Source: http://patent-de.com/20061116/EP1707399.html
Timestamp: 2019-12-13 21:20:49
Document Index: 186782129

Matched Legal Cases: ['arts 10', 'arts 1', 'arts 10', 'arts 1', 'arts 10', 'arts 10', 'arts 30', 'art 10', 'arts 30', 'arts 1', 'arts 10', 'arts 10', 'arts 30', 'arts 30', 'art 10', 'arts 10', 'arts 30', 'art 10', 'arts 30']

WÄRMEEMPFINDLICHES AUFZEICHUNGSMEDIUM FÜR LASERAUFZEICHNUNGEN - Dokument EP1707399
Dokumentenidentifikation EP1707399 16.11.2006
EP-Veröffentlichungsnummer 0001707399
Titel WÄRMEEMPFINDLICHES AUFZEICHUNGSMEDIUM FÜR LASERAUFZEICHNUNGEN
Erfinder NATSUI, Nippon Paper Industries Co., Junpei, Tokyo 114-0002, JP;
KIMURA, Nippon Paper Ind. Co., Yoshihide, Tokyo 114-0002, JP;
HIRAI, Nippon Paper Industries Co., Kenji, Tokyo 114-0002, JP
EP-Aktenzeichen 057038564
WO-Anmeldetag 13.01.2005
PCT-Aktenzeichen PCT/JP2005/000626
WO-Veröffentlichungsnummer 2005068208
IPC-Hauptklasse B41M 5/28(2006.01)A, F, I, 20060905, B, H, EP
The present invention relates to a laser recording thermally sensitive recording medium characterizing that an image can be recorded by irradiation of laser beam.
Among direct recording method which does not need a developing and a fixing process, a thermally sensitive recording paper material which uses electron-donating leuco dye and electron-accepting colour developing agent as a colour developing agent is widely applied in a facsimile or a printer because of its excellent easy handling and maintenance. However, since this method is characterized to record an image by heat by contacting a thermal head or an exothermic IC pen with a thermally sensitive recording medium directly, fused colour forming substance is adhered to the thermal head or the exothermic IC pen, and a trouble such as deposit of dregs or sticking is caused, and there are problem of recording failure or deteriorate the quality of recorded image. In particular, in the case to draw a line continuously along with the flow direction of a record such as plot printer, it is actually impossible to print continuously without causing a problem of deposit of dregs. Further, in the case of recording method using a thermal head, it is said that to improve a resolution to 8 lines/mm or more is difficult.
As a method to dissolve troubles such as deposit of dregs or sticking and to further improve a resolution, a non-contact recording method using laser beam having wavelength close to near-infrared is proposed in Patent Document 1 or Patent Document 2.
However, since said methods are characterized to prepare a light absorbing thermally sensitive colour developing layer by adding a near-infrared absorbing agent directly to a coating for a thermally sensitive colour developing layer, coating and drying, for the purpose to obtain good colour developing ability, it is necessary to increase the adding amount of a near-infrared absorbing agent which absorbs laser beam having wavelength closed to near-infrared and to convert it to heat, and these absorbing agents themselves are slightly coloured and deteriorate background colour. Further, when adding amount is reduced aiming to lighten the colouring of background colour, sufficient colour developing density can not be obtained. As a countermeasure, a method to contain a near-infrared absorbing agent in a different layer from a thermally sensitive colour developing layer and to accumulate these layers is proposed, however, multi-layers construction is disadvantageous from the view point of production.
Further, in a recent plate making system for news paper, in preparation for PS (Pre-Sensitized) plate which is a plate to print a news paper, plate making process is shifting from conventional printing paper (silver halide film) method to a dry film method which can be recorded by laser, because the conventional method is troublesome in a developing process, has problems of waste liquid and gas, and an operation in a darkroom is necessary. When an error is pointed out at proofreading process, it is necessary to repeat various processes as far as PS, namely, dry film → correction by patch work → reading by a scanner → conversion to electronic information→dry film, in the processes to prepare a PS plate. As a dry film, for example, laser recording thermally sensitive proof disclosed in Patent Document 3 containing a dye which absorbs laser ray and carry out photo-thermal conversion and a colour developing material in a thermally sensitive layer can be used.
However, as mentioned above, in a case of conventional recording medium, usually, near-infrared absorbing agents are slightly coloured. Therefore, even if a recorded image can be read with naked eyes of human, in a case of optical readout such as a scanner, since contrast of a background colour part and an image part is not good, it is difficult to obtain high resolving degree. Accordingly, the conventional recording medium is not actually recognized sufficiently as a dry film which can replace with a printing paper in a plate making system.
In Patent Document 4, following technique is disclosed for the purpose to reduce the background colour. That is, a pigment which can convert laser ray to thermal energy and becomes colourless by reacting with a radical and a radical generating agent which generate a radical by irradiating ultra violet ray of 400nm wavelength or less are contained in a thermally sensitive recording layer and after recorded by laser ray, change the background colour to white or colourless by achromatic reaction.
In the meanwhile, opportunities that a thermally sensitive recording medium is used for a good-luck lottery, or a betting ticket for horse racing or motorboat racing are becoming larger. In these uses, since there is a possibility that one thermally sensitive recording paper becomes a one with very high value, it is desired to establish a technique to prevent the forgery which makes impossible to tamper by adding a postscript.
However, in general, a thermally sensitive recording medium is a recording medium which can be added a postscript to non-recorded part after recorded, therefore, it has a problem that other data can be recorded easily. Further, in a case of laser recording thermally sensitive recording medium, high precise letters or image can be recorded, which can not be recorded by a conventional thermal head, there is a peril that tampered point can not be recognized by human's naked eye.
Accordingly, in a photo recording medium containing a pigment which can convert laser ray to thermal energy and a colour developing agent, for example, in patent document 5, a technique to make addition of postscript impossible by deactivate the photo/thermo converting ability by decomposing a pigment with irradiation of ray having specific wavelength after image is recorded is disclosed.
Patent Document 1: JPA S58-209594 publication
Patent Document 2: JPA S58-94494 publication
Patent Document 3: JPA 2000-23843 publication
Patent Document 4: JPA H5-278330 publication
Patent Document 5: JPA H7-172054 publication
JP-A-05 229 251 teaches a leuco/acid thermosensitive laser recording material employing a compound of formula (I) as an infrared absorber.
As shown in Patent Documents 4 and 5, a technique to prevent addition of postscript by deactivation of photo absorbing material and discolouring are public known, however, in any case, colour developing ability or decomposing ability of pigment are not sufficient, and considerable amount of photo absorbing agent is needed to obtain high recording sensitivity, further, there is an disadvantageous for operation using ultra violet ray irradiation.
Further, since these photo absorbing agent lacks stability against ray, in a case when is left in the state to be exposed in natural light (room light such as fluorescent lamp or sun light) these agents are decomposed gradually and deactivate a photo/thermal conversion ability and sufficient colour developing ability can not be obtained when printed. This is a problem on actual.
Considering above mentioned situation, the object of the present invention is to provide a laser recording thermally sensitive recording medium having excellent light resistance against natural light during preservation term before actual use, having good contrast superior in laser recording aptitude such as photo recording sensitivity and scanner readout ability of recorded image to make impossible to add a postscript by precise letter or image which is specialized in laser recording.
The inventors of the present invention have conduced intensive study to dissolve the above mentioned problem and have found out that the above mentioned problem can be dissolved by following laser recording thermally sensitive recording medium. That is, a thermally sensitive recording medium as defined in claim 1 comprising a thermally sensitive recording layer containing at least a photo absorbing material which absorbs laser ray and covert it to heat, an electron donating leuco dye and an electron accepting colour developing agent on a substrate as main components, wherein said photo absorbing material is a compound represented by general formula (1), wherein, n indicates an integer from 1 to 4, and structural formula of Xn, Yn and Zn- are indicated in Table 1.
Xn N(C2H5)2 N(C2H5)2 N(CH3)2 N(C2H5)2 Yn N(C2H5)2 N(C2H5)2 H OCH3 Zn- CF3SO3 - CF3SO3 -
The laser recording thermally sensitive recording medium of the present invention is characterized to be excellent in recording sensitivity and colorization of background colour is suppressed, because using amount of a photo absorbing agent is small. Further, since it is possible to make background colour white or colourless by deactivation of photo absorbing material resulting by light irradiation, a laser recording thermally sensitive recording medium having good contrast superior in scanner readout can be prepared.
Therefore, in a plate making process of news paper, the laser recording thermally sensitive recording medium of the present invention can be used as a recording medium of new system which can replace with a printing paper, therefore it is recognized as a very useful product. Further, since said product is characterized as a recording material which makes addition of postscript impossible, it can be expected to be applied to a note because it has excellent feature for preventing the forgery such as tampering.
Further, a thermally sensitive recording medium as defined in claim 1 prepared by containing a compound represented by above mentioned general formula (1) as a photo absorbing agent and an anti fading agent, or an ultra violet ray absorbing agent or an antioxidant agent (hindered amine photo stabilizing agent) has excellent light resistance against natural light too, therefore, a photo absorbing agent is not decomposed during preservation term before use, thus a laser recording thermally sensitive recording medium which can maintain stable photo/thermo converting ability for long term can be obtained. And likewise to above mentioned thermally sensitive recording medium, this laser recording thermally sensitive recording medium is characterized as follows, that is, a photo absorbing material is decomposed by irradiation of light having specific wavelength and deactivating photo/thermo converting ability and makes adding of prescript of image with high resolving degree impossible. Further, by becoming an absorption of photo absorption agent at visible light region to zero, background colour part becomes white or colourless so as to have a good contrast which is excellent in a readout of recorded image by a scanner. Therefore, in a plate making of news paper, the thermally sensitive recording medium of the present invention can be used as a recording medium of new system which can be replaced with a use of a printing paper and is very useful. Furthermore, since the thermally sensitive recording medium of the present invention is characterized that the addition of postscript is impossible, it can be expected to be applied to a note because it has excellent feature for preventing the forgery such as tampering.
By adding a compound represented by general formula (2) to the thermally sensitive recording medium mentioned above as a discolouring agent, (in the formula, R1, R2, R3 and R4 are respectively independently indicating alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkinyl group, sillyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted allyl group, substituted aralkyl group, substituted alkenyl group, substituted alkinyl group or substituted sillyl group, at least one of R1, R2, R3 or R4 is an alkyl group of carbon number 1-12, R5, R6, R7 and R8 are respectively independently indicating hydrogen atom, alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkinyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted allyl group, substituted aralkyl group, substituted alkenyl group, or substituted alkinyl group),
decomposition of a compound represented by general formula (1) is remarkably accelerated and a thermally sensitive recording medium which prevents addition of postscript and tampering by deactivation of photo/thermo converting ability and has good contrast by discolouration can be easily obtained.
Further, among compounds represented by general formula (2), especially a compound represented by general formula (3) is desirable, because said compound has good discolouring ability. (in the formula, m indicates a integer of 1-3, and structural formulae of Zm- are shown in Table 2).
The present invention will be illustrated more specifically.
A photo absorbing material to be used in the present invention is a substance which absorbs the light of recording source and converts the light to heat and discharge it to the outside. Therefore, the substance which can absorb the light of recording source as broad as possible and convert it to heat and the adsorption of light which is equal to laser oscillation wave-length region (approximately 760-1100nm) or the substance whose absorption of light having near-infrared range wave-length which is closed to laser wave-length region is especially high, is desirable from the viewpoint of heat conversion effect and generated heat quantity.
In particular, in the present invention, 4 kinds of compound represented by above mentioned general formula (1) (hereinafter, shortened to compound (1)) are used as a photo absorbing material. Light absorbing ability of compound (1) is very strong and even if the amount of use is small, photo/heat conversion can be carried out effectively. Therefore, it is considered that a thermally sensitive recording medium of high contrast can be obtained controlling colouring of background colour. Further, since compound (1) has a feature to be decomposed by light irradiation, it is possible to deactivate photo/heat converting ability so as to make impossible the addition of postscript and since light absorption at visible light region becomes zero, background colour becomes white or pale colour, a thermally sensitive recording medium which is more excellent in contrast can be obtained.
As the light to deactivate the compound (1), light of laser wavelength region to be used for record or light of visible light wavelength region which have energy not a thermally sensitive layer to develop colour is desirably used. When light of ultra violet wavelength region is used, deactivation is slightly difficult. And when the light to be used for deactivation is same as the recording wavelength, an apparatus can be simplified and is advantageous. Further, when heated by the level not a thermally sensitive layer developing colour (approximately 50°C or less) simultaneously with light irradiation, decomposition is further accelerated and is effective.
For the purpose to realize high accurate scanner readout, it is desirable that the difference of reflection ratio between image part and ground part when light of longer than 600nm is irradiated is 60% or more, desirably 70% or more. The thermally sensitive recording medium of the present invention is characterized that the difference of absorbing intensity of image part and ground part at main wavelength for scanner readout is in good contrast.
A discolouring agent used in the present invention is a substance which decomposes and generates a radical by light irradiation. The generated radical acts effectively to compound (1), which is a light absorbing material, and acts a role to deactivate photo/thermo converting function and accelerate discolouration.
Specifically, said discolouring agent is a compound represented by above mentioned general formula (2), especially, among these compounds, 3 kinds of compounds indicated by general formula (3) are more desirable, because these compounds display good discolouring ability when used together with compound (1).
An anti fading agent used in the present invention acts to prevent gradual decomposition when is left in the condition exposed in natural light (room light such as fluorescent lamp or sun light) or acts to suppress an excess reaction with a discolouring agent. Accordingly, an anti fading agent is used aiming to prevent an actual problem, that is, photo absorbing material deactivates photo/thermo converting ability, and sufficient colour developing ability can not be obtained when printed.
As a desirable anti fading agent, at least one selected from the group consisting of heat resistance antioxidant, metal oxide and metal soap can be used. The reason why the anti fading agent used in the present invention displays anti fading function is not clear, however, it is considered because a polar group such as phenolic hydroxide group, hydroquinone group or sulfone group is existing in the anti fading agent, a basic polar group is existing on the surface of metal oxide and an ionic polar group such as carboxyl group is existing in metal salt. That is, ion pair of light absorbing material of compound (1), which is an ionic complex or discolouring agent such as compound (3), becomes stable when anionic acid group exists, and stability to light or heat of these compounds is improved. Therefore, when said heat resistance antioxidant, metal oxide and metal soap are existing together with in a series which uses an light absorbing material such as compound (1) or a discolouring agent such as compound (3), excess decomposition is controlled.
As a specific example of heat resistance antioxidant, for example, hydroquinone derivatives antioxidant such as 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone or hydroquinonemonoethylether;
alkylated phenol or phenol derivatives antioxidant such as
p-hydroxymethylbenzoate, p-hydroxyethylbenzoate, p-hydroxypropylbenzoate, bis(4-dihydroxyphenyl)sulfone, 2,2-bis(4-hydroxyphenyl)propane, 3,4-dihydroxy-4'-methyldiphenylsulfone, n-methylgallate, n-propylgallate, stearylgallate, laulylgallate, resolcinol, 1-oxy-3-methyl-4-isopropylbenzene, 2,6-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-sec-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl- a -dimethylamino-p-cresol, 2-(1-methylcyclohexyl)4,6-dimethylphenol, styrenated phenol or alkylated phenol;
phosphorus acid esters antioxidant such as
1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenylbutane, 4,4'-butylidenebis-(3-methyl-6-t-butylphenol), 2,2-thiobis(4'-hydroxy-3',5'-di-t-butylphenyl)phosphite, tris(mix mono and di-nonylphenyl)phosphite, phenyldiisodecylphosphite, diphenylmono(2-ethylhexyl)phoaphite, diphenylmonotridecylphosphite, diphenylisodecylphosphite, diphenylisooctylphosphite, diphenylisooctylphosphite, triphenylphosphite, tris(tridecyl)phosphate or tetraphenyldipropyleneglycolphosphite can be mentioned. These heat resistance antioxidants can be used alone or as a mixture of 2 or more.
Among these heat resistance antioxidants, p-hydroxymethylbenzoate, p-hydroxyethylbenzoate, bis(4-dihydroxyphenyl)sulfone, 2,2-bis(4-hydroxyphenyl)propane, 3,4-dihydroxy-4'-methyldiphenylsulfone, n-methylgallate, n-propylgallate, stearylgallate, laulylgallate or resolcinol are desirable, because these compounds are superior in transparency and whiteness.
Amount of heat resistance antioxidant as an anti fading agent to be used is 0.1-500 weight parts, desirably 0.5 to 100 weight parts to 1 weight part of photo absorbing material. When amount of heat resistance antioxidant is too small, preventing effect for colour fading is not sufficient and when amount is too much, colouring is obstructed and sensitivity is deteriorated.
As a specific example of above mentioned metal oxide, for example, MgO, Al2O3, SiO2, Na2O, SiO2·MgO, SiO2·Al2O3, Al2O3·Na2O·CO2 or MgO· Al2O3·CO2 can be mentioned. These compounds can be used alone or together with. Among these metal oxides, MgO, mixture of MgO and SiO2 or Al2O3, Na2O, SiO2·MgO, SiO2·Al2O3, Al2O3·Na2O·CO2 or MgO·Al2O3· CO2 are especially superior in anti fading ability and are desirably used.
Amount of metal oxide as an anti fading agent to be used is 0.1-500 weight parts, desirably 0.5 to 100 weight parts to 1 weight part of photo absorbing material. When amount of heat resistance antioxidant is too small preventing effect for fading is not sufficient and when amount is too much colouring is obstructed and sensitivity is deteriorated.
As a specific example of above mentioned metal soap, stearic acid salt such as lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, cadmium stearate or lead stearate, lauric acid salt such as cadmium laurate, calcium laurate or barium laurate, chlorostearic acid salt such as calcium chlorostearate, barium chlorostearate or cadmium chlorostearate, 2-ethylhexyl acid salt such as barium 2-ethylhexylate, zinc 2-ethylhexylate or lead 2-ethylhexylate, recinolic acid salt such as barium recinolate, zinc recinolate or cadmium recinolate, lead di-basic stearate such as 2PbO· Pb(C17H35COO)2; salicylate such as lead salicylate, tin salicylate, zinc salicylate or chrome salicylate; lead tri-basicsalicylate such as 3PbO· Pb(C4H35COO)2; lead tri-basic malate such as 3PbO·Pb(CH2O4)2; lead di-basic phthalate such as 2PbO·Pb(C8H35COO)2, lead di-basic phthalate can be mention. These metallic soap can be used alone or together with. In these mentioned metallic salt, zinc stearate, calcium stearate, magnesium stearate, calcium laurate, zinc salicylate, zinc recinolate, balium zinc recinolate or barium 2-ethylhexylate are desirable from a view point of whiteness.
Amount of metallic soap to be used is 0.1-500 weight parts, desirably 0.5 to 100 weight parts to 1 weight part of photo absorbing material. When amount of heat resistance antioxidant is too small preventing effect for fading is not sufficient and when amount is too much, colouring is obstructed and sensitivity is deteriorated.
As a specific example of an ultra violet ray absorbing agent, for example, benzophenones ultra violet ray absorbing agent such as
4-hydroxybensophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecylxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, salicylic acids ultra violet ray absorbing agent such as phenyl salicylate, p-t-butylphenylsalicilate or p-octylphenylsalicilate, triazoles ultra violet ray absorbing agent such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole <Tomisoap600>, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2'-[2'-hydroxy-3'-(3",4",5",6"-tetra hydrophthalimidemethyl)-5'-methylphenyl]benzotriazole, 2,2-methylene bis[4-(1,1,3,3-tetramwthylbutyl)-6-(2H-benzotriazole-2-yl)phenol <Adeca stabLA-31>, aqueous emulsion polymer ultra violet ray absorbing agents disclosed in JP 2001-150810 or benzooxadinones ultra violet ray absorbing agents can be mentioned, and these agents can be used alone or together with.
The reason why these ultra violet ray absorbing agents used in the present invention displays colour fading preventing function is not clear, however, it is conjectured as follows. That is, a photo absorbing material such as compound (1) lacks stability to natural light, and by adding an ultra violet absorbing agent together with, total integrated amount of light irradiated to the photo absorbing material is remarkably reduced and colour fading, accordingly deterioration of photo absorbing material is prevented.
Further, in general, since an electron donating leuco dye changes colour to yellowish by being exposed in the natural light, when the photo absorbing material is discoloured and ground part of paper becomes achromatic, said yellowish colour change deteriorates appearance of a product and becomes a ground to injure the impression. However, by adding above mentioned ultra violet ray absorbing agent, not only colour fading of photo absorbing material but also yellowish colour change of leuco dye is greatly prevented, and a good contrast can be obtained.
Among these mentioned ultra violet ray absorbing agent, compound having triazole structure is desirable, because said compound has high ultra violet ray absorbing ability and is superior in preventing ability of colour fading.
Blending amount of an ultra violet ray absorbing agent is 1-500 weight parts desirably 1-300 weight parts to 1 weight part of photo absorbing agent to be used. When the amount is too small, the preventing ability for colour fading is not sufficient and when the amount is too much, not only further improvement of preventing ability for colour fading can not be expected but also producing cost becomes higher.
Hindered amines photo stabilizing agent used in the present invention is used for the purpose to prevent remarkably deterioration of photo absorbing material and yellowish colour change of leuco dye by obstructing activity of excess radicals generated when exposed to natural light, especially it's effect is remarkable when used together with an ultra violet ray absorbing agent. The reason of above mentioned phenomenon is not clear, however, it is conjectured as follows. That is, an ultra violet ray absorbing agent absorbs ray of ultra violet region contained in natural light, and activity of radicals generated by ray of different region or by unabsorbed ultra violet ray is obstructed by a hindered amines photo stabilizing agent, and the hindered amines photo stabilizing agent is acting effectively to prevent discolouration of a photo absorbing material and to prevent yellowish colour change of leuco dye.
As a specific example of hindered amines photo stabilizing agent, for example, hindered amine compound such as polycondensated product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidil amino)hexane and dibromoethane, polycondensated product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidil amino) hexane and 2,4-dichloro-6-morpholino-s-triazine, polycondensated product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidil amino)hexane, polycondensated product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidilamino)hexane and 2,4-dichloro-6-tertiaryoctylamino2,4-s-triazine, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidilamino)-s-triazine-6-yl)-1,5,8,12-tetr aazadodecane, 1,5,8,12-tetra-tetraxis[2,4-bis(N-butyl-N-(1,2,2,6,6'-penta methyl-4-piperidilamino)-s-triazine-6-yl-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidil)amino)-s-triazine-6-yl aminoundecane, 1,6,11-tris[2,4bis(N-butyl-N-(2,2,6,6-pentamethyl-4-piperidil)amino)-s-triazine-6-ylaminoundecane can be mentioned. These compounds can be used alone or together with. Especially, (2,2,6,6-tetramethyl-4-piperidil/tridecyl)-1,2,3,4-butanetetracarboxylate and tetrakis(2,2,6,6- tetramethyl-4-piperidil)-1,2,3,4-butanetetracarboxylate are desirable.
Blending amount of a hindered amines photo stabilizing agent is 1-500 weight parts desirably 1-300 weight parts to 1 weight part of photo absorbing agent to be used, and is 0.1-50 weight parts desirably 0.1-10 weight parts to 1 weight part of ultra violet ray absorbing agent. When the amount is too small, the preventing ability for colour fading is not sufficient and when the amount is too much, colour developing ability may be obstructed.
As an electron donating leuco dye used in the present invention, any public known compound can be used. These compounds can be used alone or together with, and suitably selected along with the required quality or characteristics. As a specific example, following compounds can be mentioned, however, not intending to be limited to them.
3-(4-dimethylamino-2-methylphenyl)-3-(4-dimethylaminophenyl) phthalide,
3,3'-bis(2-4(-dimethylaminophenyl)-2-(4-methoxyphenyl)ethenyl)-4,5,6,7-tet rachlorophthalide <NIR-Black>,
3-diethylamino-6-chloro-7-(&bgr;-ethoxyethylamino)fluorane,
3-diethylamino-6-chloro-7-(&ggr;-chloropropylamino)fluorane,
Almost all leuco dyes mentioned above absorbs light of visible light region, further mainly absorbs light of wavelength smaller than 600nm. In the present invention, besides above mentioned leuco dye, the leuco dye which has the main wave length of absorption to the ray longer than 600nm is used. Especially, the leuco dye which indicates strong absorption to the wave length of 600-700nm is desirably used. As a specific example of said leuco dye, fluorane leuco dye and/or phthalide leuco dye are desirably used. As a fluorane leuco dye,
3-(N-p-tolyl-N-ethylamino)-(1'-N-ethyl-2',2',4'-trimethylpyridil)-[a] -fluorane <H-1046> can be mentioned. Further, as the phthalide leuco dye,
3,3-bis(2-(4-diethylaminophenyl)-2-(4-methoxyphenyl)ethenyl)4,5,6,7-tetrachlorophthalide <NIR-Black> can be mentioned.
As an electron accepting colour developing agent used in the present invention, inorganic acidity compound such as activated clay, attapulgite, colloidal silica or aluminum silicate,
bis-(4-hydroxy-2,5-dimethylphenyl)sulfide or
&agr;,&agr;'-bis-(3-methyl-4-hydroxyphenyl)-m-diisopropylbenzophenone or
&agr;,&agr;',&agr;"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene,
4,4' -thiobis(6-t-butyl-m-cresol),
complex zinc salt of terephtalicaldehyde acid with other organic carboxylic acid can be mentioned. These compounds can be used alone or can be used together with. In particular, among these compounds, bishydroxyphenylsulfones such as bis(4-hydroxyphenyl)sulfone <bisphenol S> or 4-hydroxyphenylarylsulfones such as 4-hydroxy-4'-isopropoxy dipehnylsulfone are desirable.
can be mentioned. Ordinary, 0.1 to 10 weight parts of these mentioned sensitizers is used to 1 weight part of an electron donating leuco dye.
can be mentioned. Ordinary, 0.1 to 10 weight parts of these mentioned preserving sensitizers is used to 1 weight part of electron donating leuco dye.
As a specific example of a binder used in the present invention, water soluble binder such as starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinylalcohol, denatured polyvinyl alcohol by carboxyl, denatured polyvinyl alcohol by acetoacetyl group, denatured polyvinyl alcohol by silicon, alkaline salt of isobutylene-maleic anhydride copolymer, alkaline salt of styrene-maleic anhydride copolymer, alkaline salt of ethylene-maleic anhydride copolymer or alkaline salt of styrene-acrylic acid copolymer, latexes such as styrene-butadiene copolymer or acrylonitrile-butadiene copolymer, water dispersible binder such as urea resin, melamine resin, amide resin or polyurethane resin can be mentioned. At least one kind of these mentioned binder is used by 15-80 weight % to the total solid weight in a thermally sensitive layer, an over coat layer, an intermediate layer, an undercoat layer and a back coat layer.
As a substrate used for the thermally sensitive recording medium of the present invention, paper such as wood free paper, middle grade paper, recycled paper or coated paper can be mainly used, however, various non-woven cloth, plastic film, synthetic paper metal foil or a complex sheet combining these sheets can be also suitably used.
Furthermore, it is possible to form an over coat layer composed of polymer compound over the thermally sensitive recording layer for the purpose to improve the preserving property, and an under coat layer composed of polymer compound containing a filler under the thermally sensitive recording layer for the purpose to improve the colour developing sensitivity. It is also possible to form an intermediate layer between the thermally sensitive recording layer and the over coat layer.
The thermally sensitive recording medium of the present invention can be prepared according to the conventional well-known method using various materials mentioned above. Regarding the method for preparation of a coating for each layers of the thermally sensitive recording material is not restricted, and generally can be prepared by mixing and stirring photo absorbing material, electron donating leuco dye, electron receiving colour developing agent, additionally, binder and filler and slipping agent which are added when the need is arisen, using water as a dispersing medium. As the method to prepare an aqueous coating using leuco dye and a colour developing agent, following methods can be mentioned. The method to pulverize leuco dye and a colour developing agent separately using a sand grinder, an attriter or a ball mill and disperse them in water then mixing together, or the method to prepare micro capsules in which leuco dye or a colour developing agent is immobilized then obtain aqueous coating are well-known. The ratio of using amount of leuco dye and a colour developing agent is suitably selected according to the kind of leuco dye and a colour developing agent and is not particularly restricted, however, 1-50 weight parts, desirably 0.1-10 weight parts of colour developing agent is used to 1 weight part of leuco dye.
Regarding a photo absorbing material, in the present invention, even if the using amount is small, specifically less than 0.1 weight parts to 1 weight part of leuco dye, excellent colour developing ability can be obtained. Especially; approximately 0.01-0.08 weight parts is desirable. To total solid part of thermally sensitive recording layer, using amount of a photo absorbing material is 0.5-5 weight % desirably 0.05-3 weight %. A discolouring agent is used about 0.01-3 weight parts, desirably 0.05-10 weight parts to 1 weight part of photo absorbing material. In the present invention, when the photo absorbing material is used together with a sensitizer by previously dispersed, dissolved or fused, the photo absorbing property can be enhanced, therefore said method is effective. Further, it is desirable that the photo absorbing material is pulverized to fine particles smaller than 3 µm of average particle size after dispersed or mixed with a sensitizer. As a sensitizer, same ones used in the thermally sensitive recording layer can be used.
It is desirable to pulverize a near-infrared ray absorbing agent and colour developing materials (leuco dye, colour developing agent, sensitizer) to fine particles whose average particle size is not to exceed 3 µm. The reason why is thought as follows. That is, by pulverizing materials finer, the dot size of colour developed printed part becomes same size to the size of spot of laser ray, which is ray source, and forms uniform dots, and clear printing or a line drawing suited for the readout by a scanner are obtained.
The method for forming of each layer of thermally sensitive recording layer is not restricted and methods such as air knife coating, Valiber blade coating, pure blade coating, rod blade coating, short dwell coating, curtain coating or die coating can be voluntarily selected. For example, a coating for thermally sensitive recording layer is coated on a substrate and dried, then a coating for over coat layer is coated over the thermally sensitive recording layer and dried. Further, the coating amount of the coating for thermally sensitive recording layer is approximately 2-12g/m2, desirably 3-10g/m2 by dry weight and, the coating amount of the coating for under coat layer, intermediate layer or over coat layer is approximately 0.1-15g/m2, desirably 0.5-10g/m2 by dry weight.
Furthermore, the thermally sensitive recording medium of the present invention is possible to provide a back coat layer at the reverse side of the substrate so as to improve the preservability more. Still further, after each layer is formed, it is possible carry out the smoothing treatment such as super calendaring.
And the process for discolouring is carried out by irradiating light to whole surface after image recording. Wavelength of said light to be irradiated is preferably visible light of 600nm or near-infrared ray of 800nm. Further, it is desirable to carry out heat treatment of level which does not develop colour at same time, because by said heat treatment, discolouring is accelerated.
The present invention will be illustrated more specifically according to the Examples and the Comparative Examples, however, not intended to be limited by them. In the Examples and the Comparative Examples, "parts" and "%" indicate "weight parts" and "weight %".
To the laser recording thermally sensitive recording media obtained in Examples 1-18 and Comparative Example 1-2, recording by laser is carried out using dry plotter-GX-3700 (wavelength 830nm), which is a product of Matsushita Electric Works Graphic Printing Ltd., and the colour density of the printed part and the background colour part are measured by Macbeth densitometer RD-19.
After that, whole surface is irradiated by a visible light lamp of 600nm wavelength, so as to deactivate the photo absorbing material and to make achromatic (discolour) and the colour density of background colour part is measured by Macbeth densitometer RD-19.
Further, readability when readout by a scanner (readout wavelength is 630nm) is indicated as,
○: can be readout well
×: accuracy for readout is bad (or can not be readout)
Further, after the laser recording thermally sensitive recording medium is discoloured, laser recording process is carried out again, and a preventing ability for forgery ("addition of a postscript is impossible" is good) is indicated as,
○: not develop colour, addition of a postscript is impossible
&Dgr;: slightly develops colour
×: develops colour and a postscript is possible
Example 1 A solution (Dispersion of colour developing agent)
4-hydroxy-4'-isopropoxydephenylsulfone < D-8> 6.0 parts 10% aqueous solution of polyvinylalcohol 20.0 parts water 10.0 parts
Mixture of above mentioned components is ground to average particle size of 1 µm using a sand grinder.
B solution (Dispersion of photo absorbing material)
Photo absorbing agent represented by following structural formula (1)
<product of Showa Denko Co., Ltd., IR2MF> 0.3 parts 1,2-bis(phenoxymethyl)benzene <PMB-2> 5.0 parts 10% aqueous solution of polyvinylalcohol 10.0 parts water 6.0 parts
Mixture of above mentioned components is ground to average particle size of 1 µ m using a sand grinder.
C solution (dispersion of discolouring agent)
Discolouring agent represented by following structural formula (2)
<product of Showa Denko Co., P3B> 0.3 parts 1,2-bis(phenoxymethyl)benzene <PMB-2> 5.0 parts 10% aqueous solution of polyvinylalcohol 10.0 parts water 6.0 parts
D solution (Dispersion of dye)
3-dibutylamino-6-methyl-7-anilino fluorane <OBD-2> 3.0 parts 10% aqueous solution of polyvinylalcohol 5.0 parts water 2.0 parts
A solution 40.0 parts B solution 5.0 parts C solution 10.0 parts D solution 10.0 parts 30% silica dispersion 30.0 parts
The obtained coating is coated on one surface of 60g/m2 paper so as the coating amount to be 7.0g/m2 and dried, and the laser recording thermally sensitive recording medium is prepared (in a thermally sensitive recording layer, using amount of photo absorbing material is 0.02 parts to 1 part of leuco dye).
By the same process as Example 1 except changing the discolouring agent of Example 1 to following discolouring agent represented by following structural formula, a laser recording thermally sensitive recording medium is obtained. <product of Showa Denko Co., Ltd., BP3B>
By the same process as Example 1 except changing the discolouring agent of Example 1 to following discolouring agent represented by following structural formula, a laser recording thermally sensitive recording medium is obtained. <product of Showa Denko Co., Ltd., N3B>
By the same process as Example 1 except not using C solution (discolouring agent), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 1 except changing the photo absorbing material of Example 1 to following photo absorbing material represented by following structural formula, a laser recording thermally sensitive recording medium is obtained. <product of Showa Denko Co., Ltd., IR13F>
By the same process as Example 2 except changing the photo absorbing material of Example 2 to IR13F (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 3 except changing the photo absorbing material of Example 3 to IR13F (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 4 except changing the photo absorbing material of Example 1 to IR13F (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 1 except changing the photo absorbing material of Example 1 to following photo absorbing material represented by following structural formula, a laser recording thermally sensitive recording medium is obtained. <product of Showa Denko Co., Ltd. IRB>
By the same process as Example 2 except changing the photo absorbing material of Example 2 to IRB (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 3 except changing the photo absorbing material of Example 3 to IRB (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 4 except changing the photo absorbing material of Example 4 to IRB (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 1 except changing the photo absorbing material of Example 1 to following photo absorbing material represented by following structural formula, a laser recording thermally sensitive recording medium is obtained. <product of Showa Denko Co., Ltd. IRT>
By the same process as Example 2 except changing the photo absorbing material of Example 2 to IRT (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 3 except changing the photo absorbing material of Example 3 to IRT (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 4 except changing the photo absorbing material of Example 4 to IRT (product of Showa Denko Co., Ltd.), a laser recording thermally sensitive recording medium is obtained.
Besides A, B, C and D solutions of Example 1, E solution is prepared.
E solution (Dispersion of leuco dye which absorbs light of 600-700nm wavelength)
3,3-bis(4-diethylamino-2-ethoxyphenol)-4-azaphthalide <GN-2> 1.0 part 10% aqueous solution of polyvinylalcohol 5.0 parts water 2.0 parts
A solution 40.0 parts B solution 5.0 parts C solution 10.0 parts D solution 10.0 parts E solution 10.0 parts 30% silica dispersion 30.0 parts
The obtained coating is coated on one surface of 60g/m2 paper so as the coating amount to be 7.0g/m2 and dried, and the laser recording thermally sensitive recording medium is prepared.
On the laser recording thermally sensitive recording medium obtained in Example 1 laser recording is carried out and by the same method as Example 1 except using an ultra violet ray lamp of wavelength 360nm at discolouration process, evaluation test is carried out.
By the same process as Example 1 except changing the photo absorbing material of Example 1 to CY-20 (product of Nihon Kayaku Co., Ltd., cyanine photo absorbing material), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 1 except changing the photo absorbing material of Example 1 to NK-6288 (product of Hayashi Protist Chemical Laboratory, cyanine photo absorbing material), a laser recording thermally sensitive recording medium is obtained.
Photo absorbing materials and discolouring agents used in above Examples and Comparative Examples are summarized in Table 3 and results are summarized in Table 4.
Photo absorbing material Discolouring agent
Example 1 IR2MF P3B Example 2 IR2MF BP3B Example 3 IR2MF N3B Example 4 Reference IR2MF - Example 5 IR13F P3B Example 6 IR13F BP3B Example 7 IR13F N3B Example 8 Reference IR13F - Example 9 IRB P3B Example 10 IRB BP3B Example 11 IRB N3B Example 12 Reference IRB - Example 13 IRT P3B Example 14 IRT BP3B Example 15 IRT N3B Example 16 Reference IRT - Example 17 IR2MF P3B Example 18 IR2MF P3B Comparative Example 1 CY-20 P3B Comparative Example 2 NK-6288 P3B
Machbeth density before discolouring background colour part scanner readout preventing ability for forgery image part background colour part
Example 1 1.48 0.08 0.18 ○ ○ Example 2 1.45 0.09 0.18 ○ ○ Example 3 1.44 0.08 0.17 ○ ○ Example 4 Reference 1.49 0.15 0.21 ○ ○ Example 5 1.45 0.07 0.20 ○ ○ Example 6 1.42 0.08 0.19 ○ ○ Example 7 1.46 0.08 0.19 ○ ○ Example 8 Reference 1.48 0.16 0.22 ○ ○ Example 9 1.53 0.07 0.17 ○ ○ Example 10 1.51 0.07 0.16 ○ ○ Example 11 1.50 0.08 0.17 ○ ○ Example 12 Reference 1.55 0.13 0.19 ○ ○ Example 13 1.50 0.09 0.18 ○ ○ Example 14 1.49 0.08 0.18 ○ ○ Example 15 1.52 0.08 0.19 ○ ○ Example 16 Reference 1.48 0.14 0.21 ○ ○ Example 17 1.45 0.08 0.16 ○ ○ Example 18 1.48 0.13 0.18 ○ ○ Comparative Example 1 0.72 0.18 0.22 × &Dgr; Comparative Example 2 1.41 0.26 0.26 × ×
Examples 19-36 and Comparative Examples 3-5 are indicating laser recording thermally sensitive recording media in a thermally sensitive layer of which, a photo absorbing material and an anti fading agent are contained together with.
As evaluation test, to the laser recording thermally sensitive recording media obtained in Examples 19-36 and Comparative Example 3-5, recording by laser is carried out using dry plotter-GX-3700 (wavelength 830nm), which is a product of Matsushita Electric Works Graphic Printing Ltd., and the colour density of the printed part and the background colour part are measured by Macbeth densitometer RD-19.
not develop colour, addition of a postscript is impossible
slightly develops colour
develops colour and a postscript is possible
Then, for the evaluation of light resistance stability during preservation of the medium in the state to be exposed in natural light (room light such as fluorescent lamp or sun light), the laser recording thermally sensitive recording media obtained in Examples 19-36 and Comparative Example 3-5 are left for 24 hours exposing to a fluorescent lamp of 5000 Lx, then recording by laser is carried out on each specimen using a dry plotter-GX-3700 (wavelength 830nm), which is a product of Matsushita Electric Works Graphic Printing Ltd., and the colour density of the printed part and the background colour part are measured by Macbeth densitometer RD-19. Light resistance stability by exposing to natural light is indicated as,
fading of background colour part is not observed and has good colour developing ability
although background colour part is slightly faded, has good colour develop ability
does not develop colour and actual use is impossible
Example 19 A solution (Dispersion of colour developing agent)
<product of Showa Denko Co., Ltd., IR2MF> 0.3 parts 1,2-bis(phenoxymethyl)benzene <PMB-2> 5.0 parts 10°/ aqueous solution of polyvinylalcohol 10.0 parts water 6.0 parts
F solution (dispersion of heat resistance antioxidant)
2,2-bis(4-hydroxyphenyl)propane 6.0 parts 10% aqueous solution of polyvinylalcohol 20.0 parts water 10.0 parts
A solution 40.0 parts B solution 5.0 parts C solution 10.0 parts D solution 10.0 parts F solution 6.0 parts 30% silica dispersion 30.0 parts
By the same process as Example 19 except changing the discolouring agent of Example 19 to following discolouring agent represented by following structural formula, <product of Showa Denko Co., Ltd., BP3B>
and changing heat resistance antioxidant to 3,4-dihydroxypehnyl-p-tolyl sulfone, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except changing the discolouring agent of Example 19 to following discolouring agent represented by following structural formula, <product of Showa Denko Co., Ltd., N3B>
and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of MgO, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except not using C solution (discolouring agent) and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of zinc stearate, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except changing the photo absorbing material of Example 19 to following photo absorbing material represented by following structural formula, <product of Showa Denko Co., Ltd., IR13F>
and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of zinc stearate, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 20 except changing the photo absorbing material of Example 20 to IR13F and changing a heat resistance antioxidant to 2,2-bis(4-hydroxyphenyl)propane, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 21 except changing the photo absorbing material of Example 21 to IR13F and changing a heat resistance antioxidant to 3,4-dihydroxyphenyl-p-tolyl sulfone, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 22 except changing the photo absorbing material of Example 22 to IR13F and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of MgO, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except changing the photo absorbing material of Example 19 to following photo absorbing material represented by following structural formula, <product of Showa Denko Co., Ltd. IRB>
By the same process as Example 20 except changing the photo absorbing material of Example 20 to IRB and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of zinc stearate, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 20 except changing the photo absorbing material of Example 20 to IRB and changing a heat resistance antioxidant to 2,2-bis(4-hydroxyphenyl)propane, a laser recording thermally sensitive recording medium is obtained.
Example 30 (Reference)
By the same process as Example 22 except changing the photo absorbing material of Example 22 to IRB and changing a heat resistance antioxidant to 3,4-dihydroxyphenyl-p-tolyl sulfone, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except changing the photo absorbing material of Example 19 to following photo absorbing material represented by following structural formula, <product of Showa Denko Co., Ltd. IRT>
and changing a heat resistance antioxidant to 3,4-dihydroxyphenyl-p-tolyl sulfone, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 20 except changing the photo absorbing material of Example 20 to IRT, and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of MgO, a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 21 except changing the photo absorbing material of Example 20 to IRT, and changing F solution (dispersion of heat resistance antioxidant) to 20% dispersion of zinc stearate, a laser recording thermally sensitive recording medium is obtained.
Example 34 (Reference)
By the same process as Example 22 except changing the photo absorbing material of Example 20 to IRT, and changing a heat resistance antioxidant to 2,2-bis(4-hydroxyphenyl)propane, a laser recording thermally sensitive recording medium is obtained.
Besides A, B, C, D and F solutions of Example 19, G solution is prepared. G solution (Dispersion of leuco dye which absorbs light of 600-700nm wavelength)
A solution 40.0 parts B solution 5.0 parts C solution 10.0 parts D solution 10.0 parts F solution 6.0 parts G solution 10.0 parts 30% silica dispersion 30.0 parts
On the laser recording thermally sensitive recording medium obtained in Example 19 laser recording is carried out and by the same method as Example 19 except using an ultra violet ray lamp of wavelength 360nm at discolouration process, evaluation test is carried out.
By the same process as Example 19 except changing the photo absorbing material of Example 19 to CY-20 (cyanine photo absorbing material), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except changing the photo absorbing material of Example 19 to NK-6288 (cyanine photo absorbing material), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 19 except not using F solution (dispersion of heat resistance antioxidant), a laser recording thermally sensitive recording medium is obtained.
Photo absorbing materials, discolouring agents and an anti fading agent used in above Examples and Comparative Examples are summarized in Table 5 and results are summarized in Table 6.
Photo absorbing material Discoloring agent Anti fading agent
Example 19 IR2MF P3B 2,2-bis(4-hydroxyphenyl)propane Example 20 IR2MF BP3B 3,4-dihydroxyphenyl-p-tolylsulfone Example 21 IR2MF N3B MgO Example 22 Reference IR2MF - zinc stearate Example 23 IR13F P3B zinc stearate Example 24 IR13F BP3B 2,2-bis(4-hydroxyphenyl)propane Example 25 IR13F N3B 3,4-dihydroxyphenyl-p-tolylsulfone Example 26 Reference IR13F - MgO Example 27 IRB P3B MgO Example 28 IRB BP3B zinc stearate Example 29 IRB N3B 2,2-bis(4-hydroxyphenyl)propane Example 30 Reference IRB - 3,4-dihydroxyphenyl-p-tolylsulfone Example 31 IRT P3B 3,4-dihydroxyphenyl-p-tolylsulfone Example 32 IRT BP3B 3,4-dihydroxyphenyl-p-tolylsulfone Example 33 IRT N3B MgO Example 34 Reference IRT - zinc stearate Example 35 IR2MF P3B 2,2-bis(4-hydroxyphenyl)propane Example 36 IR2MF P3B 2,2-bis(4-hydroxyphenyl)propane Comparative Example 3 CY-20 P3B 2,2-bis(4-hydroxyphenyl)propane Comparative Example 4 NK-6288 P3B 2,2-bis(4-hydroxyphenyl)propane Comparative Example 5 IR2ME P3B -
Machbeth density before discoloring background colour part scanner readout preventing ability for forgery light resistance stability image part background colour part
Exp.19 1.47 0.08 0.17 ○ ○ ○ Exp.20 1.44 0.88 0.19 ○ ○ ○ Exp.21 1.45 0.09 0.16 ○ ○ ○ Exp.22 Reference 1.50 0.14 0.20 ○ ○ ○ Exp.23 1.44 0.08 0.21 ○ ○ ○ Exp.24 1.45 0.08 0.18 ○ ○ ○ Exp.25 1.44 0.08 0.17 ○ ○ ○ Exp.26 Reference 1.45 0.17 0.22 ○ ○ ○ Exp.27 1.53 0.07 0.16 ○ ○ ○ Exp.28 1.50 0.08 0.17 ○ ○ ○ Exp.29 1.53 0.08 0.17 ○ ○ ○ Exp.30 Reference 1.52 0.12 0.20 ○ ○ ○ Exp.31 1.49 0.09 0.18 ○ ○ ○ Exp.32 1.46 0.08 0.17 ○ ○ ○ Exp.33 1.53 0.08 0.20 ○ ○ ○ Exp.34 Reference 1.48 0.14 0.21 ○ ○ ○ Exp.35 1.47 0.08 0.15 ○ ○ ○ Exp.36 1.48 0.14 0.18 ○ ○ ○ Co. Exp. 3 0.70 0.19 0.23 × &Dgr; &Dgr; Co. Exp. 4 1.43 0.28 0.28 × × ○ Co. Exp. 5 1.45 0.08 0.19 ○ ○ ×
Examples 37-54 and Comparative Examples 6-8 are indicating cases of laser recording thermally sensitive recording media in a thermally sensitive layer of which, a photo absorbing material and an ultra violet ray absorbing agent, or an ultra violet ray absorbing agent and a hindered amine photo stabilizing agent are contained together with.
Evaluation tests are same as Examples 19-35 and Comparative Examples 3-5.
A solution (dispersion of colour developing agent), B solution (dispersion of photo absorbing agent IR2MF), C solution (dispersion of discolouring agent P3B) and D solution (dispersion of dye) are prepared by same process of Example 19, and as a dispersion of ultra violet ray absorbing agent, following H solution is prepared.
H solution (Dispersion of ultra violet ray absorbing agent)
2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phen ol] <Adekastab LA-31> 3.0 part 10% aqueous solution of polyvinylalcohol 6.0 parts water 6.0 parts
I solution (dispersion of hindered amines photo stabilizing agent)
hindered amine photo stabilizing agent represented by following structural formula (8)
<Adekastab LA-31> 3.0 parts 10% aqueous solution of polyvinylalcohol 6.0 parts water 6.0 parts
Mixture of above mentioned components is ground to average particle size of 1 µm using a sand grinder. Then above mentioned dispersions are mixed by the following ratio and a coating is obtained.
A solution 40.0 parts B solution 5.0 parts C solution 10.0 parts D solution 10.0 parts H solution 10.0 parts I solution 10.0 parts 30% silica dispersion 30.0 parts
The obtained coating is coated on one surface of 60g/m2 paper so as the coating amount to be 7.0g/m2 and dried, and the laser recording thermally sensitive recording medium is prepared (in thermally sensitive recording layer, amount of photo absorbing agent is 0.02parts to 1 part of leuco dye).
By the same process as Example 37 except changing the discolouring agent used in Example 37 (BP3B; product of Showa Denko) to 2-(2'-hydroxy-3' -t-butyl-5'-methylphenyl)-5-chlorobenzotriazol <Tomisoap 600> which is ultra violet absorbing agent and not using hindered amines photo stabilizing agent, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 37 except changing the discolouring agent used in Example 37 (BP3B; product of Showa Denko) to aqueous emulsion of polymer ultra violet ray absorbing agent (30% shortened to UVA1) disclosed in JP2001-150810 publication, a laser recording thermally sensitive recording medium is prepared.
Example 40 (Reference)
By the same process as Example 38 except not using C solution (discolouring agent) of Example 38 and changing ultra violet ray absorbing agent to 2,2'-p-phenylenebis(4H-3,1-benzooxadine-4-on) (shortened to UVA2), a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 37 except changing the photo absorbing agent to the photo absorbing material (IR13F; product of Showa Denko) used in Example 37, changing ultra violet ray absorbing agent to 2,2'-p-phenylenebis(4H-3,1-benzooxadine-4-on) and not using hindered amines photo stabilizing agent, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 38 except changing the photo absorbing agent to IR13F, which is a product of Showa Denko, changing ultra violet ray absorbing agent to 2,2-methylenebis[4-(1,1,3,3-tetrabutyl)-6-(2H-benzotriazole-2-yl)phenol] <Adekastab LA-31>, and changing hindered amines photo stabilizing agent of I solution to 10 parts of hindered amine photo stabilizing agent represented by structural formula (9), <Adekastab LA-57>
a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 39 except changing the photo absorbing agent of Example 39 to IR13F, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazol <Tomisoap 600>, a laser recording thermally sensitive recording medium is prepared.
Example 44 (Reference)
By the same process as Example 40 except changing the photo absorbing agent of Example 40 to IR13F, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to aqueous emulsion of polymer ultra violet ray absorbing agent (30%) disclosed in JP2001-150810 publication, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 37 except changing the photo absorbing agent of Example 37 to the photo absorbing agent used in Example 37 (IRB; a product of Showa Denko), changing ultra violet ray absorbing agent to aqueous emulsion of polymer ultra violet ray absorbing agent (30%) disclosed in JP2001-150810 publication and not using hindered amines photo stabilizing agent, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 38 except changing the photo absorbing agent of Example 38 to IRB, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to 2,2'-p-phenylenebis(4H-3,1-benzooxadine-4-on), a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 39 except changing the photo absorbing agent to IRB, which is a product of Showa Denko, changing ultra violet ray absorbing agent to 2,2-methylenebis[4-(1,1,3,3-tetrabutyl)-6-(2H-benzotriazole-2-yl)phenol] <Adekastab LA-31>, and changing hindered amines photo stabilizing agent of I solution to 10 parts of hindered amine photo stabilizing agent represented by structural formula (10), <Adekastab LA-67>
Example 48 (Reference)
By the same process as Example 40 except changing the photo absorbing agent of Example 40 to IRB, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazol <Tomisoap 600>, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 37 except changing the photo absorbing agent of Example 40 to the photo absorbing agent used in Example 13 (IRT; a product of Showa Denko), which is a product of Showa Denko, changing ultra violet ray absorbing agent to 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazol <Tomisoap 600> and not using hindered amines photo stabilizing agent, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 38 except changing the photo absorbing agent of Example 38 to IRT, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to aqueous emulsion of polymer ultra violet ray absorbing agent (30%) disclosed in JP2001-150810 publication, a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 39 except changing the photo absorbing agent of Example 39 to IRT, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to dispersion of 2,2'-p-phenylene bis(4H- 3,1-benzooxadine-4-on) (UVA2), a laser recording thermally sensitive recording medium is prepared.
Example 52 (Reference)
By the same process as Example 40 except changing the photo absorbing agent of Example 40 to IRT, which is a product of Showa Denko, and changing ultra violet ray absorbing agent to 2,2-methylenebis[4-(1,1,3,3 -tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] <Adekastab LA-31> and adding 10 parts of hindered amine photo stabilizing agent of I solution, a laser recording thermally sensitive recording medium is prepared.
Besides A, B, C, D, H and I solutions, J solution is prepared. J solution (Dispersion of leuco dye which absorbs light of 600-700nm wavelength)
3,3-bis(4-diethylamino-2-ethoxyphenyl-4-azaphthalide <GN-2> 1.0 part 10% aqueous solution of polyvinylalcohol 5.0 parts water 2.0 parts
A solution 40.0 parts B solution 5.0 parts C solution 10.0 parts D solution 10.0 parts H solution 10.0 parts I solution 10.0 parts J solution 10.0 parts 30% silica dispersion 30.0 parts
The obtained coating is coated on one surface of 60g/m2 paper so as the coating amount to be 7.0g/m2 and dried, and a laser recording thermally sensitive recording medium is prepared.
On the laser recording thermally sensitive recording medium obtained in Example 37 laser recording is carried out and by the same method as Example 37 except using an ultra violet ray lamp of wavelength 360nm at discolouration process, evaluation test is carried out.
By the same process as Example 37 except changing photo absorbing material of Example 37 to CY-20 (cyanine photo absorbing material), which is a product of Nihon Kayaku Co., Ltd., a laser recording thermally sensitive recording medium is prepared.
By the same process as Example 37 except changing the photo absorbing material of Example 37 to NK-6288 (product of Hayashi Protist Chemical Laboratory, cyanine photo absorbing material), a laser recording thermally sensitive recording medium is obtained.
By the same process as Example 37 except not using H solution (ultra violet ray absorbing agent) and I solution (hindered amine photo stabilizing agent), a laser recording thermally sensitive recording medium is obtained.
Photo absorbing materials, discolouring agents, ultra violet ray absorbing agent and an hindered amine photo stabilizing agent used in above Examples and Comparative Examples are summarized in Table 7 and results are summarized in Table 8.
photo absorbing material discoloring agent ultraviolet ray absorbing agent hindered amine photo stabilizing agent
Example 37 IR2MF P3B Adekastab LA-31 Adekastab LA-52 Example 38 IR2MF BP3B Tomi soap 600 - Example 39 IR2MF N3B UVA1 - Example 40 Reference IR2MF - UVA2 - Example 41 IR13F P3B UVA2 - Example 42 IR13F BP3B Adekastab LA-31 Adekastab LA-57 Example 43 IR13F N3B Tomi soap 600 - Example 44 Reference IR13F - UVA1 - Example 45 IRB P3B UVA1 - Example 46 IRB BP3B UVA2 - Example 47 IRB N3B Adekastab LA-31 Adekastab LA-67 Example 48 Reference IRB - Tomi soap 600 - Example 49 IRT P3B Tomi soap 600 - Example 50 IRT BP3B UVA1 - Example 51 IRT N3B UVA2 - Example 52 Reference IRT - Adekastab LA-31 Adekastab LA-52 Example 53 IR2MF P3B Adekastab LA-31 Adekastab LA-52 Example 54 IR2MF P3B Adekastab LA-31 Adekastab LA-52 Co. Example 6 CY-20 P3B Adekastab LA-31 Adekastab LA-52 Co. Example 7 NK-6288 P3B Adekastab LA-31 Adekastab LA-52 Co. Example 8 IR2ME P3B - -
UVA1: aqueous emulsion polymer ultra violet ray absorbing agents disclosed in JP 2001-150810
UVA2: 2,2'-p-phenylenebis(4H-3,1-benzooxadine-4-on)
Machbeth density (before discoloring) ground color part scanner readout preventing ability for forgery light resistance stability image part ground color part
Example 37 1.48 0.08 0.17 ○ ○ ⊚ Example 38 1.45 0.08 0.18 ○ ○ ○ Example 39 1.47 0.08 0.16 ○ ○ ○ Example 40 Reference 1.50 0.15 0.19 ○ ○ ○ Example 41 1.46 0.08 0.20 ○ ○ ○ Example 42 1.45 0.09 0.18 ○ ○ ⊚ Example 43 1.46 0.08 0.18 ○ ○ ○ Example 44 Reference 1.46 0.16 0.21 ○ ○ ○ Example 45 1.51 0.07 0.17 ○ ○ ○ Example 46 1.52 0.08 0.18 ○ ○ ○ Example 47 1.53 0.08 0.16 ○ ○ ⊚ Example 48 Reference 1.50 0.13 0.19 ○ ○ ○ Example 49 1.47 0.08 0.19 ○ ○ ○ Example 50 1.46 0.09 0.17 ○ ○ ○ Example 51 1.51 0.08 0.21 ○ ○ ○ Example 52 Reference 1.48 0.15 0.21 ○ ○ ⊚ Example 53 1.47 0.09 0.16 ○ ○ ⊚ Example 54 1.48 0.16 0.19 ○ ○ ⊚ Co. Example 6 0.72 0.20 0.24 × &Dgr; &Dgr; Co. Example 7 1.45 0.27 0.28 × × ○ Co. Example 8 1.45 0.08 0.19 ○ ○ ×
Wärmeempfindliches Aufzeichnungsmedium für die Laser-Aufzeichnung, umfassend eine wärmeempfindliche Aufzeichnungsschicht, die mindestens ein photoabsorbierendes Material, das Laser-Licht absorbiert und das Laser-Licht in Wärme umwandelt, einen elektronenspendenden Leukofarbstoff und ein elektronenaufnehmendes Farbentwicklungsmittel auf einem Substrat als Hauptkomponenten umfasst, wobei es sich beim photoabsorbierenden Material um eine Verbindung der allgemeinen Formel (1) handelt wobei n eine ganze Zahl mit einem Wert von 1 bis 4 ist und Xn, Yn und Zn- die in Tabelle 1 angegebenen Bedeutungen haben
Xn N(C2H5)2 N(C2H5)2 N(CH5)2 N(C2H5)2 Yn N(C2H5)2 N(C2H5)2 H OCH3 Zn - CF3SO3 - CF3SO3 -
wobei das wärmeempfindliche Aufzeichnungsmedium für die Laser-Aufzeichnung ferner eine Verbindung der Formel (2) als Entfärbungsmittel umfasst wobei R1, R2, R3 und R4 jeweils unabhängig voneinander ausgewählt sind aus einer Alkylgruppe, Arylgruppe, Allylgruppe, Aralkylgruppe, Alkenylgruppe, Alkinylgruppe, Silylgruppe, heterocyclischen Gruppe, substituierten Alkylgruppe, substituierten Arylgruppe, substituierten Allylgruppe, substituierten Aralkylgruppe, substituierten Alkenylgruppe, substituierten Alkinylgruppe und substituierten Silylgruppe; und mindestens einer der Reste R1, R2, R3 und R4 eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen bedeutet; R5, R6, R7 und R8 jeweils unabhängig voneinander ausgewählt sind aus einem Wasserstoffatom, einer Alkylgruppe, Arylgruppe, Allylgruppe, Aralkylgruppe, Alkenylgruppe, Alkinylgruppe, heterocyclischen Gruppe, substituierten,Alkylgruppe, substituierten Arylgruppe, substituierten Allylgruppe, substituierten Aralkylgruppe, substituierten Alkenylgruppe und substituierten Alkinylgruppe. Wärmeempfindliches Aufzeichnungsmedium für die Laser-Aufzeichnung nach Anspruch 1, wobei es sich beim Entfärbungsmittel um eine verbindung der Formel (3) handelt wobei m eine ganze Zahl mit einem Wert von 1 bis 3 ist und Strukturformeln von Zm- in Tabelle 2 aufgeführt sind.
Wärmeempfindliches Aufzeichnungsmedium für die Laser-Aüfzeichnung nach Anspruch 1 oder 2, ferner umfassend einen der Bestandteile ① bis ③: ① ein Mittel gegen Verblassung, ② ein UV-Strahlen absorbierendes Mittel und ③ ein UV-Strahlen absorbierendes Mittel und ein Photostabilisierungsmittel auf der Basis eines sterisch gehinderten Amins, bei dem es sich um ein Antioxidationsmittel handelt. Wärmeempfindliches Aufzeichnungsmedium für die Laser-Aufzeichnung nach Anspruch 3, wobei es sich beim Mittel gegen Verblassen um mindestens eine Verbindung handelt, die aus der Gruppe Wärmeresistenz-Antioxidationsmittel, Metalloxid oder Metallseife ausgewählt ist. Wärmeempfindliches Aufzeichnungsmedium für die Laser-Aufzeichnung nach Anspruch 3, wobei es sich beim UV-Strahlen absorbierenden Mittel um ein UV-Strahlen absorbierendes Mittel auf der Basis von Benzotriazol handelt. Verfahren zur Verwendung des wärmeempfindlichen Aufzeichnungsmediums für die Laser-Aufzeichnung nach einem der Ansprüche 1 bis 5, umfassend die Durchführung einer Laser-Aufzeichnung auf dem wärmeempfindlichen Aufzeichnungsmedium für die Laser-Aufzeichnung, anschließend das Bestrahlen mit Licht mit einem Niveau, das keine Farbentwicklung der wärmeempfindlichen Aufzeichnungsschicht hervorruft, um ein photoabsorbierendes Material zu desaktivieren und das Hinzufügen eines Postscripts zu verhindern.
A laser recording thermally sensitive recording medium comprising, a thermally sensitive recording layer comprising at least a photo absorbing material which absorbs laser light and converts the laser light to heat, an electron donating leuco dye and an electron accepting colour developing agent on a substrate as main components, wherein said photo absorbing material is a compound represented by general formula (1), wherein n is an integer of from 1 to 4, and Xn, Yn and Zn - are as indicated in Table 1.
Xn N (C2H5) 2 N (C2H5) 2 N (CH3) 2 N (C2H5) 2 Yn N (C2H5) 2 N (C2H5) 2 H OCH3 Zn - CF3SO3 - CF3SO3 -
said laser recording thermally sensitive recording medium further comprising, a compound of formula (2) as a discolouring agent, wherein R1, R2, R3 and R4 are respectively independently chosen from alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkinyl group, sillyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted allyl group, substituted aralkyl group, substituted alkenyl group, substituted alkinyl group and substituted sillyl group; and at least one of R1, R2, R3 or R4 is an alkyl group of carbon number 1 to 12; R5, R6, R7 and R8 are respectively independently chosen from hydrogen atom, alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkinyl group, heterocyclic group, substituted alkyl group, substituted aryl group, substituted allyl group, substituted aralkyl group, substituted alkenyl group and substituted alkinyl group. A laser recording thermally sensitive recording medium according to claim 1, wherein the discolouring agent is a compound of formula (3), wherein, m is a integer of from 1 to 3, and structural formulae of Zm- are shown in Table 2.
The laser recording thermally sensitive recording medium according to claim 1 or 2, further comprising any one of ① to ③, ① an anti fading agent, ② an ultra violet ray absorbing agent, ③ an ultra violet ray absorbing agent and a hindered amine photo stabilizing agent, which is an antioxidant. A laser recording thermally sensitive recording medium according to claim 3, wherein the anti fading agent is at least one compound selected from the group consisting of heat resistance antioxidant, metal oxide or metal soap. A laser recording thermally sensitive recording medium according to claim 3, wherein the ultra violet ray absorbing agent is benzotriazol ultra violet ray absorbing agent. A method for use of the laser recording thermally sensitive recording medium according to anyone of claims 1 to 5, comprising, carrying out laser recording on the laser recording thermally sensitive recording medium, then irradiating with light of a level that does not cause colour development of a thermally sensitive recording layer in order to deactivate a photo absorbing material and preventing addition of a postscript.
Support d'enregistrement thermosensible pour enregistrement par laser, comprenant une couche d'enregistrement thermosensible comprenant au moins une matière photoabsorbante qui absorbe une lumière laser et transforme la lumière laser en chaleur, un leucodérivé de colorant donneur d'électrons et un agent de développement de couleur accepteur d'électrons sur un substrat, comme principaux composants, dans lequel ladite matière photoabsorbante est un composé représenté par la formule générale (1), dans laquelle n est un nombre entier de 1 à 4, et Xn, Yn et Zn - sont tels qu'indiqués dans le tableau 1,
Xn N(C2H5)2 N(C2H5)2 N(CH3)2 N(C2H5)2 Yn N(C2H5)2 N(C2H5)2 H OCH3 Zn - CF3SO3 - CF3SO3 -
ledit support d'enregistrement thermosensible pour enregistrement par laser comprenant en outre un composé de formule (2) comme agent décolorant, dans laquelle R1, R2, R3 et R4 sont respectivement choisis indépendamment parmi un groupe alkyle, un groupe aryle, un groupe allyle, un groupe aralkyle, un groupe alcényle, un groupe alcynyle, un groupe silyle, un groupe hétérocyclique, un groupe alkyle substitué, un groupe aryle substitué, un groupe allyle substitué, un groupe aralkyle substitué, un groupe alcényle substitué, un groupe alcynyle substitué et un groupe silyle substitué ; et au moins l'un de R1, R2, R3 ou R4 est un groupe alkyle ayant de 1 à 12 atomes de carbone ; R5, R6, R7 et R8 sont respectivement choisis indépendamment parmi un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe allyle, un groupe aralkyle, un groupe alcényle, un groupe alcynyle, un groupe hétérocyclique, un groupe alkyle substitué, un groupe aryle substitué, un groupe allyle substitué, un groupe aralkyle substitué, un groupe alcényle substitué et un groupe alcynyle substitué. Support d'enregistrement thermosensible pour enregistrement par laser selon la revendication 1, dans lequel l'agent décolorant est un composé de formule (3) dans laquelle m est un nombre entier de 1 à 3, et les formules développées de Zm - sont indiquées dans le tableau 2.
Support d'enregistrement thermosensible pour enregistrement par laser selon la revendication 1 ou 2, comprenant en outre l'un quelconque de ① à ③, ① un agent antidécoloration, ② un agent absorbant les rayons ultraviolets, ③ un agent absorbant les rayons ultraviolets et un agent photostabilisant de type amine empêchée, qui est un anti-oxydant. Support d'enregistrement thermosensible pour enregistrement par laser selon la revendication 3, dans lequel l'agent antidécoloration est au moins un composé choisi dans l'ensemble constitué d'un anti-oxydant résistant à la chaleur, un oxyde de métal ou un savon métallique. Support d'enregistrement thermosensible pour enregistrement par laser selon la revendication 3, dans lequel l'agent absorbant les rayons ultraviolets est un agent absorbant les rayons ultraviolets de type benzotriazole. Procédé d'utilisation du support d'enregistrement thermosensible pour enregistrement par laser selon l'une quelconque des revendications 1 à 5, comprenant les étapes consistant à effectuer un enregistrement laser sur le support d'enregistrement thermosensible pour enregistrement par laser, ensuite à irradier avec une lumière d'un niveau qui ne provoque pas un développement de la couleur d'une couche d'enregistrement thermosensible de façon à désactiver une matière photoabsorbante et à empêcher l'addition d'un post-scriptum.