CN118206898A - Waterproof ink for carpet and production process thereof - Google Patents
Waterproof ink for carpet and production process thereof Download PDFInfo
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- CN118206898A CN118206898A CN202410414414.2A CN202410414414A CN118206898A CN 118206898 A CN118206898 A CN 118206898A CN 202410414414 A CN202410414414 A CN 202410414414A CN 118206898 A CN118206898 A CN 118206898A
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- fluororubber
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Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920001971 elastomer Polymers 0.000 claims abstract description 28
- 239000011256 inorganic filler Substances 0.000 claims abstract description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 28
- 239000005060 rubber Substances 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 240000000491 Corchorus aestuans Species 0.000 claims abstract description 24
- 235000011777 Corchorus aestuans Nutrition 0.000 claims abstract description 24
- 235000010862 Corchorus capsularis Nutrition 0.000 claims abstract description 24
- -1 polyethylene Polymers 0.000 claims abstract description 16
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000000049 pigment Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 11
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 44
- 229920001973 fluoroelastomer Polymers 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004576 sand Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims 7
- 238000002360 preparation method Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 72
- 230000000052 comparative effect Effects 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 125000006414 CCl Chemical group ClC* 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of ink preparation, and discloses waterproof ink for carpets and a production process thereof, wherein the ink comprises the following raw materials: acrylic acid, acrylamide, methacrylate, butyl acrylate, polyethylene wax emulsion, functional rubber, benzoyl peroxide, sodium dodecyl benzene sulfonate, pigment, modified inorganic filler, polyethylene glycol, tributyl phosphate and deionized water; wherein the functional rubber contains unsaturated double bonds, siloxane bonds and fluorine-containing groups in the structure; the modified inorganic filler is prepared by grafting halloysite and jute fiber, and then the wear resistance of the ink is improved by utilizing the ball effect. The ink prepared by the invention can obviously improve the water resistance, high temperature resistance and wear resistance of the carpet and prolong the service life of the carpet.
Description
Technical Field
The invention relates to the technical field of ink preparation, in particular to waterproof ink for carpets and a production process thereof.
Background
The carpet ink is ink used in the production process of the carpet, and is composed of substances such as pigment, binder, filler, additives and the like, after certain processing treatment, a fluid with specific properties is formed, the ink is required to meet the special properties of carpet materials, compared with the common ink, the carpet ink is required to have higher waterproof property, so that the carpet is prevented from being polluted by water stains, stains and the like in the use process due to poor waterproof property of the ink, the problems of decoloration, color change and the like occur in the use process of the carpet, the aesthetic appearance and the service life of the carpet are influenced, the high temperature resistance of the common ink is poor, and if the high temperature resistance of the carpet is poor, the color and the pattern of the carpet are unclear, the adhesive force is insufficient, the quality and the aesthetic degree of the carpet are influenced, the carpet is poorer in wear resistance due to the fact that the carpet is subjected to different degrees of wear in the use process, the ink is required to have higher wear resistance, the phenomena such as surface damage, pilling and the like of the carpet are avoided, and the service life of the carpet is influenced.
At present, one of the most common ways to improve the water resistance, high temperature resistance and wear resistance of the ink is to modify the additive, but the ink with the water resistance, high temperature resistance and wear resistance is very small, for example, the invention patent with the application number of CN201811175224.0 discloses a water-resistant composite modified polyvinyl alcohol water-based ink and a preparation method thereof, and the polyvinyl alcohol modified twice is used as a connecting material, so that the prepared ink has good water resistance, moderate viscosity and good film forming property, but the ink is not improved in the aspects of high temperature resistance and wear resistance. For example, the invention patent with the application number of CN201811244020.8 discloses wear-resistant water-based ink and a preparation process thereof, wherein the wear resistance of the ink is enhanced by carrying out grafting modification treatment on starch, and the hiding power of the ink is enhanced and the service life of the ink is prolonged by adding an auxiliary agent synthesized by polyvinyl alcohol and lactic acid, but the improvement on the high temperature resistance and the water resistance of the ink is not carried out. Along with the continuous progress of the living standard of people, the requirements on the waterproof, high-temperature-resistant and wear-resistant performance standard of the ink are continuously improved, so that the ink with high performance waterproof, high-temperature-resistant and wear-resistant properties is developed, and has important significance.
Disclosure of Invention
The invention aims to provide waterproof ink for carpets and a production process thereof, which solve the following technical problems:
(1) Solves the problem of poor waterproof performance of the ink;
(2) Solves the problem of poor high temperature resistance of the ink;
(3) Solves the problem of poor wear resistance of the ink.
The aim of the invention can be achieved by the following technical scheme:
A production process of waterproof ink for carpets comprises the following steps:
(1) Adding 30-40 parts of acrylic acid, 10-20 parts of acrylamide, 10-15 parts of methacrylate, 8-12 parts of butyl acrylate, 10-20 parts of polyethylene wax emulsion, 3-6 parts of functional rubber, 0.5-2 parts of benzoyl peroxide and 2-4 parts of sodium dodecyl benzene sulfonate into a reactor according to parts by weight, ultrasonically stirring for 1-3 hours at 50-70 ℃, standing for 5-15 minutes, and continuously stirring for 30-50 minutes to obtain a mixed solution;
(2) Adding 10-15 parts of pigment, 8-10 parts of modified inorganic filler, 0.5-2.5 parts of polyethylene glycol, 1-5 parts of tributyl phosphate and 40-50 parts of deionized water into the mixed solution prepared in the step (1) according to parts by weight, ultrasonically stirring for 1-2 hours at 20-40 ℃, and then dispersing in a sand mill to obtain the waterproof ink.
Further, in the step (2), the pigment is any one of pigment yellow 12, pigment yellow 14, phthalocyanine blue BGS, phthalocyanine blue B, magenta 6B, magenta 8B, or pigment carbon black.
Further, the production process of the functional rubber comprises the following steps:
S1: adding the carboxyl-terminated liquid fluororubber into tetrahydrofuran, stirring until the fluororubber is completely dissolved, then adding lithium aluminum hydride, reacting for 6-8 hours at 50-60 ℃, after the reaction is finished, dropwise adding hydrochloric acid for quenching, and then filtering, washing and drying to obtain the hydroxyl-terminated liquid fluororubber;
S2: adding hydroxyl-terminated liquid fluororubber into an organic solvent under the protection of argon, uniformly mixing, adding chloromethyl dimethyl chlorosilane, stirring and reacting for 3-6 hours at 50-60 ℃, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain modified fluororubber;
S3: adding the modified fluororubber and the hydroxyethyl methacrylate into an organic solvent, uniformly mixing, adding triethylamine, uniformly stirring, reacting for 1-3 hours at 70-80 ℃, and after the reaction, distilling under reduced pressure, washing and drying to obtain the functional rubber.
Further, in step S1, the number average molecular weight of the carboxyl-terminated liquid fluororubber is 2000 to 8000.
Further, in step S2, the organic solvent is any one of 1, 4-dioxane, N-dimethylformamide or dimethyl sulfoxide.
Further, in the step S3, the mass ratio of the hydroxyethyl methacrylate to the modified fluororubber is 1:1-3.
According to the technical scheme, under the action of the reducing agent, the carboxyl-terminated liquid fluororubber is reduced into hydroxyl-terminated liquid fluororubber, under the action of triethylamine, the hydroxyl of the hydroxyl-terminated liquid fluororubber can react with Si-Cl in a chloromethyl dimethyl chlorosilane structure, so that chloromethyl dimethyl chlorosilane is grafted into the hydroxyl-terminated liquid fluororubber structure to obtain modified fluororubber, then under the high temperature condition, halogen in the modified fluororubber structure can undergo substitution reaction with hydroxyl in a hydroxyethyl methacrylate structure, and hydroxyethyl methacrylate is grafted into the modified fluororubber structure to obtain the functional rubber.
Further, the production process of the modified inorganic filler comprises the following steps:
I: adding jute fiber and deionized water into a reactor, uniformly stirring, adding 3- (2, 3-glycidoxy) propyl trimethoxy silane, then starting to dropwise add acetic acid, regulating the pH value of the system to be 3-4, reacting for 1-3 h at normal temperature after the dropwise adding is finished, and filtering and washing after the reaction is finished to obtain modified jute fiber;
II: adding halloysite into N, N-dimethylformamide, dispersing uniformly, adding sodium hydroxide solution, treating for 1-3 h at 50-60 ℃, adding modified jute fiber, raising the temperature to 70-80 ℃, stirring and reacting for 6-8h, and washing and drying after the reaction is finished to obtain the modified inorganic filler.
Further, in the step I, the diameter of the jute fiber is 10-20 mu m, and the length is 1-2 mm.
Further, in the step II, the mass fraction of the sodium hydroxide solution is 10-20%.
According to the technical scheme, the 3- (2, 3-glycidoxy) propyl trimethoxy silane is used for modifying jute fibers to obtain modified jute fibers, epoxy groups in the modified jute fibers can react with hydroxyl groups in pretreated halloysite, and the pretreated halloysite and the modified jute fibers are grafted to obtain the modified inorganic filler.
The invention has the beneficial effects that:
(1) The invention uses functional rubber to carry out cross-linking polymerization with acrylic acid, acrylamide, methyl acrylic ester, butyl acrylate and polyethylene wax emulsion monomer to form an ink binder molecular chain with high cross-linking degree, so that the interface bonding is more compact, on one hand, the heat resistance of the ink can be improved, the ink can keep stability in a high-temperature environment, on the other hand, the adhesion fastness of the ink to a substrate can be improved, the ink is not easy to fall off and fade, and meanwhile, the wear resistance of the ink can be enhanced, and the service life of the ink can be prolonged; the functional rubber contains fluorine atom groups, and due to the unique characteristics of C-F, stable covalent bonds can be formed with other elements in the ink, and a layer of compact waterproof layer is formed on the surface of the ink, so that water molecules are difficult to wet and permeate on the surface of the ink, and the waterproof performance of the ink is improved.
(2) According to the modified inorganic filler, the jute fiber is natural fiber, the surface roughness is high, natural grooves and cracks are formed, halloysite is firmly fixed on the surface of the jute fiber through chemical bonding, the halloysite has a spherical structure, the firm bonding enables the halloysite to improve the wear resistance of the ink by utilizing the ball effect, when the ink is subjected to friction force, the halloysite plays a role of a micro ball on the surface of a friction pair, the direct contact and friction area is reduced, the friction force is reduced, the wear rate of the surface of the ink is further reduced, the wear resistance of the ink is improved, a more uniform and stable dispersion system can be formed in the ink, and the wear resistance of the ink is further improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum test chart of the functional rubber prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the jute fiber of the present invention and the modified inorganic filler prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of functional rubber
S1: adding 5g of carboxyl-terminated liquid fluororubber with the number average molecular weight of 5000 into tetrahydrofuran, stirring until the fluororubber is completely dissolved, then adding 0.12g of lithium aluminum hydride, reacting for 7 hours at 55 ℃, dropwise adding 30ml of hydrochloric acid with the concentration of 2mol/L for quenching after the reaction is finished, and then filtering, washing and drying to obtain the hydroxyl-terminated liquid fluororubber;
s2: under the protection of argon, adding 6g of hydroxyl-terminated liquid fluororubber into 1, 4-dioxane, uniformly mixing, adding 0.2g of chloromethyl dimethyl chlorosilane, stirring at 55 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain modified fluororubber;
S3: adding 5g of modified fluororubber and 2.5g of hydroxyethyl methacrylate into 1, 4-dioxane, uniformly mixing, adding 1.5g of triethylamine, uniformly stirring, reacting for 2 hours at 75 ℃, decompressing, distilling, washing and drying after the reaction is finished to obtain the functional rubber.
The infrared test is carried out on the hydroxyl-terminated liquid fluororubber, the modified fluororubber and the functional rubber by using a Bruker company Vertex 70v type Fourier infrared spectrometer in the U.S.A., as shown in figure 1, the sample is prepared by adopting a potassium bromide tabletting method, the spectrum scanning range is 4000cm -1～500cm-1, analysis is obtained, in the infrared spectrum of the hydroxyl-terminated liquid fluororubber, the 3378cm -1 part is the stretching vibration peak of a hydroxyl group, in the infrared spectrum of the modified fluororubber, the 1093cm -1 part is the stretching vibration peak of Si-O, the 695cm -1 part is the stretching vibration peak of C-Cl, the stretching vibration peak of the hydroxyl group disappears, in the infrared spectrum of the functional rubber, the 1769cm -1 part is the stretching vibration peak of an ester group C=O, the stretching vibration peak of alkenyl group C-H at 3039cm -1, the stretching vibration peak of Si-O at 1098cm -1, the absorption peak intensity of Si-O bond becomes large, and the stretching vibration peak of C-Cl disappears, because the hydroxyl group of the hydroxyl-terminated liquid fluororubber reacts with Si-Cl in the chloromethyl dimethyl chlorosilane structure, chloromethyl dimethyl chlorosilane is grafted into the hydroxyl-terminated liquid fluororubber structure, halogen in the modified fluororubber structure reacts with hydroxyl group in the hydroxyethyl methacrylate structure, and hydroxyethyl methacrylate is grafted into the modified fluororubber structure, thereby indicating success of grafting.
2. Preparation of modified inorganic filler
I: adding 5g of jute fiber and deionized water into a reactor, uniformly stirring, adding 3.5g of 3- (2, 3-glycidoxy) propyl trimethoxy silane, then starting to dropwise add acetic acid, adjusting the PH of the system to 4, reacting for 2 hours at normal temperature after the dropwise addition is finished, and filtering and washing after the reaction is finished to obtain modified jute fiber;
II: adding 1.5g of halloysite into N, N-dimethylformamide, dispersing uniformly, adding 15ml of sodium hydroxide solution with mass fraction of 15%, treating for 2 hours at 50-60 ℃, adding 4g of modified jute fiber, raising the temperature to 75 ℃, stirring and reacting for 7 hours, and washing and drying after the reaction is finished to obtain the modified inorganic filler.
The morphology analysis of jute fiber and modified inorganic filler is carried out, the test result is shown in fig. 2, wherein A is jute fiber, B is modified inorganic filler, and as can be seen from fig. 2, the surface of jute fiber is rough, and spherical matters appear on the surface of modified inorganic filler, because halloysite is grafted on the surface of jute fiber through modification treatment, so that the spherical matters halloysite appear on the surface of jute fiber.
3. Preparation of waterproof ink
(1) Adding 30 parts of acrylic acid, 10 parts of acrylamide, 10 parts of methacrylate, 8 parts of butyl acrylate, 10 parts of polyethylene wax emulsion, 3 parts of functional rubber, 0.5 part of benzoyl peroxide and 2 parts of sodium dodecyl benzene sulfonate into a reactor according to parts by weight, ultrasonically stirring for 1h at 50 ℃, standing for 5min, and continuously stirring for 30min to obtain a mixed solution;
(2) According to parts by weight, adding 10 parts of phthalocyanine blue B, 8 parts of modified inorganic filler, 0.5 part of polyethylene glycol, 1 part of tributyl phosphate and 40 parts of deionized water into the mixed solution prepared in the step (1), ultrasonically stirring for 1h at 20 ℃, and then dispersing in a sand mill to obtain the waterproof ink.
Example 2
Preparation of waterproof ink
(1) According to parts by weight, adding 35 parts of acrylic acid, 15 parts of acrylamide, 12 parts of methacrylate, 10 parts of butyl acrylate, 15 parts of polyethylene wax emulsion, 5 parts of functional rubber, 1 part of benzoyl peroxide and 3 parts of sodium dodecyl benzene sulfonate into a reactor, ultrasonically stirring for 2 hours at 60 ℃, standing for 10 minutes, and continuously stirring for 40 minutes to obtain a mixed solution;
(2) According to parts by weight, adding 12 parts of phthalocyanine blue B, 9 parts of modified inorganic filler, 1.5 parts of polyethylene glycol, 3 parts of tributyl phosphate and 45 parts of deionized water into the mixed solution prepared in the step (1), ultrasonically stirring for 1.5 hours at 30 ℃, and then dispersing in a sand mill to obtain the waterproof ink.
Wherein the preparation method of the functional rubber and the modified inorganic filler is the same as in example 1.
Example 3
Preparation of waterproof ink
(1) Adding 40 parts of acrylic acid, 20 parts of acrylamide, 15 parts of methacrylate, 12 parts of butyl acrylate, 20 parts of polyethylene wax emulsion, 6 parts of functional rubber, 2 parts of benzoyl peroxide and 4 parts of sodium dodecyl benzene sulfonate into a reactor according to parts by weight, ultrasonically stirring for 3 hours at 70 ℃, standing for 15 minutes, and continuously stirring for 50 minutes to obtain a mixed solution;
(2) 15 parts of phthalocyanine blue B, 10 parts of modified inorganic filler, 2.5 parts of polyethylene glycol, 5 parts of tributyl phosphate and 50 parts of deionized water are added into the mixed solution prepared in the step (1) according to parts by weight, and the mixed solution is ultrasonically stirred for 2 hours at 40 ℃ and then is dispersed in a sand mill to obtain the waterproof ink.
Wherein the preparation method of the functional rubber and the modified inorganic filler is the same as in example 1.
Comparative example 1
Preparation of ink
(1) According to parts by weight, adding 35 parts of acrylic acid, 15 parts of acrylamide, 12 parts of methacrylate, 10 parts of butyl acrylate, 15 parts of polyethylene wax emulsion, 5 parts of functional rubber, 1 part of benzoyl peroxide and 3 parts of sodium dodecyl benzene sulfonate into a reactor, ultrasonically stirring for 2 hours at 60 ℃, standing for 10 minutes, and continuously stirring for 40 minutes to obtain a mixed solution;
(2) According to parts by weight, adding 12 parts of phthalocyanine blue B, 1.5 parts of polyethylene glycol, 3 parts of tributyl phosphate and 45 parts of deionized water into the mixed solution prepared in the step (1), ultrasonically stirring for 1.5 hours at 30 ℃, and then dispersing in a sand mill to obtain the printing ink.
Wherein the preparation method of the functional rubber is the same as in example 1.
Comparative example 2
Preparation of ink
(1) According to parts by weight, adding 35 parts of acrylic acid, 15 parts of acrylamide, 12 parts of methacrylate, 10 parts of butyl acrylate, 15 parts of polyethylene wax emulsion, 1 part of benzoyl peroxide and 3 parts of sodium dodecyl benzene sulfonate into a reactor, ultrasonically stirring for 2 hours at 60 ℃, standing for 10 minutes, and continuously stirring for 40 minutes to obtain a mixed solution;
(2) Adding 12 parts of pigment, 9 parts of modified inorganic filler, 1.5 parts of polyethylene glycol, 3 parts of tributyl phosphate and 45 parts of deionized water into the mixed solution prepared in the step (1) according to parts by weight, ultrasonically stirring for 1.5 hours at 30 ℃, and then dispersing in a sand mill to obtain the printing ink.
Wherein the modified inorganic filler was prepared in the same manner as in example 1.
Comparative example 3
Preparation of ink
(1) According to parts by weight, adding 35 parts of acrylic acid, 15 parts of acrylamide, 12 parts of methacrylate, 10 parts of butyl acrylate, 15 parts of polyethylene wax emulsion, 3 parts of hydroxyl-terminated liquid fluororubber, 2 parts of chloromethyl dimethyl chlorosilane, 1 part of benzoyl peroxide and 3 parts of sodium dodecyl benzene sulfonate into a reactor, ultrasonically stirring for 2 hours at 60 ℃, standing for 10 minutes, and continuously stirring for 40 minutes to obtain a mixed solution;
(2) According to parts by weight, adding 12 parts of phthalocyanine blue B, 9 parts of modified inorganic filler, 1.5 parts of polyethylene glycol, 3 parts of tributyl phosphate and 45 parts of deionized water into the mixed solution prepared in the step (1), ultrasonically stirring for 1.5 hours at 30 ℃, and then dispersing in a sand mill to obtain the printing ink.
Wherein the modified inorganic filler was prepared in the same manner as in example 1.
Comparative example 4
Preparation of ink
(1) According to parts by weight, adding 35 parts of acrylic acid, 15 parts of acrylamide, 12 parts of methacrylate, 10 parts of butyl acrylate, 15 parts of polyethylene wax emulsion, 5 parts of functional rubber, 1 part of benzoyl peroxide and 3 parts of sodium dodecyl benzene sulfonate into a reactor, ultrasonically stirring for 2 hours at 60 ℃, standing for 10 minutes, and continuously stirring for 40 minutes to obtain a mixed solution;
(2) According to parts by weight, adding 12 parts of phthalocyanine blue B, 9 parts of halloysite, 1.5 parts of polyethylene glycol, 3 parts of tributyl phosphate and 45 parts of deionized water into the mixed solution prepared in the step (1), ultrasonically stirring for 1.5 hours at 30 ℃, and then dispersing in a sand mill to obtain the printing ink.
Wherein the preparation method of the functional rubber is the same as in example 1.
Comparative example 5
Preparation of ink
(1) According to parts by weight, adding 35 parts of acrylic acid, 15 parts of acrylamide, 12 parts of methacrylate, 10 parts of butyl acrylate, 15 parts of polyethylene wax emulsion, 1 part of benzoyl peroxide and 3 parts of sodium dodecyl benzene sulfonate into a reactor, ultrasonically stirring for 2 hours at 60 ℃, standing for 10 minutes, and continuously stirring for 40 minutes to obtain a mixed solution;
(2) According to parts by weight, adding 12 parts of phthalocyanine blue B, 1.5 parts of polyethylene glycol, 3 parts of tributyl phosphate and 45 parts of deionized water into the mixed solution prepared in the step (1), ultrasonically stirring for 1.5 hours at 30 ℃, and then dispersing in a sand mill to obtain the printing ink.
Performance detection
Uniformly scraping the ink prepared in the examples 1-3 and the comparative examples 1-4 on A4 paper to serve as a sample, cutting the sample into 25cm multiplied by 6cm by using a QD-3031 ink abrasion resistance tester, placing the sample on an abrasion resistance tester to fix, cutting blank A4 paper into 20cm multiplied by 5cm to fix on a friction sliding block, adding weights to weigh, setting the pressure to be 4 pounds, setting the friction times to 100 times, and observing the surface flooding condition of the blank A4 paper and the surface decoloring condition of the sample after the test; the inks prepared in examples 1 to 3 and comparative examples 1 to 4 were uniformly knife coated on the surface of PET as a sample, dried at 70℃and then immersed in water for 24 hours, and the immersed portion was observed to be different from the non-immersed portion; the inks prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to the adhesion fastness performance test as samples according to GB/T13217-2009 method for liquid ink adhesion fastness test; the inks prepared in examples 1 to 3 and comparative examples 1 to 4 were uniformly drawn on the surface of PET as a sample, dried, and then dried at 120℃for 12 hours, and the difference between the dried portion and the non-dried portion was observed, and the test results were as follows:
，
As can be seen from the data in the above table, the samples prepared in examples 1 to 3 of the present invention all have excellent water resistance, high temperature resistance and abrasion resistance; the samples prepared in comparative example 1 and comparative example 4 are added with functional rubber, the samples are not wrinkled, discolored, cracked and foamed, and have good waterproof performance and high temperature resistance, but the samples prepared in comparative example 1 are not added with modified inorganic filler, compared with the examples, the samples are obviously decolorized, so that the abrasion resistance is poor, the samples prepared in comparative example 4 are added with halloysite, compared with the examples, the samples are slightly decolorized, the halloysite is presumably not capable of generating a ball effect in the preparation process of the ink, and the formed dispersibility is uneven and unstable, so that the abrasion resistance of the ink is reduced; the samples prepared in comparative example 2 and comparative example 3 are added with modified inorganic filler, the samples are not decolored and have good wear resistance, but the samples prepared in comparative example 2 are not added with functional rubber, compared with the examples, the samples have obvious wrinkling, discoloration, cracking and foaming phenomena, the adhesion fastness is reduced, the water resistance and the high temperature resistance of the samples are poor, the samples prepared in comparative example 3 are added with hydroxyl-terminated liquid fluororubber and chloromethyl dimethyl chlorosilane, compared with the examples, the samples have micro wrinkling, discoloration, cracking and foaming, presumably because the hydroxyl-terminated liquid fluororubber is incompatible in a matrix, the fluorine radical group cannot form stable covalent bonds with other elements in the ink, and no silicon-oxygen bond is formed, so that the water resistance and the high temperature resistance of the ink are poor; the sample prepared in comparative example 5 was poor in water resistance, high temperature resistance and abrasion resistance, and neither functional rubber nor modified inorganic filler was added.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. The production process of the waterproof ink for the carpet is characterized by comprising the following steps of:
(1) Adding 30-40 parts of acrylic acid, 10-20 parts of acrylamide, 10-15 parts of methacrylate, 8-12 parts of butyl acrylate, 10-20 parts of polyethylene wax emulsion, 3-6 parts of functional rubber, 0.5-2 parts of benzoyl peroxide and 2-4 parts of sodium dodecyl benzene sulfonate into a reactor according to parts by weight, ultrasonically stirring for 1-3 hours at 50-70 ℃, standing for 5-15 minutes, and continuously stirring for 30-50 minutes to obtain a mixed solution;
(2) Adding 10-15 parts of pigment, 8-10 parts of modified inorganic filler, 0.5-2.5 parts of polyethylene glycol, 1-5 parts of tributyl phosphate and 40-50 parts of deionized water into the mixed solution prepared in the step (1) according to parts by weight, ultrasonically stirring for 1-2 hours at 20-40 ℃, and then dispersing in a sand mill to obtain the waterproof ink.
2. The process for producing a water-repellent ink for carpets according to claim 1, wherein in the step (2), the pigment is any one of pigment yellow 12, pigment yellow 14, phthalocyanine blue BGS, phthalocyanine blue B, magenta 6B, magenta 8B, and pigment black.
3. The process for producing a waterproof ink for carpets according to claim 1, wherein the process for producing the functional rubber comprises the steps of:
S1: adding the carboxyl-terminated liquid fluororubber into tetrahydrofuran, stirring until the fluororubber is completely dissolved, then adding lithium aluminum hydride, reacting for 6-8 hours at 50-60 ℃, after the reaction is finished, dropwise adding hydrochloric acid for quenching, and then filtering, washing and drying to obtain the hydroxyl-terminated liquid fluororubber;
S2: adding hydroxyl-terminated liquid fluororubber into an organic solvent under the protection of argon, uniformly mixing, adding chloromethyl dimethyl chlorosilane, stirring at 50-60 ℃ for reaction for 3-6 hours, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain modified fluororubber;
S3: adding the modified fluororubber and the hydroxyethyl methacrylate into an organic solvent, uniformly mixing, adding triethylamine, uniformly stirring, reacting for 1-3 hours at 70-80 ℃, and after the reaction, distilling under reduced pressure, washing and drying to obtain the functional rubber.
4. The process for producing a water-repellent ink for carpets according to claim 3, wherein in step S1, the carboxyl-terminated liquid fluororubber has a number average molecular weight of 2000 to 8000.
5. The process for producing a water-repellent ink for carpets according to claim 3, wherein in step S2, the organic solvent is any one of 1, 4-dioxane, N-dimethylformamide or dimethyl sulfoxide.
6. The process for producing a water-repellent ink for carpets according to claim 3, wherein in step S3, the mass ratio of the hydroxyethyl methacrylate to the modified fluororubber is 1:1 to 3.
7. The process for producing a waterproof ink for carpets according to claim 1, wherein the process for producing the modified inorganic filler comprises the steps of:
I: adding jute fiber and deionized water into a reactor, uniformly stirring, adding 3- (2, 3-glycidoxy) propyl trimethoxy silane, then starting to dropwise add acetic acid, regulating the pH value of the system to be 3-4, reacting for 1-3 h at normal temperature after the dropwise adding is finished, and filtering and washing after the reaction is finished to obtain modified jute fiber;
II: adding halloysite into N, N-dimethylformamide, dispersing uniformly, adding sodium hydroxide solution, treating for 1-3 h at 50-60 ℃, adding modified jute fiber, raising the temperature to 70-80 ℃, stirring and reacting for 6-8h, and washing and drying after the reaction is finished to obtain the modified inorganic filler.
8. The process for producing a water-repellent ink for carpets according to claim 7, wherein in step i, the jute fiber has a diameter of 10 to 20 μm and a length of 1 to 2mm.
9. The process for producing a water-repellent ink for carpets according to claim 7, wherein in step ii, the mass fraction of the sodium hydroxide solution is 10 to 20%.
10. A water-repellent ink for carpets, characterized in that it is produced by the production process according to claim 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585904A (en) * | 2008-05-21 | 2009-11-25 | 北京高盟燕山科技有限公司 | Method for preparing binder resin for water-based ink and application thereof |
| US20130079447A1 (en) * | 2010-05-26 | 2013-03-28 | Toyo Ink Co., Ltd. | Aqueous inkjet ink composition |
| CN111471186A (en) * | 2020-05-29 | 2020-07-31 | 中国工程物理研究院化工材料研究所 | A kind of high-performance copolymerized liquid fluororubber, preparation method and application |
| CN111876016A (en) * | 2020-08-27 | 2020-11-03 | 厦门欧化实业有限公司 | High-temperature-resistant ink and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585904A (en) * | 2008-05-21 | 2009-11-25 | 北京高盟燕山科技有限公司 | Method for preparing binder resin for water-based ink and application thereof |
| US20130079447A1 (en) * | 2010-05-26 | 2013-03-28 | Toyo Ink Co., Ltd. | Aqueous inkjet ink composition |
| CN111471186A (en) * | 2020-05-29 | 2020-07-31 | 中国工程物理研究院化工材料研究所 | A kind of high-performance copolymerized liquid fluororubber, preparation method and application |
| CN111876016A (en) * | 2020-08-27 | 2020-11-03 | 厦门欧化实业有限公司 | High-temperature-resistant ink and preparation method thereof |
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