EP0284932B1 - Farbentwicklermassen - Google Patents

Farbentwicklermassen Download PDF

Info

Publication number
EP0284932B1
EP0284932B1 EP88104428A EP88104428A EP0284932B1 EP 0284932 B1 EP0284932 B1 EP 0284932B1 EP 88104428 A EP88104428 A EP 88104428A EP 88104428 A EP88104428 A EP 88104428A EP 0284932 B1 EP0284932 B1 EP 0284932B1
Authority
EP
European Patent Office
Prior art keywords
colour
color
parts
carboxylic acids
aromatic hydrocarbon
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
EP88104428A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0284932A3 (en
EP0284932A2 (de
Inventor
Robert Dr. Zellerhoff
Arnold Dr. Alscher
Hans-Juergen Zick
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.)
Verkaufsgesellschaft fur Teererzeugnisse (Vft) MbH
Original Assignee
Verkaufsgesellschaft fur Teererzeugnisse (Vft) MbH
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
Application filed by Verkaufsgesellschaft fur Teererzeugnisse (Vft) MbH filed Critical Verkaufsgesellschaft fur Teererzeugnisse (Vft) MbH
Publication of EP0284932A2 publication Critical patent/EP0284932A2/de
Publication of EP0284932A3 publication Critical patent/EP0284932A3/de
Application granted granted Critical
Publication of EP0284932B1 publication Critical patent/EP0284932B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 color developer compositions for the production of pressure or heat-sensitive recording materials such.
  • the recording is carried out by developing a color image from a colorless organic compound which is dissolved in a high-boiling organic solvent and is capable of forming a color, the color donor.
  • the color is developed by reacting these colorants with an acidic developer with intimate contact of these reactants.
  • the contact is usually made by the printing pressure appropriately coated carrier, but also z. B. in thermocopying by localized heat and thereby caused reaction of the color generator.
  • acidic, inorganic salts such as. B. clays or salts of strong organic acids and weak bases, free organic acids or phenol derivatives.
  • these substances have the disadvantage that they have to be fixed on the carrier with the aid of a binder.
  • Corresponding mixtures of aromatic hydroxycarboxylic acids with polystyrene according to DE-OS 23 48 639 or with phenolic resins according to DE-OS 26 18 271 require a certain improvement in terms of the typeface, but they are unsatisfactory in terms of their color development speed.
  • the direct use of acidic polymers as color developers is much more advantageous.
  • Phenol-containing polymers such as phenol-aldehyde condensation resins and phenol polymerization resins are preferably used as developer resins of this type.
  • Phenol-aldehyde condensation resins have the disadvantages that, on the one hand, the papers coated with them yellow slightly and that there are toxicological concerns during recycling because there is a risk of formaldehyde being split off.
  • phenol polymerization resins for this use are those by copolymerization of phenols with acetylene under pressure and at higher Temperature, ie expensive alkylphenol acetylene resin and di- and oligomeric alkenylphenols produced under conditions which are not problem-free.
  • DE-OS 26 47 696 and DE-OS 27 03 574 show dimeric substituted alkenylphenols and in EP-A-0 029 323 vinylphenol oligomers as color developer resins.
  • EP-A-0 029 323 vinylphenol oligomers as color developer resins.
  • these products are also quite expensive, they have the difficulty that they have a relatively high softening point which, moreover, cannot be changed in the desired range.
  • EP-A-0 029 323 it is known from EP-A-0 029 323 to change the softening point of oligovinylphenol by varying the degree of polymerization, the unsubstituted dimer of vinylphenol already has a softening point of 93 ° C., while higher polymerized vinylphenol or the dimers of the substituted vinylphenols have one have a higher softening point.
  • the softening point should be in the range from 55 to 110.degree. C., but preferably in the range from 70 to 90.degree. C., in order to have an optimal solution behavior in the solvent of the color donor and thus good color development.
  • phenol-modified hydrocarbon resins with a softening point in the range from 55 to 110 ° C. are therefore claimed as developer resins. They have the disadvantage of certain aging problems such as B. Yellowing effects.
  • the object of the invention is therefore to provide color developer compositions which meet the abovementioned. Do not have disadvantages and in which the color developers, in addition to excellent aging, light and water resistance, have no surface changes, are harmless to health, are soluble in water and solvents and can be used in all color reaction systems.
  • the color developer compositions used are those which contain aromatic hydrocarbon resins modified with aromatic carboxylic acids as color developers.
  • the compositions according to the invention can contain the acid-modified, aromatic hydrocarbon resins as the sole color developers, but also in combination of the resins with one or more other known color developers, such as active clay minerals, organic or inorganic metal salts, in particular zinc salts, phenol-modified resin or metal stearates.
  • aromatic hydrocarbon resins modified according to the invention and modified with aromatic carboxylic acids are known from DE-OS 33 24 817.
  • resins obtained when polymerizing unsaturated aromatic compounds such as. B. indene, styrene, methylstyrene, methylinden or vinyltoluene, which can be used as pure substances or in a mixture, aromatic carboxylic acid such as o-, m- or p-toluic, phenylacetic, cinnamon, phenoxyacetic or alkoxybenzoic acid, in particular but aromatic hydroxycarboxylic acids such as o-, m- or p-hydroxybenzoic or hydroxynaphthoic acid can also be copolymerized.
  • the corresponding resins have, depending on the selection of the starting products and depending on the polymerization conditions, melting points in the range from 20 to 190 ° C. and acid numbers in the range from 10 to 300. They are soluble in many organic solvents and in alkaline aqueous solution.
  • these resins show the following advantages that distinguish them as color developers in color developer compositions: Soluble in higher concentrations in organic solvents, in the alkaline range, soluble in water, lower melting range, very good aging resistance, low surface impact due to time, radiation or temperature, excellent color development with all known colorants, strong color reaction with higher color contrast, when used in copy systems, after the color reaction process, they can be used both in solution and in dispersed form, when used in thermoreaction systems, the color reaction is additionally enhanced and accelerated by the lower melting range, easy processing in coating compositions due to lower viscosity and good flow properties, good processing in the paper composition as a reaction or marking substance.
  • the resins are also particularly suitable as binders for the coating compositions.
  • the acid-modified, aromatic hydrocarbon resins contained in the color developer composition are therefore preferably used alone or with the aid of a further binder in order to achieve optimum adhesion to the corresponding layer support.
  • the aromatic hydrocarbon resin modified with aromatic carboxylic acids in a solvent or -mixed or dissolved or dispersed in an alkaline aqueous solution.
  • the resin can contain admixtures of fillers and additives or other resins. The admixture of clay minerals, titanium dioxide, aluminum oxide, calcium silicates, calcium carbonate, silicon dioxide, coating kaolin, stearates and organic pigments proved to be advantageous in order to improve the printability of the coated materials and to control the penetration of the coating materials into the carrier material.
  • the aromatic hydrocarbon resin modified with aromatic carboxylic acids can be present both in acidic and in salt form.
  • the salt form is when the carboxyl groups of the resins introduced by the aromatic carboxylic acids are present in whole or in part as alkali, alkaline earth or heavy metal salt groups, in particular as zinc salt groups.
  • the salt form is obtained by reacting the acid form of the resin in a manner known per se with an oxide, hydroxide or salt of a weak acid of an alkali, alkaline earth or heavy metal. This reaction can take place in an aqueous medium or in the melt.
  • the color developer compositions can contain further carrier components such as oils and auxiliaries such as emulsifiers, antioxidation products, UV stabilizers, plasticizers, Antifoam and fungicide.
  • the proportion of aromatic hydrocarbon resins modified with aromatic carboxylic acids in these color developer compositions is 5 to 100%, preferably 5 to 20% by weight.
  • carrier materials These masses are applied to carrier materials, the amount applied being adjusted so that 0.5 to 6 g of aromatic hydrocarbon resins modified with aromatic carboxylic acids or their metal salts are applied per m2 of carrier material.
  • Paper in various thicknesses, synthetic papers, foils or textile materials are considered as preferred carrier materials.
  • the color developer composition can be applied to the carrier material using organic solvents, water, in melt form alone or with admixtures of waxes or other meltable products, as a printing ink, with the aid of carrier oils, by impregnating the intended carrier material or as a liquid solution or dispersion.
  • the color former products required for the color reaction are incorporated in a common or separate carrier material, preferably in the form of color solutions in microcapsules, in order to avoid a premature color reaction.
  • a common or separate carrier material preferably in the form of color solutions in microcapsules
  • aromatic hydrocarbon resin or its metal salt used as a color developer according to the invention and modified with aromatic carboxylic acids can preferably be applied in dispersed or dissolved form. It has also been found that incorporating the color developer in the form of microcapsules is very advantageous for certain applications.
  • a colorant composition having the following composition was produced as the test material: 10% crystal violet lactone 3% polymeric vinyl acetate 30% calcium carbonate 55% toluene The mass was applied to a carrier paper (50 g / m2) using a doctor blade and the solvents were evaporated using temperature. The application amount (dry fabric) was 2 g / m2.
  • the color developers were dispersed or dissolved and brought into contact with the color donor composition applied to the paper using a glass rod. After drying out (evaporation of the liquid components) the properties were compared.
  • a hydrocarbon resin modified with salicylic acid prepared by polymerizing a fraction of unsaturated aromatic hydrocarbons boiling in the range from 140 to 220 ° C., was used as the resin according to the invention (Example 9).
  • the resin has a softening point in the range of 45 to 55 ° C and an acid number of 150 to 155.
  • the color developer compositions corresponding to the examples were prepared by mixing the components together and applied in the stated amount to commercially available writing paper and dried.
  • a commercial CB sheet containing microencapsulated crystal violet lactone was used as the color donor, which was placed on the papers coated with the test compositions in such a way that the color donor and color developer components came into contact with one another.
  • the color reaction was triggered by applying pressure to the two superimposed papers.
  • the color developers used in the mixtures were aromatic hydrocarbon resins used according to the invention with the following key figures:
  • the base paper weight was: 50 g / m2
  • a visible color reaction was generated under the pressure of an untreated sheet on the coated surface, which could also be recognized as a wrong mirror image up to the side of the paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Dry Development In Electrophotography (AREA)
  • Liquid Developers In Electrophotography (AREA)
EP88104428A 1987-03-31 1988-03-19 Farbentwicklermassen Expired - Lifetime EP0284932B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0077687A AT399126B (de) 1987-03-31 1987-03-31 Farbentwicklermassen für farbreaktionssysteme
AT776/87 1987-03-31

Publications (3)

Publication Number Publication Date
EP0284932A2 EP0284932A2 (de) 1988-10-05
EP0284932A3 EP0284932A3 (en) 1989-06-07
EP0284932B1 true EP0284932B1 (de) 1992-05-06

Family

ID=3499458

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88104428A Expired - Lifetime EP0284932B1 (de) 1987-03-31 1988-03-19 Farbentwicklermassen

Country Status (5)

Country Link
EP (1) EP0284932B1 (enrdf_load_stackoverflow)
AT (2) AT399126B (enrdf_load_stackoverflow)
DE (1) DE3870695D1 (enrdf_load_stackoverflow)
ES (1) ES2004322T3 (enrdf_load_stackoverflow)
GR (2) GR890300003T1 (enrdf_load_stackoverflow)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5819474B2 (ja) * 1974-09-30 1983-04-18 富士写真フイルム株式会社 キロクシ−ト
JPS5819475B2 (ja) * 1975-11-28 1983-04-18 住友ノ−ガタック株式会社 感圧複写紙用呈色紙
JPS5331405A (en) * 1976-08-12 1978-03-24 Asahi Dow Ltd Color paper for pressure sensitized copy sheets
WO1983003077A1 (en) * 1982-03-03 1983-09-15 Torii, Takahiro Color-developing sheet for use in no-carbon recording system
DE3246539A1 (de) * 1982-12-16 1984-06-20 Rütgerswerke AG, 6000 Frankfurt Entwicklerharze fuer leucopigmente
DE3324817A1 (de) * 1983-07-09 1985-01-17 Rütgerswerke AG, 6000 Frankfurt Saeuremodifizierte, aromatische kohlenwasserstoffharze und verfahren zu ihrer herstellung
DE3337296A1 (de) * 1983-10-13 1985-04-25 Bayer Ag, 5090 Leverkusen Thermoreaktives aufzeichnungsmaterial, seine herstellung und die verwendung von sauermodifizierten polymerisaten als akzeptoren in diesem aufzeichnungsmaterial
JPS61149390A (ja) * 1984-12-25 1986-07-08 Mitsubishi Paper Mills Ltd 感圧記録用顕色シ−ト

Also Published As

Publication number Publication date
DE3870695D1 (de) 1992-06-11
AT399126B (de) 1995-03-27
ATE75667T1 (de) 1992-05-15
ES2004322T3 (es) 1993-01-01
EP0284932A3 (en) 1989-06-07
GR3005110T3 (enrdf_load_stackoverflow) 1993-05-24
ATA77687A (de) 1994-08-15
GR890300003T1 (en) 1989-03-08
ES2004322A4 (es) 1989-01-01
EP0284932A2 (de) 1988-10-05

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