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
  • B41M5/165—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 characterised by the use of microcapsules; Special solvents for incorporating the ingredients
  • B41M5/1655—Solvents

Definitions

• the present invention relates to microcapsules useful in particular for making carbonless pressure-sensitive paper, containing an organic solution of a compound of hydrophobic interest, in particular a chromogenic agent, the solvent of which is at least partly a terpene derivative or a derivative of abietic acid.
• the invention also relates to pressure-sensitive paper coated on one side with a layer of such microcapsules and to the bundle of pressure-sensitive paper comprising at least one paper according to the invention.
• microcapsules in various fields such as perfumery, food industry, agrochemistry.
• the invention relates generally to CB, CFB and autonomous sheets.
• the operating principle of carbonless pressure-sensitive paper consists in bursting the microcapsules under the pressure of a pen or under the shock caused by a typewriter strike or by the needles of a dot-matrix printer or more generally by all the so-called "impact" printing processes.
• the internal phase contained in the microcapsules thus released flows on the CF receiving layer and the chromogenic agents react with the developer to form the colored image.
• biodegradable solvents of natural origin, can be used advantageously in place of vegetable oils, these are terpenic derivatives derived from wood, citrus peel, etc. and abietic acid derivatives obtained from rosin for example.
• the object of the present invention relates to new microcapsules and to the subsequent carbonless papers making it possible to overcome the drawbacks described above.
• the invention therefore relates firstly to a microcapsule useful in particular for copying paper sensitive to pressure, containing an organic solution of a hydrophobic chromogenic agent, characterized in that the solvent comprises a terpene derivative and / or an abietic acid derivative .
• terpene derivatives generally includes the terpenes themselves and the derivatives of these terpenes (alcohols, esters, aldehydes, ketones, hydrogenated compounds, etc.).
• abietic acid derivatives generally includes abietic acid itself and the esterified derivatives, in particular hydrogenated derivatives or the polymerization products thereof.
• Liquid products at room temperature are preferred.
• abietic acid derivatives could be considered as terpene derivatives since they are diterpenes. More generally, the invention therefore extends to all terpene derivatives (terpenes, diterpenes in particular, but a person skilled in the art could also envisage triterpenes or tetraterpenes, provided that these can be suitable for use).
• Terpene derivatives and abietic derivatives can be present alone or as a mixture.
• the microcapsules according to the invention have many advantages, in particular better storage stability, better UV resistance, better revelation of chromogenic agents, and, in most cases, a higher encapsulation rate.
• the microcapsules according to the invention have the advantage of being biodegradable. These are products of natural origin, the source of which is renewable. They are safe for the environment (common uses in pharmacies, cosmetics and especially in perfumery).
• the microcapsules according to the invention Compared to microcapsules containing vegetable oils, the microcapsules according to the invention have the advantage of better resistance to cold, less coloring, a more pleasant odor, greater coloring power, taking into account the solvent power of terpene compounds and a smaller diameter dispersion.
• phthalic type derivatives such as 3.3 bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (CVL) and 3.3 bis (1-octyl-2-methylindole).
• 3-yl) phthalide or fluorane derivatives such as 2-anilino-3-methyl-6-dialkylamino-2 '- (N'-ethyl-N-phenylamino-4'-methylfluorane) or 2'-anilino -3 '-methyl -6 diethylamino fluorane, 6'-dimethylamino-2' (N-ethyl-N-phenylamino-4'methylfluorane), 3'-chloro-6'-cyclohexylaminofluorane or 3,7 bis (dimethylamino) -10 -benzoylphenotiazine (BLMB) and bisarylcarbazolylmethane compounds.
• BLMB benzoylphenotiazine
• the solution of chromogenic agent in the solvent is around 5% by weight.
• microcapsules advantageously, but not exclusively, those formed from a wall of crosslinked gelatin.
• the invention also relates to microcapsules containing in solution products such as: perfumes, flavors, food or pharmaceutical products, pesticides, biocides, fungicides, herbicides, dyes, catalysts, chemical reagents etc ... insofar as the solvent used for dissolving these active ingredients contains at least 10% of terpene derivatives.
• terpene or abietic acid derivatives can be used alone or in mixtures, with one another, or with conventional solvents or with vegetable oils.
• solvents are most often mixed with diluents such as kerosene, light mineral oils or alkylbenzenes (for example docecylbenzene) etc.
• Vegetable oils are those commonly used, such as soybean, rapeseed, olive, flaxseed, peanut, palm kernel, corn, sunflower, copra, sesame, castor oil, palm, babassu, jojoba, etc., especially in U.S. patents 2,712,507, 2,730,457, 3,016,308.4 783,196, 4,923,641 and European patent Application No. 86 636, 155 593, 262 569. It is also possible to use triglycerides called the Anglo-Saxon term "tall - oil” containing a high proportion of trioleate glycerol.
• These vegetable oils can advantageously be replaced in part or in whole by fatty acid esters.
• Transesterification is the chemical operation which consists in exchanging glycerol in an acidic or basic medium by a monoalcohol or dialcohol, generally with a short chain, which leads to the formation of a mono- or di-ester.
• the fatty acid esters are formed from a fatty acid residue and a residue of alcohol RO, advantageously in C 1 to C 8 .
• alcohol residues mention may be made of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexanol.
• the fatty acid hydrocarbon chain can be saturated or unsaturated, branched or linear.
• the length of the fatty acid residue can vary from 3 to 20 carbon atoms.
• the fatty acid ester is saturated.
• residues of saturated fatty acids mention may be made, without implying any limitation, of the residues of lauric, myristic and palmitic acid.
• residues of saturated fatty acids could also be envisaged, for example residues of branched fatty acids.
• the solvent only comprises one or more terpene derivatives and / or one or more abietic acid derivatives.
• the solvent comprises one or more terpene and / or abietic acid derivatives mixed with one or more mineral oil (s) and / or one or more vegetable oils or fatty acid ester (s) .
• the solvent comprises 20 to 80% of terpene derivatives and 80 to 20% of mineral oil.
• the solvent comprises at least 10% of terpene derivatives or abietic acid derivatives, 0 to 50% of a vegetable oil or a fatty acid ester and 0 to 70% of a mineral oil .
• a saturated fatty acid ester (capric acid, lauric acid, myristic acid, palmitic acid, stearic acid) or a mixture of esters obtained by transesterification from a vegetable oil, for example the ester, will be used.
• the preferred products are terpineols, nopol, terpenyl acetate, nopyle acetate, sesquiterpenes.
• abietic acid derivatives these are the methyl esters of dihydroabietic acid such as the products marketed by Herculès under the brands Abalyn E, Hercolyn DE, Metalyn 200.
• the invention also relates to a process for the preparation of such microcapsules.
• an emulsion of a hydrophobic phase consisting of an organic solution as described above is formed in an aqueous phase comprising several colloids, including gelatin and one or more other anionic colloids, among which mention may be made of carboxymethylcellulose.
• CMC carboxymethylcellulose
• PVMMA copolymer of ethervinylmethyl and maleic anhydride
• EMA copolymer of ethylene and maleic anhydride
• the temperature is then raised and one proceeds to coacerve the emulsion by adding an appropriate acid, in particular acetic acid, in order to adjust the pH to around 4.
• an appropriate acid in particular acetic acid
• Microcapsules with liquid walls are thus formed by formation of the coacervate around the droplets of emulsified oil. Cooling the mixture to about 10 ° C causes the walls of liquid coacervate to solidify.
• a curing agent such as formalin or glutaraldehyde is then added in order to crosslink said solid walls of coacervate and to obtain the desired microcapsules.
• the emulsion obtained is of the oil in water type and comprises droplets of the hydrophobic phase whose diameter is between 1 and 12 micrometers (preferably 3 to 8 micrometers).
• microcapsules obtained are mixed with starch binders or latexes, a spacer, generally calibrated wheat starch and various additives such as optical brightener, water retaining etc.
• the subject of the invention is also a pressure-sensitive paper coated on one side with a layer of microcapsules as described above.
• This paper support constituting the emitting sheet, called CB, with a grammage generally between 40 and 90 g / m 2 was coated by coating the suspension of microcapsules, then these microcapsules were dried to obtain the paper according to the invention.
• the method of coating and the formulation of the coating bath are not critical to the invention.
• a subject of the invention is also a bundle of pressure-sensitive paper comprising, as has been described in the preamble to the present description, a transmitting sheet and a receiving sheet, and optionally one or more intermediate sheets (CFB) and also sheets say autonomous obtained by coating the front of a mixture of microcapsules and receiving layer.
• CFRB intermediate sheets
• the CF receptor paper associated with the CB sheet is preferably of the "active clay" type as described in French patents 2,581,350 or US 4,422,670, but it is also possible to use a CF phenolic type receptor paper such as those described. in US Patents 4,559,242 or 4,769,305, or a CF of the zinc salicylate type.
• the use of the solvent according to the invention makes it possible to improve, in addition to the viscosity and the quality of the emulsion, the degree of encapsulation in a completely surprising manner, but also the intensity and the light fastness of writing.
• the organic phase and the aqueous phase are mixed with stirring and emulsified using an Ultra-TURRAX type apparatus until particles having an average diameter of between 5 and 6 ⁇ m are obtained (the diameter measurement is carried out using a Coulter LS100 laser granulometer).
• Carboxymethylcellulose has a degree of substitution of the order of 0.8 and a viscosity in 3% aqueous solution at 20 ° C of between 60 and 100 mPas measured using a Haake VT 181 viscometer with MVI coaxial cylinders at 180 rpm.
• the temperature is raised to 60 ° C and acetic acid is added over 30 minutes to adjust the pH to 4.3.
• Example 1 is reproduced by replacing the terpineol with ⁇ terpineol from DRT (mixture of terpineols comprising more than 70% of ⁇ -terpineol),
• Example 1 is reproduced by replacing the terpineol with ⁇ -terpineol from DRT (mixture of terpineols comprising more than 85% of ⁇ -terpineol).
• Example 1 is reproduced by replacing the terpineol with pine oil from DRT (trademark DERTOL 90)
• Example 1 is reproduced by replacing the terpineol with terpinolene from DRT (mixture of terpene derivatives comprising at minus 95% of 1-4 (8) paramenthadiene).
• Example 1 is reproduced by replacing the terpineol with nopol from DRT (mixture of terpene alcohols essentially consisting of 6,6-dimethyl- (3,1,1), bicyclo -2-heptene -2-ethanol.)
• Example 1 is reproduced by replacing the terpineol with terpenyl acetate from DRT
• Example 1 is repeated, replacing the terpineol with a 50/50 mixture of terpineol and light naphthenic oil NYTEX 800.
• Example 8 is repeated, replacing the terpineol in the mixture with terpenyl acetate.
• Example 8 is reproduced by replacing Terpineol with nopol.
• Example 8 is reproduced by replacing Terpineol with Abalyn E from Hercules (methyl ester of dihydroabietic acid).
• Example 1 is repeated, replacing the Terpineol with a 50/50 mixture of Terpineol and coconut oil.
• Example 1 is repeated, replacing the Terpineol with a 50/50 mixture of terpenyl acetate and 2 ethyl hexyl laurate.
• Example 12 is repeated, replacing the coconut oil of the mixture with 2-ethylhexyl laurate.
• Example 1 is repeated, replacing the Terpineol with a 30/30/40 ternary mixture of Terpineol / coconut oil / light naphthenic oil.
• Example 15 is repeated, replacing the terpineol of the ternary mixture with terpenyl acetate.
• Example 15 is repeated by filling the Terpineol with the ternary mixture with oil M from DRT (mixture of sesquiterpenes).
• Example 1 is repeated, replacing the Terpineol with a 10/50/40 ternary mixture of Terpineol / 2-ethylhexyl laurate / light naphthenic oil.
• Example 1 is repeated, replacing the Terpineol with a 20/50/30 ternary mixture of Terpineol / 2-ethylhexyl laurate / norpar 12 (paraffinic oil).
• Example 1 is repeated, replacing the terpineol with a 25/25/50 ternary mixture of Abalyn E / coconut oil / Norpar 12
• the loss of reactivity of the CB is measured by crushing with the calender before and after aging.
• the loss of whiteness of the CF due to the migration of part of the chromogenic agents present in the microcapsules is measured compared to a blank test on the same CF.

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• Color Printing (AREA)
• Manufacturing Of Micro-Capsules (AREA)

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Citations (30)

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• 1994
  • 1994-12-02 FR FR9414545A patent/FR2727633A1/fr active Granted
• 1995
  • 1995-12-01 DE DE1995615807 patent/DE69515807T2/de not_active Expired - Fee Related
  • 1995-12-01 EP EP95402716A patent/EP0714786B1/de not_active Expired - Lifetime

Patent Citations (31)

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