WO2003101751A1 - Matiere d'enregistrement et feuille d'enregistrement - Google Patents

Matiere d'enregistrement et feuille d'enregistrement Download PDF

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Publication number
WO2003101751A1
WO2003101751A1 PCT/JP2003/006818 JP0306818W WO03101751A1 WO 2003101751 A1 WO2003101751 A1 WO 2003101751A1 JP 0306818 W JP0306818 W JP 0306818W WO 03101751 A1 WO03101751 A1 WO 03101751A1
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Prior art keywords
group
recording material
integer
formula
alkyl
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PCT/JP2003/006818
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English (en)
Japanese (ja)
Inventor
Hiroshi Fujii
Shinichi Sato
Tadashi Kawakami
Original Assignee
Nippon Soda Co.,Ltd.
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Priority claimed from JP2002295706A external-priority patent/JP2004130584A/ja
Priority claimed from JP2002367645A external-priority patent/JP2004195820A/ja
Priority claimed from JP2003027583A external-priority patent/JP2004237503A/ja
Priority claimed from JP2003106234A external-priority patent/JP2004160974A/ja
Application filed by Nippon Soda Co.,Ltd. filed Critical Nippon Soda Co.,Ltd.
Priority to AU2003241954A priority Critical patent/AU2003241954A1/en
Publication of WO2003101751A1 publication Critical patent/WO2003101751A1/fr
Priority to US10/999,630 priority patent/US7390771B2/en

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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
    • 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

Definitions

  • the present invention relates to a recording material having excellent coloring sensitivity and excellent storage stability of background and images, and a recording sheet having a recording material layer formed from the recording material on a base sheet.
  • Background art :
  • a recording material that utilizes color development by the reaction between a color-forming dye and a developer can be recorded in a relatively simple apparatus in a short time without performing complicated processing such as development and fixing. Widely used as heat-sensitive recording materials or pressure-sensitive copying materials for output recording.
  • the compound represented by the formula (1) of the present invention is described in WO 01/25193, a compound represented by the formula (10), and a compound represented by the formula (11).
  • the compound and / or the composition of the compound represented by the formula (12) is disclosed in WO 02/82129, but the recording material using these can always satisfy the coloring sensitivity. Not something
  • the present invention has been made in view of the above circumstances, has no background capri, is excellent in coloring sensitivity, and has excellent background and image storability, and a recording material on a base sheet. It is an object to provide a recording sheet having a recording material layer formed. Disclosure of the invention:
  • the present invention is a.
  • Shaku 1 and! 1 2 each independently represent a hydrogen atom or a C 1 through C 6 alkyl group
  • a 1 represents an integer of. 1 to 6
  • n 1 represents 0, 1 or 2 integer
  • m 1 And m 2 each independently represent 0 or an integer of 1 to 3.
  • m 1 and m 2 are not simultaneously 0.
  • R 3 and R 4 are each independently a nitro group, a carbonyl group, a halogen atom C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkyl force Ruponiru group or C.
  • 1 to C 6 alkoxy force Lupo two group 1 [1 3 and 111 4 are each independently 0, 1 or 2 of an integer, 111 3 and 111 4 are respectively When 2, R 3 and R 4 may be different from each other, and Y 1 is CO or NR 5 CO (wherein, R 5 has a hydrogen atom, a C 1 -C 6 alkyl group, A phenyl group or a benzyl group which may have a substituent.).
  • X 1 and X 2 are each independently a straight-chain or branched hydrocarbon which may have 1 to 12 carbon atoms which may have a saturated, unsaturated or ether bond.
  • R 1 2 represents a methylene group or an ethylene group
  • R 1 3 is. Representing a hydrogen atom or an alkyl group C. 1 to C 4
  • represents a group represented by 6 ⁇ ! ⁇ 1 1 are each independent, a halogen atom, a C 1 ⁇ C 6 alkyl group or C. 2 to C 6 alkenyl group and table, ms m 1.
  • Each independently represents 0 or an integer of 1 to 4, and when it is an integer of 2 or more, R e R 11 may be the same or different, and b is 0 or 1 to 10 Represents an integer.
  • a recording material comprising at least one compound selected from the compounds represented by the formula: However, when the compound represented by the formula (2) is contained, at least two or more kinds of the compound represented by the formula (1) are contained.
  • R 1 , RRR nmmmm 4 and Y 1 represent the same meaning as described above.
  • R 1 R 2 , R 3 , R 4 , 1 , nm 1 , m 2 , m 3 , m 4 and Y 1 represent the same meaning as described above.
  • a recording material comprising at least one compound represented by the formula: and a benzotriazole derivative.
  • R 1 , RRR anmmmm 4 and Y 1 represent the same meaning as described above.
  • a recording material characterized by containing at least one compound represented by the formula (1) and containing amorphous silicon.
  • R 1 R 2 R 3 R 4 a 1, 1 1 m 1, m 2 m 3 m 4 ⁇ Pi Y 1 are as defined above.
  • a recording material comprising at least one compound represented by the formula: and 4-1 benzyloxy-4 '-(2-methylglycidyloxy) diphenylsulfone.
  • X 1 and X 2 are each independently a straight-chain or branched hydrocarbon which may have a saturated or unsaturated C 1 C 12 or an ether bond.
  • R 1 2 represents a methylene group or an ethylene group
  • R 1 3 is. Representing a hydrogen atom or an alkyl group C 1 through C 4
  • represents a group represented by 6 ⁇ ! ⁇ 1 1 are each independent, halogen atom, and display the C. 1 to C 6 alkyl group or C. 2 to C 6 alkenyl group
  • ms m 1 ° are each independently 0 or 1-4
  • Represents an integer and when it is an integer of 2 or more, Re R 11 may be the same or different
  • b represents 0 or an integer of 1 to 10.
  • a recording material comprising at least one compound represented by the formula:
  • the phthalic acid derivative has the formula (5)
  • R 14 and R 15 each independently represent a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, an aryl group which may have a substituent or a substituent.
  • R 16 represents a hydroxyl group, a halogen atom, a C 1 -C 6 alkyl group or a C 2 -C 6 alkenyl group, and m 11 represents 0 or 1 to 4 When m 11 is an integer of 2 or more, R 16 may be different.
  • the recording material according to 1. or 2., characterized by being represented by:
  • the hydroxybenzoic acid derivative has the formula (6)
  • R 17 is a hydroxyl group, a halogen atom, ⁇ 1 to. 6 represents an alkyl group or ⁇ 2-6 alkenyl group, m 12 represents an integer of 0 or 1 to 4, and when m 12 is an integer of 2 or more, R 17 may be different; 18 represents a C1-C6 alkyl group, a C2-C6 alkenyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent.
  • the recording material described in 1. or 2. characterized by the following.
  • the anilide derivative has the formula (7)
  • R 19 is a C 1 -C 18 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylene group, Represents an aryl group or an aralkyl group which may have a substituent;
  • R 2 Q is a hydrogen atom; a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, Represents an aryl group or an aralkyl group which may have a substituent, and
  • R 21 represents a halogen atom, a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 alkoxy groups, C.
  • anilide derivative is a single acetate toluidide.
  • the biphenyl derivative has the formula (8)
  • R 2 2 and R 2 3 are each independently a hydroxyl group, a force Rupokishiru group, C 1 ⁇ C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C 1 To C 6 alkyl carbonyl group, C 1 to C 6 alkyl carbonyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent, m 14 and m 15 They are each independently an integer of 0 or from 1 to 5 when m 1 4 and m 1 5 is an integer of 2 or more, respectively, R 2 2 and R 2 3 may be different from each other.
  • the recording material according to 1. or 2., characterized by being represented by:
  • the benzotriazole derivative has the formula (9)
  • R 2 4 and R 2 5 each independently represents a hydroxyl group, a halogen atom, C l to C 8 alkyl group, a C. 2 to C 6 alkenyl or C 1 through C 8 alkoxy group
  • m 1 6 represents an integer of 0 or 1-4, when m 1 6 is an integer of 2 or more, R 2 4 is different connexion may
  • m 1 7 represents an integer of 0 or from 1 to 5, m
  • R 25 may be different.
  • R 2 6 and R 2 7 independently represent a hydrogen atom or a C 1 through C 6 alkyl le group, a 2 represents an integer of. 1 to 6, n 2 is 0, M 18 represents 0 or an integer of 1 to 3;
  • R 2 8 and R 2 9 are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C 1 through C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C 1 represents ⁇ C 6 alkyl group or a C. 1 to C 6 alkoxycarbonyl two Le group, m 1 9 and m 2 ° each independently represent 0, 1 or 2 integer, m 1 9 and m 2 .
  • R 28 and R 29 may be different from each other, and Y 2 is CO or NR 3 ° CO (where R 3 ° is a hydrogen atom, a C1-C6 alkyl group, A phenyl group which may have a substituent or a benzyl group which may have a substituent.). And at least one compound represented by the formula (11):
  • R 3 1 and R 3 2 are each independently, represent a hydrogen atom or a C. 1 to C 6 alkyl le group, a 3 represents an integer of. 1 to 6, n 3 is 0, Represents an integer of 1 or 2, m 2 1 represents an integer of 0 or 1-3.
  • R 3 3 and R 34 are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C. 1 to C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C. 1 to represents C 6 alkyl force Ruponiru group or C. 1 to C 6 alkoxy force Lupo two Le group, m 2 2 and m 2 3 are each independently 0, 1 or 2 of an integer, m 2 2 ⁇ Pi when m 2 3 are each 2, R 3 3 ⁇ Pi R 34 may be different from each other, Y 3 is, CO or NR 3 5 C_ ⁇ (wherein, R 3 5 is a hydrogen atom, C. 1 to C 6 represents an alkyl group, a phenyl group which may have a substituent or a benzyl group which may have a substituent.) At least one compound represented by the formula: and Z or the formula (12)
  • R 3 6 and R 3 7 each independently represent a hydrogen atom or a C. 1 to C 6 alkyl le group
  • a 4 represents an integer of. 1 to 6
  • n 4 is 0, 1 or an integer 2
  • m 2 4 represents an integer of 0 or 1-3.
  • R 3 8 and R 3 9 are each independently, a nitro group, a force Rupokishiru group, a halogen atom, C. 1 to C 6 alkyl group, C. 2 to C 6 alkenyl group, C 1 through C 6 alkoxy group, C 1 represents ⁇ C 6 alkyl force Ruponiru group or C. 1 to C 6 alkoxy force Lupo two Le group, m 2 5 and m 2 6 each independently represent 0, 1 or 2 integer, m 2 5 and when m 2 6 are each 2, R 3 8 and R 3 9 may be different from each other, Y 4 is, CO or NR 3 5 C_ ⁇ (wherein, R 3 5 is a hydrogen atom, C.
  • the recording material layer formed from the recording material of the present invention is excellent in color development sensitivity and excellent in background and preservation of images. Further, the recording material of the present invention does not cause background capri.
  • the present invention relates to a recording material containing a chromogenic dye, comprising at least one compound represented by the formula (1), and further comprising a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, and biphenic acid.
  • a chromogenic dye comprising at least one compound represented by the formula (1), and further comprising a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, and biphenic acid.
  • Derivatives benzotriazole derivatives, amorphous silica, 4-benzyloxy 4 '-(2-methyldaricyloxy) diphenyl sulfone, and a small number of compounds selected from the compounds represented by the formula (2). It is characterized by containing at least one.
  • the content of the phthalic acid derivative is arbitrary, it is usually 10 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). Parts by weight, more preferably in the range of 30 to 70 parts by weight.
  • the content of the hydroxybenzoic acid derivative is arbitrary, but is usually 1 to 100 parts by weight, preferably 10 to 3 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). It is in the range of 100 parts by weight, more preferably 20 to 100 parts by weight.
  • the content of the anilide derivative is optional, it is usually 10 to 100 parts by weight, preferably 20 to 20 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably 30 to 100 parts by weight.
  • the content of the biphenyl derivative is optional, but is usually 10 to 100 parts by weight; preferably 100 to 100 parts by weight, preferably 20 to 30 parts by weight, per 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably in the range of 30 to 200 parts by weight.
  • the content of the benzotriazole derivative is arbitrary, but is usually from 10 to 200 parts by weight, preferably from 20 to 10 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably 30 to 70 parts by weight.
  • the content of the amorphous silica is arbitrary, it is usually 50 to 100 parts by weight, preferably 75 to 70 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). 0 parts by weight, more preferably 100 to 500 parts by weight.
  • the content of the 4-benzyloxy-4 ′-(2-methyldalicydyloxy) diphenylsulfone is arbitrary, but is not limited to 100 parts by weight of the compound represented by the formula (1). On the other hand, it is usually in the range of 10 to 200 parts by weight, preferably 20 to 170 parts by weight, more preferably 30 to 150 parts by weight.
  • the content of the compound represented by the formula (2) is arbitrary, it is usually 1 Q to 500 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). It is in the range of 10 to 300 parts by weight, more preferably 10 to 100 parts by weight.
  • the compound of the present invention represented by the formula (10), and the compound represented by the formula (11) and / or the compound represented by the formula (12) are used as a developer mixture.
  • the mixing method includes mixing with each powder, melt mixing, addition and mixing during crystallization of the compound represented by the above formula (10), and o-hydroxylazine as the raw material hydroxylazine. There is a method in which a reaction is performed using a mixture of phosphorus, m-hydroxydirin, p-hydroxydirin and the like, and two or three or more compounds are simultaneously synthesized and contained.
  • R 1 and R 2 are each independently a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group, etc.
  • a 1 represents an integer of. 1 to 6
  • n 1 represents 0, 1 or 2.
  • m 1 and m 2 each independently represent 0 or an integer of 1 to 3, provided that 111 1 and 111 2 are not simultaneously 0.
  • R 3 and R 4 are each independently a nitro group; a propyloxyl group; a halogen atom such as fluorine, chlorine, bromine or iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n C 1 -C 6 alkyl groups such as pentyl and n-hexyl groups; C 2 -C 6 alkenyl groups such as probenyl, isopropenyl and butenyl groups; methoxy, ethoxy, n-propoxy, isopropoxy, C1-C6 alkoxy groups such as n-butoxy, sec-butoxy and t-butoxy groups; methylcarbonyl, ethylcarbonyl, n-propyl-lponyl, isopropyl-lponyl, n-butylpropyl, t-butylpropyl and the like C
  • n 3 and m 4 each independently represent 0, 1 or 2
  • Y 1 represents CO or NR Represents 5 Co.
  • R 5 is a hydrogen atom; a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, etc .; A phenyl group which may be substituted; a benzyl group which may have a substituent; As a substituent of a phenyl group which may have a substituent and a benzyl group which may have a substituent, a nitro group; a carboxyl group; a halogen atom such as a fluorine, chlorine, bromine or iodine atom; C 1 -C 6 alkyl groups such as, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl; C such as probenyl, is
  • R 2 6 and R 2 7 are each independently a hydrogen atom; hexyl methyl, E chill, n- propyl, isopropyl, n- butyl, t-butyl, n- pentyl, n- Represents a C1-C6 alkyl group such as a group.
  • a 2 represents an integer of. 1 to 6
  • n 2 represents 0, 1 or 2.
  • m 18 represents 0 or an integer of 1 to 3.
  • R 2 8 and R 2 9 are each independently, a nitro group; force Rupokishiru group; fluorine, chlorine, bromine, halogen atom such as an iodine atom; methyl, Echiru, n- propyl, I an isopropyl, n- butyl, t —C 1 -C 6 alkyl group such as butyl, n-pentyl, n-hexyl group; C 2 -C 6 alkenyl group such as propenyl, isoprobenyl, butenyl group; methoxy, ethoxy, n— C1-C6 alkoxy groups such as propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy; methylcarbonyl, ethylcarbonyl, n-propylcapillonyl, isopropylcarbonyl, n-butylcarbonyl, t —C 1 -C 6 alky
  • n 19 and m 2 each independently represents 0, 1 or 2
  • Y 2 represents CO or NR 30 C 0.
  • R 3 Q is a hydrogen atom; a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group; A phenyl group which may have a benzyl group which may have a substituent; As a substituent of the phenyl group which may have a substituent and the benzyl group which may have a substituent, a nitro group; a carbonyl group; a halogen atom such as a fluorine, chlorine, bromine, iodine atom; C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl; propyl, isopropyl, butenyl,
  • C2-C6 alkenyl group C1-C6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group; methyl carbonyl C :!
  • C6 alkyl propylonyl groups such as ethoxypropyl, n-propyl propylonyl, isopropyl propylonyl, n-butyl propylonyl, t-butyl carbonyl, etc .
  • methoxycarbonyl And C-C6 alkoxycarbonyl groups such as X-ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl and t-butoxycarbonyl.
  • R 3 1 and R 3 2 are each independently a hydrogen atom; methyl, E chill, n- propyl, isopropyl, n- butyl, t - butyl, n- pentyl, n- Represents a C1-C6 alkyl group such as a xyl group.
  • a 3 represents an integer of. 1 to 6
  • n 3 represents 0, 1 or 2.
  • m 2 1 represents an integer of 0 or 1-3.
  • R 3 3 and R 3 4 are each independently, a nitro group; force Rupokishiru group; fluorine, chlorine, bromine, halogen atom such as an iodine atom; methyl, Echiru, n- propyl, I an isopropyl, n- heptyl, t C 1 -C 6 alkyl groups such as -butyl, n-pentyl and n-hexyl groups; C 2 -C 6 alkenyl groups such as probenyl, isopropenyl and butenyl groups; methoxy, ethoxy, n-propoxy C 1 -C 6 alkoxy groups such as, isopropoxy, n-butoxy, sec-butoxy, t-butoxy; C1-C6 alkylcarbonyl groups such as rucarbonyl, ethylcarbonyl, n-propylcapillon, isopropylcarbonyl, n-butylcarbon
  • n 2 2 and m 2 3 each independently represent 0, 1 or 2
  • Y 3 represents CO or NR 3 5 C 0.
  • R 3 5 is a hydrogen atom; -; the location substituent methyl, Echiru, n- propyl, isopropyl, n- butyl Le, t-butyl, n- pentyl, C. 1 to C 6 alkyl group such as hexyl group n- A phenyl group which may have a benzyl group which may have a substituent; As a substituent of a phenyl group which may have a substituent and a benzyl group which may have a substituent, a nitro group; a carbonyl group; a halogen atom such as a fluorine, chlorine, bromine or iodine atom; C1-C6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group; C such as propyl, is
  • R 3 6 and R 3 7 are each independently a hydrogen atom; hexyl methyl, E chill, n- propyl, isopropyl, n- butyl, t-butyl, n- pentyl, n- Represents a C1-C6 alkyl group such as a group.
  • a 4 is an integer of. 1 to 6, n 4 represents 0, 1 or 2.
  • m 2 4 represents an integer of 0 or 1-3.
  • R 3 8 and R 3 9 are each independently, a nitro group; force Rupokishiru group; fluorine, chlorine, bromine, halogen atom such as an iodine atom; methyl, Echiru, n- propyl, I an isopropyl, n- heptyl, t 1-butyl, n-pentyl, n-hexyl, etc.
  • C 2 to C 6 alkenyl groups such as propenyl, isopropenyl and butenyl groups; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t —
  • a C 1 -C 6 alkoxy group such as a butoxy group
  • a C 1 -C 6 alkylcarbonyl group such as a methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, t-butylcarbonyl group
  • Represents a C 1 -C 6 alkoxycarbonyl group such as carbonyl, X toxiccarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and t-butoxycarbonyl.
  • 111 25 and 11 26 each independently represent 0, 1 or 2, and Y 4 represents CO or NR 4 ° C.
  • R 40 is a hydrogen atom; a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, etc .; A phenyl group which may be substituted; a benzyl group which may have a substituent; As a substituent of the phenyl group which may have a substituent and the benzyl group which may have a substituent, a nitro group; a carbonyl group; a halogen atom such as a fluorine, chlorine, bromine, iodine atom; C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl groups; probenyl, isoprob
  • C2-C6 alkenyl group C1-C6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group; methyl carbonyl, ethyl C1 to C6 alkyl propylonyl groups such as rucarponyl, n-propyl propylonyl, isopropyl propylonyl, n-butyl propylonyl, t-butylcarbonyl group, etc .; C1 to C6 alkoxycarbonyl groups such as ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and t-butoxycarbonyl group.
  • a compound in which Y 1 is NR 5 C ⁇ is preferable, and a compound in which Y 1 is NHC 0 is more preferable.
  • Examples of the compound represented by the formula (1) include N— (2′-hydroxyphenylthio) acetyl-2-hydroxydiline and N— (3′-hydroxyphenyl). Enylthio) acetyl-2-hydroxyaline, N-(4'-hydroxyphenylthio) acetyl-2-hydroxyaniline, N-(2 '-hydroxyphenyl) acetyl-4-hydroxyaniline, N-(3' —Hydroxyphenylthio) acetyl-4—Hydroxyphenyl, N— (4′-hydroxyphenyl) acetyl-4—Hydroxyphenyl, N- (2′-hydroxyphenylthio) acetyl-3-hydroxy Diphosphorus, N— (3′-hydroxyphenylthio) a-cetyl-3-hydroxyhydrin, N— (4′-hydroxyphenylthio) acetyl-3-hydroxycarbinyl and the like.
  • Preferred examples of the compound represented by the formula (10) and a mixture of the compounds represented by the formulas (11) and / or (12) include the following (a) to (c).
  • X 1 and X 2 each independently represent a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group.
  • R e R 11 is each independently a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group C 1 -C 6 groups such as t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl Alkyl group; pinyl group, aryl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanenyl group, 2-methyl-2-propenyl group, C1-C6 alkenyl groups such as 1-pentenyl group, 2-
  • the compound represented by the formula (2) can be produced, for example, according to a known method such as the method described in WO97 / 16420.
  • R 14 and R 15 are each independently a methyl, ethyl, n-butyl pill, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl group, etc.
  • the benzene ring, naphthalene ring and pyridine ring may further have a substituent.
  • substituents include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; methyl, ethyl, n-propyl, C 1 -C 6 alkyl groups such as isopropyl, n-butyl, t-butyl, n-pentyl and n-hexyl; C 2 -C 6 alkenyl such as propenyl, isopropyl and butenyl; No.
  • R 16 is a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine or iodine atom; C 1 to C- such as methylethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl and n-hexyl group.
  • C 6 alkyl group represents a C 2 to C 6 alkenyl group such as probenyl, isopropylidene, butenyl group, and m 11 represents 0 or an integer of 1 to 4.
  • phthalic acid derivative examples include dimethyl isophthalate, dimethyl terephthalate, getyl isophthalate, diphenyl isophthalate, dibenzyl terephthalate, etc., and these may be used alone or in combination of two or more. You can also. Among these, dimethyl terephthalate is preferred.
  • R 17 is a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine or iodine atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n—
  • a C 1 -C 6 alkyl group such as a hexyl group
  • a C 2 -C 6 alkenyl group such as a propenyl, isopropenyl or butenyl group
  • m 12 represents 0 or an integer of 1-4;
  • R 18 is a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl; propenyl, isoprobenyl
  • a C 2 -C 6 alkenyl group such as a butenyl group; an aryl group such as a phenyl, naphthyl, or pyridyl group; an aralkyl group such as a benzyl group or a phenyl group; a benzene ring, a naphthalene ring, and a pyridine ring of an aryl group and an aralkyl group; It may further have a substituent.
  • substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and n. —C 1 to C 6 alkyl groups such as pentyl and n—hexyl groups; and C 2 to C 6 alkenyl groups such as propenyl, isopropenyl and butenyl groups. That.
  • halogen atoms such as fluorine, chlorine, bromine, and iodine atoms
  • C 1 to C 6 alkyl groups such as pentyl and n—hexyl groups
  • C 2 to C 6 alkenyl groups such as propenyl, isopropenyl and buten
  • Hydroxybenzoic acid derivatives include 4-hydroxymethyl benzoate and 3-hydroxymethylbenzoate. Ethyl hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, and the like. One type or a mixture of two or more types can be used. Among these, benzyl 4-hydroxybenzoate is preferred.
  • R 19 is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n— Nonyl, n-tesinole, n-indesi, n-doors, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heppudecyl, n -C18 alkyl group; C2-C6 alkenyl group such as probenyl, isoprobenyl, butenyl group; methylcarbonylmethylene, ethylcarbonylmethylene, n-propylcapillonylmethylene, isopropylcarbonylmethylene, methylcarbonyl C 1 -C 6 alky
  • aryl group such as a C1-C6 alkylcarbonyl group, phenyl, naphthyl, and pyridyl group; an aralkyl group such as a benzyl group and a phenethyl group; Also, R
  • R 2 D or a substituent represented by R 2 1, Ariru group or Ararukiru group location
  • the substituent may be substituted because the benzene ring, naphthalene ring or pyridine ring of the aryl group or the aralkyl group may further have a substituent, such as fluorine, Halogen atoms such as chlorine, bromine and iodine atoms; C1-C6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, and n-hexyl groups; And C 2 -C 6 alkenyl groups such as benzyl, isopropenyl and butenyl groups.
  • m 13 represents 0 or an integer of 1 to 5.
  • anilide derivatives include acetoacetate anilide, p—acetotoluidide, o—acetotoluidide, m—acetotoluidide, o—acetoanisidide, m—acetoanisidide, p—acetoanisidide, and N—acetoacetide.
  • p-acetotoluzide is preferred.
  • R 2 2 and R 2 3 are each independently a hydroxyl group, a force Rupokishiru group; methyl, Echiru, n - propyl, isopropyl, n- butyl, t one heptyl, n- pentyl, n - C 1 -C 6 alkyl group such as hexyl group; C 2 -C 6 alkenyl group such as propenyl, isoprobenyl, butenyl group; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , T — C 1 -C 6 alkoxy group such as butoxy group; methyl C -C 6, such as methyl carbonyl, ethyl carbonyl, n-propylcarbonyl, isopropyl carbonyl, n-butyl carbonyl, t-butyl carbonyl Alkyl carboxy group; methyl carboxy, n
  • the gin ring may further have a substituent.
  • a substituent a C 1 -C 6 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc .;
  • C 2 -C 6 alkenyl groups such as benzyl, isopropenyl and butenyl groups.
  • m 14 and m 15 each independently represent 0 or an integer of 1 to 5;
  • biphenyl derivatives examples include biphenyl, 2,2′-biphenyl, 4,4′-biphenyl, 4,4′-diacetoxybiphenyl, 4-acetoxybiphenyl, 4-acetylbiphenyl, 4-methoxybiphenyl, 4,4'-Diacetyl biphenyl, 4,4'-Dimethyl biphenyl, 4-benzylbiphenyl, m-Ethyl phenyl, etc. These may be used alone or in combination of two or more. Can also be used. Among these, 4-acetylbiphenyl is preferred.
  • R 2 4 and R 2 5 are each independently a hydroxyl group; fluorine, chlorine, a bromine, a halogen atom such as an iodine atom; methyl, Edjiru, n- propyl, isopropyl, n - butyl, C 1 -C 8 alkyl groups such as t-butyl, n-pentyl, isopentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl; propyl and isopropyl C 2 -C 6 alkenyl groups such as enyl and butenyl groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec—butoxy, t-butoxy, pentoxy, hexoxy, heptoxy, octoxy groups represents C. 1 to C 8 alkoxy group such as, m
  • Benzotriazole derivatives include 2- (2, -hydroxy-5'-methylphenyl) benzotriazole, 2- (2, -hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'- Hydroxy—3 ', 5'-di-1: monobutylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-clobenzobenzotriazole, 2-((2'-hydroxy-3 ', 5'-di-t-butylphenyl) -15-chlorobenzotriazole, 2- (2'-hydroxy-13', 5'-d-amylphenyl) benzotriazo 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-1,3- (3 ", 4", 5 ", 6, '- Tetrahydrophthalimidome Tyl) 1 5'-methylphenyl] benzotriazole, 2,2'
  • the compound represented by the formula (9) is preferable.
  • 2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2- ( 2'-Hydroxy- 5'-t-Butylphenyl) benzotriazole, 2- (2'-Hydroxy-3,, 5'-T-butylbutyl) benzotriazole, 2- (2, —Hydroxy-1 3 ′ —t—Butyl_5, —Methylphenyl) -1 5
  • the present invention contains at least one kind of the coloring dye and at least one kind of the compound represented by the formula (1), and further comprises a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, and a biphenyl derivative.
  • Derivatives benzotriazole derivatives, amorphous silicic acid, at least one compound selected from the group consisting of 4-benzyloxy-4 '-(2-methyldaricyloxy) diphenylsulfone and the compound represented by the formula (2).
  • Any kind of recording material containing one kind can be used for any purpose. For example, it can be used as a heat-sensitive recording material or a pressure-sensitive copying material.
  • the color-forming dye used in the recording material of the present invention is not particularly limited as long as it is a color-forming dye that forms a color when it comes into contact with a developer which is an acidic substance.
  • Specific examples thereof include leuco dyes such as fluoran, phthalide, lactam, 1, phenylmethane, phenothiazine and spiropyran.
  • fluoran-based color-forming dyes include, for example, 3- (ethylethylamino 6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, and 3- (N-ethyl-1-N-isobutylamino) 6—Methyl—7—A Nilinofluoran, 3— (N—Methyl-N—Propylamino) 1 6—Methyl-1 7-Anilinofluoran, 3 -— (N—Ethylu N—Isopentylamino) — 6—Me Cyl-1 7-anilinofluorane, 3-Jetylamino-1 7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-(N-ethyl-p-toluidino 1) 6-methyl-7-anilin
  • phthalide-based coloring dyes examples include 3- ⁇ 4- [4- (4-anilino) -anilino] anilino ⁇ —6-methyl-7-chloro fluoran and 3,3-bis [2-1- (4-dimethylaminophenyl) _2 -— (4-methoxyphenyl) vinyl] 1,4,5,6,7-tetrachlorophthalide, 3,6,6 'tris (dimethylamino ) Spiro (fluorene-9,3'-phthalide), 3,3-bis (4'-getylaminophenol) -16-getylaminophthalide.
  • coloring dyes can be used alone to obtain a recording material of the coloring color, but two or more of them can be used in combination.
  • a recording material that develops a true black color can be manufactured by using a mixture of three primary color developing dyes of red, blue, and green or a black dye.
  • the recording material of the present invention includes a coloring dye, a compound represented by the above formula (1), a phthalic acid derivative, a hydroxybenzoic acid derivative, an anilide derivative, a biphenyl derivative, a benzotriazole derivative, and an amorphous compound.
  • One, two or more kinds of fillers, dispersants, antioxidants, desensitizers, anti-adhesives, defoamers, light stabilizers, optical brighteners and the like can be contained as necessary.
  • these chemicals may be contained in the color-forming layer. However, in the case of a multilayer structure, they may be contained in any layer such as a protective layer. In particular, when an overcoat layer or an undercoat layer is provided above and / or below the coloring layer, these layers may contain an antioxidant, a light stabilizer and the like. Further, an antioxidant and a light stabilizer can be contained in these layers in a form encapsulated in microcapsules as necessary.
  • the former includes, for example, bisphenol A, 4, 4'-sec-butylidene bisphenol, 4, 4 '—cyclohexylidenebisphenol, 2,2 1-dimethyl-3,3-bis (4-hydroxyphenyl) butane, 2,2'-dihydroxydiphenyl, pentamethylene-bis (4-hydroxybenzoate), 2 : 2 mono-dimethyl-3,3-di Bisphenol compounds such as (4-hydroxyphenyl) pentane, 2,2-di (4-hydroxyphenyl) hexane; 4,4'-dihydroxy-opened xidiphenylthioether, 1,7-di (4-hydroxy Phenylthio) ⁇ 3,5-dioxaheptane, 2,2'-bis (4-hydroxyphenylthio) diethyl ether, 4,4'dihydroxy-3,3'-dimethyldiphenylthioether Bisphenol compound;
  • Metal salts of benzoic acid such as zinc benzoate, zinc 4-benzotobenzoate, etc.
  • Salicylic acids such as 4- [2- (4-methoxyphenyloxy) ethyloxy] salicylic acid; zinc salicylate, bis [4-1] (Octyloxycarponylamino) I 2 -hydroxybenzoic acid] Metal salt of salicylic acid such as zinc;
  • 2-hydroxyphthalic acid diesters 2-hydroxy-6-esters of hydroxynaphthoic acid such as carboxynaphthalene Trihalomethyl sulfones such as tribromomethylphenylsulfone; sulfonyl pereas such as 4,4, -bis (-toluenesulfonylaminocarbonylamino) diphenylmethane; hydroxyacetophenone, p-phenylphenol, Examples include benzyl 4-hydroxyphenylacetate, p-benzylphenol, hydroxyquinone-monobenzyl ether, 2,4-dihydroxy-12'-methoxybenzanilide, tetracyanoquinodimethane and the like.
  • a developer for the pressure-sensitive recording material for example, acid clay, activated clay, avatargite, bentonite, colloidal silica, aluminum silicate, magnesium silicate Inorganic acidic substances such as nesidum, zinc silicate, tin silicate, calcined kaolin, and talc; aliphatic sulfonic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, and stearic acid; benzoic acid, P—t —Butyl benzoic acid, phthalic acid, gallic acid, salicylic acid,
  • image storage stabilizers include, for example, epoxy group-containing diphenylsulfones such as 4,4′-diglycidyloxydiphenylsulfone; 1,4-diglycidyloxybenzene, and 4- [a- (hydroxymethyl) benzyloxy ] — 4 '—Hydroxydiphenyl sulfone, 2-propanol derivative, salicylic acid derivative, oxynaphthoic acid derivative metal salt (especially zinc salt), 2,2,2-methylenebis (4,6-t-butylphenyl) phosphate And other water-insoluble zinc compounds.
  • epoxy group-containing diphenylsulfones such as 4,4′-diglycidyloxydiphenylsulfone; 1,4-diglycidyloxybenzene, and 4- [a- (hydroxymethyl) benzyloxy ] — 4 '—Hydroxydiphenyl sulfone, 2-propanol derivative, salicylic acid derivative
  • sensitizers include, for example, higher fatty acid amides such as stearate amide; benzamide, thioacetamide; dibenzyl oxalate, dioxalate (4-methylpentyl), dioxalate (4 —Cross-opening benzyl), bis (t-butylphenol) s; diphenylsulfone and its derivatives; 4,4′dimethoxydiphenylsulfone, 4,4′diethoxydiphenylsulfone, 4,4 ′ — Dipropoxydiphenylsulfone, 4,4'diisopropoxydiphenylsulfone, 4,4'-dibutoxydiphenylsulfone, 4,4'diisobutoxydiphenylsulfone,
  • 4,4'-dihydroxydiphenylsulfone such as 4,4'-dipentyloxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, etc .; 2,4, dimethoxydiphenylsulfone, 2 , .4 'One Jet Nyl sulfone, 2, 4 'dipropoxy diphenyl sulfone, 2, 4' diisopropoxy diphenyl sulfone, 2, 4 'dibutoxy diphenyl sulfone, 2, 4' diisobutoxy diphenyl sulfone, 2, 4 'Diethers of 2,4'-dihydroxydiphenylsulfone such as dipentyloxydiphenylsulfone, 2,4,1-dihexyloxydiphenylsulfone;
  • fillers include, for example, silica, clay, kaolin, sintering power, talc, satin white, aluminum hydroxide, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium silicate, aluminum silicate, Plastic pigments and the like.
  • salts of alkaline earth metals and more preferred are carbonates such as calcium carbonate and magnesium carbonate.
  • dispersing agent examples include sulfosuccinates such as dioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfate, and fatty acid salt.
  • Antioxidants include, for example, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2, -methylenebis (4-ethyl-6-t-butylphenol), 4,4′-propylmethylene Bis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-t-butyl-5-methyl) 1,1,3—tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,
  • desensitizer examples include aliphatic higher alcohols, polyethylene glycol, guanidine derivatives and the like.
  • antiadhesive examples include stearic acid, zinc stearate, calcium stearate, carnauba wax, paraffin wax, ester wax and the like.
  • salicylic acid UV absorbers such as phenylsalicylate, Pt-butylphenylsalicylate, and p-octylphenylsalicylate; 2,4-dihydroxybenzophenone , 2-hydroxy 1-4-methoxybenzophenone, 2-hydroxy 4-benzyloxybenzophenone, 2-hydroxy 4-octyloxybenzophenone, 2-hydroxy 4-dodecyloxy Benzophenone, 2, 2'-dihydroxy-1-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-14-methoxy-1 5-sulfobenzo Benzophenone ultraviolet rays such as phenone, bis (2-methoxy-4
  • Each of the above-mentioned color developers, image stabilizers, sensitizers, fillers, dispersants, antioxidants, desensitizers, anti-adhesives, defoamers, light stabilizers, fluorescent brighteners, etc. is used alone. Alternatively, two or more kinds can be used in combination.
  • the amount of each is usually 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of the chromogenic dye. You.
  • the recording sheet of the present invention has a recording material layer formed by using the recording material of the present invention on a base sheet.
  • the base sheet include a paper base sheet, a synthetic resin film or a synthetic resin sheet.
  • Paper base sheets include, for example, thin paper, craft paper, titanium paper, phosphor paper, paperboard, woodfree paper, coated paper, art paper, parchment paper, dalasin paper, parchment paper, paraffin paper, Recycled paper and the like.
  • the synthetic resin film or sheet include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene monoacetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, and polyethylene na.
  • Examples include films or sheets of phthalate, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, and polycarbonate.
  • a paper base sheet is preferred.
  • the thickness of the base sheet is not particularly limited. 5500 m.
  • the recording material layer can be formed, for example, by applying a solution or dispersion of the recording material on a base sheet by a known coating method.
  • the amount of coating depends on the concentration of the solution or dispersion of the recording material, but is usually 0.1 OO g Zm 2 after drying, preferably; It is in the range of ⁇ 2 0 g / m 2.
  • Examples of the method of applying the solution or dispersion of the recording material of the present invention on a substrate sheet include a roll coating method, a curtain flow coating method, a myaba coating method, a reverse coating method, a gravure coating method, and a gravure reverse coating method. Air-knife coat method, kiss coat method, blade coat method, smooth coat method, roll knife coat method and the like.
  • the recording material layer may be formed directly on the base material sheet, may be formed by interposing another layer such as an anchor coat layer, or a protective layer may be further provided on the recording material layer. It can also be formed.
  • an anchor coat layer and a protective layer can be formed from a solution or a dispersion containing one or more of known synthetic resins, and include the above-mentioned other developers, other image stabilizers, and other photosensitive materials. Agents, other fillers, dispersants, antioxidants, desensitizers, anti-adhesives, defoamers, light stabilizers, optical brighteners, etc. Can be.
  • the recording sheet of the present invention is preferably a thermosensitive recording paper / a pressure-sensitive copying paper.
  • the thermosensitive recording paper is prepared, for example, by dispersing fine particles of a color-forming dye and fine particles of a recording material in an aqueous solution of a water-soluble binder such as polyvinyl alcohol or cellulose, and preparing a dispersion. It can be manufactured by coating on a material sheet and drying.
  • a chromogenic dye microencapsulated by a known method is dispersed with an appropriate dispersant to prepare a chromogenic dye dispersion, and the dispersion is placed on the first paper base sheet.
  • a developer dispersion is applied to a second paper base sheet to form a color developer sheet, and the obtained sheets are combined.
  • the recording material of the present invention is dispersed in one or both of the color dye dispersion and the developer dispersion.
  • the pressure-sensitive copying paper is composed of an upper paper having a microphone opening capsule containing an organic solvent solution of a color-forming dye applied and carried on the lower surface, and a lower paper having a developer (acidic substance) applied and carried on the upper surface. Or a so-called self-content paper in which microcapsules containing an organic solvent solution of a chromogenic dye and a developer are applied on the same paper surface. There may be. Examples of the developer include those similar to those listed as usable as the developer for the pressure-sensitive recording material. Brief invention of drawings:
  • FIG. 1 is a graph showing the results of a comparative test of dynamic color sensitivity (Test Example 1).
  • FIG. 2 is a graph showing the results of a comparative test in the near infrared absorption region (Test Example 4).
  • FIG. 3 is a graph showing the results of a comparative test of dynamic color sensitivity (Test Example 5).
  • FIG. 4 is a graph showing the results of a dynamic color sensitivity comparison test (Test Example 10).
  • dispersions (A to D liquids) containing the following components were prepared. However, each component used was sufficiently crushed with a sand grinder.
  • the coating liquid for the recording material was applied to a wire rod (trade name: wire bar, No.
  • a recording material was prepared in the same manner as in Example 1 except that di (4-methylbenzyl) oxalate was used in place of the dimethyl terephthalate in the auxiliary dispersion (liquid C) of Example 1. Then, a thermal recording paper was made.
  • Test example 1 (dynamic color sensitivity)
  • Example 1 A part of the heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was cut out and used as each test paper.
  • a thermal paper coloring tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) at 0.38 and 0.50 mJ per dot. Heat was applied to develop a saturated checkerboard pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth).
  • Table 1 Measurement results of dynamic color sensitivity
  • Test Example 2 Image light fastness test
  • Example 1 A part of the heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was cut out, and saturated coloring was performed in the same manner as in Test Example 1. Next, the saturated color image was subjected to a light fastness tester (trade name: Ultraviolet Long Life Fed Dome Ichiyo FAL-5, manufactured by Suga Test Machine Co., Ltd.) to obtain a wavelength of 380.
  • Example 1 A part of the thermal recording paper prepared in Example 1 and Comparative Example 1 was cut out, and each test paper was subjected to a constant temperature incubator (trade name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 0 ° C., 100 ° C. and 110 for 24 hours.
  • a constant temperature incubator (trade name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 0 ° C., 100 ° C. and 110 for 24 hours.
  • the skin density was measured after holding for 24 hours in a constant temperature incubator.
  • Table 3 shows the measurement results.
  • Table 3 Surface heat resistance test measurement results
  • Test example 4 Near infrared absorption measurement test
  • Example 2 A part of the heat-sensitive recording paper prepared in Example 1 and Comparative Example 1 was cut out, and saturated coloring was performed in the same manner as in Test Example 1. Then, the saturated color image was measured with a self-recording altimeter (U-340, manufactured by Hitachi, Ltd.). Table 4 shows the results.
  • FIG. 2 shows an example of the measurement chart (500 nm to 800 nm).
  • Table 4 (Near infrared absorption measurement results) Example 2
  • Example 2 A part of the heat-sensitive recording paper prepared in Example 2 and Comparative Example 1 was cut out and used as each test paper.
  • a thermal paper color tester (trade name: TH-PMD type, manufactured by Oshoku Denki Co., Ltd.), and apply 0.38 and 0.50 mJ per dot. Then, heat was applied to cause saturated color development of the checkerboard pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-5514, manufactured by Macbeth).
  • the results are shown in Table 5 and FIG. Table 5 (Results of measurement of dynamic color sensitivity) Test Example 6 (Image light fastness test)
  • a recording material was prepared in the same manner as in Example 1 except that p-acetotoluid was used instead of dimethyl terephthalate in the auxiliary agent dispersion liquid (liquid C) of Example 1.
  • Thermal recording paper was made. As a result of visual observation of the obtained heat-sensitive recording paper, no background blur was observed.
  • Test Example 7 (Dynamic color sensitivity)
  • Example 7 A part of the heat-sensitive recording paper prepared in Example 3 and Comparative Example 1 was cut out and used as each test paper.
  • a thermal paper coloring tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) at 0.38 and 0.50 mJ per dot. Heat was applied to develop a saturated checkerboard pattern, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 7.
  • Table 7 Measurement results of dynamic color sensitivity
  • Test Example 8 Skin heat resistance test
  • thermosensitive recording paper prepared in Example 3 and Comparative Example 1 was cut out, and each test paper was heated at a constant temperature and constant temperature (trade name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 90 and at 100 ° C. for 24 hours.
  • the skin density (Macbeth value) was measured after holding for 24 hours in a constant temperature incubator. Table 8 shows the measurement results. Table 8 (Surface heat resistance test measurement results) Test Example 9 (Image light fastness test)
  • thermosensitive recording material was prepared in the same manner as in Example 1 except that 4-acetyl phenyl biphenyl was used instead of dimethyl terephthalate in the auxiliary agent dispersion liquid (solution C) of Example 1, and a thermosensitive recording was performed. Created paper. As a result of visual observation of the obtained thermosensitive recording paper, no background capri was observed.
  • Test example 10 (Dynamic color sensitivity)
  • Example 4 A part of the heat-sensitive recording paper prepared in Example 4 and Comparative Example 1 was cut out and used as each test paper.
  • a thermal paper coloring tester (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.) and heat at 0.32 and 0.44 mJ per dot.
  • Macbeth value The measurement was performed with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 10 and FIG. Table 10 (Measurement results of dynamic color sensitivity) Test Example 1 1 (Surface heat resistance test)
  • thermosensitive recording paper prepared in Example 4 and Comparative Example 1 was cut out, and each test paper was heated at a constant temperature and constant temperature (product name: DK-400, manufactured by Yamato Scientific Co., Ltd.). It was kept at 90 ° C and 100 for 24 hours.
  • Example 6 In the same manner as in Example 1, except that dimethyl terephthalate was replaced with 2- (2-benzotriazolyl) -p-cresol in the auxiliary dispersion (liquid C) in Example 1 Then, a recording material was prepared to prepare a thermal recording paper. As a result of visually observing the obtained heat-sensitive recording paper, no background strength was observed.
  • Example 6 In the same manner as in Example 1, except that dimethyl terephthalate was replaced with 2- (2-benzotriazolyl) -p-cresol in the auxiliary dispersion (liquid C) in Example 1 Then, a recording material was prepared to prepare a thermal recording paper. As a result of visually observing the obtained heat-sensitive recording paper, no background strength was observed.
  • Example 6 Example 6
  • Example 1 (2′-hydroxy 3 ′, 5′-di-t-butylphenyl) benzotriazole was used in the auxiliary dispersion (solution C) instead of dimethyl terephthalate.
  • a recording material was prepared in the same manner as in the method described in Example 1 to prepare a thermal recording paper. As a result of visual observation of the obtained heat-sensitive recording paper, no ground capri was observed. Comparative Example 2
  • a recording material was prepared in the same manner as in Example 1 except that the auxiliary dispersion liquid (liquid C) of Example 1 was not used, and a thermosensitive recording paper was prepared.
  • Test example 1 2 (Dynamic color sensitivity)
  • Test Example 1 3 (Image light fastness test)
  • Test example 1 4 (background light resistance test)
  • Example 7 (Preparation of thermal recording paper) First, dispersions ( ⁇ ′ to ⁇ ′) containing the following components were prepared. However, each component used was sufficiently crushed with a sand grinder.
  • thermosensitive recording paper A recording material was prepared in the same manner as in Example 7, except that the composition of the D 'solution of the coating solution of Example 7 was changed to 1 part by weight, to prepare a thermosensitive recording paper. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed.
  • Example 9 Preparation of thermal recording paper
  • a recording material was prepared in the same manner as in Example 7, except that the composition of the D 'solution of the coating solution in Example 7 was changed to 2 parts by weight, to prepare a thermosensitive recording paper. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed. Comparative Example 3
  • a recording material was prepared in the same manner as in Example 7 except that the image stabilizer dispersion liquid (D 'liquid) of Example 7 was not used, and a thermosensitive recording paper was prepared.
  • Test Example 15 Image plasticizer resistance test
  • thermal recording paper prepared in Examples 7 to 9 and Comparative Example 3 was cut out and used as each test paper.
  • a thermal paper color tester (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.) under the conditions of 0.08 to 0.72 mJ per dot. Heat was applied to make the checkered pattern saturated.
  • a vinyl chloride wrap film was adhered to the color-developing surface and the back surface of each of the test papers, and the state was maintained at 40 at 32 hours. Measure the optical density of the image immediately after saturation and after holding at 40 ° C for 32 hours with a Macbeth reflection densitometer (trade name: RD-514, filter used: # 106, manufactured by Macbeth) did. The results are shown in Table 15. Table 15 (Image plasticizer resistance test results)
  • Test Example 15 Each test paper that had been saturated and colored in the same manner as in Test Example 15 was immersed in salad oil and kept at room temperature for 24 hours. The optical densities of the images were measured with a Macbeth reflection densitometer immediately after saturation coloring and after 24 hours at room temperature. The results are shown in Table 16. Table 16 (Image oil resistance test results)
  • Amorphous silica (P-603, manufactured by Mizusawa Chemical Industry Co., Ltd.) 27.8 parts Polyvinyl alcohol 10% aqueous solution 26.2 parts Water 7 1 part Parts by weight, 2 parts by weight of the liquid B '', and 4 parts by weight of the liquid C were mixed to prepare a coating liquid for a recording material for thermosensitive recording paper.
  • Example 1 1 the coating liquid for the recording material was applied to a wire rod (trade name: Wire Par, No. 1 2, applied using the Webster Inc.) white paper (coating weight - about dry weight 5. 5 g / m 2), and dried and then treated one seat calender, a heat-sensitive recording paper did. As a result of visually observing the obtained thermal recording paper, no background capri was observed.
  • a wire rod trade name: Wire Par, No. 1 2, applied using the Webster Inc.
  • white paper coating weight - about dry weight 5. 5 g / m 2
  • Example 10 The amorphous silica (P—527, P—527, P—603, manufactured by Mizusawa Kagaku Kogyo Co., Ltd.) of the inorganic pigment dispersion liquid (C ′′ liquid) of Example 10 was used. A recording material was prepared in the same manner as in Example 10 except for changing to Mizusawa Chemical Industry Co., Ltd.), and a thermosensitive recording paper was prepared. As a result of visual observation of the obtained heat-sensitive recording paper, no ground capri was observed. Comparative Example 4
  • thermosensitive recording paper was prepared in the same manner as described in Example 10 except that the method was changed to).
  • thermosensitive recording paper prepared in Examples 10 and 11 and Comparative Example 4 was cut out and used as each test paper.
  • a thermal paper color tester (trade name: TH-PMD type, manufactured by Okura Electric Co., Ltd.) for each test paper, the conditions were 0.38 and 0.50 mJ per dot. Heat was applied to make the checkered pattern develop a saturated color, and the print density (Macbeth value) was measured with a Macbeth reflection densitometer (trade name: RD-514, manufactured by Macbeth). The results are shown in Table 17.
  • Table 17 Results of measurement of dynamic color sensitivity
  • dispersions ( ⁇ ′ ′′ to ⁇ ′′ ′ ′) containing the following components were prepared. However, each component used was sufficiently crushed with a sand grinder. Dye dispersion ( ⁇ "'liquid)
  • c represents an integer of 2 to 10. 1 6 parts Polypinyl alcohol 10% aqueous solution 8 4 parts-Filler dispersion ( ⁇ '' 'liquid)
  • the coating liquid for the recording material was applied to white paper using a wire rod (trade name: wire bar, No. 12, manufactured by Webster) (applied amount-about 5% by dry weight). After drying at 5 g / m 2 ), the sheet was calendered to produce a thermal recording paper. As a result of visually observing the obtained thermal recording paper, no background capri was observed.
  • a wire rod trade name: wire bar, No. 12, manufactured by Webster
  • Example 12 Recording was performed in the same manner as in Example 12 except that dimethyl terephthalate was changed to di (4-methylpendyl) oxalate in the sensitizer dispersion liquid (C '' 'liquid) of Example 12. The materials were prepared and thermal recording paper was made. As a result of visual observation of the obtained thermal recording paper, no ground capri was observed. Comparative Example 5
  • Example 12 The procedure was the same as that described in Example 2 except that the image stabilizer dispersion liquid (D 'liquid) was not used and the composition of the C' '' liquid of the coating liquid was 1 part by weight.
  • the recording material was prepared in this manner, and a thermal recording paper was prepared.
  • Test Example 1 9 Image plasticizer resistance test
  • Test Example 20 (Image oil resistance test) Each test paper saturated with the same method as in Test Example 19 was immersed in salad oil and kept at room temperature for 24 hours. The optical densities of the images were measured with a Macbeth reflection densitometer immediately after saturation coloring and after 24 hours at room temperature. The results are shown in Table 20. Table 20 (Image oil resistance test results) Industrial applicability:
  • a recording material and a recording sheet which are free from background capri, have excellent color development sensitivity, and have excellent background and image storage stability.
  • the recording material containing the phthalic acid derivative of the present invention is particularly excellent in the heat resistance of the background and the light resistance of the image, and is capable of reading barcodes in the near infrared region.
  • the recording material containing the hydroxybenzoic acid derivative of the present invention can significantly improve the color sensitivity particularly, and is excellent in light fastness of an image.
  • the recording material containing the anilide derivative of the present invention is particularly excellent in heat resistance of the background and light resistance of images.
  • the recording material containing the biphenyl derivative of the present invention is particularly excellent in heat resistance of the background
  • the recording material containing the benzotriazole derivative of the present invention is particularly excellent in light resistance of the background.
  • the recording material containing the amorphous silica of the present invention can greatly improve the coloring sensitivity, in particular, and is excellent in the light resistance of the background.
  • the recording material containing 4'-benzyloxy 4 '-(2-methyldalicydyloxy) diphenyl sulfone of the present invention is particularly excellent in the plasticizer resistance and oil resistance of images,
  • the compound of the present invention represented by the above formula (2) is particularly excellent in plasticizer resistance and oil resistance of an image.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

L'invention concerne une matière d'enregistrement ne provoquant pas de voile, et présentant une excellente sensibilité de développement couleur, ainsi qu'une excellente stabilité de conservation de zones de non-image et d'images, ainsi que des feuilles d'enregistrement obtenues par la formation d'une couche d'enregistrement à partir de matière d'enregistrement, sur une feuille de support. La matière d'enregistrement contient un colorant de formation de couleur, et est caractérisée par ce qu'elle contient au moins un composé de formule (1). Dans cette formule R1 et R2 sont chacun hydrogène ou alkyle C1-6; a1 est un nombre entier compris entre 1 et 6; n1 est un nombre entier égal à 0, 1 ou 2; m1 et m2 sont chacun des nombres entiers compris entre 0 et 3, à la condition qu'à la fois m1 et m2 ne soient pas égal à 0; R3 et R4 sont chacun nitro, carboxyle, halogène, alkyle C1-6, ou analogue; m3 et m4 sont chacun des nombres entiers égal à 0, 1 ou 2; et Y1 désigne CO ou NR5CO, et au moins un composé sélectionné parmi les dérivés d'acide phtalique, des dérivés d'acide hydroxybenzoïque, des dérivés d'anilide, des dérivés biphényle, des dérivés de benzotriazole, de la silice amorphe, du 4-benzyloxy-4'-(2-méthylglycidyloxy)-diphényle sulfone et des composés de formule (2).
PCT/JP2003/006818 2001-04-04 2003-05-30 Matiere d'enregistrement et feuille d'enregistrement WO2003101751A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003241954A AU2003241954A1 (en) 2002-06-03 2003-05-30 Recording material and recording sheet
US10/999,630 US7390771B2 (en) 2001-04-04 2004-11-30 Recording material and recording sheet

Applications Claiming Priority (20)

Application Number Priority Date Filing Date Title
JP2002162055 2002-06-03
JP2002162058 2002-06-03
JP2002-162058 2002-06-03
JP2002-162055 2002-06-03
JP2002227021 2002-08-05
JP2002-227021 2002-08-05
JP2002278780 2002-09-25
JP2002-278780 2002-09-25
JP2002-295706 2002-10-09
JP2002295706A JP2004130584A (ja) 2002-10-09 2002-10-09 記録材料及び記録シート
JP2002-356280 2002-12-09
JP2002356280 2002-12-09
JP2002367645A JP2004195820A (ja) 2002-12-19 2002-12-19 記録材料及び記録シート
JP2002-367645 2002-12-19
JP2003027583A JP2004237503A (ja) 2003-02-04 2003-02-04 記録材料及び記録シート
JP2003-26674 2003-02-04
JP2003026674 2003-02-04
JP2003-27583 2003-02-04
JP2003106234A JP2004160974A (ja) 2002-09-25 2003-04-10 記録材料及び記録シート
JP2003-106234 2003-04-10

Related Child Applications (2)

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US10/472,125 Continuation-In-Part US20040198603A1 (en) 2001-04-04 2002-03-29 Recording material and recording sheet
US10/999,630 Continuation-In-Part US7390771B2 (en) 2001-04-04 2004-11-30 Recording material and recording sheet

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7390771B2 (en) 2001-04-04 2008-06-24 Nippon Soda Co., Ltd. Recording material and recording sheet
WO2008001391A3 (fr) * 2006-06-27 2009-03-05 Jawaharlal Nehru Ct For Advanc Inhibiteurs spécifiques de site de l'histone méthyltransférase [hmtase] et procédé permettant de les préparer

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63153182A (ja) * 1986-12-17 1988-06-25 Fuji Photo Film Co Ltd 記録材料
WO2001025193A1 (fr) * 1999-10-04 2001-04-12 Nippon Soda Co., Ltd. Composes phenoliques et supports d'enregistrement les contenant
JP2002113951A (ja) * 2000-10-06 2002-04-16 Mitsui Chemicals Inc 感熱記録材料
JP2002137554A (ja) * 2000-10-31 2002-05-14 Asahi Denka Kogyo Kk 感熱記録材料
JP2002264538A (ja) * 2001-03-12 2002-09-18 Nippon Soda Co Ltd 記録材料および記録シート
JP2002301873A (ja) * 2001-04-04 2002-10-15 Nippon Soda Co Ltd 記録材料及び記録シート
WO2002081229A1 (fr) * 2001-04-04 2002-10-17 Nippon Soda Co., Ltd. Matériau et feuille d'enregistrement

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63153182A (ja) * 1986-12-17 1988-06-25 Fuji Photo Film Co Ltd 記録材料
WO2001025193A1 (fr) * 1999-10-04 2001-04-12 Nippon Soda Co., Ltd. Composes phenoliques et supports d'enregistrement les contenant
JP2002113951A (ja) * 2000-10-06 2002-04-16 Mitsui Chemicals Inc 感熱記録材料
JP2002137554A (ja) * 2000-10-31 2002-05-14 Asahi Denka Kogyo Kk 感熱記録材料
JP2002264538A (ja) * 2001-03-12 2002-09-18 Nippon Soda Co Ltd 記録材料および記録シート
JP2002301873A (ja) * 2001-04-04 2002-10-15 Nippon Soda Co Ltd 記録材料及び記録シート
WO2002081229A1 (fr) * 2001-04-04 2002-10-17 Nippon Soda Co., Ltd. Matériau et feuille d'enregistrement

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7390771B2 (en) 2001-04-04 2008-06-24 Nippon Soda Co., Ltd. Recording material and recording sheet
WO2008001391A3 (fr) * 2006-06-27 2009-03-05 Jawaharlal Nehru Ct For Advanc Inhibiteurs spécifiques de site de l'histone méthyltransférase [hmtase] et procédé permettant de les préparer
US7875741B2 (en) 2006-06-27 2011-01-25 Jawaharlal Nehru Centre For Advanced Scientific Research Site-specific inhibitors of histone methyltransferase [HMTase] and process of preparation thereof
US8003698B2 (en) 2006-06-27 2011-08-23 Jawaharlal Nehru Centre For Advanced Scientific Research Site-specific inhibitors of histone methyltransferase (HMTASE) and process of preparation thereof

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