JP2006293209A - Optical writing display element and method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical writing display element excellent in thermal stability and repeated durability. <P>SOLUTION: The optical writing display element has on a support a barrier layer, an organic layer and a layer containing a photochromic dye, wherein the barrier layer and the organic layer are alternately stacked by at least one layer each. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical writing display element and a display method for writing an image by light and displaying an image by coloring using a photochromic dye whose absorption reversibly changes with light.

  In recent years, there has been a demand for providing full-color display materials that are bright and easy to see and have low power consumption. For example, self-luminous elements such as CRT, PDP, and ELD are bright and easy to see, but have a problem of high power consumption. Also, various display methods have been proposed as an image display device called so-called electronic paper.

As for a liquid crystal display element (LCD), since a transmissive LCD uses a backlight, power consumption is somewhat large, and it is dependent on a viewing angle and cannot be said to be bright and easy to see.
In addition, the reflective LCD consumes less power, but has a viewing angle dependency, and forms a color image by the side-by-side mixing method using color filters. However, this method cannot express white, resulting in a dark screen. There is a problem of becoming. Furthermore, in the reflection type display element, in which two to three layers of elements are laminated, the structure becomes complicated, and technical problems for establishing the manufacturing process are difficult, and there is a problem that the manufacturing cost becomes high. .

On the other hand, there is a photochromic element as a display element using a so-called photochromic dye that reversibly changes light absorption of a substance by light. A photochromic dye is a dye having a function capable of reversibly controlling color development and decoloration by ultraviolet light and visible light. Since the display of the photochromic element can be controlled only by light, an electrode is not required, the element structure is simple, and since it is a light absorption type, a clear display with no viewing angle dependency can be obtained even under strong external light. For this reason, it has the characteristic outstanding as a glare-proof mirror for motor vehicles, and light control glass. A photochromic element does not require a polarizing plate or the like, has no viewing angle dependency, has a light receiving type, has excellent visibility, has a simple structure, and can be easily enlarged. In addition, by selecting a thin film containing the photochromic dye, various color tones can be obtained, and the display state can be stopped (memory property). Furthermore, there are various advantages such as no external stimulus required to maintain the display state and low power consumption (see, for example, Non-Patent Document 1).
However, the photochromic dye has a problem of low thermal stability and low durability when used repeatedly.

Conventionally, there has been a report that thermal stability is improved by coating a polyvinyl alcohol (PVA) layer on a photochromic element, but the level is still not sufficient (see, for example, Patent Document 1).
JP 2004-198689 A SID03DIGEST, page 851, 2003

  The present invention has been made in view of the above-described problems, and an object thereof is to provide an optical writing display element having excellent thermal stability and repeated durability.

As a result of intensive studies, the present inventor obtained a knowledge that an unexpected effect of improving the display contrast ratio can be obtained by combining a specific barrier layer and a photochromic dye on the support. Based on further investigation, the present invention has been completed.
Means for solving the above-mentioned problems are as follows.

(1) An optical writing display having a barrier layer, an organic layer, and a layer containing a photochromic dye on a support, wherein the barrier layer and the organic layer are alternately stacked. element.

(2) A layer containing a photochromic dye is provided between the two supports, and the barrier layer and the organic layer are provided on the side of the support opposite to the surface on which the layer containing the photochromic dye is provided. The optical writing display element according to the above (1), wherein a laminated body is provided.

(3) The optical writing display element according to (1) or (2), wherein the barrier layer is an inorganic barrier layer.

(4) The optical writing display element according to any one of (1) to (3), wherein the layer containing the photochromic dye includes a plurality of photochromic dyes that develop different colors.

(5) The optical writing display element according to (4), wherein the layer containing the photochromic dye contains a photochromic dye that develops yellow, magenta, and cyan.

(6) The optical writing display element according to any one of (1) to (5), wherein the photochromic dye is a fulgide derivative or a diarylethene derivative.

(7) The optical writing display element according to any one of (1) to (6), wherein the support is a plastic substrate.

(8) Using the optical writing display element according to any one of (1) to (7),
An optical writing display method characterized in that a pattern is formed by irradiating light in a visible region after color is developed by irradiation with ultraviolet light.

  ADVANTAGE OF THE INVENTION According to this invention, the optical writing display element excellent in thermal stability and repetition durability can be provided.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<Support>
As the support used in the present invention, a plastic substrate, a glass substrate, paper, metal, or the like can be used, but a plastic substrate is preferable. The plastic substrate is not particularly defined as long as it does not depart from the gist of the present invention, but polyester, polyimide, polymethyl methacrylate, polystyrene, polypropylene, polyethylene, polyamide, nylon, polyvinyl chloride, polyvinylidene chloride, polycarbonate, poly Polymer films and plate-like substrates such as ether sulfones, silicone resins, polyacetal resins, fluororesins, cellulose derivatives, and polyolefins are preferably used. When used as a transmissive optical writing display element, a plastic substrate having a light transmittance of at least 50% or more is preferably used.

<Barrier layer and organic layer>
Hereinafter, the barrier layer and the organic layer used in the present invention will be described. In the present invention, the barrier layer and the organic layer are provided at least one layer each other. Thus, by providing the barrier layer and the organic layer in a stacked manner, intrusion of oxygen and water can be prevented. It is said that photochromic dyes are usually deteriorated by addition or hydrolysis due to singlet oxygen. By laminating this barrier layer and organic layer, the infiltration of oxygen and water is more efficient than the case of only one barrier layer. The decomposition of the photochromic dye can be remarkably controlled.

The laminate of the barrier layer and the organic layer may be provided on at least one surface side of the layer containing the photochromic dye, so as to prevent moisture and oxygen from entering the layer containing the photochromic dye described later. In this case, it is provided on both sides of the layer containing the photochromic dye.
In addition, a layer containing a photochromic dye is provided between the two supports, and a laminate of a barrier layer and an organic layer is disposed on the side of the support opposite to the surface provided with the layer containing the photochromic dye. Is more preferable from the viewpoint of manufacturing.

Further, the number of layers is not particularly defined, but preferably 1 to 5 sets, more preferably 1 to 3 sets, when the combination of the barrier layer and the organic layer is 1 set.
The total thickness of the laminate of the barrier layer and the organic layer is preferably 1 μm to 100 μm, and more preferably 1 μm to 50 μm.

(Barrier layer)
In the present invention, the barrier layer refers to a layer provided in order to prevent moisture and oxygen from entering.
The method for producing the barrier layer of the present invention is not particularly defined as long as it does not depart from the gist of the present invention, but a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable. The methods described in JP-A-2002-322561 and JP-A-2002-361774 can be preferably employed.

  The barrier layer of the present invention is very preferably an inorganic barrier layer composed of an inorganic material, for example, an oxide containing one or more of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like. More preferred are oxides, nitrides, oxynitrides, etc., oxides containing one or more of Si, Al, Ti, nitrides or oxynitrides are more preferred, and oxides, nitrides containing Si, or nitrides are particularly preferred. It is an oxynitride.

  Although it does not specifically limit regarding the thickness of a barrier layer, It is preferable that the thickness of one barrier layer is the range of 5 nm-1000 nm, More preferably, it is 10 nm-1000 nm, Most preferably, it is 10 nm-200 nm. When two or more barrier layers are provided, each layer may have the same composition or different compositions.

In order to achieve both moisture penetration barrier properties and high transparency, it is preferable to use silicon oxide or silicon oxynitride as the barrier layer.
Silicon oxide is expressed as SiO _x . For example, when SiO _x is used as the barrier layer, 1.6 <x <1.9 is obtained in order to obtain better moisture penetration barrier properties and high light transmittance. It is preferable.
Silicon oxynitride is expressed as SiO _x N _y, and the ratio of x and y is an oxygen-rich film in order to further improve the adhesion, 1 <x <2, 0 <y <1 Are preferable, and 1.0 <x <1.8 and 0.2 <y <1.0 are more preferable. In order to further improve the moisture penetration barrier property, a nitrogen-rich film is used, and 0 <x <0.8 and 0.8 <y <1.3 are preferable, and 0 <x <0.7 and 1.0 <Y <1.3 is more preferable.

(Organic layer)
In the present invention, the barrier layer and the organic layer are laminated in order to improve the brittleness of the barrier layer and improve the barrier property.

  The thickness of the organic layer is not particularly limited, but is preferably 10 nm to 5000 nm, more preferably 10 to 2000 nm, and most preferably 10 nm to 5000 nm. By setting it as such thickness, the structural defect of the said barrier layer can be filled with an organic layer more efficiently, and barrier property improves more. On the other hand, if the organic layer is too thick, the organic layer is likely to crack due to an external force such as bending, which causes a problem that the barrier property is lowered.

  As the organic layer, for example, (1) a method using an inorganic oxide layer produced by using a sol-gel method, and (2) a method in which an organic material is laminated by coating or vapor deposition and then cured by ultraviolet rays or electron beams. Can be formed. Moreover, (1) and (2) may be used in combination. For example, after forming a thin film on the resin film by the method of (1), an inorganic oxide layer is prepared, and then (2) A thin film may be formed by a method.

(1) Sol-gel method In the sol-gel method in the present invention, a metal alkoxide is preferably hydrolyzed and polycondensed in a solution or a coating film to obtain a dense thin film. At this time, an organic-inorganic hybrid material may be used in combination with a resin.
As the metal alkoxide, alkoxysilane and / or metal alkoxide other than alkoxysilane is used. As the metal alkoxide other than alkoxysilane, zirconium alkoxide, titanium alkoxide, aluminum alkoxide and the like are preferable.

The resin used together during the sol-gel reaction preferably has a hydrogen bond forming group.
Examples of resins having a hydrogen bond-forming group include polymers having hydroxyl groups and derivatives thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymers, phenol resins, methylol melamine, and derivatives thereof); Polymers and derivatives thereof (single or copolymer containing units of polymerizable unsaturated acid such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, and esterified products of these polymers (vinyl esters such as vinyl acetate, Homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate)); polymers having ether bonds (polyalkylene oxides, polyoxyalkylene glycols, polyvinyl ethers, silicon resins, etc.); amide bonds (> N (C R) -bond, that is, a trivalent group consisting of N (COR) (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent). N-acylated products of polyoxazoline and polyalkyleneimine));> NC (O) -linkage, that is, polyvinylpyrrolidone having a trivalent group consisting of NC (O) and derivatives thereof; polyurethane having urethane bond A polymer having a urea bond, and the like.
The usage-amount of resin is 0.1-10 mol with respect to 1 mol of metal alkoxides, More preferably, it is 0.5-5 mol.

In addition, an organic-inorganic hybrid material can be produced by using a monomer in combination during the sol-gel reaction and polymerizing during or after the sol-gel reaction. Examples of such a monomer include acrylate, methacrylate, and isocyanate.
The usage-amount of the monomer used together at the time of sol-gel reaction is 0.1-100 mol with respect to 1 mol of metal alkoxides, More preferably, it is 0.5-50 mol.

During the sol-gel reaction, the metal alkoxide is hydrolyzed and polycondensed in water and an organic solvent. At this time, it is preferable to use a catalyst. As the hydrolysis catalyst, an acid (organic or inorganic acid) is generally used.
The amount of the acid used is preferably 0.0001 to 0.05 mol, more preferably 1 mol per 1 mol of metal alkoxide (alkoxysilane and other metal alkoxide in the case of containing alkoxysilane and other metal alkoxide). Is 0.001 to 0.01 mol.
After hydrolysis, a basic compound such as an inorganic base or an amine may be added to bring the pH of the solution to near neutrality to promote condensation polymerization.

  In addition, other sol-gel catalysts such as metal chelate compounds having Al, Ti, and Zr as the central metal, organometallic compounds such as tin compounds, and metal salts such as alkali metal salts of organic acids can be used in combination. The ratio of the sol-gel catalyst compound in the composition is preferably 0.01 to 50% by weight, more preferably 0.1 to 50% by weight, and still more preferably 0.1% by weight with respect to the alkoxysilane that is the raw material of the sol liquid. 5 to 10% by weight.

Next, the solvent used for the sol-gel reaction will be described. The solvent uniformly mixes each component in the sol solution, and at the same time prepares the solid content of the composition of the present invention, so that it can be applied to various coating methods to improve the dispersion stability and storage stability of the composition. Is. These solvents are not particularly limited as long as they can fulfill the above purpose. Preferable examples of these solvents include water and organic solvents that are highly miscible with water.
The amount of the solvent used is preferably 1 to 100,000% by mass, more preferably 10 to 10,000% by mass per equivalent of metal alkoxide.

For the purpose of adjusting the speed of the sol-gel reaction, an organic compound capable of multidentate coordination may be added to stabilize the metal alkoxide. Examples thereof include β-diketones and / or β-ketoesters, and alkanolamines.
Specific examples of the β-diketone and / or β-ketoester include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate Acetic acid-sec-butyl, acetoacetic acid-tert-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.
These compounds capable of multidentate coordination can also be used for the purpose of adjusting the reaction rate when the metal chelate compound is used as a sol-gel catalyst.
The amount of the compound capable of multidentate coordination is 0.1 to 100 mol, more preferably 0.5 to 50 mol, per 1 mol of the metal alkoxide.

Next, a method for applying the sol-gel reaction composition will be described. The sol solution can form a thin film on the film by a coating method such as curtain flow coating, dip coating, spin coating or roll coating.
In this case, the hydrolysis may be performed at any time during the production process. For example, a method of preparing a desired sol solution by subjecting a liquid having a required composition to hydrolysis partial condensation, and applying and drying the solution, and preparing a liquid having a required composition and drying while subjecting it to hydrolysis partial condensation at the same time. For example, a method of applying and hydrolyzing by applying a water-containing liquid necessary for hydrolysis after coating and primary drying can be suitably employed. In addition, the coating method can take various forms. However, when productivity is important, each of the lower layer coating solution and the upper layer coating solution is required on a slide Geyser having a multistage discharge port. A method (simultaneous multi-layer method) is preferably used in which the discharge flow rate is adjusted so that the coating amount is obtained, and the formed multilayer flow is continuously placed on a support and dried.

  The drying temperature after application of the sol-gel reaction composition is preferably 150 to 350 ° C, more preferably 150 to 250 ° C, and still more preferably 150 to 200 ° C.

In order to further refine the organic layer after coating and drying, irradiation with energy rays may be performed. Although there is no restriction | limiting in particular in the kind of irradiation radiation, In consideration of the influence with respect to a deformation | transformation and modification | denaturation of a support body, irradiation of an ultraviolet-ray, an electron beam, or a microwave can be used especially preferable.
The irradiation intensity is preferably ^{30mJ / cm 2 ~500mJ / cm 2} , more preferably ^{50mJ / cm 2 ~400mJ / cm 2} . The irradiation temperature can be employed without limitation between room temperature and the deformation temperature of the support, and is preferably 30 ° C to 150 ° C, more preferably 50 ° C to 130 ° C.

(2) A method of laminating an organic substance by coating or vapor deposition, and then curing with an ultraviolet ray or an electron beam A case where an organic layer is formed by crosslinking a monomer with an ultraviolet ray or an electron beam will be described. The monomer is not particularly limited as long as it contains a group that can be cross-linked by ultraviolet rays or an electron beam, but it is preferable to use a monomer having an acryloyl group, a methacryloyl group, or an oxetane group.
For example, epoxy (meth) acrylate, urethane (meth) acrylate, isocyanuric acid (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (meth) acrylate, ethylene glycol (meth) acrylate, polyester (meth) acrylate, etc. Among these, it is preferable that the main component is a polymer obtained by crosslinking a monomer having a bifunctional or higher functional acryloyl group or methacryloyl group. These monomers having a bifunctional or higher acryloyl group or methacryloyl group may be used as a mixture of two or more kinds, or as a mixture of monofunctional (meth) acrylates.
Moreover, as a thing which has an oxetane group, it is preferable to use the thing which has a structure described in Unexamined-Japanese-Patent No. 2002-356607 General formula (3)-(6). In this case, you may mix these arbitrarily.

  In addition, from the viewpoint of heat resistance and solvent resistance required for display applications, it is mainly composed of isocyanuric acid acrylate, epoxy acrylate, urethane acrylate having a high degree of crosslinking and a glass transition temperature of 200 ° C. or higher. Further preferred.

In the method (2), the method for applying or vapor-depositing the organic substance is not particularly limited.
For example, when an organic layer is formed by a vacuum film formation method, a film formation method such as vapor deposition or plasma CVD is preferable, and a resistance heating vapor deposition method that easily controls the film formation rate of the organic material monomer is more preferable.
When the coating method is used, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.

  In the method (2), there is no restriction on the method of crosslinking the organic monomer, but the crosslinking by electron beam or ultraviolet rays is easy to attach in the vacuum chamber and the high molecular weight by the crosslinking reaction is rapid. This is desirable.

(Water absorbent)
In the present invention, the following is shown between the substrate and the laminate composed of the organic layer and the barrier layer, between the uppermost layer of the laminate, the organic layer and the barrier layer, or in the organic layer or the barrier layer. Such a water absorbent may be used in combination.
The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. For example, BaO, SrO, CaO, MgO, etc. are mentioned. Furthermore, it can also be selected from metal elements such as Ti, Mg, Ba, and Ca.

  The particle diameter of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.

In the case of separately providing a layer containing a water absorbent, it may be prepared by using a vacuum deposition method or the like as in the above-described barrier layer, or nanoparticles may be prepared by various methods. These are preferably used at a layer thickness of 1 to 100 nm, more preferably 1 to 10 nm.
The coating amount of the water absorbing agent is preferably ^{10 -4 g / m 2 ~10 2} g / m 2, and more preferably ^{10 -3 g / m 2 ~10g /} m 2.

When adding to a barrier layer, it is preferable to use a co-evaporation method.
When adding to an organic layer, it is preferable to produce by mixing and apply | coating organic substance and a water absorbent.

<Layer containing photochromic dye>
The layer containing the photochromic dye in the invention is not particularly defined as long as the photochromic dye is included, and is preferably used in a state where the photochromic dye is dispersed or dissolved in the binder.
The content ratio of the binder with respect to the photochromic dye is preferably 10% by mass to 10,000% by mass, and more preferably 50% by mass to 1,000% by mass.

  Examples of the polycondensation resin component used as the binder include polyurethane, polyester, polyamide, polyurea, and polycarbonate. Specific examples are illustrated below in the form of raw material monomers. However, although P-23 is illustrated in the form of a polymer, the present invention is not limited thereto. All acidic groups in each polymer are represented in non-dissociated form. In addition, regarding components produced by a condensation reaction such as polyester and polyamide, the constituent components are all expressed as dicarboxylic acids, diols, diamines, hydroxycarboxylic acids, aminocarboxylic acids, etc., regardless of the raw materials. The ratio in parentheses means the mole percentage ratio of each component.

  P-1: Toluene diisocyanate / ethylene glycol / 1,4-butanediol (50/15/35)

  P-2: 4,4'-diphenylmethane diisocyanate / 1,3-propanediol / polypropylene glycol (Mw = 1000) (50/45/5)

  P-3: Toluene diisocyanate / hexamethylene diisocyanate / ethylene glycol / polyethylene glycol (Mw = 600) / 1,4-butanediol (40/10/20/10/20)

  P-4: 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / diethylene glycol / 1,6-hexanediol (25/25/35/15)

  P-5: 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20/20/10)

  P-6: 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol / ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20/20/10)

  P-7: 1,5-naphthylene diisocyanate / butanediol / 4,4′-dihydroxy-diphenyl-2,2′-propane / polypropylene glycol (Mw = 400) / 2,2-bis (hydroxymethyl) propionic acid (50/20/5/10/15)

  P-8: 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid / polybutylene oxide (Mw = 500) (35/15/25/25)

  P-9: Isophorone diisocyanate / diethylene glycol / neopentyl glycol / 2,2-bis (hydroxymethyl) propionic acid (50/20/20/10)

  P-10: Toluene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid / polyethylene glycol (Mw = 1000) / cyclohexanedimethanol (50/10/10/30)

  P-11: Diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / butanediol / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10/10/33/7)

  P-12: Diphenylmethane diisocyanate / hexamethylene diisocyanate / butanediol / ethylene glycol / 2,2-bis (hydroxymethyl) butanoic acid / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10 / 20/15/10/5)

  P-13: terephthalic acid / isophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (25/25/25/15/10)

  P-14: terephthalic acid / isophthalic acid / 4,4'-dihydroxy-diphenyl-2,2-propane / tetraethylene glycol / ethylene glycol (30/20/20/15/15)

  P-15: terephthalic acid / isophthalic acid / cyclohexanedimethanol / neopentyl glycol / diethylene glycol (20/30/25/15/10)

  P-16: terephthalic acid / isophthalic acid / 4,4'-benzenedimethanol / diethylene glycol / neopentyl glycol (25/25/25/15/10)

P-17: terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / ethylene glycol / neopentyl glycol (24/24/2/25/25)

  P-18: terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (22/22/6/25/15/10)

  P-19: Isophthalic acid / 5-sulfoisophthalic acid / cyclohexanedimethanol / ethylene glycol (40/10/40/10)

  P-20: cyclohexanedicarboxylic acid / isophthalic acid / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid / cyclohexanedimethanol / ethylene glycol (30/20/5/25/20)

P-21: 11-aminoundecanoic acid (100)
P-22: 12-aminododecanoic acid (100)
P-23: Reaction product of poly (12-aminododecanoic acid) and maleic anhydride (50/50)

P-24: 11-aminoundecanoic acid / 7-aminoheptanoic acid (50/50)
P-25: Hexamethylenediamine / Adipic acid (50/50)
P-26: Tetramethylenediamine / Adipic acid (50/50)
P-27: Hexamethylenediamine / Sebacic acid (50/50)

  P-28: N, N-dimethylethylenediamine / adipic acid / cyclohexanedicarboxylic acid (50/20/30)

  P-29: Toluene diisocyanate / 4,4'-diphenylmethane diisocyanate / hexamethylenediamine (30/20/50)

P-30: Nonamethylenediamine / urea (50/50)
P-31: Hexamethylenediamine / nonamethylenediamine / urea (25/25/50)

  P-32: Toluene diisocyanate / hexamethylenediamine / 2,2-bis (hydroxymethyl) propionic acid (50/40/10)

  P-33: 11-aminoundecanoic acid / hexamethylenediamine / urea (33/33/33)

As the monomer for forming the vinyl polymer of the present invention, acrylic acid esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert- Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethyl Aminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyla Relate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso -Propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate ( Addition mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, etc. I can get lost.
In addition, the following monomers can be used.

Methacrylic acid esters:
Specific examples thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofur Furyl methacrylate, fu Nyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl Methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxypolyethylene glycol Examples thereof include methacrylate (addition mole number n = 6), acrylic methacrylate, dimethylaminoethylmethyl chloride methacrylate salt, and the like.

Vinyl esters:
Other specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like. .

Acrylamide:
For example, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, isopropyl acrylamide, n-butyl acrylamide, sec-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, Examples include phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide, and the like.

Methacrylamide:
For example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, isopropylmethacrylamide, n-butylmethacrylamide, sec-butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethacrylamide , Chlorobenzylmethacrylamide, octylmethacrylamide, stearylmethacrylamide, sulfopropylmethacrylamide, N-ethyl-N-phenylaminoethylmethacrylamide, 2- (3-phenylpropyloxy) ethylmethacrylamide, dimethylaminophenoxyethylmethacrylate Amides, furfuryl methacrylamide, tetrahydrofurfuryl methacrylamide, phenyl Tacrylamide, cresyl methacrylamide, naphthyl methacrylamide, 2-hydroxyethyl methacrylamide, 4-hydroxybutyl methacrylamide, triethylene glycol monomethacrylamide, dipropylene glycol monomethacrylamide, 2-methoxyethyl methacrylamide, 3-methoxybutyl Methacrylamide, 2-acetoxyethyl methacrylamide, 2-acetoacetoxyethyl methacrylamide, 2-ethoxyethyl methacrylamide, 2-iso-propoxyethyl methacrylamide, 2-butoxyethyl methacrylamide, 2- (2-methoxyethoxy) ethyl Methacrylamide, 2- (2-ethoxyethoxy) ethyl methacrylamide, 2- (2-butoxyethoxy) ethyl methacrylamide, ω-me Examples include toxipolyethylene glycol methacrylamide (addition mole number n = 6), acrylic methacrylamide, dimethylamino methacrylamide, diethylamino methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like.

Olefins:
Examples thereof include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Styrenes:
Examples thereof include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester, and the like.

Vinyl ethers:
Examples thereof include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like.

  Other examples include butyl crotonate, hexyl crotonate, dibutyl itaconate, dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl Examples include methacrylate, N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemolone nitrile, vinylidene, and the like.

  The monomer used in the polycondensate or polymer of the present invention uses two or more monomers as comonomers according to various purposes (for example, improvement in solubility, hardness, softness, tensile strength, etc.). May be. The monomers of the present invention in the polymer are preferably methacrylate, acrylamide, and methacrylamide.

In the present invention, the photochromic dye is defined as a compound having a function capable of reversibly changing between an absorption state and a non-absorption state by light.
The photochromic dye used in the present invention may have any absorption maximum and absorption band, but has an absorption maximum in the yellow range (Y), magenta range (M), or cyan range (C). Is preferred. Two or more kinds of photochromic dyes may be used, and the layer containing the photochromic dye preferably contains a plurality of photochromic dyes that develop different colors, and a mixture of photochromic dyes having absorption maximums in Y, M, and C. Is preferably used.
The method of performing full color display by mixing a yellow dye, a magenta dye, and a cyan dye is detailed in “Color Chemistry” (written by Sumio Tokita, Maruzen, 1982). Here, the yellow region is a range of 430 to 490 nm, the magenta region is a range of 500 to 580 nm, and the cyan region is a range of 600 to 700 nm.

Next, the chromophore used for the photochromic dye of the present invention will be described.
The photochromic dye may have any chromophore, and examples thereof include fulgide derivatives, diarylethene derivatives, merocyanine derivatives, azobenzene derivatives, and spiropyran derivatives. From the viewpoint of high thermal stability, fulgide derivatives and diarylethene derivatives are preferred.
Although the specific example of the photochromic pigment | dye which can be used for this invention below is shown, this invention is not limited at all by the following specific examples.

The photochromic dye can be synthesized by combining known methods.
The coating amount of the photochromic dye is preferably 0.1 mol to 1,000 mol, more preferably 1 mol to 100 mol per square meter.

<Functional layer>
In the present invention, various functional layers may be provided. Examples of functional layers include optical functional layers such as antireflection layers, polarizing layers, UV absorbing layers, white reflective layers, light extraction efficiency improving layers, mechanical functional layers such as hard coat layers and stress relaxation layers, and antistatic properties. Examples thereof include an electrical functional layer such as a layer / conductive layer, an antifogging layer, an antifouling layer, and a printing layer. In particular, the antistatic layer is excellent in that it stably imparts a high barrier ability. Details are shown below.

(Undercoat layer)
For example, in order to achieve adhesion between a substrate and a laminate composed of a barrier layer and an organic layer, after surface activation treatment, a method of directly applying a functional layer on a film to obtain adhesive force, and surface treatment Or a method of applying a functional layer thereon by providing an undercoat layer (adhesive layer) without surface treatment. Various arrangements have also been made for the constitution of the undercoat layer. A layer often adjacent to the support (hereinafter referred to as the undercoat first layer) is provided as the first layer, and a functional layer is often used as the second layer thereon. There is a so-called multi-layer method in which an undercoat second layer to be bonded is applied.

  In the single layer method, good adhesion is often achieved by expanding the substrate and interfacial mixing with the undercoat layer material. Examples of the undercoat polymer preferably used in the present invention include water-soluble polymers, cellulose acylates, latex polymers, and water-soluble polyesters. Examples of water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, and maleic anhydride copolymers. Cellulose acylates include carboxymethyl cellulose and hydroxyethyl cellulose. Etc. Examples of the latex polymer include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylate ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer.

  In the first subbing layer in the multi-layer method, for example, a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like is used. As oligomers or polymers of polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose and the like (for details, see EH Immergut "Polymer Handbook IV" 187-231, Interscience Pub. New York 1966, etc.) ).

The undercoat layer optionally applied to the substrate used in the present invention may contain inorganic or organic fine particles as a matting agent so as not to substantially impair the transparency of the functional layer. As the inorganic fine particle matting agent, silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, magnesium carbonate and the like can be preferably used. Examples of the organic fine-particle matting agent include polymethyl methacrylate, cellulose acetate propionate, polystyrene, a treatment solution-soluble one described in US Pat. No. 4,142,894, US Pat. Polymers described in US Pat. No. 4,396,706 can be used. These fine particle matting agents preferably have an average particle diameter of 0.01 to 10 μm, more preferably 0.05 to 5 μm. Moreover, the content is preferably 0.5 to 600 mg / m ² , more preferably 1 to 400 mg / m ² . The undercoating liquid is generally a well-known coating method such as dip coating, air-knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or U.S. Pat. 2, 681, 294 can be applied by an extrusion coating method using a hopper described in the specification.

(Antistatic layer)
Antistatic processing is a function to prevent the resin film from being charged when the resin film is handled. Specifically, a layer containing an ion conductive substance or conductive fine particles is provided. By doing. Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples include ionic polymer compounds.

  Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-B-49-23827, and JP-B-47-28937; JP-B-55-734, JP-A-50 Ionene type polymers having a dissociating group in the main chain as seen in JP-B-54672, JP-B-59-14735, JP-B-57-18175, JP-B-57-18176, JP-B-57-56059, etc .; JP-B 53-13223, JP-B 57-15376, JP-B 53-45231, JP-B 55-145783, JP-B 55-65950, JP-B 55-67746, JP-B 57-11342, Side chains as seen in JP-B-57-19735, JP-B-58-56858, JP-A-61-27853, JP-B-62-9346 And the like can be given; cationic pendant polymer having a cationic dissociative group.

  Of these, the conductive material is preferably in the form of fine particles, and these are finely dispersed and added to the resin. As a preferable conductive material used in these, a metal oxide or a composite thereof can be used. It is desirable to contain conductive fine particles made of oxides, ionene conductive polymers as described in JP-A-9-203810, quaternary ammonium cation conductive polymer particles having intermolecular crosslinking, and the like. The preferred particle size is in the range of 5 nm to 10 μm, and the more preferred range depends on the type of fine particles used.

Examples of metal oxides that are conductive fine particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _5, etc. Complex oxides are preferred, and ZnO, TiO ₂ and SnO ₂ are particularly preferred. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta, etc. to TiO ₂ , and addition of Sb, Nb, halogen elements, etc. to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

These metal oxide powders having electrical conductivity have a volume resistivity of 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less, a primary particle diameter of 100 to 0.2 μm, and a high-order structure. It is preferable that the conductive layer contains a powder having a specific structure having a major axis of 30 nm or more and 6 μm or less in a volume fraction of 0.01% or more and 20% or less.

The cross-linked cationic conductive polymer as a dispersible granular polymer is characterized by having a high concentration and high density of the cationic component in the particles, so that it has not only excellent conductivity but also low conductivity. Even when the relative humidity is low, the conductivity is not deteriorated and the particles are well dispersed in the dispersed state. It has excellent adhesion to other substances such as supports, and has excellent chemical resistance.
These cross-linked cationic conductive polymers used in the antistatic layer are generally in the particle size range of about 10 nm to 1000 nm, and preferably in the range of 0 nm to 300 nm. As used herein, a dispersible particulate polymer is a polymer that appears as a transparent or slightly turbid solution by visual observation, but appears as a particulate dispersion under an electron microscope. By using a coating composition that does not substantially contain dust (foreign matter) larger than the particle diameter corresponding to the film thickness of the upper layer in the lower layer coating composition, failure of foreign matter in the upper layer can be prevented.

  The ratio of the fine particles to the resin is preferably 0.5 to 4 parts by mass of the resin with respect to 1 part by mass of the fine particles, and particularly the adhesion after ultraviolet irradiation is 1 to 1 part by mass of the fine particles with respect to 1 part by mass of the resin. It is preferable that it is -2 mass parts. Furthermore, organic electronically conductive organic compounds can also be used. For example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphosphazene and the like. These are preferably used in a complex with polystyrene sulfonic acid, perchloric acid or the like as an acid donor.

  The resin used here is, for example, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, or cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate, or copolybutylene / terephthalate. / Polyesters such as isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene polymers containing norbornene compounds, polymethyl methacrylate, polyethyl methacrylate, polypropylyl methacrylate, Acrylics such as polybutyl methacrylate and polymethyl acrylate It can be used a copolymer of fat or acrylic resin and other resins but not particularly limited thereto. Among these, a cellulose derivative or an acrylic resin is preferable, and an acrylic resin is most preferably used.

  As the resin used for the resin layer such as the antistatic layer, the above-mentioned thermoplastic resin having a weight average molecular weight exceeding 400,000 and a glass transition point of 80 to 110 ° C. is in terms of optical characteristics and surface quality of the coating layer. preferable.

  The glass transition point can be determined by the method described in JIS K7121 (2000 version). The resin used here is preferably 60% by mass or more, more preferably 80% by mass or more of the entire resin used in the lower layer, and an actinic ray curable resin or thermosetting resin is added as necessary. You can also. These resins are coated as a binder in a state dissolved in the above-mentioned appropriate solvent.

In the coating composition for coating the antistatic layer, the following solvents are preferably used. As the solvent, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents can be used by appropriately mixing them, but are not particularly limited thereto.
Among these solvents, a solvent having a low boiling point is likely to condense moisture in the air by evaporation, and easily incorporates moisture into the coating composition in the liquid preparation step and the coating step. In particular, it is easily affected by an increase in external humidity during rainfall, and the influence becomes prominent in an environment where the humidity is 65% RH or higher. Especially when the dissolution time of the resin is long in the liquid preparation process, the time that the coating composition is exposed to air in the coating process is long, or the contact area between the coating composition and air is large. Becomes bigger.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert- Examples include butanol, pentanol, 2-methyl-2-butanol, and cyclohexanol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, Examples thereof include methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate. Examples of glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ester. As propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters, propylene glycol monomethyl Examples of ether acetate, propylene glycol monoethyl ether acetate, and other solvents include N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

  The method for applying the coating composition in the present technology is doctor coat, extrusion coat, slide coat, roll coat, gravure coat, wire bar coat, reverse coat, curtain coat, extrusion coat, or U.S. Pat. No. 2,681,294. It can apply | coat so that it may become a dry film thickness of 0.1-10 micrometers by the extrusion coating method etc. which use the hopper as described in above. Preferably, it is applied so as to obtain a dry film thickness of usually 0.1 to 1 μm.

(Sliding layer)
A sliding layer may be placed on the film of the present technology. The sliding layer can contain inorganic or organic fine particles as a matting agent to such an extent that the transparency of the functional layer is not substantially impaired. Silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, magnesium carbonate and the like can be used as the inorganic fine particle matting agent. Examples of the organic fine-particle matting agent include polymethyl methacrylate, cellulose acetate propionate, polystyrene, a treatment solution-soluble one described in US Pat. No. 4,142,894, US Pat. Polymers described in 396 and 706 can be used. These fine particle matting agents preferably have an average particle size of 0.01 to 10 μm. More preferably, it is 0.05-5 micrometers. Further, the content thereof is preferably 0.5~600mg / m ^2, is more preferably from 1 to 400 mg / m ^2.
The undercoating liquid may be a well-known coating method such as dip coating, air-knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or U.S. Pat. 2, 681, 294 can be applied by an extrusion coating method using a hopper described in the specification.

(White reflective layer)
In the image display device of the present invention, a white reflective layer containing titanium oxide or the like may be provided on the support. In addition, as described in the support, a white support having light reflectivity can be used. In this case, a plastic substrate to which an inorganic pigment such as titanium oxide or zinc oxide is added as a support can also be used.

(Primer layer, other inorganic thin film layer)
In the element of the present invention, a known primer layer or inorganic thin film layer may be provided.
As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin, or the like can be preferably used. In particular, an organic-inorganic hybrid layer, or an inorganic vapor deposition layer or a dense inorganic coating thin film by a sol-gel method is more preferable. . As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

<Optical writing display element>
DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of an optical writing display element according to the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic sectional view showing an optical writing display device according to the present invention. The optical writing display element according to the present embodiment shown in FIG. 1 includes a photochromic layer 5, a support 4, and a support 7. A barrier layer and an organic layer are laminated on the support 4 and the support 7, respectively, and a barrier layer 1, an organic layer 2 and a barrier layer 3 are laminated on the support 4, and the support 7 has a barrier layer. 8, the organic layer 9, and the barrier layer 10 are laminated | stacked.

  In the photochromic layer 5 according to this embodiment, there are three types of photochromic dyes that develop yellow (Y), magenta (M), and cyan (C), which are the three primary colors. In this embodiment, a configuration for bright full-color display is used. However, the optical writing display element according to the present invention may use a display body that develops an arbitrary color other than YMC.

  A white reflective layer 6 is laid between the one support 7 and the photochromic layer 5.

Further, although not shown, it is also preferable to provide an undercoat layer between the support 4 and the barrier layer 3 and between the support 7 and the barrier layer 8.
The antistatic layer is preferably provided on the barrier layer 1.
The sliding layer is preferably provided below the barrier layer 10.

  As a preferable display method of the present invention, a step of irradiating ultraviolet light from the upper side of FIG. 1 to completely develop the photochromic dye, and then a visible light from the upper side of FIG. An image can be formed by irradiating light with a two-dimensional distribution.

  Further, in writing with this three-wavelength writing light, the coloring density is controlled as an image forming means corresponding to the light intensity, or the coloring density is controlled corresponding to the time by irradiating with light of a certain intensity. Good.

  Any light source may be used for the writing light, and a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, an infrared semiconductor SHG laser, or a combination of a xenon lamp and an optical filter can be used as an ultraviolet light source. . As a light source for visible light, a combination of a white light source and an optical filter, an LED, an LD, or the like can be used.

  The display element of the present invention can be suitably used as a point card as a rewritable display medium, a material used only temporarily, and a medium for displaying an image.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]
<1. Fabrication of plastic substrate>
A PEN (Dupont-Teijin Q65A) was produced in the same manner as the production of the sample 101 of Example 1 of JP-A-2000-105445. However, no dye was added.
That is, 100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-die, and stretched 3.3 times at 140 ° C., followed by 130 The film was stretched by 3.3 times at 0 ° C., and further heat fixed at 250 ° C. for 6 seconds to obtain a plastic substrate (PEN) 101 having a thickness of 90 μm.

<2. Installation of functional layer>
(Coating undercoat layer)
After the corona discharge treatment, UV irradiation treatment, and glow discharge treatment were performed on both sides of the above support, gelatin 0.1 g / m ² and sodium α-sulfodi-2-ethylhexyl succinate 0.01 g / m ^{2 on one side} , Salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ ═CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensation An undercoat solution of 0.02 g / m ² was applied (10 mL / m ² , using a bar coater), and an undercoat layer 2 was provided.
Thereafter, drying was performed at 115 ° C. for 6 minutes. The rollers and the conveying device in the drying zone were all set to 115 ° C. The thickness of the obtained undercoat layer 102 was 0.5 μm.

(Coating of back layer (antistatic layer and sliding layer))
An antistatic layer having the following composition and a sliding layer were coated as a back layer on one surface of the above-coated support.

(Coating of antistatic layer)
A dispersion of fine particle powder (secondary agglomerated particle diameter of about 0.08 μm) of a tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm with a specific resistance of 5 Ω · cm is 0.2 g / m ² and gelatin is 0.05 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , polyoxyethylene-p-nonylphenol (degree of polymerization 10) 0.005 g / m ² and resorcin 0.22 g / m ^{2 was} applied to prepare an antistatic layer 103. The film thickness of the antistatic layer 103 was 1.0 μm.

(Preparation of sliding layer)
Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (9 mg / m ² ) The mixture was applied to produce the sliding layer 104. This mixture was prepared by melting at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1), pouring and dispersing in normal temperature propylene glycol monomethyl ether (10 times amount), and then dispersing in acetone. The product (average particle size 0.01 μm) was added. Silicon dioxide particles (0.3 μm) were added as a matting agent so as to be 15 mg / m ² . Drying was performed at 115 ° C. for 6 minutes. The rollers and the conveying device in the drying zone were all set to 115 ° C.
The sliding layer 4 had a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load of 100 g, speed of 6 cm / min) and static friction coefficient of 0.07 (clip method). The dynamic friction coefficient between the display surface and the sliding layer was also excellent at 0.12. The thickness of the sliding layer 104 was 1.0 μm.

  Further, a hard coat layer 105 was placed on the sliding layer 104 by the method described in JP-A-6-123806. The film thickness of the hard coat layer 105 was 1.0 μm.

<3. Installation of barrier layer (inorganic layer)>
Using the support provided with the functional layer prepared in 2 above, the treatment was performed in the following steps.
A roll-to-roll type sputtering apparatus was used. This apparatus has a vacuum chamber, and a drum for cooling the plastic film in contact with the surface is disposed at the center thereof. The vacuum tank is provided with a feed roll and a take-up roll for winding a plastic film. The plastic film wound on the feed roll is wound on the drum via the guide roll, and the plastic film is further wound on the roll via the guide roll. As a vacuum exhaust system, the vacuum chamber is always exhausted from the exhaust port by a vacuum pump. As a film forming system, a target is mounted on a cathode connected to a direct current type discharge power source to which pulse power can be applied. The discharge power source is connected to a controller, and the controller is further connected to a gas flow rate adjusting unit that supplies the vacuum tank with a reaction gas introduction amount adjusted through a pipe. The vacuum chamber is configured to be supplied with a constant flow rate of discharge gas.
Specific conditions are shown below.

Si was set as a target, and a pulse application type DC power source was prepared as a discharge power source. A support body provided with the functional layer having a thickness of 100 μm as a plastic film is prepared, and this is applied to the delivery roll so that the support layer is sputtered onto the functional layer on the surface side. It was hung and passed to the take-up roll.
After completing the preparation of the substrate to the sputtering apparatus, the vacuum chamber door was closed and the vacuum pump was started to start vacuuming and cooling the drum. When the ultimate pressure reached 4 × 10 ⁻⁴ Pa and the drum temperature reached 5 ° C., the support (plastic film) started to run. Argon was introduced as a discharge gas, the discharge power source was turned on, plasma was generated on the Si target at a discharge power of 5 kW and a film formation pressure of 0.3 Pa, and pre-sputtering was performed for 3 minutes. Thereafter, oxygen was introduced as a reaction gas. After the discharge was stabilized, the amounts of argon and oxygen gas were gradually reduced to lower the film forming pressure to 0.1 Pa. After confirming the stability of the discharge at 0.1 Pa, silicon oxide (SiO ₂ ) was deposited for a certain period of time to produce the barrier layer 106. After completion of the film formation, the vacuum chamber was returned to atmospheric pressure, and the support provided with the barrier layer and the functional layer was taken out. The obtained barrier layer 106 was 0.1 μm.

<4. Installation of organic layer>
Next, a radical initiator (Irgacure was added to a solution in which (1) tetraethylene glycol diacrylate, (2) caprolactone acrylate, and (3) tripropylene glycol monoacrylate were mixed at a weight ratio of 7: 1.2: 1.4. 651: manufactured by Ciba Geigy Co.) was dissolved in a solvent, applied to the surface provided with the 0.1 mm-thick barrier layer (inorganic layer), dried and then cured by UV irradiation to obtain a thickness of about A 1 μm organic layer was prepared. The obtained organic layer 107 was 1.0 μm.

(Lamination of barrier layer and organic layer)
The above steps 3 and 4 are repeated, and a laminated body in which the barrier layer 106, the organic layer 107, and the barrier layer 108 are laminated in this order on the surface of the support on which the functional layer is not provided is formed on the PEN film. did. The thickness of the laminate was 5 μm.

(White reflective layer)
A white pigment made of titanium oxide whose surface activity was eliminated by surface treatment was dispersed together with 5% by mass of carboxycellulose to prepare a white reflective layer coating solution. This coating solution was applied to the surface of the support on which the barrier layer was not provided to produce a white reflective layer 120.

<5. Preparation of photochromic layer>
Specific examples of the photochromic dye used in the present invention include compound No. (1-9) and (1-10) were synthesized according to the method described in the literature (Chem. Rev., 100, 1685, 2000). Photochromic dye no. (1-3) was purchased from Tokyo Kasei.
Photochromic dye no. (1-3), (1-9), (1-10) 0.2 g each and polyvinyl butyral 2 g were dissolved in 20 ml of a mixed solvent of cyclohexane / ethyl acetate = 50/50. The solution was applied on the PEN film with the barrier layer on the side where the barrier layer was not provided so as to have a dry film thickness of 14 μm, and the photochromic layer 109 was prepared.

<6. Production of photochromic element>
Separately, the PEN film including the undercoat layer 112, the antistatic layer 113, the sliding layer 114, the hard coat layer 115, the barrier layer 116, the organic layer 117, and the barrier layer 118 is sequentially performed from the support 111. Was made.
4. this PEN film; The PEN film having the photochromic layer and the laminate produced in step 1 was bonded so as to sandwich the photochromic layer, thereby producing the photochromic element of the present invention. A schematic cross-sectional view of the obtained photochromic element is shown in FIG.

(Image writing and erasing)
When this display device was irradiated with UV light (manufactured by Ushio, UV irradiator spot cure) at 25 ° C. for 1 minute, the entire surface was colored black. Next, when the color filter and white light (xenon lamp) were used for exposure, the decolorization reaction proceeded according to the wavelength of the irradiated light, and a full-color image having a desired pattern was formed.
Thereafter, the same operation was repeated and the coloring / decoloring cycle was repeated 1000 times. As a result, the color density during color development and the transparency during color erasing were hardly changed.

[Example 2]
In Example 1, the same operation as that in Example 1 was performed except that silicon oxide (SiO ₂ ) was used as the barrier layer in place of SiOx (x = 1.7). Was made.
With respect to the display element of Example 2, even when the coloring / decoloring cycle was repeated 1200 times, the color strength during color development and the transparency during color erasing were hardly changed.

[Example 3]
In Example 1, the same operation as in Example 1 was performed except that silicon oxide (SiO ₂ ) was used for the barrier layer and changed to SiOxNy (x = 0.6, y = 1.0). A display element of Example 2 was produced.
With respect to the display element of Example 2, even when the coloring / decoloring cycle was repeated 1200 times, the color strength during color development and the transparency during color erasing were hardly changed.

[Comparative Example 1]
In Example 1, instead of the film with the laminate of the barrier layer and the organic layer, the same operation as in Example 1 was performed except that the film without the laminate was used, and a comparative display element was obtained. Produced.

(Image writing and erasing)
With respect to this display device, when the color development / decoloration cycle was repeated 1000 times, it was visually confirmed that the color density during color development gradually decreased and the transparency during color erase gradually decreased.
That is, it was confirmed that the display element according to the present invention in which the barrier layer and the organic layer are laminated has higher stability when repeated than the display element.

[Comparative Example 2]
In Example 1, in place of the film with the laminate of the barrier layer and the organic layer, as described in Japanese Patent Application Laid-Open No. 2004-198689, except that a film in which a polyvinyl alcohol layer was coated with a thickness of 5 μm was used. The same operation as in No. 1 was performed to produce a comparative display element.

(Image writing and erasing)
With respect to this display device, when the color development / decoloration cycle was repeated 1000 times, it was visually confirmed that the color density during color development gradually decreased and the transparency during color erase gradually decreased.
That is, it was confirmed that the display element according to the present invention in which the barrier layer and the organic layer are laminated has higher stability when repeated than the display element.

It is a schematic cross section which shows an example of the optical writing display element of this invention. It is a schematic cross section which shows the optical writing display element of an Example.

Explanation of symbols

1, 3, 8, 10 Barrier layer 2, 9 Organic layer 4, 7 Support 5 Photochromic layer 6 White reflective layer 101, 111 Support 102, 112 Undercoat layer 103, 113 Antistatic layer 104, 114 Sliding layer 105, 115 Hard coat layer 106, 108, 116, 118 Barrier layer 107, 117 Organic layer 109 Photochromic layer 120 White reflective layer

Claims (8)

  An optical writing display device comprising a barrier layer, an organic layer, and a layer containing a photochromic dye on a support, wherein the barrier layer and the organic layer are alternately stacked.   A layered product of the barrier layer and the organic layer on the side opposite to the surface of the support on which the layer containing the photochromic dye is provided, comprising a layer containing a photochromic dye between the two supports. The optical writing display element according to claim 1, wherein:   The optical writing display element according to claim 1, wherein the barrier layer is an inorganic barrier layer.   The optical writing display element according to any one of claims 1 to 3, wherein the layer containing the photochromic dye includes a plurality of photochromic dyes that develop different colors.   The optical writing display element according to claim 4, wherein the layer containing the photochromic dye contains a photochromic dye that colors yellow, magenta, and cyan.   The optical writing display element according to claim 1, wherein the photochromic dye is a fulgide derivative or a diarylethene derivative.   The optical writing display element according to claim 1, wherein the support is a plastic substrate. Using the optical writing display element according to any one of claims 1 to 7,
An optical writing display method characterized in that a pattern is formed by irradiating light in a visible region after color is developed by irradiation with ultraviolet light.

Images