CN103834285A - Electrophoretic coating liquid and electrophoretic display layer and preparation methods thereof - Google Patents
Electrophoretic coating liquid and electrophoretic display layer and preparation methods thereof Download PDFInfo
- Publication number
- CN103834285A CN103834285A CN201210472770.7A CN201210472770A CN103834285A CN 103834285 A CN103834285 A CN 103834285A CN 201210472770 A CN201210472770 A CN 201210472770A CN 103834285 A CN103834285 A CN 103834285A
- Authority
- CN
- China
- Prior art keywords
- coating fluid
- microcapsule
- electrophoresis
- water
- electrophoresis coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention provides an electrophoretic coating liquid and a preparation method thereof, the electrophoretic coating liquid includes an adhesive and a microcapsule dispersing in the adhesive, the microcapsule comprises a suspension and charged pigment particles dispersing in the suspension, the outer capsule wall of the microcapsule is prepared by use of a natural water-soluble polymer compound, and the adhesive comprises the water-soluble polymer compound and aqueous polyurethane. The invention also provides an electrophoretic display layer and a preparation method thereof, and the electrophoretic display layer is prepared by use of the electrophoretic coating liquid. The electrophoretic coating liquid achieves a good balance in mechanical properties, coating film properties, photoelectric properties and other aspects, and has the characteristic of being easy to coat a film, excellent in coating film appearance and the like, and the electrophoretic display layer prepared by use of the electrophoretic coating liquid has high mechanical performances and good photoelectric performances.
Description
Technical field
The present invention relates to electrophoretic display technology field, relate in particular to a kind of electrophoresis coating fluid and preparation and application.
Background technology
Electrophoresis image shows (EPID, be electrophoretic image display) be to utilize colloid dispersed particle that the phenomenon of swimming occurs under electric field action, its advantage be high-contrast, with great visual angle, highly show lightness, low price, easily realize large plane demonstration etc.Its shortcoming is poor reliability, and threshold property is not easy to control, especially in dispersed system particulate easily reunite, the phenomenon such as precipitation, so the life-span that EPID shows is shorter.A kind of electrophoretic display apparatus is disclosed in Japanese Patent JP2551783, the concept of electric ink (encapsulated electrophoretic ink) is wherein proposed, i.e. micro encapsulation electrophoretic display technology (encapsulated electrophoretic display).Utilize electrophoresis showed principle, innovatively granules of pigments and dark dye solution are wrapped in micro-capsule, in micro-capsule, have realized electrophoresis showed, thereby suppressed electrophoretic particles in the shortcoming such as reunion, deposition being greater than in capsule range scale, improve its stability, increased the service life.Electric ink is a kind of suspended substance of ink shape, under External Electrical Field, can realize reversible, bistable state, flexible demonstration, a kind of flexible display material and technology that merges the subjects such as physics, chemistry, electronics, have good visuality, reduce power consumption, information be written into ability strong, easy to carry, manufacture the advantages such as cheap, electromagnetic-radiation-free, and can fundamentally solve the deficiency of existing flat panel display.
Current electric ink adopts the smooth microcapsule coated dielectric medium suspension of spherical transparent of 30-300 micron, charged electrophoretic particles adrift in suspension, these microcapsule are distributed in and in sizing agent, form electrophoresis coating fluid, by its coating or be printed on flexible ITO(indium tin oxide) on conductive film, the flexible EPID Electronic Paper of principle of compositionality type.But also there are many problems in the electrophoresis coating fluid of preparation at present.For example, because sizing agent and microcapsule do not have choose reasonable, cause and be difficult to reach balance between the each side such as mechanical property, film performance and photoelectric properties, normal occur because of microcapsule be difficult to dispersed, levelling property is poor or bad mechanical property etc., while causing coating, be difficult to be coated with open, appearance of film is poor, and electrophoresis showed layer easily departs from conductive layer; In coating fluid drying process, often occur convergent force and not cause capsule not yielding, between capsule, space is large, and occurs breakage because microcapsule can not get protection, finally causes the problems such as the photoelectric properties of electrophoresis showed layer are poor.
Publication number is CN102093785A, the Chinese patent application that open day is on June 15th, 2011 discloses a kind of electrophoresis coating fluid and preparation method thereof, in the electrophoresis coating fluid that it provides, adopting water-soluble high-molecular compound solution is sizing agent, although this sizing agent can reduce the reunion between microcapsule, but exist also prepared electrophoresis showed layer physical strength inadequate, may occur departing from the risk of conductive layer.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of electrophoresis coating fluid and preparation method thereof is provided, and adopt electrophoresis showed layer of this electrophoresis coating fluid preparation formation and preparation method thereof.The features such as the electrophoresis coating fluid providing reaches good balance in each side such as mechanical property, film performance and photoelectric properties, has the film of being easy to, and appearance of film is good, the electrophoresis showed layer that it forms has stronger mechanical property and good photoelectric properties.
A kind of electrophoresis coating fluid, it comprises sizing agent and is dispersed in the microcapsule in sizing agent, in described microcapsule, include suspension and be scattered in the charged pigment particle in suspension, the outer cyst wall of described microcapsule adopts water-soluble macromolecular compound to be prepared from, and contains water-soluble high-molecular compound and aqueous polyurethane in described sizing agent.
Further, described electrophoresis coating fluid, the outer cyst wall of microcapsule is that gelatin and the first cyst material form, described the first cyst material is selected from one or more in gum arabic, natural gum, peach gum, pectin.
Further, described electrophoresis coating fluid, the water-soluble high-molecular compound containing in sizing agent is selected from one or more the combination in carboxymethyl cellulose, Natvosol, Vltra tears, Zulkovsky starch, carboxymethyl starch, gum arabic, gelatin, natural gum, soybean protein, casein, polyvinyl alcohol, polyoxyethylene glycol, polyacrylamide, polyvinylpyrrolidone.
Described electrophoresis coating fluid, described aqueous polyurethane is selected from one or more the combination in aqueous polyurethane solution, aqueous polyurethane emulsion, aqueous polyurethane dispersion.
Preferably, described electrophoresis coating fluid, with respect to the microcapsule of 100 weight parts, water-soluble high-molecular compound and aqueous polyurethane used in sizing agent are respectively 0.15 ~ 2.5 weight part and 8 ~ 50 weight parts.
The present invention also provides a kind of method of preparing electrophoresis coating fluid as described above, and described preparation method comprises the steps:
(1) water-soluble high-molecular compound is dissolved in the water, makes water-soluble polymer solution, the water-soluble polymer solution making and microcapsule are mixed evenly, obtain preliminary electrophoresis coating fluid;
(2) suitable quantity of water based polyurethane is joined in the preliminary electrophoresis coating fluid that step (1) makes, stirring and evenly mixing obtains electrophoresis coating fluid.
The present invention also provides a kind of electrophoresis showed layer, and described electrophoresis showed layer is that electrophoresis coating fluid is by mentioned earlier coated on a conductive layer and formed.
The present invention also provides a kind of method of preparing electrophoresis showed layer as described above, and electrophoresis coating fluid mentioned above is coated on conductive layer, treats that electrophoresis coating fluid is dry to form described electrophoresis showed layer.
Further, the described method of preparing electrophoresis showed layer, its electrophoresis coating fluid is prepared as follows:
(1) water-soluble high-molecular compound is dissolved in the water, makes water-soluble polymer solution, the water-soluble polymer solution making and microcapsule are mixed evenly, obtain preliminary electrophoresis coating fluid;
(2) suitable quantity of water based polyurethane is joined in the preliminary electrophoresis coating fluid that step (1) makes, stirring and evenly mixing obtains electrophoresis coating fluid.
The present invention further provides a kind of electrophoretic display apparatus, it has a pair of substrate with conductive layer and is present in the electrophoresis showed layer between substrate, and described electrophoresis showed layer is electrophoresis showed layer mentioned above.According to those skilled in the art's understanding, electrophoresis showed layer a pair of can be both the situation that only has electrophoresis showed layer between two substrates with the implication between the substrate of conductive layer, also can be between two substrates except described electrophoresis showed layer, also there are other structures, such as glue layer etc.
The present invention also provides a kind of preparation method of electrophoretic display apparatus mentioned above, its step comprises the preparation of electrophoresis coating fluid and the preparation of electrophoresis showed layer, the preparation of described electrophoresis showed layer is that electrophoresis coating fluid mentioned above is coated on conductive layer, treat that electrophoresis coating fluid is dry, form electrophoresis showed layer.
Technical scheme provided by the invention compared with prior art, has following beneficial effect:
1. electrophoresis coating fluid provided by the invention, the sizing agent with water-soluble high-molecular compound and aqueous polyurethane of selecting cleverly the cyst wall material of microcapsule and arranging in pairs or groups with it, on the one hand, water-soluble polymer in sizing agent can well be compatible with microcapsule, thereby reducing surface tension is soaked the cyst wall of microcapsule well, contribute to reach microcapsule homodisperse effect in sizing agent, the while also reduces the phenomenons such as the reunion between microcapsule, and sizing agent used has water-soluble high-molecular compound and aqueous polyurethane, the electrophoresis coating fluid viscosity that is dispersed with microcapsule is strengthened, improve its mechanical property, strengthen the bounding force between electrophoresis coating fluid and conductive layer, be not prone to film and depart from from base material, on the other hand, ingenious between sizing agent and microcapsule coordinates the formed electrophoresis coating fluid with good mechanical properties and levelling property, not only make electrophoresis coating fluid be easy to coating, improve coating outward appearance, also make the microcapsule that are scattered in wherein better be protected, be difficult in coating process, during later stage stores and occur microcapsule breakage in use procedure, coating fluid sizing agent in drying process can produce certain contraction simultaneously, thereby certain deformation occurs capsule reduces the space between capsule, finally make the electrophoresis showed layer forming there are preferably contrast gradient and good photoelectric properties.
2. electrophoresis coating fluid provided by the invention also has enough flexibilities in having good physical strength, makes prepared electrophoretic display apparatus be difficult for, because of the bending defect of introducing, being difficult for forming hole because being exposed under the environment such as high temperature.
3. electrophoresis coating fluid provided by the invention; in preparation process, adopt rational proportioning raw materials; the performance of water-soluble high-molecular compound and aqueous polyurethane is well brought into play; and when being can be uniformly dispersed, microcapsule can also be protected better; make the electrophoresis coating fluid of preparation reach good balance at aspects such as mechanical property, film performance and photoelectric properties, there is suitable viscosity and levelling property and contrast gradient preferably.
4. the preparation method of electrophoresis coating fluid provided by the invention; in its preparation process, adopt specific sizing agent feed way; because the character of the character of water-soluble high-molecular compound and the cyst wall of microcapsule approaches; first increasing water-soluble polymer can make microcapsule more easily disperse; and then adding urethane to protect microcapsule, thereby play the effect that prevents that microcapsule are destroyed.If first add aqurous ployurethane, can make microcapsule be combined with aqurous ployurethane, then add water-soluble high-molecular compound just can not produce the effect that microcapsule are disperseed.Therefore, use preparation method provided by the invention can make the dispersion that microcapsule can well be uniform and stable in sizing agent, reduce the damage that microcapsule may produce because of friction or shock etc., avoid material in microcapsule to outward leakage, the quality that guarantees electrophoretic display apparatus prepared by the later stage, makes it have preferably contrast gradient.
5. electrophoresis showed layer provided by the invention adopts specific electrophoresis coating fluid, and the appearance of film that it is formed after coating (comprising the coating processes such as roller coating, silk screen printing, spraying) is good, is not prone to the defects such as ignore, scratch, salient point and bad point.The electrophoretic display apparatus that adopts this electrophoresis showed layer to make has good photoelectric properties and contrast gradient preferably, has high reliability while repeatedly demonstration; And the easy single flat of microcapsule in coating fluid is laid on conductive layer, and after coating fluid is dry, microcapsule produce certain deformation, thereby at utmost reduce interelectrode distance, increased effective display area, also made the required driving voltage of the electrophoretic display apparatus that makes less.Prepared electrophoretic display apparatus has the various premium propertiess such as the permanent stability of performance demonstration, and its contrast gradient or visibility of image are good.
Accompanying drawing explanation
Fig. 1 is the diagrammatic cross-section of the electrophoretic display apparatus that makes of embodiment 26;
Fig. 2 is the Photomicrograph of the electrophoresis showed layer that makes of comparative example 1;
Fig. 3 is the Photomicrograph of the electrophoresis showed layer that makes of comparative example 2;
Fig. 4 is the Photomicrograph of the electrophoresis showed layer that makes of embodiment 1.
Description of reference numerals in Fig. 1:
1-PET film; 2-plaque layer; 3-transparency conducting layer; 4-glue layer; 5-electrophoresis showed layer; 51-microcapsule.
Embodiment
Its particle diameter of aqueous polyurethane solution <0.001 micron described in literary composition, appearance transparent; Its particle diameter of described aqueous polyurethane dispersion is 0.001-0.1 micron, and outward appearance is translucent; Its particle diameter of described aqueous polyurethane emulsion >0.1 micron, outward appearance gonorrhoea.
Microcapsule used in electrophoresis coating fluid of the present invention, its outer cyst wall adopts water-soluble macromolecular compound to be prepared from, and contains water-soluble high-molecular compound and aqueous polyurethane in sizing agent used.Wherein, the outer cyst wall of microcapsule adopts gelatin and the first cyst material to be prepared from, and described the first cyst material is selected from one or more in gum arabic, natural gum, peach gum, pectin.Water-soluble high-molecular compound in sizing agent is preferably one or more the combination in carboxymethyl cellulose, Natvosol, Vltra tears, Zulkovsky starch, carboxymethyl starch, gum arabic, gelatin, natural gum, soybean protein, casein, polyvinyl alcohol, polyoxyethylene glycol, polyacrylamide, polyvinylpyrrolidone.Described aqueous polyurethane is selected from one or more the combination in aqueous polyurethane solution, aqueous polyurethane emulsion, aqueous polyurethane dispersion.
In electrophoresis coating fluid of the present invention, contained microcapsule are not limited to individual layer capsule, can be bilayer or multilayer capsule.The present invention's microcapsule used adopt the preparation method of prior art to make.About the Micro-Encapsulation Technique in electrophoretic display technology, have at present lot of documents and patent report both at home and abroad.At present, the method for preparing microcapsule has chemical method, physico-chemical processes and mechanical process, and wherein chemical method comprises coacervation, interfacial polymerization, situ aggregation method etc.Nakamura etc. described a kind of gelatin gum arabic system by complex coacervation the microcapsule (literature reference: Eiji Nakamura for the preparation of electrophoretic display technology, et al., Proceedings ofSID ' 98International Symposium, May 1998, p1014-1017), this microcapsule solvent stability is good, but because gelatin and gum arabic are all natural macromolecular materials, poor stability, life-time service will affect the performance of microcapsule.U.S. Patent application US 6262833 discloses a kind of situ aggregation method that utilizes and has adopted urea-formaldehyde resin to seal the microcapsule preparation method of electrophoresis liquid.
The preparation method of two kinds of microcapsule for reference is provided below.
Reference method 1:
Step 1: prepare respectively 20ml massfraction and be gum arabic (the water-soluble macromolecular compound B) solution that 2% gelatin (water-soluble macromolecular compound A) solution and 20ml massfraction are 2%;
Step 2: get 5mg EX-SF DISPERSE BLUE EX-SF 300 BF dyestuff and 5mg polybutene succinyl-ammonia PIBI joins in the zellon of 5ml, at 50 ℃ of ultrasonic lower dispersion 60min in left and right; The gumwater that adds 20ml to prepare under 700rpm rotating speed stirs, continues to stir 3min; Then rotating speed is adjusted to 300rpm, the gelatin solution that adds 20ml to prepare; The acetum that is 10% with massfraction afterwards regulates pH to 4 left and right, and below slow cooling to 10 ℃, adding 5ml massfraction is 5% glutaraldehyde solution, stirs 1h.
Step 3: the microcapsule that step 2 is made import in vibratory screening apparatus, limit vibrosieve, appropriate distilled water wash microcapsule for limit, can make microcapsule used in electrophoresis coating fluid thus.
Reference method 2:
The preparation method of a kind of microcapsule that provide with reference to Chinese patent application 201210156409.3, water-soluble high score compd A wherein, B are respectively gelatin and gum arabic.The method comprises the steps:
Step 1: prepare individual layer microcapsule---in the aqueous gelatin solution dissolving, add the electrophoresis suspensioning liquid that is dispersed with electrophoresis particle, stir and obtain the first emulsion, the weight ratio of wherein said electrophoresis suspensioning liquid and gelatin is 1 ~ 30:1; In the time that particle diameter reaches 20-100um, add the gum arabic aqueous solution, then add acid, adjust pH value in 3.5-5.5 interval, wherein, the weight ratio of gelatin and gum arabic is 1:1 ~ 3; Cool the temperature to 5-12 ℃, add linking agent to be cured, be warming up to 20-35 ℃ and keep reaction to carry out 4-10 hour, make the first microcapsule;
Step 2: described the first microcapsule are screened, select second microcapsule of particle diameter between 25-55um;
Step 3: prepare bilayered microcapsule---using described the second microcapsule as capsule-core, adopt situ aggregation method to form outer cyst wall at described the second microcapsule outside surface.Particularly, in step 3, prepare bilayered microcapsule and specifically comprise following steps: trimeric cyanamide and formaldehyde are mixed according to mol ratio 1:1.5 ~ 3, regulating pH value with trolamine is 8 ~ 10, at 60 ~ 80 ℃ of temperature, reacts 0.5 ~ 3h, obtains terpolycyantoamino-formaldehyde resin prepolymer solution; Described the second microcapsule are dispersed in the aqueous solution, regulating temperature of reaction is 30 ~ 60 ℃, adds acid solution to adjust pH value between 2.5 ~ 3.5, is added dropwise to described terpolycyantoamino-formaldehyde resin prepolymer solution, adjust pH value between 2.5 ~ 3.5, continue reaction 0.5 ~ 3 hour; Reaction finishes pH value to be adjusted into 6 ~ 7 with trolamine afterwards, makes bilayered microcapsule.
Be described in further detail technical scheme of the present invention and technique effect below in conjunction with embodiment and comparative example.
This example of embodiment 1(is the preparation example of electrophoresis coating fluid)
Prepare electrophoresis coating fluid, adopt following steps preparation:
(1) prepare microcapsule according to the microcapsule preparation method of reference method 2 mentioned above, wherein water-soluble macromolecular compound A, B are respectively gelatin and gum arabic;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) 0.6g gelatin (component A) is dissolved in 2.4g water, after filtration, makes gelatin solution, and it is mixed with the microcapsule of step (2), stir 1.0h with the rotating speed of 250rpm, mix to obtain preliminary electrophoresis coating fluid;
(4) the aqueous polyurethane solution (B component) that takes 20g joins in the preliminary electrophoresis coating fluid that step (3) makes, and stirs 1.0h, obtains electrophoresis coating fluid.
The component A that table 1: embodiment 1 ~ 25 is used and B component and consumption thereof
This example of embodiment 26(is the preparation example of electrophoresis showed layer, referring to Fig. 1)
Preparation electrophoresis showed layer, adopts following steps preparation:
Using coating instrument the electrophoresis coating fluid preparing to be coated on to the ITO(indium tin oxide of PET film 1) on transparency conducting layer 3, baking and curing, forms electrophoresis showed layer 5.On electrophoresis showed layer 5, add again the substrate 2 of lid layer with some pixel electrodes, be bonded together by the pixel electrode on substrate 2 and 5 hot pressing of electrophoresis showed layer or with transparent glue.Adopt in the present embodiment transparent glue that the pixel electrode on substrate 2 and electrophoresis showed layer 5 are bonded together, now between substrate 2 and electrophoresis showed layer 5, be formed with a glue layer 4.
Comparative example 1:
(1) adopt microcapsule preparation method for reference mentioned above (reference method 2) to prepare microcapsule, wherein water-soluble macromolecular compound A, B are respectively gelatin solution and gumwater;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) take 4.0g gelatin and be dissolved in 36.0g water, after the gelatin solution having dissolved is filtered, mix with the microcapsule of step (2), under unsettled agitator, stir 1.0h with the rotating speed of 250rpm, mix and obtain electrophoresis coating fluid.
(4) prepare electrophoresis showed layer, step is substantially with the preparation process of the electrophoresis showed layer in embodiment 26, and difference is that electrophoresis coating fluid used adopts prepared electrophoresis coating fluid in comparative example 1.
Comparative example 2:
(1) adopt microcapsule preparation method for reference mentioned above (reference method 2) to prepare microcapsule, wherein water-soluble macromolecular compound A, B are respectively gelatin and gum arabic;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) take the aqueous polyurethane emulsion of 20g, the microcapsule that make with step (2) mix, and stir 1.0h with the rotating speed of 250rpm under unsettled agitator, mix and obtain electrophoresis coating fluid.
(4) prepare electrophoresis showed layer, step is substantially with the preparation process of the electrophoresis showed layer in embodiment 26, and difference is that electrophoresis coating fluid used adopts prepared electrophoresis coating fluid in comparative example 2.
Comparative example 3:
(1) adopt microcapsule preparation method for reference mentioned above (reference method 2) to prepare microcapsule, wherein water-soluble macromolecular compound A, B are respectively gelatin and gum arabic;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) take 4.0g polyoxyethylene glycol and be dissolved in 36.0g water, after the gelatin solution having dissolved is filtered, mix with the microcapsule of step (2), under unsettled agitator, stir 1.0h with the rotating speed of 250rpm, mix and obtain electrophoresis coating fluid.
(4) prepare electrophoresis showed layer, step is substantially with the preparation process of the electrophoresis showed layer in embodiment 26, and difference is that electrophoresis coating fluid used adopts the prepared electrophoresis coating fluid of comparative example 3
Comparative example 4:
(1) adopt microcapsule preparation method for reference mentioned above (reference method 2) to prepare microcapsule, wherein water-soluble macromolecular compound A, B are respectively gelatin and peach gum;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) the aqueous polyurethane solution that takes 25g mixes with the microcapsule that step (2) makes, and stirs 1.0h with the rotating speed of 250rpm under unsettled agitator, mixes and obtains electrophoresis coating fluid.
(4) prepare electrophoresis showed layer, step is substantially with the preparation process of the electrophoresis showed layer in embodiment 26, and difference is that electrophoresis coating fluid used adopts prepared electrophoresis coating fluid in comparative example 4.
Comparative example 5
(1) adopt microcapsule preparation method for reference mentioned above (reference method 2) to prepare microcapsule, wherein water-soluble macromolecular compound A, B are respectively gelatin and gum arabic;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) take 4.0g gum arabic and be dissolved in 36.0g water, after the gumwater having dissolved is filtered, mix with the microcapsule of step (2), under unsettled agitator, stir 1.0h with the rotating speed of 250rpm, obtain electrophoresis coating fluid.
(4) prepare electrophoresis showed layer, step is substantially with the preparation process of the electrophoresis showed layer in embodiment 26, and difference is that electrophoresis coating fluid used adopts the prepared electrophoresis coating fluid of comparative example 5
Comparative example 6
(1) adopt microcapsule preparation method for reference mentioned above (reference method 2) to prepare microcapsule, wherein water-soluble macromolecular compound A, B are respectively gelatin and gum arabic;
(2) take the prepared microcapsule 100g of step (1) that centrifugal good solid content is 45%, for subsequent use;
(3) take the aqueous polyurethane dispersion of 20g, the microcapsule that make with step (2) mix, and stir 1.0h with the rotating speed of 250rpm under unsettled agitator, mix and obtain electrophoresis coating fluid.
(4) prepare electrophoresis showed layer, step is substantially with the preparation process of the electrophoresis showed layer in embodiment 26, and difference is that electrophoresis coating fluid used adopts prepared electrophoresis coating fluid in comparative example 6.
Performance test
1. test the data such as black and white reflectivity, contrast gradient of the prepared electrophoresis showed layer of the electrophoresis coating fluid being made by embodiment 1 ~ 25 and comparative example 1 ~ 6 (forming by making with reference to the preparation process of embodiment 26 of electrophoresis showed layer) adding after electric drive with spectrophotometer.The results are shown in Table 2, as known from Table 2, the prepared electrophoretic display apparatus of electrophoretic display coating fluid that adopts the present invention to prepare has high-contrast and high white reflectivity.Wherein, although added a large amount of aqueous polyurethanes in embodiment 12,19, its white reflectivity still can reach more than 38, and contrast gradient can reach 8.8.
Table 2: black and white reflectivity, contrast gradient test result
Note: 1.L* numerical value has embodied the reflective light intensity that shows film, and L* value is higher just means that reflectivity is stronger.
2.R numerical value has embodied the reflectivity values that shows film, R=((L*+16)/116) 3*100
Contrast gradient=R white/R is black
2. tensile test
The Electronic Paper membrane cutting that adopts the electrophoretic display coating fluid of embodiment 1-25 provided by the invention, comparative example 1-6 to be coated with is out slit into the sample of 34cm × 2.5cm, sample size: 5, then with ito glass substrate take laminating temperature as 110 ℃, lamination pressure is 70 pounds/square inch, roller rotating speed is that the lamination of 0.6m/min is laminated into tensile test sample, on measurer for pulling force with the velocity test of 300mm/min, in test process, get a point every 10mm, get altogether 8 points, after averaging, test result is in table 3:
Table 3
| Comparative example 1,3,5 | Comparative example 2,4,6 | |
|
| Value of thrust (gf) | 200～221 | 575～610 | 580～605 |
As known from Table 3, the value of thrust of electrophoresis showed layer that adopts electrophoretic display coating fluid provided by the invention to form is suitable with the value of thrust of the electrophoresis showed layer that use urethane forms as sizing agent separately, the value of thrust of the electrophoresis showed layer all forming as sizing agent apparently higher than independent use water-soluble polymer, illustrate that electrophoresis disclosing solution provided by the invention has good mechanical property, viscosity between electrophoresis showed layer and the base material of its formation is good, the phenomenon that this makes it in life-time service and in harsh environment and all there will not be film and base material to depart from.
3. Photomicrograph, is shown in Fig. 2 ~ 4.
The Photomicrograph of the electrophoresis showed layer that Fig. 2 ~ Fig. 4 is respectively comparative example 1, comparative example 2 and embodiment 1 under same magnification, from Fig. 2 ~ Fig. 4 relatively, the electrophoresis showed layer that adopts embodiment 1 its electrophoretic display coating fluid of technical solution of the present invention to form, microcapsule can be uniform and stable dispersion, between microcapsule, arrange more tight, damaged few, dry rear microcapsule can produce certain deformation.This is consistent with the result that electrophoretic display coating fluid provided by the invention has sufficient contrast gradient (in table 2).Embodiments of the invention 2 ~ 25 have the result substantially similar to embodiment 1, and Fig. 4 illustrates as representative graph.
4. properties of microcapsules test
To adopt the embodiment 1-25 of technical solution of the present invention and the electrophoretic display coating fluid wet film preparing device that comparative example 1-6 makes to be coated on common ITO conductive film, at 60 ℃, be dried 60 minutes, whether examine under a microscope microcapsule on device has and breaks or Fragmentation Phenomena, result shows that various embodiments of the present invention gained microcapsule seldom have and breaks or Fragmentation Phenomena (<2%), but the sample of comparative example 1-6 has microcapsules rupture in various degree, wherein comparative example 1 has 5 ~ 15% microcapsules rupture.
5. film yield
The Electronic Paper diaphragm outward appearance that adopts the electrophoretic display coating fluid of the embodiment 1-25 of technical solution of the present invention to be coated with is out better, there is no the macroscopic irregularity such as bad point, ignore, obtains yield higher, approaches 40%.The dispersion of this and microcapsule is better, arranges more relevant.And the Electronic Paper diaphragm outward appearance that adopts the electrophoretic display coating fluid of comparative example 1-6 to be coated with out has more bad point, ignore phenomenon, impact coating yield, diaphragm loss is larger, and yield only has 20%.
From above-mentioned test result, the electrophoresis coating fluid that embodiment 1 ~ 25 provides, the microcapsule of employing, it has by water-soluble macromolecular compound prepares and next outer cyst wall, and the sizing agent of arranging in pairs or groups with it.On the one hand, make microcapsule can reach homodisperse effect in sizing agent, the phenomenons such as the reunion between minimizing microcapsule; On the one hand, sizing agent used strengthens the electrophoresis coating fluid viscosity that is dispersed with microcapsule, improves its mechanical property, strengthens the bounding force between electrophoresis coating fluid and conductive layer, is not prone to film and departs from from base material; On the other hand; ingenious between sizing agent and microcapsule coordinates the formed electrophoresis coating fluid with good mechanical properties and levelling property; not only make electrophoresis coating fluid be easy to coating; improve coating outward appearance; also make the microcapsule that are scattered in wherein better be protected; be difficult in the coating process intermediary and later stages store and in use procedure, occur microcapsule breakage, coating fluid sizing agent in drying process can produce certain contraction simultaneously, reduces the space between capsule thereby certain deformation occurs capsule.The final electrophoresis showed layer forming has sufficient contrast gradient and good photoelectric properties.
So, electrophoretic display coating fluid provided by the invention, it reaches good balance in each side such as mechanical property, film performance and photoelectric properties, has the film of being easy to, appearance of film is good, and the electrophoresis showed layer that it forms has stronger mechanical property and good photoelectric properties.
The above embodiment, not the present invention is done to any pro forma restriction, do not depart from the content of technical solution of the present invention therefore all,, all still belong in the scope of technical solution of the present invention any simple modification made for any of the above embodiments, equivalent variations and modification according to technical spirit of the present invention.
Claims (9)
1. an electrophoresis coating fluid, it comprises sizing agent and is dispersed in the microcapsule in sizing agent, in described microcapsule, include suspension and be scattered in the charged pigment particle in suspension, it is characterized in that, the outer cyst wall of described microcapsule adopts water-soluble macromolecular compound to be prepared from, and contains water-soluble high-molecular compound and aqueous polyurethane in described sizing agent.
2. electrophoresis coating fluid according to claim 1, is characterized in that, the outer cyst wall of microcapsule is that gelatin and the first cyst material form, and described the first cyst material is selected from one or more in gum arabic, natural gum, peach gum, pectin.
3. electrophoresis coating fluid according to claim 1, it is characterized in that, the water-soluble high-molecular compound containing in sizing agent is selected from one or more the combination in carboxymethyl cellulose, Natvosol, Vltra tears, Zulkovsky starch, carboxymethyl starch, gum arabic, gelatin, natural gum, soybean protein, casein, polyvinyl alcohol, polyoxyethylene glycol, polyacrylamide, polyvinylpyrrolidone.
4. electrophoresis coating fluid according to claim 1, is characterized in that, described aqueous polyurethane is selected from one or more the combination in aqueous polyurethane solution, aqueous polyurethane emulsion, aqueous polyurethane dispersion.
5. electrophoresis coating fluid according to claim 1, is characterized in that, with respect to the microcapsule of 100 weight parts, water-soluble high-molecular compound and aqueous polyurethane used in sizing agent are respectively 0.15 ~ 2.5 weight part and 8 ~ 50 weight parts.
6. a method of preparing the electrophoresis coating fluid described in claim 1 ~ 5 any one, is characterized in that, described preparation method comprises the steps:
(1) water-soluble high-molecular compound is dissolved in the water, makes water-soluble polymer solution, the water-soluble polymer solution making and microcapsule are mixed evenly, obtain preliminary electrophoresis coating fluid;
(2) suitable quantity of water based polyurethane is joined in the preliminary electrophoresis coating fluid that step (1) makes, stirring and evenly mixing obtains electrophoresis coating fluid.
7. an electrophoresis showed layer, is characterized in that, described electrophoresis showed layer is to be coated on a conductive layer and formed by the electrophoresis coating fluid described in claim 1 ~ 5 any one.
8. a method of preparing electrophoresis showed layer as claimed in claim 7, is characterized in that, the electrophoresis coating fluid described in claim 1 ~ 6 any one is coated on conductive layer, treats that electrophoresis coating fluid is dry to form described electrophoresis showed layer.
9. the method for preparing electrophoresis showed layer according to claim 8, is characterized in that, described electrophoresis coating fluid is prepared as follows:
(1) water-soluble high-molecular compound is dissolved in the water, makes water-soluble polymer solution, the water-soluble polymer solution making and microcapsule are mixed evenly, obtain preliminary electrophoresis coating fluid;
(2) suitable quantity of water based polyurethane is joined in the preliminary electrophoresis coating fluid that step (1) makes, stirring and evenly mixing obtains electrophoresis coating fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210472770.7A CN103834285B (en) | 2012-11-20 | 2012-11-20 | Electrophoresis coating fluid and electrophoresis showed layer and their preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210472770.7A CN103834285B (en) | 2012-11-20 | 2012-11-20 | Electrophoresis coating fluid and electrophoresis showed layer and their preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103834285A true CN103834285A (en) | 2014-06-04 |
| CN103834285B CN103834285B (en) | 2016-05-11 |
Family
ID=50798194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210472770.7A Active CN103834285B (en) | 2012-11-20 | 2012-11-20 | Electrophoresis coating fluid and electrophoresis showed layer and their preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103834285B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107175055A (en) * | 2017-06-28 | 2017-09-19 | 常州麒通国际贸易有限公司 | A kind of electron ink microcapsule and preparation method thereof |
| CN107656408A (en) * | 2017-09-26 | 2018-02-02 | 无锡威峰科技股份有限公司 | Electronic-paper display screen and its manufacture method |
| JP2020521172A (en) * | 2017-06-16 | 2020-07-16 | イー インク コーポレイション | Electro-optic medium containing encapsulated pigment in gelatin binder |
| WO2021133794A1 (en) * | 2019-12-23 | 2021-07-01 | E Ink Corporation | Color electrophoretic layer including microcapsules with nonionic polymeric walls |
| CN113168063A (en) * | 2018-12-12 | 2021-07-23 | 伊英克公司 | Edible electrode and use in electro-optic displays |
| CN113717596A (en) * | 2021-08-18 | 2021-11-30 | 深圳秋田微电子股份有限公司 | Electrophoretic display coating liquid, preparation method thereof and electrophoretic display assembly |
| US11520210B2 (en) | 2019-09-30 | 2022-12-06 | E Ink Corporation | Electrically-actuated variable transmission film having very low haze and a visible grid in a clear state |
| US11708720B2 (en) | 2013-10-22 | 2023-07-25 | E Ink Corporation | Light-modulating electrophoretic device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506416A (en) * | 2002-12-09 | 2004-06-23 | 西北工业大学 | Prepn of green electronic ink |
| US20050035941A1 (en) * | 1995-07-20 | 2005-02-17 | Albert Jonathan D. | Retroreflective electrophoretic displaya and materials for making the same |
| CN1704176A (en) * | 2004-06-02 | 2005-12-07 | 精工爱普生株式会社 | Manufacturing method of electrophoretic display sheet material, electrophoretic display sheet material and purposes thereof |
| CN102585676A (en) * | 2011-01-05 | 2012-07-18 | 广州奥熠电子科技有限公司 | Electrophoretic display coating liquid and preparation method thereof |
-
2012
- 2012-11-20 CN CN201210472770.7A patent/CN103834285B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050035941A1 (en) * | 1995-07-20 | 2005-02-17 | Albert Jonathan D. | Retroreflective electrophoretic displaya and materials for making the same |
| CN1506416A (en) * | 2002-12-09 | 2004-06-23 | 西北工业大学 | Prepn of green electronic ink |
| CN1704176A (en) * | 2004-06-02 | 2005-12-07 | 精工爱普生株式会社 | Manufacturing method of electrophoretic display sheet material, electrophoretic display sheet material and purposes thereof |
| CN102585676A (en) * | 2011-01-05 | 2012-07-18 | 广州奥熠电子科技有限公司 | Electrophoretic display coating liquid and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李绍雄等: "《聚氨酯树脂及其应用》", 31 May 2002, 化学工业出版社 * |
| 王铭等: "电子墨水微胶囊的制备及性能研究", 《影像技术》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11708720B2 (en) | 2013-10-22 | 2023-07-25 | E Ink Corporation | Light-modulating electrophoretic device |
| US10983410B2 (en) | 2017-06-16 | 2021-04-20 | E Ink Corporation | Electro-optic media including encapsulated pigments in gelatin binder |
| JP2020521172A (en) * | 2017-06-16 | 2020-07-16 | イー インク コーポレイション | Electro-optic medium containing encapsulated pigment in gelatin binder |
| CN107175055A (en) * | 2017-06-28 | 2017-09-19 | 常州麒通国际贸易有限公司 | A kind of electron ink microcapsule and preparation method thereof |
| US11347125B2 (en) | 2017-09-26 | 2022-05-31 | Wuxi Vision Peak Technology Co., Ltd. | Electronic paper display screen and manufacturing method thereof |
| CN107656408A (en) * | 2017-09-26 | 2018-02-02 | 无锡威峰科技股份有限公司 | Electronic-paper display screen and its manufacture method |
| CN113168063A (en) * | 2018-12-12 | 2021-07-23 | 伊英克公司 | Edible electrode and use in electro-optic displays |
| US11520210B2 (en) | 2019-09-30 | 2022-12-06 | E Ink Corporation | Electrically-actuated variable transmission film having very low haze and a visible grid in a clear state |
| US11762258B2 (en) | 2019-09-30 | 2023-09-19 | E Ink Corporation | Electrically-actuated variable transmission film having very low haze and a visible grid in a clear state |
| WO2021133794A1 (en) * | 2019-12-23 | 2021-07-01 | E Ink Corporation | Color electrophoretic layer including microcapsules with nonionic polymeric walls |
| US11747701B2 (en) | 2019-12-23 | 2023-09-05 | E Ink Corporation | Color electrophoretic layer including microcapsules with nonionic polymeric walls |
| JP7464718B2 (en) | 2019-12-23 | 2024-04-09 | イー インク コーポレイション | Color electrophoretic layers containing microcapsules with non-ionic polymer walls. |
| CN113717596A (en) * | 2021-08-18 | 2021-11-30 | 深圳秋田微电子股份有限公司 | Electrophoretic display coating liquid, preparation method thereof and electrophoretic display assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103834285B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103834285A (en) | Electrophoretic coating liquid and electrophoretic display layer and preparation methods thereof | |
| US8199395B2 (en) | Particles for use in electrophoretic displays | |
| US9158174B2 (en) | Electrophoretic particles and processes for the production thereof | |
| JP4297170B2 (en) | Electrophoretic display sheet, electrophoretic display device, electrophoretic display device manufacturing method, and electronic apparatus | |
| CN102093785B (en) | Electrophoretic display coating fluid and preparation method thereof | |
| CN102847495B (en) | Electrophoretic display microcapsule and its manufacturing method | |
| CN102585676B (en) | Electrophoretic display coating liquid and preparation method thereof | |
| WO2019161647A1 (en) | Electrophoretic display diaphragm, electrophoretic display, and electrophoretic display coating liquid | |
| JP4578270B2 (en) | Electrophoretic display liquid, display medium using the same, and display device | |
| JP5385577B2 (en) | Display device driving method, display device, and electronic apparatus | |
| KR20130109842A (en) | Electrophoretic particle and electrophoretic device and electrophoretic display using the same | |
| CN104813225B (en) | Electrophoresis equipment and display unit | |
| JP2007233178A (en) | Method for manufacturing display panel of microcapsule-type electrophoretic display | |
| US9541812B2 (en) | Electrophoretic particles, production methods of electrophoretic particles, and electrophoretic display devices | |
| CN100432817C (en) | Method for producing electrophoretic particles, electrophoretic dispersion solution, micro-capsule, electrophoresis display device and electronic machine | |
| CN101850229B (en) | Electrophoretic microcapsules formed by complex coacervation of carboxyl butyronitrile/gelatin and Arabic gum and preparation method thereof | |
| CN113717596B (en) | Electrophoretic display coating liquid, preparation method thereof and electrophoretic display assembly | |
| CN103059251B (en) | Aqueous polyurethane emulsion as well as application thereof on electrophoretic display coating liquid and display device | |
| JP2006259170A (en) | Dispersion for electrophoresis display element, and electrophoresis display element using same | |
| WO2015151409A1 (en) | Display unit and electronic apparatus | |
| JP2012053184A (en) | Display sheet and method for manufacturing display device | |
| JP2011227109A (en) | Manufacturing method of display sheet, display sheet, display device and electronic device | |
| CN117903621A (en) | Electrophoretic coating liquid, electrophoretic display panel and display device | |
| KR20120024084A (en) | Electrophoretic particles, display device and image sheet having the same | |
| JP2007114800A (en) | Display panel for electrophoresis display |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 511458 building B, No. 3, Li Wei Road, Nansha District West Industrial Zone, Guangdong, Guangzhou, China Patentee after: GUANGZHOU OED TECHNOLOGIES CO., LTD. Address before: 511458 building B, No. 3, Li Wei Road, Nansha District West Industrial Zone, Guangdong, Guangzhou, China Patentee before: Guangzhou OED Technologies Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder |