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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
• • 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
  • Y10S428/914—Transfer or decalcomania
• • 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
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
  • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
  • Y10T428/277—Cellulosic substrate

Definitions

• the present invention relates to a color developing sheet and color developing agent in which the disadvantages that a polyvalent metal salt of an aromatic carboxylic acid still has as a color developing agent are eliminated.
• Pressure sensitive recording sheets are known as carbonless copy papers. When using mechanical pressure or impact pressure when writing or typing on a typewriter, they produce a colored impression and thus allow the simultaneous production of several copies. A colored image is formed due to the color development reaction between an electron donating colorless dye and an electron accepting color developing agent.
• Typical color developing agents are inorganic solid acids such as activated clay, attapulgite, etc. (described in USP 2712507); substituted phenols and diphenols (described in Japanese Patent Publication 9309/1965); p-subst. phenol-formaldehyde polymers (described in Japanese Patent Publication 20144/1967); Metal salts of aromatic carboxylic acids (described in Japanese Patent Publications 10856/1974 and 1327/1977, etc.); 2,2 ⁇ -bis-phenolsulfone compounds (described in JP-OS 10 6313/1979 etc.).
• polyvalent metal salts of an aromatic carboxylic acid such as 3,5-di ( ⁇ -methylbenzyl) salicylic acid zinc salt are commonly used because they give a color developing sheet with superior durability of the colored image to the effects of light, moisture, heat and plasticizer.
• the color development sheet containing a polyvalent metal salt of an aromatic carboxylic acid has the disadvantages that the color development speed and final color development intensity are not satisfactory.
• the object of the invention is to provide a color developing agent for pressure-sensitive recording sheets which is largely free from the above disadvantages, i.e. has a superior color development speed and an improved intensity of final color development ("final color development intensity").
• the inventors have surprisingly found after many studies that polyvalent metal salts of an aromatic carboxylic acid in combination with a polyvalent metal salt of a carboxylated terpene phenolic resin and / or a reaction product of a carboxylated terpene phenolic resin, an aromatic carboxylic acid and a compound of a polyvalent metal have a superior color development speed and an improved final color development intensity result, and that the great fastness is retained as an advantage of using a polyvalent metal salt of aromatic carboxylic acid.
• the metal salts of aromatic carboxylic acids used in this invention are those that in Japanese Patent Publications 10856/1974 and 1327/1977.
• aromatic carboxylic acids include benzoic acid, p-hydroxybenzoic acid, chlorobenzoic acid, bromobenzoic acid, nitrobenzoic acid, methoxybenzoic acid, ⁇ thoxybenzoeklare, toluic acid, ⁇ thylbenzoeklare, pn-propylbenzoic acid, p-isopropylbenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid , 3-methoxy-4-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-benzoylbenzoic acid, p-cyclohexylbenzoic acid, salicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3,5-di-tertiary-butylsalicylic acid, 5-nonylsalicylic acid, 5 -Cyclohexylsalicylic acid, 3-cyclohexy
• carboxylic acids monocarboxylic acids are preferred.
• Typical examples of the polyvalent metals of the metal salts of aromatic carboxylic acids are magnesium, aluminum, cadmium, calcium, titanium, zinc, nickel. Cobalt, manganese, vanadium, etc .; Magnesium, aluminum and zinc are preferred; Zinc is most preferred.
• the polyvalent metal salt of a carboxylated terpene phenol resin according to the invention and the reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a compound of a polyvalent metal according to the invention are new color developing agents. They have better resistance to yellowing over time and superior plasticizer resistance.
• Cas carboxylated terpene phenol resin is produced by the following method as described in Japanese Patent Application No. 159540/1985.
• cyclic monoterpene and phenol is carried out in a suitable solvent, for example a petroleum product, in the presence of an acidic catalyst, for example aluminum trichloride, boron trifluoride, sulfuric acid, polyphosphoric acid, etc., to give a condensation product.
• an acidic catalyst for example aluminum trichloride, boron trifluoride, sulfuric acid, polyphosphoric acid, etc.
• Typical examples of the cyclic monoterpene are pinene, limonene, terpinolene, mentadiene, gum turpentine oil, which contains ⁇ -pinene as the main component, dipentene, which contains ⁇ -limonene as the main component, and so on.
• Typical examples of the phenol are monophenols such as carbolic acid, alkylphenol, alkoxyphenol, halogenated phenol, etc .; and polyhydric phenols, for example resorcinol, pyrocatechol etc.
• suitable solvents are benzene, toluene, xylenes, n-hexane, n-heptane, halogenated solvents, for example dichloromethane, chloroform, trichloromethane, bromobenzene and the like.
• the condensation product is made alkaline by adding alkali metal, alkali metal hydroxide or carbonate and is introduced at 140-180 ° C and 5-30 atm with introduction of carbon dioxide gas. treated in an autoclave (Kolbe-Schmitt reaction), the carboxy group being introduced into the condensation product.
• the solvent is distilled lation removed.
• the product is washed out to remove the unreacted compounds.
• the product is further extracted with a dilute basic aqueous solution and then neutralized, whereby the carboxylated terpene phenolic resin is excreted.
• the resin obtained is filtered off and washed out in order to obtain the purified carboxylated terpene phenol resin.
• the polyvalent metal salt of a carboxylated terpene phenol resin is prepared by reacting a carboxylated terpene phenol resin with a polyvalent metal oxide, hydroxide, chloride, carbonate, sulfate or the like in the presence of an inorganic ammonium salt with melting, or a carboxylated terpene phenol resin with alkali metal hydroxide in one Solvents such as water, alcohol, etc. dissolve, add and react with a polyvalent metal salt, or the like.
• polyvalent metals examples include magnesium, aluminum, calcium, cadmium, titanium, zinc, nickel, cobalt, manganese, etc .; Magnesium, aluminum and zinc are preferred. Zinc is most preferred.
• the reaction product between the above carboxylated Terpene phenolic resin, aromatic carboxylic acid and polyvalent metal compound is prepared by uniformly mixing the carboxylated terpene phenolic resin, aromatic carboxylic acid and polyvalent metal compound and then reacting with each other, or by mixing two of the above three ingredients and then with one other component can react.
• Uniform mixing is achieved by dissolving these ingredients in a solvent with stirring, or melting with heating, or by other methods.
• solvents are alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc .; and organic solvents such as alcohol, acetone, etc .; and the mixture of them.
• aromatic carboxylic acid (monocyclic or polycyclic) is one in which the carboxy group is bonded directly to the ring.
• aromatic carboxylic acid are: benzoic acid, p-hydroxybenzoic acid, chlorobenzoic acid, bromobenzoic acid, nitrobenzoic acid, methoxybenzoic acid, ethoxy benzoic acid, toluic acid, ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, p-tert.-butylbenzoic acid, o-benzoylbenzoic acid -Cyclohexylbenzoic acid, salicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3,5-di-tertiary-butylsalicylic acid, 5-n
• carboxylic acids the monocarboxylic acids are preferred.
• suitable polyvalent metal compounds are oxides, halides, carbonates, sulfates, nitrates, acetates, formats, oxalates, benzoates, acetylacetone salts and salicylates of magnesium, aluminum, Cadmium, calcium, titanium, zinc, nickel, cobalt, manganese, vanadium, etc .; Magnesium, aluminum and zinc compounds are preferred; Zinc compounds are most preferred.
• the amount of the polyvalent metal salt of a terpene phenol resin and / or the reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a compound of a polyvalent metal based on the metal salt of an aromatic carboxylic acid is not particularly limited, and is preferably at least 1% by weight, more preferably at least 30% by weight.
• a color developing sheet is prepared by applying the coating slip obtained above as a simple layer on a substrate.
• multi-layer coating methods can also be used, in which case a coating composition containing a color developing agent is first applied to a substrate and then another coating composition containing another color developing agent, and the like.
• the color developing agents of the present invention are used in all fields related to pressure sensitive recording sheets. Examples are: Pressure sensitive recording sheets, e.g. have a middle sheet, lower sheet, single recording sheet, etc., or in which the color developing agent of the present invention is coated on or mixed with the support material; Test means for a leuco dye after dissolving in an organic solvent; Spot printing ink mixed with a wax; pressure sensitive ink using the color developing agent and / or microcapsules containing the leuco dye.
• the coating slip according to the invention is produced by mixing kaolin clay, calcium carbonate, treatment starch, polyvinyl alcohol, synthetic or natural latex etc. and imparting the mixture with suitable viscosity and spreadability. It is advantageous to use 10-70% by weight of color developing agent, based on the total solids in the coating slip. With less than 10% by weight of color developing agent, the color developing ability is insufficient, with more than 70% by weight of color developing agent, on the other hand, the surface properties of the color developing sheet deteriorate.
• color development layer it is also advantageous to apply the color development layer to a support in a coating amount of at least 0.5 g / m2, preferably 1.0-10.0 g / m2.
• the color developing agent of the present invention is suitable for many known dyes used in pressure sensitive recording sheets.
• Triphenylmethane series dyes such as crystal violet lactone, malachite green lactone, 3-dimethylaminotriphenylmethanephthalide, etc .
• Fluoran series dyes such as 3,6-dimethoxyfluorane, 3-N-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 1,2-benzo-6-dimethylaminofluorane, 1,2-benzo- ( 2 ⁇ -diethylamino) -6-diethylamino-fluoran, 3-diethylamino-7-dibenzylamino-fluoran, 3-diethylamino-6-methyl-7-dibenzylamino-fluoran, 3-diethylamino-5-methyl-7-dibenzylamino-fluoran, 3 -Diethylamino-7-anilino-fluoran, 3-die
• the method of manufacturing a transfer sheet in which microcapsules containing the pressure sensitive dye were coated on a sheet of fine paper, and the evaluation method of the color development sheet using the transfer sheet is as follows.
• dilution water 90 parts was mixed with 90 parts of a 10% aqueous solution of ethylene-maleic anhydride copolymer (trade name EMA, manufactured by Monsanto Co.). 10 parts of urea and 1 part of resorcinol were dissolved in this mixed solution, then the pH of the solution was adjusted to 3.4.
• EMA ethylene-maleic anhydride copolymer
• an oil mixture of alkyl diphenylethane (trade name: Hisol SAS 296, manufactured by Nisseki Kogaku Co.) and diisopropylnaphthalene (trade name KMC-113, manufactured by Kureka Kogaku Co.) was prepared in a weight ratio of 1: 1.
• the core substance to be encapsulated there were prepared: (a) an oil of a blue color developing pressure sensitive dye by dissolving 3% crystal violet lactone and 1% benzoyl leucomethylene blue in the above oil mixture; and (b) an oil of a black color developing pressure sensitive dye by dissolving 5% 3-diethylamino-6-methyl-7-anilinofluorane, 1% 3- Diethyl-amino-6-methyl-7-diphenylmethylaminofluoran and 0.5% 3-diethylamino-6-methyl-7-chlorofluoran in the above oil mixture.
• a coating composition 180 parts of capsule slurry, 35 parts of wheat starch and 85 parts of an 8% aqueous oxidized starch solution were mixed to prepare a coating composition.
• the coating composition was applied in a coating amount of 4.5 g / m2 on a base paper of 45 g / m2 and dried. In this way, two transfer sheets, that is, (A) a transfer paper developing blue color, and (B) a transfer paper developing a black color.
• a CB sheet in which a support is coated with a microcapsule containing pressure-sensitive dye and a color developing sheet in which a support is coated with a color developing agent are laid so that the coated surfaces of the sheets touch each other.
• a color image is generated with the grid plate roll calender.
• the reflectance of the sheet is measured with a Hunter reflectometer (D-type; from Toyo Seiki Co.) measured using an amber filter.
• the color development speed (J1 or J2) is calculated from the reflectance I0 before the color development, the reflectance I1 of 10 seconds after the color development or the reflectance I2 of 24 hours after the color development.
• the image density at 10 seconds after color development is calculated according to the following equation:
• Terpene phenolic resin was made from ⁇ -pinene and carbolic acid.
• a coating composition of the following formulation was made using the above suspension.
• Suspension 40 parts Calcium carbonate 100 parts Styrene butadiene latex (concentration: 40%) 15 parts Oxidized starch 15 parts Water 415 parts
• the coating mass was applied with a Meyer stick Paper of 50 g / m2 basis weight was applied so that the amount of coating composition applied after drying was 5.5 g / m2.
• a reaction product was prepared from a carboxylated terpene phenolic resin (using gum turpentine and carbolic acid), salicylic acid, and zinc chloride in place of the carboxylated terpene phenolic zinc salt of Example 1.
• a color developing agent suspension, a coating material and a color developing sheet were prepared from the obtained reaction product as in Example 1.
• a carboxylated terpene phenolic resin was produced from ⁇ -pinene and carbolic acid.
• a coating composition and a color developing sheet were prepared from the obtained color developing agent suspension in the same manner as in Example 1.
• a color developing sheet was prepared from the obtained color developing agent suspension in the same manner as in Example 3.
• a color developing sheet was prepared from the obtained color developing agent suspension in the same manner as in Example 1.
• a color developing sheet was prepared using 3,4-di-tert-butylsalicylic acid zinc salt in the same manner as in Comparative Example 1.
• the color development sheet the color development layer of which contains a metal salt of an aromatic carboxylic acid in combination with a carboxylated terpene phenol resin zinc salt and / or a reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a zinc compound, has a superior color development speed and an improved final color development intensity compared to a color development sheet containing only a polyvalent metal salt of an aromatic carboxylic acid.
• the invention exhibits both a superior color development rate (color development speed) and an improved final color development intensity while maintaining the superior fastness of the color image as an advantage of the color development sheet containing a metal salt of aromatic carboxylic acids as a color developing agent.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Color Printing (AREA)

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• 1987
  • 1987-01-16 JP JP62007529A patent/JPS63176176A/ja active Granted
  • 1987-12-29 US US07/140,146 patent/US4833119A/en not_active Expired - Fee Related
• 1988
  • 1988-01-13 CA CA000556384A patent/CA1285765C/fr not_active Expired - Lifetime
  • 1988-01-14 EP EP88100475A patent/EP0275108B1/fr not_active Expired - Lifetime
  • 1988-01-14 DE DE3855303T patent/DE3855303D1/de not_active Expired - Fee Related

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