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 the production of carbonless pressure-sensitive paper containing a solution organic of a hydrophobic compound of interest, in particular a chromogenic agent the solvent of which is at least partly a terpene derivative, abietic acid, or an acid derivative abietic.
• the invention also relates to pressure-sensitive paper coated on one side of a layer of such microcapsules and the wad of paper sensitive to pressure comprising at least one paper according to the invention.
• microcapsules in different fields such as perfumery, agrifood, agrochemicals.
• the invention relates generally to CB, CFB and autonomous.
• the operating principle of carbon-sensitive paper pressure consists in bursting the microcapsules under the pressure of a pen or shock from typewriter or needle dot matrix printer or more generally by all printing processes called "impact".
• impact The internal phase contained in the microcapsules thus released flows on the CF receptor layer and the chromogenic agents react with the developer to form the colored image.
• EP-A-0 674 942 mentions among a list of solvents, terpene derivatives for the realization of microcapsules containing a hydrophobic solvent.
• EP-A 0 674 942 constitutes the state of the art according to Article 54 (3) (4) EPC.
• US Patent 4,342,473 relates to a CF reagent (sheet particular).
• a bundle of carbonless paper chemical includes a CB layer based on microcapsules such as those described in the present invention and a so-called CF receiving layer. After rupture of the microcapsules, the color formers react with the reagents contained in the CF layer to form the colored image.
• the solvents used in this case can be all the solvents usable in the chemical carbonless (cf. col. 7, lines 14 to 27), the terpenes such as turpentine (turpentine).
• turpentine turpentine
• the preferred solvents include alkylated naphthalenes.
• biodegradable solvents of natural origin, can be used advantageously instead of oils vegetable, these are terpene derivatives 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 subsequent carbonless papers to overcome the drawbacks described above.
• abietic acid derivatives broadly encompasses esterified derivatives, hydrogenated in particular or products polymerization of abietic acid.
• Liquid products at room temperature are preferred.
• abietic acid and derivatives of abietic acid could be considered as derivatives of terpenes since they are diterpenes.
• Terpene derivatives, abietic acid and derivatives of abietic acid may be present alone or mixed.
• microcapsules according to the invention Compared to microcapsules containing oil-based solvents vegetable, the microcapsules according to the invention have numerous advantages, in particular better storage stability, better UV resistance, better revelation of chromogenic agents, and in most cases a higher encapsulation rate.
• microcapsules according to the invention Compared to microcapsules containing conventional solvents, of origin petroleum, mentioned above, the microcapsules according to the invention have the advantage of being biodegradable. These are products of natural origin whose source is renewable. They are safe for the environment (uses common in pharmacy, cosmetics and especially in perfumery).
• microcapsules according to the invention Compared to microcapsules containing vegetable oils, microcapsules according to the invention have the advantage of better resistance to cold, less coloring, more pleasant odor, greater coloring power, taking into account the solvent power of terpene compounds and smaller diameter dispersion.
• the invention relates in particular to the microcapsules containing in solution products such as: chromogenic agents, perfumes, aromas, products food or pharmaceutical, pesticides, biocides, fungicides, herbicides, dyes, catalysts, chemical reagents.
• phthalic derivatives such as 3,3 bis (4-dimethylamino-phenyl) -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 the compounds of bis of bis (dimethylamino) -10-benzoylphenot
• the solution of chromogenic agent in the solvent is around 5% by weight.
• microcapsules it will be advantageous to mention, but not exclusively, those formed of a cross-linked gelatin wall.
• terpene or abietic acid derivatives or abietic acid can be used alone or in mixtures with each other, or with conventional solvents or with vegetable oils.
• solvents are most often mixed with diluents such as kerosene, light mineral oil or alkylbenzene (e.g. docecylbenzene) etc.
• diluents such as kerosene, light mineral oil or alkylbenzene (e.g. docecylbenzene) etc.
• Vegetable oils are those commonly used, such as soybean, rapeseed, olive, flax, peanut, palm kernel, corn, sunflower, copra, sesame, castor oil, palm, babassu, jojoba etc., especially in American patents 2,712,507, 2,730,457, 3,016,308, 4,783,196, 4,923,641 and patent applications European No. 86 636, 155 593, 262 569. It is also possible to use the triglycerides called from the Anglo-Saxon term "tall oil” comprising a strong proportion of glycerol trioleate.
• These vegetable oils can advantageously be partially replaced or entirely by fatty acid esters.
• the transesterification is the chemical operation which consists in exchanging in an acid medium or basic glycerol by a monoalcohol or dialcohol, in general with 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 .
• alcohols 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 remaining fatty acid can vary from 3 to 20 carbon atoms.
• the fatty acid ester is saturated.
• the solvent only comprises one or several terpene derivatives and / or one or more abietic acid derivatives and / or abietic acid.
• the solvent comprises one or more compounds chosen from abietic acid, terpene derivatives and / or abietic acid mixed with one or more mineral oil (s) and / or one or more oils vegetable or fatty acid ester (s).
• the solvent comprises 20 to 80% of terpene derivatives of abietic acid or abietic acid derivatives and 80 to 20% mineral oil.
• the solvent comprises at least 10% of abietic acid or of derivatives terpenics or abietic acid derivatives, 0 to 50% of a vegetable oil or 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, by example, rapeseed methyl ester, soy isopropyl ester, palmitate isopropyl, methyl oleate, 2-ethylhexylcocoate, methyl isostearate, propylene glycol caprate / dicaprylate and as mineral oil is an oil paraffinic is a hydrogenated naphthenic oil.
• Preferred products are terpineols, nopol, acetate terpenyl, nopyle acetate, sesquiterpenes.
• acid derivatives abietic these are the methyl esters of dihydroabietic acid such as 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 phase is formed hydrophobic consisting of an organic solution as described previously, in an aqueous phase comprising several colloids including gelatin and one or more other anionic colloids, including may mention carboxymethylcellulose (CMC) and an anhydride copolymer maleic such as a copolymer of ethervinylmethyl and anhydride maleic (PVMMA) or a copolymer of ethylene and anhydride maleic (EMA).
• CMC carboxymethylcellulose
• PVMMA ethervinylmethyl and anhydride maleic
• EMA copolymer of ethylene and anhydride maleic
• Liquid-walled microcapsules thus constitute by formation of the coacervate around the oil droplets emulsified. Cooling the mixture down to around 10 ° C causes solidification of the liquid coacervate walls.
• a curing agent such as formalin or glutaraldehyde in order to crosslink said solid coacervate walls and obtain the desired microcapsules.
• the emulsion obtained is of the oil in water type and contains droplets of the hydrophobic phase whose diameter is between 1 and 12 micrometers (preferably 3 to 8 micrometers).
• microcapsules obtained are mixed with binders starch or latex, a spacer, usually calibrated wheat starch and various additives such as optical brightener, water retentive etc.
• the subject of the invention is also a paper sensitive to the pressure coated on one side with a layer of microcapsules such as have been described previously.
• This paper support constituting the transmitting sheet, called CB, of a grammage generally between 40 and 90 g / m2 has been coated with coating the suspension of microcapsules and then these microcapsules were dried to obtain the paper according to the invention.
• the coating method and the formulation of the coating bath are not critical to the invention.
• the subject of the invention is also a wad of paper sensitive to pressure comprising as described in the preamble to the present description a transmitting sheet and a receiving sheet, and possibly one or more intermediate sheets (CFB) and also so-called autonomous sheets obtained by coating the front of a mixture of microcapsules and receptor layer.
• a transmitting sheet and a receiving sheet and possibly one or more intermediate sheets (CFB) and also so-called autonomous sheets obtained by coating the front of a mixture of microcapsules and receptor layer.
• CFB intermediate sheets
• the CF receiving paper associated with the CB sheet is preferably "activated clay" type as described in French patents 2,581,350 or US 4 422 670, but you can also use a phenolic type CF receiving paper such as those described in US Patents 4,559,242 or 4,769,305, or a CF of the type zinc salicylate.
• the organic phase and the aqueous phase are mixed with stirring and emulsified using an Ultra-TURRAX type device until obtaining particles with an average diameter of between 5 and 6 ⁇ m (the diameter measurement is carried out using a Coulter laser granulometer LS100).
• the carboxymethylcellulose has a degree of substitution of the order of 0.8 and a viscosity in 3% aqueous solution at 20 ° C 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 in 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 repeated, replacing the terpineol with oil pine from DRT (trademark DERTOL 90)
• Example 1 is repeated, replacing the terpineol with terpinolene from DRT (mixture of terpene derivatives comprising at least minus 95% of 1-4 (8) paramenthadiene).
• Example 1 is reproduced by replacing terpineol with nopol from DRT (mixture of terpene alcohols consisting essentially 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 reproduced by 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 reproduced by replacing Terpineol with a 50/50 mixture of Terpineol and coconut oil.
• Example 1 is reproduced by replacing Terpineol with a 50/50 mixture of terpenyl acetate and 2 ethyl hexyl laurate.
• Example 12 is repeated, replacing the coconut oil of the mixing with 2-ethylhexyl laurate.
• Example 1 is reproduced by replacing Terpineol with a 30/30/40 ternary mixture of Terpineol / coconut oil / naphthenic oil slight.
• Example 15 is repeated, replacing the Terpineol in the mixture ternary with terpenyl acetate.
• Example 15 is repeated, replacing the Terpineol in the mixture ternary with M oil from DRT (mixture of sesquiterpenes).
• Example 1 is reproduced by replacing Terpineol with a 10/50/40 ternary mixture of Terpineol / 2-ethyl-hexyl laurate / oil light naphthenic.
• Example 1 is reproduced by replacing Terpineol with a 20/50/30 ternary mixture of Terpineol / 2-ethyl-hexyl laurate / norpar 12 (paraffinic oil).
• Example 1 is reproduced by replacing the terpineol with a 25/25/50 ternary mixture of Abalyn E / coconut oil / Norpar 12
• Example 1 is reproduced by replacing the Terpineol with refined coconut oil
• Example 1 is reproduced by replacing the Terpineol by a 50/50 mixture of coconut oil / light naphthenic oil
• the loss of reactivity of the CB is measured by crushing with the grille 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 compared to a blank test on the same CF.

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

Applications Claiming Priority (2)

Publications (2)

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Citations (1)

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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/fr not_active Expired - Lifetime

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