CN112721492B - Temperature-resistant porphyrin grafted silica toner and preparation method and application thereof - Google Patents
Temperature-resistant porphyrin grafted silica toner and preparation method and application thereof Download PDFInfo
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- CN112721492B CN112721492B CN202011466925.7A CN202011466925A CN112721492B CN 112721492 B CN112721492 B CN 112721492B CN 202011466925 A CN202011466925 A CN 202011466925A CN 112721492 B CN112721492 B CN 112721492B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims abstract description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003094 microcapsule Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000013504 Triton X-100 Substances 0.000 claims description 12
- 229920004890 Triton X-100 Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000010023 transfer printing Methods 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
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- Silicon Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
The invention discloses a temperature-resistant porphyrin grafted silica toner and a preparation method and application thereof, wherein the toner is prepared by modifying carboxyl and (3-aminopropyl) triethoxysilane groups on porphyrin dye to obtain temperature-resistant porphyrin; uniformly mixing n-heptane, n-heptanol and a surfactant, adding water as a dispersion phase, then adding temperature-resistant porphyrin, stirring to form water-in-oil microcapsules, adding tetraethoxysilane into a microcapsule system, stirring uniformly, finally adding an alkali liquor for hydrolysis, and centrifuging and drying after the reaction is finished to obtain the temperature-resistant porphyrin grafted silica toner. The toner can be used for holographic water transfer printing, has excellent temperature resistance, and can resist long-time baking without deterioration.
Description
Technical Field
The invention belongs to the technical field of anti-counterfeiting, and particularly relates to a temperature-resistant porphyrin grafted silica toner, a preparation method and application thereof in holographic water transfer.
Background
Holographic water transfer printing is a new technology combining water transfer printing technology and laser holographic molding technology. In specific use, the interference fringes of the hologram are printed on the holographic recording material by a holographic die pressing process and a high-temperature baking process, and then the interference fringes are transferred to complex non-planar objects such as plastic, metal, glass, ceramic surfaces and the like by water. In recent years, the holographic water transfer printing technology is rapidly developed along with the market demand, and the market potential is huge.
In the high-temperature baking process, the holographic water transfer film needs to be baked for 30 minutes at 200 ℃ to be firmly adhered to a complex non-planar object, so that the holographic recording material needs to have long-time temperature resistance, otherwise, the holographic effect of the product is influenced. At present, the temperature resistance of toner in the holographic recording material is not durable, and the holographic recording material can generate the deterioration phenomena such as chemical oxidation, carbonization and the like in long-time baking, thereby causing the adverse consequences such as light loss, color change and the like of holographic patterns. Therefore, the industry is eagerly expected to effectively solve the problem that the temperature resistance of the toner is not ideal.
Disclosure of Invention
The invention provides a temperature-resistant porphyrin grafted silica toner, a preparation method and application thereof.
The technical scheme provided by the invention is that the temperature-resistant porphyrin grafted silica toner is prepared by grafting silicon dioxide with porphyrin dye modified with carboxyl and (3-aminopropyl) triethoxysilane groups, wherein the mass ratio of the temperature-resistant porphyrin to the silicon dioxide is 0.1-0.5: 0.3-3.
Further, the silica is provided by ethyl orthosilicate.
The invention also relates to a method for preparing the temperature-resistant porphyrin grafted silica toner, which comprises the following steps:
s1, modifying carboxyl and (3-aminopropyl) triethoxysilane groups on porphyrin dye to obtain temperature-resistant porphyrin;
s2, uniformly mixing n-heptane, n-heptanol and a surfactant, adding water as a dispersion phase, then adding temperature-resistant porphyrin, stirring to form water-in-oil microcapsules, adding tetraethoxysilane into a microcapsule system, uniformly stirring, finally adding an alkali liquor for hydrolysis, and centrifuging and drying after the reaction is finished to obtain the temperature-resistant porphyrin grafted silica toner.
Further, the structure of the temperature-resistant porphyrin obtained in S1 is shown in the following formula I,
wherein at least one of R1, R2 and R3 is carboxyl, and the others are any groups; r4 is a (3-aminopropyl) triethoxysilane group.
Further, the surfactant described in S1 is Triton X-100.
Furthermore, the weight ratio of the n-heptanol to the n-heptane to the surfactant to the water to the heat-resistant porphyrin to the ethyl orthosilicate to the alkali liquor is 1: 1-10: 0.5-4: 2.5-15: 0.1-0.5: 1-10: 1-20.
Further, in S2, the reaction temperature is 25-45 ℃ and the reaction time is 8-24 h.
The invention also relates to application of the temperature-resistant porphyrin grafted silica toner in holographic water transfer printing, which has high temperature stability and can meet the requirements of holographic water transfer printing.
The invention has the following beneficial effects:
1. the invention modifies carboxyl and (3-aminopropyl) triethoxy silane group on the dye to realize graft copolymerization with ethyl orthosilicate, forms heat-resistant porphyrin grafted silica toner by in-situ hydrolysis of ethyl orthosilicate and (3-aminopropyl) triethoxy silicon-based porphyrin in water phase, and the formation of microcapsule system in the reaction, the proportion of reaction substrate and the type and dosage of catalyst in the hydrolysis process are key in the preparation process, thus finally preparing the holographic water transfer toner with excellent heat resistance. And the preparation method is simple and efficient and has low production cost.
2. The invention grafts the silicon dioxide toner by the heat-resistant porphyrin to form an organic-inorganic cross-linked composite Si-O-Si network structure, wherein the bond energy of the silicon-oxygen bond is high and can not break, while the porphyrin is taken as a macrocyclic conjugated system and has excellent heat resistance, the porphyrin and the macrocyclic conjugated system are combined to obtain excellent heat resistance, the obtained toner can keep stability for hours at the temperature of 200 ℃, the heat resistance requirement of holographic water transfer printing on the toner can be met, and the toner can not deteriorate in the high-temperature baking process.
3. The preparation method of the temperature-resistant porphyrin grafted silica toner is simple, the used raw materials are simple and easy to synthesize, and the toner is harmless to human bodies and environments, and the high-yield temperature-resistant toner can be obtained by adopting a one-pot hydrolysis reaction during preparation, and has good repeatability.
Drawings
Fig. 1 is a graph showing the ultraviolet-visible absorption spectrum of the toner obtained in example 1 in dimethyl sulfoxide, wherein the abscissa is the wavelength and the ordinate is the absorbance.
FIG. 2 is a stability test chart of the toner of example 1 at 200 degrees, wherein the abscissa is time and the ordinate is absorbance at 416 nm.
FIG. 3 is a stability test chart of the toner of example 2 at 200 degrees, wherein the abscissa is time and the ordinate is absorbance at 416 nm.
FIG. 4 is a stability test chart of the toner of example 3 at 200 degrees, wherein the abscissa is time and the ordinate is absorbance at 416 nm.
FIG. 5 is a stability test chart of the toner of example 4 at 200 degrees, wherein the abscissa is time and the ordinate is absorbance at 418 nm.
FIG. 6 is a stability test chart of the toner of example 5 at 200 degrees, wherein the abscissa is time and the ordinate is absorbance at 420 nm.
Detailed Description
The invention will be further elucidated with reference to the following examples.
Example 1:
modifying carboxyl and (3-aminopropyl) triethoxysilane groups on porphyrin dye to obtain temperature-resistant porphyrin; the structure is shown as (II).
Synthesizing a temperature-resistant porphyrin grafted silica toner with a structure shown in a formula (II):
uniformly mixing n-heptane, n-heptanol and surfactant Triton X-100 according to a certain proportion, adding a proper amount of water as a dispersion phase, then adding a certain amount of temperature-resistant porphyrin (II), stirring for 5min to form water-in-oil microcapsules, then adding tetraethoxysilane into a microcapsule system, stirring uniformly, adding a proper amount of alkali liquor for hydrolysis, and the whole reaction time is 8 h. The ratio of the amounts of n-heptanol, n-heptane, surfactant Triton X-100, water, temperature-resistant porphyrin, ethyl orthosilicate and alkali liquor in the reaction system is 1:4: 0.5: 2.5:0.1:1:1.1. After the reaction is finished, centrifuging and drying to obtain the temperature-resistant porphyrin-silica toner with the yield of 85 percent.
The temperature-resistant porphyrin-silica toner obtained in example 1 is used as holographic water transfer toner, the maximum absorption peaks of ultraviolet visible absorption spectrum in dimethyl sulfoxide are 416nm, 514nm, 550nm, 589nm and 644nm, and the stable existence time is more than 2.5h at 200 ℃, specifically shown in fig. 1 and fig. 2.
Example 2:
synthesizing a temperature-resistant porphyrin grafted silica toner with a structure shown in a formula (III):
uniformly mixing n-heptane, n-heptanol and surfactant Triton X-100 according to a certain proportion, adding a proper amount of water as a dispersion phase, then adding a certain amount of temperature-resistant porphyrin (III), stirring for 5min to form water-in-oil microcapsules, then adding tetraethoxysilane into a microcapsule system, stirring uniformly, adding a proper amount of alkali liquor for hydrolysis, and the whole reaction time is 16 h. The ratio of the amounts of n-heptanol, n-heptane, surfactant Triton X-100, water, temperature-resistant porphyrin, ethyl orthosilicate and alkali liquor in the reaction system is 1:1: 1: 3.5:0.2:3:5. After the reaction is finished, centrifuging and drying to obtain the temperature-resistant porphyrin-silica toner with the yield of 89%.
The temperature-resistant porphyrin-silica toner obtained in example 2 is used as holographic water transfer toner, the maximum absorption peaks of ultraviolet visible absorption spectrum of the toner in dimethyl sulfoxide are 416nm, 514nm, 550nm, 589nm and 644nm, and the toner stably exists for more than 1.5h at the temperature of 200 ℃, as shown in figure 3.
Example 3:
synthesis of temperature-resistant porphyrin grafted silica toner with structure of formula (IV):
uniformly mixing n-heptane, n-heptanol and surfactant Triton X-100 according to a certain proportion, adding a proper amount of water as a dispersion phase, then adding a certain amount of temperature-resistant porphyrin (IV), stirring for 5min to form water-in-oil microcapsules, then adding tetraethoxysilane into a microcapsule system, stirring uniformly, adding a proper amount of alkali liquor for hydrolysis, and the whole reaction time is 20 h. The ratio of the amounts of n-heptanol, n-heptane, surfactant Triton X-100, water, temperature-resistant porphyrin, ethyl orthosilicate and alkali liquor in the reaction system is 1:10: 4: 10:0.5:10:11. After the reaction is finished, centrifuging and drying to obtain the temperature-resistant porphyrin-silica toner with the yield of 95%.
The temperature-resistant porphyrin-silica toner obtained in example 3 is used as holographic water transfer toner, the maximum absorption peaks of ultraviolet visible absorption spectrum of the toner in dimethyl sulfoxide are 416nm, 514nm, 550nm, 589nm and 644nm, and the toner stably exists for more than 1.25h at the temperature of 200 ℃, as shown in FIG. 4.
Example 4:
synthesizing a temperature-resistant porphyrin grafted silica toner with a structure shown as a formula (V):
uniformly mixing n-heptane, n-heptanol and surfactant Triton X-100 according to a certain proportion, adding a proper amount of water as a dispersion phase, then adding a certain amount of temperature-resistant porphyrin (V), stirring for 5min to form water-in-oil microcapsules, then adding tetraethoxysilane into a microcapsule system, stirring uniformly, adding a proper amount of alkali liquor for hydrolysis, and the whole reaction time is 24 h. The ratio of the amounts of n-heptanol, n-heptane, surfactant Triton X-100, water, temperature-resistant porphyrin, ethyl orthosilicate and alkali liquor in the reaction system is 1:8: 3: 15:0.5:8:20. After the reaction is finished, centrifuging and drying to obtain the temperature-resistant porphyrin-silica toner with the yield of 91%.
The temperature-resistant porphyrin-silica toner obtained in example 4 is used as holographic water transfer toner, the maximum absorption peaks of the toner in the ultraviolet visible absorption spectrum in dimethyl sulfoxide are 418nm, 516nm, 552nm, 590nm and 648nm, and the toner stably exists for more than 0.8h at the temperature of 200 ℃, as shown in FIG. 5.
Example 5:
synthesis of temperature-resistant porphyrin grafted silica toner of formula (VI):
uniformly mixing n-heptane, n-heptanol and surfactant Triton X-100 according to a certain proportion, adding a proper amount of water as a dispersion phase, then adding a certain amount of temperature-resistant porphyrin (VI), stirring for 5min to form water-in-oil microcapsules, then adding tetraethoxysilane into a microcapsule system, stirring uniformly, adding a proper amount of alkali liquor for hydrolysis, and the whole reaction time is 18 h. The ratio of the amounts of n-heptanol, n-heptane, surfactant Triton X-100, water, temperature-resistant porphyrin, ethyl orthosilicate and alkali liquor in the reaction system is 1:6: 2.6: 10:0.5:5:5.6. After the reaction is finished, centrifuging and drying to obtain the temperature-resistant porphyrin-silica toner with the yield of 95%.
The temperature-resistant porphyrin-silica toner obtained in example 5 is used as holographic water transfer toner, the maximum absorption peaks of ultraviolet visible absorption spectrum of the toner in dimethyl sulfoxide are 420nm, 518nm, 555nm, 592nm and 650nm, and the toner stably exists for more than 1h at the temperature of 200 ℃, as shown in FIG. 6.
The stabilization time in the above examples was judged by the change in the uv-vis absorption spectrum of the toner, and was considered to be no longer stable when the time decreased to 90% or less of the original value.
Claims (7)
1. A temperature-resistant porphyrin grafted silica toner is characterized in that: silicon dioxide is grafted by porphyrin dye modified with carboxyl and (3-aminopropyl) triethoxysilane groups, wherein the mass ratio of the heat-resistant porphyrin to the silicon dioxide is 0.1-0.5: 0.3-3;
the structure of the temperature-resistant porphyrin is shown as the following formula I,
wherein R is1，R2，R3At least one of them is carboxyl, and the others are arbitrary groups; r4Is a (3-aminopropyl) triethoxysilane group.
2. The temperature-resistant porphyrin-grafted silica toner of claim 1, characterized in that: the silica is provided by ethyl orthosilicate.
3. A method of preparing a temperature-resistant porphyrin-grafted silica toner as claimed in claim 1 or 2, comprising the steps of:
s1, modifying carboxyl and (3-aminopropyl) triethoxysilane groups on porphyrin dye to obtain temperature-resistant porphyrin;
s2, uniformly mixing n-heptane, n-heptanol and a surfactant, adding water as a dispersion phase, then adding temperature-resistant porphyrin, stirring to form water-in-oil microcapsules, adding tetraethoxysilane into a microcapsule system, uniformly stirring, finally adding an alkali liquor for hydrolysis, and centrifuging and drying after the reaction is finished to obtain the temperature-resistant porphyrin grafted silica toner.
4. The method of claim 3, wherein: the surfactant in S2 is triton X-100.
5. The method of claim 3, wherein: the weight ratio of the n-heptanol to the n-heptane to the surfactant to the water to the heat-resistant porphyrin to the ethyl orthosilicate is 1: 1-10: 0.5-4: 2.5-15: 0.1-0.5: 1-10: 1-20.
6. The method of claim 3, wherein: in S2, the reaction temperature is 25-45 ℃ and the reaction time is 8-24 h.
7. Use of a temperature-resistant porphyrin-grafted silica toner according to any one of claims 1-2 as a toner for holographic water transfer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4552818A (en) * | 1984-05-10 | 1985-11-12 | At&T Technologies, Inc. | Silicone encapsulant containing porphyrin |
| TWI238405B (en) * | 2002-11-01 | 2005-08-21 | Ind Tech Res Inst | Application of porphyrin on fluorescent multilayer recording medium and manufacturing method thereof |
| US7223628B2 (en) * | 2003-07-25 | 2007-05-29 | The Regents Of The University Of California | High temperature attachment of organic molecules to substrates |
| CN101840124B (en) * | 2010-05-06 | 2011-12-14 | 宁波大学 | Preparation method of porphyrin coupled silicon dioxide organic-inorganic nonlinear optical material |
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