JPH05204152A - Sheet-formed optical recording material - Google Patents

Abstract

PURPOSE:To directly form a sharp image by using an iron-arene type compound as a photocationic reaction initiator and a specified polyacrylate type derivative and/or polymethacrylate type derivative. CONSTITUTION:A coating layer composed essentially of the photocationic reaction initiator of the iron-arene compound, a sensitizing dye, a color developing dyestuff, and the poly-acrylate or methacrylate type derivative represented by formula I is formed on a sheet of a substrate. In the formula, R1 is >=2C alkyl, cycloalkenyl, cycloalkanyl, or aralkyl; R2 is H, halogen, amino, nitro, cyano, or alkyl optionally substituted by one of the above groups; and n is an integer of 5-10000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet-shaped optical recording material. More specifically, the present invention relates to a sheet-shaped optical recording material useful as an optical recording material by laser beam irradiation.

[0002]

2. Description of the Related Art In recent years, optical information processing technology applying optical fiber and laser technology has been developed. Among the optical information processing technology, as an optical recording medium which is a data output medium, there is an electrophotographic system represented by a printer using a helium / neon laser or a semiconductor laser, which is a small and inexpensive light source. To form
To fix the toner, latent image formation, toner development, toner transfer and fixing are required. This complicates the mechanism of the printer, increases the size of the main body of the printer, and increases power consumption. Therefore, maintenance and management of the printer requires a great deal of expense and labor.

Therefore, there is a demand for the development of an optical recording material which uses a small and low-priced laser such as a helium-neon laser or a semiconductor laser as a light source, does not require toner transfer and fixing processing, and can directly record an image. It had been. These helium / neon lasers and semiconductor lasers have a small laser light output, and it is necessary to improve the sensitivity of the coating layer of the optical recording material.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to provide a sheet-shaped optical recording material which satisfies the above-mentioned requirements.

[0005]

A sheet-like optical recording material according to the present invention comprises a photoreaction initiator, a sensitizing dye, a coloring dye, and a polyacrylic acid ester derivative and / or a polyacrylate derivative and / or a pigment on at least one surface of a sheet-like substrate. Polymethacrylic acid ester derivative (hereinafter, these components are referred to as coloring composition)
It has a coating layer containing as a main component. In this color-forming composition, various photocationic reaction initiators are effective as photoreaction initiators, and it is proposed in JP-A-3-96950 that various sensitizing dyes are effective for sensitization. .. It was shown in Japanese Patent Application No. 2-94994 that an iron-arene compound is effective as the photocation reaction initiator.
Then, as a result of further detailed study, an iron-arene compound was used as a photocationic reaction initiator, and a polyacrylic acid ester derivative and / or a polymethacrylic acid ester derivative (hereinafter referred to as an acrylic polymer)
It was found that a clear recorded image can be obtained by using a color-forming composition containing the present invention, and the present invention has been completed.

That is, the sheet-shaped optical recording material of the present invention comprises a photo-cationic reaction initiator, a sensitizing dye, a coloring dye, a polyacrylic acid ester derivative and / or a polymethacrylic acid ester on at least one surface of the sheet-shaped substrate. A sheet-like optical recording material provided with a coating layer containing a system derivative as a main component, wherein the photocationic reaction initiator is an iron-arene compound and the polyacrylic acid ester derivative and / or polymethacrylic acid. The ester derivative is a compound represented by the following general formula (1).

[0007]

[Chemical 2]

The acrylic polymer used in the present invention has a function of amplifying the production of protonic acid. That is, the acrylic polymer reacts with the acid generated by the photodecomposition of the photocationic reaction initiator to generate a polyacrylic acid derivative or / and a polymethacrylic acid derivative and a protonic acid. Further, this protonic acid reacts with other acrylic polymer to successively produce a polyacrylic acid derivative or / and a polymethacrylic acid derivative and a protonic acid.

Further, the sheet-like optical recording material of the present invention may contain a mixture of the above-mentioned color-forming composition and a pigment in order to improve the printability and writability of the coating layer. The sheet-like optical recording material having such a coating layer is
By irradiating a laser beam, a clear recorded image can be obtained directly.

Next, the action of each component in the present invention will be described. The sensitizing action of the sensitizing dye is brought into an excited state by absorption of light in the oscillation wavelength range of a helium / neon laser or a semiconductor laser, and the sensitizing dye in the excited state causes the acid generation reaction of the photocationic initiator. Facilitate. next,
This acid reacts with the acrylic polymer of the present invention to generate a polyacrylic acid derivative and / or a polymethacrylic acid derivative and a protonic acid. The protonic acid generated from the carboxyl group in the polyacrylic acid derivative and / or the polymethacrylic acid derivative or the proton released when the acrylic polymer is decomposed into the polyacrylic acid derivative and / or the polymethacrylic acid derivative. It is understood that one of the acids reacts with the color-forming dye to develop a color, and an image can be directly obtained without developing.

As the photocationic reaction initiator used in the present invention, iron-based compounds described in Japanese Patent Application No. 2-94994 are used.
An arene compound can be used. That is, the iron-arene compound used in the present invention is a compound in which divalent iron ions form a complex of a cyclopentazine ring and a benzene ring.
More specifically, the iron-arene compounds used in the present invention are described in K.K. Meler et al. Imag. Sc
i. , Vol. 30, 174 (1986), which comprises an iron coordinate-bonded with a cyclopentazine ring and a benzene ring further coordinated, and the benzene ring includes benzene, naphthalene, and anthracene. , Pyrene and perylene. Examples of the anion to be paired tetrafluoroborate (BF ₄ ^-), fluoro phosphate
(PF ₆ ⁻ ), fluoroantimonate (SbF ₆ ⁻ ), triflate (CF ₃ SO ₃ ⁻ ), fluoroarsenate (AsF ₆ ⁻ ), and the like can be used. Further, in order to facilitate coordination of iron with the benzene ring, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a halogen atom such as chlorine or bromine, or a ketone having a carbonyl structure is formed on the benzene ring. The thing which added the group, the ester group, the carboxyl group, etc. can also be used.

The coloring dyes usable in the present invention include triphenylmethane dyes, triphenylmethanephthalide dyes, phenothiazine dyes, phenoxazine dyes, fluorane dyes, indolylphthalide dyes and azaphthalide dyes. There are dyes, diphenylmethane dyes, clomepyrazole dyes, leukoauramine dyes, rhodamine lactam dyes, azomethine dyes and leucoxanthene dyes, and triphenylmethanephthalide dyes, indolylphthalide dyes, azaphthalides. System pigment,
Fluoran dyes, rhodamine lactam dyes and leucoxanthene dyes are particularly preferred.

The sensitizing dyes that can be used in the present invention include cyanine dyes, rhodacyanine dyes, oxonol dyes, styryl dyes, merocyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, pyrylium salt dyes, Thiopyrylium salt dyes, squarylium dyes, croconium dyes, azurenium dyes, dithiol metal salt dyes, naphthoquinone dyes, anthraquinone dyes, indophenol dyes, azo dyes, triphenylmethane dyes, porphyrin dyes, There are coumarin dyes, xanthene dyes, thioxanthene dyes, thionine dyes, trisbipyridine ruthenium complex dyes and indigo dyes. These sensitizing dyes can be used properly according to the oscillation wavelength and output of the laser light source used.

The polymethacrylic acid ester derivative usable in the present invention is described in H. Ito et al. Macromo
Lecules, Volume 21, 1475 (1988), or a method in which a carboxyl group of a polyacrylic acid-based polymer or a polymethacrylic acid-based polymer is converted to an alkyl group having 2 or more carbon atoms or a cycloalkene group. A polymer that can be obtained by esterification with an alcohol having a cycloalkane group or an aromatic derivative and is represented by the following general formula (1).

[0015]

[Chemical 3]

For the purpose of adjusting the hardness of the coating layer and imparting heat resistance, a copolymer with a styrene derivative monomer represented by the following general formula (2) may be used.

[0017]

[Chemical 4]

The preferred compounds are shown below, but the present invention is not limited to these compounds.

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8] As described above, the exemplified polymethacrylic acid ester derivatives are
It also has a function of binding the color forming composition in the coating layer.

The coating layer of the sheet-shaped optical recording material of the present invention comprises:
The color-forming composition or the color-forming composition is mixed with an adhesive. As the adhesive, for example, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, oxidized starch, water-soluble adhesive such as casein,
In addition, a commonly used adhesive such as a synthetic polymer such as a styrene-butadiene-based copolymer, an acrylic-based copolymer, an ethylene-vinyl acetate-based copolymer can be used.

In the present invention, the compounding ratio of the color forming composition is 0.0001 to 10 moles, preferably 0.001 to 1 mole of the sensitizing dye, and 1 to 1 mole of the photocationic reaction initiator. 0.1 to 10 mol, preferably 0.5 to 5 mol, and 0.01 to 10000 parts by weight, preferably 0.1 to 100 parts by weight of the polymethacrylate derivative.
~ 1000 parts by weight. Further, the compounding amount of the adhesive in the color forming composition in the coating layer is 0 to 2000 parts by weight, preferably 0 to 1000 parts by weight, based on 1 mol of the photocationic reaction initiator.

In the present invention, in order to improve the printability and writability of the sheet-shaped optical recording material, it is preferable that the coating layer contains a pigment together with the color-forming composition. Examples of such pigments include clay, calcium carbonate, aluminum hydroxide, silica, satin white, titanium dioxide, talc, barium sulfate, calcium sulfate, calcium sulfite, organic pigments, etc., which are used for ordinary pigment-coated paper. You can use pigments that are
Alternatively, two or more kinds may be mixed and used. The amount of the pigment is 10 to 100 parts by weight of the coloring composition.
It is 1000 parts by weight, preferably 50 to 300 parts by weight.

The sheet-like substrate used in the optical recording material of the present invention includes a porous substrate such as paper, non-woven fabric and cloth, synthetic paper, polymer film, metal foil and the like.
These may be used alone or may be used in the form of a laminated body of these.

The sheet-like optical recording material in the present invention contains a reaction accelerator, a reaction modifier, a wetting agent, and a film-forming agent in a coating solution containing a color-forming composition as a main component unless the purpose of use is impaired. It may contain an auxiliary agent, a diluent solvent, a stabilizer and the like.

To form a coating layer containing a color-forming composition on a sheet-like substrate, a coating solution having a predetermined composition is used.
According to a conventional method, it may be applied on a sheet-shaped substrate with a roll coater or the like, and dried and cured. Further, as long as the quality of the coating layer formed is not impaired, an ultraviolet curing device or an electron beam curing device may be used in combination for drying and curing.

As the laser light source used in the present invention, a laser light source having an oscillation wavelength in the visible light region such as an argon laser, a helium / cadmium laser, a krypton laser, a helium / neon laser, a semiconductor laser, and a ruby laser can be used. Is. The infrared laser can also use visible light whose wavelength is converted by a nonlinear optical crystal.

The sheet-shaped optical recording material of the present invention can directly record an image by irradiation with a laser beam of a laser printer. Further, it is possible to obtain a clear printing with a writing instrument or a printed image with printing ink.

[0031]

EXAMPLES The present invention will now be described in more detail with reference to examples.

Arene compound - [0032] Iron as in Example 1 photo cationic initiator [(1-methylethyl) eta ⁶ - benzene] [eta ⁵ -
Cyclopentadienyl] iron (II) -fluorophosphate (Irgacure 261, manufactured by Ciba Geigy) 0.01 mol per 1 part of cyanine sensitizing dye (NK-529, manufactured by Japan Photosensitive Dye Research Institute) , And 1 mol of a fluoran-based dye (Red-3, manufactured by Yamamoto Kasei Co., Ltd.) as a coloring dye while being dispersed and dissolved in methyl ethyl ketone, and then blended, and then with the acrylic ester derivative and the styrene derivative of the above formula (14). 200 parts by weight of the above copolymer is mixed with 1 mol of the photocationic initiator, and an acrylic copolymer (LR-347, manufactured by Mitsubishi Rayon Co., Ltd.) is used as an adhesive in an amount of 10 parts by mol of the photocationic initiator. A coating liquid was prepared by adding parts by weight. Then, using a PET film having a thickness of 50 μm as a sheet-shaped substrate, the above coating solution was applied by a roll coater so that the coating amount after drying was 3 g / m ² , and dried at 100 ° C. for 2 minutes to coat. The layers were formed to prepare a sheet-shaped optical recording material. A laser beam from a helium / neon laser (oscillation wavelength 633 nm, output 20 mw) was condensed by a condenser lens on the surface of the coating layer of the sheet-like optical recording material thus obtained, and it was irradiated according to a pattern of a predetermined image. A red recorded image was obtained.

Example 2 As a photocationic reaction initiator, 1 mol of iron-arene compound [η ⁶ -naphthalene] [η ⁵ -cyclopentadienyl] iron (II) -fluorophosphate was used.
0.001 mol of a thiazine dye (methylene blue) and 1 mol of an azaphthalide dye (CVL, Hodogaya Chemical Co., Ltd.) as a coloring dye are dispersed in methyl ethyl ketone.
It was mixed while being dissolved, and further 200 parts by weight of the polymethacrylic acid ester derivative of the formula (6) was mixed with 1 mol of the photocationic reaction initiator. Then the above formulation 1
To 100 parts by weight of clay, 100 parts by weight of clay was mixed and dispersed, and similarly 300 parts by weight of an acrylic copolymer adhesive (COPONYL 4025, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was added to prepare a coating liquid. did. Next, as a sheet-shaped substrate, a 110 μm thick polyolefin-based synthetic paper (Yupo FP
G110, manufactured by Oji Oka Synthetic Paper Co., Ltd.), the above coating solution is applied by a roll coater so that the applied amount after drying is 3 g / m ² , and dried at 100 ° C. for 2 minutes to form a coating layer. Then, a sheet-shaped optical recording material was prepared. A laser beam from a semiconductor laser light source (oscillation wavelength of 670 nm, output of 20 mW) was condensed by a condenser lens on the surface of the coating layer of the sheet-like optical recording material thus obtained, and when it was irradiated in accordance with a pattern of a predetermined image, a clear image was obtained. A blue recorded image was obtained.
Also, normal offset printing and printing with office writing instruments were possible.

Comparative Example 1 Example 1 was repeated except that the coating solution used in Example 1 did not contain the copolymer of the acrylic ester derivative of the formula (14) and the styrene derivative. A sheet-like optical recording material was prepared and evaluated in the same manner as, but only an unclear recorded image was obtained.

Comparative Example 2 A sheet-like optical recording was carried out in the same manner as in Example 2 except that the coating solution used in Example 2 did not contain the polymethacrylic acid ester derivative of the above formula (6). The material was prepared and evaluated, but no recorded image was obtained.

[0036]

INDUSTRIAL APPLICABILITY The sheet-like optical recording material of the present invention can directly obtain a clear recorded image by irradiating a laser beam from a laser light source, and does not require a developing treatment operation. It is extremely useful.

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Claims (1)

[Claims] 1. A coating layer containing a photocationic reaction initiator, a sensitizing dye, a coloring dye and a polyacrylic acid ester derivative and / or a polymethacrylic acid ester derivative as main components on at least one surface of a sheet substrate. The sheet-shaped optical recording material provided, wherein the photocationic reaction initiator is an iron-arene compound, and the polyacrylic acid ester derivative and / or the polymethacrylic acid ester derivative is represented by the following general formula (1): ) A sheet-like optical recording material, which is a compound represented by [Chemical 1]