CN109876743A - A kind of light-sensitive microcapsule and the preparation method and application thereof containing photosensitive colour-changing material - Google Patents
A kind of light-sensitive microcapsule and the preparation method and application thereof containing photosensitive colour-changing material Download PDFInfo
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Abstract
The invention discloses a kind of light-sensitive microcapsules containing photosensitive colour-changing material, it is made of cyst wall and capsule-core, the material of the cyst wall is cyst wall polymer, it is to be polymerize to be formed by illumination by the monomer of photopolymerization or photo-crosslinking, the material of the capsule-core is Photochromic Polymers or photochromic polymer.Light-sensitive microcapsule containing photosensitive colour-changing material of the invention has good thermal stability; deformation and stretching are not generated when heated; with good mechanical performance, the complete and resilient protection capsule-core substance of utricule is kept under external impacts and is isolated with external environment；Simultaneously there is good light transmission, enable ultraviolet light or daylight unhinderedly through cyst wall and be irradiated to capsule-core off-color material rush bring it about light sensitive effect.
Description
Technical field
The invention belongs to technical field of polymer materials, specifically, being related to a kind of containing the photosensitive of photosensitive colour-changing material
Microcapsules and the preparation method and application thereof.
Background technique
Photochromism refers to certain chemical substances after being excited by light, in two states with different colours
Between reversible transition process.Such as: azobenzene, fulgides, spiro-pyrans class, spirooxazine class, diarylethene and several
The photochromic reactions of kind novel organic photochromic material, and comparing its advantage and disadvantage includes stability and fatigue resistance,
In, diarylethene system is due to aobvious between high thermal stability, excellent antifatigue degree and different isomer state
The physical and chemical performance difference of work is one of the chromic systems for most having application prospect at present.Photochromic material belongs to
Light-sensitive material in field of new materials.Early in just there is scientist to carry out report to photochromic material in 19th century, and light-induced variable
It is in 1956 that color material, which really starts to attract attention, and Hirshberg proposes that photochromic material can be applied to light memory and deposit
In terms of memory device.21 century is stepped into, with the continuous improvement of modernization of information level, people are to high information storage capacity and high speed
The demand of transmission is growing day by day, and as traditional disc information storage mode since information storage capacity is limited, storage speed
It crosses slowly, will inevitably be replaced by storage material of new generation, and photochromic material is likely to become alternative materials.
Organic photochromic material has become scientists in recent years and chases as important a member in photochromic material
Hot spot.Because the storage mode of organic photochromic material belongs to photon memory module, in the effect of visible light or ultraviolet light
Under, medium can change the chemical structure of itself by capture photon to change the physical and chemical performance of itself, to reach
The purpose of information storage.The features such as this storage mode has storage density high, and storage speed is fast and superelevation storage resolution.This
Outside, in terms of organic photochromic material applies also for photo chromic glass and military field, people's living standard and guarantee are being improved
Meaning in terms of national security is growing.
Organic photochromic material is mainly used in three broad aspects: light recall info storage aspect, household chemicals industry
In terms of aspect and military field.
Photochromism refers to a compound (A) by certain wavelength (λ1) light irradiation, carry out specified chemical reaction life
At product (B), apparent variation occurs for absorption spectrum；In another wavelength (λ2) under the action of light irradiation is lower or heat, and it is extensive
Original form is arrived again.
Photochromic is a kind of reversible chemical reaction, this is an important judgment criteria.Occur under light action
Irreversible reaction may also lead to the variation of color, be pertaining only to general photochemistry scope, and be not belonging to photochromic scope.Light
Electrochromic compound is caused to be broadly divided into two classes: inorganic photochromic compound and photochromic compounds, wherein organic light
Causing electrochromic compound is compound in molecule containing photochromic functionalities, their photochromic properties from point
The photochromic group contained in son.Photochromic compounds can be divided into azobenzene, fulgides, spiro-pyrans class,
Spirooxazine class and diarylethene etc..
United States Patent (USP) US4399209, US4416906, US4440846 individually disclose one kind and utilize radiation sensitive component
Photo-hardening microencapsulation material.The characteristics of this material is will be comprising that can occur the coating for the microcapsules that photo-hardening reacts specific
It is exposed under wavelength light, so that according to different degrees of light exposure corresponding photo-hardening occurs for the photo-hardening component inside microcapsules
Reaction, then applies certain pressure to coating, the color precursor so that microcapsules rupture of unexposed portion, inside microcapsules
It contacts and chemically reacts with the substance that show color outside microcapsules, forming visible image makes information leave-on.
United States Patent (USP) US4682194, US4446376, US4411979, US4742043 application discloses a kind of microcapsule coated
The technology of temperature-sensitive information material.Its feature is that dyestuff former forms microcapsules, and cyst wall uses polyurethane, and capsule-core, which does not contain, to be drawn
Agent and reaction monomers are sent out, so that the microcapsules containing dyestuff and color developing agent and other additives is formed coating, using including hot print
Heating of the heat source for imaging layer-selective including head adjusts the penetrating power of microcapsule wall for showing by the variation of temperature
Shadow.After temperature reduces, microcapsule wall hardens that there is no thus stability that penetrating power improves image again.
Chinese patent CN1386095A application discloses a kind of image forming medium containing heat developable photosensitive microcapsule, microcapsules and
Color developing agent is coated between a transparent support and an opaque support.It is separately included pair inside several difference microcapsules
In the photolytic activity chemicals of different wave length light sensitivity, in favor of microcapsules can be issued in the exposure of different wavelengths of light it is stiff
Change.Microcapsules are preferably dimensioned to be 0.8 μm~2.0 μm.Different microcapsules are mixed into coating when coating or are respectively formed coating,
Different colors can be formed after heating, to constitute colored or panchromatic image.
United States Patent (USP) US4682194, US4446376, US4411979, US4742043 and Chinese patent CN1386095A
(ZL01802048.8), CN1731276A uses non-photochemistry interfacial polymerization techniques in microcapsules polymerization, reacts in heating
Under the conditions of, the stability for the organic off-color material being wrapped by and the completeness of interface polymerization reaction are all insufficient.
In view of this, it is necessary to provide a kind of micro- glue prepared by " the illumination interface polymerization reaction " using " efficient, quick "
Capsule.
Summary of the invention
The object of the present invention is to provide a kind of light-sensitive microcapsules containing photosensitive colour-changing material.
It is a further object to provide the preparation sides of the light-sensitive microcapsule described in one kind containing photosensitive colour-changing material
Method.
It is also another object of the present invention to provide the purposes of the light-sensitive microcapsule described in one kind containing photosensitive colour-changing material.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The first aspect of the invention provides a kind of light-sensitive microcapsule containing photosensitive colour-changing material, is by cyst wall and capsule
Core composition, the material of the cyst wall are cyst wall polymer, are to be polymerize by the monomer of photopolymerization or photo-crosslinking by illumination
It is formed, the material of the capsule-core is Photochromic Polymers or photochromic polymer.
The monomer of the photopolymerization or photo-crosslinking be acrylate and methacrylate, containing acrylate and
Epoxy resin, acrylonitrile, vinyl benzene, vinyl ethers or the maleimide low polymer of methacrylate；Preferably propylene
Nitrile, butyl acrylate, Glycerin triacrylate (TMPTA), pentaerythritol tetracrylate (PETTA), three acrylic acid
Pentaerythritol ester (PETA), tetramethyl pentaerythritol tetracrylate, three contracting dipropylene glycol diacrylates (TPGDA), new penta
Omega-diol diacrylate (NPGDA), 1,6 hexanediol diacrylate (HDDA), isobornyl acrylate (IBOA), benzene oxygen second
Base acrylate (PHEA), acrylic acid epoxy resin (SM6200, SM6318, UA333, UA320 etc.), polyester acrylate
(PEA400), two contractings/tripropylene glycol double methacrylate (DPGDA), double pentaerythritol methacrylate (DPHA), polyethylene glycol
Bis- (methyl) acrylate (PEGDA, PEGDMA).In addition in the widely used various similar polymer monomers in photochemistry field or
Oligomer, if it is possible to which it is all available for meeting the requirement of the present patent application content.
The Photochromic Polymers or photochromic polymer are selected from azobenzene photochromic polymer, prisoner's essence
Anhydride photochromic polymer, spiro-pyrans class photochromic polymer, spirooxazine class photochromic polymer, diarylethene
Photochromic polymer, the photochromic polymer of the structure containing sulfocarbazone, the Photochromic Polymers containing imine structure,
The Photochromic Polymers of structure containing Phenoxynaphthacenequinones, polycyclic quinone photochromic polymer, aniline derivatives species
Photochromic polymer, benzo pyran photochromic polymer, purpurine class photochromic material, transition-metal oxide class material
At least one of material, metal halide species material, photochromic rare earth compounding.
The diarylethene photochromic polymer is two heteroaromatic ethylene, the photochromic polymerization of dithiazole ethylene
Object, preferably maleic anhydride are the di-thiofuran ethylene compound of alkene bridge.
The transition-metal oxide class material is WO3、MoO3、TiO2At least one of.
The metal halide species material in calcium iodide and mercuric iodixde mixed crystal, copper chloride, silver chlorate at least
It is a kind of.
The partial size of the light-sensitive microcapsule containing photosensitive colour-changing material is 200~1000nm, preferably 300~800nm.
The second aspect of the invention provides the preparation side of the light-sensitive microcapsule described in one kind containing photosensitive colour-changing material
Method, comprising the following steps:
The monomer of photopolymerization or photo-crosslinking, Photochromic Polymers or photochromic polymer are added to
In internal irradiation type quartz photochemical reactor, be warming up to 60~100 DEG C, be stirred, it is to be cooled to close to room temperature when table is added
Face activating agent continues to stir；The monomer of photopolymerization or photo-crosslinking, Photochromic Polymers or photochromic polymerization
Object, surfactant mass ratio be (1~100): (80~400): 1；
Deionized water high-speed stirred is added in photochemical reactor, photoinitiator or photosensitizer and molten are added into system
Agent continues to stir, and opens ultraviolet light source 1~5h of illumination reaction under conditions of wavelength is 365nm or 254nm；Photoinitiator
Or the mass ratio of the monomer of photosensitizer, photopolymerization or photo-crosslinking is 1:(5~50)；
Illumination reaction terminates, and is warming up to 40~60 DEG C, continues to be stirred to react 0.1~2h, cold filtration is obtained containing photosensitive
The novel light-sensitive microcapsule of off-color material.
The monomer of the photopolymerization or photo-crosslinking be acrylate and methacrylate, containing acrylate and
Epoxy resin, acrylonitrile, vinyl benzene, vinyl ethers or the maleimide low polymer of methacrylate；Preferably propylene
Nitrile, butyl acrylate, Glycerin triacrylate (TMPTA), pentaerythritol tetracrylate (PETTA), three acrylic acid
Pentaerythritol ester (PETA), tetramethyl pentaerythritol tetracrylate, three contracting dipropylene glycol diacrylates (TPGDA), new penta
Omega-diol diacrylate (NPGDA), 1,6 hexanediol diacrylate (HDDA), isobornyl acrylate (IBOA), benzene oxygen second
Base acrylate (PHEA), acrylic acid epoxy resin (SM6200, SM6318, UA333, UA320 etc.), polyester acrylate
(PEA400), two contractings/tripropylene glycol double methacrylate (DPGDA), double pentaerythritol methacrylate (DPHA), polyethylene glycol
Bis- (methyl) acrylate (PEGDA, PEGDMA).In addition in the widely used various similar polymer monomers in photochemistry field or
Oligomer, if it is possible to which it is all available for meeting the requirement of the present patent application content.
The Photochromic Polymers or photochromic polymer are selected from azobenzene photochromic polymer, prisoner's essence
Anhydride photochromic polymer, spiro-pyrans class photochromic polymer, spirooxazine class photochromic polymer, diarylethene
Photochromic polymer, the photochromic polymer of the structure containing sulfocarbazone, the Photochromic Polymers containing imine structure,
The Photochromic Polymers of structure containing Phenoxynaphthacenequinones, polycyclic quinone photochromic polymer, aniline derivatives species
Photochromic polymer, benzo pyran photochromic polymer, purpurine class photochromic material, transition-metal oxide class material
At least one of material, metal halide species material, photochromic rare earth compounding.
The diarylethene photochromic polymer is two heteroaromatic ethylene, the photochromic polymerization of dithiazole ethylene
Object, preferably maleic anhydride are the di-thiofuran ethylene compound of alkene bridge.
The transition-metal oxide class material is WO3、MoO3、TiO2At least one of.
The metal halide species material in calcium iodide and mercuric iodixde mixed crystal, copper chloride, silver chlorate at least
It is a kind of.
The surfactant is anhydrous sorbitol palm acid monoester, sorbitan fatty ester.
The photoinitiator is water-soluble light trigger, preferably the thioxanthone of propoxyl group trimethyl methanesulfonic acid ammonium substitution
Benzophenone derivates (WB-4784, WB-4782, WB- that (TS-2S, TS-3S series), quaternary ammonium salt or sulfonic acid group replace
OMe, WB-4785, WB-4698, WB-4789 etc.), hydroxyalkylphenyl ketone derivatives (HMPP-1, HMPP-2, HMPP-3,
HMPP-4 etc.).
The photosensitizer be water-soluble material, preferably propoxyl group trimethyl methanesulfonic acid ammonium replace thioxanthone (TS-2S,
TS-3S series), quaternary ammonium salt or sulfonic acid group benzophenone derivates (WB-4784, WB-4782, WB-OMe, WB- for replacing
4785, WB-4698, WB-4789 etc.), hydroxyalkylphenyl ketone derivatives (HMPP-1, HMPP-2, HMPP-3, HMPP-4 etc.
Deng).
The solvent is acetone.
Another aspect of the invention provides the light-sensitive microcapsule described in one kind containing photosensitive colour-changing material for changing colour
The purposes of nail polish, lipstick.
When the light-sensitive microcapsule containing photosensitive colour-changing material is used for color changeable nail enamel, lipstick, additional amount is discoloration
Nail polish, lipstick mass percent be 100~400%.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
Light-sensitive microcapsule containing photosensitive colour-changing material of the invention, which has, prepares quick and easy, good thermal stability,
Deformation and stretching are not generated when heated；With good mechanical performance, the complete and elastic of utricule is kept under external impacts
It protects capsule-core substance and is isolated with external environment；Thin cyst simultaneously has good light transmission, makes ultraviolet light or energy of the sun
It enough unhinderedly penetrates cyst wall and is irradiated to capsule-core off-color material rush and bring it about light sensitive effect.And existing " interface thermal polymerization
In the method for reaction ", the general organic matter such as Photochromic Polymers or photochromic polymer is easy to be by thermal oxide or old
Change；Surfactant is heated its surface-active of malleable.
Detailed description of the invention
Fig. 1 is the cladding situation schematic diagram of the light-sensitive microcapsule containing photosensitive colour-changing material prepared by embodiment 1.
When Fig. 2 is that the light-sensitive microcapsule containing photosensitive colour-changing material prepared by embodiment 1 is tested with spectrophotometer, high speed
Disperse 8000 turns/10min microcapsule coated situation schematic diagram.
When Fig. 3 is that the light-sensitive microcapsule containing photosensitive colour-changing material prepared by embodiment 1 is tested with spectrophotometer, high speed
Disperse 8000 turns/20min microcapsule coated situation schematic diagram.
When Fig. 4 is that the light-sensitive microcapsule containing photosensitive colour-changing material prepared by embodiment 1 is tested with spectrophotometer, high speed
Disperse 8000 turns/40min microcapsule coated situation schematic diagram.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Light-sensitive microcapsule containing photosensitive colour-changing material of the invention has good thermal stability, does not generate when heated
Deformation and stretching；With good mechanical performance, the complete and resilient protection capsule-core substance of utricule is kept simultaneously under external impacts
And it is isolated with external environment；There is good light transmission simultaneously, ultraviolet light or daylight is enable unhinderedly to penetrate cyst wall simultaneously
It is irradiated to capsule-core off-color material rush and brings it about light sensitive effect.
The photopolymerization of the cyst material of light-sensitive microcapsule containing photosensitive colour-changing material of the invention or photo-crosslinkable component
Prepolymer including unsaturated compound containing double bonds or its low molecular weight.They can penetrate free radical or other modes
Addition polymerization or polycondensation reaction are crosslinked, and polymer wall is formed.The polymer both can with capsule-core substance independently,
Again solid solution can be formed with capsule-core substance.The monomer of photopolymerization or photo-crosslinking can be simple function group or multifunctional
Group, is also possible to prepolymer.Cyst wall polymer is to polymerize to be formed by illumination.
The preparation method of light-sensitive microcapsule containing photosensitive colour-changing material of the invention, be in quartz Photoreactor,
By adjusting mixing speed, so that oil-based system is dispersed to certain granules partial size in water phase, be added in water phase at this time light-initiated
Agent and photosensitizer open light source, in oily phase under the irradiation of certain wavelength light -- and aqueous phase interface is formed by the way that interfacial polymerization occurs
Coat the polymer microcapsule of photosensitive medium.By adjusting the revolving speed and optical source wavelength, photoinitiator and photosensitizer that are dispersed with stirring
Type, so that the average grain diameter of the light-sensitive microcapsule containing photosensitive colour-changing material of aforementioned present invention preparation is 200~1000nm.
Embodiment 1
By 28 grams of floating smart acid anhydrides (FULGIDE, Beijing east China make every effort to open up development in science and technology Co., Ltd), 10 grams of tetrapropylenes sour season penta
Four alcohol esters (PETTA, purchased from upper caldron along International Trading Company Ltd) are added to internal irradiation type 500ml quartz photochemical reactor
In (L60-45, Beijing Bo Feilai Science and Technology Ltd.), be warming up to 80 DEG C, be stirred, it is to be cooled to close to room temperature when be added
0.25 gram of Span40 (anhydrous sorbitol palm acid monoester, this disk -40, Jiangsu Hai'an petrochemical plant) continues stirring 30 minutes.
150ml deionized water, 3000 revs/min of revolving speed high-speed stirred 5 minutes, to system are added in above-mentioned photochemical reactor
(benzophenone is the derivative of parent to middle 0.5 gram of WB-4784 of addition, and substituent group is 2- hydroxy propyloxy group-trimethyl ammonium chloride
Salt, AR, upper caldron is along International Trading Company Ltd, group) and 5ml acetone, continue stirring 30 minutes, opens ultraviolet light source and exist
Wavelength is illumination reaction 1.5h under conditions of 365nm.
Illumination reaction terminates, and is warming up to 50 DEG C, continues to be stirred to react 0.5h, cold filtration, obtaining average grain diameter is 450nm
The novel light-sensitive microcapsule containing photosensitive colour-changing material.
Method 1: laser particle analyzer Mastersizer2000 determines the novel light-sensitive microcapsule containing photosensitive colour-changing material
Average grain diameter is 450nm.
Method 2: flying-spot microscope (SEM)+power spectrum (EDS) determines the novel light-sensitive microcapsule containing photosensitive colour-changing material
Form and substance distribution: whether there is or not capsule-core organic matters for the space i.e. except the organic matter composition, capsule of capsule surface C-H-O structure
Matter.As shown in Figure 1, Fig. 1 is the cladding situation schematic diagram of the light-sensitive microcapsule containing photosensitive colour-changing material prepared by embodiment 1.
It will be seen from figure 1 that cladding is all right.
Method 3: infrared spectroscopy (IR), which is used to measure in the solution (filtering off capsule) by filtering, no longer contains " photosensitive colour-changing
Material organic matter ", organic radicals appearance do not have organic matter characteristic peak at 2850,1700 etc. in solution.
Method 4: thermogravimetric analysis (TG) determines: during heating, there are two main peaks: capsule for the microcapsules by filtering
The polymer of core phase-change material and cyst wall illustrates that there are two organic systems: polymer and being wrapped by object.They are respectively at oneself
Softening point (polymer), fusing point (being wrapped by organic photosensitive small molecule) appearance (heat absorption/heat release).
Method 5: as shown in table 1 with spectrophotometric determination data result:
Table 1
| High speed dispersion instrument revolving speed/time | 8000 turns/0min | 8000 turns/10min | 8000 turns/20min | 8000 turns/40min |
| Light transmittance % | 92 | 91.5 | 92 | 91.2 |
As shown in figs. 2 to 4, Fig. 2 is the light-sensitive microcapsule spectrophotometric containing photosensitive colour-changing material prepared by embodiment 1
When instrument is tested, high speed dispersion 8000 turns/10min microcapsule coated situation schematic diagram；Fig. 3 is the preparation of embodiment 1 containing photosensitive
When the light-sensitive microcapsule of off-color material is tested with spectrophotometer, the signal of high speed dispersion 8000 turns/20min microcapsule coated situation
Figure；When Fig. 4 is that the light-sensitive microcapsule containing photosensitive colour-changing material prepared by embodiment 1 is tested with spectrophotometer, high speed dispersion
8000 turns/40min microcapsule coated situation schematic diagram.From figure 2 it can be seen that the light-sensitive microcapsule containing photosensitive colour-changing material
Keep complete with 8000 turns/10min of high speed dispersion treated microcapsules utricule, cyst wall intensity and toughness can be resistant to high speed
Disperse 8000 turns/10min.Although photosensitive micro- containing photosensitive colour-changing material from figure 3, it can be seen that there is minimal amount of fragment
Treated that microcapsules utricule is kept completely substantially by 8000 turns/20min of capsule high speed dispersion, and cyst wall intensity and toughness are basic
8000 turns/20min of high speed dispersion can be resistant to.Although containing photosensitive colour-changing figure 4, it is seen that there is minimal amount of fragment
8000 turns/the 40min of light-sensitive microcapsule high speed dispersion of material treated the microcapsules utricule overwhelming majority keeps complete, capsule
Wall intensity and toughness can be resistant to the intensity of 8000 turns/40min of high speed dispersion.From Fig. 1~4 it can be appreciated that high-intensitive, high
Under fast dispersion condition, although microcapsules experienced sharp impacts, due to the toughness and intensity of material itself, utricule does not occur aobvious
The rupture event of work.
Above-mentioned five detection method parallel detections, indispensable, detection data need to meet the requirements simultaneously.It is described containing photosensitive
The novel light-sensitive microcapsule of off-color material is made of cyst wall and capsule-core, and it is by light that the material of the cyst wall, which is cyst wall polymer,
The monomer of polymerization perhaps photo-crosslinking polymerize that form the monomer of photopolymerization or photo-crosslinking be that tetrapropylene is sour by illumination
Pentaerythritol ester, the material of the capsule-core are floating smart acid anhydrides.
Embodiment 2
By 30 grams of maleic anhydrides be alkene bridge di-thiofuran ethylene compound (2-Vinylthiophene, AR pacify resistance to Jilin Chemical
Co., Ltd), 8.0 grams of 1,6- hexanediyl esters (HDDA, purchased from upper caldron along International Trading Company Ltd) are added to
In internal irradiation type 500ml quartz photochemical reactor, be warming up to 80 DEG C, be stirred, it is to be cooled to close to room temperature when be added
0.25 gram of Span80 (sorbitan fatty ester, Jiangsu Hai'an petrochemical plant) continues stirring 30 minutes.
150ml deionized water is added in photochemical reactor, 5000 revs/min of revolving speed high-speed stirred 5 minutes adds into system
Enter 0.5 gram of WB-4784 (benzophenone be parent derivative, substituent group be 2- hydroxy propyloxy group-trimethyl ammonia chloride ammonium salt, AR,
Upper caldron is along International Trading Company Ltd, group) and 5ml acetone, continue stirring 30 minutes, opens ultraviolet light source (wavelength
365nm or 254nm) illumination reaction 2h.
Illumination reaction terminates, and is warming up to 50 DEG C, continues to be stirred to react 0.5h, cold filtration obtains average grain diameter 300nm's
Novel light-sensitive microcapsule containing photosensitive colour-changing material.The novel light-sensitive microcapsule containing photosensitive colour-changing material is by cyst wall
It is formed with capsule-core, it is to pass through illumination by the monomer of photopolymerization or photo-crosslinking that the material of the cyst wall, which is cyst wall polymer,
Polymerization is formed, and the monomer of photopolymerization or photo-crosslinking is 1,6- hexanediyl ester, and the material of the capsule-core is horse
Carry out the di-thiofuran ethylene compound that acid anhydrides is alkene bridge.
Embodiment 3
28 grams of azobenzenes (being purchased from Shanghai Shi Feng Biotechnology Co., Ltd), 8 grams of acrylonitrile (are purchased from the Jiangsu AN Si Erbang
Petrochemical industry Co., Ltd), 1.2 grams of butyl acrylates (being purchased from Pinghu petrochemical industry Co., Ltd) be added to internal irradiation type 500ml quartz light
In chemical reactor, be warming up to 80 DEG C, be stirred, it is to be cooled to close to room temperature when 0.3 gram of Span40 be added continue stirring 30
Minute.
150ml deionized water, 3500 revs/min of revolving speed high-speed stirred 15 minutes, into system are added in photochemical reactor
0.5 gram of WB-4698 is added, and (benzophenone is the derivative of parent, and substituent group is 2- sodium methanesulfonate, and AR, upper caldron is along group
International Trading Company Ltd) and 8ml acetone, continue stirring 30 minutes, opens ultraviolet light source (wavelength 365nm) illumination reaction
2.5h。
Illumination reaction terminates, and is warming up to 50 DEG C, continues to be stirred to react 0.5h, cold filtration obtains average grain diameter 650nm's
Novel light-sensitive microcapsule containing photosensitive colour-changing material.The novel light-sensitive microcapsule containing photosensitive colour-changing material is by cyst wall
It is formed with capsule-core, it is to pass through illumination by the monomer of photopolymerization or photo-crosslinking that the material of the cyst wall, which is cyst wall polymer,
Polymerization is formed, and the monomer of photopolymerization or photo-crosslinking is acrylonitrile, butyl acrylate, and the material of the capsule-core is azo
Benzene.
Comparative example 1
28 grams of azobenzenes (being purchased from Shanghai Shi Feng Biotechnology Co., Ltd), 8 grams of acrylonitrile (are purchased from the Jiangsu AN Si Erbang
Petrochemical industry Co., Ltd), 1.2 grams of butyl acrylates (being purchased from Pinghu petrochemical industry Co., Ltd) be added to 500ml three-necked flask reactor
In, be warming up to 80 DEG C, be stirred, it is to be cooled to close to room temperature when 0.2 gram of Span40 be added continue stirring 30 minutes.
150ml deionized water, 3500 revs/min of revolving speed high-speed stirred 15 minutes, to system are added in three-necked flask reactor
0.5 gram of WB-4698 and 8ml acetone of middle addition continues stirring 30 minutes.
Reaction terminates, and is warming up to 50 DEG C, continues to be stirred to react 1.5h, cold filtration obtains containing for average grain diameter 950nm
The light-sensitive microcapsule of photosensitive colour-changing material.
The test of clad ratio passes through the method for " thermogravimetric " in table 1: being that pure cyst material and pure core materials are surveyed respectively first
The normal data of " peak position out " and " heat release " of its fixed heat analysis；Then reactant filtering is washed with water three times, filter cake 25
DEG C vacuum drying, sampling weighing do heat analysis.The position of pure material is corresponded to according to the ratio of the sample of Unit Weight its exothermic peak
" microcapsule coated rate " value is obtained with heat release value.Partial size determines capsule average grain diameter by laser particle analyzer Mastersizer2000
Or the interior scale measurement of flying-spot microscope (SEM).Compare the covered effect of photochemistry and heat chemistry polymerization, the embodiment of the present invention
The production that the novel light-sensitive microcapsule partial size containing photosensitive colour-changing material of 1~3 preparation is prepared relative to 1 thermal chemical reaction of comparative example
The light-sensitive microcapsule partial size that product contain photosensitive colour-changing material is small, the embodiment of the present invention 1~3 prepare containing photosensitive colour-changing material
Novel light-sensitive microcapsule clad ratio is greater than photosensitive micro- glue that the product of 1 thermal chemical reaction of comparative example preparation contains photosensitive colour-changing material
The clad ratio of capsule, covered effect are good.
The reaction type of Examples 1 to 3 and comparative example 1, partial size, the results are shown in Table 2 for clad ratio:
Table 2
| Reaction type | Partial size nm | Clad ratio % | |
| Embodiment 1 | Photochemistry | 450 | 92 |
| Embodiment 2 | Photochemistry | 300 | 90 |
| Embodiment 3 | Photochemistry | 650 | 87 |
| Comparative example 1 | Heat chemistry | 950 | 65 |
Embodiment 4
Novel light-sensitive microcapsule containing photosensitive colour-changing material of the invention is in color changeable nail enamel, lipstick:
2 parts of novel light-sensitive microcapsule containing photosensitive colour-changing material prepared by Example 1, are added 1.1 parts of Methyl celluloses
Element stirs 0.5-1.0 hours at room temperature, the water-based ink containing off-color material is made, water-based ink is ejected in formation figure on paper
Case becomes the discoloration scraps of paper, or is applied to nail as Photochromic nail polish, and coating is finished when under daylight or under ultraviolet lamp
When, color, which is presented, switchs to " bluish violet " by " orange red ".
5 parts of novel light-sensitive microcapsule containing photosensitive colour-changing material prepared by Example 3, are added 1.8 parts of Methyl celluloses
Element stirs 0.5-1.0 hours at room temperature, and color-changing lipstick is made, and coating finishes when under daylight or under ultraviolet lamp, and color is in
" bluish violet " is now switched to by " orange red ".
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention
Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.
Claims (10)
1. a kind of light-sensitive microcapsule containing photosensitive colour-changing material, it is characterised in that: be made of cyst wall and capsule-core, the cyst wall
Material be cyst wall polymer, be to be polymerize to be formed by illumination by the monomer of photopolymerization or photo-crosslinking, the capsule-core
Material is Photochromic Polymers or photochromic polymer.
2. the light-sensitive microcapsule according to claim 1 containing photosensitive colour-changing material, it is characterised in that: the photopolymerization or
The monomer of person's photo-crosslinking is acrylate and methacrylate, the asphalt mixtures modified by epoxy resin containing acrylate and methacrylate
Rouge, acrylonitrile, vinyl benzene, vinyl ethers or maleimide low polymer；Preferably acrylonitrile, butyl acrylate, trihydroxy
Propane triacrylate, pentaerythritol tetracrylate, pentaerythritol triacrylate, tetramethyl tetrapropylene acid pentaerythrite
Ester, three contracting dipropylene glycol diacrylates, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, isoborneol propylene
Acid esters, phenoxyethyl acrylate, acrylic acid epoxy resin, polyester acrylate, two contractings/tripropylene glycol double methacrylate,
Bis- (methyl) acrylate of double pentaerythritol methacrylate, polyethylene glycol.
3. the light-sensitive microcapsule according to claim 1 containing photosensitive colour-changing material, it is characterised in that: described photochromic
High molecular material or photochromic polymer are selected from azobenzene photochromic polymer, fulgides photochromic polymerize
Object, spirooxazine class photochromic polymer, diarylethene photochromic polymer, contains spiro-pyrans class photochromic polymer
The photochromic polymer of sulfocarbazone structure, the Photochromic Polymers containing imine structure, naphtho naphthoquinone containing phenoxy group
Class formation Photochromic Polymers, polycyclic quinone photochromic polymer, aniline derivatives species photochromic polymer, benzene
And pyran photochromic polymer, purpurine class photochromic material, transition-metal oxide class material, metal halide species material
At least one of material, photochromic rare earth compounding.
4. the light-sensitive microcapsule according to claim 3 containing photosensitive colour-changing material, it is characterised in that: the diaryl second
Alkene photochromic polymer is two heteroaromatic ethylene, dithiazole ethylene photochromic polymer；
The transition-metal oxide class material is WO3、MoO3、TiO2At least one of；
The metal halide species material is selected from least one of calcium iodide and mercuric iodixde mixed crystal, copper chloride, silver chlorate.
5. the light-sensitive microcapsule according to claim 1 containing photosensitive colour-changing material, it is characterised in that: described containing photosensitive
The partial size of the light-sensitive microcapsule of off-color material is 200~1000nm.
6. a kind of preparation method of the light-sensitive microcapsule described in any one of claim 1 to 5 containing photosensitive colour-changing material, special
Sign is: the following steps are included:
The monomer of photopolymerization or photo-crosslinking, Photochromic Polymers or photochromic polymer are added to interior photograph
In formula quartz photochemical reactor, be warming up to 60~100 DEG C, be stirred, it is to be cooled to close to room temperature when that surface is added is living
Property agent continues to stir；The monomer of photopolymerization or photo-crosslinking, Photochromic Polymers or photochromic polymer, table
The mass ratio of face activating agent is (1~100): (80~400): 1；
Deionized water high-speed stirred is added in photochemical reactor, photoinitiator or photosensitizer and solvent are added into system, after
Ultraviolet light source 1~5h of illumination reaction under conditions of wavelength is 365nm or 254nm is opened in continuous stirring；Photoinitiator is photosensitive
The mass ratio of the monomer of agent, photopolymerization or photo-crosslinking is 1:(5~50)；
Illumination reaction terminates, and is warming up to 40~60 DEG C, continues to be stirred to react 0.1~2h, cold filtration is obtained containing photosensitive colour-changing
The novel light-sensitive microcapsule of material.
7. the preparation method of the light-sensitive microcapsule according to claim 6 containing photosensitive colour-changing material, it is characterised in that: institute
The monomer for stating photopolymerization or photo-crosslinking is acrylate and methacrylate, contains acrylate and methacrylic acid
Epoxy resin, acrylonitrile, vinyl benzene, vinyl ethers or the maleimide low polymer of ester；Preferably acrylonitrile, acrylic acid fourth
Ester, Glycerin triacrylate, pentaerythritol tetracrylate, pentaerythritol triacrylate, tetramethyl tetrapropylene acid
It is pentaerythritol ester, three contracting dipropylene glycol diacrylates, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, different
Borneol acrylate, phenoxyethyl acrylate, acrylic acid epoxy resin, polyester acrylate, two contractings/tripropylene glycol double third
Bis- (methyl) acrylate of olefin(e) acid ester, double pentaerythritol methacrylate, polyethylene glycol；
The Photochromic Polymers or photochromic polymer are selected from azobenzene photochromic polymer, fulgide
Class photochromic polymer, spiro-pyrans class photochromic polymer, spirooxazine class photochromic polymer, diarylethene are photic
Electrochromic polymer, the Photochromic Polymers containing imine structure, contains benzene at the photochromic polymer of the structure containing sulfocarbazone
Oxygroup naphtho naphthoquinone class formation Photochromic Polymers, polycyclic quinone photochromic polymer, aniline derivatives species are photic
Electrochromic polymer, benzo pyran photochromic polymer, purpurine class photochromic material, transition-metal oxide class material,
At least one of metal halide species material, photochromic rare earth compounding；
The surfactant is anhydrous sorbitol palm acid monoester, sorbitan fatty ester.
8. the preparation method of the light-sensitive microcapsule according to claim 6 containing photosensitive colour-changing material, it is characterised in that: institute
Stating photoinitiator is water-soluble light trigger, preferably thioxanthone, quaternary ammonium salt or the sulphur of propoxyl group trimethyl methanesulfonic acid ammonium substitution
Benzophenone derivates, the hydroxyalkylphenyl ketone derivatives of acid groups substitution.
9. the preparation method of the light-sensitive microcapsule according to claim 6 containing photosensitive colour-changing material, it is characterised in that: institute
Stating photosensitizer is water-soluble material, preferably thioxanthone, quaternary ammonium salt or the sulfonic acid group of propoxyl group trimethyl methanesulfonic acid ammonium substitution
Substituted benzophenone derivates, hydroxyalkylphenyl ketone derivatives；
The solvent is acetone.
10. a kind of light-sensitive microcapsule described in any one of claim 1 to 5 containing photosensitive colour-changing material is for the nail that changes colour
The purposes of oil, lipstick.
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| CN111234121A (en) * | 2020-03-12 | 2020-06-05 | 沈阳化工研究院有限公司 | Aqueous photochromic microcapsule dispersoid and preparation method thereof |
| CN112724808A (en) * | 2020-12-25 | 2021-04-30 | 上海甘田光学材料有限公司 | Photochromic coating and preparation method thereof |
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| CN111234121A (en) * | 2020-03-12 | 2020-06-05 | 沈阳化工研究院有限公司 | Aqueous photochromic microcapsule dispersoid and preparation method thereof |
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| CN114031818A (en) * | 2021-10-25 | 2022-02-11 | 江苏视科新材料股份有限公司 | Organic/inorganic nano composite microsphere visual light material and application thereof |
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| CN114130321A (en) * | 2021-11-02 | 2022-03-04 | 武汉中科先进技术研究院有限公司 | Double-layer wall material coated photosensitive microcapsule and preparation method thereof |
| CN114790323A (en) * | 2022-03-28 | 2022-07-26 | 金发科技股份有限公司 | Photochromic material and preparation method and application thereof |
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Application publication date: 20190614 |