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

Definitions

• the invention relates to a color developing agent for pressure-sensitive recording sheets and color developing sheets containing this agent.
• Pressure sensitive recording sheets are known as carbonless copy papers. They result when using mechanical pressure or impact pressure when writing or striking a typewriter makes a colored impression and thus allow the simultaneous production of several copies.
• the pressure-sensitive transfer recording sheets are constructed approximately as follows:
• the microcapsules have a shell made of a polymeric film, such as gelatin, urea-formaldehyde resin and melamine-formaldehyde resin, and a solution of a colorless, color-forming pressure-sensitive dye (leuco dye) in a non-volatile oil and is enclosed by the shell.
• the underside and the surface of the middle (CFB) sheet are accordingly with the pressure sensitive Chen dye-containing microcapsules and coated with a layer of the color developing agent.
• Localized pressure by a ballpoint pen, typewriter, or the like is applied to the pressure-sensitive recording sheets composed of a CB sheet, a CF sheet and optionally one or more CFB sheets with the surface coated with microcapsules adjacent to the surface coated with the layer containing the color developing agent, the microcapsules break under the applied pressure, and the solution of the colorless dye moves into the layer containing the color developing agent.
• the dye reacts with the color developing agent to form a colored image in the desired recording pattern.
• the microcapsules containing the dye and the color developing agent are applied in different layers or as a mixture in one layer to the same surface of the base sheet.
• Another type of pressure sensitive recording sheet is a recording sheet in which the printing ink containing the pressure sensitive dye Contains microcapsules or the color developing agent as such or in capsule form, on which base paper is printed.
• the color developing agent dissolved in a solvent is often used to check the condition of the surface coated with the microcapsules containing the dye.
• the color developing agent of the present invention can be used for color developing sheets, color developing printing ink, color developing agent solutions, etc.
• Known electron accepting 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-substituted phenol-formaldehyde polymers (described in Japanese Patent Publication 20144/1967); Metal salts of aromatic carboxylic acids (described in Japanese Patent Publication 1856/1974); 2,2-bis-phenol sulfone compounds (described in JP-OS 106313/1979).
• 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-substituted phenol-formaldehyde polymers (described in Japanese Patent Publication 20144/1967); Metal salts of aromatic carboxylic acids (described in Japanese Patent Publication 1856/1974); 2,2-bis-phenol
• inorganic solid acids have the advantage that they are inexpensive and have a rapid color development, but they have the disadvantage that the color development ability suffers when stored, for example due to the absorption of gases and moisture from the atmosphere, and that the image fades and a color change upon exposure of sunlight and fluorescent light.
• the substituted phenols have insufficient color development and poor image density.
• the ⁇ -substituted phenol formaldehyde polymers (for example p-phenylphenol novolak resin) give good color development, but have the disadvantage that the sheet yellows when exposed to sunlight or when stored due to the action of the gases in the atmosphere.
• the metal salts of aromatic carboxylic acids have the advantages of good resistance to the colored image and superior resistance to yellowing to light, gases, etc., but the disadvantage is insufficient resistance of the colored image to water or plasticizer.
• the invention is based on the object of providing a color developing agent for pressure-sensitive recording sheets and a color developing sheet which are used in white hold, the color-forming ability and the color image of the sheet are superior and do not undergo any change during storage due to the gases and moisture in the atmosphere, water and chemicals such as plasticizers, and light such as sunlight and fluorescent light.
• the previous organic color developing agents, especially phenolic color developing agents, and the color developing sheets obtained when they are used have the disadvantages that they are exposed to UV light. and the gases in the atmosphere turn yellow and the colored pictures go out easily.
• the aim of this invention is to overcome these disadvantages.
• a polyvalent metal salt of a carboxylated terpene phenol resin is prepared by condensing the cyclic monoterpene with the phenol using an acid catalyst, introducing carboxyl groups into the condensed product, and then reacting this product with a polyvalent metal leaves.
• the polyvalent metal salt of a carboxylated terpene obtained phenolic resin and the color developing sheet in which this resin is applied to a base material such as paper, etc. have less yellowing under the influence of atmospheric gases and UV rays, superior color-forming ability of the pressure-sensitive dye and excellent resistance to fading under the influence of sunlight, plasticizers etc. on.
• the condensation reaction of cyclic monoterpene and phenol according to the invention can be carried out by known processes (for example described in USP 2811564).
• the resin of the invention is e.g. prepared by dissolving a phenol in a solvent such as an aromatic hydrocarbon such as dichloromethane, chloroform, etc., an ether, aliphatic hydrocarbon, carbon disulfide and the like, adding an acid catalyst to the product obtained, and then slowly adding the cyclic monoterpene in a temperature range of Drops in room temperature up to 70 ° C,
• cyclic monoterpene limonene, isolimone, terpin oil, terpinene, phellandrene, bornylene, camphor, 2.8 (9) -p-mentadiene and so on, as well as the cyclic monoterpene occurring in nature.
• p ene for example gum turpentine oil, which is a mixture and contains ⁇ -pinene as the main component, pine oil, dipentene, which contains ⁇ -limonene as the main component, and the like.
• Typical examples of the phenol according to the invention are alkyl-substituted and alkoxy-substituted phenols, for example carbolic acid, cresol, tert-butylphenol, isopropylphenol, ethylphenol, tert-octylphenol, nonylphenol, cumylphenol, phenylphenol, cyclohexylphenol, benzylphenol, p-methoxyphenol, methoxyphenol butylphenol, tertiary amylphenol; polyhydric phenols such as pyrocatechol, resorcinol, hydroquinone, orcin, pyrogallol, oxyhydroquinone, phloroglucin, etc .; halogenated phenols such as chlorophenol, bromophenol, etc .; Naphthol; Dioxynaphthalene, and the like.
• carbolic acid cresol, tert-butylphenol, is
• phenols can be selected in consideration of the demands placed on the pressure sensitive recording sheet and the manufacturing cost, carbolic acid is preferred.
• the ratio of terpene to phenol is not particularly limited, but is 0.1-10 mol, preferably 0.4-5 Mol, per 1 mol terpene.
• the acid catalyst examples include boron trifluoride, aluminum trichloride, tin chloride, zinc chloride, phosphoric acid, polyphosphoric acid, aromatic sulfonic acid, sulfuric acid, hydrochloric acid, etc.
• the reaction temperature and time vary depending on the different raw materials, the type of catalyst and the desired product, but are from room temperature to 90 ° C. and 3 to 30 hours, preferably 30 to 50 ° C. and 6 to 9 hours.
• the solvent is e.g. removed by steam distillation and the catalyst is removed by decomposition.
• terpene phenolic resins are available depending on the reaction temperature, time, the type and amount of the acid catalyst and the ratio of terpene to phenol.
• the average molecular weight of the terpene phenolic resin is preferably 350 to 1000 (by GPC- Analysis determined) and the melting point is preferably at least 70 ° C.
• the structure of the terpene phenolic resin is very complicated.
• a-pinene as cyclic monoterpene and carbolic acid (phenol)
• the condensation reaction and the products can be represented schematically as follows: 1 mole of phenol is added to 1 mole of a-pinene (the product (1)), a-pinene-phenol addition product is ring-opened, phenol or a-pinene are successively and repeatedly added to the opened product and thus condensed, so that Products (2), (3) etc. and the terpene phenolic resin.
• the carboxy group is introduced into the terpene phenol resin obtained, and various known methods for introducing a carboxy group into an aromatic compound can be used.
• the Kolbe-Schmitt reaction i.e. the reaction in which carbon dioxide and alkali such as metallic sodium, metallic potassium or sodium bicarbonate are applied under heating and pressure is particularly preferred.
• reaction of the carboxylated terpene phenol resin with polyvalent metal salt is e.g. as follows:
• the carboxylated terpene phenol resin obtained is reacted both with a polyvalent metal oxide, hydroxide, chloride, carbonate, sulfate or the like, and with an inorganic ammonium salt, such as ammonium carbonate, with heating and melting at 100-150 ° C., or the carboxy gated terpene phenol resin is dissolved in alcohol together with alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, and the alcoholic polyvalent metal salt is added and reacted therewith.
• the carboxylated terpene phenol resin obtained is then neutralized, extracted, etc. to remove the unnecessary solvents and unreacted inorganic compounds. It is then washed and dried and the polyvalent metal salt of the carboxylated terpene phenol resin according to the invention is obtained.
• Examples of the multivalued are magnesium, aluminum, calcium, cadmium, titanium, zinc, nickel, cobalt, manganese, etc .; Magnesium, aluminum and zinc are preferred, zinc is most preferred.
• the obtained polyvalent metal salt of the carboxylated terpene phenol resin is a new color developing agent having a structure previously unknown to a color developing agent of a pressure sensitive recording sheet. It can be used in admixture with an inorganic solid acid such as activated clay, phenol formaldehyde novolac resin, substituted phenolic resin, a metal salt thereof or a metal salt of an aromatic carboxylic acid, etc.
• an inorganic solid acid such as activated clay, phenol formaldehyde novolac resin, substituted phenolic resin, a metal salt thereof or a metal salt of an aromatic carboxylic acid, etc.
• 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 / m 2 , preferably 1.0-10.0 g / m 2 .
• the color developing agent of the present invention is suitable for many known dyes used in pressure sensitive recording sheets.
• the polyvalent metal salt of the carboxylated terpene phenol resin according to the invention has superior yellowing resistance of the colored image with good image density and color development speed is unclear. But it is assumed that the yellowing of the color developing agent by quinone formation of the phenoli is caused by the hydroxyl group, it can be assumed that the lower yellowing is due to the prevention of the quinone formation of the phenolic hydroxyl group due to the carboxyl group introduced and to the presence of the polyvalent metal salt.
• the complex formed from the color developing agent of the present invention is due to the presence of carboxy groups and the polyvalent metal salt, has a stronger interaction than the complex formed from the previous organic color developing agents (especially from the phenolic color developing agents).
• This stronger interaction means that the color developing agent according to the invention is sparingly soluble in the plasticizer, so that the complex is stable. Therefore, according to the invention, the plasticizer resistance is also superior.
• the good color development rate is due to the superior solubility of the inventor color developing agent of the present invention in aromatic solvents (solvent for the pressure sensitive dye), and that the good image density is caused by the improved color developing ability of the phenolic hydroxyl group and the presence of the polyvalent metal salt.
• the terpene-phenol resin was obtained in the same manner as in 1- (1), but resin-terpetin to carbolic acid behaved like 1 to 5. 8.4 g of metallic sodium was added to the terpene phenol resin and the carboxyl group was introduced in the same manner as in 1- (2) -. As in 1- (3), the mixture was heated and melted to give the zinc salt of the carboxylated terpene phenol (this was referred to as Compound No. 3).
• the terpene phenol resin was obtained in the same manner as in 1- (1) of Synthesis Example 1, except that the type and the mixing ratio of cyclic monoterpene and the phenol, and the type of acid catalyst according to Table 1 were changed.
• the carboxyl group was introduced in the same manner as in Synthesis Example 1- (2), except that the type and amount of alkali per 100 g of the terpene phenol resin were changed according to Table 1.
• the type and amount of the chemicals and the manufacturing process for forming the polyvalent metal salt are shown in Table 1.
• the superior yellowing and better plasticizer resistance of the color developing agent according to the invention appear very clearly in a color developing sheet in which the color developing agent is applied as a coating composition in a small amount to a base sheet. Therefore, the invention is illustrated by the following examples of color development sheets.
• the properties of the color development sheets are determined according to the following test methods.
• 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.) using an amber filter. From the reflectance 1 0 before Color development, the reflectance I 1 of 10 seconds after the color development or the reflectance 1 2 of 24 hours after the color development, the color development speed (J 1 or J 2 ) is calculated.
• the image density at 10 seconds after color development is calculated according to the following equation:
• the plasticizer resistance value is expressed by the following equation:
• Plasticizer resistance values of more than 100% mean an increase in image density due to the coating with the plasticizer.
• the whiteness retention (H l ) is calculated according to the following equation. Higher whiteness retention values indicate less yellowing of the leaf when exposed to sunlight.
• the undyed color developing sheets are left under an atmosphere of N0 2 gas for 2 hours (measured according to the test method of JIS L-1055-1961).
• the reflectance K 0 of the sheet before the test and the reflectance K 2 of the sheet after the test are measured using a Hunter reflectometer (using a blue filter).
• the retention (H 2 ) of the whiteness is calculated according to the following equation.
• the colored surface of the image 24 hours after color development, which was generated according to the method described in (1), is measured with a Fade-O-Meter Irradiated for 6 hours.
• the reflectance 1 4 after the irradiation is measured in the same manner as in the test method (1).
• the color development intensity J 4 after irradiation is calculated according to the following equation:
• the color development intensity J 2 before the irradiation and the color development intensity J 4 after the irradiation become the light fastness value calculated as follows.
• dilution water 90 parts was mixed with 90 parts of a 10% aqueous solution of ethylene-maleic anhydride copolymer (trade name: EMA, from Monsanto Co.). 10 parts of urea and 1 part of resorcinol were dissolved in this mixed solution, and 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: 2.
• a core substance to be encapsulated (a) was an oil of a pressure-sensitive dye developing a blue color
• an oil of a black color developing pressure sensitive dye was prepared by dissolving 5% 3-diethylamino-6-methyl-7-anilinofluorane, 1% 3-diethylamino 6-methyl-7-diphenylmethylaminofluoran and 0.5% 3-diethylamino-6-methyl-7-chlorofluorane in the oil mixture, and (c) an oil of a red color developing pressure sensitive dye was obtained by dissolving 3% 8 -Diethylaminobenzo (C) fluoran and 2% 3,3-bis (1-ethyl-2-methyl-indol-yl) phthalide in the 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 / m 2 to a base paper of 45 g / m 2 and dried.
• three transfer sheets that is, (A) a blue color developing transfer paper, (B) a black color developing transfer paper and (C) a red color developing transfer paper.
• Each of the three transfer sheets and a color developing sheet using Compound No. 1 prepared by the above-described method were put on each other so that a color was formed.
• the color development sheets according to the invention are in superior to all test results compared to the color development sheets of comparative examples, have particularly preferred yellowing resistance and plasticizer resistance and are particularly suitable as color development agents and sheets for pressure-sensitive recording sheets.
• the zinc salt of the carboxylated terpene phenol resin was prepared from the terpene phenol resin of Synthesis Example 1- (1) by the method of Synthesis Example 2- (3). Color development was performed using the zinc salt of the carboxylated terpene phenolic resin lungsblatt prepared in the same manner as in Example 1.
• a p-tertiary octylformaldehyde polymer (referred to as pop) was prepared in the same manner as in Comparative Example 2.
• the zinc salt of the polymer was prepared in the same manner as in Synthesis Example 2- (3).
• a color developing sheet was produced using the zinc salt of the pop resin in the same manner as in Comparative Example 1.
• a color development sheet was made using the Zinc salt of 3 (4 '- ( ⁇ '-dimethylbenzyl, phenyl) -5- ( ⁇ '-dimethylbenzyl) salicylic acid prepared in the same manner as in Comparative Example 1.
• the color development sheets according to the invention have good yellowing resistance and better properties than the color development sheet of Comparative Example 1.
• the color development sheets according to the invention give good results. Color developability and significantly better yellowing resistance to light and NO x gases, plasticizer resistance and light fastness than the color development sheets of Comparative Examples 2 and 3. Furthermore, the color development sheets according to the invention provide superior plasticizer resistance and light fastness in comparison with the color development sheet of Comparative Example 4.
• the color developing sheet using the zinc salt of the carboxylated terpene phenolic resin of the present invention is much better in color developing ability, light fastness and plasticizer resistance than that using the addition product in USP 4540998 as shown in Table 2.
• the carboxy group in the zinc salt of the carboxylated terpene phenol resin according to the invention.
• the carboxy group is linked to the phenol added to the terpene in the para or ortho position. Additional carboxylic acid groups are contained in the same molecule, and a salt with a strong ion bond is formed by zinc between two carboxylic acids that are present in the same or different molecules.
• a polyvalent metal salt of the carboxylated terpene phenolic resin is prepared by condensing a cyclic monoterpene with a phenol using an acid catalyst, introducing the carboxyl group into the condensed product, and then reacting with a polyvalent metal.
• the color developing sheets in which this resin is used as the color developing agent give the same or better color-developing ability and significantly better yellowing resistance to NOx gases in the atmos- phere, sunlight and fluorescent light than the previous color-developing sheets. These colors also show improved lightfastness and significantly superior plasticizer resistance.
• the invention thus offers great advantages since, in the case of an image with a desired hue obtained by the mixture of pressure-sensitive dyes, the hue change and fading by plasticizers, light. etc. can be largely avoided.
• the invention has the advantage that the production costs are low, and therefore the color developing sheets according to the invention are cheaper than the previous color developing sheets with organic color developing agents, because the abundant, cheap, naturally occurring materials, for example terpene oil, pine oil, dipentene, etc., than Raw materials can be used.

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

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• 1985
  • 1985-07-19 JP JP60159540A patent/JPS6219486A/ja active Pending
• 1986
  • 1986-06-09 US US06/872,184 patent/US4749680A/en not_active Expired - Lifetime
  • 1986-06-13 AU AU58713/86A patent/AU574923B2/en not_active Ceased
  • 1986-07-04 CA CA000513072A patent/CA1270274A/fr not_active Expired
  • 1986-07-16 DE DE8686109770T patent/DE3676416D1/de not_active Expired - Lifetime
  • 1986-07-16 EP EP86109770A patent/EP0218810B1/fr not_active Expired - Lifetime
• 1987
  • 1987-04-30 US US07/044,987 patent/US4759797A/en not_active Expired - Lifetime

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