CN117247702A - Environment-friendly pencil coating and preparation method thereof - Google Patents
Environment-friendly pencil coating and preparation method thereof Download PDFInfo
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- CN117247702A CN117247702A CN202311302373.XA CN202311302373A CN117247702A CN 117247702 A CN117247702 A CN 117247702A CN 202311302373 A CN202311302373 A CN 202311302373A CN 117247702 A CN117247702 A CN 117247702A
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- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 20
- 239000012782 phase change material Substances 0.000 claims abstract description 20
- 239000011162 core material Substances 0.000 claims abstract description 19
- MFTUNRMUCZGYSG-UHFFFAOYSA-N 2-ethenylpropane-1,3-diol Chemical compound OCC(CO)C=C MFTUNRMUCZGYSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- XAAILNNJDMIMON-UHFFFAOYSA-N 2'-anilino-6'-(dibutylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCCC)CCCC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 XAAILNNJDMIMON-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004743 Polypropylene Substances 0.000 claims abstract description 12
- 229920001155 polypropylene Polymers 0.000 claims abstract description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 69
- 238000003756 stirring Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- 229920001220 nitrocellulos Polymers 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000003208 petroleum Substances 0.000 claims description 16
- 229920000180 alkyd Polymers 0.000 claims description 14
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 14
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 241000220479 Acacia Species 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003973 paint Substances 0.000 abstract description 10
- 239000003094 microcapsule Substances 0.000 abstract description 6
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002023 wood Substances 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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/16—Esters of inorganic acids
- C09D101/18—Cellulose nitrate
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/26—Thermosensitive paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses an environment-friendly pencil coating and a preparation method thereof, and relates to the technical field of pencils. The invention uses S- (-) -tert-butylamine-1, 2-propylene glycol, 3-ethoxy-2-acryl isocyanate, 2-vinyl propane-1, 3-diol, hexamethylene diisocyanate and polypropylene glycol-500 to prepare the microcapsule wall material capable of self-repairing, and uses low-melting point phase-change material and dye ODB-2 as core materials to prepare the microcapsule, so that the color change of the pencil can occur when the pencil is used, the self-repairing performance of the wall material enables the paint color to dynamically and circularly change, the spheroid-like structure of the microcapsule can be used as anti-skid particles, the friction coefficient of the pencil is improved, self-made microsphere particles can be inserted between adjacent propylene paint molecules, smooth transitional microprotrusions are formed on the surface of the coating, and the glossiness and the hand feeling of the pencil are not influenced while the anti-skid performance is ensured.
Description
Technical Field
The invention relates to the technical field of pencils, in particular to an environment-friendly pencil coating and a preparation method thereof.
Background
The pencil paint is paint coated on the surface of the pencil stick to increase the beauty of the pencil stick. The pencil paint can prevent the pencil holder from absorbing moisture from the air to generate bending deformation and glue opening, and prolong the preservation time and the service life of the pencil.
The nitrolacquer has the characteristics of quick drying and good decoration, so that the nitrolacquer is applied to pencil lacquer, however, the surface of a painted wooden pencil is smoother, hands easily slide down in the long-time use process, the holding distance is required to be continuously adjusted, and hand fatigue is easy to cause.
The pencil holder of the existing pencil usually achieves the aim of multicolor by brushing paints of various colors on the surface of the pencil holder so as to attract the eyes of consumers, but brushing the paints of various colors causes the pencil to have heavy smell, so that the health of children can be influenced to a certain extent, and the consumers can lose interest and cause the loss of the consumers due to single color for a long time.
Disclosure of Invention
The invention aims to provide an environment-friendly pencil coating and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: an environment-friendly pencil coating comprises self-made microsphere particles, nitrocotton, an acrylic compound, a photoinitiator, bisphenol A and the like.
Furthermore, the self-made microsphere particles are prepared by taking modified polyurethane as a wall material and taking a low-melting-point phase change material and dye ODB-2 as core materials.
Further, the modified polyurethane is prepared from S- (-) -tert-butylamino-1, 2-propanediol, 3-ethoxy-2-acryl isocyanate, 2-vinyl propane-1, 3-diol, hexamethylene diisocyanate, polypropylene glycol-500.
Further, the propylene compound comprises acrylic acid, methacrylic acid and methyl methacrylate.
Further, the photoinitiator comprises an initiator 819 and an initiator ITX.
Further, the preparation method of the environment-friendly pencil coating comprises the following preparation steps:
(1) Mixing S- (-) -tert-butylamine-1, 2-propylene glycol, methylene dichloride and 3-ethoxy-2-acryloyl isocyanate according to a mass ratio of 1:8-15:0.8-2.0, stirring at 30-70 rpm for 9-15 h at room temperature, adding petroleum ether/ethyl acetate solution with the volume of 2-5 times of that of the reaction solution and 50-60 ℃, stirring until solid is separated out, and carrying out suction filtration to obtain the self-repairing modifier;
(2) Mixing polypropylene glycol-500, a self-repairing modifier and N, N-dimethylformamide according to the mass ratio of 11.9:2.4-7.0:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1.0-1.2 times of that of 2-vinyl propane-1, 3-diol, and stirring for 3-6 hours at 80-85 ℃ and 100rpm to obtain a modified polyurethane prepolymer solution;
(3) Mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia with the mass of 0.03-0.05 times of that of the mixed liquid, emulsifying for 30min at 5000-8000 rpm, adding 2-vinyl propane-1, 3-diol with the mass of 0.2-0.5 times of that of the modified polyurethane prepolymer solution, reacting for 4-8 h at 60-80 ℃, carrying out suction filtration, taking solid, washing for 6 times by using 30% ethanol water solution according to mass fraction, and drying for 24h at room temperature to obtain self-made microsphere particles;
(4) Mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 60-70:3-4.5:2-5:1, adding acrylic modified alkyd resin, acrylic compound, photoinitiator, bisphenol A, defoamer BYK141 and carboxymethyl cellulose according to a mass ratio of 45-65:15-34:1.5-2.5:1-7:0.3-0.7:1.0-1.5 under 200-300 rpm, and stirring for 20-30 min to obtain the environment-friendly pencil coating, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 1:3-2:7, and then the speed is increased to 1200-1400 rpm.
Further, the volume ratio of petroleum ether to ethyl acetate in the petroleum ether/ethyl acetate solution in the step (1) is 10-20:1.
Further, the preparation method of the core liquid in the step (3) comprises the following steps: mixing n-decanoic acid and 1-octadecanol according to the mass ratio of 80-90:10-20, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass of 0.004-0.008 times of that of the low-melting-point phase-change material liquid, and stirring for 20-30 min at 60 ℃ and 80 rpm.
Further, the mass ratio of the acrylic acid, the methacrylic acid and the methyl methacrylate in the propylene compound in the step (4) is 15-25:2-6:1-3.
Further, in the photoinitiator in the step (4), the mass ratio of the initiator 819 to the initiator ITX is 2-4:1.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the self-made microsphere particles, the nitrocotton liquid, the propylene compound and other raw materials are used as primer coating to coat the surface of the pencil wood, so that the LED lamp can be quickly cured, in addition, the self-made microsphere particles are used as anti-slip particles to be attached to the surface of the pencil while the color-changing performance is realized, so that the pencil has good anti-slip performance, double bonds of the self-made microsphere particles can be crosslinked with the propylene compound under photoinitiation, and can be inserted between adjacent coating molecules, so that the intermolecular stress is reduced, the hand feeling of the pencil coating is improved, and meanwhile, the self-made microsphere particles can be coated by the coating molecules to form smooth transition microprotrusions, so that dirt accumulation is avoided while the slip is prevented.
The invention utilizes methyl amino of S- (-) -tert-butylamino-1, 2-propylene glycol to react with acyl isocyanate of 3-ethoxy-2-acryloyl isocyanate to form a ureido structure, introduces side tert-butyl with large steric hindrance on nitrogen atom of urea bond to realize dynamic reversible reaction at room temperature, then utilizes hydroxyl to participate in polymerization of polypropylene glycol-500, 2-vinyl propane-1, 3-diol and isocyanic acid compound to form polyurethane, introduces self-repairing hindered ureido into polyurethane molecular chain to realize room temperature self-repairing, then uses self-repairing polyurethane as wall material and uses low melting point phase change material and dye ODB-2 as core material to obtain capsule microsphere particles, when children use pencil, microsphere particles in pencil surface coating are affected by external force to generate slight damage, along with long-time holding of the pencil, the finger temperature is transferred into the microsphere to enable the low melting point paraffin to drive dye to flow out, and contact with external color developing agent to generate color, and when the self-repairing is not used, the polyurethane self-repairs and pore diameter capillary is formed in self-repairing process, and dye is re-adsorbed again, thereby realizing dynamic cyclic change of the inner color of the pencil.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the method in detail, the environment-friendly pencil coating manufactured in the following examples is directly poured into a paint hopper of a pencil lacquering machine, the pencil is directly subjected to drawing construction, then a led lamp is adopted, the pencil with a coating is manufactured by drying for 70s at 40 ℃, and the pencil is tested:
smell: the odor was tested according to the popular car odor detection method VW50180 standard.
Adhesion force: adhesion rating was tested according to GB 9286.
Gloss level: paint film gloss was measured according to QB/T1951.1.
Color change properties: 30 volunteers are selected and respectively divided into children, young and middle-aged groups, the surface color change condition is observed by writing for 5min by using a pencil with a coating, and after the surface color change condition is observed again after the surface color change condition is circularly used for 10 times.
Coefficient of friction: the coefficient of friction is tested with reference to GB/T1006.
Example 1
(1) Mixing S- (-) -tert-butylamine-1, 2-propylene glycol, methylene dichloride and 3-ethoxy-2-acryloyl isocyanate according to a mass ratio of 1:8:0.8, stirring at room temperature at 30rpm for 9 hours, adding a petroleum ether/ethyl acetate solution with a volume ratio of petroleum ether to ethyl acetate of 10:1 and with a volume ratio of 50 ℃ which is 2 times that of the reaction solution, stirring until solid is separated out, and carrying out suction filtration to obtain the self-repairing modifier;
(2) Mixing polypropylene glycol-500, a self-repairing modifier and N, N-dimethylformamide according to a mass ratio of 11.9:2.4:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1 times that of 2-vinyl propane-1, 3-diol, and stirring at 80 ℃ for 3 hours at 100rpm to obtain a modified polyurethane prepolymer solution;
(3) Mixing n-decanoic acid and 1-octadecanol according to the mass ratio of 80:10, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass 0.004 times of that of the low-melting-point phase-change material liquid, and stirring at 60 ℃ and 80rpm for 20min to obtain core liquid; mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia with the mass of 0.03 times of that of the mixed liquid, emulsifying for 30min at 5000rpm, adding 2-vinyl propane-1, 3-diol with the mass of 0.2 times of that of the modified polyurethane prepolymer solution, reacting for 4h at 60 ℃, carrying out suction filtration, taking solid, washing for 6 times by using 30% ethanol water solution with the mass fraction, and drying for 24h at room temperature to obtain self-made microsphere particles;
(4) Mixing acrylic acid, methacrylic acid and methyl methacrylate according to a mass ratio of 15:2:1 to obtain a propylene compound; mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 60:3:2:1, adding acrylic modified alkyd resin, a propylene compound, a photoinitiator, bisphenol A, a defoamer BYK141 and carboxymethyl cellulose according to a mass ratio of 45:15:1.5:1:0.3:1.0 at 200rpm, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 1:3, the mass ratio of an initiator 819 and an initiator ITX in the photoinitiator is 2:1, and then increasing the speed to 1200rpm, and stirring for 20min to obtain the environment-friendly pencil coating.
Example 2
(1) Mixing S- (-) -tert-butylamine-1, 2-propylene glycol, methylene dichloride and 3-ethoxy-2-acryloyl isocyanate according to a mass ratio of 1:11.5:1.4, stirring at room temperature at 50rpm for 12 hours, adding a petroleum ether/ethyl acetate solution with a volume ratio of petroleum ether to ethyl acetate of 15:1, which is 3.5 times of the volume of the reaction solution, stirring until solid is separated out, and carrying out suction filtration to obtain the self-repairing modifier;
(2) Mixing polypropylene glycol-500, a self-repairing modifier and N, N-dimethylformamide according to a mass ratio of 11.9:4.7:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1.1 times that of 2-vinyl propane-1, 3-diol, and stirring for 4.5 hours at the temperature of 82 ℃ and at the speed of 100rpm to obtain a modified polyurethane prepolymer solution;
(3) Mixing n-decanoic acid and 1-octadecanol according to a mass ratio of 85:15, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass of 0.006 times that of the low-melting-point phase-change material liquid, and stirring at 60 ℃ and 80rpm for 25min to obtain core liquid; mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia with the mass of 0.04 times of that of the mixed liquid, emulsifying at 6000rpm for 30min, adding 2-vinyl propane-1, 3-diol with the mass of 0.35 times of that of the modified polyurethane prepolymer solution, reacting at 70 ℃ for 6h, filtering, taking solid, washing with 30% ethanol water solution for 6 times, and drying at room temperature for 24h to obtain self-made microsphere particles;
(4) Mixing acrylic acid, methacrylic acid and methyl methacrylate according to a mass ratio of 20:4:2 to obtain a propylene compound; mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 65:3.8:3.5:1, adding acrylic modified alkyd resin, a propylene compound, a photoinitiator, bisphenol A, a defoaming agent BYK141 and carboxymethyl cellulose according to a mass ratio of 55:24.5:2:4:0.5:1.2 at 250rpm, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 1.5:5, the mass ratio of an initiator 819 to an initiator ITX in the photoinitiator is 3:1, then increasing the speed to 1300rpm, and stirring for 25min to obtain the environment-friendly pencil coating.
Example 3
(1) Mixing S- (-) -tert-butylamine-1, 2-propylene glycol, methylene dichloride and 3-ethoxy-2-acryloyl isocyanate according to a mass ratio of 1:15:2, stirring at 70rpm for 15 hours at room temperature, adding a petroleum ether/ethyl acetate solution with a volume ratio of petroleum ether to ethyl acetate of 20:1, stirring until solid is separated out, and performing suction filtration to obtain the self-repairing modifier, wherein the volume ratio of petroleum ether to ethyl acetate in the petroleum ether/ethyl acetate solution is 5 times of that of the reaction solution;
(2) Mixing polypropylene glycol-500, a self-repairing modifier and N, N-dimethylformamide according to a mass ratio of 11.9:7:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1.2 times that of 2-vinyl propane-1, 3-diol, and stirring at 85 ℃ for 6 hours at 100rpm to obtain a modified polyurethane prepolymer solution;
(3) Mixing n-decanoic acid and 1-octadecanol according to the mass ratio of 90:20, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass 0.008 times of that of the low-melting-point phase-change material liquid, and stirring at 60 ℃ and 80rpm for 30min to obtain core liquid; mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia which is 0.05 times of the mixed liquid in mass, emulsifying for 30min at 8000rpm, adding 2-vinyl propane-1, 3-diol which is 0.5 times of the modified polyurethane prepolymer solution in mass, reacting for 8h at 80 ℃, carrying out suction filtration, taking solid, washing for 6 times by using 30% ethanol water solution in mass fraction, and drying for 24h at room temperature to obtain self-made microsphere particles;
(4) Mixing acrylic acid, methacrylic acid and methyl methacrylate according to a mass ratio of 25:6:3 to obtain a propylene compound; mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 70:4.5:5:1, adding acrylic modified alkyd resin, a propylene compound, a photoinitiator, bisphenol A, a defoamer BYK141 and carboxymethyl cellulose according to a mass ratio of 65:34:2.5:7:0.7:1.5 at 300rpm, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 2:7, the mass ratio of an initiator 819 to an initiator ITX in the photoinitiator is 4:1, and then increasing the speed to 1400rpm, and stirring for 20-30 min to obtain the environment-friendly pencil coating.
Comparative example 1
Comparative example 1 differs from example 2 in that there is no step (1), step (2) is changed to: mixing polypropylene glycol-500, S- (-) -tert-butylamine-1, 2-propylene glycol and N, N-dimethylformamide according to a mass ratio of 11.9:4.7:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1.1 times of that of 2-vinyl propane-1, 3-diol, and stirring at 82 ℃ and 100rpm for 4.5 hours to obtain a modified polyurethane prepolymer solution; the rest of the procedure is the same as in example 2.
Comparative example 2
(1) Mixing S- (-) -tert-butylamine-1, 2-propylene glycol, methylene dichloride and 3-ethoxy-2-acryloyl isocyanate according to a mass ratio of 1:11.5:1.4, stirring at room temperature at 50rpm for 12 hours, adding a petroleum ether/ethyl acetate solution with a volume ratio of petroleum ether to ethyl acetate of 15:1, which is 3.5 times of the volume of the reaction solution, stirring until solid is separated out, and carrying out suction filtration to obtain the self-repairing modifier;
(2) Mixing polypropylene glycol-500, a self-repairing modifier and N, N-dimethylformamide according to a mass ratio of 11.9:4.7:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1.1 times that of 2-vinyl propane-1, 3-diol, and stirring for 4.5 hours at the temperature of 82 ℃ and at the speed of 100rpm to obtain a modified polyurethane prepolymer solution;
(3) Mixing n-decanoic acid and 1-octadecanol according to a mass ratio of 85:15, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass of 0.006 times of the low-melting-point phase-change material liquid and bisphenol A with the mass of 0.006 times of the low-melting-point phase-change material liquid, and stirring at 60 ℃ and 80rpm for 25min to obtain core liquid; mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia with the mass of 0.04 times of that of the mixed liquid, emulsifying at 6000rpm for 30min, adding 2-vinyl propane-1, 3-diol with the mass of 0.35 times of that of the modified polyurethane prepolymer solution, reacting at 70 ℃ for 6h, filtering, taking solid, washing with 30% ethanol water solution for 6 times, and drying at room temperature for 24h to obtain self-made microsphere particles;
(4) Mixing acrylic acid, methacrylic acid and methyl methacrylate according to a mass ratio of 20:4:2 to obtain a propylene compound; mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 65:3.8:3.5:1, adding acrylic modified alkyd resin, a propylene compound, a photoinitiator, a defoaming agent BYK141 and carboxymethyl cellulose according to a mass ratio of 55:24.5:2:0.5:1.2 at 250rpm, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 1.5:5, the mass ratio of an initiator 819 to an initiator ITX in the photoinitiator is 3:1, and then increasing the speed to 1300rpm, and stirring for 25min to obtain the environment-friendly pencil coating.
Comparative example 3
Comparative example 3 differs from example 2 in that there are no steps (2), (3), step (4) being changed to: mixing acrylic acid, methacrylic acid and methyl methacrylate according to a mass ratio of 20:4:2 to obtain a propylene compound; mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 65:3.8:3.5:1, adding acrylic modified alkyd resin, a propylene compound, a photoinitiator, bisphenol A, a defoamer BYK141, carboxymethyl cellulose and a dye ODB-2 according to a mass ratio of 55:24.5:2:4:0.5:1.2:4 at 250rpm, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 1.5:5, the mass ratio of an initiator 819 to an initiator ITX in the photoinitiator is 3:1, then increasing the speed to 1300rpm, and stirring for 25min to obtain the environment-friendly pencil coating; the rest of the procedure is the same as in example 2.
Comparative example 4
Comparative example 4 differs from example 2 in that step (3) was changed to: mixing n-decanoic acid and 1-octadecanol according to a mass ratio of 85:15, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass of 0.006 times that of the low-melting-point phase-change material liquid, and stirring at 60 ℃ and 80rpm for 25min to obtain core liquid; mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia with the mass of 0.04 times of that of the mixed liquid, emulsifying at 6000rpm for 30min, adding S- (-) -tert-butylamino-1, 2-propanediol with the mass of 0.35 times of that of the modified polyurethane prepolymer solution, reacting at 70 ℃ for 6h, filtering, taking solid, washing for 6 times with 30% ethanol water solution with mass fraction, and drying at room temperature for 24h to obtain self-made microsphere particles; the rest of the procedure is the same as in example 2.
Effect example
The results of performance analysis of the environmental pencil coatings of examples 1 to 3 and comparative examples 1 to 4 using the present invention are given in the following table 1.
TABLE 1
As can be found from the comparison of experimental data of examples and comparative examples, the self-repairable microcapsule wall material is prepared by using S- (-) -tert-butylamino-1, 2-propylene glycol, 3-ethoxy-2-acryl isocyanate, 2-vinyl propane-1, 3-diol, hexamethylene diisocyanate and polypropylene glycol-500, so that the cyclic color change of a coating is realized, and the microcapsule is prepared by using a low-melting-point phase-change material and dye ODB-2 as core materials, so that the color change of the pencil can occur when the pencil is used, the spheroid structure of the microcapsule can be used as anti-slip particles, the friction coefficient of the pencil is improved, meanwhile, double bonds of self-made microsphere particles can penetrate between adjacent paint molecules, smooth transitional microprotrusions are formed on the surface of the coating, and the glossiness and the hand feeling of the pencil are not influenced while the anti-slip is ensured.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The environment-friendly pencil coating is characterized by comprising self-made microsphere particles, nitrocotton, propylene compounds, photoinitiators, bisphenol A and the like.
2. The environment-friendly pencil coating as claimed in claim 1, wherein the self-made microsphere particles are made of modified polyurethane as a wall material and a low-melting-point phase-change material and dye ODB-2 as core materials.
3. The environment-friendly pencil coating according to claim 2, wherein the modified polyurethane is prepared from S- (-) -tert-butylamino-1, 2-propanediol, 3-ethoxy-2-acryloylacrylate, 2-vinyl propane-1, 3-diol, hexamethylene diisocyanate and polypropylene glycol-500.
4. The environment-friendly pencil coating of claim 1 wherein the acrylic compound comprises acrylic acid, methacrylic acid and methyl methacrylate.
5. The environmentally friendly pencil coating of claim 1 wherein said photoinitiator comprises an initiator 819, initiator ITX.
6. The preparation method of the environment-friendly pencil coating is characterized by comprising the following preparation steps:
(1) Mixing S- (-) -tert-butylamine-1, 2-propylene glycol, methylene dichloride and 3-ethoxy-2-acryloyl isocyanate according to a mass ratio of 1:8-15:0.8-2.0, stirring at 30-70 rpm for 9-15 h at room temperature, adding petroleum ether/ethyl acetate solution with the volume of 2-5 times of that of the reaction solution and 50-60 ℃, stirring until solid is separated out, and carrying out suction filtration to obtain the self-repairing modifier;
(2) Mixing polypropylene glycol-500, a self-repairing modifier and N, N-dimethylformamide according to the mass ratio of 11.9:2.4-7.0:38, stirring and dissolving, adding hexamethylene diisocyanate with the mass 1.0-1.2 times of that of 2-vinyl propane-1, 3-diol, and stirring for 3-6 hours at 80-85 ℃ and 100rpm to obtain a modified polyurethane prepolymer solution;
(3) Mixing core liquid and modified polyurethane prepolymer solution according to a mass ratio of 3:2 to obtain mixed liquid, adding acacia with the mass of 0.03-0.05 times of that of the mixed liquid, emulsifying for 30min at 5000-8000 rpm, adding 2-vinyl propane-1, 3-diol with the mass of 0.2-0.5 times of that of the modified polyurethane prepolymer solution, reacting for 4-8 h at 60-80 ℃, carrying out suction filtration, taking solid, washing for 6 times by using 30% ethanol water solution according to mass fraction, and drying for 24h at room temperature to obtain self-made microsphere particles;
(4) Mixing nitrocotton, ethyl acetate, butyl acetate and absolute ethyl alcohol according to a mass ratio of 60-70:3-4.5:2-5:1, adding acrylic modified alkyd resin, acrylic compound, photoinitiator, bisphenol A, defoamer BYK141 and carboxymethyl cellulose according to a mass ratio of 45-65:15-34:1.5-2.5:1-7:0.3-0.7:1.0-1.5 under 200-300 rpm, and stirring for 20-30 min to obtain the environment-friendly pencil coating, wherein the mass ratio of the acrylic modified alkyd resin to the nitrocotton is 1:3-2:7, and then the speed is increased to 1200-1400 rpm.
7. The method for preparing the environment-friendly pencil coating, as claimed in claim 6, wherein the volume ratio of petroleum ether to ethyl acetate in the petroleum ether/ethyl acetate solution in the step (1) is 10-20:1.
8. The method for preparing the environment-friendly pencil coating as set forth in claim 6, wherein the method for preparing the core liquid in the step (3) comprises the following steps: mixing n-decanoic acid and 1-octadecanol according to the mass ratio of 80-90:10-20, sealing and placing in a constant temperature drying oven at 80 ℃, heating to completely melt, uniformly stirring to obtain low-melting-point phase-change material liquid, adding dye ODB-2 with the mass of 0.004-0.008 times of that of the low-melting-point phase-change material liquid, and stirring for 20-30 min at 60 ℃ and 80 rpm.
9. The method for preparing the environment-friendly pencil coating, as claimed in claim 6, wherein the mass ratio of acrylic acid, methacrylic acid and methyl methacrylate in the acrylic compound in the step (4) is 15-25:2-6:1-3.
10. The method for preparing the environment-friendly pencil coating, as claimed in claim 6, wherein the mass ratio of the initiator 819 to the initiator ITX in the photoinitiator in the step (4) is 2-4:1.
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| CN1650230A (en) * | 2002-04-19 | 2005-08-03 | 亨斯迈先进材料（瑞士）有限公司 | Photocurable compositions containing reactive particles |
| CN113861808A (en) * | 2021-10-22 | 2021-12-31 | 天津中晶建筑材料有限公司 | Roller coating UV white primer with excellent UV ink wettability and preparation method thereof |
| CN113881334A (en) * | 2020-07-30 | 2022-01-04 | 九天起宏(江苏)检测有限公司 | Self-repairing waterborne polyurethane coating composition and coating |
| CN115286762A (en) * | 2022-05-10 | 2022-11-04 | 华南理工大学 | UV-induced self-crosslinking polyurethane aqueous dispersion and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1650230A (en) * | 2002-04-19 | 2005-08-03 | 亨斯迈先进材料（瑞士）有限公司 | Photocurable compositions containing reactive particles |
| CN113881334A (en) * | 2020-07-30 | 2022-01-04 | 九天起宏(江苏)检测有限公司 | Self-repairing waterborne polyurethane coating composition and coating |
| CN113861808A (en) * | 2021-10-22 | 2021-12-31 | 天津中晶建筑材料有限公司 | Roller coating UV white primer with excellent UV ink wettability and preparation method thereof |
| CN115286762A (en) * | 2022-05-10 | 2022-11-04 | 华南理工大学 | UV-induced self-crosslinking polyurethane aqueous dispersion and preparation method and application thereof |
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