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
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/337—Additives; Binders
  • B41M5/3375—Non-macromolecular compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/913—Material designed to be responsive to temperature, light, moisture
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/165—Thermal imaging composition

Definitions

• One of the two colorless compounds includes crystal violet lactones and benzo indolino spiropyrans, and another includes, for example, clays, such as acid clay, zeolite, kaolin, attapulgite, and the like; mineral acids, such as hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, and the like; organic acids, such as benzoic acid, p-chlorobenzoic acid, gallic acid, phthalic acid, salicylic acid, oxalic acid, maleic acid, citric acid, stearic acid, and the like; and phenols, such as p-butylphenol, p-phenylphenol, a-naphthol, catechol, resorcinol, and the like.
• clays such as acid clay, zeolite, kaolin, attapulgite, and the like
• mineral acids such as hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, and the
• an object of the present invention is to provide a heat sensitive copying sheet in which such color development fog is not formed before heating and develops color instantly on heating.
• the developed color image is excellent in light resistance and resistance to water.
• the heat sensitive copying sheet of this invention is one having a spiro compound, represented by Formula A wherein R and R each is a hydrogen atom, an alkyl group having from .1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group, or a phenyl group, a solid organic sulfonic acid, represented by the Formula B DETAILED DESCRIPTION OF THE INVENTION
• R and R each is a hydrogen atom, an alkyl group having from .1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group, or a phenyl group
• a solid organic sulfonic acid represented by the Formula B DETAILED DESCRIPTION OF THE INVENTION
• a nearly colorless spiro compound, an organic sulfonic acid and a thermofusible material, as described above, are sufliciently mixed in a solution or suspension of a binder in an organic solvent or water, and coated on a support such as paper, natural or synthetic resin films, and the like, and dried.
• the above liquid mixture can be combed into the support.
• an opacifying agent can be added and mixed therein.
• the heat sensitive copying sheet of the present invention is not limited to this technique.
• the abovementioned spiro compound and the thermofusible material can be mixed in the binder solution, and alternatively the organic sulfonic acid and the thermofusible material can be mixed in the binder solution, and then both solutions can be mixed and coated on a support, or the former solution may be coated on the support and then the latter solution may be coated thereon.
• the amount of each component to be used for producing the heat sensitive copying sheet of the present invention is from 1 to 2. parts by weight of the spiro compound (the Formula A); from 1 to 6 parts by weight of the organic sulfonic acid (the Formula -B); from 3 to 30 parts by weight of the thermofusible material; from 3 to 15 parts by weight of the binder; and from 20 to 300 parts by weight of solvent.
• spiro compounds can be prepared by condensing Q-NH-Q-SO H 2-hydroxyl-l-napthoaldehyde with the respective corresponding ketones as described in the literature references.
• thermofusible materials are acetanilide, urea, diphenylamine, diphenyl, naphthalene, benzoin, anaphthol, fi-naphthol, para-t-butyl phenol, para-phenylphenol, 4,4'-cyclohexyiidene diphene diphenol, 4,4-isopropylidene diphenol, phthalic anhydride, maleic anhydride, stearic acid, benzoic acid, a-naphthyl acetic acid, methyl para-hydroxybenzoate, diphenyl phthalate, triphenyl phosphate, para-hydroxydiphenyl ether, and the like.
• These compounds are colorless or lightly colored solids at ordinary temperatures of lower than 50 C. and have sharp melting points near the temperature suitable as the heating temperature for copying, that is, from 50 to 180 0., and dissolve the above spiro compounds (the Formula A) and the organic sulfonic acids (the Formula B) in the fused state.
• the above three components are not necessarily used on or in the same support, and one or two of said components can be used on two separate supports.
• binders to be used in the present invention are ex emplified by styrene-butadiene copolymers, alkyd resins, polybutylmethacrylates, vinyl chloride-vinyl acetate copolymers, styrene maleic anhyride copolymers, synthetic rubbers, gum arabic, polyvinyl alcohol, hydroxyethylcellulose, and the like.
• thermofusible materials bind the above spiro compounds (the Formula A) and the thermofusible materials and not easily discolored on heating. They can be used alone or in combination.
• the solvents to be used in the present invention are examplified by organic solvents such as benzene, toluene, hexane, xylene, ligroin, acetone, ethyl acetate, and the like; and water.
• organic sulfonic acids having an amino group in the Formula B an organic solvent or water may be optionally used.
• organic sulfonic acids not having an amino group or ones easily soluble in an organic solvent water is preferable.
• organic sulfonic acids easily soluble in water use of water is allowed. This appears to result from the lack of solubility of the coupler represented by the Formula A in water.
• Pacifying agents which can be used in the present invention are exemplified by titanium oxide, zinc oxide, barium sulfate, calcium sulfate, starch and the like.
• the heat sensitive copying sheet of this invention has the advantages that a color development fog is not formed during the preparation and during the period after drying and before heating even though the compounds of the Formulas A and B are in contact with each other, that, even if the sheet is exposed before copying color develop ment, it is good in stability during the lapse of time without any lowering of the color developing ability, and that, when copying using a heatsensitive copying machine, the copied part develops color instantly and the developed color is good in light resistance and resistance to Water.
• the sheet When substituting phenols, such as, for example, parabutyl phenol, para-phenylphenol, a-naphthol, catechol, resorcinol, 2,2'-methylene-bis (4-chlorophenol), 4,4-iso propylidine diphenol, and the like for the compounds represented by the Formula B, the sheet does not develop color even on; heating, and thus is not practical.
• phenols such as, for example, parabutyl phenol, para-phenylphenol, a-naphthol, catechol, resorcinol, 2,2'-methylene-bis (4-chlorophenol), 4,4-iso propylidine diphenol, and the like
• the sheet has the disadvantage of forming a color development fog during mixing in the solvent and immediately after coat ing and drying.
• Example 1.35 g. of coupler No. I, 31 g. of organic sulfonic acid No. 17, 39 g. of acetanilide, 120 g. of styrenebutadiene copolymer, and 1200 g. of toluene were mixed and ground in a ball mill for 2 days.
• the solution mixture was coated on a paper and dried at 40 C. to obtain a heat sensitive copying sheet.
• This sheet was superposed on an original drawing and heated by means of a heat sensitive copying machine (manufactured by Thermofax Secretary 3M Co.) to obtain a blue-violet image.
• the copied image was exposed to sunlight for 20 hours.
• the developed color image was not lowered in concentration at all and undeveloped portion, i.e. non-image part, remained white as it was initially and was not changed. That is the light resistance was excellent. Even on allowing the sheet to stand at a temperature of 50 C. and a relative humidity of for 20 hours, or even on wettingit with water immediately after it was obtained, the concern tration of the color developed image was not lowered. That is, resistance to water was excellent.
• a heat sensitive copying sheet was prepared using crystal violet lactone (a known coupler), gallic acid an organic acid), acetanilide (a thermofusible material), a styrene-butadiene copolymer (a binder) and toluene (a solvent) in the same manner as described above.
• the heat sensitive copying sheet was heated in the same manner as described above to obtain a blue-violet image. The image faded and disappeared in the test for light resistance and resistance to water under the same condition as described above.
• Example 2.35 g. of coupler No. II, 70 g. of organic sulfonic acid No. 57,500 g. of ,S-naphthol and 800 g. of ligroin were mixed and ground in a ball mill for 1 day. Subsequently, g. of a styrene-butadiene copolymer and 800 g. of toluene were added thereto and mixed and ground for 2 hours. The solution was coated on a film and dried at 40 C. to obtain a heat sensitive copying sheet.
• the sheet was superposed on an original drawing and heated by means of a heat sensitive copying machine (trademark: *Risofax; manufactured by Riso Kagaku Co., Ltd.) to obtain a blue image which was similarly excellent as in Example 1 in light resistance and resistance to water.
• a heat sensitive copying machine (trademark: *Risofax; manufactured by Riso Kagaku Co., Ltd.)
• Example 3.50 g. of coupler No. IH, 300 g. of urea and 600 g. of acetone were mixed and ground in a ball mill for 2 days.
• 30 g. of organic sulfonic acid No. 8, 300 g. of urea, 200 g. of polybutyl-methacrylate, and 600 g. of ethyl acetate were mixed and ground in a ball mill.
• the ground materials were mixed and further treated in a ball mill for 5 hours.
• the resulting mixture, thus treated, was coated on a support and dried to obtain a heat sensitive copying sheet.
• the sheet was heated in the same manner as in Example 1 to obtain a blue image.
• the light resistance and resistance to water of the image were similarly excellent as in Example 1.
• Example 4.l g. of coupler No. IV, 20 g. of organic sulfonic acid No. 36, 200 g. of stearic acid, 70 g. of styrenemaleic anhydride copolymer and 2000 g. of xylene were treated in the same manner as in Example 1 to obtain a heat sensitive copying sheet.
• the sheet was heated in the same manner as in Example 1 to obtain a blue image. In case of the omission of the organic sulfonic acid, the color was not developed.
• Example 5.-10 g. of coupler No. V, 30 g. of organic sulfonic acid No. 49, 100 g. of p-phenylphenol, 40 g. of chlorinated rubber, and 3000 g. of benzene were treated in the same manner as in Example 1 to obtain a heat sensitive copying sheet which was then heated to obtain a blue image. In case of the omission of the organic sulfonic acid, the color was not developed at all.
• Example 6.-10 g. of ground coupler No. VI, and 100 g. of acetanilide were dispersed in a solution of 30 g. of polyvinyl alcohol and 500 g. of water.
• 10 g. of ground organic sulfonic acid No. 29 and 50 g. of acetanilide were dispersed in a solution of 15 g. of polyvinyl alcohol and 300 g. of water. Both dispersions were mixed and were treated in a ball mill for hours, and then were coated on a paper and dried to obtain a heat sensitive copying sheet which was then heated to obtain a blue image.
• salicyclic acid for organic sulfonic acid No. 29 (solfosalicyclic acid)
• the color was not developed.
• Example 7 Example 1 was repeated using coupler Nos. VII, VHI, IX and X, respectively, to obtain a blue image.
• Example 8 g. of coupler No. X, g. of organic sulfonic acid No. 18, 140 g. of benzoic acid, 50 g. of a vinyl chloride-vinyl acetate copolymer and 1500 g. of toluene were mixed and ground in a ball mill for 2 days, and were coated on a paper and dried to obtain a heat sensitive copying sheet. The sheet was superposed on an original drawing and heated by means of a heat sensitive copying machine to obtain a blue image coresponding to the characters on the original drawing. Also, the sheet was treated in the same manner as described above, in the exception of substituting 50 g. of hydroxyethylcellulose and 1500 g. of water for vinylchloride-vinyl acetate copolymer and toluene to obtain the same result.
• Example 9 The color development of the respective combination of couplers Nos. I to X and organic sulfonic acids Nos. 1 to 60 in the same manner as in Examples 1 to 8 was blue. However, in using the coupler No. l, the color developed was blue violet, and in using the coupler No. VII, the color obtained first was blue by increasing the amount of an organic sulfonic acid to be used by about 30% by weight.
• a heat sensitive copying sheet comprising a support having coated thereon a layer comprising (a) a spiro compound having the Formula A I -O O wherein R and R each is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group and a phenyl group, (b) a solid organic sulfonic acid having the Formula B,
• R is selected from the group consisting of an amino group, an N-substituted amino alkyl group having from 2 to 18 carbon atoms, an unsubstituted amino alkyl group having from 2 to 18 carbon atoms, an alkyl group having from 10 to 20 carbon atoms, an alkoxy group having from 10 to 20 carbon atoms, an alkyl group substituted with a carboxylic acid group, said alkyl group having from 6 to 18 carbon atoms, an alkyl group, and an aromatic ring, and (c) a thermofusible material having a melting point ranging from 50 to C., from 1 to 2 parts by weight of the spiro compound being present for every 1 to 6 parts by weight of the solid organic sulfonic acid.
• spiro compound is selected from the group consisting of 2,2-spirobi-(benzolflchromene), 3-methyl- 2,2'-spirobi( benzo [f 1 chromene) 3-isopropyl-2,2'-spirobi- (benzo [f] chromene 3-amyl-2,2'-spirobi (benzo [f] chromene), 3-octyl-2,2'-spirobi(benzo[f]chromene), 3,3'-dimethyl-2,2-spirobi (benzo [f 1 chromene) 3,3 '-dicarboethoxy-2,2-spirobi (benzo [f chromene 3-benzyl-2,2'-spirobi (benzo [f] chromene) 3-phenylethyl-2,2'-spirobi (benzo- [f]chromene), or 3-phenyl-2,2-spirobi(benzo[f]chromene).
• thermofusible material is selected from the group consisting of acetoanilide, urea, diphenylamine, diphenyl, naphthalene, benzoin, a-naphthol, fi-naphthol, p-t-butylphenol, p-phenylphenol, 4,4'-cyclohexylidine-diphenol, phthalic anhydride, maleic anhydride, stearic acid, benzoic acid, u-naphthyl acetic acid, methyl p-hydroxybenzoate, diphenyl phthalate, triphenyl phosphate or p-hy droxydiphenyl ester.
• a heat sensitive copying sheet comprising a support having coated thereon a layer comprising (a) a spiro compound having the Formula A Ill; R1
• R is selected from the group consisting of an amino group, an N-substituted amino alkyl group having from 2 to 18 carbon atoms, an unsubstituted amino alkyl group having from 2 to 18 carbon atoms, an alkyl group having from 19 to 20 carbon atoms, an alkoxy group having from 10 to 20 carbon atoms, an alkyl group substituted with a carboxyl group, said alkyl group having from 6 to 18 carbon atoms, an aralkyl group, and an aromatic ring, (c) a thermofusible material having a melting point ranging from 50 to 180 C. and which is substantially colorless at a temperature lower than 50 C., and (d) a binder, from 1 to 2 parts by weight of the spiro compound being present for every 1 to 6 parts by weight of the solid organic sulfonic acid.
• said binder is selected from the group consisting of styrene-butadiene copolymers, alkyd resins, polybutyl methacrylates, vinyl chloride-vinyl acetate copolymers, styrene-maleic anhydride copolymers, synthetic rubbers, gum arabic, polyvinyl alcohol and hydroxyethyl cellulose.
• a heat sensitive copying sheet comprising a support having coated thereon (a) a spiro compound having the Formula A wherein R and R each is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group and a phenyl group, (b) a solid organic sulfonic acid having the Formula B wherein R is selected from the group consisting of an amino group, an N-substituted amino alkyl group having from 2 to 18 carbon atoms, an unsubstituted amino alkyl group having from 2 to 18 carbon atoms, an alkyl group having from 1-0 to 20 carbon atoms, an alkoxy group having from to carbon atoms, a carboxylic acid substituted alkyl group, said alkyl group having from 6 to 18 carbon atoms, an aralkyl group, or an aromatic ring, and (c) a thermofusible material having a melting point
• Heat sensitive copying sheets comprising a combination of two supports, one support having coated thereon a layer comprising (a) a spiro compound having the Formula A Y CCCXXQ wherein R and R each is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group and a phenyl group, and (b) as a coupler, a solid organic sulfonic acid having the Formula B R SO3H (B) wherein R is selected from the group consisting of an amino group, an N-substituted amino-alkyl group having from 2 to 18 carbon atoms, an unsubstituted amino alkyl group having from 2 to 18 carbon atoms, an alkoxy group having from 10 to 20 carbon atoms, a carboxylic acid substituted alkyl group, said alkyl group having from 6 to 18 carbon atoms, an aralkyl group, and an aromatic ring
• Heat sensitive copying sheets comprising a combination of two supports, one support having coated thereon a layer comprising (a) a spiro compound having the Formula A,
• R and R each is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group and a phenyl group, and (b) a thermofusible material having a melting point ranging from 50 to C., the other support having coated thereon a layer comprising a solid organic sulfonic acid having the Formula B,
• R is selected from the group consisting of an amino group, an N-substituted amino alkyl group having from 2 to 18 carbon atoms, an unsubstituted amino alkyl group having from 2 to 18 carbon atoms, an alkyl group having from 10 to 20 carbon atoms, an alkoxy group having from 10 to 20 carbon atoms, a carhoxylic acid substituted alkyl group, said alkyl group having from 6 to 18 carbon atoms, an aralkyl group, and an aromatic ring, from 1 to 2 parts by weight of the spiro compound being present for every 1' to 6 parts by weight of the solid organic sulfonic acid.
• Heat sensitive copying sheets comprising a combination of two surfaces, one surface having coated thereon a layer comprising a spiro compound having the Formula A,
• R and R each is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, a carboxylic acid ester, an aralkyl group and a phenyl group, the other surface having coated thereon a layer comprising (a) a solid organic sulfonic acid having the Formula B wherein R is selected from the group consisting of an amino group, an N-substituted amino alkyl group having from 2 to 18 carbon atoms, an unsubstituted amino alkyl group having from 2 to 18 carbon atoms, an alkyl group having from 10 to 20 carbon atoms, an alkoxy group having from 10 to 20 carbon atoms, a carboxylic acid substituted alkyl group, said alkyl group having from 6 to 18 carbon atoms, an aralkyl group, and an aromatic ring, and (b) a thermofusible material having a melting point ranging from 50 to 180 C., from 1 to 2 parts by weight of the
• thermofusible material is substantially colorless at a temperature lower than 50 C., and is present in an amount of from 3 to 30 weight parts.
• thermofusible material is present in an amount from 3 to 30 weight parts and said binder is present in an amount of from 3 to 15 weight parts.
• thermofusible material is substantially colorless at a temperature lower than 50 C., and is present in an amount of from 3 to 30 weight parts.
• thermofusible material is substantially colorless at temperatures lower than 50 C., and is present in an amount of from 3 to 30 weight parts.
• thermofusible material is substantially colorless at temperatures lower than 50 C., and is present in an amount from 3 to 30 weight parts.
• thermofusible material is substantially colorless at temperatures lower than 50 C., and is present in an amount from 3 to 30 weight parts.

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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)
• Color Printing (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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Publications (1)

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Family Applications (1)

Country Status (7)

Cited By (16)

Families Citing this family (3)

• 1969
  • 1969-05-26 JP JP44040719A patent/JPS4833712B1/ja active Pending
• 1970
  • 1970-05-25 FR FR7018948A patent/FR2092172A5/fr not_active Expired
  • 1970-05-26 NL NL7007577A patent/NL7007577A/xx unknown
  • 1970-05-26 CH CH775970A patent/CH560112A5/xx not_active IP Right Cessation
  • 1970-05-26 GB GB25302/70A patent/GB1260593A/en not_active Expired
  • 1970-05-26 DE DE19702025816 patent/DE2025816B2/de active Granted
  • 1970-05-26 US US40732A patent/US3666525A/en not_active Expired - Lifetime

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