JPH07159923A - 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 a three-dimensional crosslinked polymer 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 three-dimensional crosslinked polymer 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 may be used. Further, it is preferable that the three-dimensional crosslinked polymer has hard coating property. As for the three-dimensional crosslinked polymer having hard coating property, such materials as melamine resin, epoxy resin, diethyleneglycol bisallylcarbonate resin, divinylbenzene resin and organopolysiloxane hardened material are used.

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 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 composed of a three-dimensional crosslinked polymer in this order. In the present invention, the base material is not particularly limited, and both organic and inorganic materials can be used. Among them, the visible light reflectance is 30 in that the contrast between the colored portion and the non-colored portion becomes large. % Or more of the base material is suitable.

As the organic material, olefin resin such as polyethylene resin and polypropylene resin; styrene resin; polyester resin; vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol resin and other vinyl resin; nylon resin Examples of the resin include polyamide resins such as resins; acrylic resins; polycarbonate resins; diethylene glycol bisallyl carbonate resins; polyimide resins; polyphenylene sulfide resins; epoxy resins; urethane resins. 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 high purity, does not contain ions of alkali metal, alkaline earth metal, and the like, and has a high reflectance necessary for improving contrast, and TTV (Total Thickness V)
), LTV (Local Thick)
A highly-accurate processed silicon wafer, which has excellent flatness of the base material indicated by “Nest Variation” and the like, is most preferable.

Further, even if a reflection film containing a metal such as Al as a main component or an inorganic thin film is provided on the surface of the substrate, 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, chromene compounds, diarylethene compounds, azo compounds, fulgide compounds, triarylmethane compounds, salicylidene compounds. Examples thereof include aniline compounds and 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, cellulose derivatives, and melamine resins. Examples thereof include resins, polycarbonate-based resins, polyolefin-based resins and the like. 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 a 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 tends not to be well dispersed in the resin. The range of 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.
In the polymer solution used for coating the photochromic layer,
Singlet oxygen quenchers represented by nickel salts, nitroxy radical compounds, antioxidants represented by hindered amine compounds or polymers thereof, light stabilizers such as ultraviolet absorbers and triplet quenchers, and sensitizers It may be added. Further, the solid content concentration in the solution varies depending on the applied coating method, coating conditions, etc.
The range of -45 wt% is preferable.

Na, K, F contained in the photochromic solution used to form the photochromic layer.
The content of e and Ca is preferably 1.0 ppm or less in order to prevent contamination of the clean room. More preferably, it is 0.1 ppm or less. The number of particles of 0.5 μm or more contained in the photochromic solution used for forming the photochromic layer is preferably 100 particles / ml or less. 10
When the number is 0 or more, it tends to cause coating unevenness and surface defects when forming the photochromic layer, and more preferably 50 or less.

The photochromic solution can be applied by any of the commonly used methods such as dipping, spraying, spin coating, bar coating, roller coating, flow coating, offset printing and screen printing. However, the spin coating method is most preferable from the viewpoint of accurately obtaining a thin coating film.

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 a three-dimensional crosslinked polymer on the surface of the photochromic layer for the purpose of improving the surface hardness.

The three-dimensional crosslinked polymer in the present invention preferably has a hard coat property, and as the three-dimensional crosslinked polymer having a hard coat property, a melamine resin, an epoxy resin, a diethylene glycol bisallyl carbonate resin. , Divinylbenzene-based resins and organopolysiloxane-based cured products,
In terms of hardness and easiness of formation, an organopolysiloxane-based cured product is preferable, and a cured product of a composition containing at least an organosilicon compound represented by the following general formula (A) and / or a hydrolyzate thereof is particularly preferable. R ¹ _a R ² _b SiX _4-ab (A) (In the formula, R ¹ and R ² are each an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a halo group, a glycidoxy group, an epoxy group, an amino group, and a mercapto. Group, a substituent selected from a (meth) acryloyloxy group and a cyano group, X represents a hydrolyzable group, and a and b each represent 0 or 1.) Organic compound represented by the general formula (A) Among the silicon compounds, R ¹ and R ^{2 each} have an alkyl group, an alkenyl group, a phenyl group, an epoxy group or a glycidoxy group having 1 to 4 carbon atoms from the viewpoints of adhesion, surface hardness improvement, heat resistance, weather resistance and the like. Organic groups are preferred.

Specific examples of the organosilicon compound represented by the general formula (A) and / or its hydrolyzate include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate and se.
Tetraalkoxysilanes such as c-butyl silicate and tert-butyl silicate and / or hydrolysates thereof; methyltrimethoxysilane, methyltriethoxysilane, methyldimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltriethylsilane Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyldimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane , Γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methac Liloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl)
-Γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α -Glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α -Glycidoxypropyltriethoxysilane,
β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-
Glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ- Glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ
-(3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl)
Trialkoxysilanes such as butyltriethoxysilane, triacyloxysilanes and triphenoxysilanes and / or their hydrolysates; dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ -Chloropropylmethyldimethoxysilane, γ
-Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methyl Vinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β- Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropyl Cyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glyce Sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane , Γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxy B pills phenyl dimethoxy silane, .gamma. dialkoxysilane such as glycidoxypropyl phenyl diethoxy silane, and di phenoxy silanes and diacyl oxy silanes and / or hydrolysates thereof.

These organosilicon compounds may be used alone or in combination.
It is also possible to use more than one species. The organosilicon compound is preferably hydrolyzed before use because it can be cured at a low temperature and the curing time is short. The hydrolysis can be carried out by an ordinary hydrolysis method, for example, by adding an acidic aqueous solution of pure water, hydrochloric acid, sulfuric acid, acetic acid or the like, or an alkaline aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide or the like. . Of these, pure water and acetic acid aqueous solution are particularly preferable in that there is little concern about contamination of the clean room. The temperature at the time of hydrolysis is not particularly limited and should be controlled to the required temperature according to the purpose.

The method for forming the transparent protective layer comprising the three-dimensional cross-linked polymer in the present invention is a dipping method, a spraying method, a spin coating method, a bar coating method, a roller coating method or a flow coating which is usually carried out with a coating liquid. Method, offset printing method,
It is possible to apply by a method such as a screen printing method and subsequently cure by electron beam irradiation, electromagnetic wave irradiation or heating. As the coating method, the spin coating method is most preferable from the viewpoint of obtaining a thin coating film with high accuracy. As electromagnetic waves used for curing, γ rays, X rays, ultraviolet rays, infrared rays and microwaves can be applied, but ultraviolet rays, infrared rays and microwaves are preferable and ultraviolet rays are most preferable in terms of safety and curing time. When curing is performed by heating, it is preferable to add various curing catalysts for the purpose of low temperature curing and shortening of curing time. Examples of the curing catalyst include various amines, various ammonium salts, alkali metal salts of carboxylic acids, and chelate compounds such as Al, Ti and Zr. Of these, various ammonium salts, particularly tetraalkylammonium hydroxide, are preferable because they are less likely to cause contamination of the clean room.

The thickness of the transparent protective layer formed of the three-dimensional crosslinked polymer in the present invention is preferably 0.1 to 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, when a transparent protective layer made of a three-dimensional crosslinked polymer having a hard coat property is formed, an organic photochromic compound is previously added for the purpose of improving the adhesion to the polymer layer containing the organic photochromic compound. It is also possible to pretreat the surface of the contained polymer layer.
As a pretreatment method, activated gas treatment, especially low temperature plasma treatment, is preferable from the viewpoint of preventing the decomposition of the photochromic compound and developing the improvement of adhesion. The type of gas used for the activation gas treatment should be appropriately selected depending on the type of the polymer layer containing the organic photochromic compound, but oxygen gas is generally preferable.

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. Examples of such electromagnetic waves include gamma rays, X-rays, ultraviolet rays, and visible light, but ultraviolet rays and visible light are most preferable because they have an excellent balance of photochromic layer coloring and durability. More preferably, g
A photomask having a desired pattern may be used for image recording which is line, i-line and escimer laser light.

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 preferably in the range of 50 to 100 mJ / cm ² . When the exposure amount is less than this range, the coloration of the photochromic layer is small, and when the exposure amount is more 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 tends to be difficult to detect an image.

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

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 has 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.

[0033]

[Chemical 6] (In the formula, R ³ is selected from hydrogen, a methyl group and a fluoro group, α is an integer of 2 to 4, β is an integer of 3 to 14,
γ is 0 or 1, and δ = 2-γ. )

[Chemical 7] (R ⁴ and R ⁵ are each selected from hydrogen, a methyl group and an ethyl group, ε is an integer of 2 to 4, ζ is an integer of 2 or 3, and η = 3-ζ.)

[Chemical 8] (Where Y is the following general formula (5)

[Chemical 9] Or the following general formula (6)

[Chemical 10] Wherein R ³ is selected from hydrogen, a methyl group and a fluoro group, α is an integer from 2 to 4, and β is 3
Is an integer from 1 to 14, γ is 0 or 1, and δ = 2-γ. R ⁶ is selected from a methyl group, an ethyl group, a fluoroalkyl group and Y. ) The number (α) of methylene in the ester residue of the fluoroalkyl (meth) acrylic monomer represented by the general formula (1) is preferably 2 or more from the viewpoint of chemical stability of the ester. If the number is 5 or more, the reason is unknown, but when the coated surface is viewed obliquely, it may become cloudy and unusable in some cases. The number (β) of perfluoromethylene is preferably 3 to 14. Two
If the number is less than this, the water and oil repellency effects are not sufficient. If the number is 15 or more, the solubility in a solvent is extremely lowered, a practical solvent cannot be obtained, and white turbidity may occur when the coated surface is viewed obliquely. Preferably β 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) 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 Those α-fluoroacrylates, or 2- (perfluorobutyl) hydroxypropyl (meth) acrylate, 2- (perfluoropentyl) hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) hydroxypropyl (meth). Axle , 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 constituent of the copolymer in an amount of 1 mol% to 50 mol%. More preferably 5 mol% or more and 25 mol%
The range is as follows.

As another copolymerization component, alkyl (meth) is used.
Acrylates and styrene derivatives can also be added.

The fluoroalkyl (meth) acrylic monomer can be produced by a known polymerization method such as a solution polymerization method, a suspension polymerization method and 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 of methylenes (α) 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 may become cloudy and unusable in some cases. The number (β) of perfluoromethylene is preferably 3 to 14. With 2 or less,
Water and oil repellency are not sufficient. If the number is 15 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 β 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 then 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, spin coating, bar coating, roller coating, flow coating, offset printing and screen printing. However, the spin coating method is most preferable from the viewpoint of obtaining a thin 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 is 100 nm or more, there is a problem in film strength, which is not preferable. Fifty
It is more preferably not more than 10 nm, most preferably not more than 10 nm.

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.

[0048]

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 was 5 at a load of 1.5 kg on the surface of the image-recorded article using Hize Gauze 4 manufactured by Asahi Chemical Industry Co., Ltd.
Rubbing back and forth and scratch resistance were evaluated on a scale of 5 from highest A to lowest E.

The contact angle was measured for water and hexadecane with a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd., and evaluated as antifouling property.

Example 1 (1) Preparation of photochromic solution Ethyl lactate (45.0 g) and methyl benzoate (3
Polymethyl methacrylate (15.0 g) was added to a mixed solvent consisting of 7.0 g), and the mixture was stirred at 80 ° C. until dissolved. After cooling the solution to room temperature, 1,3,3-trimethylindolino-6-nitrobenzopyrrilospirane (3.0
g) 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) Preparation of coating liquid for transparent protective layer Methyltrimethoxysilane (167 g) and vinyltriethoxysilane (116) were placed in a reactor equipped with a rotor.
g), acetic acid (6.7 g) and ethanol (11.4
g) and 0.01N hydrochloric acid (99.1 g) at a liquid temperature of 10 with stirring using a magnetic stirrer.
The solution was added dropwise while maintaining the temperature at 0 ° C., and after completion of the addition, stirring was continued for 1 hour for hydrolysis. Xylene (200 g), butyl acetate (200 g) and butanol (1070 g) were added to the obtained hydrolyzed solution, and the mixture was sufficiently stirred to give a transparent protective layer coating liquid.

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

(4) Formation of transparent protective layer The coating liquid obtained in (2) above was applied to the upper layer of the photochromic layer by Spin Coater SK manufactured by Dainippon Screen Mfg. Co., Ltd.
Rotation speed of 400 on a silicon wafer using W-636
After coating under the condition of 0 rpm, it was dried at 90 ° C. for 1 hour. (5) Evaluation The evaluation results are shown in Table 1. 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- (1).

(2) Preparation of coating liquid for transparent protective layer In a reactor equipped with a rotor, γ-glycidoxypropyltrimethoxysilane (24 g), γ-glycidoxypropylmethyldiethoxysilane (24 g) and Vinyltriethoxysilane (147 g) was charged, and 0.1 N acetic acid (51 g) was added with stirring using a magnetic stirrer.
g) was added dropwise while maintaining the liquid temperature at 10 ° C., and after completion of the addition, stirring was continued for 30 minutes for hydrolysis. Aluminum acetylacetonate (5.6 g) and ethanol / water (80/20 weight ratio) in the obtained hydrolysis solution.
(71.0 g), butanol (830 g) and silicone surfactant (0.6 g) were added and sufficiently stirred to obtain a coating liquid for transparent protective layer.

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

Then, methyl isobutyl ketone (50
After adding g), a large amount of water was added instantaneously. 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.

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

(5) Formation of transparent protective layer A transparent protective layer was formed on the photochromic layer in the same manner as in Example 1- (4) except that the transparent protective layer coating liquid of (2) was used. did.

(6) Formation of Organic Coat Layer On the upper layer of the transparent protective layer, the spin coater S manufactured by Dainippon Screen Mfg. Co., Ltd. was applied with the organic coating solution prepared in (3) above.
After coating on the photochromic layer using KW-636 at a rotation speed of 4000 rpm, the temperature is 3 at room temperature.
After drying for 0 minutes, curing was performed in an oven at 70 ° C. for 1 hour to form an organic coat layer.

(7) 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- (1).

(2) Preparation of coating liquid for transparent protective layer A coating liquid for transparent protective layer was prepared in the same manner as in Example 1- (2).

(3) Preparation of organic coating solution 2- (perfluorooctyl) ethylmethacrylate (50.0 g, 90 mol%), γ-methacryloxypropyltrimethoxysilane (2.59 g, 10 mol%),
γ-mercaptopropyltrimethoxysilane (0.41
g), azobisisobutyronitrile (0.17 g), methyl isobutyl ketone (42.0 g) and hexafluoroisopropanol (10.5 g) were placed in a glass ampoule and freeze-deaerated according to a standard method of radical polymerization. Repeatedly to remove dissolved oxygen. The ampoule is then sealed, 7
Polymerization was carried out at 5 ° 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 at a weight ratio of 5%, and a small amount of 0.1N hydrochloric acid 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.

(4) Formation of photochromic layer A photochromic solution was coated in the same manner as in Example 1- (3). (5) Formation of transparent protective layer A transparent protective layer was formed in the same manner as in Example 2- (5).

(6) Formation of Organic Coat Layer An organic coat layer was formed in the same manner as in Example 2- (6) except that the organic coat solution in (3) above was used.

(7) 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- (1).

(2) Formation of photochromic layer A photochromic solution was coated in the same manner as in Example 1- (3). (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- (1).

(2) Preparation of Transparent Protective Layer Coating Liquid A transparent protective layer coating liquid was prepared in the same manner as in Example 1- (2).

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

(4) Formation of transparent protective layer A transparent protective layer was formed in the same manner as in Example 1- (4) except that the rotation speed was adjusted so that the film thickness was about 1 μm.

(5) 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- (1).

(2) Preparation of Transparent Protective Layer Coating Liquid A transparent protective layer coating liquid was prepared in the same manner as in Example 2- (2).

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

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

(5) 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 2- (5).

(6) 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 (3) above was used.

(7) 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.

[0087]

[Table 1]

[0088]

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

Claims (12)

[Claims] 1. A substrate having a visible light reflectance of 30% or more,
An image recording article comprising a polymer layer containing an organic photochromic compound and a transparent protective layer composed of a three-dimensional crosslinked polymer in this order. 2. The transparent protective layer according to claim 1, wherein
An image recording article having a film thickness of 1 to 0.8 μm. 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 ,
10% contrast in the wavelength range of 30 ± 50 nm
An image recording article having the above. 4. An image recording article according to claim 1, wherein the three-dimensional crosslinked polymer is an organopolysiloxane cured product. 5. The cured product of organopolysiloxane according to claim 4, which is a cured product of a composition containing at least an organosilicon compound represented by the following general formula (A) and / or a hydrolyzate thereof. Image recording articles. R ¹ _a R ² _b SiX _4-ab (A) (In the formula, R ¹ and R ² are each an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a halo group, a glycidoxy group, an epoxy group, an amino group, and a mercapto. Group, (meta)
It represents a substituent selected from an acryloyloxy group and a cyano group, X represents a hydrolyzable group, and a and b each represent 0 or 1. ) 6. The image recording article according to claim 1, wherein the base material is a silicon wafer having a substantially circular shape. 7. The image recording article according to claim 1, wherein the organic photochromic compound is a spiropyran compound. 8. The Na, K, F contained in the photochromic solution used for forming the polymer layer containing the organic photochromic compound according to claim 1.
An image recording article, characterized in that the contents of e and Ca are each 1.0 ppm or less. 9. The particles of 0.5 μm or more contained in the photochromic solution used for forming the polymer layer containing the organic photochromic compound are 100 particles / ml or less in claim 1. An image recording article characterized by the above. 10. 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 thickness of 100 nm or less. Image recording articles. 11. The fluoroalkyl (meth) acrylic monomer represented by the following general formula (1) or (2) and the group represented by the following general formula (3) according to claim 10. An image-recording article comprising a fluoroalkyl (meth) acrylic monomer having the following formula and a monomer having a double bond capable of copolymerization as a polymerization component. [Chemical 1] (In the formula, R ³ is selected from hydrogen, a methyl group and a fluoro group, α is an integer of 2 to 4, β is an integer of 3 to 14,
γ is 0 or 1, and δ = 2-γ. ) [Chemical 2] (R ⁴ and R ⁵ are each selected from hydrogen, a methyl group and an ethyl group, ε is an integer of 2 to 4, ζ is an integer of 2 or 3, and η = 3-ζ.) 12. The organic coating layer according to claim 10, having a siloxane unit represented by the following general formula (4):
An image recording article comprising polysiloxane as a main component. [Chemical 3] (Where Y is the following general formula (5): Or the following general formula (6): Wherein R ³ is selected from hydrogen, a methyl group and a fluoro group, α is an integer from 2 to 4, and β is 3
Is an integer from 1 to 14, γ is 0 or 1, and δ = 2-γ. R ⁶ is selected from a methyl group, an ethyl group, a fluoroalkyl group and Y. )