EP0271081B1 - Farbentwicklungsmittel für druckempfindliche Aufzeichnungsblätter und Aufzeichnungsblätter, die dieses Mittel enthalten - Google Patents

Farbentwicklungsmittel für druckempfindliche Aufzeichnungsblätter und Aufzeichnungsblätter, die dieses Mittel enthalten Download PDF

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Publication number
EP0271081B1
EP0271081B1 EP87118246A EP87118246A EP0271081B1 EP 0271081 B1 EP0271081 B1 EP 0271081B1 EP 87118246 A EP87118246 A EP 87118246A EP 87118246 A EP87118246 A EP 87118246A EP 0271081 B1 EP0271081 B1 EP 0271081B1
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EP
European Patent Office
Prior art keywords
colour developing
acid
developing agent
recording sheets
polyvalent metal
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
EP87118246A
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German (de)
English (en)
French (fr)
Other versions
EP0271081A2 (de
EP0271081A3 (en
Inventor
Hiroaki Central Research Laboratory Umeda
Mamoru Central Research Laboratory Suzuki
Akira Central Research Laboratory Hasegawa
Kunio Central Research Laboratory Hata
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.)
Jujo Paper Co Ltd
Original Assignee
Jujo Paper Co Ltd
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Filing date
Publication date
Application filed by Jujo Paper Co Ltd filed Critical Jujo Paper Co Ltd
Publication of EP0271081A2 publication Critical patent/EP0271081A2/de
Publication of EP0271081A3 publication Critical patent/EP0271081A3/de
Application granted granted Critical
Publication of EP0271081B1 publication Critical patent/EP0271081B1/de
Anticipated expiration legal-status Critical
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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
    • 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 agent for pressure sensitive recording sheets having improved color developing ability and light fastness, and to recording sheets containing this agent.
  • Electron-accepting color developing agents are known.
  • 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.).
  • inorganic solid acids have the advantage that they are inexpensive and develop color quickly, but the disadvantage that the color developability suffers on storage, e.g. because of the absorption of gases and moisture from the atmosphere, and that the image fades and there is a change in color when exposed to sunlight and fluorescent light.
  • the substituted phenols have insufficient color development and poor image density.
  • the p-subst. Phenol formaldehyde polymers (for example p-phenylphenol novolak resin) give good color development, but have the disadvantage that the sheet yellows when irradiated with sunlight or when stored due to the action of the gases in the atmosphere.
  • the metal salts of aromatic carboxylic acids have advantages of good durability of the colored image and superior yellowing resistance to light, gases, etc., but a disadvantage of insufficient color developability and insufficient resistance of the colored image to water or plasticizer. These properties often occur with color development sheets.
  • EP-A-218.810 belongs to the state of Tecknik for the named contracting states BE, CH, DE, FR, GB, LI, and SE.
  • the inventors in EP-A-218.810 have a color development sheet which is new Color developing agent contains a polyvalent metal salt of a carboxylated terpene phenol resin, proposed to improve the yellowing resistance to gases of the atmosphere and light, and the hue change and fading of the colored image by chemicals such as plasticizers, etc.
  • both the color developing agent and the color developing sheet obtained by using the polyvalent metal salt of a carboxylated terpene phenol resin are not entirely satisfactory in light fastness and color developing ability, particularly color development speed.
  • the invention has for its object to provide a color developing agent for pressure-sensitive recording sheets and a color developing layer which are superior in light fastness resistance and color developability.
  • the inventors made many studies and finally found the following.
  • the color developing agent for pressure sensitive recording sheets in which a reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a polyvalent metal compound has a superior color developing ability, particularly a better color developing speed, and a considerably improved light fastness of the image.
  • the carboxylated terpene phenol resin as described in Japanese Patent Application No. 159540/1985 is produced by the following method.
  • cyclic monoterpene and phenol is carried out in a petroleum hydrocarbon solvent in the presence of an acid catalyst such as aluminum trichloride, boron trifluoride, sulfuric acid, polyphosphoric acid, etc. to obtain a condensation product.
  • an acid catalyst such as aluminum trichloride, boron trifluoride, sulfuric acid, polyphosphoric acid, etc.
  • Typical examples of the cyclic monoterpene are pinene, limonene, terpinolene, menthadiene, gum turpentine oil, which contains ⁇ -limonene as the main component, dipentene, which contains ⁇ -limonene as the main component, and so on.
  • Typical examples of the phenol are monophenols, for example carbolic acid, alkylphenol, alkoxyphenol, ("alk” preferably C1-C4) halogenated phenol, etc .; and fortified phenols, for example resorcinol, pyrocatechol, etc.
  • Typical Examples of petroleum hydrocarbon solvents are benzene, toluene, xylene, n-hexane, n-heptane, halogenated solvents, for example dichloromethane, chloroform, trichloroethane, 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-Schmidt reaction), the carboxy group being introduced into the condensation product.
  • the aromatic carboxylic acid (monocyclic or polycyclic) is the one in which the carboxy group is attached directly to the ring.
  • aromatic carboxylic acid Typical examples of the aromatic carboxylic acid are: Benzoic acid, p-hydroxybenzoic acid, chlorobenzoic acid, bromobenzoic acid, nitrobenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, toluic acid, ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-methoxybenzoic acid, 3-methoxybenzoic acid hydroxybenzoic acid, p-tert-butylbenzoic acid, o-benzoyl-benzoic acid, p-cyclohexylbenzoic acid, salicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3,5-di-tertiary-butylsalicylic acid, 5-nonylsalicylic acid, 5-cyclohexylsalicylic acid Cyclohexy
  • the ratio of terpene phenolic resin to aromatic carboxylic acid is not particularly limited.
  • the aromatic carboxylic acid is usually in a comparable equivalence, preferably it is 5-50 equivalent%, based on the carboxylated terpene phenol resin. With less than 5 equivalent%, the improvement effect of the color development speed decreases, and with more than 50 equivalent%, the water dispersion tends to deteriorate.
  • Typical examples of the compound of the polyvalent metal are oxides, halides, carbonates, sulfates, nitrates, acetates, formats, oxalates, benzoates, acetylacetates 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 reaction product of the above carboxylated terpene phenolic resin, the aromatic carboxylic acid and the polyvalent metal compound (it is called a combined polyvalent metal salt) is prepared by uniformly mixing the carboxylated terpene phenolic resin, the aromatic carboxylic acid and the polyvalent metal compound and then reacting with each other or by mixing two of three of the above ingredients and then with the other Component can react.
  • Uniform mixing is achieved by dissolving these constituents in a solvent with stirring or melting them with heating or treating them by other methods.
  • Suitable solvents are alkaline aqueous solutions, for example sodium hydroxide, potassium hydroxide, sodium carbonate, etc .; and organic solvents such as alcohol, acetone, etc.
  • the combined polyvalent metal salt according to the invention can be prepared, for example, as follows: The required amount of the carboxylated terpene phenol resin and the aromatic carboxylic acid is added to a methanol solution containing sodium hydroxide, then it is evenly dissolved in this solution with stirring, and the solution obtained is heated to about 50 ° C. Then the aqueous solution or the methanol solution of the polyvalent metal compound, for example zinc chloride compound, is slowly added dropwise to the heated solution while stirring. After the reaction has ended, the solvent is removed under vacuum, and the reaction product is optionally washed out, neutralized and extracted to obtain the combined polyvalent metal salt.
  • the production of the combined polyvalent metal salt by fusion is done as follows.
  • the desired amount of the carboxylated terpene phenol resin and the aromatic carboxylic acid is melted with stirring in a glass vessel at 100-200 ° C and a uniform melt is formed.
  • Ammonium salt, for example ammonium carbonate, and a polyvalent metal compound, for example zinc oxide, aluminum chloride, etc. are gradually added to the melt and allowed to react with stirring. After the reaction is cooled to room temperature and the combined polyvalent metal salt obtained is obtained.
  • the resultant combined polyvalent metal salt is a new color developing agent which, while maintaining the advantages of the carboxylated terpene phenol resin, that is, maintaining better yellowing resistance to atmospheric gases and superior image softening resistance, has improved color development speed and light fastness.
  • the combined polyvalent metal salt of the present invention alone has sufficiently superior properties as a color developing agent. It can be used in admixture with another color developing agent such as 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 combined polyvalent metal salt according to the invention is used in all fields in connection with pressure-sensitive recording sheets.
  • pressure-sensitive recording sheets such as middle sheet, lower sheet, single recording sheet, etc., in which the combined polyvalent metal salt of the present invention is coated on the base material or mixed into the base material; Test means for the leuco dye after dissolving in an organic solvent; Spot inks 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. 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
  • solubility of the product in the capsule oil is lowered a little, so that the color development speed is slower and the light fastness of the image is lowered a little because of the formation of an unstable compound when reacting with the leuco dye.
  • the terminal carboxyl groups in the resin easily form the polyvalent metal salts and the number of free carbo in the reaction xyl groups are significantly reduced. Therefore, the above problem is likely to be solved.
  • the combined product was washed out with water and dried with anhydrous sodium sulfate.
  • the solvent and unreacted products were removed by distillation under vacuum at 180-200 ° C.
  • the unreacted part of the carbolic acid and the terpene oil was removed by steam distillation, whereby 1400 g of terpene phenol resin was obtained.
  • the terpene phenol resin was dissolved in 2000 ml of xylene and placed in an autoclave of 500 ml. 77 g of metallic sodium were added to this solution, heated to 150 ° C. and stirred for one hour. Thereafter, carbon dioxide gas was introduced into the autoclave up to a pressure of 40 kg / m2. The reaction was continued for 2 hours.
  • a transfer sheet in which the microcapsules containing the pressure sensitive dye were coated on a sheet of fine paper was prepared as described below.
  • 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.
  • an oil of a blue color developing pressure sensitive dye was prepared by dissolving 3% crystal violet lactone and 1% benzoyl leucomethylene blue in the oil mixture
  • an oil of a black color developing pressure sensitive dye was prepared by 5% 3-diethylamino-6-methyl-7-anilinofluoran, 1% 3-diethylamino-6-methyl-7-diphenylmethylaminofluoran and 0.5% 3-diethylamino-6-methyl-7-chlorofluorane dissolved 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 / m2 on a base paper of 45 g / m2 and dried. In this way two transfer sheets, i.e. (A) a transfer paper developing a blue color; and (B) a transfer paper developing a black color.
  • Each of the two transfer sheets and a color development sheet using Compound No. 1 prepared by the method described above are placed on top of each other so that one Color forms.
  • 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.
  • the color development speed (J2 or J2) is calculated from the reflectance Iriya before the color development, the reflectance I2 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 using the following equation: And the color development speed after 24 hours or the intensity of the final color development is calculated according to the following equation: Higher color development speed and intensity of final color development are desirable.
  • the reflectance I3 after irradiation is measured in the same way as in the test method (1).
  • the color development intensity J3 after irradiation will follow after calculated the equation From the color development intensity J2 before the irradiation and the color development intensity J3 after the irradiation, the light fastness H2 is calculated as follows. Higher lightfastness is desirable.
  • the carboxylated terpene phenol resin with an acid number of 253 was obtained in the same manner as in Example 1, limonene and carbolic acid being used as raw materials.
  • Example 1 A water suspension and a color development sheet were obtained in the same manner as in Example 1. The color development sheet obtained was tested as indicated above, and the test results are shown in Table 1.
  • a carboxylated terpene phenol resin with an acid number of 207 was obtained in the same manner as in Example 1, rubber-turpentine oil and O-cresol being used as raw materials. 100 parts of the carboxylated terpene phenol resin, 45 parts of 3,5-di-tert-butylsalicylic acid and 25 parts of sodium hydroxide were added in 1000 ml Dissolved methanol. Compound No. 3 was obtained in the same manner as in Example 1 and also a color development sheet in the same manner as in Example 1. The color development sheet obtained was tested, and the test results are shown in Table 1.
  • the carboxylated terpene-phenolic resin with an acid number of 234 was obtained in the same manner as in Example 1, using rubber-turpentine oil and carbolic acid as raw materials.
  • Compound No. 4 was obtained in the same manner as in Example 2, using 120 parts of the carboxylated terpene phenol resin and 10 parts of naphthoic acid. Then, a color development sheet was obtained in the same manner as in Example 1. The color development sheet obtained was tested, and the test results are shown in Table 1.
  • Example 2 100 parts of the carboxylated terpene phenol resin obtained in Example 2, in which limonene and carbolic acid were used as raw materials, and 45 parts Benzoic acid were placed in a glass jar and heated in an oil bath at 140-150 ° C to melt. 8.5 parts of ammonium bicarbonate and 4.7 parts of zinc oxide were gradually added with stirring and then cooled to obtain a yellow-blue tabular compound No. 5.
  • a color development sheet was prepared and tested from Compound No. 5 in the same manner as in Example 1, and the test results are shown in Table 1.
  • Example 2 120 parts of the carboxylated terpene phenol resin obtained in Example 2 using limonene and carbolic acid as raw materials and 3 parts of salicylic acid were mixed and treated with a zinc salt in the same manner as in Example 2 to obtain Compound No. 6.
  • a color developing sheet was prepared and tested from Compound No. 6 as a color developing agent in the same manner as in Example 1, and the test results are shown in Table 1.
  • Example 7 70 parts of the carboxylated terpene phenol resin obtained in Example 1 using ⁇ -pinene and carbolic acid as raw materials and 80 parts of cresotinic acid were treated with zinc salt in the same manner as in Example 5 to obtain Compound No. 7.
  • a color development sheet was prepared and tested in the same manner as in Example 1, and the test results are shown in Table 1.
  • a color development sheet was made using the Compound No. 8 prepared and tested as a color developing agent in the same manner as in Example 1, and the test results are shown in the table.
  • the combined polyvalent metal salt according to the invention is better in color development speed, final color development intensity and light fastness than the polyvalent metal salt of the carboxylated terpene phenol from the comparative example.
  • the reaction product of a carboxylated terpene phenol resin, an aromatic carboxylic acid and a polyvalent metal compound has both a superior color development rate and an improved light fastness while maintaining the superior resistance to light, gases, etc. and the chemical resistance of the image.
  • the polyvalent metal salt of the carboxylated terpene phenol is somewhat inferior in color development speed and light fastness of the image.
  • the compound according to the invention can be produced in an industrially simple manner from easily and cheaply commercially available raw material.
  • the color developing agent of the present invention is superior in manufacturing, color developing ability and durability before and after use for pressure-sensitive recording sheets and is industrially advantageous.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP87118246A 1986-12-10 1987-12-09 Farbentwicklungsmittel für druckempfindliche Aufzeichnungsblätter und Aufzeichnungsblätter, die dieses Mittel enthalten Expired - Lifetime EP0271081B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP294509/86 1986-12-10
JP61294509A JPS63147682A (ja) 1986-12-10 1986-12-10 感圧複写紙用顕色剤及び顕色シート

Publications (3)

Publication Number Publication Date
EP0271081A2 EP0271081A2 (de) 1988-06-15
EP0271081A3 EP0271081A3 (en) 1988-08-24
EP0271081B1 true EP0271081B1 (de) 1991-01-02

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Application Number Title Priority Date Filing Date
EP87118246A Expired - Lifetime EP0271081B1 (de) 1986-12-10 1987-12-09 Farbentwicklungsmittel für druckempfindliche Aufzeichnungsblätter und Aufzeichnungsblätter, die dieses Mittel enthalten

Country Status (5)

Country Link
US (2) US4784692A (enrdf_load_stackoverflow)
EP (1) EP0271081B1 (enrdf_load_stackoverflow)
JP (1) JPS63147682A (enrdf_load_stackoverflow)
CA (1) CA1336031C (enrdf_load_stackoverflow)
DE (1) DE3766947D1 (enrdf_load_stackoverflow)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63173681A (ja) * 1987-01-14 1988-07-18 Jujo Paper Co Ltd 感圧複写紙用顕色シ−ト
DE3818354A1 (de) * 1987-05-30 1988-12-08 Ricoh Kk Leukofarbstoffe und diese enthaltende aufzeichnungsmaterialien
DE3881654T2 (de) * 1987-12-01 1994-01-13 Kanzaki Paper Mfg Co Ltd Entwickler für druckempfindliche Aufzeichnungsschichten, eine wässerige Entwicklerdispersion des Entwicklers und Verfahren zur Herstellung des Entwicklers.
US5034370A (en) * 1989-12-08 1991-07-23 Sumitomo Durez Company, Ltd. Color developer for pressure-sensitive recording paper
EP0459942B1 (de) * 1990-05-10 1995-02-22 Ciba-Geigy Ag Tinten
US5261953A (en) * 1990-05-10 1993-11-16 Ciba-Geigy Corporation Inks
JPH04212882A (ja) * 1990-12-03 1992-08-04 Jujo Paper Co Ltd 感圧複写紙
DE4218561A1 (de) * 1992-06-05 1993-12-09 Bayer Ag Thermoreaktives Aufzeichnungsmaterial mit besonderer Stabilität
US5807933A (en) * 1992-06-22 1998-09-15 The Mead Corporation Carboxyl-containing phenolic resin developer and method of preparation
US6514917B1 (en) * 2001-08-28 2003-02-04 United Color Manufacturing, Inc. Molecular tags for organic solvent systems
US7815723B2 (en) * 2006-04-19 2010-10-19 Crayola Llc Water-based ink system
US7727319B2 (en) * 2006-04-19 2010-06-01 Crayola Llc Water-based ink system

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US2811564A (en) * 1954-10-21 1957-10-29 Pittsburgh Plate Glass Co Preparation of terpene diphenolic compounds
FR2315003A1 (fr) * 1975-06-18 1977-01-14 Laprade Bernard Dispositif de regulation du melange air-carburant des moteurs a combustion interne
FR2315004A1 (fr) * 1975-06-18 1977-01-14 Laprade Bernard Dispositif de regulation du melange air-carburant des moteurs a combustion interne
US4165103A (en) * 1978-05-31 1979-08-21 Ncr Corporation Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developing agent
US4546365A (en) * 1984-05-23 1985-10-08 Appleton Papers Inc. Record member
US4540998A (en) * 1984-05-23 1985-09-10 Appleton Papers Inc. Record member
US4573063A (en) * 1984-05-23 1986-02-25 Appleton Papers Inc. Record member
US4620874A (en) * 1984-06-28 1986-11-04 Btl Specialty Resins Corporation Metal modified phenolic resin color developers
JPS6219486A (ja) * 1985-07-19 1987-01-28 Jujo Paper Co Ltd 感圧複写紙用顕色剤及び顕色シ−ト

Also Published As

Publication number Publication date
JPS63147682A (ja) 1988-06-20
US4784692A (en) 1988-11-15
EP0271081A2 (de) 1988-06-15
US4806521A (en) 1989-02-21
EP0271081A3 (en) 1988-08-24
CA1336031C (en) 1995-06-20
JPH0428235B2 (enrdf_load_stackoverflow) 1992-05-13
DE3766947D1 (de) 1991-02-07

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