USRE36321E - Heat-sensitive recording material - Google Patents

Heat-sensitive recording material Download PDF

Info

Publication number
USRE36321E
USRE36321E US07/209,196 US20919688A USRE36321E US RE36321 E USRE36321 E US RE36321E US 20919688 A US20919688 A US 20919688A US RE36321 E USRE36321 E US RE36321E
Authority
US
United States
Prior art keywords
heat
sensitive recording
recording layer
carbon atoms
iaddend
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/209,196
Inventor
Toshitake Suzuki
Naoto Arai
Shoji Aoyagi
Toranosuke Saito
Masakatu Kitani
Takashi Ishibashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanko Kaihatsu Kagaku Kenkyusho KK
New Oji Paper Co Ltd
Original Assignee
KANSAKI PAPER MANUFACTURING Co Ltd
Sanko Kaihatsu Kagaku Kenkyusho KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP58166011A external-priority patent/JPS6056588A/en
Priority claimed from JP59137565A external-priority patent/JPS6116888A/en
Application filed by KANSAKI PAPER MANUFACTURING Co Ltd, Sanko Kaihatsu Kagaku Kenkyusho KK filed Critical KANSAKI PAPER MANUFACTURING Co Ltd
Priority to US07/209,196 priority Critical patent/USRE36321E/en
Assigned to OJI PAPER CO., LTD. reassignment OJI PAPER CO., LTD. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: KANZAKI PAPER MANUFACTURING CO., LTD.
Application granted granted Critical
Publication of USRE36321E publication Critical patent/USRE36321E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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

  • This invention relates to heat-sensitive recording materials, and more particularly to heat-sensitive recording materials having excellent whiteness in a recording layer and suited to high-speed recording.
  • Heat-sensitive recording materials are well known which are adapted to produce record images by thermally contacting a colorless or pale-colored basic dye with a color acceptor for a color forming reaction.
  • heat-sensitive recording devices such as heat-sensitive facsimile systems, heat-sensitive printers, etc. using the above heat-sensitive recording materials in recent years, these heat-sensitive recording devices are made operable at a high speed.
  • heat-sensitive recording materials must meet the requirements of having a high recording sensitivity, and many proposals have been made.
  • the conventional recording materials have the drawback, for example, that the recording layer decreases in whiteness with an increase in recording sensitivity.
  • An object of the present invention is to provide a heat-sensitive recording material having an enhanced recording sensitivity without entailing the decrease of whiteness of the recording layer.
  • the invention provides a heat-sensitive recording material incorporating a colorless or pale-colored basic dye and a color acceptor which is reactive with the basic dye to form a color when contacted therewith, the recording material being characterized in that at least one compound represented by the formula I!
  • R 1 to R 4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R 1 and R 2 and/or substituents R 3 and R 4 may link together to form aromatic ring(s), n is an integer of 1 to 10.
  • R 1 to R 4 are preferably each hydrogen atom, alkyl having 1 to 4 carbon atoms, phenyl, benzyl, chlorine atom, methoxy, methylthio, cyano or nitro. Further, n is preferably 1 to 6, more preferably 1 to 4 and most preferably 2 or 4.
  • heat-fusible materials can generally be prepared by Williamson's synthesis of ether and are usable singly or a mixture of at least two of them. Further, the heat-fusible materials of the invention preferably have melting points in the range of 70° to 130° C.
  • fatty acid amide such as stearic acid amide, stearic acid methylenebisamide, oleic acid amide, palmitic acid amide, coconut fatty acid amide, etc; hindered phenols such as 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, etc.; ultraviolet absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-hydroxy-4-benzyloxybenzophenone; etc.; and various known heat-fusible substances.
  • the amount to be used of the above heat-fusible materials having the specific structure is not particularly limited but is usually 10 to 1000 parts by weight, preferably 50 to 500 parts by weight per 100 parts by weight of the color accept
  • Triarylmethane-based dyes e.g., 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole-3-yl)-6-dimethylaminophthalide, 3,3-bis(2-phenylindole-3-yl)-6-dimethylaminophthalide, 3-p-dimethyla
  • Diphenylmethane-based dyes e.g., 4,4'-bis-dimethylaminobenzhydryl benzyl ether, N-halophenyl-leucoauramine, N-2,4,5-trichlorophenyl-leucoauramine, etc.
  • Thiazine-based dyes e.g., benzoyl-leucomethyleneblue, p-nitrobenzoyl-leucomethyleneblue, etc.
  • Spiro-based dyes e.g., 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-(6'-methoxybenzo)spiropyran, 3-propyl-spiro-dibenzopyran, etc.
  • Lactam-based dyes e.g., rhodamine-B-anilinolactam, rhodamine-(p-nitroanilino)lactam, rhodamine-(o-chloroanilino)lactam, etc.
  • Fluoran-based dyes e.g., 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6,7-dimethylfluoran, 3-(N-ethyl-p-toluidino)-7-methylfluoran, 3-diethylamino-7-(N-acetyl-N-methylamino)fluoran, 3-diethylamino-7-N-methylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-(N-methyl-N-benzylamino)fluoran, 3-diethylamino-7-(N-chloroethyl-N-methyla
  • the color acceptor which is used in combination with the above basic dye is not particularly limited.
  • Various color acceptors can be employed which are fusible or vaporous by heating and produce record images by contact with the basic dye.
  • useful color acceptors are 4-tert-butylphenol, ⁇ -naphthol, ⁇ -naphthol, 4-acetylphenol, 4-tert-octylphenol, 4,4'-sec-butylidenediphenol, 4-phenylphenol, 4,4'-dihydroxy-diphenylmethane 4,4'-isopropylidenediphenol, hydroquinone, 4,4'-cyclohexylidenediphenol, 4,4'-dihydroxydiphenylsulfide, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-dihydroxy-diphenylsulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone, 2,4-dihydroxybenzophen
  • the proportions of basic dye and color acceptor to be used for the recording layer are usually 100 to 700 parts by weight, preferably 150 or 400 parts by weight, of the latter per 100 parts by weight of the former.
  • Each of the basic dye and the color acceptor can be used singly or in mixture of at least two of them.
  • the basic dye, the color acceptor and the heat-fusible material are dispersed, together or individually, into water serving as a dispersion medium, using stirring and pulverizing means such as a ball mill, attritor or sand mill.
  • the coating composition has incorporated therein a binder in an amount of 2 to 40% by weight, preferably 5 to 25% by weight, based on the total solids content of the composition.
  • binders examples include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salt, styrene-butadiene copolymer emulsion, etc.
  • auxiliary agents can be further added to the coating composition.
  • useful agents are dispersants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfuric acid ester, fatty acid metal salts, etc., defoaming agents, fluorescent dyes, coloring dyes, etc.
  • inorganic pigment such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, kieselguhr, finely divided anhydrous silica, activated clay, etc.
  • composition may be added, in order to prevent sticking upon contact of the heat-sensitive recording layer with a recording device or thermal head, a dispersion or emulsion of stearic acid, polyethylene, carnauba wax, paraffin wax, calcium stearate, zinc stearate, ester wax or the like.
  • the method of forming the recording layer of the heat-sensitive recording material of the invention is not particularly limited, but conventional techniques are usable.
  • the coating composition is applied to a substrate by an air knife coater, blade coater or like suitable means.
  • the amount of coating composition to be applied which is not limited particularly, is usually 2 to 12 g/m 2 , preferably 3 to 10 g/m 2 , based on dry weight.
  • a substrate (support) to be coated may be used a paper, synthetic fiber paper, plastic film or the like, but a paper is most preferably used.
  • an over-coat layer on the recording layer to protect the layer.
  • Various other known techniques in the field of heat-sensitive recording material can be applied. For example, it is possible to form a primary coating layer on the support.
  • composition (A) Composition (A)
  • Composition (B) having an average particle size of 3 ⁇ m.
  • a 165-part quantity of Composition (A), 130 parts of Composition (B), 30 parts of finely divided anhydrous silica, 150 parts of 20% aqueous solution of oxidized starch and 55 parts of water were mixed with stirring to prepare a coating composition.
  • the coating composition was applied to a paper substrate weighing 50 g/m 2 in an amount of 7.5 g/m 2 by dry weight to prepare a heat-sensitive recording paper.
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(2-isopropylphenoxy)-2-naphthoxy(2)-naphthoxy(2)-ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(2-phenylphenoxy)-2-phenoxyethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-phenylphenoxy)-2-(2-methylphenoxy)ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1,4-diphenoxybutane (Example 5) or 1,4-di(4-methylphenoxy)butane (Example 6) was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1,2-diphenoxyethane (Example 7), 1-(4-methylphenoxy)-2-phenoxyethane (Example 8), 1-(3,4-dimethylphenoxy)-2-phenoxyethane (Example 9), 1,2-di(3-methylphenoxy)ethane (Example 10), 1-(4-methylphenoxy)-2-(3-methylphenoxy)ethane (Example 11), 1-(3,4-dimethylphenoxy)-2-(4-methylphenoxy)ethane (Example 12), 1-(2,5-dimethylphenoxy)-2-(4-methylphenoxy)ethane (Example 13) or 1,2-di(2,4-dimethylphenoxy)ethane (Example 14) was used in place of 1-phenoxy-2-naphthoxy(1)ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-ethylphenoxy)-2-(3-methylphenoxy)ethane (Example 15), 1-(4-isopropylphenoxy)-2-phenoxyethane (Example 16) or 1-phenoxy-2-(4-tert-butylphenoxy)ethane (Example 17) was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that ⁇ -naphthyl phenoxyacetate was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that p-tolyl ⁇ -naphthoxyacetate was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-methoxyphenoxy)-2-phenoxyethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-chlorophenoxy)-2-phenoxyethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-cyanophenoxy)-2-(2-methylphenoxy)ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1,2-di(3-methylphenoxy)ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A), and benzyl p-hydroxybenzoate was used in place of 4,4'-isopropylidenediphenol in the preparation of Composition (B).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that stearic acid amide was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
  • a heat-sensitive recording paper was prepared in the same manner as in Example 1 except that stearic acid amide was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A), and benzyl p-hydroxybenzoate was used in place of 4,4'-isopropylidenediphenol in the preparation of Composition (B).
  • the 25 kinds of beat-sensitive recording papers thus prepared were checked for recording sensitivity and whiteness of recording layer.
  • the results were shown in Table 1 below.
  • the recording sensitivity was evaluated by feeding the paper to a high-speed heat-sensitive facsimile system (Hitachi HIFAX-700 Model, G III type, a product of Hitachi Ltd.) for recording and checked for color density by Macbeth densitometer (Model RD-100R, a product of Macbeth Corp.).
  • the whiteness was given with use of a Hunter multipurpose reflectometer before the recording.

Landscapes

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

Abstract

In a heat-sensitive recording material incorporating a colorless or pale-colored basic dye and a color acceptor which is reactive with the basic dye to form a color when contacted therewith, the recording material characterized in that at least one compound represented by the formula I! is contained in a heat-sensitive recording layer ##STR1## wherein X is --O-- or --COO--, R1 to R4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and/or R2 or substituents R3 and R4 may link together to form aromatic ring(s), n is an integer of 1 to 10.

Description

This invention relates to heat-sensitive recording materials, and more particularly to heat-sensitive recording materials having excellent whiteness in a recording layer and suited to high-speed recording.
Heat-sensitive recording materials are well known which are adapted to produce record images by thermally contacting a colorless or pale-colored basic dye with a color acceptor for a color forming reaction. With progress in heat-sensitive recording devices such as heat-sensitive facsimile systems, heat-sensitive printers, etc. using the above heat-sensitive recording materials in recent years, these heat-sensitive recording devices are made operable at a high speed. For use with such high-speed hardware, heat-sensitive recording materials must meet the requirements of having a high recording sensitivity, and many proposals have been made. However, the conventional recording materials have the drawback, for example, that the recording layer decreases in whiteness with an increase in recording sensitivity. For example, many techniques have been proposed to enhance the recording sensitivity by employing a heat-fusible material together with a combination of basic dye and color acceptor. Stearic acid amide, palmitic acid amide and like fatty acid amide are known as the heat-fusible material but these compounds bring the decrease in whiteness of the recording layer. Thus, sufficient results were not so far achieved.
An object of the present invention is to provide a heat-sensitive recording material having an enhanced recording sensitivity without entailing the decrease of whiteness of the recording layer.
Stated specifically, the invention provides a heat-sensitive recording material incorporating a colorless or pale-colored basic dye and a color acceptor which is reactive with the basic dye to form a color when contacted therewith, the recording material being characterized in that at least one compound represented by the formula I! is contained in a heat-sensitive recording layer ##STR2## wherein X is --O-- or --COO--, R1 to R4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and R2 and/or substituents R3 and R4 may link together to form aromatic ring(s), n is an integer of 1 to 10.
In the above, R1 to R4 are preferably each hydrogen atom, alkyl having 1 to 4 carbon atoms, phenyl, benzyl, chlorine atom, methoxy, methylthio, cyano or nitro. Further, n is preferably 1 to 6, more preferably 1 to 4 and most preferably 2 or 4.
Although the reason why the above specific heat-fusible material gives an excellent recording sensitivity without decrease in whiteness is unknown, this feature of the material appears attributable to the fact that it resembles to the basic dye or organic color acceptor in chemical structure and dissolves in the recording layer with an enhanced mutual solubility.
Examples of useful heat-fusible materials are as follows. In parentheses are given melting points of the compounds. ##STR3##
Further, the following compounds are exemplified as the heat-fusible materials of the invention. In parentheses are given melting points of the compounds.
1,2-Diphenoxyethane (96° C.), 1-(2-methylphenoxy)-2-phenoxyethane (71.5° C.), 1-(3-methylphenoxy)-2-phenoxyethane (76° C.), 1-(4-methylphenoxy)-2-phenoxyethane (99.5° C.), 1-(2,3-dimethylphenoxy)-2-phenoxyethane (106° C.), 1-(2,4-dimethylphenoxy)-2-phenoxyethane (76.5° C.), 1-(3,4-dimethylphenoxy)-2-phenoxyethane (101° C.), 1-(3,5-dimethylphenoxy)-2-phenoxyethane (77.5° C.), 1-(4-ethylphenoxy)-2-phenoxyethane (107° C.), 1-(4-isopropylphenoxy)-2-phenoxyethane (94° C.), 1-(4-tert-butylphenoxy)-2-phenoxyethane (92° C.), 1,2-di(2-methylphenoxy)ethane (84° C.), 1-(4-methylphenoxy)-2-(2-methylphenoxy)ethane (88.5° C.), 1-(3,4-dimethylphenoxy)-2-(2-methylphenoxy)ethane (81.5° C.), 1-(4-ethylphenoxy)-2-(2-methylphenoxy)ethane (77° C.), 1-(4-isopropylphenoxy)-2-(2-methylphenoxy)ethane (87° C.), 1-(4-tert-butylphenoxy)-2-(2-methylphenoxy)ethane (96° C.), 1,2-di(3-methylphenoxy)ethane (98° C.), 1-(4-methylphenoxy)-2-(3-methylphenoxy)ethane (94° C.), 1-(2,3-dimethylphenoxy)-2-(3-methylphenoxy)ethane (71° C.), 1-(2,4-dimethylphenoxy)-2-(3-methylphenoxy)ethane (76° C.), 1-(3,4-dimethylphenoxy)-2-(3-methylphenoxy)ethane (78° C.), 1-(4-ethylphenoxy)-2-(3-methylphenoxy)ethane (106° C.), 1-(4-isopropylphenoxy)-2-(3-methylphenoxy)ethane (83.5° C.), 1-(4-tert-butylphenoxy)-2-(3-methylphenoxy)ethane (89.5° C.), 1,2-di(4-methylphenoxy)ethane (135° C.), 1-(2,3-dimethylphenoxy)-2-(4-methylphenoxy)ethane (94° C.), 1-(2,4-dimethylphenoxy)-2-(4-methylphenoxy)ethane (77° C.), 1-(2,5-dimethylphenoxy)-2-(4-methylphenoxy)ethane (93° C.), 1-(3,4-dimethylphenoxy)-2-(4-methylphenoxy)ethane (110° C.), 1-(4-ethylphenoxy)-2-(4-methylphenoxy)ethane (134° C.). 1-(4-isopropylphenoxy)-2-(4-methylphenoxy)ethane (116° C.). 1-(4-tert-butylphenoxy)-2-(4-methylphenoxy)ethane (118° C.), 1,2-di(2,3-dimethylphenoxy)ethane (120° C.), 1-(2,5-dimethylphenoxy)-2-(2,3-dimethylphenoxy)ethane (87.5° C.), 1,2-di(2,4-dimethylphenoxy)ethane (111.5° C.), 1-(4-ethylphenoxy)-2-(2,4-dimethylphenoxy)ethane (72° C.), 1-(4-tert-butylphenoxy)-2-(2,4-dimethylphenoxy)ethane (82° C.), 1,2-di(2,5-dimethylphenoxy)ethane (80° C.), 1-(3,4-dimethylphenoxy)-2-(2,5-dimethylphenoxy)ethane (86° C.), 1-(4-ethylphenoxy)-2-(2,5-dimethylphenoxy)ethane (99.5° C.), 1-(4-tert-butylphenoxy)-2-(2,5-dimethylphenoxy)ethane (86° C.), 1,2-di(3,4-methylphenoxy)ethane (105° C.), 1,2-di(3,5-dimethylphenoxy)ethane (97.5° C.), 1,2-di(4-ethylphenoxy)ethane (151.5° C.), 1,3-di(4-methylphenoxy)propane (93.5° C.), 1-(4-methylphenoxy)-2-naphthoxy(1)-ethane (84.5° C.), 1-(2,5-dimethylphenoxy)-2-naphthoxy(1)-ethane (112° C.), 1,2-dinaphthoxy(1)-ethane (129° C.).
1-(2-Chlorophenoxy)-2-phenoxyethane (81° C.), 1-(2-chlorophenoxy)-2-(2-methylphenoxy)ethane (87° C.), 1-(2-chlorophenoxy)-2-(3-methylphenoxy)ethane (85° C.), 1-(2-chlorophenoxy)-2-(4-methylphenoxy)ethane (89° C.), 1-(4-chlorophenoxy)-2-phenoxyethane (100° C.), 1-(4-chlorophenoxy)-2-(2-methylphenoxy)ethane (81.5° C.). 1-(4-chlorophenoxy)-2-(3-methylphenoxy)ethane (79.5° C.), 1-(4-chlorophenoxy)-2-(4-methylphenoxy)ethane (132° C.), 1-(4-acetylphenoxy)-2-phenoxyethane (139° C.), 1-(4-acetylphenoxy)-2-(2-metylphenoxy)ethane (119.5° C.), 1-(4-propionylphenoxy)-2-phenoxyethane (120° C.), 1-(2-methoxyphenoxy)-2-(4-methylphenoxy)ethane (89° C.), 1-(3-methoxyphenoxy)-2-(4-methylphenoxy)ethane (75° C.), 1,2-di(4-methoxyphenoxy)ethane (128° C.), 1-(4-methoxyphenoxy)-2-phenoxyethane (103° C.), 1-(4-methoxyphenoxy)-2-(2-methylphenoxy)ethane (80° C.), 1-(4-methoxyphenoxy)-2-(3-methylphenoxy)ethane (112° C.), 1-(4-methoxyphenoxy)-2-(4-methylphenoxy)ethane (129° C.), 1-(4-methylthiophenoxy)-2-phenoxyethane, (112° C.), 1-(4-methoxycarbonylphenoxy)-2-phenoxyethane (106° C.), 1-(4-cyanophenoxy)-2-phenoxyethane (110° C.), 1-(4-cyanophenoxy)-2-(2-methylphenoxy)ethane (98° C.), 1-(4-cyanophenoxy)-2-(3-methylphenoxy)ethane (96.5° C.), 1-(4-cyanophenoxy)-2-(4-methylphenoxy)ethane (111.5° C.), 1-(4-nitrophenoxy)-2-phenoxyethane (87° C.), 1-(4-nitrophenoxy)-2-(4-methylphenoxy)ethane (103° C.), 1-(4-cycloheyenylphenoxy)-2-phenoxyethane (116° C.), 1-(4-chlorophenoxy)-2-(4-tert-butylphenoxy)ethane (111° C.), 1-(4-methoxyphenoxy)-2-(4-tert-butylphenoxy)ethane 109.5° C.), 1-(4-acetylphenoxy)-2-(4-tert-butylphenoxy)ethane (101.5° C.), 1-(4-methylthiophenoxy)-2-(4-tert-butylphenoxy)ethane (98° C.). 1-(4-acetylphenoxy)-4-phenoxybutane (106° C.), 1-(4-methoxyphenoxy)-4-phenoxybutane (100° C.), 1-(4-methylthiophenoxy)-4-phenoxybutane (109° C.), 1-(4-cyanophenoxy)-4-phenoxybutane (72° C.), etc. These heat-fusible materials can generally be prepared by Williamson's synthesis of ether and are usable singly or a mixture of at least two of them. Further, the heat-fusible materials of the invention preferably have melting points in the range of 70° to 130° C.
Further, to the recording layer may be added in an amount which does not cause adverse effect, fatty acid amide such as stearic acid amide, stearic acid methylenebisamide, oleic acid amide, palmitic acid amide, coconut fatty acid amide, etc; hindered phenols such as 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(6-tert-butyl-3-methylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, etc.; ultraviolet absorbers such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-hydroxy-4-benzyloxybenzophenone; etc.; and various known heat-fusible substances. The amount to be used of the above heat-fusible materials having the specific structure is not particularly limited but is usually 10 to 1000 parts by weight, preferably 50 to 500 parts by weight per 100 parts by weight of the color acceptor.
Various known colorless or pale-colored basic dyes are used in the recording layer of the present heat-sensitive recording material. Examples of useful dyes are:
Triarylmethane-based dyes, e.g., 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide, 3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole-3-yl)-6-dimethylaminophthalide, 3,3-bis(2-phenylindole-3-yl)-6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrole-3-yl)-6-dimethylaminophthalide, etc.
Diphenylmethane-based dyes, e.g., 4,4'-bis-dimethylaminobenzhydryl benzyl ether, N-halophenyl-leucoauramine, N-2,4,5-trichlorophenyl-leucoauramine, etc.
Thiazine-based dyes, e.g., benzoyl-leucomethyleneblue, p-nitrobenzoyl-leucomethyleneblue, etc.
Spiro-based dyes, e.g., 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-(6'-methoxybenzo)spiropyran, 3-propyl-spiro-dibenzopyran, etc.
Lactam-based dyes, e.g., rhodamine-B-anilinolactam, rhodamine-(p-nitroanilino)lactam, rhodamine-(o-chloroanilino)lactam, etc.
Fluoran-based dyes, e.g., 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6,7-dimethylfluoran, 3-(N-ethyl-p-toluidino)-7-methylfluoran, 3-diethylamino-7-(N-acetyl-N-methylamino)fluoran, 3-diethylamino-7-N-methylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-(N-methyl-N-benzylamino)fluoran, 3-diethylamino-7-(N-chloroethyl-N-methylamino)fluoran, 3-diethylamino-7-N-diethylaminofluoran, 3-(N-ethyl-p-toluidino)-6-methyl-7-phenylaminofluoran, 3-(N-ethyl-p-toluidino)-6-methyl-7-(p-toluidino)fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3-dibutylamino-6-methyl-7-phenylaminofluoran, 3-diethylamino-7-(2-carbomethoxyphenylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenylaminofluoran, 3-pyrrolidino-6-methyl-7-phenylaminofluoran, 3-piperidino-6-methyl-7-phenylaminofluoran, 3-diethylamino-6-methyl-7-xylidinofluoran, 3-diethylamino-7-(o-chlorophenylamino)fluoran, 3-dibutylamino-7-(o-chlorophenylamino)fluoran, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluoran, 3-(N-methyl-N-n-amylamino)-6-methyl-7-phenylaminofluoran, 3-(N-ethyl-N-n-amylamino)-6-methyl-7-phenylaminofluoran, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-phenylaminofluoran, 3-(N-methyl-N-n-hexylamino)-6-methyl-7-phenylaminofluoran, 3-(N-ethyl-N-n-hexylamino)-6-methyl-7-phenylaminofluoran, 3-(N-ethyl-N-β-ethyl-hexylamino)-6-methyl-7-phenylaminofluoran, etc.
In the invention, the color acceptor which is used in combination with the above basic dye is not particularly limited. Various color acceptors can be employed which are fusible or vaporous by heating and produce record images by contact with the basic dye. Examples of useful color acceptors are 4-tert-butylphenol, α-naphthol, β-naphthol, 4-acetylphenol, 4-tert-octylphenol, 4,4'-sec-butylidenediphenol, 4-phenylphenol, 4,4'-dihydroxy-diphenylmethane 4,4'-isopropylidenediphenol, hydroquinone, 4,4'-cyclohexylidenediphenol, 4,4'-dihydroxydiphenylsulfide, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-dihydroxy-diphenylsulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, sec-butyl 4-hydroxybenzoate, pentyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, tolyl 4-hydroxybenzoate, chlorophenyl 4-hydroxybenzoate, phenylpropyl 4-hydroxybenzoate, phenethyl 4-hydroxybenzoate, p-chlorobenzyl 4-hydroxybenzoate, p-methoxybenzyl 4-hydroxybenzoate, novolak phenol resin, phenolic polymer and like phenolic compounds; benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3-benzylsalicylic acid, 3-(α-methylbenzyl)salicylic acid, 3-chloro-5-(α-methylbenzyl)salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di-α-methylbenzylsalicylic acid and like aromatic carboxylic acids; also, salts of such phenolic compounds or aromatic carboxylic acids with zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel and like polyvalent metals, etc.
With the heat-sensitive recording materials of the invention, the proportions of basic dye and color acceptor to be used for the recording layer are usually 100 to 700 parts by weight, preferably 150 or 400 parts by weight, of the latter per 100 parts by weight of the former. Each of the basic dye and the color acceptor can be used singly or in mixture of at least two of them.
For preparing a coating composition comprising the foregoing components, the basic dye, the color acceptor and the heat-fusible material are dispersed, together or individually, into water serving as a dispersion medium, using stirring and pulverizing means such as a ball mill, attritor or sand mill. Usually the coating composition has incorporated therein a binder in an amount of 2 to 40% by weight, preferably 5 to 25% by weight, based on the total solids content of the composition. Examples of useful binders are starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salt, styrene-butadiene copolymer emulsion, etc.
Various other auxiliary agents, as required, can be further added to the coating composition. Examples of useful agents are dispersants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfuric acid ester, fatty acid metal salts, etc., defoaming agents, fluorescent dyes, coloring dyes, etc.
In addition, to the composition may be added in order to prevent the adhesion of tailings to the thermal head face and improve the whiteness of the recording layer, inorganic pigment such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, kieselguhr, finely divided anhydrous silica, activated clay, etc.
Further, to the composition may be added, in order to prevent sticking upon contact of the heat-sensitive recording layer with a recording device or thermal head, a dispersion or emulsion of stearic acid, polyethylene, carnauba wax, paraffin wax, calcium stearate, zinc stearate, ester wax or the like.
The method of forming the recording layer of the heat-sensitive recording material of the invention is not particularly limited, but conventional techniques are usable. For example, the coating composition is applied to a substrate by an air knife coater, blade coater or like suitable means. The amount of coating composition to be applied, which is not limited particularly, is usually 2 to 12 g/m2, preferably 3 to 10 g/m2, based on dry weight.
As a substrate (support) to be coated, may be used a paper, synthetic fiber paper, plastic film or the like, but a paper is most preferably used.
Further, it is possible to form an over-coat layer on the recording layer to protect the layer. Various other known techniques in the field of heat-sensitive recording material can be applied. For example, it is possible to form a primary coating layer on the support.
The heat-sensitive recording materials thus obtained suited to high-speed recording, have excellent whiteness and have a well-balanced characteristics in qualities.
The invention will be described below in more detail with reference to Examples and Comparison Examples by no means limited to, in which parts and percentages are all by weight, unless otherwise specified.
EXAMPLE 1 (1) Composition (A)
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenylaminofluoran (10 parts), 20 parts of 1-phenoxy-2-naphthoxy(1)-ethane, 15 parts of 5% aqueous solution of methyl cellulose and 120 parts of water were pulverized by a sand mill to prepare Composition (A) having an average particle size of 3 μm.
(2) Composition (B)
4,4'-Isopropylidenediphenol (30 parts), 30 parts of 5% aqueous solution of methyl cellulose and 70 parts of water were pulverized by a sand mill to obtain Composition (B) having an average particle size of 3 μm.
(3) Preparation of a recording layer
A 165-part quantity of Composition (A), 130 parts of Composition (B), 30 parts of finely divided anhydrous silica, 150 parts of 20% aqueous solution of oxidized starch and 55 parts of water were mixed with stirring to prepare a coating composition. The coating composition was applied to a paper substrate weighing 50 g/m2 in an amount of 7.5 g/m2 by dry weight to prepare a heat-sensitive recording paper.
EXAMPLE 2
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(2-isopropylphenoxy)-2-naphthoxy(2)-naphthoxy(2)-ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 3
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(2-phenylphenoxy)-2-phenoxyethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 4
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-phenylphenoxy)-2-(2-methylphenoxy)ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLES 5 AND 6
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1,4-diphenoxybutane (Example 5) or 1,4-di(4-methylphenoxy)butane (Example 6) was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLES 7 TO 14
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1,2-diphenoxyethane (Example 7), 1-(4-methylphenoxy)-2-phenoxyethane (Example 8), 1-(3,4-dimethylphenoxy)-2-phenoxyethane (Example 9), 1,2-di(3-methylphenoxy)ethane (Example 10), 1-(4-methylphenoxy)-2-(3-methylphenoxy)ethane (Example 11), 1-(3,4-dimethylphenoxy)-2-(4-methylphenoxy)ethane (Example 12), 1-(2,5-dimethylphenoxy)-2-(4-methylphenoxy)ethane (Example 13) or 1,2-di(2,4-dimethylphenoxy)ethane (Example 14) was used in place of 1-phenoxy-2-naphthoxy(1)ethane in the preparation of Composition (A).
EXAMPLE 15 TO 17
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-ethylphenoxy)-2-(3-methylphenoxy)ethane (Example 15), 1-(4-isopropylphenoxy)-2-phenoxyethane (Example 16) or 1-phenoxy-2-(4-tert-butylphenoxy)ethane (Example 17) was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 18
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that β-naphthyl phenoxyacetate was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 19
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that p-tolyl β-naphthoxyacetate was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 20
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-methoxyphenoxy)-2-phenoxyethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 21
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-chlorophenoxy)-2-phenoxyethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 22
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1-(4-cyanophenoxy)-2-(2-methylphenoxy)ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
EXAMPLE 23
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that 1,2-di(3-methylphenoxy)ethane was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A), and benzyl p-hydroxybenzoate was used in place of 4,4'-isopropylidenediphenol in the preparation of Composition (B).
COMPARISON EXAMPLE 1
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that stearic acid amide was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A).
COMPARISON EXAMPLE 2
A heat-sensitive recording paper was prepared in the same manner as in Example 1 except that stearic acid amide was used in place of 1-phenoxy-2-naphthoxy(1)-ethane in the preparation of Composition (A), and benzyl p-hydroxybenzoate was used in place of 4,4'-isopropylidenediphenol in the preparation of Composition (B).
The 25 kinds of beat-sensitive recording papers thus prepared were checked for recording sensitivity and whiteness of recording layer. The results were shown in Table 1 below. The recording sensitivity was evaluated by feeding the paper to a high-speed heat-sensitive facsimile system (Hitachi HIFAX-700 Model, G III type, a product of Hitachi Ltd.) for recording and checked for color density by Macbeth densitometer (Model RD-100R, a product of Macbeth Corp.). The whiteness was given with use of a Hunter multipurpose reflectometer before the recording.
              TABLE 1
______________________________________
Recording   White-             Recording
                                      White-
Sensitivity ness               Sensitivity
                                      ness
______________________________________
Ex. 1 1.15      81.0    Ex. 14   1.03   81.5
Ex. 2 1.05      80.5    Ex. 15   1.18   81.2
Ex. 3 1.05      80.6    Ex. 16   1.20   81.3
Ex. 4 1.02      81.5    Ex. 17   1.19   80.3
Ex. 5 1.08      80.8    Ex. 18   1.13   80.7
Ex. 6 1.18      81.3    Ex. 19   1.15   80.5
Ex. 7 1.28      81.0    Ex. 20   1.20   80.5
Ex. 8 1.25      80.8    Ex. 21   1.23   81.0
Ex. 9 1.19      81.0    Ex. 22   1.18   81.5
Ex. 10
      1.23      81.1    Ex. 23   1.30   81.0
Ex. 11
      1.24      81.0
Ex. 12
      1.04      81.3    Com. Ex. 1
                                 1.70   80.0
Ex. 13
      1.20      80.7    Com. Ex. 2
                                 1.10   80.3
______________________________________

Claims (12)

We claim:
1. In a heat-sensitive recording material .Iadd.comprising a heat-sensitive recording layer .Iaddend.incorporating a colorless or pale-colored basic dye.Iadd., .Iaddend.and a color acceptor which is reactive with the basic dye to form a color when contacted therewith, the recording material characterized in that at least one compound represented by the formula I! is contained in the heat-sensitive recording layer ##STR4## wherein X is --O-- . .or --COO--.!., R1 to R4 are each a hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and. ./or.!. R2 .Iadd.and/.Iaddend.or substituents R3 and R4 may link together to form aromatic ring(s), and n is an integer of 1 to 10.Iadd., wherein said recording layer is deposited on a substrate.Iaddend..
2. A heat-sensitive recording material as defined in claim 1 wherein X is --O-- . .or --COO--.!., R1 to R4 are each hydrogen atom, alkyl having 1 to 4 carbon atoms, phenyl, benzyl, chlorine atom, methoxy, methylthio, cyano or nitro, substituents R1 and R2 and/or substituents R3 and R4 may link together to form aromatic ring(s).
3. A heat-sensitive recording material as defined in claim 2 wherein X is oxygen atom.
4. A heat-sensitive recording material as defined in claim 1 wherein the compound represented by the formula I! is used in an amount of 10 to 1000 parts by weight per 100 parts by weight of the color acceptor.
5. A heat-sensitive recording material as defined in claim 1 wherein the color acceptor is used in an amount of 100 to 700 parts by weight per 100 parts by weight of the basic dye. .Iadd.
6. In a heat-sensitive recording material comprising a substrate and a heat-sensitive recording layer deposited on said substrate, wherein the heat-sensitive recording layer comprises a colorless or pale-colored basic dye and a color acceptor which is thermally reactive with said dye to form a color record when thermally activated; the improvement comprising, in said heat-sensitive recording layer, at least one recording sensitivity enhancing compound according to the formula (I); ##STR5## wherein X is --O--, R1 to R4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and R2 and/or substituents R3 and R4 may link together to form aromatic ring(s), n is an integer of 1 to 10; wherein said basic dye, said color acceptor and said at least one recording sensitivity enhancing compound are deposited on the substrate in the form of fine particles. .Iaddend..Iadd.7. In a color record, corresponding to a thermal contact with a thermally sensitive recording material comprising a substrate having a thermally sensitive recording layer disposed thereon; wherein said color record comprises the thermal reaction product of a colorless or pale-colored basic dye with a color acceptor thermally reactive therewith; the improvement comprising, in said thermally sensitive recording layer, a sensitivity enhancing quantity of at least one compound according to the formula (I); ##STR6## wherein X is --O--, R1 to R4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and R2 and/or substituents R3 and R4 may link together to form aromatic ring(s), n is an integer of 1 to 10.
.Iaddend..Iadd.8. In a heat-sensitive recording material, having improved recording sensitivity, consisting essentially of a substrate having deposited thereon a heat-sensitive recording layer comprising colorless or pale-colored basic dye, a color acceptor thermally reactive therewith; the improvement comprising, in said heat-sensitive recording layer, a sensitivity enhancing quantity of at least one compound according to the formula (I); ##STR7## wherein X is --O--, R1 to R4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and R2 and/or substituents R3 and R4 may link together to form aromatic ring(s), n is an integer of 1 to 10.
.Iaddend..Iadd.9. A heat sensitive recording material as claimed in claim 8 wherein said heat-sensitive recording layer further includes a binder. .Iaddend..Iadd.10. A heat-sensitive recording material as claimed in claim 8 wherein said heat-sensitive recording layer further includes at least one auxiliary material in an amount which does not cause adverse effects.
.Iaddend..Iadd.11. A heat-sensitive recording material as claimed in claim 8, wherein each of said components of said heat-sensitive recording layer is separately dispersed as fine particles in said recording
material. .Iaddend..Iadd.12. In a process of producing record images by:
coating a substrate with a heat-sensitive recording layer composition comprising a colorless or pale-colored basic dye and a color acceptor,
subjecting said coated substrate to a thermal recording, color forming reaction, and
recovering said substrate having thermally recorded images thereon;
the improvement which comprises:
including in said heat-sensitive recording layer at least one compound represented by the formula (I): ##STR8## wherein X is --O--, R1 to R4 are each hydrogen atom, alkyl having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 9 carbon atoms, chlorine atom, acetyl, propionyl, methoxy, methylthio, methoxycarbonyl, cyano, nitro or cyclohexenyl, substituents R1 and R2 and/or substituents R3 and R4 may link together to form aromatic ring(s), n is an integer of 1 to 10, thereby providing a recording layer of enhanced recording sensitivity;
thermally recording images on said enhanced sensitivity recording layer; and
recovering from said thermal recording step said substrate and recording layer thereon of substantially undiminished whiteness having printed
thereon thermally recorded images. .Iaddend..Iadd.13. A process of producing record images as claimed in claim 12 wherein said heat-sensitive recording layer further includes a binder. .Iaddend..Iadd.14. A process of producing record images as claimed in claim 12 wherein said heat-sensitive recording layer further includes at least one auxiliary material in an
amount which does not cause adverse effects. .Iaddend..Iadd.15. A process of producing record images as claimed in claim 12 wherein each of said components is separately dispersed as fine particles in said recording material. .Iaddend.
US07/209,196 1983-09-08 1988-06-20 Heat-sensitive recording material Expired - Lifetime USRE36321E (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US07/209,196 USRE36321E (en) 1983-09-08 1988-06-20 Heat-sensitive recording material

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP58-166011 1983-09-08
JP58166011A JPS6056588A (en) 1983-09-08 1983-09-08 Thermal sensitive recording medium
JP59137565A JPS6116888A (en) 1984-07-02 1984-07-02 Heat sensitive recording body
JP59-137565 1984-07-02
US06/642,816 US4531140A (en) 1983-09-08 1984-08-21 Heat-sensitive recording material
US07/209,196 USRE36321E (en) 1983-09-08 1988-06-20 Heat-sensitive recording material

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06/642,816 Reissue US4531140A (en) 1983-09-08 1984-08-21 Heat-sensitive recording material

Publications (1)

Publication Number Publication Date
USRE36321E true USRE36321E (en) 1999-09-28

Family

ID=26470822

Family Applications (2)

Application Number Title Priority Date Filing Date
US06/642,816 Ceased US4531140A (en) 1983-09-08 1984-08-21 Heat-sensitive recording material
US07/209,196 Expired - Lifetime USRE36321E (en) 1983-09-08 1988-06-20 Heat-sensitive recording material

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US06/642,816 Ceased US4531140A (en) 1983-09-08 1984-08-21 Heat-sensitive recording material

Country Status (5)

Country Link
US (2) US4531140A (en)
EP (1) EP0141170B1 (en)
KR (1) KR910007066B1 (en)
AU (1) AU578908B2 (en)
DE (1) DE3463630D1 (en)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6110487A (en) * 1984-06-26 1986-01-17 Kanzaki Paper Mfg Co Ltd Thermal recording material
GB2165953B (en) * 1984-08-31 1988-07-27 Fuji Photo Film Co Ltd Thermal recording material
JPS61104887A (en) * 1984-10-27 1986-05-23 Kanzaki Paper Mfg Co Ltd Thermal recording material
JPS61262184A (en) * 1985-05-16 1986-11-20 Fuji Photo Film Co Ltd Thermal recording sheet
AU593591B2 (en) * 1985-11-08 1990-02-15 Fuji Photo Film Co., Ltd. Recording material
JPS62181183A (en) * 1986-02-06 1987-08-08 Fuji Photo Film Co Ltd Thermal recording material
JPH0649390B2 (en) * 1986-06-11 1994-06-29 富士写真フイルム株式会社 Thermal recording material
JPS6317081A (en) * 1986-07-10 1988-01-25 Kanzaki Paper Mfg Co Ltd Thermal recording medium
JPS63151478A (en) * 1986-12-15 1988-06-24 Fuji Photo Film Co Ltd Recording material
JP2710160B2 (en) * 1988-06-08 1998-02-10 王子製紙株式会社 Thermal recording medium
EP0357409B1 (en) * 1988-09-02 1994-07-20 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
JP2739079B2 (en) * 1989-11-30 1998-04-08 王子製紙株式会社 Thermal recording medium
US5066633A (en) * 1990-02-09 1991-11-19 Graphic Controls Corporation Sensitizer for heat sensitive paper coatings
JP3265638B2 (en) * 1992-09-22 2002-03-11 大日本インキ化学工業株式会社 Color developing performance improver and heat-sensitive recording medium using the same
EP0798127A1 (en) * 1996-03-28 1997-10-01 Oji Paper Co., Ltd. Heat sensitive recording material and method of using it
US5955398A (en) * 1997-04-25 1999-09-21 Appleton Papers Inc. Thermally-responsive record material
CA2295197A1 (en) 1999-09-08 2001-03-08 Appleton Papers Inc. Thermally-responsive record material
ATE317335T1 (en) 2000-01-05 2006-02-15 Appleton Paper Inc HEAT SENSITIVE RECORDING MATERIAL
US6835691B2 (en) 2000-01-05 2004-12-28 Appleton Papers Inc. Thermally-responsive record material
EP1573685A4 (en) 2002-11-12 2008-09-17 Appleton Paper Inc Secure point of sale imageable substrate
JP2004306262A (en) * 2003-02-18 2004-11-04 Sanko Kk 1,2-bis (3-methylphenoxy) ethane composition and thermal recording body using the same
CN100379580C (en) * 2003-02-18 2008-04-09 三光株式会社 1,2-bis(3-methylphenoxy)ethane composition and thermal recording media made by using the same
JP4825854B2 (en) * 2007-12-14 2011-11-30 三菱製紙株式会社 Thermal lithographic printing plate
US9126451B2 (en) 2013-12-18 2015-09-08 Appvion, Inc. Thermal recording materials
US20200019077A1 (en) 2018-07-11 2020-01-16 Appvion Operations, Inc. Media Adapted for Both Direct Thermal Recording and Memjet-Type Printing
KR102215243B1 (en) * 2018-10-30 2021-02-15 주식회사 인실리코 Thermochromic composition and thermochromic microcapsule comprising the same
US12115803B2 (en) 2020-12-10 2024-10-15 Appvion, Llc Fade-resistant water-dispersible phenol-free direct thermal media
WO2022125104A1 (en) 2020-12-10 2022-06-16 Appvion, Llc Multi-purpose phenol-free direct thermal recording media
DE202020006063U1 (en) 2020-12-10 2024-08-27 Appvion, Llc Phenol-free multipurpose direct thermal recording media
US20240059090A1 (en) 2022-08-10 2024-02-22 Appvion, Llc Direct thermal recording media with diarylurea combinations for oil resistance

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4251593A (en) * 1978-08-01 1981-02-17 Ricoh Company, Ltd. Heat-sensitive recording sheet
JPS578194A (en) * 1980-06-19 1982-01-16 Ricoh Co Ltd Heat sensitive recording material
JPS5714094A (en) * 1980-06-30 1982-01-25 Ricoh Co Ltd Heatsensitive recording material
US4342473A (en) * 1978-06-26 1982-08-03 Champion International Corporation Pressure-sensitive copy systems containing phenolic ester as color-stabilizers
JPS5871191A (en) * 1981-10-26 1983-04-27 Fuji Photo Film Co Ltd Heat-sensitive recording material
JPS58110289A (en) * 1981-12-24 1983-06-30 Fuji Photo Film Co Ltd Thermo-sensitive recording material
US4444844A (en) * 1981-06-10 1984-04-24 Ricoh Co., Ltd. Thermosensitive recording material
US4479138A (en) * 1981-10-06 1984-10-23 Fuji Photo Film Co., Ltd. Heat-sensitive recording materials

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4342473A (en) * 1978-06-26 1982-08-03 Champion International Corporation Pressure-sensitive copy systems containing phenolic ester as color-stabilizers
US4251593A (en) * 1978-08-01 1981-02-17 Ricoh Company, Ltd. Heat-sensitive recording sheet
JPS578194A (en) * 1980-06-19 1982-01-16 Ricoh Co Ltd Heat sensitive recording material
JPS5714094A (en) * 1980-06-30 1982-01-25 Ricoh Co Ltd Heatsensitive recording material
US4444844A (en) * 1981-06-10 1984-04-24 Ricoh Co., Ltd. Thermosensitive recording material
US4479138A (en) * 1981-10-06 1984-10-23 Fuji Photo Film Co., Ltd. Heat-sensitive recording materials
JPS5871191A (en) * 1981-10-26 1983-04-27 Fuji Photo Film Co Ltd Heat-sensitive recording material
JPS58110289A (en) * 1981-12-24 1983-06-30 Fuji Photo Film Co Ltd Thermo-sensitive recording material

Also Published As

Publication number Publication date
KR910007066B1 (en) 1991-09-16
EP0141170A3 (en) 1985-07-03
AU3242884A (en) 1985-03-14
DE3463630D1 (en) 1987-06-19
US4531140A (en) 1985-07-23
EP0141170B1 (en) 1987-05-13
AU578908B2 (en) 1988-11-10
KR850005098A (en) 1985-08-21
EP0141170A2 (en) 1985-05-15

Similar Documents

Publication Publication Date Title
USRE36321E (en) Heat-sensitive recording material
US4420538A (en) Heat-sensitive recording materials
US4948775A (en) Heat-sensitive record material
US4977133A (en) Heat sensitive recording material
US5079212A (en) Heat-sensitive recording material
US5401708A (en) Heat-sensitive recording material
US4511909A (en) Heat-sensitive recording materials
US4626877A (en) Heat-sensitive recording material
US4540999A (en) Heat-sensitive record material
US5091359A (en) Heat-sensitive record material
US4904636A (en) Heat-sensitive recording material
EP0329384B1 (en) Heat-sensitive record material
US4771033A (en) Heat-sensitive record material
US4523205A (en) Heat-sensitive recording materials
US4906604A (en) Multi-color heat sensitive recording material
US4612557A (en) Hydroxydiphenyl sulfone derivative and heat-sensitive recording material using the derivative
US5017545A (en) Heat sensitive recording material
US4985393A (en) Heat sensitive recording material
US4950637A (en) Heat sensitive recording material
EP0439148B1 (en) Heat-sensitive recording material
EP0478263B1 (en) Heat-sensitive recording material
US5276001A (en) Heat sensitive recording material
US5019548A (en) Heat sensitive recording material
US4713364A (en) Heat-sensitive recording material
US5173472A (en) Heat sensitive recording material

Legal Events

Date Code Title Description
AS Assignment

Owner name: OJI PAPER CO., LTD., JAPAN

Free format text: MERGER;ASSIGNOR:KANZAKI PAPER MANUFACTURING CO., LTD.;REEL/FRAME:009054/0074

Effective date: 19971003