JP3414928B2 - Thermal recording material for infrared laser - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, especially a laser.
Laser light energy to heat energy for recording
The present invention relates to a heat-sensitive recording material for lasers. [0002] 2. Description of the Related Art In general, a thermosensitive recording material is formed on a support by an electronic device.
Donor, usually colorless or pale color dye precursor and electron acceptor
And a heat-sensitive recording layer containing a developer as a main component,
By heating with a thermal head, hot pen, laser light, etc.
The colorless dye precursor and the developer react instantaneously,
Is obtained, and JP-B-43-4160 and JP-B-4
It is disclosed in JP-A-5-14039. [0003] Such a thermal recording material is a thermal head.
Records can be obtained with a relatively simple device that uses
It has advantages such as simplicity and no noise.
Measurement recorder, facsimile, printer,
Computer terminals, labels, ticket vending machines, etc.
Used in a wide range of fields. However, when using a thermal head,
It is necessary to scan the thermal recording material in close contact with the thermal head.
It is necessary to wear the thermal head,
Components adhere to the surface of the thermal head as scum
Therefore, defects such as lack of a recorded image are likely to occur. Also,
Thermal recording using such a thermal head is a heating element.
Response of heating and cooling of the heating element
There is a limit in element density, and there is a limit in high-speed recording and high-resolution recording
there were. Furthermore, the thermal head must be
A large pressure is applied to the heat-sensitive layer of the recording material, which alleviates this
Pigments or lubricants that do not directly contribute to image formation
The degree of freedom in designing the thermal layer is limited, and the solution of the recording material itself is
There was a limit to the image quality. [0005] The light energy of laser light is converted to heat energy.
Do not directly contact the thermosensitive layer when converting to
Heat can be applied to the heat-sensitive layer in a non-contact manner.
Measurement flexibility, high-speed recording, high-density recording
So many suggestions have been made so far
(For example, Japanese Patent Application Laid-Open Nos. 50-23617 and 54-54).
121140, 57-11090, 58-56
No. 890, No. 58-94494, No. 58-13479
No. 1, No. 58-145493, No. 59-89192
And JP-A-62-56195). However feeling
Since the thermal layer generally has low absorption of laser light,
Laser light-absorbing substance was added, and no efforts were made to increase thermal sensitivity.
It has been. Conventionally, carbon brass
Has been used, but the visible part is strongly colored,
Only available for the ceremony. The laser has an oscillation wavelength in the near infrared region.
Use a laser that absorbs laser light and
Transparent to visible light as a substance that converts to heat energy
When using an infrared absorbing dye that is
It is preferable because it can be used for both images and transmission images. Red like this
JP-A-5-116450 and JP-A-5-116450 as external line absorbing dyes
JP-A-5-124338, JP-A-5-124339,
JP-A-5-124340 and JP-A-7-32739
Cyanine dyes and phthalocyanine colors shown in each publication
Element, pyrylium / thiapyrylium dye, azulene color
Squirry disclosed in JP-A-7-25153
Dyes, metal complex salt dyes such as Ni and Cr, India
Phenol dye, naphthoquinone dye, anthraquino
Dyes, indophenol dyes, indoaniline dyes
Dye, triphenylmethane dye, triallylmethane
Dye, aminium dye, diimonium dye, nitro
Compounds, but the coloring of the visible portion is small.
At present, there is no dye with high heat conversion efficiency.
You. [0007] SUMMARY OF THE INVENTION The present invention is directed to coloring a visible portion.
Has developed an infrared-absorbing dye with a small
Obtaining a thermal recording material for laser that can be recorded by contact
Aim. [0008] Means for Solving the Problems The present inventor has a spiro ring.
Cyanine dye has low absorption in the visible region and is light-colored
And found that it had excellent heat conversion efficiency.
The above objectives have been achieved. That is, the present invention relates to a method in which at least
An infrared absorbing dye represented by the formula [1],Or red of Chemical 34
External absorption dye and image forming componentContainingThe infrared absorption
Pigment converts the light energy of laser light into heat energy
In this case, the image forming component develops or loses its color.
FormThermal recording material for infrared laser
Fees. [0010] Embedded image Embedded image In the general formula [1], R¹, R^TwoAre each other
Which may be the same or different, an alkyl group,
Represents a kenyl group and an aralkyl group.Y ¹¹ , Y ¹² ,
Y ^{twenty one} , And Y ^{twenty two} Are the same or different
Well, at leastY ¹¹ And Y ¹² Or Y ^{twenty one} And Y ^{twenty two} ButNitrogen
Non-gold that forms a cyclic hydrocarbon with the carbon atom at the 3-position of the ring
Group of atoms in which one or more carbon atoms are heteroatoms
It may be substituted. Z¹, Z^TwoAre the same as each other
May be different, substituted or unsubstituted benzene ring
Alternatively, the atom groups necessary to form a naphthalene ring
You. L¹~ L^ThreeRepresents an unsubstituted or substituted methine group,
m is 2 or 3. X represents an anion, and n is a molecule
Represents the number required to adjust the electric charge in to 0. Next, the heat-sensitive recording material of the present invention will be further described.
explain in detail. In the present invention, it exists near the image forming component.
The absorbed infrared absorbing dye heats the light energy of the laser light.
Is converted into energy, and this heat causes the color of the image forming components to develop
Alternatively, the image is formed by decoloring. Infrared absorbing dye image
It may be contained in the same layer as the forming layer, or it may be imaged
A layer provided near a layer containing an image forming component (for example, an adjacent layer)
It may be contained therein. Therefore, as an image forming component
Image types used for thermal recording materials including known transfer methods
It can be applied to all of the components. The infrared absorbing dye used in the present invention
Is a compound represented by the general formula [1]And 34
CompoundIt is. Specifically, in the general formula [1],R ¹ , R
^Two Is an alkyl group which may have a substituent (for example,
Methyl group, ethyl group, n-propyl group, isopropyl
Group, n-butyl group, n-pentyl group, etc.) or alkenyl
Group (for example, allyl group, methallyl group, etc.) or arral
A kill group (for example, a benzyl group, a β-phenylethyl group,
α-naphthylmethyl group). Replace
Specific examples of the group include a sulfonic acid group, a carboxyl group,
Phosphonic acid group, hydroxy group, halogen atom, alkoxy
And a cyano group and a cyano group. Also, the substituent
Is an acid substituent, an alkali metal salt such as Na or K;
g, alkaline earth metal salts such as Ca, ammonium salts,
Triethylammonium salt, tributylammonium salt,
Organic ammonium salts such as pyridinium salts
It may be. [0014]Y ¹¹ And Y ¹² Or Y ^{twenty one} And Y ^{twenty two} ButNitrogen-containing ring
The hydrocarbon rings formed with the carbon atom at the 3-position of
Same or different, preferably 4-7 membered hydrocarbon
And a specific example of the hydrocarbon ring is cyclobuta
Ring, cyclopentane ring, cyclohexane ring, cyclo
And a butane ring. In addition, the hydrocarbon ring
One or more carbon atoms may be replaced by heteroatoms
And specific examples include tetrahydropyran rings.
it can.Y ¹¹ And Y ¹² Or Y ^{twenty one} And Y ^{twenty two} The hydrocarbon ring of
It may have a substituent, as specific examples of the substituent,
Examples of lower alkyl groups such as methyl group and ethyl group
it can. Z¹, Z^TwoMay be the same or different
And the elements necessary to form the benzene and naphthalene rings
Shows offspring. Z¹, Z^TwoMay have a substituent, and the substituent
Specific examples of sulfonic acid group, carboxyl group,
Kill group, aralkyl group, aryl group, halogen atom,
Ano group, nitro group, alkoxy group, hydroxy group, al
Coxycarbonyl group, carbamoyl group, sulfamoyl
Group, sulfonamide group, carboxamide group, etc.
Can be. When the substituent is an acid substituent, Na,
Alkali metal salts such as K, alkaline earth gold such as Mg and Ca
Genus salt, ammonium salt, triethylammonium salt,
Organic anions such as libutylammonium salts and pyridinium salts
It may be in the form of a monium salt or the like. L¹~ L^ThreeIs an unsubstituted or substituted methine group
And specific examples of the substituent include a halogen atom,
Roxy group, carboxyl group, alkyl group, aralkyl
Group, aryl group, alkoxy group, alkoxycarbonyl
Group, carbamoyl group, sulfamoyl group, sulfonamido
And a carboxamide group. Further
And a 6-membered group having three methine groups in which substituents are bonded to each other
Forms a ring, such as a 4,4-dimethylcyclohexane ring
May be. Also, m indicating the length of the methine chain is 2 or
3, and more preferably 3. As the anion represented by X, halogen
Ion, perchlorate ion, aryl sulfonate ion,
Alkyl sulfate ions and the like can be mentioned. here,
n is 1 or 2, when the dye forms an inner salt
Is 1. Specific examples of the compound represented by the above general formula [1]
Examples are shown below, but the present invention is not limited to these.
There is no. [0019] Embedded image [0020] Embedded image [0021] Embedded image [0022] Embedded image [0023] Embedded image[0024] Embedded image [0025] Embedded image [0026] Embedded image [0027] Embedded image [0028] Embedded image [0029] Embedded image[0030] Embedded image [0031] Embedded image [0032] Embedded image [0033] Embedded image [0034] [0035] Embedded image [0036] Embedded image[0037] Embedded image [0038] Embedded image [0039] Embedded image [0040] Embedded image [0041] Embedded image [0042] Embedded image [0043] Embedded image [0044] Embedded image[0045] Embedded image [0046] Embedded image [0047] Embedded image The dye compound in the present invention has been conventionally known.
Compared to simple polymethine cyanine dyes
There is something surprising at the new absorption concentration,
Indosi without spiro ring by introducing b ring
Excellent heat conversion performance compared to anine dye, and also visible
The fact that the coloration is small and light color depends on the examples described later.
It becomes clear. A method for synthesizing these compounds useful in the present invention will be described.
Japanese Patent Application Laid-Open Nos. 2-187751 and 2-2239
No. 44 and JP-A-3-95548.
Have been. The amount of the infrared absorbing dye to be added is particularly limited.
Although there is no limit, when the coating layer is used,
Generally, the heat generatedlargeBecause of the laser light used
It is preferable that the absorption concentration be 2 or more at the wavelength.
New Naturally, the maximum absorption wavelength of the infrared absorbing dye used
(Λmax) Adds dyes closer to the wavelength of laser light
The amount can be reduced, which is preferable. In addition, the generated heat
For efficient use, the above absorption concentration should be as thin as possible.
Is preferably achieved. Its existence form is dye
Dispersion in microcapsules or in binder
Any form of uniform dissolution may be used. Its content is
0.05-1.0 g / m^TwoIs appropriate. Next,Image forming componentsAs the heating part
In the case of a positive type to be colored, an electron-donating dye precursor and a developer
Using photodegradable diazo compounds and
Utilizing the color development reaction of Wappler, imino compounds and
A method using a color reaction of a cyanate (Japanese Patent Laid-Open No. 3-1)
No. 50190), etc., which are used with the heating part decolored
In the case of a negative type, the electron donor dye precursor and a developer
Of decoloring by applying a decoloring agent to color formers or pigments
Is available. Here, the electron donating dye precursor and the developer
An example of a thermosensitive recording material utilizing the color development reaction will be described. The electron-donating, usually colorless used in the present invention
Or light-colored dye precursors are generally
Representatively used for thermal recording paper, etc.
It is not done. As a specific example, for example,
However, the present invention is not limited to these.
Not something. Triarylmethane compound and Indori
As the ruphthalide compound, 3,3-bis (p-dimethyl
Tylaminophenyl) -6-dimethylaminophthalide
(Crystal violet lactone), 3,3-bis
(P-dimethylaminophenyl) phthalide, 3- (p-
Dimethylaminophenyl) -3- (1,2-dimethyli
And ndol-3-yl) phthalide, 3- (p-dimethyla
Minophenyl) -3- (2-methylindole-3-i
Ru) phthalide, 3- (2-methyl-4-dimethylamino)
Phenyl) -3- (2-methylindol-3-yl)
Phthalide, 3- (p-dimethylaminophenyl) -3-
(2-phenylindol-3-yl) phthalide, 3,
3-bis (1,2-dimethylindol-3-yl)-
5-dimethylaminophthalide, 3,3-bis (1,2-
Dimethylindol-3-yl) -6-dimethylamino
Phthalide, 3,3-bis (9-ethylcarbazole-3
-Yl) -5-dimethylaminophthalide, 3,3-bis
(2-phenylindol-3-yl) -5-dimethyl
Aminophthalide, 3-p-dimethylaminophenyl-3
-(1-methylpyrrol-2-yl) -6-dimethyla
Minophthalide, 3- (1-ethyl-2-methylindole)
Ru-3-yl) -3- (4-dimethylamino-2-ethy
(Xyphenyl) -4-azaphthalide, 3- (1-ethyl)
-2-methylindol-3-yl) -3- (4-dimension
Tylamino-2-ethoxyphenyl) -7-azaphthalate
Do, 3- (1-ethyl-2-methylindole-3-i
) -3- (4-Dimethylamino-2-ethoxyphenyl)
) -4,7-diazaphthalide, 3,3-bis (4-di
Ethylamino-2-ethoxyphenyl) -4-azaphtha
Lido, 3- (4-diethylamino-2-ethoxyphenyl)
) -3- (4-N-phenyl-N-ethylamino-2)
-Ethoxyphenyl) -4-azaphthalide and the like, As the diphenylmethane-based compound, 4,
4'-bis (dimethylaminophenyl) benzhydryl
Benzyl ether, N-chlorophenylleuco aurami
, N-2,4,5-trichlorophenylleucoura
Min and others Fluoran compounds and xanthene compounds
As a product, 3-diethylamino-6-methyl-7-a
Nilinofluoran, 3-piperidino-6-methyl-7-
Anilinofluoran, 3-pyrrolidino-6-methyl-7
-Anilinofluoran, 3-diethylamino-6-methyl
Ru-7- (4-methylanilino) fluoran, 3-die
Tylamino-6-methyl-7- (4-n-butylanily
G) Fluoran, 3-diethylamino-6-methyl-7
-(4-ethoxyanilino) fluoran, 3-pyrrolidine
No-6-methyl-7- (4-methylanilino) fluora
3-pyrrolidino-6-methyl-7- (4-n-butyl
Luanilino) fluoran, 3-pyrrolidino-6-methyl
-7- (4-ethoxyanilino) fluoran, 3-di-
n-propylamino-6-methyl-7-anilinofluor
Run, 3-di-n-butylamino-6-methyl-7-a
Nilinofluoran, 3-di-n-pentylamino-6-
Methyl-7-anilinofluoran, 3- (N-methyl-
Nn-propyl) amino-6-methyl-7-anilino
Fluoran, 3- (N-ethyl-Nn-propyl) a
Mino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl-N-isoamyl) amino-6-methyl-7-
Anilinofluoran, 3- (N-ethyl-N-amyl)
Amino-6-methyl-7-anilinofluoran, 3-
(N-ethyl-N-isobutyl) amino-6-methyl-
7-anilinofluoran, 3- (N-methyl-N-cycl
Rohexyl) amino-6-methyl-7-anilinofluor
Run, 3- (N-methyl-N-tetrahydrofuran-2
-Ylmethyl) amino-6-methyl-7-anilinofur
Oran, 3- (N-ethyl-N-tetrahydrofurylme
Tyl) amino-6-methyl-7-anilinofluoran,
3- (N-methyl-N-tetrahydrofuran-2-i
L) amino-6-methyl-7-anilinofluoran, 3
-(N-ethyl-N-tetrahydrofuryl) amino-6
-Methyl-7-anilinofluoran, 3-dimethylamido
No-6-methyl-7-anilinofluoran, 3- (N-
Methyl-N-ethyl) amino-6-methyl-7-anili
Nofluoran, 3-isopentylamino-6-methyl-
7-anilinofluoran, 3-Di-n-butylamino-6-methyl-
7- (2-fluoroanilino) fluoran, 3-dibutyl
Ruamino-6-methoxy-7-anilinofluoran, 3
-Di-n-butylamino-6-methyl-7- (2,6-
Dimethylanilino) fluoran, 3- (N-ethyl-N
-3-ethoxypropyl) amino-6-methyl-7-a
Nilinofluoran, 3- (N-methyl-N-3-ethoxy)
(Cipropyl) amino-6-methyl-7-anilinofluor
Run, 3-diethylamino-6-methyl-7- (3-to
Trifluoromethylanilino) fluoran, 3-diethyl
Amino-7- (3-trifluoromethylanilino) fur
Oran, 3-diethylamino-7- (2-chloroanily
G) Fluoran, 3-diethylamino-7- (3-chloro
(Roanilino) fluoran, 3-di-n-butylamino-
7- (3-chloroanilino) fluoran, 3-diethyl
Amino-7- (2-fluoroanilino) fluoran, 3
-Diethylamino-7- (2-methoxyanilino) fur
Oran, 3-pyrrolidino-7- (2-chloroanilino)
Fluoran, 3-pyrrolidino-7- (3-chloroanili
G) Fluorane, 3-pyrrolidino-7- (2-methoxy)
Anilino) fluoran, 3-diethylamino-7- (2
-Isopentyloxycarbonylanilino) fluora
, 3- (N-ethyl-N-p-tolyl) amino-6-
Methyl-7-anilinofluoran, 3-pyrrolidino-7
-Cyclohexylaminofluoran, 3-diethylamido
No-7-dibenzylaminofluoran, 3-diethyla
Mino-7-n-octylaminofluoran, 3-diethyl
Lumino-7-phenylfluoran, 3-diethylamido
No-7-chlorofluoran, 3-diethylamino-6
Chloro-7-methylfluoran, 3-diethylamino-
6-methyl-7-chlorofluoran, 3-di-n-butyi
Ruamino-6-methyl-7-chlorofluoran, 3-di
Ethylamino-7- (3,4-dichloroanilino) fur
Orane, 3-ethylamino-6-chlorofluoran, 3
-Cyclohexylamino-6-chlorofluoran, 3-
Diethylamino-7,8-benzofluoran, 3-die
Tylamino-7-dibenzylaminofluoran, 3-di
-N-butylamino-7- (2-chlorobenzylamido
G) fluoran, 3,6-dimethoxyfluoran, 3,
6-diethoxyfluoran, rhodamine B anilinolac
Tom, rhodamine B-p-chloroanilinolactam, etc.
But, Others include benzoyl leuco methyle
Blue, p-nitrobenzoyl leucomethylene blue
Thiazine-based compounds such as 3-methylspirodinaphtopira
, 3-ethylspirodinaphthopyran, 3,3'-dic
Lolospirodinaphthopyran, 3-benzylspirodinaph
Topirane, 3-methylnaphtho- (3-methoxybenzo)
Spiropyran and 3-propylspirobenzopyran
Pyropyran compound, 3 ', 6'-bisdiethylamino
-5-diethylaminospiro (isobenzofuran-1,
9'-fluoren) -3-one, 3 ', 6'-bisdim
Tylamino-5-dimethylaminospiro (isobenzof
Fluorescein such as run-1,9'-fluoren) -3-one
3,3-bis- [2- (4-meth
(Xyphenyl) -2- (4-dimethylaminophenyl)
Ethenyl] -4,5,6,7-tetrachlorophthalide
List of vinylogous triarylmethane compounds
These dye precursors can be used alone or as a mixture of two or more.
Can be used in combination. As an electron-accepting color developer, a pressure-sensitive recording is generally used.
Represented by acidic substances used for recording paper, thermal recording paper, etc.
However, there is no particular limitation. For example, phenol induction
Conductor, aromatic carboxylic acid derivative, N, N'-diaryl
Polyvalent metal salts such as thiourea derivatives and zinc salts of organic compounds
Can be used. As the phenol derivative, specifically,
p-phenylphenol, p-hydroxyacetopheno
4-hydroxy-4'-methyldiphenylsulfo
4-hydroxy-4'-isopropoxydiphenyl
Sulfone, 4-hydroxy-4'-benzenesulfonyl
Oxydiphenyl sulfone, 1,1-bis (p-hydro
Xyphenyl) propane, 1,1-bis (p-hydroxy
Cyphenyl) pentane, 1,1-bis (p-hydroxy
Phenyl) hexane, 1,1-bis (p-hydroxyf
Phenyl) cyclohexane, 2,2-bis (p-hydroxy
Cyphenyl) propane, 2,2-bis (p-hydroxy
Phenyl) hexane, 1,1-bis (p-hydroxyf
Enyl) -2-ethylhexane, 2,2-bis (3-
(Rolo-4-hydroxyphenyl) propane, 1,1-bi
(P-hydroxyphenyl) -1-phenylethane,
1,3-di- [2- (p-hydroxyphenyl) -2-
Propyl] benzene, 1,3-di- [2- (3,4-di
Hydroxyphenyl) -2-propyl] benzene, 1,
4-di- [2- (p-hydroxyphenyl) -2-pro
Pill) benzene, 4,4'-dihydroxydiphenylate
4,4'-dihydroxydiphenylsulfone, 3,
3'-dichloro-4,4'-dihydroxydiphenyls
Rufone, 3,3'-diallyl-4,4'-dihydroxy
Diphenyl sulfone, 3,3'-dichloro-4,4'-
Dihydroxydiphenyl sulfide, 2,2-bis (4
-Hydroxyphenyl) methyl acetate, 2,2-bis (4
-Hydroxyphenyl) butyl acetate, 4,4'-thiobi
(2-t-butyl-5-methylphenol), 2,
2'-bis (4-hydroxyphenylthio) diethyl
-Tel, 1,7-di (4-hydroxyphenylthio)-
3,5-dioxaheptane, p-hydroxybenzoic acid
Benzyl, chlorobenzyl p-hydroxybenzoate, 4-
Dimethyl hydroxyphthalate, benzyl gallate, gallic
Stearyl citrate, 5,5'-benzylidenebis- (1,
3-diethyl-thiobarbituric acid), salicylanili
And 5-chlorosalicylanilide. These colors
Two or more agents may be used in combination. Usually colorless or pale color dye precursor and developer
The amount of each component of the thermosensitive recording layer containing
Normally, the amount of dye smear is 0.1 to 3.0 g / m^TwoIs suitable
But especially 0.50 to 2.0 g / m^TwoHigh color intensity
It is preferable because the degree can be obtained. Also, the developer smear
The amount is suitably from 5 to 400% by weight based on the dye precursor.
However, the content is particularly preferably 20 to 300% by weight. The heat-sensitive recording material of the present invention has
In order to improve the thermal response of the thermal recording layer,
It can be contained as needed. In this case, 60
C. to 180.degree. C. are preferred.
Those having a melting point of 0 ° C to 140 ° C are more preferred. The heat for improving such thermal response is as follows.
Specific examples of the fusible substance (sensitizer) include N-
Hydroxymethyl stearamide, stearic acid
Mid, palmitic amide, oleic amide, ethyl
Bis stearic acid amide, ricinoleic acid amide
De, paraffin wax, microcrystalline wax
, Polyethylene wax, rice wax, carnauba
Waxes such as wax, 2-benzyloxynaphtha
Naphthol derivatives such as len, p-benzylbiphenyl,
Biphenyl derivatives such as 4-allyloxybiphenyl,
1,2-bis (3-methylphenoxy) ethane, 2,
2'-bis (4-methoxyphenoxy) diethyl ether
And poly (bis (4-methoxyphenyl) ether)
-Tel compound, diphenyl carbonate, dibenzyl oxalate,
Carbonic acid such as di (p-chlorobenzyl) oxalate
Or oxalic acid diester derivatives.
You. These sensitizers may be used alone or in combination of two or more.
Can be used. In addition, sufficient thermal response
For example, 20 to 400% by weight based on the colorless dye precursor
Preferably, it is used. Next, a negative type thermosensitive recording material will be described.
The electron-donating dye precursor and the developer are melted by heating or
Dissolve in solvent or dissolve in organic solvent and then remove solvent
When removed, a colored body is formed. Such a colored body is fine powder
Crushed and dispersed in water with binder polymer or organic
The solution dissolved in the solvent is emulsified in water with a surfactant.
By applying the dispersed dispersion to the film,
Rum. In addition, the solvent dissolved in the organic solvent
Even if the liquid is applied directly to the film, it should be a colored film
Can be. This coloring is thermally eliminated by the addition of a decolorizing agent.
Can be In the present invention, the decoloring agent is usually an electron-donating
Colorless or pale color dye precursor and electron accepting developer
Any compound that can decolor the color formed by the reaction
It can be used without being limited to, specifically, the following
Compounds. 1,3-dicyclohexyl-2-f
Enylguanidine, 1,3-dicyclohexyl-2-
(2,5-dimethylphenyl) guanidine, 1,3-di
-Ortho tolyl guanidine, 1,2,3-triphenyl
Guanidin such as guanidine and 1,3-diphenylguanidine
Gins, 1,2,3,4-butanetetracarboxylic acid tet
Lakis (1,2,2,6,6-pentamethyl-4-pipe
Lysyl), 1,2,3,4-butanetetracarboxylic acid
Thrakis (2,2,6,6-tetramethyl-4-piperi
Jill), bis (1,2,2-octanedicarboxylate)
2,6,6-pentamethyl-4-piperidyl), 1,8
Bis (2,2,6,6-tetraoctanedicarboxylic acid)
Methyl-4-piperidyl), 1,2,3,4-butane
Tetrakis tracarboxylate (1-methyl-4-piperidi
), N, N'-diphenylforma
Midine, N, N'-bis (2-methylphenyl) form
Amidine, N, N'-diphenylbenzamidine, N,
N'-bis (4-methylphenyl) -N'-phenyl
Amidines such as N, N'-isophthaloy
Ru-di (N-cyclohexyl-N-methylamide),
N, N'-terephthaloyl-di (N-phenyl-N-E
Aromatic dicarboxylic acid diamides such as
Morpholines such as 4'-dithiodimorpholine, N, N '
Piperazines such as distearoylpiperazine; The decoloring agent is located at a position where the color former can be decolorized.
As long as it is present, it may be contained in the same layer as the color forming body
However, it may be included in a layer adjacent to the color forming layer. Also a microphone
It can also be included in a capsule. The amount added
It depends on the alkali strength and the form of the colorant
The amount may be determined experimentally, but usually the developer is
About 0.2 to 3 times is appropriate. In the recording layer constituting the heat-sensitive recording material of the present invention,
Is used to improve the fog resistance and thermal response of uncolored areas.
Various additives can be used. For example, N-s
Tearyl-N '-(2-hydroxyphenyl) urea,
N-stearyl-N '-(3-hydroxyphenyl) u
Rare, N-stearyl-N '-(4-hydroxyphenyl
Le) urea, p-stearoylaminophenol, o-
Stearoylaminophenol, p-lauroylamino
Phenol, p-butyrylaminophenol, m-acetate
Tylaminophenol, o-acetylaminophenol
, P-acetylaminophenol, o-butylamino
Carbonylphenol, o-stearylaminocarboni
Lephenol, p-stearylaminocarbonylpheno
, 1,1,3-tris (3-tert.-butyl-
4-hydroxy-6-methylphenyl) butane, 1,
1,3-tris (3-tert.-butyl-4-hydro
Xy-6-ethylphenyl) butane, 1,1,3-tri
-(3,5-di-tert.-butyl-4-hydroxy
Phenyl) butane, 1,1,3-tris (3-ter
t. -Butyl-4-hydroxy-6-methylphenyl)
Propane, 1,2,3-tris (3-tert.-butyl
4-hydroxy-6-methylphenyl) butane,
1,1,3-tris (3-phenyl-4-hydroxyf
Enyl) butane, 1,1,3-tris (3-cyclohexyl)
Sil-4-hydroxy-5-methylphenyl) butane,
1,1,3-tris (3-cyclohexyl-4-hydro
(Xy-6-methylphenyl) butane, 1,1,3,3-
Tetra (3-phenyl-4-hydroxyphenyl) pro
Bread, 1,1,3,3-tetra (3-cyclohexyl-
4-hydroxy-6-methylphenyl) propane, 1,
1-bis (3-tert.-butyl-4-hydroxy-
6-methylphenyl) butane, 1,1-bis (3-cycl
Rohexyl-4-hydroxy-6-methylphenyl) butane
It is possible to add compounds such as tan. In addition, if necessary, a pigment may be added to the heat-sensitive recording layer.
Can be used. Examples of pigments include diatoms
Earth, talc, kaolin, calcined kaolin, calcium carbonate
, Magnesium carbonate, titanium oxide, zinc oxide, silicon oxide
Element, aluminum hydroxide, barium sulfate, colloidal
Inorganic pigments such as Rica, urea-formalin resin, polyether
Tylene particles, nylon particles, styrene particles, starch particles
And organic pigments such as pigments. In addition, if necessary,
Agents, UV absorbers, surfactants, fluorescent dyes, etc.
Is also good. Thermal recording constituting the thermal recording material of the present invention
Electron-donating usually colorless to light-colored dye precursor in the layer,
Electron accepting color developer, decolorant or laser light absorbing material
As a method for containing each compound, each compound is used alone
Or a method of dissolving or emulsifying / dispersing in an organic solvent,
Combine each compound and add to water or organic solvent
Dissolution or emulsification / dispersion method, heating each compound
Dissolve and homogenize, then cool and dissolve in water or organic solvent
Alternatively, each solution obtained by emulsification / dispersion
Mix liquid or dispersion, print on support, apply and dry
There is a method to do. Emulsify and disperse in water or organic solvents
In this case, the dispersed particles are finely divided to an average particle diameter of 10 μm or less.
It is necessary to be a
Preferably it is 2 μm or less. Also, if necessary, individually
Or it can be mixed and encapsulated in microcapsules
it can. In addition, the individually encapsulated microcapsules
The recording layer can be formed by mixing them. The above-mentioned heat-sensitive recording material of the present invention,
A binder is appropriately added to each component, and the component is coated on the support.
Clothed. The above components are dispersed in water as a binder
When producing recording materials as aqueous coating liquids,
Starches, hydroxyethylcellulose, methylcellulo
Glucose, carboxymethylcellulose, gelatin, casei
, Polyvinyl alcohol, modified polyvinyl alcohol
, Sodium polyacrylate, acrylamide / acrylic
Acid ester copolymer, acrylamide / acrylic acid ester
Ter / methacrylic acid terpolymer, styrene / male anhydride
Alkaline salt of formic acid copolymer, ethylene / maleic anhydride
A water-soluble binder such as an alkali salt of an acid copolymer; and
And styrene / butadiene copolymer, acrylonitrile
/ Butadiene copolymer, methyl acrylate / butadiene
Use latex-based water-insoluble binders such as copolymers.
Can be used. In addition, electron donor dye precursors
When a coloring layer is formed by dissolving a coloring agent in an organic solvent,
Laser light absorption by dissolving laser light absorbing dye in organic solvent
When forming a layer, various binders soluble in organic solvents
-For example, polyvinyl butyral, polyvinyl acetate,
Various organic solvent-soluble poly such as acrylate
Can be used. As the support of the heat-sensitive recording material of the present invention,
Paper, coated paper, various nonwoven fabrics, woven fabrics, synthetic resin films,
There are synthetic resin laminated paper, synthetic paper, metal foil, glass, etc.
Or a composite sheet that combines them according to the purpose.
It can be used freely. In addition, it can be transparent, translucent or
Any of transparent, limited to these
is not. In the case of transparent or translucent,
Irradiation with laser light is more preferable. Also support
The thickness of the body is not particularly limited because it varies depending on the application
Is 20 to 4000 μm, preferably 40 to 3000 μm
m. The heat-sensitive recording material of the present invention
In order to prevent the deterioration of the recording layer, the uppermost thermosensitive recording layer
It is preferable to provide a protective layer thereon. With a heat-sensitive recording layer
Intermediate between the support and / or the thermosensitive recording layer and the protective layer
Layers can also be provided. And each or one
Part of the thermosensitive recording layer and / or other layers and / or
The surface on which the thermal recording layer is provided and / or
A material whose surface can record information electrically, magnetically, and optically
May be included. The surface on which the heat-sensitive recording layer is provided
On the opposite side to prevent curling and antistatic.
A back coat layer may be provided,
You may. The protective layer used in the heat-sensitive recording material of the present invention
Materials to be formed include water-soluble polymers, latexes,
There are polymerizable compounds and the like. For example, polyurethane resin, poly
Ester resin, epoxy resin, melamine resin, polyvinyl
Alcohol, nitrocellulose, methacrylate
Ter, acrylic acid oligomer, acrylic acid ester
Sesame and the like. Epoxidation if necessary
Compounds, urea derivatives, crosslinking agents such as vinyl compounds, phosphoric acid
Type, sulfonic acid type, polyamide type, amine type curing agent
Etc. can be added. In addition, polyethylene,
Transparent film such as ethylene terephthalate
And put it on the top of the thermal recording layer
The protective layer can be formed in steps. In this case, it is necessary
If necessary, an intermediate layer may be provided between the heat-sensitive recording layer and the protective layer.
it can. The printability and sensitivity of the heat-sensitive recording material of the present invention are improved.
In order to raise the height, a heat insulating layer may be provided on the support.
Efficiently contains air with a large heat insulating effect as a heat insulating layer
It is desired to have smoothness at the same time. This insulation layer
For example, various hollow particles, air containing air inside
-Capsules, inorganic and organic pigments with many pores, etc.
To provide on a support with a binder and other components as main components
Is obtained. In order to obtain the effect of the heat insulation layer,
0.5 to 30 g / m^TwoIs preferred. Not in this range
If it is full, the effect on sensitivity improvement is not enough.
In some cases, it is difficult to obtain a uniform smooth surface. Each layer constituting the heat-sensitive recording material of the present invention is supported.
The method of forming on the holding body is not particularly limited,
It can be formed by a conventional method. For example, air
-Knife coater, blade coater, bar coater,
Smearing equipment such as curtain coaters, planographic, letterpress, intaglio,
Lexo, gravure, screen, hot melt, etc.
Various printing machines and the like can be used. More normal
In addition to the drying process, each layer is held by UV irradiation and EB irradiation.
I can make it. By these methods, one layer at a time
Can be smeared and printed simultaneously in multiple layers. [0077] EXAMPLES The present invention will be described more specifically with reference to examples.
However, the present invention is not limited to the following examples unless it exceeds the gist of the invention.
It is not limited. In the examples,
All parts and percentages are by weight. Embodiment 1 The following lower layer coating solution and upper layer coating solution are applied to a 0.4 mm wire bar.
At 100μmThick transparent polyethylene terephthalate
(PET) layered on film, heat sensitive for infrared laser
A recording material was obtained.   Lower layer coating liquidCompound [Formula 34]                                0.5 parts               50 parts of a 3% solution of polyvinyl butyral in dichloromethane   Upper layer coating liquid   After separately dispersing the following solution A and solution B in a ball mill for 2 days, A: B =   The mixture was stirred and mixed at a ratio of 1: 2 to obtain a coating liquid.     Solution A 1 part 3-Diethylamino-6-methyl-7-anilinofluoran           6 parts of 5% aqueous solution of hydroxyethyl cellulose     Liquid B 4,4'-isopropylidene diphenol 1 part           6 parts of 5% aqueous solution of hydroxyethyl cellulose Comparative Example 1 Example 1Compound [Formula 34]Commercial instead of
Dye IR820B (laser light absorption color manufactured by Nippon Kayaku)
Red) in the same manner as in Example 1 except that 0.5 part of
A heat-sensitive recording material for external laser was obtained. Comparative Example 2 Example 1Compound [Formula 34]Compare instead of
Heptamethine cyanine color of the infrared absorbing dye [Chemical Formula 32]
Infrared was carried out in the same manner as in Example 1 except that 0.5 part of sulfur was added.
A heat-sensitive recording material for laser was obtained. [0081] Embedded image Thermal recording obtained in Example 1 and Comparative Example 1
830nm wavelength laser beam from the support side of the material
When irradiated like an image, in Example 1, 20 μm was irradiated.mDod
Thus, a black image composed of the same was obtained. Recording material
User energy and image dot size and irradiation time?
Calculation of the recording energy from
300mJ / cm^TwoIt turned out to be. Comparative Example 1 and
In Comparative Example 2, the irradiation time was tripled and five times, respectively.
Dots were slightly observed. In addition, Comparative Example 1 and
In Comparative Example 2, the coloring of the dye was strong, and the coloring of the dye was
Looked through. Thus, the compound of the present invention [34
ofLess coloring in visible part by using dye
High-sensitivity thermal recording material for infrared lasers
Was confirmed. Embodiment 2 The following lower layer coating solution and upper layer coating solution are 0.5 mm wire bar
At 100μmThick transparent polyethylene terephthalate
(PET) Laminated sequentially on film, black color heat-sensitive
Provide a recording layer to obtain a thermosensitive recording material for negative type infrared laser
Was.   Lower layer coating solution 3-dibutylamino-6-methyl-7-anilinofluoran                                                               1.2 copies               5,5'-benzylidenebis- (1,3-diethyl-thiobarbi               Tool acid) 0.8 parts               Compound [Formula 34]                                0.4 parts               25 parts of a 5% solution of polyvinyl butyral in methyl ethyl ketone               5 parts of toluene   Upper layer coating solution 1,3-dicyclohexyl-2- (2,5-dimethylphenyl)               Guanidine 10 parts               5% polyvinyl alcohol aqueous solution 200 parts                 Disperse in ball mill for 2 days Next, in the same manner as in Example 1,
When irradiated with a laser beam, the color is erased transparently in dots.
In addition, a negative image having extremely high contrast was obtained. this
At the time, the recording energy is 500 mJ / cm^TwoMet. Embodiment 3 Example 2Compound [Formula 34]Illustrated instead of
Exactly the same as Example 2 except that compound [Formula 9] was used.
In the above, heat-sensitive recording for negative type infrared laser colored black
The recording material was obtained. Next, a laser beam with a wavelength of 780 nm
And used in the same manner as in Example 1.
When the light was irradiated, the color was transparently erased in the form of dots.
A negative image with high contrast was obtained. At this time, record
Energy is 400mJ / cm^TwoMet. [0086] The thermal recording material for infrared laser of the present invention is
General formula [1]And 34Having a spiro ring
Since the dye is used as an infrared absorbing dye, visible light
Laser light despite its low absorption and light color
The efficiency of converting light energy into heat energy is high,
Capable of recording with a small, low-power laser with excellent thermal sensitivity
Noh.

Continuation of front page (56) References JP-A-3-203695 (JP, A) JP-A-4-43078 (JP, A) JP-A-6-199045 (JP, A) JP-A-2-286392 (JP) JP-A-7-32738 (JP, A) JP-A-6-328842 (JP, A) JP-A-5-301447 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) B41M 5/26 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims 1] An infrared absorbing dye represented by at least the general formula [1] or an infrared absorbing color of Chemical formula 33 on a support
And an infrared-absorbing dye containing
Converting the light energy of laser light into heat energy
The heat-sensitive recording material for an infrared laser , wherein the image-forming component develops or decolors to form an image . Embedded image (In the general formula [1], R ^1, R ² may be different be the same as each other, an alkyl group which may have a substituent, alkenyl group and aralkyl group. Y
^11, Y ^12, Y ^21, and Y ²² may be different be the same as each other, at least Y ¹¹ and Y ¹² or Y ^21,
Y ²² is a group of nonmetallic atoms forming a cyclic hydrocarbon together with the carbon atom at the 3-position of the nitrogen-containing ring, and one or more carbon atoms may be substituted with a hetero atom. Z ¹ and Z ² may be the same or different from each other, and represent an atomic group necessary for forming a substituted or unsubstituted benzene ring or naphthalene ring. L ^{1 to} L ³ represent an unsubstituted or substituted methine group, and m is 2 or 3. X represents an anion, and n represents a number required to adjust the intramolecular charge to zero. )