JPS6228458B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved photosensitive recording material and a method for recording information by exposing this material to informationally modulated activating electromagnetic radiation. Published German Patent Application (Dt-OS) No. 2436132 describes a method for making a searchable record of information that utilizes a recording layer containing an organotellurium compound as the imaging material. In this method, a halogen, preferably chlorine, is directly bonded to the tellurium atom,
Also, an organotellurium compound containing at least one organic substituent having a carbonyl group is visually reduced by an exposed photoreductant such as a polynuclear quinone. Formation of the tellurium image is carried out by thermal development, for example by heating the exposed material globally to 80-200°C. The reaction scheme below illustrates the method by which this tellurium metal image is formed. In the formula, PQ is a photoreductant such as phenanthrenequinone ¹ PQ is the first excited singlet state of the quinone ³ PQ is the triplet state of the quinone RH is a hydrogen donor such as an organic hydroxy compound PQ・H ₂ is a photoreduction The cyclic state of the body (R ¹ ) 2.Te.Cl _{2 is} a reducible organic tellurium compound, and R ¹ is, for example (C ₆ H ₅ COCH ₂ ). It is a matter of low gender. Using a recording material having a blocking layer or sheet on top of the recording layer which prevents the permeation of vapor or gas into and the dissipation of vapor or gas from the layer during thermal development may be used to achieve a certain maximum optical density required. It has been experimentally confirmed that the exposure energy is significantly reduced. According to the present invention, on the support, in the binder medium (1) an organic tellurium compound as an image-forming substance in which a halogen atom and at least one organic substituent having at least one carbonyl group are directly bonded to a tellurium atom; , (2) a photoreductant, and (3) a recording layer comprising a mixture of hydrogen-donating compounds from which hydrogen can be exposed and removed by the photoreductant, and the recording layer is coated directly or with one or more hydrogen-donating compounds. The blocking layer or sheet is permanently bonded through the subbing layer, which prevents vapor or gas from seeping into the recording layer and dissipating from the recording layer during post-exposure heat treatment, and also prevents vapor or gas from escaping from the recording layer. A recording material is provided in which the body and/or the blocking layer or sheet have characteristics that allow the actinic radiation to pass therethrough in order to enable exposure of the recording layer to said radiation. The term "actinic radiation" means electromagnetic radiation, such as ultraviolet and/or visible light, to which the recording layer is sensitive for imaging. The term "blocking layer" includes a single layer as well as a stack of such layers. The gas or vapor impermeability of the layer or sheet is determined by control material A-- as described in Example 1.
A tellurium image obtained by processing the same material but not coated with such a layer or sheet under the same exposure and development conditions, when a recording layer of 0 is coated with said layer or sheet by visual exposure and thermal development of the coating material. Preferably, the tellurium image is such that a tellurium image is obtained with a maximum optical density (D) that is at least 0.2 greater than the maximum optical density of . The blocking layer or sheet is made from polymeric materials (including natural, modified natural, and synthetic resins). For example, cellulose esters such as cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polystyrene, polyvinyl acetate, polyvinyl chloride, silicone resins, poly(acrylic ester) and poly(methacrylic ester) resins and fluorinated hydrocarbon resins , as well as mixtures thereof. Examples of useful synthetic polymer materials obtained by addition polymerization include poly(isobutyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl methacrylate),
Copolymer of vinylidene fluoride and trifluorochloroethylene, polyvinyl-n-butyral, copoly(vinyl acetate/vinyl chloride), copoly(acrylonitrile/butadiene/
styrene), copoly(vinyl chloride/vinyl acetate/vinyl alcohol) and poly(N
-methoxymethylacrylamide). Besides polymers obtained by addition polymerization of unsaturated monomers, polymers obtained by polyaddition, such as polyurethanes, or polymers obtained by polycondensation, such as polyamides and polyester resins, are also useful blocking layers or sheets for the recording materials of the invention. used to make. According to one embodiment, the blocking layer of the recording material according to the invention comprises a polymer or a mixture of polymers containing reactive hydrogen atoms, such as free hydroxyl groups, -
NHCO—O— and those containing hydrogen atoms forming part of one or several groups of —COOH and a number of etherified N-methylol groups as cross-linking agents, preferably —N—CH ₂ OCH ₃ It is made from a cross-linked polymer mass obtained by the acid-catalyzed reaction of organic compounds containing Polymers having reactive hydrogens forming part of the free hydroxyl groups and suitable for acid-catalyzed crosslinking with compounds containing etherified N-methylol groups include, for example, polyesters containing free hydroxyl groups, polyvinyl alcohol starting materials. Polyvinyl acetal, a copolymer of vinyl alcohol and vinyl chloride, or vinyl chloride, in which some of the hydroxyl groups are not acetalized,
It is a copolymer of vinyl acetate and vinyl alcohol. Preferably utilized polymers containing free hydroxyl groups are polyvinyl butyral having 80-90% by weight vinyl butyral units, 7-20% by weight vinyl alcohol units and 0-3% by weight vinyl ester units, e.g. vinyl acetate units. be. The molecular weight of polyvinyl butyral can vary over a wide range, but is preferably between 45,000 and 55,000. in ethanol
Particularly useful are polyvinyl butyrals with an intrinsic viscosity of 0.75 to 1.25 dl/g measured at 20°C. Polymers having reactive hydrogen constituting a part of the -NH-CO-O- group and suitable for acid-catalyzed crosslinking with a compound having an etherified N-methylol group include polyurethane polymers, such as U.S. Pat. No. 3,743,833. It is as described in the No. Examples of commercially available useful polyurethane polymers include Estane 5707F-1
(Estan is a registered trademark of a polyurethane resin manufactured by BF Gutdrich Chemical Company, Cleveland, Ohio, USA). Suitable crosslinkers having a large number of etherified N-methylol groups are obtained by reacting formaldehyde with urea or melamine. Particularly useful cross-linking compounds for use in combination with the polyvinyl butyral have the structural formula Hexakis(methoxymethyl)-melamine is represented by Such compounds are available as Cymel 300 from the American Cyanamid Company of New York, USA.
It is commercially available under the registered trademark name. It is believed that the acid-catalyzed cross-linking reaction between the above compound and a polymer having reactive hydrogen is carried out as follows. (wherein R represents an organic group of the included polymer) This reaction preferably proceeds at high temperature. The preferred cross-linking temperature (also called curing temperature) is 80~
The temperature is 160℃. Preferably, the amount of crosslinking agent relative to the crosslinkable polymer(s) is between 5 and 20% by weight. In practice, strong acids such as hydrochloric acid,
Preference is given to using phosphoric acid, monobutyl phosphate, polystyrene sulfonic acid, p-toluenesulfonic acid. Preferably p-toluenesulfonic acid is used, which is an acid that is soluble in an organic solvent such as ethanol in which the crosslinkable polymer, such as polyvinyl butyral, is soluble. Preferably, the amount of catalyst relative to the crosslinkable polymer is from 0.2 to 4% by weight. As is clear from the above reaction formula, since hydrochloric acid is produced during thermal development, cross-linking can be carried out at that location during thermal development. The dry thickness of the blocking means in the form of a coating on the recording layer is at least 5 μm, e.g.
Preferably it is 200 μm. This blocking coating is usually the outermost coating. However, recording materials further coated on top of such coatings are also within the scope of the invention. The blocking coating is applied using a polymer solution or dispersion, such as a latex, and evaporation of the solvent or liquid dispersion medium leaves behind a continuous polymer layer. Care should be taken to apply this polymer solution or dispersion using a liquid medium that does not dissolve the binder of the recording layer or cause swelling of the binder. Suitable blocking coatings can also be applied in sheet form by lamination. An adhesive layer is usually used to bond such a coating more firmly to the recording layer. Adhesives and compositions for protective laminates are described, for example, in US Pat. No. 3,164,719 to Herbert Bauer, issued January 5, 1965. According to one simple embodiment, a commercially available pressure sensitive adhesive sheet is used to obtain the desired blocking of the recording layer. Blocking sheets useful for the purposes of the present invention applied by adhesive means have a thickness of 50 to 200 μm.
It is. According to yet another embodiment, a layer of polymerizable monomer is applied and polymerized in situ on the recording layer. A suitable monomer for making the blocking layer in this way is acrylamide. A reducible organic tellurium compound (1) particularly suitable for use in the recording material of the present invention is represented by the general formula below. RxTeCly where R is bonded to the tellurium atom through a carbon atom and represents an organic group having at least one carbonyl group; x is 1, 2 or 3; x+
y is 4. Such compounds and their preparation are described in Published German Patent Application No. 2436132 (DT-OS). A preferred group of image forming agents are organic tellurium compounds represented by the following general formula. (Ar--CO--CH ₂ ) ₂ TeCl ₂ where Ar is a substituted or unsubstituted aromatic group such as phenyl, methoxyphenyl, tolyl or naphthyl. Bis(phenacil)-tellurium dichloride is a preferred imaging agent for use in the present invention in combination with a photoreductant, a hydrogen donor, and optionally at least one acid-sensitive reducing agent precursor. Any compound that acquires reducing power for the tellurium compound by removing hydrogen from the hydrogen-donating compound (3) with light can be used as the photoreductant (2). The photoreductant is described in Research Disclosure, October 1974, pp. 14-17, No. 12617. Preferred photoreductants (2) used according to the invention are aromatic diketones, especially 1,2- and 1,4-benzoquinones having at least one fused carbocyclic aromatic ring. Examples of photoreductants are shown in Table 1 below, along with their approximate photosensitive ranges.

【table】

[Table] The following are typical photoreductants that are sensitive up to about 400 nm and are therefore useful only in the ultraviolet region. Benzophenone; Acetophenone; 1,5-
Diphenyl-1,3,5-pentantrione; Ninhydrin; 4,4'-dibromobenzophenone;
2-t-Butylanthraquinone and 1,8-dichloroanthraquinone 9,10-phenanthrenequinone and 2-t-butylanthraquinone are particularly satisfactory for the reduction of the organotellurium compounds. The hydrogen-donating compound (3) is described in, for example, U.S. Patent No.
Any conventional source of labile hydrogen such as those described in US Pat. No. 3,881,930. The patent describes hydrogen-donating compounds in which a hydrogen atom is attached to a carbon atom, and also an oxygen atom of a hydroxy group and/or a trivalent nitrogen atom of an amine substituent. A preferred hydrogen-donating compound (3) from which hydrogen can be removed by the exposed photoreductant is represented by the following general formula. In the formula, R ¹⁰ and R ¹¹ are the same or different groups, each of which is hydrogen, a straight chain, branched chain, or cyclic hydrocarbon group that may have a substituent, such as an alkyl group,
It represents a hydroxyalkyl group, a cycloalkyl group, an aryl group, or an alkoxycarbonyl group, such as a C ₂ H ₅ -O-CO- group, where Z is a single bond,
Ethynylene group - [(C≡C) -] _o or group

[Formula]; n is an integer, for example 1 or 2, R ¹² and R ¹³ are the same or different groups, hydrogen or an alkyl group such as methyl or jointly a carbocyclic or heterocyclic ring such as a phenylene ring; can constitute a section. Examples of such hydrogen-donating compounds are shown in Table 2 below, and are also described in German Patent Application No. P2719023.

[Table] Methods for producing these compounds are well known to those skilled in the art. A particularly preferred hydrogen donating compound is phenyl-1,2-ethanediol (compound 2 in Table 2). In addition to the above compounds (1) to (3), organic reducing agent precursors can be used, and this is disclosed in patent application No.
No. P2802666 increases the photographic speed of recording materials. The reducing agent is liberated image-wise from the organic reducing agent precursor by the action of an acid such as HCl produced during the image-forming reaction, thereby effecting image-wise reduction of the organo-tellurium compound. When using an acid-sensitive organic reducing agent precursor, it is not recommended to simultaneously use a coating layer that indiscriminately contains acids that will cause overall curing or cross-linking of the coating layer. This is because some of the acid reaches the recording layer, liberating the reducing agent throughout the recording layer and indiscriminately reducing the tellurium compounds, causing spine fog. A group of organic reducing agent precursors from which the reducing agent for the organotellurium compound is liberated by the action of an acid, at least one hydroxy group being esterified and the remaining hydroxy groups (if any)
Included are para- and ortho-dihydroxy aromatic compounds in which are etherified. By acid-catalyzed hydrolysis, this hydroxyl group becomes free again and the reducing properties are restored. Another group of acid-sensitive organic reducing agent precursors are derived from pyrazolidin-3-one reducing agents in which the active hydrogen atom in the 2-position is temporarily blocked, for example by reaction with an isocyanate or an acid halide. Representative examples of both classes of reducing agent precursors are shown in Table 3 below.

【table】

[Table] The manufacturing method of these compounds is described in the above-mentioned patent application No.
Described in No. P2802666. Particularly preferred binders for use in the recording layer of the present invention are organic polymeric materials. Typical thereof are cyanoethylated starches, celluloses and amyloses with a degree of cyanoethylation substitution of at least 2; polyvinylbenzophenone; polyvinylidene chloride; polyethylene terephthalate; cellulose esters and ethers such as cellulose acetate, cellulose propionate, cellulose. Butyrate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl carbazole, polyvinyl chloride; polyvinyl methyl ketone, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid and polymethacrylic acid alkyl esters such as polymethyl methacrylate and polyethyl methacrylate copolymers of polyvinyl methyl ether and maleic anhydride; various grades of polyvinyl formal resins, such as the so-called 12/85, 6/95E, 15/95S, 15 commercially available under the trademark Formvar (registered trademark) of Monsanto Company, Missouri, USA; /
95E, B-79, B-98, etc. Particularly useful is polyvinyl formal 15/
95E, it is a white free-flowing powder with a molecular weight of 24000-40000 and a formal content expressed as polyvinyl formal% of about 82%, with high thermal stability and good mechanical resistance. . A dry photographic coating containing each of the above components serves as a medium for dispersing or dissolving the binder or binder mixture with other suitable components, and is removed from the coating composition by evaporation, leaving the solid photographic recording layer on a suitably selected support. It is made by dissolving it in an inert solvent such that it remains above. The support can be of any type used in silver halide photographic materials, such as resin films. The photoreductant is used in this recording material in an amount that is preferably at least equimolar to the organotellurium compound. The coating amount of the organic tellurium compound is preferably 1 to 10 g per square meter. Preferably, the amount of hydrogen donating compound is at least 50% by weight, based on the organotellurium compound. The amount of acid-sensitive reducing agent precursor is not critical. Significant improvements in photosensitivity are achieved with amounts of 50 to 100% by weight, based on the organotellurium compound. The present invention also includes a recording method that utilizes the recording material described above. The method includes the steps of informationally exposing the material to activating electromagnetic radiation to which the photoreductor is sensitive and generally heating to develop a tellurium image in the recording material. Informative UV exposure is usually used when using aromatic diketones as photoreductants. Heat development is preferably carried out at 80°C to 200°C, and is usually carried out for about 30 seconds to 300 seconds, depending on the temperature. The heating required to create tellurium metal images can be accomplished in a variety of ways. The recording material is developed, for example, by heat transfer from a hot body, such as a plate or roller, or by contact with a hot gas, such as hot air. Furthermore, it is also possible to create metal images using infrared light. The present invention will be explained below with reference to examples, but these are not intended to limit the invention. Unless otherwise specified, all percentages or ratios are by weight. Example 1 Control material A-0 4.2 g of phenanthrenequinone, 10.2 g of 2-t-butylanthraquinone, 1-phenyl-1,2-
22.8g ethanediol and bis(fenacil)
9g of tellurium dichloride to methylene chloride
I melted it to 150g. The resulting solution was mixed with vinylite VAGH (Union).
240 g of a 20% methyl ethyl ketone solution of Carbide &Carbon's copoly (vinyl chloride/vinyl acetate/vinyl alcohol) (registered trademark name: 3/6/91) and 1 ml of a 2% methylene chloride solution of silicone oil as a coating aid. were mixed. The resulting coating composition is coated with 2 organic tellurium compounds.
It was applied by dip coating onto a polyethylene terephthalate film support at a coating weight of g/m ² . The coating was dried for 8 hours at 40°C with ventilation. The obtained photosensitive recording material A-0 was heated to a maximum wavelength of approx.
Exposure was carried out for 10 seconds through a step wedge of constant 0.3 using a "Spectraproof" (registered trademark) exposure device manufactured by Siegfried Timer GmbH, Obersatzbach 6481, West Germany, which also has a 350 nm 200 W lamp. The exposed material was developed by heating the entire exposed material to 160°C for 5 minutes. Recording material A-1 The manufacturing method of recording material A-1 is control material A-
Same as 0 but with 10% of poly(N-methoxymethylacrylamide) on top of the recording layer.
It was prepared by applying a methanol solution to a dry weight coating amount of 4.4 g/m ² . Exposure and heating of material A-1 were performed in the same manner as for control material A-0. Attached figure 1
The figure shows the density (D) of the wedge images obtained with control material A-0 (curve A-0) and this material A-1 (curve A-1) versus photon exposure energy/cm ² (erg/cm2). A curve is shown. From these curves, material A-1 having a blocking layer according to the present invention is different from control material A-0.
It can be seen that the photosensitivity is more than 100 times better. Example 2 Control Material B-0 5.4 g of 2-t-butylanthraquinone, 1.4 g of 1-phenyl-1,2-ethanediol and 1.5 g of bis(phenacil)-tellurium dichloride were dissolved in 50 ml of methylene chloride. The resulting solution was mixed with 60 g of a 20% solution of Vinyrite VAGH (registered trademark) in methyl ethyl ketone and 1 ml of a 2% methylene chloride solution of silicone oil. This coating solution was mixed with 2.5 g of the organic tellurium compound/
It was applied by dip coating to a polyethylene terephthalate support in a coating weight of m ² . Drying was carried out in the same manner as for control material A-0 of Example 1. The photosensitive recording material obtained was exposed for 100 seconds through a step wedge with a constant of 0.3 in the previously described "Spectraproof" (registered trademark) apparatus. The exposed material was developed by heating in an Oikonics Thermal Processor E-Day 199 (Oikonics is a registered trademark of Oikonics Corporation, Burlington, Mass., USA) at 120 DEG C. for 5 minutes. Recording material B-1 The manufacturing method of recording material B-1 is the same as material B-0, except that pressure-sensitive adhesive cellophane (registered trademark name)
The only difference was that the tape was adhered to this recording layer. Exposure and heating of material B-1 was carried out similarly to material B-0. Recording Material B-2 The manufacturing method of Recording Material B-2 was the same as that of Material B-0, except that a polyethylene terephthalate sheet with a thickness of 0.1 mm was adhered to the recording layer with one drop of silicone oil. Material B-2 was exposed and heated in the same manner as material B-0. Figure 2 shows these materials B-0, B-1 and B-
Concentration (D) of 2 vs. photon lightning energy/cm ² (erg/
(cm2) is shown. Example 3 Control material C-0 2-isopropoxy-1,4-naphthoquinone 5
g, 1-phenyl-1,2-ethanediol 17.4
g and 9.42 g of bis(phenacil)-tellurium dichloride were dissolved in 260 g of tetrahydrofuran. The resulting solution was mixed with 300 g of a 28% methyl ethyl ketone solution of Vinyrite VAGH (registered trademark) and 1 ml of a 2% methylene chloride solution of silicone oil. The resulting coating composition has an organic tellurium compound content of 2.7
It was applied as a dip coat to a polyethylene terephthalate film support at a coating weight of g/m ² . The coating was dried with ventilation at 40°C for 8 hours. The resulting photosensitive recording material was exposed for 10 seconds through a step wedge with a constant of 0.3 in a Spectraproof® exposure apparatus. The exposed material was developed by heating the whole to 150° C. for 5 minutes in a drying stove. Recording material C-1 The manufacturing method of recording material C-1 is the same as material C-0, except that Butvar B76・8.5g, Cymel
300・1.5g and silicone 0.05g with ethanol
A 100 ml solution was used to coat the recording layer. Butovar is manufactured by Siyaunigan Products Corp. in New York, USA, and has a molecular weight of 45,000 ~
Cymel 300 is a registered trademark of a vinyl-n-butyral polymer with a vinyl alcohol unit content of 13%. It is. This coating was carried out so that the amount of vinyl-n-butyral polymer applied was 20 g/m ² . Exposure was carried out in the same manner as for material C-0. Heat exposed material C-1 at 160℃ in a drying stove.
The whole was heated for 5 minutes and developed. FIG. 3 shows density (D) versus photon exposure energy/cm ² (ergs/cm ² ) curves for materials C-0 and C-1 developed at 160°C.

[Brief explanation of the drawing]

Figures 1 to 3 of the attached drawings show the densities of wedge images obtained using the control material (alphabet letters with 0 added) and the recording material according to the present invention (alphabet letters and numbers 1 and 2). (D)
(vertical axis) versus photon exposure energy per square centimeter (ergs/cm²) (horizontal axis), respectively.

Claims (1)

[Scope of Claims] 1. In the binder medium, (i) as an image-forming substance,
an organotellurium compound containing at least one organic substituent containing at least one carbonyl group and a halogen directly bonded to a tellurium atom; (ii) a photoreductant; and (iii) a photoreductant exposed therefrom. In a photosensitive recording material having a recording layer on a resin support containing a hydrogen-donating compound in the form of a mixture from which hydrogen can be taken up, the blocking layer or sheet may be applied directly or via one or several subbing layers. The resin support is permanently bonded to the recording layer to prevent vapor or gas from permeating into the recording layer and dissipating from the recording layer during post-exposure heat treatment of the recording material. A photosensitive recording material characterized in that the body and/or the blocking layer or sheet are transparent to actinic radiation. 2. Photosensitive recording according to claim 1, in which the blocking layer or sheet is made of a natural or modified natural resin or of a polymeric material obtained by addition polymerization of unsaturated monomers or by polyaddition or polycondensation. material. 3. The photosensitive recording material according to claim 2, wherein the blocking layer or sheet is made of cellulose ester, poly(N-methoxymethylacrylamide) or polyester. 4 The blocking layer consists of a polymer or polymer mixture containing reactive hydrogen atoms and a large number of etherified N-
A photosensitive recording material according to claim 1, which is made from a cross-linked polymer mass obtained by acid-catalyzed reaction of an organic compound containing methylol groups. 5. The photosensitive recording material according to claim 1, wherein the blocking sheet is an adhesive sheet having a pressure-sensitive adhesive coating. 6 Organotellurium compounds have the general formula RxTeCly (wherein R represents an organic group bonded to the tellurium atom through a carbon atom and having at least one carbonyl group; x is 1, 2, or 3; x+y is 4; The photosensitive recording material according to any one of claims 1 to 5, which is a compound represented by: 7. The photosensitive recording material according to any one of claims 1 to 6, wherein the photoreductant is an aromatic diketone. 8 The hydrogen donating compound has the general formula (In the formula, R ¹⁰ and R ¹¹ are the same or different groups,
Each is hydrogen, a straight chain, branched chain, or cyclic hydrocarbon that may have a substituent, or an alkoxycarbonyl group, and Z is a single bond, an ethylene group - [(C≡
C) - _{] o} or a group [formula], where n is an integer, and R ¹² and R ¹³ are the same or different groups, each representing hydrogen or an alkyl group, or jointly representing a part of a carbocyclic or heterocyclic ring. )
Claims 1--
The photosensitive recording material according to any of item 7.