WO2019031525A1 - 感熱記録材料及び積層体 - Google Patents
感熱記録材料及び積層体 Download PDFInfo
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- WO2019031525A1 WO2019031525A1 PCT/JP2018/029661 JP2018029661W WO2019031525A1 WO 2019031525 A1 WO2019031525 A1 WO 2019031525A1 JP 2018029661 W JP2018029661 W JP 2018029661W WO 2019031525 A1 WO2019031525 A1 WO 2019031525A1
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- WIPO (PCT)
- Prior art keywords
- heat
- sensitive recording
- recording layer
- formula
- recording material
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
Definitions
- the present invention relates to a heat-sensitive recording material and a laminate having good color developing sensitivity, low color development in the white part even at high temperatures, good storage stability of the printed part, and excellent contrast between the white part and the printed part.
- a heat-sensitive recording material having a heat-sensitive recording layer containing as a main component a color developing agent which reacts with leuco dye (hereinafter sometimes abbreviated as "dye") to develop color is paper, film, card, etc. It has been widely put to practical use in applications.
- a thermal printer or the like incorporating a thermal head is used. This thermal recording method is (a) no noise during recording, (b) no need for development and fixing, (c) maintenance free, (d) equipment, as compared with other recording methods that have been put into practical use in the past.
- thermosensitive paper is desired in which the white part does not develop even under high temperature conditions and the storage stability of the printed part is good, that is, the contrast between the printed part and the white part is good.
- Patent Document 1 describes 4-isopropoxy-4'-hydroxydiphenyl sulfone which is a color developing agent having a good color developing sensitivity and a good image storability.
- Patent Documents 2 and 3 disclose 4-propoxy-4'-hydroxydiphenyl sulfone which is a color developing agent having a good color developing sensitivity and a good storage stability of a white portion at high temperature.
- Patent Document 4 bis (4-allyloxydiphenyl) sulfone is added to 4-allyloxy-4'-hydroxydiphenylsulfone as a developer having high sensitivity and good image heat resistance and moisture resistance storage resistance. And mixtures of 4,4'-dihydroxydiphenyl sulfone and 2,4-dihydroxydiphenyl sulfone are described. Furthermore, Patent Document 5 discloses that 4-hydroxy to color developer 4-isopropoxy-4'-hydroxydiphenyl sulfone is used as a hydrate to prevent background stains during preparation and storage of the dispersion. A mixture of alkylated bis (4-hydroxyphenyl) sulfones, such as phenyl-3'-isopropyl-4'-hydroxyphenylsulfone, is described.
- Patent Document 1 4-isopropoxy-4'-hydroxydiphenyl sulfone described in Patent Document 1 has good color forming sensitivity and image storability, but preservation of the white portion under high temperature It turned out that there is a problem that the sex is extremely inferior. Therefore, as in Patent Document 5, when alkylated bis (4-hydroxyphenyl) sulfone is mixed with 4-isopropoxy-4'-hydroxydiphenyl sulfone, the temperature can not be used as a general color developer to a high level. It was found that the preservability of the white part below is deteriorated.
- Patent Documents 2 and 3 Although 4-propoxy-4'-hydroxydiphenyl sulfone described in Patent Documents 2 and 3 is excellent in color development sensitivity and storage stability of white part at high temperature, storage of printed part at high temperature It has been found that there is a problem of lack of sex.
- Patent Document 4 discloses a developer of 4-allyloxy-4'-hydroxydiphenyl sulfone having good preservation of the white portion under high temperature, 4,4'-diallyloxydiphenyl sulfone and 4,4 ' -A mixture of dihydroxydiphenyl sulfone and 2,4-dihydroxydiphenyl sulfone is used, but a compound having a color developing ability such as 4,4'-dihydroxydiphenyl sulfone or 2,4-dihydroxydiphenyl sulfone is mixed Then, it was found that although the storability of the printed portion under high temperature is improved, the storability of the white portion under high temperature is significantly reduced.
- the conventionally developed developers including the developers of Patent Documents 1 to 5 have excellent color forming sensitivity, little color development in the white part even at high temperatures, and all the preservability of the printed part is satisfied.
- no thermosensitive recording material has been found. Therefore, the object of the present invention is to solve the above-mentioned drawbacks of the prior art, to be excellent in color development sensitivity, less color development in white part even under high temperature, good storage stability of printed part, after being placed under high temperature It is an object of the present invention to provide a heat-sensitive recording material and a laminate excellent in the contrast between the white area and the printing area.
- the heat-sensitive recording material and the laminate containing the specific diphenyl sulfone compound and the related compound in the heat-sensitive recording layer in a specific ratio have good color development sensitivity and conditions under high temperature.
- the preservability of the printed part and the white part and the contrast thereof are good.
- thermosensitive recording material comprising a thermosensitive recording layer on a support, the thermosensitive recording layer comprising a compound represented by the following formula (1) and a compound represented by the following formula (2) And a heat-sensitive recording material wherein the content of the compound represented by the formula (2) is 0.01 to 2.0% by weight relative to the total amount of these.
- R 1 and R 2 which may be the same or different, each represents an alkyl group of 1 to 3 carbon atoms, an alkenyl group of 1 to 3 carbon atoms, or a benzyl group, and m and n Each independently represents an integer of 0 to 4; ]
- R 3 and R 4 which may be the same or different, each represents an alkyloxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, or a benzyloxy group, o and p each independently represent an integer of 1 to 3.
- compounds represented by the formula (2) include 4,4′-dipropoxydiphenylsulfone, 4,4′-diallyloxydiphenylsulfone, 4,4′-diisopropoxydiphenylsulfone, and
- the sensitizer 1,2-di- (3-methylphenoxy) ethane, 1,2-diphenoxyethane, fatty acid amide having 10 to 21 carbon atoms, ⁇ -benzyloxynaphthalene, diphenyl sulfone, p
- the heat-sensitive recording material according to [6] which contains at least one selected from toluenesulfonamide and oxalic acid-di-p-methylbenzyl ester.
- thermosensitive recording layer on a support, the thermosensitive recording layer containing a compound represented by the following formula (1) and a compound represented by the following formula (2), And a laminate wherein the content of the compound represented by the formula (2) is 0.01 to 2.0% by weight relative to the total amount of these.
- R 1 and R 2 which may be the same or different, each represents an alkyl group of 1 to 3 carbon atoms, an alkenyl group of 1 to 3 carbon atoms, or a benzyl group, and m and n Each independently represents an integer of 0 to 4; ]
- R 3 and R 4 which may be the same or different, each represents an alkyloxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, or a benzyloxy group, o and p each independently represent an integer of 1 to 3.
- compounds represented by the formula (2) include 4,4′-dipropoxydiphenylsulfone, 4,4′-diallyloxydiphenylsulfone, 4,4′-diisopropoxydiphenylsulfone, and The laminate according to [8] or [9], comprising at least one selected from 4,4′-dibenzyloxydiphenyl sulfone.
- thermosensitive recording layer contains a leuco dye
- thermosensitive recording layer [13] The laminate according to any one of [8] to [12], which contains a sensitizer in the thermosensitive recording layer.
- sensitizer examples include 1,2-di- (3-methylphenoxy) ethane, 1,2-diphenoxyethane, fatty acid amide having 10 to 21 carbon atoms, ⁇ -benzyloxynaphthalene, diphenyl sulfone, p
- the layered product according to [13] which contains at least one selected from toluenesulfonamide and oxalic acid-di-p-methylbenzyl ester.
- thermosensitive recording material having good color development sensitivity, little color development in the white part even at high temperatures, good storage stability of the printed part, and good contrast between the white part and the printed part A laminate is provided.
- thermosensitive recording material of the present invention is a thermosensitive recording material provided with a thermosensitive recording layer on a support, and in the thermosensitive recording layer, a compound (compound (1)) represented by the following formula (1) Containing 0.01 to 2.0% by weight of the compound represented by the formula (2) based on the total amount of the compounds represented by the following formula (2) (compound (2))
- the “thermosensitive recording material” may be in any form such as paper, film, synthetic paper, card, etc. as long as it has a thermosensitive recording layer on a support.
- the compound (1) usually functions as a developer.
- “on support” means on at least one side of the support, usually on one side.
- “provided on a support” means that the layer is present on at least a part of the support.
- R 1 and R 2 which may be the same or different, each represents an alkyl group of 1 to 3 carbon atoms, an alkenyl group of 1 to 3 carbon atoms, or a benzyl group, and m and n Each independently represents an integer of 0 to 4; ]
- R 3 and R 4 which may be the same or different, each represents an alkyloxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, or a benzyloxy group, o and p each independently represent an integer of 1 to 3.
- the heat-sensitive recording material of the present invention comprises a heat-sensitive recording layer on a support, but as described later, a top coat layer (protective layer), an undercoat layer, a back coat layer, an intermediate coat layer, etc. May be included. That is, the heat-sensitive recording material of the present invention is usually in the form of a laminate. That is, the laminate of the present invention is a laminate having a thermosensitive recording layer on a support, and the compound represented by the above formula (1) (compound (1)) and the thermosensitive recording layer Containing 0.01 to 2.0% by weight of the compound represented by the formula (2) based on the total amount of the compounds represented by the above formula (2) (compound (2)) It is characterized by
- the heat-sensitive recording material and laminate of the present invention have the effects of good color development, little color development in the white part even at high temperatures, good storage stability of the printed part, and good contrast between the white part and the printed part. Play.
- This is characterized in that the melting point of the compound (1) is higher by about 25 ° C. than a compound having a similar chemical structure such as 4-isopropoxy-4′-hydroxydiphenyl sulfone, and the white part is difficult to develop color even at high temperatures It is thought that it depends on the matter.
- the compound (2) in the range of 0.01 to 2.0, the compatibility between the compound (1) and the dye is enhanced, and the compound (1) and the dye It is considered that the storability of the printing unit is improved in order to stabilize the bonding state.
- thermosensitive recording material and the laminate of the present invention have a thermosensitive recording layer, and the thermosensitive recording layer contains the compound (1) and the compound (2) in a specific ratio.
- the heat-sensitive recording layer contains, in addition to these compounds, a developer, a sensitizer, a stabilizer, a binder, a crosslinking agent, a pigment, a lubricant and other additives) May be included.
- R 1 and R 2 in the formula (1) may be the same as or different from each other, and represent an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group. And methyl, ethyl, propyl, isopropyl, vinyl, allyl and benzyl, preferably propyl, isopropyl, allyl and benzyl, more preferably propyl and allyl. is there.
- M and n in the formula (1) are each independently an integer of 0 to 4 and indicate the number of R 1 and R 2 .
- m and n being 0 means that R 1 and R 2 are not present, respectively, and 4 hydrogen atoms are bonded to the respective aromatic rings.
- the m R 1 s may be the same as or different from each other.
- n R 2 s may be the same as or different from each other.
- m is preferably 0 or 1, more preferably 0, ie, a hydrogen atom.
- n is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0, ie, a hydrogen atom.
- R 1 and R 2 are present, their positions are not particularly limited.
- R 3 and R 4 in the formula (2) may be the same as or different from each other, and represent an alkyloxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, or a benzyloxy group.
- examples include methoxy, ethoxy, propoxy, isopropoxy, allyloxy and benzyloxy groups, preferably propoxy, isopropoxy and allyloxy groups, and more preferably propoxy and allyloxy groups. It is.
- O and p in the formula (2) are each independently an integer of 0 to 3, and indicate the number of R 3 and R 4 .
- that o and p are 0 means that R 3 and R 4 do not exist, respectively, and 5 hydrogen atoms are bonded to each aromatic ring.
- o R 3 s may be the same as or different from each other.
- p R 4 may be the same as or different from each other.
- o is preferably 1 or 2, more preferably 1.
- p is preferably 1 or 2, more preferably 1.
- R 3 and R 4 are present, their positions are not particularly limited.
- the compound (2) 4,4′-dipropoxydiphenyl sulfone, 4,4′-diallyloxydiphenyl sulfone, 4,4′-diisopropoxydiphenyl sulfone and 4,4′-dibenzyloxydiphenyl It is preferable to include at least one selected from sulfones in the heat-sensitive recording layer.
- the compound (2) it is particularly preferable to include at least one selected from 4,4′-dipropoxydiphenyl sulfone and 4,4′-diallyloxydiphenyl sulfone in the heat-sensitive recording layer.
- the content of the compound (2) is 0.01% by weight or more, preferably 0.05% by weight or more, based on the total amount with the compound (1), and more preferably Is 0.08% by weight or more.
- the content of the compound (2) in the thermosensitive recording layer is 2.0% by weight or less, preferably 1.5% by weight or less, and more preferably 1.2% by weight or less.
- the present invention also provides a thermosensitive recording material and a laminate having a support, and a thermosensitive recording layer (thermosensitive color forming layer) provided on the support.
- the heat-sensitive recording layer contains a colorless or pale basic (electron donating) leuco dye and a developer for causing the basic leuco dye to develop color
- the agent contains compound (1).
- the compound (1) may be used alone or in combination of two or more.
- components other than the compound (1) and the compound (2) other color developing agents, basic leuco dyes, sensitizers, stabilizers, binders, crosslinking agents, and the like that can be used to form the heat-sensitive recording layer
- the pigments, lubricants and other additives will be described in order.
- the components other than the compound (1) and the compound (2) may be used singly or in combination of two or more.
- the binder, the crosslinking agent, the pigment and the like are not only the thermosensitive recording layer but also layers other than the thermosensitive recording layer which can be possessed by the thermosensitive recording material and laminate of the present invention (for example, top coat layer (protective layer) described later) It can also be used inside.
- a leuco dye in the thermosensitive recording layer it is preferable to use a leuco dye in the thermosensitive recording layer.
- the leuco dyes are usually basic and all those conventionally known in the pressure-sensitive or thermosensitive recording paper field can be used.
- As the leuco dyes specifically, triphenylmethane leuco dyes, fluoran leuco dyes, fluorene leuco dyes, divinyl leuco dyes and the like are preferable. Specific examples of representative colorless to pale dyes (dye precursors) are shown below.
- only one leuco dye (leuco dye precursor) may be used, or two or more leuco dyes (leuco dye precursors) may be used in combination.
- the leuco dye is preferably used in an amount of 10 to 200 parts by weight, more preferably 15 to 150 parts by weight, still more preferably 20 to 100 parts by weight, based on 100 parts by weight of the compound (1) and the compound (2). It is a department.
- triphenylmethane leuco dye 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [alias: crystal violet lactone]; 3,3-bis (p-dimethylaminophenyl) phthalide [ Alias: Malachite green lactone] etc. are mentioned.
- divinyl leuco dyes examples include 3,3-bis [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrabromophthalide; -Bis [2- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide; 3,3-bis [1,1-bis (4) -Pyrrolidinophenyl) ethylene-2-yl] -4,5,6,7-tetrabromophthalide; 3,3-bis [1- (4-methoxyphenyl) -1- (4-pyrrolidinophenyl) ethylene -2-yl] -4,5,6,7-tetrachlorophthalide and the like.
- leuco dyes include 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-diethylamino-2-) Ethoxyphenyl) -3- (1-octyl-2-methylindol-3-yl) -4-azaphthalide; 3- (4-cyclohexylethylamino-2-methoxyphenyl) -3- (1-ethyl-2-methyl) Indol-3-yl) -4-azaphthalide; 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide; 3,6-bis (diethylamino) fluoran- ⁇ - (3′-nitro) Anilinolactam; 3,6-bis (diethylamino) fluoran- ⁇ - (4'-nitro) anilinolactam; 1,1-bis [2 ′, 2 ′, 2 ′
- the heat-sensitive recording layer may contain a developer (hereinafter referred to as another developer) other than the compound (1) of the present invention as long as the effects of the present invention are not impaired.
- a developer hereinafter referred to as another developer
- all known ones in the field of conventional pressure-sensitive or heat-sensitive recording paper can be used, and although not particularly limited, they are preferably electron-accepting developers.
- the other developers may be used alone or in combination of two or more. When other developers are used, the amount thereof used is preferably 1 to 100 parts by weight, more preferably 1 to 70 parts by weight, based on 100 parts by weight of the total of compound (1) and compound (2). More preferably, it is 1 to 50 parts by weight.
- bisphenol compounds include 4,4'-isopropylidenediphenol, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2 -Bis (4-hydroxyphenyl) -4-methylpentane, 4,4'-dihydroxydiphenyl sulfide, di (4-hydroxy-3-methylphenyl) sulfide, 2,2'-thiobis (3-tert-octylphenol), 2,2'-thiobis (4-tert-octylphenol), 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-propoxydiphenyl sulfone, 4-hydroxy-4'- Isopropoxy diphenyl sulfone, 4-hydroxy- '-Allyloxydiphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulf
- urea compounds examples include 4,4′-bis (3- (phenoxycarbonylamino) methylphenylureido) diphenyl sulfone, N- (p-toluenesulfonyl) -N ′-(3-p) described in Japanese Patent No. 4601174. -Toluenesulfonyl oxyphenyl) urea and its derivative etc. are mentioned.
- novolak type phenolic compounds examples include phenol-formalin condensates described in WO 02/098674.
- inorganic acidic substances such as activated clay, attapulgite, colloidal silica, aluminum silicate, hydroquinone monobenzyl ether, benzyl 4-hydroxybenzoate, aminobenzene sulfone described in JP-A-8-59603.
- image storability heat resistance, plasticizer resistance, moisture resistance, water resistance
- sensitizers may be used.
- the sensitizer is not particularly limited.
- ethylene bisamide montanic acid wax, polyethylene wax
- p-benzylbiphenyl diphenyl sulfone
- 4-biphenyl-p-tolyl ether m-terphenyl
- 1,2-diphenoxyethane dibenzyl oxalate, oxalate Acid di (p-chlorobenzyl), oxalic acid di (p-methylbenzyl), terephthalic acid dibenzyl, p-benzyloxybenzoic acid benzyl, di-p-tolyl carbonate, phenyl- ⁇ -
- One of these sensitizers may be used alone, or two or more thereof may be used in combination. When a sensitizer is used, its amount is preferably 25 to 250 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of compound (1) and compound (2). is there.
- a stabilizer may be used in the thermosensitive recording layer in order to improve the image storability of the thermosensitive recording material and the laminate.
- Stabilizers are those having an effect of improving the storability of an image.
- the stabilizer include hindered phenol compounds, ultraviolet absorbers (for example, benzophenone compounds, triazole compounds), antioxidants, and the like.
- hindered phenol compounds are preferable in terms of improving the image storability (heat resistance, moisture resistance, water resistance, plasticizer resistance, etc.) of the recording part.
- the hindered phenol compound is a compound having usually 1 or more and 15 or less, preferably 2 or more and 6 or less hydroxyphenyl groups in one molecule.
- the molecular weight of the hindered phenol compound is usually 200 or more and 2000 or less, preferably 250 or more and 1800 or less, more preferably 300 or more and 1500 or less.
- the melting point of the hindered phenol compound is preferably 100 ° C. or more and 300 ° C. or less.
- hindered phenol compounds include tris (hydroxyphenyl) alkanes and 1,1,3-tris-substituted butane compounds described in JP-B-39-4469 or JP-A-56-40629. Etc. Two or more of these may be used in combination.
- the hindered phenol compounds may be used alone or in combination of two or more.
- the content thereof is preferably 1 to 100 parts by weight with respect to a total of 100 parts by weight of the compound (1) and the compound (2) More preferably, it is 1 to 70 parts by weight, still more preferably 1 to 50 parts by weight. If the content of the hindered phenol compound is less than the above range, the moisture resistance, water resistance and heat resistance of the recording part may be reduced, and the color development of the white paper part by heating may not be suppressed. If the amount is more than the above range, the color development sensitivity may be reduced and the plasticizer resistance of the recording portion may be reduced.
- a binder to form a thermosensitive recording layer.
- the binder for example, completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, butyral modified polyvinyl alcohol, olefin modified polyvinyl alcohol, Nitrile-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol, silicone-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polystyrene, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, etc.
- Styrene copolymer ethyl cellulose and acetyl cellulose
- Cellulose derivatives such as loin, casein, arabic gum, oxidized starch, etherified starch, dialdehyde starch, esterified starch, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylate, polyvinyl butyral, polyamide resin, silicone resin, Petroleum resin, terpene resin, ketone resin, coumarone resin etc. are mentioned.
- An appropriate amount of the binder used is about 5 to 25% by weight based on the solid content of the thermosensitive recording layer.
- the binder is generally used as a solution, an emulsion, a dispersion, a paste or a combination thereof.
- the solvent of the solution, emulsion or dispersion, or the medium of the paste include water, alcohols, ketones, esters, hydrocarbons and the like.
- Crosslinking agent for example, glyoxal, methylolmelamine, melamine formaldehyde resin, melamine urea resin, polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, Magnesium chloride, borax, boric acid, alum, ammonium chloride and the like can be mentioned.
- a crosslinking agent when a crosslinking agent is used, its amount used is preferably 0.5 to 500 parts by weight with respect to 100 parts by weight in total of compound (1) and compound (2).
- the pigment examples include silica (excluding colloidal silica), calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, and inorganic or organic pigments such as aluminum hydroxide.
- silica excluding colloidal silica
- calcium carbonate calcium carbonate
- kaolin calcined kaolin
- diatomaceous earth talc
- titanium oxide titanium oxide
- inorganic or organic pigments such as aluminum hydroxide.
- the amount thereof used is preferably 25 to 1000 parts by weight with respect to 100 parts by weight in total of compound (1) and compound (2).
- lubricant examples include fatty acid metal salts such as zinc stearate and calcium stearate, waxes, silicone resins and the like.
- fatty acid metal salts such as zinc stearate and calcium stearate
- waxes such as waxes, silicone resins and the like.
- silicone resins such as silicone resins and the like.
- its amount is preferably 0.5 to 500 parts by weight with respect to 100 parts by weight in total of compound (1) and compound (2).
- additives include, for example, dispersants, antifoaming agents, fluorescent dyes and the like.
- the amount thereof used is preferably 0.5 to 500 parts by weight with respect to 100 parts by weight in total of the compound (1) and the compound (2).
- the shape, structure, size, material and the like of the support used in the heat-sensitive recording material and laminate of the present invention are not particularly limited, and can be appropriately selected according to the purpose.
- the shape of the support may, for example, be a sheet, a roll, or a plate.
- the support may have a single layer structure or a laminate structure.
- the size of the support can be appropriately selected depending on the intended use of the heat-sensitive recording material and the laminate.
- the material of the support includes, for example, plastic film, synthetic paper, wood free paper, recycled paper pulp, recycled paper, single-glossy paper, oil-resistant paper, coated paper, art paper, cast coated paper, finely coated paper, resin laminated paper, Release paper etc. are mentioned.
- a composite sheet combining these may be used as a support.
- the thickness of the support is not particularly limited and may be appropriately selected depending on the purpose, preferably 30 to 2,000 ⁇ m, and more preferably 50 to 1,000 ⁇ m.
- top coat layer In the heat-sensitive recording material and laminate of the present invention, a top coat layer (protective layer) may be provided on the heat-sensitive recording layer.
- a top coat layer protecting layer
- the color development sensitivity at low energy is lowered.
- the compound (1) is used as a color developing agent, even when the top coat layer (protective layer) is provided on the heat-sensitive recording layer, color development sensitivity with low energy It is good.
- the types and amounts of various components used in the topcoat layer (protective layer) are determined according to the required performance and recording suitability, and are not particularly limited.
- an undercoat layer mainly containing a pigment and a binder may be provided between the support and the heat-sensitive recording layer for the purpose of further enhancing color development sensitivity.
- a back coat layer may be provided on the surface of the support opposite to the surface on which the heat-sensitive recording layer is present.
- An embodiment of each layer in the heat-sensitive recording material and laminate of the present invention includes an embodiment laminated in the order of top coat (protective layer) / heat-sensitive recording layer / undercoat layer / support / backcoat layer. It is not limited.
- An intermediate coat layer may be formed.
- the heat-sensitive recording material and laminate of the present invention usually support a coating solution containing a leuco dye, a compound (1) and a compound (2) and, if necessary, other developers, sensitizers, stabilizers and the like. It can manufacture by apply
- the coating solution can be applied according to well-known conventional techniques. There is no particular limitation on the coating means, for example, an off-machine coater or an on-machine coater equipped with various coaters such as an air knife coater, rod blade coater, vent blade coater, bevel blade coater, roll coater, curtain coater and the like. It can be used.
- the coating liquid for forming the thermosensitive recording layer may be prepared, for example, by compounding a compound (1), a compound (2) and, if necessary, a leuco dye, another color developer, a hindered phenol compound, a sensitizer and the like. After atomizing to a particle diameter of several microns or less by a grinder such as a ball mill, attritor, sand glider or a suitable emulsifying device, a binder or the like can be added thereto to form. Water, alcohol, etc. can be used as a solvent used for this coating liquid. The solid content of the coating solution is usually 20 to 40% by weight.
- the coating amount of the heat-sensitive recording layer can be appropriately selected depending on the composition, the application of the heat-sensitive recording material and the laminate, etc., but usually 1 to 20 g / m 2 , preferably 2 to 12 g / m 2 by dry weight. It is a range.
- the top coat (protective) layer, the under layer, the back layer and the intermediate layer can also be formed by applying and drying a coating solution containing the constituent components, as in the case of the above-mentioned thermosensitive recording layer.
- the heat-sensitive recording material and laminate of the present invention in which each layer is formed may be subjected to processing known in the art (for example, smoothing processing using a super calender or the like).
- the heat-sensitive recording material and laminate of the present invention can be suitably used for applications such as paper, film, IC card, friction ball pen and the like.
- thermosensitive recording layer thermosensitive coloring layer
- ⁇ D solution> -1 2-di- (3-methyl phenoxy) ethane (Sanyo company make, brand name "KS-232”): 40.0 parts-polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. "L-3266”) 10% Aqueous solution: 50.0 parts, water: 10.0 parts
- Example 1-1 to 1-3 and Comparative Examples 1-1 to 1-5 The following Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5 were performed to confirm the difference in the effect depending on the compounding amount of the compound (1) and the compound (2).
- Example 1-1 The respective solutions were mixed in the following proportions to prepare a coating solution for the thermosensitive recording layer.
- Solution A 18.87 parts
- Solution B 0.02 parts
- Solution C 10.00 parts
- Solution D 18.89 parts
- Solution E 29.75 parts
- Solution F 9.95 parts
- Solution G 32.64 parts
- thermosensitive recording layer a coating liquid of the above composition of the thermosensitive recording layer is applied to a paper on which an under layer is provided on one side of a high quality paper as a support so that the dry weight of the thermosensitive recording layer is 6 g / m 2 And dried to form a thermosensitive recording layer.
- Embodiment 1-2 A thermosensitive recording material (laminate) was produced in the same manner as in Example 1-1 except that 18.80 parts of solution A and 0.09 parts of solution B were used.
- Embodiment 1-3 A thermosensitive recording material (laminate) was produced in the same manner as in Example 1-1 except that 18.70 parts of solution A and 0.19 parts of solution B were used.
- thermosensitive recording material (laminate) was produced in the same manner as in Example 1-1 except that solution B was not used and solution A was changed to 18.89 parts.
- thermosensitive recording material (laminate) was produced in the same manner as in.
- thermosensitive recording material (laminate) was produced in the same manner as in Example 1-1 except that 17.95 parts of solution A and 0.94 parts of solution B were used.
- thermosensitive recording material (laminate) was produced in the same manner as in Example 1-1 except that 17.47 parts of solution A and 1.42 parts of solution B were used.
- Comparative Example 1-5 The solution in which 4-propoxy-4'-hydroxydiphenylsulfone in solution A was changed to 4-isopropoxy-4'-hydroxydiphenylsulfone (Nippon Soda Co., Ltd., D-8) without using solution B is 18.89 A thermosensitive recording material (laminate) was produced in the same manner as in Example 1-1 except that a part was used.
- thermosensitive recording material (laminate) obtained by the Example and the comparative example.
- ⁇ Coloring sensitivity> A gradation pattern is printed using a thermal printer (TH-M2 / PS) manufactured by Okura Electric Co., Ltd., and the image density and the white area density at an applied energy of 0.36 mJ / dot are manufactured by X-Rite (eXact density Measurement). The results are shown in Tables 1 and 2. In addition, the result of this test shows that color development sensitivity is so favorable that the value is large.
- ⁇ Heat resistance (white part test)> A thermal recording material printed in a checkered pattern with an applied energy of 0.36 mJ / dot using a thermal printer (TH-M2 / PS) manufactured by Okura Electric Co., is left at 90 ° C. and 100 ° C. for 1 hour, and then a white area The concentration was measured by X-Rite (eXact densitometer). The results are shown in Tables 1 and 2. In addition, the result of this test shows that the color development of the white part under high temperature is so small that the value is small, and is favorable.
- the heat-sensitive recording materials (laminates) of Examples 1-1 to 1-3 corresponding to the present invention develop only the compound (1) without using the compound (2) It can be seen that the same dynamic sensitivity as that of the heat-sensitive recording material of Comparative Example 1 used as an agent is exhibited. Furthermore, as apparent from Tables 1 and 2, the heat-sensitive recording material according to the present invention, which contains the compound (1) and the compound (2) in a specific ratio range, uses the compound (2) The storage stability of the white part at high temperatures such as 90 ° C. and 100 ° C. is better than that of Comparative Example 1 in which only the compound (1) is used as a developer, and the image storage stability at high temperatures can be improved. I understand.
- the amount of the compound (2) is 5.0% by weight and 7.5% by weight, as is apparent from the comparison between Examples 1-1 to 1-3 and Comparative Examples 1-3 and 1-4. It can be seen that the storage stability of the white part at high temperature is deteriorated when the value is increased. In Examples 1-1 to 1-3, the storability of the white portion at a high temperature is slightly inferior to that of Comparative Example 1-2, but the storability of the printed portion is good, and it is compared with Comparative Example 1-5. Then, it can be seen that the contrast of black and white is clear because the preservation of the white part under high temperature is extremely good.
- Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-6 The following Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-6 were performed to confirm the difference in the effects depending on the types of the compound (1) and the compound (2).
- Example 2-1 The respective solutions were mixed in the following proportions to prepare a coating solution for the thermosensitive recording layer.
- thermosensitive recording layer a coating liquid of the above composition of the thermosensitive recording layer is applied so that the dry weight of the thermosensitive recording layer is 6 g / m 2 without providing the undercoat layer on wood free paper which is a support, and dried with a blower drier.
- the thermosensitive recording layer was formed. This was smoothed by applying a pressure of 1 kgf / cm 2 with a super calender to obtain a thermosensitive recording material (laminate).
- Embodiment 2-2 A thermosensitive recording material (laminate) was produced in the same manner as in Example 2-1 except that 18.70 parts of solution A and 0.19 parts of solution B were used.
- Example 2-3 A thermosensitive recording material (laminate) was produced in the same manner as in Example 2-1 except that 4,4′-dipropoxydiphenylsulfone in solution B was changed to 4,4′-diallyloxydiphenylsulfone.
- Example 2-4 Example 2-- except that 4,4'-dipropoxydiphenyl sulfone in solution B was changed to 4,4'-diallyloxydiphenyl sulfone, solution A was changed to 18.80, and solution B to 0.09 parts In the same manner as 1), a heat-sensitive recording material (laminate) was produced.
- Example 2-5 A thermosensitive recording material (laminate) was produced in the same manner as in Example 2-2 except that 4,4′-dipropoxydiphenylsulfone in solution B was changed to 4,4′-diallyloxydiphenylsulfone.
- thermosensitive recording material (laminate) was produced in the same manner as in Example 2-1 except that 4-propoxy-4'-hydroxydiphenylsulfone in solution A was changed to 4-allyloxy-4'-hydroxydiphenylsulfone. .
- thermosensitive recording material (laminate) was produced in the same manner as in Example 2-1.
- thermosensitive recording material (laminate) was produced in the same manner as in Example 2-2 except that 4-propoxy-4'-hydroxydiphenylsulfone in solution A was changed to 4-allyloxy-4'-hydroxydiphenylsulfone. .
- thermosensitive recording material (laminate) was produced in the same manner as in Example 2-1 except that the solution A was changed to 18.80 parts and the solution B to 0.09 parts.
- thermosensitive recording material (laminate) obtained by the Example and the comparative example.
- the heat-sensitive recording material (laminate) of the present invention is all good in color development sensitivity, image storability at high temperature, and storability of white portion, and contrast of printed portion and white portion is clear even at high temperature Heat sensitive recording material can be provided.
- the heat-sensitive recording material and laminate of the present invention can be suitably used for applications such as paper, film, IC card, friction ball pen and the like.
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Abstract
Description
本発明の感熱記録材料は、支持体上に、感熱記録層を備えた感熱記録材料であって、該感熱記録層中に、下記式(1)で表される化合物(化合物(1))と下記式(2)で表される化合物(化合物(2))とを含み、かつこれらの合計量に対し、式(2)で表される化合物が0.01~2.0重量%であることを特徴とする。なお、本発明において、「感熱記録材料」とは支持体の上に感熱記録層を有するものであれば、その形態は紙、フィルム、合成紙、カード等のいずれであってもよい。なお、本発明の感熱記録材料において、化合物(1)は通常、顕色剤として機能する。ここで「支持体上」とは、支持体の少なくとも一方の面の上をいい、通常は片面である。また、「支持体上に備える」とは支持体の少なくとも一部に当該層が存在すればよい。
本発明の感熱記録材料及び積層体は、感熱記録層を有し、該感熱記録層において化合物(1)及び化合物(2)を特定の割合で含むものである。感熱記録層はこれらの化合物に加え、ロイコ染料、化合物(1)及び化合物(2)以外の顕色剤、増感剤、安定剤、バインダー、架橋剤、顔料、滑剤、その他の添加剤)等を含んでいてもよい。
式(1)中のR1及びR2は、互いに同一でも異なっていてもよく、炭素数1~3のアルキル基、炭素数1~3のアルケニル基、又はベンジル基を示し、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ビニル基、アリル基、ベンジル基が挙げられ、好ましくはプロピル基、イソプロピル基、アリル基、ベンジル基であり、より好ましくはプロピル基、アリル基である。
本発明において、感熱記録層にロイコ染料を使用することが好ましい。ロイコ染料は通常、塩基性であり、従来、感圧又は感熱記録紙分野で公知のもの全て使用することができる。ロイコ染料として、具体的には、トリフェニルメタン系ロイコ染料、フルオラン系ロイコ染料、フルオレン系ロイコ染料、ジビニル系ロイコ染料等が好ましい。以下に代表的な無色ないし淡色の染料(染料前駆体)の具体例を示す。また、これらのロイコ染料(ロイコ染料前駆体)は、1種のみを使用してもよく、2種以上を組み合わせて用いてもよい。ロイコ染料は化合物(1)及び化合物(2)の合計100重量部に対し、10~200重量部で使用することが好ましく、より好ましくは15~150重量部であり、さらに好ましくは20~100重量部である。
感熱記録層は、本発明の効果を阻害しない範囲で、本発明の化合物(1)以外の顕色剤(以降、その他の顕色剤と記す)を含有していてもよい。その他の顕色剤としては、従来の感圧又は感熱記録紙の分野で公知のものはすべて使用可能であり、特に制限されるものではないが好ましくは電子受容性顕色剤である。その他の顕色剤は、1種を単独で使用してもよく、2種以上を併用してもよい。その他の顕色剤を使用する場合、その使用量は、化合物(1)及び化合物(2)の合計100重量部に対して、好ましくは1~100重量部、より好ましくは1~70重量部、さらに好ましくは1~50重量部である。
本発明では、公知の増感剤を使用してもよい。増感剤には、特に限定は無いが、例えば、1,2-ジ-(3-メチルフェノキシ)エタン、β-ベンジルオキシナフタレン、炭素数10~21の脂肪酸アミド(例えば、ステアリン酸アミド、パルミチン酸アミド等)、エチレンビスアミド、モンタン酸ワックス、ポリエチレンワックス、p-ベンジルビフェニル、ジフェニルスルホン、4-ビフェニル-p-トリルエーテル、m-ターフェニル、1,2-ジフェノキシエタン、シュウ酸ジベンジル、シュウ酸ジ(p-クロロベンジル)、シュウ酸ジ(p-メチルベンジル)、テレフタル酸ジベンジル、p-ベンジルオキシ安息香酸ベンジル、ジ-p-トリルカーボネート、フェニル-α-ナフチルカーボネート、1,4-ジエトキシナフタレン、1-ヒドロキシ-2-ナフトエ酸フェニルエステル、o-キシレン-ビス-(フェニルエーテル)、4-(m-メチルフェノキシメチル)ビフェニル、4,4’-エチレンジオキシ-ビス-安息香酸ジベンジルエステル、ジベンゾイルオキシメタン、1,2-ジ(3-メチルフェノキシ)エチレン、ビス[2-(4-メトキシ-フェノキシ)エチル]エーテル、p-ニトロ安息香酸メチル、p-トルエンスルホン酸フェニル等を使用することができる。これらの中でも、1,2-ジ-(3-メチルフェノキシ)エタン、1,2-ジフェノキシエタン、炭素数10~21の脂肪酸アミド(例えば、ステアリン酸アミド、パルミチン酸アミド等)、β-ベンジルオキシナフタレン、ジフェニルスルホン、p-トルエンスルホンアミド、及びシュウ酸-ジ-p-メチルベンジルエステルが好ましく、低エネルギーでも高い発色感度を示す1,2-ジ-(3-メチルフェノキシ)エタンが特に好ましい。これらの増感剤は、1種のみを使用してもよく、2種以上を併用してもよい。増感剤を使用する場合、その使用量は、化合物(1)と化合物(2)の合計100重量部に対して、好ましくは25~250重量部であり、より好ましくは50~150重量部である。
本発明において感熱記録材料及び積層体の画像保存性を向上させるために、感熱記録層に安定剤を使用してもよい。安定剤とは、画像の保存性を向上させる効果があるものをいう。安定剤としては、例えば、ヒンダードフェノール系化合物、紫外線吸収剤(例えば、ベンゾフェノン系化合物、トリアゾール系化合物)、酸化防止剤等が挙げられる。これらの中でもヒンダードフェノール系化合物が、記録部の画像保存性(耐熱性、耐湿性、耐水性、耐可塑剤性等)を向上させる点で好ましい。
感熱記録層を形成するために、バインダーを使用することが好ましい。バインダーとしては、例えば、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アミド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール、オレフィン変性ポリビニルアルコール、ニトリル変性ポリビニルアルコール、ピロリドン変性ポリビニルアルコール、シリコーン変性ポリビニルアルコール、その他の変性ポリビニルアルコール、ヒドロキシエチルセルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、ポリスチレン、スチレン-無水マレイン酸共重合体、スチレン-ブタジエン共重合体等のスチレン共重合体、エチルセルロール及びアセチルセルロース等のセルロース誘導体、カゼイン、アラビヤゴム、酸化澱粉、エーテル化澱粉、ジアルデヒド澱粉、エステル化澱粉、ポリ塩化ビニル、ポリ酢酸ビニル、ポリアクリルアミド、ポリアクリル酸エステル、ポリビニルブチラール、ポリアミド樹脂、シリコーン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クマロン樹脂等が挙げられる。バインダーの使用量は、感熱記録層の固形分中、5~25重量%程度が適当である。
架橋剤としては、例えば、グリオキザール、メチロールメラミン、メラミンホルムアルデヒド樹脂、メラミン尿素樹脂、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、過硫酸カリウム、過硫酸アンモニウム、過硫酸ソーダ、塩化第二鉄、塩化マグネシウム、ホウ砂、ホウ酸、ミョウバン、塩化アンモニウム等が挙げられる。架橋剤を使用する場合、その使用量は、化合物(1)及び化合物(2)の合計100重量部に対して、好ましくは0.5~500重量部である。
顔料としては、例えば、シリカ(コロイダルシリカを除く)、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、タルク、酸化チタン、水酸化アルミニウム等の無機又は有機顔料等が挙げられる。顔料を使用する場合、その使用量は、化合物(1)及び化合物(2)の合計100重量部に対して、好ましくは25~1000重量部である。
滑剤としては、例えば、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩、ワックス類、シリコーン樹脂類等が挙げられる。滑剤を使用する場合、その使用量は、化合物(1)及び化合物(2)の合計100重量部に対して、好ましくは0.5~500重量部である。
その他の添加剤としては、例えば、分散剤、消泡剤、蛍光染料等が挙げられる。その他の添加剤を使用する場合、その使用量は、化合物(1)及び化合物(2)の合計100重量部に対して、好ましくは0.5~500重量部である。
本発明の感熱記録材料及び積層体で使用する支持体の形状、構造、大きさ、材料等については、特に制限はなく、目的に応じて適宜選択することができる。支持体の形状としては、シート状、ロール状、平板状等が挙げられる。支持体は、単層構造であっても、積層構造であってもよい。支持体の大きさは、目的とする感熱記録材料及び積層体の用途等に応じて適宜選択することができる。支持体の材料としては、例えば、プラスチックフィルム、合成紙、上質紙、古紙パルプ、再生紙、片艶紙、耐油紙、コート紙、アート紙、キャストコート紙、微塗工紙、樹脂ラミネート紙、剥離紙等が挙げられる。またこれらを組み合わせた複合シートを支持体として使用してもよい。
本発明の感熱記録材料及び積層体において、感熱記録層上に、トップコート層(保護層)を設けてもよい。一般に、感熱記録層上にトップコート層(保護層)を設けて、感熱記録材料及び積層体の画像保存性を向上させると、低エネルギーでの発色感度が低下する。しかしながら、本発明の感熱記録材料及び積層体では、化合物(1)を顕色剤として使用するため、感熱記録層上にトップコート層(保護層)を設けても、低エネルギーでの発色感度が良好である。トップコート層(保護層)に使用する各種成分の種類及び量は、要求される性能や記録適性に従って決定され、特に限定されるものではない。
本発明の感熱記録材料及び積層体においては、発色感度をさらに高める目的で、主に顔料及びバインダーを含むアンダーコート層を、支持体と感熱記録層との間に設けることもできる。また本発明の感熱記録材料及び積層体のカールの矯正を図るために、支持体の感熱記録層が存する面とは反対側の面に、バックコート層を設けてもよい。本発明の感熱記録材料及び積層体における各層の一態様として、トップコート(保護層)/感熱記録層/アンダーコート層/支持体/バックコート層の順に積層された態様が挙げられるが、これに限定されない。
さらに、支持体と前記アンダーコート層との間、前記アンダー層と感熱記録層との間、感熱記録層と前記トップコート層(保護層)との間、支持体と前記バックコート層との間に、中間コート層を形成してもよい。
本発明の感熱記録材料及び積層体は、通常、ロイコ染料、化合物(1)及び化合物(2)並びに必要に応じてその他の顕色剤、増感剤、安定剤等を含有する塗液を支持体の少なくとも片面上の少なくとも一部に塗布、乾燥して感熱記録層を形成することによって、製造することができる。この塗液は、周知慣用技術に従って塗布することができる。塗布手段に特に限定はなく、例えば、エアーナイフコーター、ロッドブレードコーター、ベントブレードコーター、ベベルブレードコーター、ロールコーター、カーテンコーター等の各種コーターを備えたオフマシン塗工機又はオンマシン塗工機を使用することができる。
本発明の感熱記録材料及び積層体は、紙、フィルム、ICカード、フリクションボールペン等の用途に好適に使用することができる。
下記のA液~G液をそれぞれ準備した。なお、A液~D液においては、各成分の平均粒子径が0.5μmになるまで、アシザワ社製ビーズミル/LMZで湿式粉砕を行った。なお、ここでの平均粒子径は、体積基準分布での平均径であり、日機装社製レーザー回折/散乱式粒度分布測定装置(Microtrac MT3000II)で測定した。
・4-プロポキシ-4’-ヒドロキシジフェニルスルホン(三菱ケミカル社製、商品名「TOMILAC KN」):40.0部
・ポリビニルアルコール(日本合成化学工業社製「GL-03」)10%水溶液:50.0部
・水:10.0部
・4,4’-ジプロポキシジフェニルスルホン:40.0部
・ポリビニルアルコール(日本合成化学工業社製「GL-03」)10%水溶液:50.0部
・水:10.0部
・3-ジブチルアミノ-6-メチル-7-アニリノフルオラン(山本化成社製、商品名「ODB-2」):36.5部
・ポリビニルアルコール(日本合成化学工業社製「L-3266」)10%水溶液:60.0部
・水:3.5部
・1,2-ジ-(3-メチルフェノキシ)エタン(三光社製、商品名「KS-232」):40.0部
・ポリビニルアルコール(日本合成化学工業社製「L-3266」)10%水溶液:50.0部
・水:10.0部
・60%固形分の炭酸カルシウム分散液(奥多摩工業社製、商品名「タマパールTP-123CS」
・36%ステアリン酸亜鉛分散液(中京油脂社製、商品名「ハイドリンZ-8-36」
・10%ポリビニルアルコール水溶液(日本合成社製、商品名「ゴーセノールNH-18」の10%水溶液)
化合物(1)と化合物(2)の配合量による効果の違いを確認するため、以下の実施例1-1~1-3及び比較例1-1~1-5を行った。
下記の割合で各液を混合して、感熱記録層の塗液を調製した。
A液:18.87部
B液: 0.02部
C液:10.00部
D液:18.89部
E液:29.75部
F液: 9.95部
G液:32.64部
A液を18.80部、B液を0.09部に変更したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
A液を18.70部、B液を0.19部に変更したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
B液を使用せず、A液を18.89部に変更したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
B液を使用せず、A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更した液を18.89部使用したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
A液を17.95部、B液を0.94部に変更したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
A液を17.47部、B液を1.42部に変更したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
B液を使用せず、A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-イソプロポキシ-4’-ヒドロキシジフェニルスルホン(日本曹達社製、D-8)に変更した液を18.89部使用したこと以外は実施例1-1と同様にして、感熱記録材料(積層体)を製造した。
実施例及び比較例で得られた感熱記録材料(積層体)について、次のような評価を行った。
大倉電機社製の感熱プリンター(TH-M2/PS)を使用して階調パターンの印字を行ない、印加エネルギー0.36mJ/dotでの画像濃度及び白紙部濃度をX-Rite社製(eXact濃度計)で測定した。結果を表-1、表-2に示す。なお、本試験の結果はその値が大きいほど発色感度が良好であることを示す。
大倉電機社製の感熱プリンター(TH-M2/PS)を使用して印加エネルギー0.36mJ/dotで市松模様に印字した感熱記録材料を、90℃及び100℃で1時間放置した後、白色部濃度をX-Rite社製(eXact濃度計)で測定した。結果を表-1、表-2に示す。なお、本試験の結果はその値が小さいほど高温下における白色部の発色が少なく、良好であることを示す。
大倉電機社製の感熱プリンター(TH-M2/PS)を使用して印加エネルギー0.36mJ/dotで市松模様に印字した感熱記録材料を、90℃及び100℃で1時間放置した後、印字部濃度をX-Rite社製(eXact濃度計)で測定した。結果を表-1、表-2に示す。なお、本試験の結果はその値が大きいほど高温下における印字部の保存性が良好であることを示す。
上記の白色部試験と印字部試験の結果の値のそれぞれについて、差を取り、白色部と印字部とのコントラストを評価した。この値が大きいほどコントラストに優れることを示す。
化合物(1)と化合物(2)の種類による効果の違いを確認するため、以下の実施例2-1~2-5及び比較例2-1~2-6を行った。
下記の割合で各液を混合して、感熱記録層の塗液を調製した。
A液:18.87部
B液: 0.02部
C液:10.00部
D液:18.89部
E液:29.75部
F液: 9.95部
G液:32.64部
A液を18.70部、B液を0.19部に変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
B液の4,4’-ジプロポキシジフェニルスルホンを4,4’-ジアリルオキシジフェニルスルホンに変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
B液の4,4’-ジプロポキシジフェニルスルホンを4,4’-ジアリルオキシジフェニルスルホンに変更し、A液を18.80、B液を0.09部に変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
B液の4,4’-ジプロポキシジフェニルスルホンを4,4’-ジアリルオキシジフェニルスルホンに変更したこと以外は実施例2-2と同様にして、感熱記録材料(積層体)を製造した。
A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更し、A液を18.80部、B液を0.09部に変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更したこと以外は実施例2-2と同様にして、感熱記録材料(積層体)を製造した。
A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更し、B液の4,4’-ジプロポキシジフェニルスルホンを4,4’-ジアリルオキシジフェニルスルホンに変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更し、B液の4,4’-ジプロポキシジフェニルスルホンを4,4’-ジアリルオキシジフェニルスルホンに変更し、A液を18.80部、B液を0.09部に変更したこと以外は実施例2-1と同様にして、感熱記録材料(積層体)を製造した。
A液の4-プロポキシ-4’-ヒドロキシジフェニルスルホンを4-アリルオキシ-4’-ヒドロキシジフェニルスルホンに変更し、B液の4,4’-ジプロポキシジフェニルスルホンを4,4’-ジアリルオキシジフェニルスルホンに変更したこと以外は実施例2-2と同様にして、感熱記録材料(積層体)を製造した。
実施例及び比較例で得られた感熱記録材料(積層体)について、次のような評価を行った。
大倉電機社製の感熱プリンター(TH-M2/PS)を使用して印加エネルギー0.36mJ/dotで市松模様に印字した感熱記録材料を、90℃で1時間放置した後、白色部濃度をX-Rite社製(eXact濃度計)で測定した。結果を表-3、表-4に示す。なお、本試験の結果はその値が小さいほど高温下における白色部の発色が少なく、良好であることを示す。
大倉電機社製の感熱プリンター(TH-M2/PS)を使用して印加エネルギー0.36mJ/dotで市松模様に印字した感熱記録材料を、90℃で1時間放置した後、印字部濃度をX-Rite社製(eXact濃度計)で測定した。結果を表-3、表-4に示す。なお、本試験の結果はその値が大きいほど高温下における印字部の保存性が良好であることを示す。
上記の白色部試験と印字部試験の結果の値のそれぞれについて、差を取り、白色部と印字部とのコントラストを評価した。この値が大きいほどコントラストに優れることを示す。
Claims (14)
- 支持体上に、感熱記録層を備えた感熱記録材料であり、該感熱記録層中に下記式(1)で表される化合物と下記式(2)で表される化合物とを含み、かつこれらの合計量に対して式(2)で表される化合物の含有量が0.01~2.0重量%である感熱記録材料。
- 前記感熱記録層に、前記式(1)で表される化合物として、4-プロポキシ-4’-ヒドロキシジフェニルスルホンを含む、請求項1に記載の感熱記録材料。
- 前記感熱記録層に、前記式(2)で化合物として、4,4’-ジプロポキシジフェニルスルホン、4,4’-ジアリルオキシジフェニルスルホン、4,4’-ジイソプロポキシジフェニルスルホン及び4,4’-ジベンジルオキシジフェニルスルホンから選ばれる少なくとも1種を含む、請求項1又は2に記載の感熱記録材料。
- 前記感熱記録層にロイコ染料を含む、請求項1乃至3のいずれか1項に記載の感熱記録材料。
- 前記式(1)で表される化合物と前記式(2)で表される化合物との合計100重量部に対し、前記ロイコ染料を10~200重量部含む、請求項4に記載の感熱記録材料。
- 前記感熱記録層に増感剤を含む、請求項1乃至5のいずれか1項に記載の感熱記録材料。
- 前記増感剤として、1,2-ジ-(3-メチルフェノキシ)エタン、1,2-ジフェノキシエタン、炭素数10~21の脂肪酸アミド、β-ベンジルオキシナフタレン、ジフェニルスルホン、p-トルエンスルホンアミド、及びシュウ酸-ジ-p-メチルベンジルエステルから選ばれる少なくとも1種を含有する、請求項6に記載の感熱記録材料。
- 支持体上に、感熱記録層を備えた積層体であり、該感熱記録層中に下記式(1)で表される化合物と下記式(2)で表される化合物とを含み、かつこれらの合計量に対して式(2)で表される化合物の含有量が0.01~2.0重量%である積層体。
- 前記感熱記録層に、前記式(1)で表される化合物として、4-プロポキシ-4’-ヒドロキシジフェニルスルホンを含む、請求項8に記載の積層体。
- 前記感熱記録層に、前記式(2)で化合物として、4,4’-ジプロポキシジフェニルスルホン、4,4’-ジアリルオキシジフェニルスルホン、4,4’-ジイソプロポキシジフェニルスルホン及び4,4’-ジベンジルオキシジフェニルスルホンから選ばれる少なくとも1種を含む、請求項8又は9に記載の積層体。
- 前記感熱記録層にロイコ染料を含む、請求項8乃至10のいずれか1項に記載の積層体。
- 前記式(1)で表される化合物と前記式(2)で表される化合物との合計100重量部に対し、前記ロイコ染料を10~200重量部含む、請求項11に記載の積層体。
- 前記感熱記録層に増感剤を含む、請求項8乃至12のいずれか1項に記載の積層体。
- 前記増感剤として、1,2-ジ-(3-メチルフェノキシ)エタン、1,2-ジフェノキシエタン、炭素数10~21の脂肪酸アミド、β-ベンジルオキシナフタレン、ジフェニルスルホン、p-トルエンスルホンアミド、及びシュウ酸-ジ-p-メチルベンジルエステルから選ばれる少なくとも1種を含有する、請求項13に記載の積層体。
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JP2012116158A (ja) * | 2010-12-03 | 2012-06-21 | Nippon Paper Industries Co Ltd | 感熱記録体 |
WO2013065704A1 (ja) * | 2011-10-31 | 2013-05-10 | 日本製紙株式会社 | フェノールスルホン酸アリールエステル、顕色剤および感熱記録材料 |
JP2016165835A (ja) * | 2015-03-10 | 2016-09-15 | 王子ホールディングス株式会社 | 感熱記録体 |
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JPH0311433A (ja) | 1989-06-09 | 1991-01-18 | Hitachi Ltd | インタフェース障害診断回路 |
JP2000168239A (ja) * | 1998-12-07 | 2000-06-20 | Nicca Chemical Co Ltd | 感熱記録材料 |
JP5160324B2 (ja) * | 2007-08-23 | 2013-03-13 | 日華化学株式会社 | 感熱記録材料 |
WO2014189044A1 (ja) * | 2013-05-22 | 2014-11-27 | 王子ホールディングス株式会社 | 感熱記録体 |
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2018
- 2018-08-07 KR KR1020207004050A patent/KR102618091B1/ko active IP Right Grant
- 2018-08-07 CN CN201880051611.5A patent/CN110997340A/zh active Pending
- 2018-08-07 WO PCT/JP2018/029661 patent/WO2019031525A1/ja unknown
- 2018-08-07 EP EP18843067.2A patent/EP3666540A4/en active Pending
- 2018-08-07 JP JP2019535686A patent/JP7067559B2/ja active Active
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2020
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Title |
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See also references of EP3666540A4 |
Also Published As
Publication number | Publication date |
---|---|
KR20200035967A (ko) | 2020-04-06 |
JP7067559B2 (ja) | 2022-05-16 |
JPWO2019031525A1 (ja) | 2020-08-20 |
EP3666540A1 (en) | 2020-06-17 |
CN110997340A (zh) | 2020-04-10 |
US20200171870A1 (en) | 2020-06-04 |
KR102618091B1 (ko) | 2023-12-27 |
EP3666540A4 (en) | 2020-09-09 |
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