CN100389968C - Heat sensitive microcapsule and multi layer colour heat sensing recording material containing said micro capsule - Google Patents
Heat sensitive microcapsule and multi layer colour heat sensing recording material containing said micro capsule Download PDFInfo
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- CN100389968C CN100389968C CNB2005101239383A CN200510123938A CN100389968C CN 100389968 C CN100389968 C CN 100389968C CN B2005101239383 A CNB2005101239383 A CN B2005101239383A CN 200510123938 A CN200510123938 A CN 200510123938A CN 100389968 C CN100389968 C CN 100389968C
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Abstract
The present invention relates to a heat sensitive microcapsule and multi layer color heat sensitive recording material containing microcapsules, which comprises a capsule core and a capsule wall, wherein the capsule wall is a polymer of dibasic alcohol or polyether glycol and isonitrile acid ester and acrylate acid ester, and the molecular weight of the dibasic alcohol or the polyether glycol is 100 to 200. The multi layer color heat sensitive recoding material is composed of a supporter, a low temperature color displayer layer, a moderate temperature color displayer layer, a high temperature color displayer layer, an interlayer and a protective layer, wherein the low temperature color displayer layer comprises a heat sensitive microcapsule. The capsule has the advantages of small granule and good wall material compactness, the reduce degree of a vitrification point can be adjusted according to the dosage of the dibasic alcohol or the polyether glycol. The multi layer color heat sensing recording material containing the heat sensitive microcapsule realizes full colors and has the advantages of low grey fog, high density and low cost.
Description
Technical field
The present invention relates to a kind of temperature-sensitive microcapsules and colored heat-sensitive recording material.
Background technology
Because the tape deck of thermal photography is easy, reliability is high, obtains very fast development in recent years; The multi layer colour heat-sensitive recording material is because its environmental protection, dry-type processing, advantage easily, in recent years be widely used, the color production theory of this recording materials is to utilize diazol and colour coupler to react and color development, or the leuco dye of power supply reacts quality with being subjected to electron compound.Owing to diazol or to the electron stain precursor high reaction activity and high is arranged, even under very low temperature, also can react with colour coupler or developer, this makes multi layer colour thermal sensitive recording technology compare with photoelectric recording, ink mist recording and individual layer thermal sensitive recording, has bigger difficulty.
U.S. Pat 20030141491, US20030008775, use xyxylene vulcabond/trimethylolpropane addition product is disclosed in US6465392 and the CN1461705 Chinese patent, the mixture of xyxylene vulcabond/bisphenol-A addition product and water reaction form the microcapsule wall material of cryogenic displaying color layer, use warm color layer microcapsule wall material in xyxylene vulcabond/trimethylolpropane addition product and the water reaction formation, use xyxylene vulcabond/trimethylolpropane addition product, the mixture of poly-methylene polyphenylene PIC and water reaction form the microcapsule wall material of high temperature color layer. but in the microcapsules preparation process of cryogenic displaying color layer, xyxylene vulcabond/bisphenol-A addition product is difficult to preparation, and the colour temp of cryogenic displaying color layer is difficult for adjusting: U.S. Pat 3281383, US3773695, US3793268 and Japan Patent JP80191/73, JP84086/73 disclose utilize many isocyanide esters easily and polyalcohol or polynary amine substance reaction prepare microcapsules, but amine substance uses when diazol type microcapsules prepare, can react with diazol, can't develop the color.
Summary of the invention
Problem to be solved by this invention provides a kind of temperature-sensitive microcapsules, and this capsule particle is tiny, and wall material compactness is good, and vitrification point is low.
The problem that another need solve of the present invention provides a kind of multi layer colour heat-sensitive recording material that contains the temperature-sensitive microcapsules, and its quality of image is good, and gradation is clearly demarcated, low cost of manufacture.
Problem to be solved by this invention is achieved through the following technical solutions:
A kind of temperature-sensitive microcapsules comprise capsule-core and cyst wall, and described cyst wall is the polymer of dihydroxylic alcohols or PPG and isocyanide ester and acrylic acid ester, and wherein, the molecular weight of dihydroxylic alcohols or PPG is 100～200.
Above-mentioned temperature-sensitive microcapsules, the mol ratio of described dihydroxylic alcohols or PPG and isocyanide ester is 0.2～4: 1, preferred 0.5～3: 1.
Above-mentioned temperature-sensitive microcapsules, described dihydroxylic alcohols or PPG are diglycol, triethylene-glycol or Macrogol 200.
Above-mentioned temperature-sensitive microcapsules, described acrylic acid ester is the trihydroxy propane trimethyl acrylic ester.
Above-mentioned temperature-sensitive microcapsules, the particle diameter of described microcapsules are 0.3～1.0 micron.
Another problem to be solved by this invention is achieved through the following technical solutions:
A kind of multi layer colour heat-sensitive recording material; form by support, cryogenic displaying color layer, middle temperature color layer, high temperature color layer, interlayer and protective layer; described cryogenic displaying color layer comprises a kind of temperature-sensitive microcapsules; this capsule comprises capsule-core and cyst wall; described cyst wall is the polymer of dihydroxylic alcohols or PPG and isocyanide ester and acrylic acid ester; wherein, the molecular weight of dihydroxylic alcohols or PPG is 100～200.
The multi layer colour heat-sensitive recording material is made up of support and a plurality of color layer, contain the microcapsules and colour coupler or the developer that include dyestuff former or diazol in the color layer, in order to obtain excellent image and tone, the hot color developing of microcapsules is just regulated and control by strictness, when microcapsules are heated when reaching the vitrification point of wall, the capsule wall fusing, the colour coupler of the diazol of pars intramuralis or dyestuff former and wall outside reacts and develops the color.
Traditional technology is to be wrapped in dyestuff former or with diazol to make emulsion in the microcapsules, can be described as: the capsule-core materials/substances is dissolved in (oil phase) in the organic solvent, oil phase is joined the aqueous phase that is dissolved with water soluble polymer make the homogeneous emulsion, in the microcapsules preparation process, add high polymer monomer or prepolymer in the oil phase as becoming wall material, therefore form microcapsule wall at the interface of oil, water two-phase.The macromolecular material that can do capsule wall has: glue, cellulose, polyureas, polyurethane, polyamide etc., and wherein, the glass temperature range of polyureas, polyurethane material is room temperature～200 ℃, optimum is done the wall material of heat-sensitive recording material.Simultaneously; when relating to the multilayer heat-sensitive recording material; then necessarily require each monochromatic color layer to have visibly different colour temp; and but the colour temp of each color layer should be according to the thickness degree accuracy controlling of the sensible heat degree of multilayer sensible heat material monolithic system and interlayer, protective layer; this requires in the preparation process of microcapsules; form the macromolecule wall material of different structure, but and the vitrification point Tg accuracy controlling of wall material.
Multi layer colour heat-sensitive recording material provided by the invention, described cryogenic displaying color layer comprises a kind of temperature-sensitive microcapsules, and the colour temp of cryogenic displaying color layer can be adjusted.
Microcapsules comprise capsule-core and cyst wall, and the material of cyst wall can be polyureas, Polyurethane, polyester, Merlon etc., preferred polyureas or Polyurethane.The polyurethane type microcapsules for many years are used in the sensible heat type recording materials because its glass ionization temperature is suitable, and for the present invention is described better, existing interface polymerization reaction technology of preparing with the polyurethane type microcapsules is summarized as follows:
Diazol or dyestuff former and isocyanide ester performed polymer are dissolved in organic solvent; this organic facies is distributed in the aqueous solution that contains protecting colloid; improve reaction temperature; utilize interface polymerization reaction; isocyanide ester performed polymer in the organic facies and aqueous phase water are reacted form polyurethane type wall material; thereby forming core is the thermal response-type microcapsules of diazol or dyestuff former; when this kind microcapsules are heated when reaching the vitrification point of wall; the capsule wall fusing, the colour coupler of the diazol of pars intramuralis or dyestuff former and wall outside reacts and develops the color.
Isocyanide ester reactivity height, Yi Heshui, amine, alcohol etc. react, thereby form the wall material of various different structures, and this is known in the Polyurethane paint field.The thermal response-type microcapsules utilize this characteristic of isocyanide ester, form the macromolecule wall material of compact texture, and concrete preparation process is with traditional thermal response-type microcapsules preparation process.
The character of isocyanide ester has determined the structure of capsule wall, being fit to isocyanide ester of the present invention can be dimethylbenzene diisocyanate and hydride thereof, the hexa-methylene diisocyanate, toluene support diisocyanate and hydride thereof, their dimer or tripolymer (biuret or trimerization isocyanide ester) when diisocyanates such as isophorone diisocyanate are primary raw material, with make addition product with polyalcohols such as trimethylolpropanes etc., preferred isocyanide ester is the performed polymer of xyxylene vulcabond (XDI) and trimethylolpropane, in the bag core with oily molten type diazol or dyestuff former, the grease separation of interior bag high boiling solvent such as tributyl phosphate, tricresyl phosphate etc., low boiling point solvent is as secondary solvent such as ethyl acetate, carrene etc.Protective colloid can be selected phthalation gelatin or polyvinyl alcohol for use, recommends to use the phthalation gelatin.Surfactant can be selected known nonionic, anionic or cationic surface active agent for use.Added catalyst dibutyl tin laurate salt before the reaction beginning, its addition is 0.02% of total system weight.
Being fit to molecular weight of the present invention and being 100～200 dihydroxylic alcohols or PPG can be diglycol, triethylene-glycol, Macrogol 200 etc., it is very easily buied in the commercial goods, and its cost is lower than the cryogenic displaying color layer wall material of xyxylene vulcabond/bisphenol-A addition product conduct of using in the traditional thermal material.Its implantation site that adds is the aqueous phase that contains protective colloid, specifically can be before organic facies be distributed to water, or after organic facies is distributed to water, before the temperature reaction.Its adding can make the vitrification point of wall material descend, and the mol ratio of its addition and many isocyanide esters is 0.2～4: 1, preferred 0.5～3: 1.If consumption less than 0.2 times, then can't realize reducing the effect of wall material temperature, greater than 4 times, then the yellow photographic fog of background is bigger than normal as if consumption.In the preparation process of microcapsules,, can obtain the different microcapsules of wall material vitrification point by adjusting above-mentioned amount ratio.
In the preparation process of temperature-sensitive microcapsules of the present invention, acrylate thing class is joined in the oil phase, the esters of acrylic acid material has the character of meeting autohemagglutination behind the water, the polyurethane type polymer that the dihydroxylic alcohols of this polymer and many isocyanide esters and aqueous phase or PPG reaction form is formed the wall material of temperature-sensitive microcapsules cyst wall jointly, and this has improved many isocyanide esters greatly and aqueous phase water reacts the performance that forms single polyurethane type wall material.Being fit to acrylate of the present invention can be EMA, butyl methacrylate, trimethylol-propane trimethacrylate etc., preferred trimethylol-propane trimethacrylate.The implantation site that adds of acrylate is in the oil phase, and the part replace organic solvent uses, and its addition is 0.2-2 a times of high boiling solvent amount in the microcapsules.
Temperature-sensitive microcapsules provided by the invention can use existing known chemistry to prepare, and comprise any in interfacial polymerization, situ aggregation method, complex coacervation and the phase separation method, preferred interfaces polymerization.
Multi layer colour heat-sensitive recording material provided by the invention can adopt known coating method to be coated with, and preferably uses sloping flow coat cloth, extrusion coated or the curtain coating method that falls, and the coating layer thickness of formation is the 25-35 micron.
Temperature-sensitive capsule particle of the present invention is tiny, and wall material compactness is good, and the reduction degree of its vitrification point can be regulated and control according to the consumption of dihydroxylic alcohols or PPG; The multi layer colour heat-sensitive recording material that contains these temperature-sensitive microcapsules is when realizing full color, and its photographic fog is little, big density height, and cost is low.
The specific embodiment
The invention will be further described below by specific embodiment.
Embodiment 1
The preparation of 1 cryogenic displaying color layer-yellow color layer
(1) preparation of microcapsule suspensions
Diazols of the following structure of each 2 gram are dissolved in the ethyl acetate of the dioctyl phthalate of 12ml and 13ml, trimethylol-propane trimethacrylate (the trade name: TMPTMA) that adds 6g, 4.5g benzil dimethyl ketal (trade name: 651), (trade name: D-110N content is 75% to add the xyxylene vulcabond (XDI) of 20g and the prepolymer of trimethylolpropane, the content of ethyl acetate is 25%, the molecular weight of prepolymer is 698), stir as oil phase.
18 gram phthalation gelatin are dissolved in the 300ml water, add surfactant neopelex solution (10%) 15ml, add diglycol 5g (mol ratio that makes diglycol and isocyanate prepolymer is 22: 1), stir as water.Above-mentioned oil phase is joined aqueous phase, high-speed stirred 15 minutes, be dispersed into the oil droplet about 0.3 micron, add pure water 250ml and be warmed up to 40 ℃, add 0.2ml dibutyl tin laurate salt as catalyst, reduce mixing speed, react after 4 hours and finish, reaction temperature is reduced to 35 ℃, add each 10 gram of ion exchange resin D-151 and D-380 (Tianjin resin processing plant), handled about 1 hour, the elimination resin obtains the microcapsules particle diameter and is 0.3 micron, diazol content and be 1.5%, glue content is 6% microcapsules liquid.
(2) the oil breast of colour coupler disperses
With following structure yellow colour coupler 6g, triphenyl guanidine 4g, 4-(2-ethylhexyl oxygen) benzsulfamide 4.2g, bis-phenol M4g, neopelex 1.8g is dissolved in 20ml ethyl acetate and the 10.6g dioctyl phthalate, stirs, as oil phase.
The 12g alkali treated gelatin adds the 112g ion exchange water, is made into aqueous gelatin solution; Above-mentioned oil phase is joined in the aqueous gelatin solution, and emulsification disperses, and emptying ethyl acetate obtains colour coupler content and be 4%, glue content is 8% oil breast.
(3) preparation of yellow color layer coating fluid
With above-mentioned microcapsule suspensions 200g, the oily newborn 125g of colour coupler mixes, and the ratio of diazol and colour coupler is 1: 2, obtains yellow color layer coating fluid.
The preparation of warm color layer-product color layer in 2
(1) preparation of microcapsule suspensions
7.5 the product diazol (A-1) that restrains following structure is dissolved in the dioctyl phthalate of 30ml, in the ethyl acetate of 70ml, trimethylol-propane trimethacrylate (the trade name: TMPTMA) that adds 8g, 3.0g benzil dimethyl ketal (trade name: 651), prepolymer (the trade name: D-110N that adds xyxylene vulcabond (XDI) with the trimethylolpropane of 60g, content is 75%, the content of ethyl acetate is 25%, the molecular weight of prepolymer is 698), 15g gathers methylene polyphenylene PIC (PAPI), stirs as oil phase.
30 gram phthalation gelatin are dissolved in the 300ml water, add surfactant neopelex solution (10%) 15ml, stir as water.
Above-mentioned oil phase is joined aqueous phase, high-speed stirred 15 minutes is dispersed into the oil droplet about 0.3 micron, adds pure water 250ml and is warmed up to 40 ℃, add 0.2ml dibutyl tin laurate salt as catalyst, reduce mixing speed, react after 4 hours and finish, reaction temperature is reduced to 35 ℃, add each 10 gram of ion exchange resin D-151 and D-380 (Tianjin resin processing plant), handled about 1 hour, the elimination resin obtains diazol content and is 1.5%, glue content is 6% microcapsules liquid.
(2) the oil breast of colour coupler disperses
Following structure magenta coupler 8g, triphenyl guanidine 6.5g, bis-phenol M12g, neopelex 2g is dissolved in 32ml ethyl acetate and 16g dioctyl phthalate, stirs, as oil phase.
The 244g alkali treated gelatin adds the 200g ion exchange water, is made into aqueous gelatin solution, and above-mentioned oil phase mixed liquor is joined in the aqueous gelatin solution, and emulsification disperses, and emptying ethyl acetate obtains colour coupler content and be 3.2%, glue content is 9.6% oil breast.
(3) preparation of product color layer coating fluid
With above-mentioned microcapsule suspensions 200g, the oily newborn 112g of colour coupler mixes, and the ratio of diazol and colour coupler is 1: 2, obtains product color layer coating fluid.
3. the preparation of high temperature color layer-blue or green color layer
(1) preparation of microcapsule suspensions
The following structure of 22 grams give the electron stain precursor, 2 gram crystal violet lactones (CVL Changshu City dye chemical industry factory) are dissolved in the dichloroethanes of 40ml, in the ethyl acetate of 10ml, add the IPDI of 60g, stir as oil phase.
30 gram phthalation gelatin are dissolved in the 300ml water, add surfactant neopelex solution (10%) 15ml, and this solution is as water.
Above-mentioned oil phase is joined aqueous phase, high-speed stirred 15 minutes, be dispersed into the oil droplet about 0.6 micron, add pure water 100ml and be warmed up to 60 ℃, add diethylenetriamine (Tianjin section close europeanized reagent development centre) 18gml as catalyst, reduce mixing speed, react end after 4 hours, obtain to body burden before the electron stain be 4.0%, glue content is 5% microcapsules liquid.
(2) preparation of developer dispersion
412.5g bisphenol-A, the acid system of 82.5g is handled glue, 75g neopelex solution (10%), the 45g calgon, ion exchange water 1500g disperses this gelatin solution ball milling on ball mill 6 hours, obtaining content of bisphenol A is 25%, and glue content is 5% dispersion liquid.
(3) preparation of blue or green color layer coating fluid
With above-mentioned microcapsule suspensions 100g, developer dispersion 250g mixes, and giving the ratio of electron stain precursor and developer is 1: 12, obtains blue or green color layer coating fluid.
The preparation of 4 interlayer coating fluids
Hard esteramides with 330g, the alkali acid system of 165g is handled glue, the neopelex solution (10%) of 85g, the calgon of 150g, the ion exchange water of 3000g mixes, mixed liquor ball milling on ball mill was disperseed 6 hours, and obtaining hard esteramides content is 10%, and glue content is 5% dispersion liquid.
The preparation of 5 protective layer coating solutions
Silica with 330g, the PVAC polyvinylalcohol 217 of 198g, the neopelex solution (10%) of 85g, the calgon of 90g, the ion exchange water of 3000g evenly mixes, mixed liquor liquid ball milling on ball mill was disperseed 6 hours, and obtaining dioxide-containing silica is 10%, and polyvinyl alcohol content is 6% dispersion liquid.
6 coating assemblings
On plastic-coated paper-based; use slope stream extrusion coating machine; be coated with blue or green color layer coating fluid from bottom to up; the interlayer coating fluid, product color layer coating fluid, interlayer coating fluid; yellow color layer coating fluid; protective layer coating solution, dry under 35 ℃, 30% damp condition then, obtain containing microcapsules liquid of the present invention, coating layer thickness is 30 microns multi layer colour heat-sensitive recording material.Use Printpix CX-400 to print 4 grades of color lumps, estimate basic sensible heat degree, circuit really sees Table 1.
Embodiment 2
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, the trimethylol-propane trimethacrylate among the embodiment 1 is replaced with butyl methacrylate; Triethylene-glycol is replaced diglycol among the embodiment 1, and consumption is 1.67g (mol ratio that makes triethylene-glycol and isocyanate prepolymer is 0.5: 1), and the microcapsules particle diameter is 0.5 micron.Coating, obtain containing microcapsules liquid of the present invention, coating layer thickness is 25 microns multi layer colour heat-sensitive recording material.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Embodiment 3
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, Macrogol 200 is replaced diglycol among the embodiment 1, and consumption is 13g (mol ratio that makes Macrogol 200 and isocyanate prepolymer is 3.1: 1), and the microcapsules particle diameter is 1.0 microns.Coating, obtain containing microcapsules liquid of the present invention, coating layer thickness is 35 microns multi layer colour heat-sensitive recording material.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Embodiment 4
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, triethylene-glycol is replaced diglycol among the embodiment 1, and consumption is 0.67g (mol ratio that makes triethylene-glycol and isocyanate prepolymer is 0.2: 1), and the microcapsules particle diameter is 0.8 micron.Coating, obtain containing the little glue of the present invention assist liquid, coating layer thickness is 30 microns multi layer colour heat-sensitive recording material.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Embodiment 5
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, the trimethylol-propane trimethacrylate among the embodiment 1 is replaced with EMA; The consumption of the diglycol among the embodiment 1 is become 9.09g (mol ratio that makes diglycol and isocyanate prepolymer is 4.0: 1), and the microcapsules particle diameter is 0.6 micron.Coating, obtain containing microcapsules liquid of the present invention, coating layer thickness is 35 microns multi layer colour heat-sensitive recording material.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Comparative Examples 1
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, omit the diglycol among the embodiment 1, obtain the multi layer colour heat-sensitive recording material of Comparative Examples 1.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Comparative Examples 2
With embodiment example 1, just in the preparation process of yellow color layer microcapsule suspensions, Macrogol 600 is replaced diglycol among the embodiment 1, consumption is 7.5g (mol ratio that makes Macrogol 600 and isocyanate prepolymer is 0.6: 1), obtains the multi layer colour heat-sensitive recording material of Comparative Examples 2.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Comparative Examples 3
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, it is 0.4 gram that the consumption of diglycol is used instead, and (mol ratio that makes diglycol and isocyanate prepolymer is 0.13: 1) obtains the multi layer colour heat-sensitive recording material of Comparative Examples 3.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Comparative Examples 4
With embodiment 1, just in the preparation process of yellow color layer microcapsule suspensions, it is 12.3 grams that the consumption of diglycol is used instead, and (mol ratio that makes diglycol and isocyanate prepolymer is 5.5: 1) obtains the multi layer colour heat-sensitive recording material of Comparative Examples 4.Use Printpix CX-400 to print 4 grades of color lumps, estimate its sensible heat degree, the results are shown in Table 1.
Table 1 The performance test results
As can be seen from the above results, the Comparative Examples 1 that adds embodiment 1, embodiment 2, embodiment 3, embodiment 4, the embodiment 5 of material of the present invention and do not add material of the present invention relatively, D3, the big density in D4 place does not have tangible reduction, but D1, the little density of D2 place density obviously improves, thereby the yellow layer of cryogenic displaying color layer of doing multi layer colour sensible heat note enlightenment material preferably, the adding molecular weight exceeds the Comparative Examples 2 of the scope of the invention 100～200 materials, though its little density place density obviously improves, but photographic fog D0 obviously increases, and can't use.Comparative Examples 3 and example 4 show: add amount of substance of the present invention and must be controlled at certain scope, if consumption is too small, D1 then, the little density of D2 place density does not have obvious raising, can't realize reducing the effect of wall material temperature, as Comparative Examples 3, if consumption is excessive, then the yellow photographic fog of background is bigger than normal, can't use, as Comparative Examples 4.
Claims (8)
1. temperature-sensitive microcapsules, comprise capsule-core and cyst wall, capsule-core adopts diazol or dyestuff former, it is characterized in that, described cyst wall is the polymer of dihydroxylic alcohols or PPG and isocyanide ester and acrylate, the mol ratio of dihydroxylic alcohols or PPG and isocyanide ester is 0.2～4: 1, and described dihydroxylic alcohols or PPG are diglycol, triethylene-glycol or Macrogol 200, molecular weight is 100～200.
2. temperature-sensitive microcapsules according to claim 1 is characterized in that the mol ratio of described dihydroxylic alcohols or PPG and isocyanide ester is 0.5～3: 1.
3. temperature-sensitive microcapsules according to claim 1 is characterized in that described acrylate is a trimethylol-propane trimethacrylate.
4. temperature-sensitive microcapsules according to claim 1 is characterized in that, the particle diameter of described microcapsules is 0.3～1.0 micron.
5. multi layer colour heat-sensitive recording material that contains the temperature-sensitive microcapsules, it is by support, the cryogenic displaying color layer, in warm color layer, the high temperature color layer, interlayer and protective layer are formed, described cryogenic displaying color layer is yellow color layer, in warm color layer be the product color layer, the high temperature color layer is blue or green color layer, described applying structure is blue or green color layer coating fluid from bottom to up, the interlayer coating fluid, product color layer coating fluid, the interlayer coating fluid, yellow color layer coating fluid and protective layer coating solution, it is characterized in that, described cryogenic displaying color layer comprises the temperature-sensitive microcapsules, capsule is made up of capsule-core and cyst wall, wherein, capsule-core adopts diazol or dyestuff former, cyst wall is the polymer of dihydroxylic alcohols or PPG and isocyanide ester and acrylate, and the mol ratio of dihydroxylic alcohols or PPG and isocyanide ester is 0.2～4: 1; Described dihydroxylic alcohols or PPG are diglycol, triethylene-glycol or Macrogol 200, and molecular weight is 100～200.
6. according to the described multi layer colour heat-sensitive recording material of claim 5, it is characterized in that the mol ratio of described dihydroxylic alcohols or PPG and isocyanide ester is 0.5～3: 1.
7. according to claim 5 or 6 described multi layer colour heat-sensitive recording materials, it is characterized in that described acrylate is a trimethylol-propane trimethacrylate.
8. according to the described multi layer colour heat-sensitive recording material of claim 7, it is characterized in that the particle diameter of described microcapsules is 0.3～1.0 micron.
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| CN104228385A (en) * | 2014-09-15 | 2014-12-24 | 长沙理工大学 | Medical thermo-sensitive paper |
| CN113308194B (en) * | 2021-05-28 | 2022-07-15 | 湖南鼎一致远科技发展有限公司 | Printing heat-sensitive coating and preparation method and application thereof |
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| CN1427771A (en) * | 2000-09-06 | 2003-07-02 | 阿普尔顿纸张公司 | In situ microencapsulated adhesive |
| US20030008775A1 (en) * | 2001-03-26 | 2003-01-09 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
| CN1461705A (en) * | 2002-05-30 | 2003-12-17 | 富士胶片株式会社 | Thermosensitive recording material |
| WO2004058910A1 (en) * | 2002-12-25 | 2004-07-15 | Matsumoto Yushi-Seiyaku Co., Ltd. | Thermally expandable microcapsule, process for producing molded foam, and molded foam |
| KR20050017498A (en) * | 2003-08-14 | 2005-02-22 | 주식회사 국제아르테미스 | A method of preparing polyester accessory changed color according to temperature |
| CN1586708A (en) * | 2004-07-16 | 2005-03-02 | 东华大学 | Process for preparing solvent resistant physically foamed micro capsule |
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