EP0490732A1 - Coating process of papers and its use in flexography - Google Patents
Coating process of papers and its use in flexography Download PDFInfo
- Publication number
- EP0490732A1 EP0490732A1 EP91403294A EP91403294A EP0490732A1 EP 0490732 A1 EP0490732 A1 EP 0490732A1 EP 91403294 A EP91403294 A EP 91403294A EP 91403294 A EP91403294 A EP 91403294A EP 0490732 A1 EP0490732 A1 EP 0490732A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anionic polymer
- papers
- flexography
- crosslinked
- water
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 238000007647 flexography Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- LVKKFNORSNCNPP-UHFFFAOYSA-N 2,2-bis(prop-2-enoylamino)acetic acid Chemical compound C=CC(=O)NC(C(=O)O)NC(=O)C=C LVKKFNORSNCNPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 239000007762 w/o emulsion Substances 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 21
- 239000000976 ink Substances 0.000 description 20
- 238000007639 printing Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- IUQJDHJVPLLKFL-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)acetate;dimethylazanium Chemical compound CNC.OC(=O)COC1=CC=C(Cl)C=C1Cl IUQJDHJVPLLKFL-UHFFFAOYSA-N 0.000 description 1
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000000424 optical density measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a process for coating papers and its application to flexography.
- Flexography is a typographic technique using flexible plates commonly used today for printing various paper-based supports such as bags or cardboard boxes, wallpapers intended for coating walls, tablecloths and napkins, envelopes, etc.
- Flexography can be mono-or polychrome and it preferably uses aqueous inks in order to remove the pollution brought by organic solvents from traditional inks.
- aqueous inks is often incompatible with high productivity and good quality printing because on conventional paper media, these aqueous inks tend to migrate, drool, smear and moreover, they take a long time to dry.
- the process according to the present invention is characterized in that the papers, cardboards and other similar articles are treated with a crosslinked anionic polymer insoluble in water, generally of high molecular weight. by high molecular weight is meant above 1 million.
- This crosslinked anionic copolymer is either a homopolymer of acrylic acid partially or fully salified with an alkali metal or ammonia, or a copolymer of acrylamide and acrylic acid partially or fully salified with an alkali metal or ammonia.
- the salification rate of acrylic acid is greater than or equal to 60%.
- the copolymers preferably contain, in molar proportions, from 1 to 20% of acrylamide.
- Crosslinking is carried out in particular with a conventional diethylenic crosslinking agent having acrylamide groups such as methylene bisacrylamide, bisacrylamidoacetic acid and preferably crosslinking is carried out with bisacrylamidoacetic acid.
- the doses of crosslinker relative to the total weight of the monomers vary from 10 to 1000 ppm, advantageously this dose is between 50 and 500 ppm and preferably 100 ppm.
- the crosslinked anionic polymer insoluble in water usable according to the invention is a high molecular weight polymer; for its implementation according to the present process, it is advantageously dispersed in the aqueous phase of a self-reversible water-in-oil emulsion, in particular in the state of discrete particles of dimensions less than 10 ⁇ m.
- a self-reversible water-in-oil emulsion consist, on the one hand, of a continuous oil phase based on a paraffinic or naphthenic-paraffinic oil, liquid at room temperature, and having a boiling point of 100 to 350 °. C, and on the other hand, an aqueous phase.
- the oils which can be used can be obtained from various suppliers such as the company SHELL.
- these emulsions contain from 65 to 75% of a dispersed aqueous phase of which 35 to 50% of an anionic hydrophilic copolymer with molecular weight greater than 106, from 2 to 7% of a mixture of emulsifiers at least one of which is soluble in the aqueous phase and the complement to 100% by an oil phase.
- a dispersed aqueous phase of which 35 to 50% of an anionic hydrophilic copolymer with molecular weight greater than 106
- a mixture of emulsifiers at least one of which is soluble in the aqueous phase and the complement to 100% by an oil phase.
- emulsifiers which can be used, there may be mentioned in particular sorbitan monooleate and nonylphenols ethoxylated with 8 to 12 molecules of ethylene oxide.
- the process according to the invention is carried out at a pH of between 4 and 5, advantageously at a pH of around 4.
- a pH of less than 4 is not desirable because of the corrosion which it causes on the materials. and a pH higher than 5 leads to coating sauces of high viscosity which are difficult to handle.
- the process according to the invention can be carried out according to conventional methods for coating papers by depositing on the paper to be treated from 1 to 30 g per square meter of crosslinked anionic polymer.
- the removal is for example carried out in an aqueous medium, at a pH of between 4 and 5, on a conventional coating machine.
- the characteristics of the papers treated by the process according to the present invention were compared with those of the treated papers. by known methods using either oxidized starch, or a carboxymethylcellulose, or a polyvinyl alcohol. Tables I and II show the results obtained.
- the paper used for the tests is a kraft wrapping paper of 70 g / m2.
- the deposits are made at the champion bar on 5 sheets. After removal, the papers are dried at 105 ° C for 5 minutes, then they are smoothed by a slight calendering. The weight of the deposits is determined by weighing.
- the printing is carried out with a red ink for flexography (ink type SL 2742, red 3 from the company MARCOLAC SIEM), diluted with water until a flow time of 21 ⁇ 1 seconds is obtained according to the method Ford N ° 4 coupe.
- the prints are made at a constant speed of 0.8 m / s on an IGT AI-C25 device, at a pressure of 500 N and with an upper aluminum wheel. A drop of ink is deposited on the aluminum wheel, then printing is started and the drop spreads over the surface of the paper. This gives an impression over a certain length which is proportional to the absorption capacity of the paper.
- Ink transfer and smudging are determined according to known techniques by measuring the optical density of the printing of the support and of the smear.
- the print density is measured using a MACBETH RD 100 reflection densitometry device, the reflection factor p is defined as the ratio Ir / Ii where Ir represents the intensity of the reflected light and Ii the intensity of the incident light, the optical density, do, is the decimal logarithm of the inverse of the reflection factor and given by the formula:
- the print gloss is judged using a GARDNER reflectometer working at 75 ° and is expressed in reflectance percentages. Before being tested, the samples are dried for 5 minutes in an oven at 105 ° C.
- the water resistance is measured by immersing strips of printed paper 55 by 300 mm in a 1 l beaker filled with water, for 45 minutes at 20 ° C, 4 times in succession and then evaluating the amount of ink remaining on the support by optical density measurement.
- the piercing is judged by examining the back of the printed sheet by the same method.
- the length of the prints makes it possible to evaluate the quantity of ink absorbed naturally by the support in a given time. To do this, a drop of ink is spread between two rollers: the length of the ink trail obtained is greater the less the support absorbs.
- the ink With the untreated support T, the ink is easily absorbed (short print length: 8.4 cm) and it penetrates deeply by giving significant piercings. Furthermore, although the printing surface is small, the printing density is low, part of the ink is lost in the support. In addition, the printing density of the smear immediately applied to the printed support remains high: the ink is absorbed quickly but is not fixed properly. Only the water resistance is good because the ink has penetrated deeply into the support.
- Product E makes it possible to reduce the defects mentioned above: it makes it possible to obtain the weakest smearing for a good printing density; the ink fixes well and quickly, while having a correct water resistance and piercing. Visual examination shows that with product E, the ink fixes on the surface, gives remarkable coverage and a soft and smooth feel, and finally, on colored supports, it leads to a fresher impression.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
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Abstract
Description
La présente invention concerne un procédé d'enduction des papiers et son application à la flexographie. La flexographie est une technique typographique par clichés souples couramment utilisée aujourd'hui pour l'impression de divers supports à base de papiers tels que les sacs ou les cartons d'emballage, les papiers peints destinés au revêtement des murs, les nappes et serviettes, les enveloppes, etc... La flexographie peut être mono-ou polychrome et elle utilise préférentiellement des encres aqueuses afin de supprimer la pollution apportée par les solvants organiques des encres traditionnelles. L'emploi d'encres aqueuses est souvent incompatible avec une productivité élevée et une impression de bonne qualité car sur les supports papier classiques, ces encres aqueuses ont tendance à migrer, à baver, à maculer et de plus, elles sont longues à sécher. On recherche donc un procédé d'enduction fournissant des papiers susceptibles d'être imprimés par flexographie avec des encres aqueuses sans causer des maculages et/ou des bavures tout en assurant une productivité élevée. Pour ce faire, on a proposé, soit, l'emploi d'encres particulières, soit la modification de l'état de surface des papiers. Parmi ces modifications, on peut citer notamment le traitement par des agents mouillants, l'emploi d'adjuvants spéciaux comme des polymères hydrosolubles, un raffinage spécial de la pâte, l'emploi de charges particulières, etc...The present invention relates to a process for coating papers and its application to flexography. Flexography is a typographic technique using flexible plates commonly used today for printing various paper-based supports such as bags or cardboard boxes, wallpapers intended for coating walls, tablecloths and napkins, envelopes, etc. Flexography can be mono-or polychrome and it preferably uses aqueous inks in order to remove the pollution brought by organic solvents from traditional inks. The use of aqueous inks is often incompatible with high productivity and good quality printing because on conventional paper media, these aqueous inks tend to migrate, drool, smear and moreover, they take a long time to dry. We therefore seek a coating process providing papers capable of being printed by flexography with aqueous inks without causing smearing and / or smearing while ensuring high productivity. To do this, it has been proposed either to use specific inks or to modify the surface condition of the papers. Among these modifications, mention may in particular be made of treatment with wetting agents, the use of special additives such as water-soluble polymers, a special refining of the paste, the use of special fillers, etc.
Ces diverses modifications ne permettent toutefois pas une impression par flexographie de bonne qualité avec une productivité élevée et un coût faible. Afin de répondre aux exigences de plus en plus drastiques du marché, la demanderesse a découvert un nouveau procédé d'enduction des papiers destinés à être imprimés par flexographie autorisant des cadences d'impression élevées, à un coût faible sans causer de maculage, de bavurees et/ou de transpercement.These various modifications do not, however, allow good quality flexographic printing with high productivity and low cost. In order to meet the increasingly drastic requirements of the market, the Applicant has discovered a new process for coating papers intended to be printed by flexography allowing high printing rates, at low cost without causing smudging, smearing and / or piercing.
Le procédé selon la présente invention est caractérisé en ce que l'on traite les papiers, cartons et autres articles similaires avec un polymère anionique réticulé insoluble dans l'eau, généralement de poids moléculaire élevé. par poids moléculaire élevé l'on entend supérieur à 1 million. Ce copolymère anionique réticulé est, soit un homopolymère d'acide acrylique partiellement ou totalement salifié avec un métal alcalin ou de l'ammoniac, soit un copolymère d'acrylamide et d'acide acrylique partiellement ou totalement salifié avec un métal alcalin ou de l'ammoniac. Avantageusement, le taux de salification de l'acide acrylique est supérieur ou égal à 60 %. Les copolymères contiennent de préférence, en proportions molaires, de 1 à 20 % d'acrylamide. La réticulation est réalisée notamment avec un réticulant classique diéthylénique possédant des groupements acrylamides tels que le méthylène bisacrylamide, l'acide bisacrylamidoacétique et de préférence la réticulation est effectuée avec l'acide bisacrylamidoacétique. Les doses de réticulant par rapport au poids total des monomères varient de 10 à 1000 ppm, avantageusement cette dose est comprise entre 50 et 500 ppm et préférentiellement de 100 ppm. Le polymère anionique réticulé insoluble dans l'eau utilisable selon l'invention est un polymère à haut poids moléculaire ; pour sa mise en oeuvre selon le présent procédé, il est avantageusement dispersé dans la phase aqueuse d'une émulsion eau dans huile auto-réversible notamment à l'état de particules discrètes de dimensions inférieures à 10 µm. Ces émulsions eau dans huile auto-réversibles sont constituées d'une part, par une phase huile continue à base d'une huile paraffinique ou naphténique-paraffinique, liquide à la température ambiante, et présentant un point d'ébullition de 100 à 350 ° C, et d'autre part, d'une phase aqueuse.
On peut obtenir les huiles utilisables auprès de divers fournisseurs tels que la société SHELL.
Pondéralement, ces émulsions contiennent de 65 à 75 % d'une phase aqueuse dispersée dont 35 à 50 % d'un copolymère hydrophile anionique de poids moléculaire supérieur à 10⁶, de 2 à 7 % d'un mélange d'émulsifiants dont au moins un est soluble dans la phase aqueuse et le complément à 100 % par une phase huile.
Parmi les émulsifiants utilisables, on peut citer notamment le monooléate de sorbitanne et les nonylphénols éthoxylés avec 8 à 12 molécules d'oxyde d'éthylène.The process according to the present invention is characterized in that the papers, cardboards and other similar articles are treated with a crosslinked anionic polymer insoluble in water, generally of high molecular weight. by high molecular weight is meant above 1 million. This crosslinked anionic copolymer is either a homopolymer of acrylic acid partially or fully salified with an alkali metal or ammonia, or a copolymer of acrylamide and acrylic acid partially or fully salified with an alkali metal or ammonia. Advantageously, the salification rate of acrylic acid is greater than or equal to 60%. The copolymers preferably contain, in molar proportions, from 1 to 20% of acrylamide. Crosslinking is carried out in particular with a conventional diethylenic crosslinking agent having acrylamide groups such as methylene bisacrylamide, bisacrylamidoacetic acid and preferably crosslinking is carried out with bisacrylamidoacetic acid. The doses of crosslinker relative to the total weight of the monomers vary from 10 to 1000 ppm, advantageously this dose is between 50 and 500 ppm and preferably 100 ppm. The crosslinked anionic polymer insoluble in water usable according to the invention is a high molecular weight polymer; for its implementation according to the present process, it is advantageously dispersed in the aqueous phase of a self-reversible water-in-oil emulsion, in particular in the state of discrete particles of dimensions less than 10 μm. These self-reversible water-in-oil emulsions consist, on the one hand, of a continuous oil phase based on a paraffinic or naphthenic-paraffinic oil, liquid at room temperature, and having a boiling point of 100 to 350 °. C, and on the other hand, an aqueous phase.
The oils which can be used can be obtained from various suppliers such as the company SHELL.
In weight, these emulsions contain from 65 to 75% of a dispersed aqueous phase of which 35 to 50% of an anionic hydrophilic copolymer with molecular weight greater than 10⁶, from 2 to 7% of a mixture of emulsifiers at least one of which is soluble in the aqueous phase and the complement to 100% by an oil phase.
Among the emulsifiers which can be used, there may be mentioned in particular sorbitan monooleate and nonylphenols ethoxylated with 8 to 12 molecules of ethylene oxide.
Ce type d'émulsions est décrit dans la littérature et pour la mise en oeuvre du procédé selon l'invention les épaississants connus pour l'impression pigmentaire à base de polymère d'acide acrylique partiellement ou totalement salifié par de l'ammoniac présentés en émulsion eau dans huile auto-réversible comme ceux décrits dans la demande de brevet européen N° 325.065 conviennent particulièrement bien.This type of emulsion is described in the literature and for the implementation of the method according to the invention the thickeners known for pigmentary printing based on acrylic acid polymer partially or totally salified with ammonia presented in emulsion Self-reversible water in oil like those described in European patent application No. 325.065 are particularly suitable.
Le procédé selon l'invention est mis en oeuvre à un pH compris entre 4 et 5, avantageusement à un pH d'environ 4. Un pH inférieur à 4 n'est pas souhaitable en raison de la corrosion qu'il entraîne sur les matériels et un pH supérieur à 5 conduit à des sauces d'enduction de viscosité élevée difficilement manipulables.The process according to the invention is carried out at a pH of between 4 and 5, advantageously at a pH of around 4. A pH of less than 4 is not desirable because of the corrosion which it causes on the materials. and a pH higher than 5 leads to coating sauces of high viscosity which are difficult to handle.
Le procédé selon l'invention peut être réalisé selon les méthodes classiques d'enduction des papiers en déposant sur le papier à traiter de 1 à 30 g par mètre carré de polymère anionique réticulé. La dépose est par exemple effectuée en milieu aqueux, à un pH compris entre 4 et 5, sur une machine d'enduction classique.The process according to the invention can be carried out according to conventional methods for coating papers by depositing on the paper to be treated from 1 to 30 g per square meter of crosslinked anionic polymer. The removal is for example carried out in an aqueous medium, at a pH of between 4 and 5, on a conventional coating machine.
Afin d'apprécier les performances des papiers traités par le procédé selon l'invention, on a procédé à la comparaison des caractéristiques des papiers traités par le procédé selon la présente invention, à celles des papiers traités par les procédés connus mettant en oeuvre, soit de l'amidon oxydé, soit une carboxyméthylcellulose, soit un alcool polyvinylique. Les tableaux I et II mentionnent les résultats obtenus. Le papier utilisé pour les essais est un papier kraft d'emballage de 70 g/m². Les déposes sont réalisées à la barre champion sur 5 feuilles. Après dépose, les papiers sont séchés à 105° C pendant 5 minutes, puis ils sont défroissés par un léger calandrage. Le poids des déposes est déterminé par pesée. L'impression est effectuée avec une encre rouge pour flexographie (encre type SL 2742, rouge 3 de la Société MARCOLAC SIEM), diluée à l'eau jusqu'à obtention d'un temps d'écoulement de 21 ± 1 secondes selon la méthode coupe Ford N°4. Les impressions sont réalisées à la vitesse constante de 0,8 m/s sur un appareil IGT AI-C25, à une pression de 500 N et avec une molette supérieure en aluminium. Une goutte d'encre est déposée sur la molette en aluminium, on déclenche ensuite l'impression et la goutte s'étale sur la surface du papier. On obtient ainsi une impression sur une certaine longueur qui est proportionnelle à la capacité d'absorption du papier.
Le tableau I mentionne les formules des bains utilisés pour l'enduction du papier avant impression. Dans ce tableau, l'amidon oxydé, désigné Aox, provient de la Société des Produits du Maïs, SPDM, et il est commercialisé sous la référence AMISOLR 5591, la carboxyméthylcellulose, désignée CMC est commercialisée par la demanderesse sous la référence TYLOSER VCLL, l'alcool polyvinylique, désigné PVA, est commercialisé par la demanderesse sous la référence MOWIOLR 98-4 et l'épaississant utilisé, désigné E, est une émulsion eau dans huile contenant pondéralement 29,3 % d'un copolymère acrylamide (AAM)-acide acrylique (AA)- acrylate d'ammonium (AANH₄), 20,5-26-53 en proportions molaires, réticulé avec 100 ppm d'acide bisacrylamidoacétique (ABAA) par rapport au poids du copolymère, 42,6 % d'eau, 23,4 % d'huile paraffinique en C₁₀-C₁₃ et 4,7 % d'un mélange d'émulsifiants dont 46,4 % est constitué par du sesquioléate de sorbitanne et le complément à 100 % par deux émulsifiants solubles dans l'eau présentant une valeur HLB supérieure à 8. Dans le tableau I toutes les quantités sont exprimées en grammes. L'ajustement du pH de certaines formules à pH=4 est réalisé par addition d'acide chlorhydrique.Table I mentions the formulas of the baths used for coating the paper before printing. In this table, the oxidized starch, designated Aox, comes from the Corn Products Company, SPDM, and it is marketed under the reference AMISOL R 5591, the carboxymethylcellulose, designated CMC is marketed by the applicant under the reference TYLOSE R VCLL , polyvinyl alcohol, designated PVA, is sold by the applicant under the reference MOWIOL R 98-4 and the thickener used, designated E, is a water-in-oil emulsion containing 29.3% by weight of an acrylamide copolymer (AAM ) -acrylic acid (AA) - ammonium acrylate (AANH₄), 20.5-26-53 in molar proportions, crosslinked with 100 ppm of bisacrylamidoacetic acid (ABAA) relative to the weight of the copolymer, 42.6% d water, 23.4% paraffinic oil C₁₀-C d'huile and 4.7% of a mixture of emulsifiers of which 46.4% consists of sorbitan sesquioleate and the complement to 100% by two emulsifiers soluble in water with an HLB value greater than 8. D In Table I all quantities are expressed in grams. The adjustment of the pH of certain formulas to pH = 4 is carried out by addition of hydrochloric acid.
Au départ des formules de bain données dans le tableau I, différentes déposes de 1 à 10 g/m² ont été réalisées. Les résultats de 10 essais successifs avec chaque formule pour différentes déposes sont appréciés dans les tests de densité d'impression, de maculage, de transpercement et de tenue à l'eau. A titre de comparaison, un support papier non traité a également été testé ; les résultats obtenus sont donnés sous la référence T. Les moyennes des valeurs obtenues dans les 10 essais effectués dans chaque test sont mentionnés dans le tableau II. Dans ce tableau, la longueur des impressions est exprimée en centimètres, la tenue à l'eau et le transpercement sont notés de 1 à 5, la valeur 1 correspond à une bonne tenue à l'eau ou à un faible transpercement, et la valeur 5 correspond à une mauvaise tenue à l'eau ou à un transpercement important. Les viscosités Brookfiekd sont exprimées en mPa.s et elles sont déterminées avec un appareil Brookfield modèle RVT à 20° C, le module et sa vitesse de rotation étant choisis dans les plages recommandées.From the bath formulas given in Table I, different deposits of 1 to 10 g / m² were carried out. The results of 10 successive tests with each formula for different deposits are appreciated in the tests of print density, smudging, piercing and water resistance. For comparison, an untreated paper support was also tested; the results obtained are given under the reference T. The means of the values obtained in the 10 tests carried out in each test are mentioned in table II. In this table, the length of the prints is expressed in centimeters, the water resistance and the piercing are noted from 1 to 5, the value 1 corresponds to a good water resistance or a weak piercing, and the value 5 corresponds to poor water resistance or significant piercing. Brookfiekd viscosities are expressed in mPa.s and are determined with a Brookfield model RVT device at 20 ° C, the module and its speed of rotation being chosen within the recommended ranges.
Le transfert d'encre et le maculage sont déterminés selon les techniques connues par mesure de la densité optique de l'impression du support et de la macule. La densité d'impression est mesurée à l'aide d'un appareil de densitométrie par réflexion MACBETH RD 100, le facteur de réflexion p est défini comme le rapport Ir/Ii où Ir représente l'intensité de la lumière réfléchie et Ii l'intensité de la lumière incidente, la densité optique, d.o, est le logarithme décimal de l'inverse du facteur de réflexion et donnée par la formule :
Le brillant d'impression est jugé à l'aide d'un réflectomètre GARDNER travaillant à 75 ° et il est exprimé en pourcentages de réflectance. Avant d'être testés, les échantillons sont séchés pendant 5 minutes en étuve à 105 ° C.The print gloss is judged using a GARDNER reflectometer working at 75 ° and is expressed in reflectance percentages. Before being tested, the samples are dried for 5 minutes in an oven at 105 ° C.
La tenue à l'eau est mesurée en plongeant des bandes de papier imprimées de 55 par 300 mm dans un bécher de 1l rempli d'eau, pendant 45 minutes à 20° C, 4 fois de suite et en évaluant ensuite la quantité d'encre restant sur le support par mesure de densité optique. Le transpercement est jugé par examen du verso de la feuille imprimée par la même méthode.The water resistance is measured by immersing strips of printed paper 55 by 300 mm in a 1 l beaker filled with water, for 45 minutes at 20 ° C, 4 times in succession and then evaluating the amount of ink remaining on the support by optical density measurement. The piercing is judged by examining the back of the printed sheet by the same method.
La longueur des impressions permet d'évaluer la quantité d'encre absorbée naturellement par le support dans un temps donné. Pour ce faire, une goutte d'encre est étalée entre deux rouleaux : la longueur de la trainée d'encre obtenue est d'autant plus grande que le support absorbe moins.The length of the prints makes it possible to evaluate the quantity of ink absorbed naturally by the support in a given time. To do this, a drop of ink is spread between two rollers: the length of the ink trail obtained is greater the less the support absorbs.
Dans le tableau III nous donnons des résultats obtenus avec une dépose de 4g/m² d'amidon Aox., de CMC et E.
Avec le support non traité T, l'encre s'absorbe facilement (longueur d'impression faible : 8,4 cm) et elle pénètre profondément en donnant des transpercements importants. Par ailleurs, bien que la surface d'impression soit faible, la densité d'impression est peu élevée, une partie de l'encre est perdue dans le support. De plus la densité d'impression de la macule appliquée aussitôt sur le support imprimé reste élevée : l'encre s'absorbe vite mais est mal fixée. Seule la tenue à l'eau est bonne car l'encre a pénétré profondément dans le support.
Le produit E permet de réduire les défauts mentionnés ci-dessus : il permet d'obtenir le maculage le plus faible pour une bonne densité d'impression ; l'encre se fixe bien et rapidement, tout en ayant une tenue à l'eau et un transpercement corrects. L'examen visuel permet de constater qu'avec le produit E, l'encre se fixe en surface, donne une couverture remarquable et un toucher doux et lisse et enfin, sur des supports colorés, il conduit à une impression plus fraiche.With the untreated support T, the ink is easily absorbed (short print length: 8.4 cm) and it penetrates deeply by giving significant piercings. Furthermore, although the printing surface is small, the printing density is low, part of the ink is lost in the support. In addition, the printing density of the smear immediately applied to the printed support remains high: the ink is absorbed quickly but is not fixed properly. Only the water resistance is good because the ink has penetrated deeply into the support.
Product E makes it possible to reduce the defects mentioned above: it makes it possible to obtain the weakest smearing for a good printing density; the ink fixes well and quickly, while having a correct water resistance and piercing. Visual examination shows that with product E, the ink fixes on the surface, gives remarkable coverage and a soft and smooth feel, and finally, on colored supports, it leads to a fresher impression.
Il résulte de tous ces essais que les formules à base de l'émulsion E contenant un polymère anionique réticulé confèrent au support traité de très bonnes propriétés : réduction du maculage, bonne densité de l'impression, bon rendement d'impression. Par ailleurs, le procédé selon l'invention permet d'obtenir un support lisse et doux très apprécié pour la confection de nombreux articles.It follows from all these tests that the formulas based on emulsion E containing a crosslinked anionic polymer give the treated support very good properties: reduction in smearing, good density of printing, good printing yield. Furthermore, the method according to the invention makes it possible to obtain a smooth and soft support which is very appreciated for the manufacture of numerous articles.
C'est pourquoi la présente invention a enfin pour objet l'application du procédé ci-dessus décrit à l'obtention de papiers ou autres articles similaires destinés à être imprimés par flexographie.This is why the present invention finally relates to the application of the process described above for obtaining papers or other similar articles intended to be printed by flexography.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9015618 | 1990-12-13 | ||
| FR9015618A FR2670516B1 (en) | 1990-12-13 | 1990-12-13 | PROCESS FOR COATING PAPERS AND ITS APPLICATION TO FLEXOGRAPHY. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0490732A1 true EP0490732A1 (en) | 1992-06-17 |
| EP0490732B1 EP0490732B1 (en) | 1995-03-01 |
Family
ID=9403198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91403294A Expired - Lifetime EP0490732B1 (en) | 1990-12-13 | 1991-12-05 | Coating process of papers and its use in flexography |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5229168A (en) |
| EP (1) | EP0490732B1 (en) |
| JP (1) | JPH0726496A (en) |
| AT (1) | ATE119224T1 (en) |
| DE (1) | DE69107811T2 (en) |
| DK (1) | DK0490732T3 (en) |
| ES (1) | ES2069252T3 (en) |
| FI (1) | FI915620A (en) |
| FR (1) | FR2670516B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0758673B1 (en) * | 1995-07-21 | 1999-10-06 | Rohm And Haas Company | Method for improving drying speed in printing process and fast dry printing ink used therein |
| ES2564269T3 (en) * | 2012-09-20 | 2016-03-21 | Omya International Ag | Print medium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325065A1 (en) * | 1987-12-18 | 1989-07-26 | SOCIETE FRANCAISE HOECHST Société anonyme dite: | Water-in-oil dispersions of hydrophilic polymers based on acrylic acid partially or fully neutralised with ammonia, process for their preparation and their use in printing ink |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3266971A (en) * | 1964-03-31 | 1966-08-16 | Formica Corp | Acrylic latex coating composition containing amine mixtures |
| US4077930A (en) * | 1974-07-16 | 1978-03-07 | Calgon Corporation | Self-inverting emulsions of dialkyldiallyl ammonium chloride polymers and copolymers |
| DE2903218A1 (en) * | 1979-01-27 | 1980-08-07 | Basf Ag | METHOD FOR PRODUCING PAPER WITH HIGH DRY RESISTANCE AND LOW WET STRENGTH |
| US4554018A (en) * | 1984-02-01 | 1985-11-19 | Allied Colloids Limited | Production of polymeric thickeners and their use in printing |
| JPH0780970B2 (en) * | 1986-08-29 | 1995-08-30 | 三菱化学株式会社 | Method for manufacturing water-absorbent composite material |
-
1990
- 1990-12-13 FR FR9015618A patent/FR2670516B1/en not_active Expired - Fee Related
-
1991
- 1991-11-28 FI FI915620A patent/FI915620A/en not_active Application Discontinuation
- 1991-11-29 JP JP3341853A patent/JPH0726496A/en active Pending
- 1991-12-05 DE DE69107811T patent/DE69107811T2/en not_active Expired - Fee Related
- 1991-12-05 EP EP91403294A patent/EP0490732B1/en not_active Expired - Lifetime
- 1991-12-05 ES ES91403294T patent/ES2069252T3/en not_active Expired - Lifetime
- 1991-12-05 AT AT91403294T patent/ATE119224T1/en not_active IP Right Cessation
- 1991-12-05 DK DK91403294.1T patent/DK0490732T3/en active
- 1991-12-13 US US07/806,188 patent/US5229168A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325065A1 (en) * | 1987-12-18 | 1989-07-26 | SOCIETE FRANCAISE HOECHST Société anonyme dite: | Water-in-oil dispersions of hydrophilic polymers based on acrylic acid partially or fully neutralised with ammonia, process for their preparation and their use in printing ink |
Non-Patent Citations (1)
| Title |
|---|
| BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY. vol. 54, no. 2, Août 1983, APPLETON US GOTO S. ET AL: '"emulsion for high gloss paper"' * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69107811T2 (en) | 1995-08-17 |
| DK0490732T3 (en) | 1995-05-22 |
| FR2670516B1 (en) | 1993-04-09 |
| DE69107811D1 (en) | 1995-04-06 |
| US5229168A (en) | 1993-07-20 |
| ES2069252T3 (en) | 1995-05-01 |
| ATE119224T1 (en) | 1995-03-15 |
| EP0490732B1 (en) | 1995-03-01 |
| FI915620A (en) | 1992-06-14 |
| JPH0726496A (en) | 1995-01-27 |
| FR2670516A1 (en) | 1992-06-19 |
| FI915620A0 (en) | 1991-11-28 |
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