, in the step (b), the molar ratio of the triethylene tetramine to the n-butyric acid is 1: 7-8.
Preferably, in step (b), the polycondensation reaction proceeds as follows: reacting for 1-1.5 h at 140-145 ℃ and 0.08-0.1 kPa, and then increasing the pressure to 60-80 kPa to continue the reaction until the acid value is reduced to below 30.
Preferably, in step (c), the ring-opening reaction catalyst is at least one of triethylamine and tetrabutylammonium bromide.
Preferably, chlorogenic acid is further grafted on the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer, and the process of grafting the chlorogenic acid is as follows: dissolving a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer and chlorogenic acid in water, adding an esterification reaction catalyst, and carrying out esterification reaction at 100-105 ℃; after the reaction, ether was added for precipitation, and the precipitate was filtered and dried.
According to the invention, hydroxyl grafted on the ethyl acrylate-triethylene tetramine copolymer and carboxyl in chlorogenic acid are subjected to esterification reaction, the chlorogenic acid is grafted on the copolymer, and the effects of antibiosis, free radical removal and antioxidation of the chlorogenic acid are utilized to endow the facial mask base cloth with the anti-inflammation and anti-aging effects.
Preferably, the mass ratio of the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer to chlorogenic acid is 1: 10-12.
Preferably, the esterification catalyst is FeCl3、Fe2(SO4)3、ZnCl2、ZnSO4At least one of (1).
A method for preparing the high-flexibility high-moisture-retention carboxymethyl cellulose fiber mask base cloth comprises the following steps:
(1) opening carboxymethyl cellulose fiber;
(2) dispersing the carboxymethyl cellulose treated in the step (1) into water to prepare a fiber suspension;
(3) adding hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer into the fiber suspension, adding an esterification reaction catalyst, fully mixing, and carrying out esterification reaction at 90-95 ℃ for 1-1.5 h;
(4) wet-laying the carboxymethyl cellulose fiber treated in the step (3) to obtain a fiber web;
(5) and (4) carrying out spunlace reinforcement on the fiber web obtained in the step (4), and drying to obtain the high-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth.
Preferably, in step (3), the catalyst is FeCl3、Fe2(SO4)3、ZnCl2、ZnSO4At least one of (1).
Compared with the prior art, the invention has the following advantages:
(1) by adding the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer, the mask base cloth disclosed by the invention has high wet strength and softness, and good hygroscopicity and moisture retention, is not easy to deform and damage after being soaked in wet water or essence liquid, is easy to attach to the skin, and has a good moisturizing function on the skin;
(2) by grafting chlorogenic acid on the ethyl acrylate-triethylene tetramine copolymer, the mask base cloth has better antibacterial, anti-inflammatory and anti-aging effects.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are intended only to illustrate the invention in detail and are not intended to limit the scope of the invention in any way.
Example 1
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 20 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.1kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.1kPa, increasing the pressure to 60kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 15:1:0.48, and performing ring-opening reaction at 90 ℃ for 3 hours; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 92 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 8 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst FeCl3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 2
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 18 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1.5; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.09kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.09kPa, increasing the pressure to 70kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 20:1:0.63, and carrying out ring-opening reaction at 95 ℃ for 2.5 h; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 90 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 10 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst Fe2(SO4)3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 3
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 23 ℃ for 2.5 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1.3; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 145 deg.C under 0.08kPa for 2 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:8, continuously carrying out polycondensation reaction at 145 ℃ and under 0.08kPa, increasing the pressure to 80kPa after 1.5h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 18:1:0.57, and carrying out ring-opening reaction at 100 ℃ for 2 hours; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 88 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 12 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst ZnCl2After fully mixing, carrying out esterification reaction at 95 ℃ for 1 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 4
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl and chlorogenic acid graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 20 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.1kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.1kPa, increasing the pressure to 60kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 15:1:0.48, and performing ring-opening reaction at 90 ℃ for 3 hours; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(1.4) chlorogenic acid graft modification: dissolving the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.3) and chlorogenic acid in water according to the mass ratio of 1: 10-12, adding an esterification reaction catalyst, and carrying out an esterification reaction at 100-105 ℃, wherein the esterification reaction catalyst is at least one of FeCl3, Fe2(SO4)3, ZnCl2 and ZnSO 4; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl and chlorogenic acid graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 92 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 8 parts of hydroxyl and chlorogenic acid graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification catalyst FeCl3Air chargerAfter mixing, carrying out esterification reaction at 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 5
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 20 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 0.5; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.1kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.1kPa, increasing the pressure to 60kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 15:1:0.48, and performing ring-opening reaction at 90 ℃ for 3 hours; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 92 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 8 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst FeCl3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 6
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 18 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 2; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.09kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.09kPa, increasing the pressure to 70kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 20:1:0.63, and carrying out ring-opening reaction at 95 ℃ for 2.5 h; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 90 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 10 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst Fe2(SO4)3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 7
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 20 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.1kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.1kPa, increasing the pressure to 60kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 10:1:0.33, and performing ring-opening reaction at 90 ℃ for 3 hours; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 92 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 8 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst FeCl3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 8
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 18 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1.5; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.09kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.09kPa, increasing the pressure to 70kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 25:1:0.78, and carrying out ring-opening reaction at 95 ℃ for 2.5 h; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 90 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 10 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst Fe2(SO4)3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 9
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 20 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.1kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.1kPa, increasing the pressure to 60kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving 4-hydroxybutyl glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 15:1:0.48, and performing ring-opening reaction at 90 ℃ for 3 hours; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 92 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 8 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst FeCl3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Example 10
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) preparing a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer:
(1.1) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine, and carrying out addition reaction at 20 ℃ for 3 hours, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1; removing methanol by reduced pressure distillation, and performing polycondensation reaction at 140 deg.C under 0.1kPa for 2.5 h;
(1.2) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to the molar ratio of 1:7, continuously carrying out polycondensation reaction at 140 ℃ under 0.1kPa, increasing the pressure to 60kPa after 1h, and continuously reacting until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(1.3) hydroxyl grafting modification: dissolving N-butyl glycidyl ether, the ethyl acrylate-triethylene tetramine copolymer obtained in the step (1.2) and triethylamine in N, N-dimethylformamide according to the mass ratio of 15:1:0.48, and carrying out ring-opening reaction at 90 ℃ for 3 hours; after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer;
(2) opening 92 parts of carboxymethyl cellulose fiber;
(3) dispersing the carboxymethyl cellulose treated in the step (2) into water to prepare a fiber suspension;
(4) adding 8 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer prepared in the step (1) into the fiber suspension, and adding an esterification reaction catalyst FeCl3After being fully mixed, the mixture is subjected to esterification reaction at the temperature of 90 ℃ for 1.5 h;
(5) wet-laying the carboxymethyl cellulose fiber treated in the step (4) to obtain a fiber web;
(6) carrying out spunlace reinforcement on the fiber web obtained in the step (5), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(7) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (6), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(7.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(7.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(7.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (7.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(7.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
Comparative example 1
A carboxymethyl cellulose fiber mask base cloth is prepared by the following method and tested for performance:
(1) opening carboxymethyl cellulose fiber;
(2) dispersing the carboxymethyl cellulose treated in the step (1) into water to prepare a fiber suspension;
(3) wet-laying the fiber suspension obtained in the step (2) to obtain a fiber web;
(5) carrying out spunlace reinforcement on the fiber web obtained in the step (4), and drying to obtain carboxymethyl cellulose fiber mask base cloth;
(6) cutting a 2cm multiplied by 2cm sample from the carboxymethyl cellulose fiber mask base cloth obtained in the step (5), and performing thickness, gram weight, wet strength, softness, hygroscopicity and moisture retention tests, wherein:
(6.1) flexibility: the bending stiffness is used for characterization, and the smaller the bending stiffness is, the better the flexibility is;
(6.2) hygroscopicity: the method is characterized by comprising the following steps of weighing a sample at 20 ℃ and 65% relative humidity, soaking the sample in deionized water for 5min, taking out the sample, vertically suspending the sample until no continuous water drops, obtaining a soaked sample, weighing the weight of the soaked sample, and calculating the water absorption according to the following formula: water absorption (wetted sample mass-dry sample mass)/dry sample mass × 100%;
(6.3) moisture retention: characterized by the amount of water lost, measured by placing the wetted sample obtained in step (6.2) in a desiccator, weighing after 1h, calculating the mass reduction of the sample within 1 h;
(6.4) wet strength: the wet tensile strength is used for characterization, and the measurement method is that the test sample is soaked in deionized water for 15min at the temperature of 20 ℃ and the relative humidity of 65 percent, the test sample is taken out and vertically suspended until no continuous water drops drop, and the tensile strength is tested.
TABLE 1
Table 1 shows the thickness, grammage, wet tensile strength, bending stiffness, water absorption rate and water loss amount of the carboxymethyl cellulose fiber mask base cloths obtained in examples 1 to 10 and comparative example 1. Wherein wet tensile strength is used to characterize wet strength, the greater the wet tensile strength, i.e., the greater the wet strength; the bending stiffness is used for representing the flexibility, and the larger the bending stiffness is, the poorer the flexibility is; the water absorption rate is used for representing the hygroscopicity, and the higher the water absorption rate is, the better the hygroscopicity is; the amount of water lost was used to characterize the moisture retention, with greater amounts indicating poorer moisture retention.
In comparison with example 1, in comparative example 1, the hydroxyl group graft-modified ethyl acrylate-triethylene tetramine copolymer was not used, and the other preparation processes were the same as example 1. According to the data of table 1, the mask base fabric obtained in example 1 has a significantly reduced wet tensile strength and water absorption rate and a significantly increased bending stiffness and water loss amount, compared to those of comparative example 1. The analysis was as follows: (1) wet strength: in example 1, the ethyl acrylate-triethylene tetramine copolymer participates in the crosslinking between the carboxymethyl cellulose fibers through the esterification reaction between the hydroxyl groups grafted on the molecular chain of the ethyl acrylate-triethylene tetramine copolymer and the carboxyl groups in the carboxymethyl cellulose, and the hydrolysis rate of ester bonds is very low and almost negligible under the condition that no catalyst exists, so that the crosslinking between the carboxymethyl cellulose fibers is not influenced by wet water, and the mask base cloth prepared in example 1 has high wet strength; (2) flexibility: in example 1, the molecular chain is endowed with larger flexibility due to the-C-N-structure which is greatly existed in the ethyl acrylate-triethylene tetramine copolymer, so that compared with the direct crosslinking among carboxymethyl cellulose fibers in comparative example 1, the softness of the mask base cloth can be improved in example 1 through the crosslinking of the ethyl acrylate-triethylene tetramine copolymer, and the mask base cloth can be more easily attached to the facial skin; (3) moisture absorption and retention: a large amount of-CONH-and-NH-existing in the ethyl acrylate-triethylene tetramine copolymer can endow the copolymer with better hydrophilicity, so that the mask base cloth has better hygroscopicity and moisture retention.
Compared with example 1, chlorogenic acid is grafted on the ethyl acrylate-triethylene tetramine copolymer used in example 4 to provide the facial mask base cloth with antibacterial, anti-inflammatory and anti-aging effects, and other preparation processes are the same as those in example 1. According to the data in table 1, the wet tensile strength of the mask base cloth obtained in example 4 was significantly reduced, but the water absorption rate was significantly increased and the water loss was significantly reduced, as compared to example 1. The analysis was as follows: in example 4, the hydroxyl group grafted on the ethyl acrylate-triethylene tetramine copolymer and the carboxyl group in the chlorogenic acid are subjected to esterification reaction, so that the chlorogenic acid is grafted on the copolymer, partial hydroxyl group on the copolymer is consumed, ester groups formed between the copolymer and the carboxymethyl cellulose are reduced, the degree of crosslinking between the carboxymethyl cellulose fibers is reduced, and the wet strength of the mask base cloth is low; in addition, in example 4, the grafted chlorogenic acid contains more hydrophilic phenolic hydroxyl groups, and can improve the moisture absorption and retention of the mask base cloth.
In example 1, when the ethyl acrylate-triethylene tetramine copolymer was prepared in step (1.1), the molar ratio of ethyl acrylate to triethylene tetramine was 1:1, and in example 5, the molar ratio was changed to 1:0.5, and the other preparation processes were the same. According to the data of table 1, the wet tensile strength of the mask base cloth prepared in example 5 was significantly reduced compared to that of example 1. The analysis was as follows: in example 5, too much ethyl acrylate was used to consume more imino groups in triethylenetetramine, resulting in a lower content of imino groups in the synthesized ethyl acrylate-triethylenetetramine copolymer and limited hydroxyl groups capable of grafting, which affects the bonding between the copolymer and carboxymethyl cellulose, resulting in lower wet strength of the mask base cloth.
In example 2, when the ethyl acrylate-triethylene tetramine copolymer was prepared in the step (1.1), the molar ratio of ethyl acrylate to triethylene tetramine was 1:1.5, and in example 6, the molar ratio was changed to 1:2, and the other preparation processes were the same. According to the data in table 1, the mask base fabric obtained in example 6 has a significantly reduced wet tensile strength and water absorption and a significantly increased water loss, compared to example 2. The analysis was as follows: in example 6, the relative amount of triethylene tetramine is too large, which results in low branching degree of the ethyl acrylate-triethylene tetramine copolymer, low wet strength due to low crosslinking degree of carboxymethyl cellulose fiber in the mask base cloth, and intermolecular hydrogen bonds formed between molecular chains of the ethyl acrylate-triethylene tetramine copolymer and-CONH-, which affects the hydrophilicity of the copolymer, and thus the moisture absorption and retention of the mask base cloth are poor.
In example 1, when the hydroxyl group is graft-modified by the ethyl acrylate-triethylene tetramine copolymer in the step (1.3), the mass ratio of 4-hydroxybutyl acrylate glycidyl ether to the ethyl acrylate-triethylene tetramine copolymer is 15:1, and in example 7, the mass ratio is replaced by 10:1, and the other preparation processes are the same. According to the data of table 1, the wet tensile strength of the mask base cloth prepared in example 7 was significantly reduced compared to that of example 1. The analysis was as follows: in example 7, too little 4-hydroxybutylacrylate glycidyl ether was used in the relative amounts, resulting in too little grafting yield, and too little hydroxyl groups on the copolymer were able to form ester groups with the carboxymethylcellulose fibers, resulting in a low degree of crosslinking of the carboxymethylcellulose fibers, which affects the wet strength of the mask base.
In example 2, when the hydroxyl group is grafted and modified by the ethyl acrylate-triethylene tetramine copolymer in the step (1.3), the mass ratio of the 4-hydroxybutyl acrylate glycidyl ether to the ethyl acrylate-triethylene tetramine copolymer is 20:1, in example 8, the mass ratio is replaced by 25:1, and the other preparation processes are the same. According to the data in table 1, the mask base cloth obtained in example 8 has an increased wet tensile strength, but a significantly increased bending stiffness, compared to example 2. The analysis was as follows: in example 8, too much 4-hydroxybutylacrylate glycidyl ether was used in the relative amounts, resulting in too high a grafting yield and too high a degree of crosslinking of the carboxymethyl cellulose fibers, which, although increasing the wet strength of the mask base cloth to some extent, adversely affected the softness thereof.
In example 1, in the step (1.3), 4-hydroxybutyl acrylate glycidyl ether is used to graft-modify the ethyl acrylate-triethylene tetramine copolymer, and after hydrolysis, a hydroxyl graft-modified ethyl acrylate-triethylene tetramine copolymer is obtained, in example 9, 4-hydroxybutyl acrylate glycidyl ether is replaced by 4-hydroxybutyl glycidyl ether, and a hydroxyl graft-modified ethyl acrylate-triethylene tetramine copolymer is obtained without hydrolysis, and other preparation processes are the same. According to the data of table 1, the wet tensile strength of the mask base cloth prepared in example 9 was significantly reduced compared to that of example 1. The analysis was as follows: the modifier 4-hydroxybutyl glycidyl ether used in example 9 contains both hydroxyl and epoxy groups, and during the graft modification, in addition to the ring-opening reaction between imino group and epoxy group, hydroxyl group can also react with epoxy group, resulting in the consumption of modifier due to the reaction between modifier molecules, and the graft ratio is reduced, which in turn affects the combination between the copolymer and carboxymethyl cellulose, resulting in lower wet strength of the mask base cloth.
In example 1, in the step (1.3), 4-hydroxybutyl acrylate glycidyl ether is used to graft-modify the ethyl acrylate-triethylene tetramine copolymer, and after hydrolysis, the hydroxyl graft-modified ethyl acrylate-triethylene tetramine copolymer is obtained, and in example 10, 4-hydroxybutyl acrylate glycidyl ether is replaced by n-butyl glycidyl ether, and the other preparation processes are the same without hydrolysis. According to the data of table 1, the water absorption rate of the mask base fabric obtained in example 10 was significantly reduced and the bending rigidity and water loss amount were significantly increased, compared to example 1. The analysis was as follows: in example 1, carboxyl of carboxymethyl cellulose mainly reacts with primary hydroxyl generated by hydrolysis of 4-hydroxybutyl acrylate glycidyl ether, so that ethyl acrylate-triethylene tetramine copolymer is connected with carboxymethyl cellulose, while in example 10, carboxyl of carboxymethyl cellulose reacts with secondary hydroxyl generated by ring-opening reaction, so that chain length between adjacent branch points in a formed network structure is short, and softness of the mask base cloth is poor; in example 1, many secondary hydroxyl groups generated by the ring-opening reaction did not react with carboxyl groups in carboxymethyl cellulose, and they imparted a network structure with better hydrophilicity and imparted a mask base fabric with better moisture absorption and retention properties.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that the embodiments may be modified or changed without departing from the spirit of the present invention within the scope of the appended claims.
Claims (9)
1. The high-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth is characterized by comprising the following raw materials in parts by weight: 88-92 parts of carboxymethyl cellulose fiber and 8-12 parts of hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer; the preparation method of the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer comprises the following steps:
(a) preparing an ethyl acrylate-triethylene tetramine copolymer: mixing ethyl acrylate and methanol to prepare a mixed solution; under the protection of inert gas, dropwise adding the mixed solution into triethylene tetramine to perform addition reaction, wherein the molar ratio of the ethyl acrylate to the triethylene tetramine is 1: 1-1.5; removing methanol by reduced pressure distillation, and then carrying out polycondensation reaction;
(b) end capping: adding triethylene tetramine and n-butyric acid into a reaction system together according to a molar ratio of 1: 7-8, and continuing to perform polycondensation until the acid value is reduced to below 30; adding water into the reaction product for extraction, separating a water layer, and performing reduced pressure evaporation on the water layer to remove water, thereby obtaining the ethyl acrylate-triethylene tetramine copolymer;
(c) hydroxyl grafting modification: dissolving 4-hydroxybutyl acrylate glycidyl ether and the ethyl acrylate-triethylene tetramine copolymer obtained in the step (b) in N, N-dimethylformamide according to the mass ratio of 15-20: 1, and adding a ring-opening reaction catalyst to perform a ring-opening reaction; after the reaction is finished, adding ether to precipitate a reaction product, filtering, dissolving the precipitate in water, adding a sodium hydroxide solution, and performing hydrolysis reaction; and after the reaction is finished, adding diethyl ether for precipitation, filtering, and drying the precipitate to obtain the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer.
2. The highly flexible highly moisturizing carboxymethylcellulose fiber mask basecloth of claim 1, wherein:
in the step (a), the temperature of the addition reaction is 18-23 ℃, and the time is 2.5-3 h; and/or
In the step (a), the temperature of the polycondensation reaction is 140-145 ℃, the pressure is 0.08-0.1 kPa, and the time is 2-2.5 h.
3. The highly flexible and highly moisturizing carboxymethylcellulose fiber mask base fabric as claimed in claim 1, wherein in step (b), the polycondensation reaction is performed as follows: reacting for 1-1.5 h at 140-145 ℃ and 0.08-0.1 kPa, and then increasing the pressure to 60-80 kPa to continue the reaction until the acid value is reduced to below 30.
4. The highly flexible and highly moisture retaining carboxymethyl cellulose fiber mask base cloth according to claim 1, wherein in the step (c), the ring-opening reaction catalyst is at least one of triethylamine and tetrabutylammonium bromide.
5. The highly flexible and highly moisturizing carboxymethyl cellulose fiber mask base cloth according to claim 1, wherein chlorogenic acid is further grafted to the hydroxyl graft-modified ethyl acrylate-triethylene tetramine copolymer, and the process of grafting chlorogenic acid is as follows: dissolving a hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer and chlorogenic acid in water, adding an esterification reaction catalyst, and carrying out esterification reaction at 100-105 ℃; after the reaction, ether was added for precipitation, and the precipitate was filtered and dried.
6. The highly flexible and highly moisture-retaining carboxymethyl cellulose fiber mask base cloth according to claim 5, wherein the mass ratio of the hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer to chlorogenic acid is 1: 10-12.
7. The highly flexible highly moisturizing carboxymethylcellulose fiber mask base fabric as claimed in claim 5, wherein the esterification catalyst is FeCl3、Fe2(SO4)3、ZnCl2、ZnSO4At least one of (1).
8. A preparation method of the highly flexible and highly moisture-retaining carboxymethyl cellulose fiber mask base cloth according to any one of claims 1 to 7, comprising the following steps:
(1) opening carboxymethyl cellulose fiber;
(2) dispersing the carboxymethyl cellulose treated in the step (1) into water to prepare a fiber suspension;
(3) adding hydroxyl graft modified ethyl acrylate-triethylene tetramine copolymer into the fiber suspension, adding an esterification reaction catalyst, fully mixing, and carrying out esterification reaction at 90-95 ℃ for 1-1.5 h;
(4) wet-laying the carboxymethyl cellulose fiber treated in the step (3) to obtain a fiber web;
(5) and (4) carrying out spunlace reinforcement on the fiber web obtained in the step (4), and drying to obtain the high-flexibility and high-moisture-retention carboxymethyl cellulose fiber mask base cloth.
9. The method for preparing highly flexible and highly moisture-retaining carboxymethyl cellulose fiber mask base cloth according to claim 8, wherein in the step (3), the catalyst is FeCl3、Fe2(SO4)3、ZnCl2、ZnSO4At least one of (1).
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| CN117554401B (en) * | 2024-01-12 | 2024-04-02 | 沧州市天津工业大学研究院 | Method for detecting heavy metals in water based on membrane enrichment and X-ray fluorescence combination |
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