EP0111943B1 - Entwicklerharze für Leucopigmente - Google Patents
Entwicklerharze für Leucopigmente Download PDFInfo
- Publication number
- EP0111943B1 EP0111943B1 EP83201316A EP83201316A EP0111943B1 EP 0111943 B1 EP0111943 B1 EP 0111943B1 EP 83201316 A EP83201316 A EP 83201316A EP 83201316 A EP83201316 A EP 83201316A EP 0111943 B1 EP0111943 B1 EP 0111943B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin
- phenol
- range
- polymerization
- resins
- 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
Links
- 229920005989 resin Polymers 0.000 title claims description 55
- 239000011347 resin Substances 0.000 title claims description 55
- 239000000975 dye Substances 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 31
- 150000002989 phenols Chemical class 0.000 claims description 28
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 24
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 7
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000009835 boiling Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 230000009965 odorless effect Effects 0.000 description 9
- 238000004383 yellowing Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001896 cresols Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003739 xylenols Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- -1 malachite green lactone Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002110 toxicologic effect Effects 0.000 description 2
- 231100000027 toxicology Toxicity 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- YLZSIUVOIFJGQZ-UHFFFAOYSA-N bis[4-(dimethylamino)phenyl]methanol Chemical compound C1=CC(N(C)C)=CC=C1C(O)C1=CC=C(N(C)C)C=C1 YLZSIUVOIFJGQZ-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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 resins for developing leuco pigments, in particular for developing colors in pressure-sensitive recording materials.
- Pressure sensitive recording materials such as e.g. Carbonless papers are coated foils with which carbonless copies can be made without the use of a color insert, e.g. of carbon paper.
- 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.
- leuco pigment This organic compound is called leuco pigment.
- the most common leuco pigments are crystal violet lactone or malachite green lactone.
- other such connections are also used, e.g. Leukauramines, acylauramines, basic, unsaturated aryl ketones, basic monoazo compounds, rhodamine B-lactams, Michler's hydrol, carbinols of crystal violet and machalite green or pyrans.
- the color development takes place by reaction of these leuco pigments with an acidic developer substance with intimate contact of these reactants.
- the contact is normally made by the writing pressure on appropriately coated foils, but also, for example, when thermocopying due to localized heat and the resulting reaction of the leuco pigment.
- acidic, inorganic salts such as. B. acidic 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 film with the aid of a binder.
- 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 slightly yellow and that there are toxicological concerns during recycling because there is a risk of formaldehyde being split off.
- phenol polymerization resins for this purpose are those by copolymerization of phenols with acetylene under pressure and at a higher temperature, i.e. H.
- Expensive alkylphenol acetylene resins and di- and oligomeric alkenylphenols produced under conditions which are not problem-free are known.
- DE-OS 2647696 and DE-OS 2703 574 disclose dimeric substituted alkenylphenols and in EP-A-0029323 vinylphenol oligomers as color developers for leuco pigments.
- 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.
- the softening point of oligovinylphenol by varying the degree of polymerization, but the unsubstituted dimer of vinylphenol already has a softening point of 95 ° C., while more polymerized vinylphenol or the dimers of the substituted vinylphenols have a higher softening point to have.
- 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 optimal dissolution behavior in the solvent of the leuco pigment and thus good color development.
- This object is achieved by resins and processes for their production according to claims 1-6.
- Phenol-modified hydrocarbon resins are commonly used polymers in the adhesives and coatings industry, which are produced by polymerizing unsaturated aromatic hydrocarbons and phenol or substituted phenols using Friedel-Crafts catalysts.
- These stabilized, phenol-modified hydrocarbon resins are produced by polymerizing unsaturated, aromatic hydrocarbons, optionally isobutene, and phenol or substituted phenols
- Use of Friedel-Crafts catalysts with a subset of the unsaturated aromatic hydrocarbons and / or the entire amount of phenols and catalyst being introduced and the polymerization being controlled by adding the remaining unsaturated aromatic hydrocarbons in such a way that after reaching the chosen polymerization temperature, which is in the range of 70 to 140 ° C, isothermally.
- EP-A-70579 and EP-A-109694 belong to the prior art under Article 54 (3) EPC, EP-A-70579 the contracting states DE, FR, GB, IT and NL and EP-A-109694 the contracting states BE , DE, FR, GB, IT and NL.
- the ratio of phenol or phenol mixture to unsaturated aromatic compounds must be adjusted so that stoichiometric addition products with a corresponding OH number can form.
- an OH number of 4.5 is already sufficient for color development, but in general the color development becomes better the higher the OH number.
- Phenolic compounds polymerizable unsaturated, aromatic hydrocarbons and possibly isobutene are used as raw materials for the resins according to the invention.
- Both mononuclear and multinuclear phenols such as the phenol itself, its alkyl-substituted homologs such as cresols or xylenols and naphthols, as well as halogen-substituted phenols such as chloro- or bromophenol and polyhydric phenols such as resorcinol or catechol can be used as phenolic compounds.
- phenol fractions which are obtained in the distillation of crude phenol are preferably used. These contain phenol, cresols, xylenols and possibly small amounts of higher alkylated phenols. The composition of these fractions varies depending on the boiling range selected.
- Unsaturated, aromatic hydrocarbons are found on the one hand in the distillates from the high-temperature tar boiling in the temperature range from 140 to about 220 ° C, on the other hand, unsaturated, aromatic hydrocarbons are formed in the cracking of naphtha or gas oil and in the pyrolysis of cracking residues and are in the range of 160-220 ° C boiling fraction, the so-called resin oil fraction, enriched.
- These fractions contain unsaturated aromatic compounds, essentially indene, vinyltoluene, methylinden, coumarone, dicyclopentadiene, methyldicyclopentadiene, styrene and a-methylstyrene, in a concentration of 50 to 70% in addition to non-reactive aromatic compounds.
- the quantitative ratios of phenols or phenol mixtures to unsaturated, aromatic compounds are between 20:80 to 50:50% by weight.
- the amounts of phenolic compounds used ensure that the resulting resins have an OH number of at least 4.5. It is possible to increase the OH number to over 9 by using polyhydric phenols.
- the polymerization of these unsaturated compounds is generally carried out using acids or Friedel-Crafts catalysts such.
- acids or Friedel-Crafts catalysts such as B. trichloroacetic acid, boron trifluoride complexes, aluminum, antimony V or tin IV chloride.
- the original reaction mixture does not yet contain any unsaturated, aromatic hydrocarbons, these are metered in such a way that the temperature of the reaction mixture first rises to the desired polymerization temperature and that the temperature is kept constant in the further course of the polymerization.
- These polymerization temperatures are in the range from 30 to 70 ° C., higher softening points being achieved on the one hand at lower temperatures, but also extending the polymerization time on the other.
- reaction temperature is in the range from 20-140 ° C. It is due to the boiling point of the isobutene and the pressure prevailing during the reaction.
- the catalyst and phenol or phenol mixture are preferably introduced as a solution in aromatic solvents and the unsaturated, aromatic hydrocarbons and the isobutene are gradually metered in in a predetermined ratio. This can be done by cooling the unsaturated, aromatic hydrocarbons and isobutene and keeping it at a temperature below the start of boiling of the mixture and metering this mixture into the phenolic compounds in portions with cooling. Then the reaction can be carried out under normal pressure. But it is also possible to mix the phenolic compounds and the catalyst to add the aromatic, unsaturated hydrocarbons and the isobutene separately without cooling in the predetermined ratio.
- the gaseous isobutene is pressed into the reaction vessel under a pressure of up to 6 bar and the reaction is carried out under a pressure of up to 4 bar.
- the neutralization of the catalyst and the further processing of the resin are carried out according to methods known per se.
- the softening points for a developer resin for pressure-sensitive recording materials are limited to a relatively narrow temperature range in that experience has shown that products with a softening point of more than 110 ° C. generally no longer cause color development. Obviously, such resins are not sufficiently dissolved by the solvent of the leuco pigment for a coloring reaction. It follows that a resin with the lowest possible softening point would be desirable for this reaction. On the other hand, the resin must not stick at room temperature and, which is particularly important with paper as the carrier material, it must remain as a layer on the carrier material and must not move into it. Based on these considerations, the softening point should be as high as possible. As a result of these restricting parameters, the softening points of the resins have a still tolerable range of 55 to 110 ° C and a range of 70 to 90 ° C preferred for carbonless papers.
- the use of polyhydric phenols in the production of the phenol-modified hydrocarbons according to the invention therefore makes it possible to set the softening points of the resins in the optimum temperature range for carbonless papers and at the same time to at least improve the developer properties.
- the amounts of vinylphenol are, depending on the desired softening point, between 10 and 30% of the components to be polymerized, with about 10 to 70% of the phenols being replaced by vinylphenol. It would also be possible to replace all of the phenolic compounds with vinylphenols, but this is not desirable for economic reasons and also results in resins with a softening point which is too high.
- the polymerization reaction also takes place by isothermal polymerization in such a way that vinylphenol, the phenolic compounds, the unsaturated, aromatic hydrocarbons and optionally isobutene are mixed with one another and a Friedel-Crafts catalyst is added.
- the polymerization reaction is optionally carried out isothermally with external cooling after reaching the selected polymerization temperature, which is in the range from 30-90 ° C.
- the mixture can be heated after 15-30 minutes to complete the polymerization reaction.
- the catalyst is then removed by washing or precipitation and filtering, and unpolymerized constituents are removed from the resin by distillation at atmospheric pressure or in vacuo and subsequent steam distillation.
- the resins obtained are almost colorless, non-yellowing, odorless products with softening points which, depending on the composition, are in the range of 70-110 ° C. When reacting with a leuco pigment, they result in a color development from OH numbers of just 4.5, which is very good for a pressure-sensitive carbonless paper.
- Percentages are percentages by weight.
- the softening points (E.P.) are determined using the Krämer-Sarnow method.
- the OH number is determined by acetylation with subsequent saponification to determine the required amount of a known KOH solution.
- a bright, non-yellowing, almost odorless resin is obtained by isothermal polymerization at 40 ° C. of a batch of 3630 g of phenol fraction according to Example 1, 80.6 g of BF 3 methyl etherate, 3000 g of resin oil fraction / boiling range 160-220 ° C., 1090 g of isobutene obtained with an EP of 60 ° C and an OH number of 5.8.
- a polyvinylphenol resin produced by polymerizing p-vinylphenol with an EP of 185 ° C. and an OH number of 14 shows no developer properties in a written test analogous to Example 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Impression-Transfer Materials And Handling Thereof (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823246539 DE3246539A1 (de) | 1982-12-16 | 1982-12-16 | Entwicklerharze fuer leucopigmente |
| DE3246539 | 1982-12-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0111943A2 EP0111943A2 (de) | 1984-06-27 |
| EP0111943A3 EP0111943A3 (en) | 1984-12-19 |
| EP0111943B1 true EP0111943B1 (de) | 1986-12-10 |
Family
ID=6180809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83201316A Expired EP0111943B1 (de) | 1982-12-16 | 1983-09-13 | Entwicklerharze für Leucopigmente |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4598138A (fi) |
| EP (1) | EP0111943B1 (fi) |
| JP (1) | JPS59131632A (fi) |
| DE (2) | DE3246539A1 (fi) |
| ES (1) | ES527127A0 (fi) |
| FI (1) | FI73230C (fi) |
| YU (1) | YU242483A (fi) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT399126B (de) * | 1987-03-31 | 1995-03-27 | Ruetgerswerke Ag | Farbentwicklermassen für farbreaktionssysteme |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4877767A (en) * | 1987-08-14 | 1989-10-31 | The Mead Corporation | Vinyl developer resins |
| DE4011117A1 (de) * | 1990-04-06 | 1991-10-10 | Ruetgerswerke Ag | Verfahren zur herstellung von saeuremodifizierten, aromatischen kohlenwasserstoffharzen und ihre salze |
| WO2006065261A1 (en) * | 2004-12-15 | 2006-06-22 | Anocoil Corporation | Improved positive working thermal plates |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3004953A (en) * | 1959-03-02 | 1961-10-17 | Dow Chemical Co | Reaction products of phenols and diisopropenylbenzene |
| US3546173A (en) * | 1968-04-10 | 1970-12-08 | Du Pont | Process for preparing condensates of para-alkyl phenols and divinyl aromatic compounds |
| JPS54159500A (en) * | 1978-06-07 | 1979-12-17 | Sumitomo Chem Co Ltd | Preparation of solid resinous material |
| NL7905548A (nl) * | 1979-07-17 | 1981-01-20 | Unilever Nv | Vaste koolwaterstofharsen. |
| EP0025241B1 (en) * | 1979-08-31 | 1984-02-01 | Dsm Resins B.V. | Production of resins based on alpha-methyl styrene, styrene and a phenol as constituents, and their use in adhesives |
| JPS5672991A (en) * | 1979-11-19 | 1981-06-17 | Mita Ind Co Ltd | Color former for coloring substance of leucoline and recording material made by use thereof |
| DE3128869A1 (de) * | 1981-07-22 | 1983-03-03 | Rütgerswerke AG, 6000 Frankfurt | Kohlenwasserstoffharze mit einer oh-zahl groesser als 6 und mit schwachem phenolgeruch sowie verfahren zu ihrer herstellung |
| DE3242782A1 (de) * | 1982-11-19 | 1984-05-24 | Rütgerswerke AG, 6000 Frankfurt | Phenolmodifizierte kohlenwasserstoffharze mit hoher oh-zahl sowie verfahren zu ihrer herstellung und ihre verwendung |
| JPH0465851A (ja) * | 1990-07-06 | 1992-03-02 | Tokyo Electron Yamanashi Kk | 検査装置 |
-
1982
- 1982-12-16 DE DE19823246539 patent/DE3246539A1/de not_active Withdrawn
-
1983
- 1983-09-13 EP EP83201316A patent/EP0111943B1/de not_active Expired
- 1983-09-13 DE DE8383201316T patent/DE3368230D1/de not_active Expired
- 1983-11-08 ES ES527127A patent/ES527127A0/es active Granted
- 1983-11-15 US US06/548,693 patent/US4598138A/en not_active Expired - Fee Related
- 1983-11-29 JP JP58223428A patent/JPS59131632A/ja active Granted
- 1983-12-13 YU YU02424/83A patent/YU242483A/xx unknown
- 1983-12-13 FI FI834574A patent/FI73230C/fi not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT399126B (de) * | 1987-03-31 | 1995-03-27 | Ruetgerswerke Ag | Farbentwicklermassen für farbreaktionssysteme |
Also Published As
| Publication number | Publication date |
|---|---|
| US4598138A (en) | 1986-07-01 |
| ES8405818A1 (es) | 1984-07-01 |
| FI73230B (fi) | 1987-05-29 |
| EP0111943A2 (de) | 1984-06-27 |
| FI834574L (fi) | 1984-06-17 |
| DE3368230D1 (en) | 1987-01-22 |
| JPS59131632A (ja) | 1984-07-28 |
| FI834574A0 (fi) | 1983-12-13 |
| YU242483A (en) | 1985-10-31 |
| EP0111943A3 (en) | 1984-12-19 |
| FI73230C (fi) | 1987-09-10 |
| JPH0586424B2 (fi) | 1993-12-13 |
| DE3246539A1 (de) | 1984-06-20 |
| ES527127A0 (es) | 1984-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69617017T2 (de) | Phenolische polymere erhalten durch aralkylierung | |
| DE2229354C3 (de) | Druckempfindliches Aufzeichnungsmaterial | |
| DE2210133C3 (de) | Verwendung von aromatischen Verbindungen als Lösungsmittel für in Mikrokapseln eingeschlossene Farbstoffvorläufer | |
| DE2834773A1 (de) | Verfahren zur herstellung von metallmodifiziertem novolakharz und seine verwendung in druckempfindlichem papier | |
| CH644551A5 (de) | Chromogene zusammensetzung. | |
| EP0111943B1 (de) | Entwicklerharze für Leucopigmente | |
| DE1795166C3 (de) | Synthetische Kautschukmischung mit verbesserter Eigenklebrigkeit | |
| DE3242782A1 (de) | Phenolmodifizierte kohlenwasserstoffharze mit hoher oh-zahl sowie verfahren zu ihrer herstellung und ihre verwendung | |
| DE2556183A1 (de) | Druckfarbenbindemittel | |
| DE2647696A1 (de) | Aufzeichnungsmaterialien | |
| DE1594288A1 (de) | Klebstoffmassen | |
| EP0070579B1 (de) | Kohlenwasserstoffharze mit einer OH-Zahl grösser als 6 und mit schwachem Phenolgeruch sowie Verfahren zu ihrer Herstellung | |
| EP0134592B1 (de) | Säuremodifizierte, aromatische Kohlenwasserstoffharze und Verfahren zu ihrer Herstellung | |
| DE1770794A1 (de) | Verfahren zur Herstellung von Petrolharzen mit hohem Erweichungspunkt | |
| EP0450168B1 (de) | Verfahren zur Herstellung von säuremodifizierten, aromatischen Kohlenwasserstoffharzen und ihre Salze | |
| DE2120920C3 (de) | Sensibilisierter Bogen für druckempfindliche Aufzeichnungsmaterialien | |
| DE2407164A1 (de) | Verfahren zur herstellung eines thermoplastischen harzes | |
| DE2805763C2 (de) | Verfahren zur Herstellung von Isobutyraldehyd-Phenol-Polykondensaten und deren Verwendung | |
| EP0816389A2 (de) | Modifizierte Kohlenwasserstoffharze | |
| EP0284932B1 (de) | Farbentwicklermassen | |
| DE2211434A1 (de) | Entwicklerhaitiger Bogen für die druckempfindliche Aufzeichnung | |
| DE2659406C2 (fi) | ||
| DE2805684C2 (de) | Isobutyraldehyd-Phenol-Harze | |
| DE4015889C2 (fi) | ||
| DE2519084A1 (de) | Verfahren zur herstellung eines harzartigen materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): BE CH DE FR GB IT LI NL |
|
| TCNL | Nl: translation of patent claims filed | ||
| ITCL | It: translation for ep claims filed |
Representative=s name: BARZANO' E ZANARDO ROMA S.P.A. |
|
| EL | Fr: translation of claims filed | ||
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Designated state(s): BE CH DE FR GB IT LI NL |
|
| 17P | Request for examination filed |
Effective date: 19841022 |
|
| ITF | It: translation for a ep patent filed | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE FR GB IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 3368230 Country of ref document: DE Date of ref document: 19870122 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19960819 Year of fee payment: 14 Ref country code: CH Payment date: 19960819 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19960904 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19960910 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19960930 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19961028 Year of fee payment: 14 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970913 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970930 Ref country code: FR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19970930 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970930 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970930 |
|
| BERE | Be: lapsed |
Owner name: RUTGERSWERKE A.G. Effective date: 19970930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980401 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19970913 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19980401 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980603 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |