JPH07159922A - Image recording article - Google Patents

Abstract

PURPOSE:To increase the surface hardness and to improve cleaning characteristics by forming a polymer layer containing an org. photochromic compd. and a transparent protective layer comprising an inorg. oxide on a base body having specified or higher reflectance for visible rays. CONSTITUTION:A polymer layer containing an org. photochromic compd. and a transparent protective layer comprising an inorg. oxide are formed in this order on a base body having >=30% reflectance for visible rays. As for the photochromic layer, such a structure that the photochromic compd. is dispersed in a polymer or incorporated into the polymer by covalent bonding can be used. In this method, it is preferable that the transparent protective layer has 0.1-0.8mum thickness. Further, the contrast is preferably >=10% for 630 + or -50nm wavelength region which is used for detection of images. Further, it is preferable to form an org. coating layer having >=90 degree and >=25 degree static contact angles for water and hexadecane, respectively, on the image recording parts.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording component capable of recording a visible image directly by sensing an electromagnetic wave emitted through a subject.

[0002]

2. Description of the Related Art Conventionally, when a visible image is directly recorded by sensing an electromagnetic wave emitted through a subject, a silver salt film is wet-developed and then finally observed as a visible image. That is, a visible image could not be obtained immediately after photographing.

On the other hand, Japanese Patent Application Laid-Open No. 2-5403,
Japanese Unexamined Patent Publication No. 2-293745 discloses an image recording article having a photochromic coating on its surface. Instead of the conventional method of directly measuring the light amount distribution on the irradiated surface with a light receiving element and converting it into an electric signal. , By radiating electromagnetic waves,
A technique relating to image recording capable of directly observing an image is disclosed.

[0004]

As the photochromic layer, a compound having a photochromic property such as spiropyran dispersed in a resin such as polymethylmethacrylate is generally used, but these resins are very soft. , The photochromic layer surface was easily scratched due to careless handling. Further, even when dirt is attached to the surface, the surface is not easily wiped off because of scratches, and as a result, the contrast decreases as the number of times of use increases.

The present invention is intended to solve the problems of the prior art, and an object thereof is to provide an image recording article having high surface hardness and excellent wiping characteristics.

[0006]

[Means for Solving the Problems] The present invention has the following constitution in order to achieve the above object.

"A polymer layer containing an organic photochromic compound on a substrate having a visible light reflectance of 30% or more,
An image recording article having a transparent protective layer made of an inorganic oxide in this order. In the present invention, both organic and inorganic materials can be used as the base material, but when the visible light reflectance is 30% or more, the contrast between the colored portion and the non-colored portion is increased. It is effective.

Examples of the organic material include polyethylene, polypropylene, polystyrene, polyester, vinyl chloride, nylon, acrylic resin, polycarbonate, diethylene glycol bisallyl carbonate, polyimide, polyphenylene sulfide, epoxy and urethane. On the other hand, from the viewpoint of the flatness and heat stability of the substrate, an inorganic material is preferable, soda lime glass, quartz glass, aluminosilicate glass, high silicate glass, borosilicate glass and other glass substrates and silicon and other inorganic materials. A crystal plate or the like is preferably used. Above all, a silicon wafer is more preferable in that it has a high purity, does not contain ions of alkali metals, alkaline earth metals, and the like, and has a high reflectance necessary for improving contrast, and TTV (Total
(Thickness Variation), LTV
(Local Thickness Variatio
A high-precision processed silicon wafer, which has an excellent flatness of the base material indicated by n) and the like, is most preferable.

Further, even if a reflecting film containing a metal such as Al as a main component, an inorganic thin film, a hard coat or the like is provided on the surface of the base material, it can be preferably used.

In the present invention, a polymer layer containing an organic photochromic compound (hereinafter referred to as a photochromic layer) is provided on a substrate.

The photochromic compound is not particularly limited, and spiropyran compounds, spirooxazine compounds, diarylethene compounds, azo compounds, fulgide compounds, triarylmethane compounds, salicylideneaniline compounds, Examples thereof include dithizone mercury compounds. Among them, spiropyran compounds, which are excellent in contrast and record storability, are preferably used.

In the present invention, as the photochromic layer, those dispersed in a polymer, those containing a photochromic compound in a polymer by a covalent bond, or the like can be used.

When dispersed in a polymer, it is useful because the photochromic layer can be easily produced. Polymers that can be used to disperse the photochromic compound in this case include acrylic resins, styrene resins, vinyl resins, polyester resins, urethane resins, epoxy resins, polyamide resins, and cellulose derivatives. To be Among them, polymethyl methacrylate, which is excellent in transparency and versatility, is preferably used. The usable polymers are not limited to these. These polymers may be used alone or in combination of two or more.

The photochromic compound is usually preferably dispersed in the polymer in an amount of 0.1 to 25 wt%. 0.1
When the content is less than wt%, the contrast is low and 25w
If it exceeds t%, the photochromic compound is not well dispersed in the resin, which is not preferable. 5 to 20 wt%
Is more preferable in terms of the balance between the two.

In the present invention, the photochromic layer is preferably provided by coating. As the solvent of the photochromic compound used when applying, alcohol solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, Glycol ether solvents such as isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethyl acetate, butyl acetate,
Amyl acetate, ethyl lactate, ester solvents such as methyl benzoate, normal hexane, normal heptane, aliphatic hydrocarbon solvents such as normal octane, cyclohexane, alicyclic hydrocarbon solvents such as ethylcyclohexane,
Various solvents such as ketone-based solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbon-based solvents such as benzene, toluene and xylene, petroleum-based solvents can be used, and these may be used alone or in combination. You can

In the photochromic layer according to the present invention, the purpose is to improve light resistance and color density.
A light stabilizer, a sensitizer and the like may be added to the polymer solution used for coating the photochromic layer.

Further, the solid content concentration in the solution varies depending on the coating method to be applied, coating conditions, etc.
A range of t% is preferred.

Na, K, F contained in the photochromic solution used to form the photochromic layer.
The content of e and Ca is 1.
It is preferably 0 ppm or less. More preferably, the number of particles of 0.5 μm or more contained in the photochromic solution used for forming the photochromic layer, which is 0.1 ppm or less, is 100 particles / ml or less. If the number exceeds 100, uneven coating when forming the photochromic layer,
It is not preferable because it causes surface defects. 50 pieces / ml
The following is more preferable.

The photochromic solution can be applied by any of the commonly used methods such as dipping method, spraying method, roller coating method, flow coating method, offset printing method and screen printing method. The spin coating method is preferable from the viewpoint of obtaining it with high accuracy.

The thickness of the photochromic layer should be determined according to the type of photochromic compound used and the characteristics of the irradiation device, but it is usually preferably in the range of 0.2 to 10 μm. In particular, 0.5 to 5 μm from the viewpoint of contrast and machine operability.
Is preferred.

In the present invention, it is necessary to provide a transparent protective layer made of an inorganic oxide on the surface of the photochromic layer for the purpose of improving the surface hardness.

The inorganic oxide in the present invention is not particularly limited. Examples thereof include silicon monoxide, silicon dioxide, zirconium oxide, aluminum oxide, yttrium oxide, ytterbium oxide, cerium oxide, hafnium oxide, tin oxide, ITO (a mixture of tin oxide and indium oxide), and the like. Of these, silicon dioxide is preferable because of its excellent hardness.

In the present invention, the method for forming the transparent protective layer is not particularly limited, but a forming means in a vacuum atmosphere is preferably used from the viewpoint of improving the adhesive strength with the coated surface and the film density. As a specific example, a vacuum vapor deposition method, an ion beam assisted vapor deposition method, an ion plating method,
A sputtering method and the like can be mentioned.

The thickness of the transparent protective layer in the present invention is 0.1.
It is preferably 0.8 μm. If it is less than 0.1 μm, the surface hardness is low, and if it exceeds 0.8 μm, the exposure light is refracted in the transparent protective layer, and accurate image recording tends to be impossible.

In the present invention, image recording on the image recording article is carried out by irradiating with an electromagnetic wave having a wavelength capable of causing coloring of the photochromic layer. Generally, it is preferable to use an electromagnetic wave having a wavelength of 450 nm or less. Such electromagnetic waves include γ rays, X rays,
Ultraviolet light and visible light can be mentioned, but in terms of excellent balance of coloring and durability of the photochromic layer,
Ultraviolet and visible light are most preferred. More preferred are g-line, i-line, and excimer laser light. A photomask having a desired pattern may be used for the additional recording. The exposure dose should be determined according to the type of photochromic compound used, the film thickness, the characteristics of the irradiation device, etc., but is usually 50 to 100 mJ / cm ²
It is preferably in the range of. If the exposure amount is less than this range, the photochromic layer becomes less colored,
On the other hand, if the exposure amount is larger than this range, the adverse effect on the durability of the photochromic layer tends to be large.

Contrast is used for image detection 6
It is preferably 10% or more in the wavelength range of 30 ± 50 nm. If it is less than 10%, it may be difficult to detect an image.

In the present invention, the contrast means
It is defined as the difference in reflectance before and after coloring at an appropriate wavelength within the wavelength range of 630 ± 50 nm. The reflectance can be measured with a general visible spectrophotometer or the like.

Further, in the present invention, for the purpose of preventing dirt from adhering to the surface of the image-recording article and improving the wiping performance of dirt, the static contact angles of water and hexadecane on the image-recording article are 90 degrees or more, respectively. It is preferable to provide an organic coat layer having a temperature of 25 degrees or more.

The organic coating layer is represented by the following general formula (1)
Alternatively, a fluoroalkyl (meth) acrylic monomer represented by (2) and a double copolymer having a group represented by the following general formula (3) and copolymerizable with the fluoroalkyl (meth) acrylic monomer It is preferable to use a copolymer having a monomer having a bond as a polymerization component, or a coating composition having a siloxane unit represented by the following general formula (4) and having polysiloxane as a main component.

[0030]

[Chemical 5] (In the formula, R ¹ is selected from H, CH ₃ and F, and a is 2 to
An integer of up to 4, b is an integer of 3 to 14, c is 0 or 1, and d = 2-c. )

[Chemical 6] (R ² is selected from H, a methyl group and an ethyl group, e is an integer of 2 to 4, f is an integer of 2 or 3, g = 3-f
Is. )

[Chemical 7] (Where X is

[Chemical 8] And R ¹ is selected from H, CH ₃ and F, and a is 2
Is an integer from 4 to 4, b is an integer from 3 to 14, c is 0 or 1, and d = 2-c. R ² is a methyl group, an ethyl group,
It is selected from a fluoroalkyl group and X. The number (a) of methylene in the ester residue of the fluoroalkyl (meth) acrylic monomer represented by the general formula (1) needs to be 2 or more from the viewpoint of chemical stability of the ester. 5
For more than one, the reason is unknown, but when the coated surface is viewed from an angle, it becomes cloudy and unusable. The number (b) of perfluoromethylene needs to be 3 to 14. If the number is 2 or less, the water and oil repellency effects are not sufficient. 1
If the number is 5 or more, the solubility in a solvent is extremely lowered, a practical solvent cannot be obtained, and white turbidity occurs when the coating surface is viewed obliquely, so that it cannot be used. Preferably b is 10 or less. Specific examples include 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluoropentyl) ethyl (meth) acrylate, 2-
(Perfluoropentyl) propyl (meth) acrylate, 2- (perfluoropentyl) butyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth)
Crylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorooctyl) butyl (meth) acrylate, 2- (perfluorodecyl)
Ethyl (meth) acrylate, 2- (perfluoro-5)
-Methylhexyl) ethyl (meth) acrylate, 2-
(Perfluoro-7-methyloctyl) ethyl (meth)
Acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate and their α-fluoroacrylates, or 2- (perfluorobutyl) hydroxypropyl (meth) acrylate, 2-
(Perfluoropentyl) hydroxypropyl (meth)
Crylate, 2- (perfluorohexyl) hydroxypropyl (meth) acrylate, 2- (perfluorooctyl) hydroxypropyl (meth) acrylate, 2-
(Perfluorodecyl) hydroxypropyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) hydroxypropyl (meth) acrylate, 2-
(Perfluoro-7-methyloctyl) hydroxypropyl (meth) acrylate, 2- (perfluoro-9-
Methyldecyl) hydroxypropyl (meth) acrylate and their α-fluoroacrylates are mentioned. These can be used alone or in combination of two or more. The fluoroalkyl (meth) acrylic monomer component is preferably contained in the copolymer in an amount of 50 mol% or more in order to obtain a satisfactory antifouling property. It is more preferably 75 mol% or more.

To obtain the durability of the film, the general formula (2) is used.
A monomer having a group represented by and having a polymerizable unsaturated group is required. Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, γ-
(Meth) acryloylpropyltrimethoxysilane, γ
Silicon-containing monomers such as (meth) acryloylpropyldimethoxymethylsilane may be mentioned.

The silicon-containing monomer is preferably contained as a component of the copolymer in an amount of 1 mol% or more and 50 mol% or less. More preferably 5 mol% or more and 25 mol%
The range is as follows.

As another copolymerization component, alkyl (meth) is used.
It is also possible to add acrylates and styrene derivatives.

The fluoroalkyl (meth) acrylic monomer can be produced by a known polymerization method such as a solution polymerization method, a suspension polymerization method or an emulsion polymerization method under a radical initiator. Upon polymerization, the silicon-containing monomer is preferably an alkoxy compound. When the polymerization is allowed to proceed in the Si—OH state, the polymer is apt to gel during the polymerization, which is not preferable.

In the production of the polymer, mercaptans can be used as a chain transfer agent for controlling the molecular weight. A preferred mercaptan is a mercaptan having an alkoxysilane group, and specific examples thereof include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyldimethoxymethylsilane and γ-mercaptoethyltrimethoxysilane.

The number (m) of methylene in the ester residue of the fluoroalkylacyl group-containing polysiloxane represented by the general formula (4) is 2 in view of the chemical stability of the ester.
More than one is preferable. If the number is 5 or more, the reason is unknown, but when the coated surface is viewed obliquely, it becomes cloudy and unusable. The number (b) of perfluoromethylene needs to be 3 to 14. If the number is 2 or less, the water and oil repellency effects are not sufficient. If it is 15 or more, the solubility in the solvent is extremely lowered, and a practical solvent cannot be obtained, and
It cannot be used because the coated surface becomes cloudy when viewed obliquely. Preferably b is 10 or less.

The compound represented by the general formula (4) is perfluoro (meth) acrylate or perfluoro-α.
It can be synthesized by an addition reaction of fluoroacrylate and SiH group.

Specific examples of perfluoro (meth) acrylate or perfluoro-α-fluoroacrylate include the following. 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluoropentyl) ethyl (meth) acrylate, 2- (perfluoropentyl) propyl (meth) acrylate, 2-
(Perfluoropentyl) butyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth)
Acrylate, 2- (perfluorooctyl) butyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-5-
Methylhexyl) ethyl (meth) acrylate, 2-
(Perfluoro-7-methyloctyl) ethyl (meth)
Acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate, and their α-fluoroacrylates.

As the silane compound, dichloroalkylsilane, dialkoxyalkylsilane, dichlorosilane, dialkoxysilane or the like can be used. The monomer is synthesized by hydrosilation and subsequently polymerized into polysiloxane by a known method. The polysiloxane can be obtained by buffing. Alternatively, the acrylates may be added to the polyorganosiloxane containing SiH groups in the presence of a catalyst.

In addition to the compound of the general formula (4), Si (O
R) _n R ′ _3-n (where R and R ′ are a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, and n =
Siloxane units having a group of 1 to 3). Specific examples include silicon containing vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, γ- (meth) acryloylpropyltrimethoxysilane, γ- (meth) acryloylpropyldimethoxymethylsilane, and the like. It can be obtained by copolymerizing the compound obtained by the addition reaction of the monomer and the hydrosilane compound with the above-mentioned perfluoro group-containing silane compound. The silicon-containing monomer is preferably copolymerized at 0.5 mol% or more and 10 mol% or less.

If necessary, a silanol dehydration condensation catalyst or a condensation aid can be used. Examples thereof include aluminum acetylacetonate, tin octylate compound, and organic carboxylic acid alkali salts.

The organic coating layer may be applied by any of the commonly used methods such as dipping, spraying, roller coating, flow coating, offset printing and screen printing. The spin coating method is preferable from the viewpoint of obtaining a coating film with high accuracy.

The thickness of the organic coating layer in the present invention is 10
It is preferably 0 nm or less. When it exceeds 100 nm, there is a problem in the strength of the film, which is not preferable. 5
It is more preferably 0 nm or less, and most preferably 10 nm or less.

The image-recording article of the present invention has a high surface hardness and is preferably used as an image-recording article excellent in wiping characteristics.

[0045]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

The evaluation method in the examples is as follows.

The contrast was measured with a spectrophotometer U-3410 manufactured by Hitachi, Ltd. at a detection wavelength of 633 nm. Coloring i-line (365nm) exposure amount 70mJ
The exposure was carried out at a dose of 1 / cm ² . The contrast was defined as the difference between the reflectance before coloring and the reflectance after coloring.

The surface hardness of the image-recorded article was 5 with a load of 1.5 kg by using Hize Gauze 4 manufactured by Asahi Kasei.
Rubbing back and forth and scratch resistance were evaluated on a scale of 5 from highest A to lowest E.

The antifouling property was evaluated by measuring the static contact angle of water and hexadecane with a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd.

Example 1 (1) Preparation of photochromic solution Polymethyl methacrylate (15.0 g) in a mixed solvent of ethyl lactate (45.0 g) and methyl benzoate (37.0 g).
Was added and stirred at 80 ° C. until dissolved. After cooling the solution to room temperature, 3.0 g of 1,3,3-trimethylindolino-6-nitrobenzopyrrolospirane was added and stirred at room temperature until dissolved. The solution was filtered through a 0.2 μm polytetrafluoroethylene filter manufactured by Advantech Toyo Co., Ltd. to prepare a photochromic solution.

(2) Formation of photochromic layer A photochromic solution was coated on a silicon wafer using a spin coater SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. at a rotation speed of 4000 rpm, and then prebaked at 100 ° C. for 3 minutes. Then, a photochromic layer was formed.

(3) Formation of transparent protective layer Silicon dioxide was vacuum-deposited on the surface of the photochromic layer under the following conditions. Deposition conditions Substrate temperature: 50 ° C. Ultimate vacuum: 1.0 × 10 ⁻⁵ Torr Center wavelength: 550 nm Set film thickness: λ / 2 (4) Evaluation Table 1 shows the evaluation results. No reduction in contrast was observed due to the formation of the transparent protective layer. Moreover, the surface hardness was high, and no scratches were formed by wiping dirt.

Example 2 (1) Preparation of Photochromic Solution A photochromic solution was prepared in the same manner as in Example 1.

(2) Preparation of organic coating solution 11.5 g (52 mol%) of dichloromethylsilane, 50 g of diethyl ether as a solvent and 50 mg of chloroplatinic acid as a catalyst were placed in a 300 ml flask equipped with a condenser, and the diethyl ether was refluxed. While gently heating and stirring, 50 g (48 mol%) of 2- (perfluorooctyl) ethyl methacrylate was added dropwise over 1 hour. Then, the mixture was heated and stirred gently for 4 hours to complete the reaction.

Then, 50 g of methyl isobutyl ketone
After the addition, a large amount of water was added instantly. A white dough-like polymer formed at the water / methyl isobutyl ketone interface. After separating the oil layer, it was heated and concentrated by a rotary evaporator to obtain an oily concentrate. The concentrate and the dough-like polymer obtained above were combined, dissolved in trichlorotrifluoroethane, added to a large amount of methanol, and the obtained polymer was recovered. A flake-like solid was obtained by vacuum drying. The yield was 63%.

The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to a solid concentration of 0.4% by weight, and 1/100 parts by weight of trichloromethylsilane was added to prepare an organic coating solution.

(3) Formation of Photochromic Layer A photochromic layer was formed in the same manner as in Example 1.

(4) Formation of transparent protective layer In the same manner as in Example 1, a transparent protective layer was formed on the surface of the photochromic layer. (5) Formation of Organic Coat Layer An organic coating solution was applied to the upper layer of the transparent protective layer using a spin coater SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd., and was coated on the photochromic layer under the condition of a rotation speed of 4000 rpm. After drying at room temperature for 30 minutes, 70 ℃
Curing was performed in the oven for 1 hour to form an organic coating layer.

(6) Evaluation The evaluation results are shown in Table 1. No reduction in contrast was observed due to the formation of the transparent protective layer and the organic coating layer. Moreover, the surface hardness was high, and no scratch was formed by wiping. Further, the static contact angle of water and hexadecane was high, and the surface was excellent in antifouling property and easy in wiping off stains.

Example 3 (1) Preparation of Photochromic Solution A photochromic solution was prepared in the same manner as in Example 1.

(2) Preparation of organic coating solution 50.0 g (90 mol%) of 2- (perfluorooctyl) ethyl methacrylate, 2.59 g (10 mol%) of γ-methacryloxypropyltrimethoxysilane, γ-
0.41 g of mercaptopropyltrimethoxysilane, 0.17 g of azobisisobutyronitrile, 42.0 g of methyl isobutyl ketone, and 10.5 g of hexafluoroisopropanol were placed in a glass ampoule, and freeze degassing operation was performed according to a standard method of radical polymerization. Repeatedly to remove dissolved oxygen. Then, the ampoule was sealed and polymerized at 75 ° C. for 20 hours. A transparent viscous liquid was obtained. The reaction solution was poured into a large amount of methanol, the precipitate was collected by filtration, washed with methanol and normal hexane, and vacuum dried at 40 ° C. for 24 hours to obtain a copolymer. The degree of polymerization determined from the weight after drying was 96%.

The obtained polymer was dissolved in perfluoro-2-butyltetrahydrofuran so that the weight ratio was 5%, and a trace amount of 1 / 10N hydrochloric acid aqueous solution was added, and the mixture was stirred until the droplets completely disappeared. did. After filtering with a filter, it was diluted with perfluoro-2-butyltetrahydrofuran to 0.2% by weight to obtain an organic coating solution.

(3) Formation of Photochromic Layer A photochromic solution was coated in the same manner as in Example 1.

(4) Formation of transparent protective layer In the same manner as in Example 1, a transparent protective layer was formed.

(5) Formation of organic coat layer An organic coat layer was formed in the same manner as in Example 2 except that the organic coat solution of (2) was used.

(6) Evaluation The evaluation results are shown in Table 1. No reduction in contrast was observed due to the formation of the transparent protective layer and the organic coating layer. Moreover, the surface hardness was high, and no scratch was formed by wiping. Further, the static contact angle of water and hexadecane was high, and the surface was excellent in antifouling property and easy in wiping off stains.

Comparative Example 1 (1) Preparation of Photochromic Solution A photochromic solution was prepared in the same manner as in Example 1.

(2) Formation of Photochromic Layer A photochromic solution was coated in the same manner as in Example 1.

(3) Evaluation The evaluation results are shown in Table 1. The surface hardness was low and it was scratched by wiping.

Comparative Example 2 (1) Preparation of Photochromic Solution A photochromic solution was prepared in the same manner as in Example 1.

(2) Formation of Photochromic Layer A photochromic layer was formed in the same manner as in Example 1.

(3) Formation of transparent protective layer A transparent protective layer was formed on the surface of the photochromic layer in the same manner as in Example 1 except that the set film thickness was 2λ.

(4) Evaluation The evaluation results are shown in Table 1. A decrease in contrast was observed due to the formation of the transparent protective layer and the organic coating layer. Further, the surface hardness was high and no scratch was formed by wiping, but the exposure light was refracted in the transparent protective layer, and the image could not be recorded accurately.

Comparative Example 3 (1) Preparation of Photochromic Solution A photochromic solution was prepared in the same manner as in Example 1.

(2) Preparation of organic coating solution An organic coating solution was prepared in the same manner as in Example 3 except that the solid content of the organic coating solution was 5% by weight.

(3) Formation of Photochromic Layer A photochromic layer was formed in the same manner as in Example 1.

(4) Formation of transparent protective layer In the same manner as in Example 1, a transparent protective layer was formed on the surface of the photochromic layer. (5) Formation of Organic Coat Layer An organic coat layer was formed in the same manner as in Example 2 except that the organic coat solution in (2) was used.

(6) Evaluation The evaluation results are shown in Table 1. A decrease in contrast was observed due to the formation of the transparent protective layer and the organic coating layer. The surface hardness of the transparent protective layer was high and the photochromic layer was not scratched by wiping, but the organic coating layer was peeled off by wiping. Further, the exposure light was refracted in the transparent protective layer and the organic coating layer, and the image could not be recorded accurately.

[0079]

[Table 1]

[0080]

EFFECT OF THE INVENTION The image-recorded article of the present invention has a sufficiently high contrast in the exposed portion, so that it can be visually recognized and the pattern of the exposed portion can be automatically measured by measuring the reflectance at a wavelength different from the exposure light. it can. Also, since the surface hardness is high, it exhibits excellent wiping characteristics that it can be wiped off without being scratched when the surface is soiled. Furthermore, when an organic coat is provided on the transparent protective layer, it exhibits excellent antifouling property that dirt itself does not easily adhere.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G11B 7/24 516 7215-5D

Claims (10)

[Claims] 1. A substrate having a visible light reflectance of 30% or more,
An image recording article having a polymer layer containing an organic photochromic compound and a transparent protective layer made of an inorganic oxide in this order. 2. The image recording article according to claim 1, wherein the film thickness of the transparent protective layer is 0.1 μm or more and 0.8 μm or less. 3. The method according to claim 1, wherein when i-line (365 nm) is exposed at an exposure dose of 50 to 100 mJ / cm ² , 630 ±
An image recording article having a contrast of 10% or more in a wavelength range of 50 nm. 4. The image recording article according to claim 1, wherein the base material is a substantially circular silicon wafer. 5. The image recording article according to claim 1, wherein the organic photochromic compound is a spiropyran compound. 6. The Na, K, Fe contained in the photochromic solution used for forming the polymer layer containing the organic photochromic compound according to claim 1.
An image recording article having a Ca content of 1.0 ppm or less. 7. The method according to claim 1, wherein the photochromic solution used for forming the polymer layer containing the organic photochromic compound has 100 or less particles of 0.5 μm or more contained in the photochromic solution. Characterized image recording articles. 8. The organic coating layer according to claim 1, wherein the transparent protective layer is provided with an organic coating layer having a static contact angle with water and hexadecane of 90 ° or more and 25 ° or more and a film thickness of 100 nm or less. Image recording article. 9. The organic coating layer according to claim 8, wherein the fluoroalkyl (meth) acrylic monomer represented by the following general formula (1) or (2) and the group represented by the following general formula (3) are used. An image recording article comprising the fluoroalkyl (meth) acrylic monomer and a monomer having a copolymerizable double bond as a polymerization component. [Chemical 1] (In the formula, R ¹ is selected from H, CH ₃ and F, and a is 2 to
An integer of up to 4, b is an integer of 3 to 14, c is 0 or 1, and d = 2-c. ) [Chemical 2] (R ² is selected from H, a methyl group and an ethyl group, e is an integer of 2 to 4, f is an integer of 2 or 3, g = 3-f
Is. ) 10. The image-recording article according to claim 6, wherein the organic coating layer contains polysiloxane having a siloxane unit represented by the following general formula (4) as a main component. [Chemical 3] (Where X is And R ¹ is selected from H, CH ₃ and F, and a is 2
Is an integer from 4 to 4, b is an integer from 3 to 14, c is 0 or 1, and d = 2-c. R ² is a methyl group, an ethyl group,
It is selected from a fluoroalkyl group and X. )