EP0328756A1 - Base paper for photographic supports - Google Patents
Base paper for photographic supports Download PDFInfo
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- EP0328756A1 EP0328756A1 EP19880120390 EP88120390A EP0328756A1 EP 0328756 A1 EP0328756 A1 EP 0328756A1 EP 19880120390 EP19880120390 EP 19880120390 EP 88120390 A EP88120390 A EP 88120390A EP 0328756 A1 EP0328756 A1 EP 0328756A1
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- EP
- European Patent Office
- Prior art keywords
- base paper
- acrylamide
- meth
- paa
- paper according
- 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.)
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Classifications
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- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
- D21H23/765—Addition of all compounds to the pulp
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
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- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Definitions
- the invention relates to a base paper for waterproof coated paper supports for photographic layers and a method for producing such a base paper for the production of layer supports.
- such a carrier material consists of a base paper with polyolefin resin coatings applied to both surfaces, of which the coating initially lying on the photographic layers usually contains at least one light-reflecting pigment (for example titanium dioxide).
- Paper coated with water-impermeable resin layers on both surfaces is protected against the ingress of water or aqueous photographic processing solutions, but not on the open edges.
- the paper core of the laminate is exposed there.
- Aqueous processing solutions can therefore penetrate into the paper core at the edges of the laminate and cannot be removed without residue by conventional washing processes.
- the base paper In order to prevent or reduce this penetration of aqueous solutions on the edges of the laminate, the base paper is usually hard-sized. Both reactive substances, for example dimerized alkyl ketene, and non-reactive substances such as higher fatty acids are known as glue for photographic base papers. Reactive sizing agents are usually processed with the use of a cationic resin without a pH change (neutral), while non-reactive sizing agents require an addition of aluminum ions and are processed acidic. DOS 32 38 865 also described a combination of these two sizing processes in order to better prevent the paper core from penetrating to protect the various components of photographic process solutions.
- the sizing agents with a hydrophobic effect are usually mixed into the fiber suspension and deposited on the surface of the fibers by adding the auxiliaries.
- an aid is, for example, an aluminum salt in the case of acidic sizing, for example a cationic polyamide-polyamine-epichlorohydrin resin in the case of neutral sizing, which is mainly used together with C16-C18 alkyl ketene dimer (J. Appl. Photographic Engineering 7. ( 1981), pp.67-72).
- other cationic substances such as cationic polyacrylamides, cationized starches or polyethyleneimines are also suitable in certain cases for improving the retention and for fixing reactive sizing agents in the paper sheet.
- sizing agents are deposited on the surface of the pulp fibers, the fiber-fiber bond is naturally weaker in a sized paper than in a non-sized paper. Therefore, water-soluble resins are widely used to improve paper strength.
- resins include polyvinyl alcohol, anionic polyacrylamide, guar resin and various starch derivatives.
- DE-OS 32 10 621 describes, for example, the use of anionic polyacrylamide together with cationic starch.
- anionic polyacrylamide is used together with cationic polyacrylamide
- DE-OS 33 28 463 describes a combination of cationic resin with anionic polysaccharide derivatives.
- the addition of these hardening resins also serves the purpose of reducing the discoloration of the edges by developers.
- a disadvantage of hard sizing of the base paper is not only the loss of strength, the drop in structural strength of laminates being particularly harmful. It also proves to be disadvantageous that the use of flocculent additives adversely affects the formation of the sheet (formation). This is due to the fact that the addition of cationic substances not only retains the glue on the surface of the fibers, but inevitably and despite countermeasures taken by mechanical engineering, fiber flakes develop because the repulsive negative charges on the fibers are largely neutralized by the cationic substances and fiber -Bridging can be facilitated. The fiber flakes have different sizes and distributions in the paper sheet, depending on the materials used and mechanical engineering devices, and determine the homogeneity and surface quality of the base paper. The structure once created in the paper sheet can no longer be changed even by strong calendering.
- DE-OS 32 10 621, DE-OS 32 16 840, DE-OS 33 28 463 and finally DE-Patent 36 06 806 has resulted in a reduction in bath penetration at the cut edges achieved, the problem of the formation, the surface quality and the structural strength received little attention. These two points were only taken into account in DE patent 36 06 806 in connection with acid sizing.
- nonionic polymers e.g. B. starch, polyvinyl alcohol or guar. This did lead to a certain improvement in sheet formation and surface quality; however, the retention of these substances was significantly poorer, the production speed had to be reduced, and when the photographic process solutions were used, the internal strength was noticeably reduced. The edges of the coated substrate split under the influence of the photographic process solutions.
- Another object of the invention is to propose a method for producing a base paper for photographic supports, according to which the values mentioned are improved both when using so-called acid sizing and so-called neutral sizing, and avoiding undesirable fluctuations in these properties and edge penetration will. Fluctuations in the number of surfaces and edge penetration of more than ⁇ 5% and the internal strength of more than ⁇ 6% are considered to be undesirable fluctuations based on the mean value.
- a base paper is used for the production of the laminate which, in addition to the sizing agents having a hydrophobic effect, contains at least one cationic resin and at least one amphoteric polyacrylamide.
- the invention thus relates to a base paper for resin-coated photographic supports and to a method for producing a base paper which contains at least one hydrophobizing sizing agent, at least one cationic resin and at least one amphoteric polyacrylamide.
- hydrophobic sizing agents are both reactive sizing agents such as dimerized alkylketenes, epoxidized fatty acid amides or fatty acid anhydrides and non-reactive sizing agents such as higher fatty acids (e.g. stearic acid) and salts of higher fatty acids.
- a particularly preferred dimerized alkyl ketene consists of at least 50% behenyl ketene or another alkyl ketene with more than 18 carbon atoms in the alkyl radical.
- two or more hydrophobizing sizing agents are contained in the paper. Thereby reactive with non-reactive Lei be combined.
- a preferred combination is, for example, a combination of alkyl ketene dimer and fatty acid, but a combination of epoxidized fatty acid amide and fatty acid is also possible within the scope of the invention.
- a cationic resin is any resin with cationic groups commonly used in papermaking as a wet strength agent. Such resins are usually used for wet strengthening and for the retention of reactive sizing agents. According to the invention, however, they are used both in combination with reactive and with non-reactive sizing agents.
- the cationic resin is an epichlorohydrin modified polyamine or polyamide amine resin.
- Other suitable resins are urea / formaldehyde resins, melamine / formaldehyde resins, polyethyleneimines and polyethyleneimine derivatives.
- the third component relevant to the success of the invention, the amphoteric polyacrylamide is a polyacrylamide which contains both anionic groups and cationic groups in the macromolecule.
- the anionic groups are carboxyl or alkali carboxylate groups.
- the cationic groups can be any cationic groups.
- preferred cationic groups are quaternized or protonated alkalyaminoalkylene (meth) acrylate or alkylaminoalkylene (meth) acrylamide groups, with quaternization preferably taking place with dimethyl sulfate or methyl chloride and salts of the protonated form preferably being sulfuric or hydrochloric acid salts.
- the introduction of the cationic groupings into a poly (meth) acrylamide is usually carried out by copolymerization in the presence of the corresponding katio African monomers, for example dialkylaminoalkylene (meth) acrylate or dialkylaminoalkylene (meth) acrylamide in the form of acid salts or in quaternized form.
- a suitable cationic comonomer is also dimethyldiallylammonium chloride.
- Cationic groups can also be formed by reacting Mannich or Hoffmann polyacrylamide or by transamination with polyamine.
- the anionic groups in the amphoteric polyacrylamide are either the result of a copolymerization in the presence of e.g. B. (meth) acrylic acid or its salts or the result of hydrolysis of acrylamide groups or copolymerized (meth) acrylic acid esters.
- the molecular weight of the amphoteric polyacrylamide is in the range from 100,000 to 2,000,000, preferably between 500,000 and 1,500,000.
- the polyacrylamide (PAA) is a modified polyacrylamide or polymethacrylamide in which the molar ratio of the amide component to the sum of the anionic and cationic groups is preferably in the range from 60:40 to 95: 5.
- the ratio of the number of cationic groups to the number of anionic groups is between 10: 1 and 1: 2.
- the poly (meth) acrylamide used can contain up to 10 mol% of a fourth comonomer (e.g. acrylic acid ester, vinyl ester or the like) contain.
- the amount used according to the invention is 0.3-3% by weight, based on the fiber material.
- Papers sized and strengthened according to the invention can contain all other usual paper additives such as pigments, dyes, fillers, optical brighteners, antioxidants or portions of synthetic fiber material without the advantages according to the invention being lost.
- the various components can be added to the pulp suspension in a different order and at different locations known to the paper manufacturer.
- Fatty acid, fatty acid anhydrides and aluminum compounds are usually added immediately after the pulp fibers have been ground, while reactive sizing agents are added to the pulp suspension relatively shortly before being fed to the paper machine.
- the amphoteric polyacrylamide can be added to both the so-called thick stock and the so-called thin stock in the course of the paper production.
- the order of addition of the three components important in the context of the invention can be different. In principle, any order is possible.
- the amphoteric polyacrylamide is mixed into the fiber suspension in the order before the cationic resin. Otherwise, the paper-making rules known to the person skilled in the art apply.
- a mixture of 90% by weight hardwood sulfate pulp and 10% by weight softwood sulfate pulp was ground at a consistency of 4% to a freeness of 35 ° SR.
- Sizing agents, amphoteric polyacrylamide (PAA), cationic resin and auxiliaries in accordance with Table 1 were then added to the pulp suspension and base papers of about 175 g / m 2 were made in a known manner from the suspensions diluted to about 1.2% by weight.
- the papers were surface-sized in a likewise known manner with a solution containing 52 g / l oxidized starch, 20 g / l NaCl and 1 g / l whitening agent and smoothed in-line.
- Table 1 Ingredients and quantities * according to example 1 sample 1.1 1.2 1.3 1.4 1.5 Stearic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 amph. PAA Ia 1.0 - - - amph. PAA Ib - 1.0 - - - amph. PAA Ic - - 1.0 - - amph. PAA Id - - - 1.0 - amph.
- Example 1 samples 1.6 to 1.8 without amphoteric PAA were produced as comparisons with the deviations 1.6 - no polyacrylamide 1.7 - with 1% cationic PAA 1.8 - with 1% anionic PAA.
- Example 2 Analogous to Example 1, base papers weighing approximately 175 g / m 2 were produced with the ingredients listed in Table 2.
- Table 2 Ingredients and amounts according to example 2 sample 2.1 2.2 2.3 2.4 2.5 2.6 Na stearate 0.5 0.5 0.5 0.5 0.5 0.5 Na aluminate 0.5 0.5 0.5 0.5 0.5 0.5 amph.
- PAA IIa 1.0 - - - - - amph.
- PAA IIb - 1.0 - - - - amph.
- PAA IIc - - 1.0 - - - amph.
- Example 2 Analogous to Example 1, base papers weighing approximately 175 g / m 2 were produced with the ingredients shown in Table 4.
- Table 4 Ingredients and amounts according to example 4 sample 4.1 4.2 4.3 4.4 4.5 4.6 Sodium stearate 0.5 0.5 0.5 0.5 0.5 - Al chloride 0.5 0.5 0.5 0.5 0.5 - amph.
- PAA IIIc 1.5 2.0 2.5 - - 2.5 amph.
- Example 2 Analogously to Example 1, two paper samples were produced using the technical teaching from DOS 32 16 841 with the following ingredients. sample 5.1 5.2 cation. PAA 1.0 2.5 Alkyl ketene dimer 0.6 0.6 Polyamide-polyamine-epichlorohydrin resin 0.5 0.5
- the alkyl ketene dimer listed in the examples is a commercial product which is synthesized from a commercially available mixture of stearic acid and palmitic acid, that is to say predominantly carries C16-alkyl radicals.
- a ketene dimer is used which contains less than 40% hydrocarbon residues with less than 20 C atoms.
- a preferred such ketene dimer is, for example, a behenyl ketene dimer.
- the effect according to the invention is not limited to the basis weight of the base paper on which the examples are based and the cellulose types indicated.
- the effect of adding amphoteric PAA is independent of the basis weight, the type of fiber and any other usual additives, for example fillers.
- amphoteric poly (meth) acrylamides used in the examples are composed as follows:
- PAA I is a copolymeric polyacrylamide with 15 mol% dimethylaminoethyl acrylate, quaternized with dimethyl sulfate, which contains different proportions of acrylic acid and sodium acrylate according to the breakdown below: PAA Ia : 2 mole% PAA Ib : 4 mole% PAA Ic : 7 mole% PAA Id : 10 mol%
- PAA II is a copolymeric polyacrylamide with 7 mol% dimethylaminomethyl methacrylate in the form of the sulfuric acid salt, which contains different proportions of acrylic acid and sodium acrylate according to the breakdown below: PAA IIa : 2 mole% PAA IIb : 4 mole% PAA IIc : 7 mole% PAA IId : 10 mol%
- PAA III is a copolymeric polyacrylamide with 10 mol% dimethylaminopropylacrylamide, quaternized with methyl chloride, which contains different proportions of acrylic acid and sodium acrylate according to the breakdown below: PAA IIIa : 2 mole% PAA IIIb : 4 mole% PAA IIIc : 7 mole% PAA IIId : 10 mol%
- PAA IV is a copolymeric polymethacrylamide with 10 mol% diethylaminoethyl acrylate in the form of the hydrochloric acid salt and with 10 mol% methacrylic acid.
- the structural strength was determined in accordance with TAPPI RC 308 with a Scott Bond gap strength tester (Internal Bond Impact Tester Model B).
- the figures in the following tables are mean values from 5 individual measurements.
- the figures in the following tables are mean values from 6 individual measurements.
- Table 5 contains the papers of Examples 1 to 4 produced according to the invention, Table 6 the test results obtained on Comparative Examples 1 to 7.
- test data contained in the tables are mean values from 5 or 6 individual measurements.
- no fluctuations were observed which reached or even exceeded ⁇ 5% based on the mean.
- the test values were surprisingly constant.
- the fluctuations were in some cases ⁇ 10%, but in no case less than ⁇ 5%.
- the decisive factor for the evaluation of the invention is the high surface quality in connection with a high structural strength.
- the surface quality is expressed in the low number of surfaces, which even with a naturally poor mixture such as Example 3 still reaches a good level.
- the good structural strength corresponds to the high "Scott bond values" in Table 5. Comparable systems from Table 6 are compared. Table 5 test results obtained on Examples 1 to 4 sample Surface area OZ Scott Bond Sc. B.
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Abstract
Description
Die Erfindung betrifft ein Basispapier für wasserfest beschichtete Papierträger für fotografische Schichten sowie ein Verfahren zur Herstellung eines solchen Basispapiers für die Herstellung von Schichtträgern.The invention relates to a base paper for waterproof coated paper supports for photographic layers and a method for producing such a base paper for the production of layer supports.
Es ist bekannt, beidseitig mit hydrophoben Harzschichten überzogenes Papier (Laminat) als Trägermaterial für naß zu entwickelnde fotografische Schichten zu verwenden. Ein solches Trägermaterial besteht in einer verbreiteten Ausführungsform aus einem Basispapier mit auf beiden Oberflächen aufgebrachten Polyolefinharzüberzügen, von denen der den fotografischen Schichten zunächst liegende Überzug üblicherweise wenigstens ein lichtreflektierendes Pigment enthält (beispielsweise Titandioxid).It is known to use paper (laminate) coated on both sides with hydrophobic resin layers as a carrier material for wet-to-develop photographic layers. In a widespread embodiment, such a carrier material consists of a base paper with polyolefin resin coatings applied to both surfaces, of which the coating initially lying on the photographic layers usually contains at least one light-reflecting pigment (for example titanium dioxide).
Ein auf beiden Oberflächen mit wasserundurchlässigen Harzschichten versehenes Papier ist flächig gegen ein Eindringen von Wasser oder wässrigen fotografischen Verarbeitungslösungen geschützt, nicht aber an den offenen Kanten. Dort liegt der Papierkern des Laminates frei. Wässrige Verarbeitungslösungen können daher an den Kanten des Laminates in den Papierkern eindringen und lassen sich durch übliche Waschprozesse nicht rückstandsfrei entfernen.Paper coated with water-impermeable resin layers on both surfaces is protected against the ingress of water or aqueous photographic processing solutions, but not on the open edges. The paper core of the laminate is exposed there. Aqueous processing solutions can therefore penetrate into the paper core at the edges of the laminate and cannot be removed without residue by conventional washing processes.
Um dieses Eindringen von wässrigen Lösungen an den Kanten des Laminates zu verhindern bzw. zu verringern, ist das Basispapier üblicherweise hart geleimt. Als Leimmittel für fotografische Basispapiere sind sowohl reaktive Substanzen, beispielsweise dimerisiertes Alkylketen, als auch nicht reaktive Substanzen wie höhere Fettsäuren bekannt. Reaktive Leimmittel werden üblicherweise unter Mitverwendung eines kationischen Harzes ohne pH-Änderung (neutral) verarbeitet, während nicht reaktive Leimmittel zur Fixierung eines Zusatzes von Aluminiumionen bedürfen und sauer verarbeitet werden. In DOS 32 38 865 wurde darüber hinaus eine Kombination dieser beiden Leimungsverfahren beschrieben, um den Papierkern noch besser gegen ein Eindringen der verschiedenen Bestandteile fotografischer Prozeßlösungen zu schützen.In order to prevent or reduce this penetration of aqueous solutions on the edges of the laminate, the base paper is usually hard-sized. Both reactive substances, for example dimerized alkyl ketene, and non-reactive substances such as higher fatty acids are known as glue for photographic base papers. Reactive sizing agents are usually processed with the use of a cationic resin without a pH change (neutral), while non-reactive sizing agents require an addition of aluminum ions and are processed acidic. DOS 32 38 865 also described a combination of these two sizing processes in order to better prevent the paper core from penetrating to protect the various components of photographic process solutions.
Die hydrophobierend wirkenden Leimungsmittel werden üblicherweise der Fasersuspension beigemischt und durch Zugabe der Hilfsmittel auf der Oberfläche der Fasern abgelagert. Ein solches Hilfsmittel ist im Fall einer sauren Leimung beispielsweise ein Aluminiumsalz, im Fall der Neutralleimung beispielsweise ein kationisches Polyamid-Polyamin-Epichlorhydrin-Harz, das vorwiegend zusammen mit C₁₆-C₁₈-Alkylketendimer zum Einsatz kommt (J. Appl. Photographic Engineering 7. (1981), S.67 - 72). Aber auch andere kationische Substanzen wie kationische Polyacrylamide, kationisierte Stärken oder Polyethylenimine eignen sich in bestimmten Fällen zur Verbesserung der Retention und zur Fixierung von reaktiven Leimungsmitteln im Papierblatt.The sizing agents with a hydrophobic effect are usually mixed into the fiber suspension and deposited on the surface of the fibers by adding the auxiliaries. Such an aid is, for example, an aluminum salt in the case of acidic sizing, for example a cationic polyamide-polyamine-epichlorohydrin resin in the case of neutral sizing, which is mainly used together with C₁₆-C₁₈ alkyl ketene dimer (J. Appl. Photographic Engineering 7. ( 1981), pp.67-72). However, other cationic substances such as cationic polyacrylamides, cationized starches or polyethyleneimines are also suitable in certain cases for improving the retention and for fixing reactive sizing agents in the paper sheet.
Da die Leimungsmittel an der Oberfläche der Zellstofffasern angelagert werden, ist natürlicherweise die Faser-Faser-Bindung in einem geleimten Papier schwächer als in einem nicht geleimten Papier. Deshalb werden in breitem Umfang wasserlösliche Harze verwandt, um die Papierfestigkeit zu verbessern. Solche Harze sind u. a. Polyvinylalkohol, anionisches Polyacrylamid, Guarharz und verschiedene Stärkederivate. DE-OS 32 10 621 beschreibt beispielsweise die Verwendung von anionischem Polyacrylamid zusammen mit kationischer Stärke. Gemäß DE-OS 32 16 840 wird anionisches Polyacrylamid zusammen mit kationischem Polyacrylamid verwendet, und in DE-OS 33 28 463 wird eine Kombination von kationischem Harz mit anionischen Polysaccharidderivaten beschrieben. Der Zusatz dieser verfestigenden Harze dient gleichzeitig dem Zweck, die Verfärbung der Kanten durch Entwickler zu verringern.Since the sizing agents are deposited on the surface of the pulp fibers, the fiber-fiber bond is naturally weaker in a sized paper than in a non-sized paper. Therefore, water-soluble resins are widely used to improve paper strength. Such resins include polyvinyl alcohol, anionic polyacrylamide, guar resin and various starch derivatives. DE-OS 32 10 621 describes, for example, the use of anionic polyacrylamide together with cationic starch. According to DE-OS 32 16 840, anionic polyacrylamide is used together with cationic polyacrylamide, and DE-OS 33 28 463 describes a combination of cationic resin with anionic polysaccharide derivatives. The addition of these hardening resins also serves the purpose of reducing the discoloration of the edges by developers.
Nachteilig an einer harten Leimung des Basispapiers ist jedoch nicht nur der Festigkeitsverlust, wobei der Abfall der Gefügefestigkeit bei Laminaten besonders schädlich ist. Als nachteilig erweist sich vor allem auch, daß durch die Verwendung flockend wirkender Zusätze die Blattbildung (Formation) nachteilig beeinflußt wird. Dies ist darin begründet, daß durch den Zusatz von kationischen Substanzen nicht nur das Leimmittel an der Faser-oberfläche retendiert wird, sondern unvermeidbarerweise und trotz entgegenwirkender maschinentechnischer Maßnahmen verstärkt Faserstoffflocken entstehen, weil die abstoßenden negativen Ladungen der Fasern durch die kationischen Substanzen weitgehend neutralisiert und FaserFaser-Brückenbildungen erleichtert werden. Die Faserstoffflocken haben in Abhängigkeit von den jeweils verwendeten Materialen und von maschinentechnischen Vorrichtungen unterschiedliche Größe und Verteilung im Papierblatt und bestimmen die Homogenität und die Oberflächengüte des Basispapieres. Die im Papierblatt einmal geschaffene Struktur kann auch durch starke Kalandrierung nicht mehr verändert werden.A disadvantage of hard sizing of the base paper is not only the loss of strength, the drop in structural strength of laminates being particularly harmful. It also proves to be disadvantageous that the use of flocculent additives adversely affects the formation of the sheet (formation). This is due to the fact that the addition of cationic substances not only retains the glue on the surface of the fibers, but inevitably and despite countermeasures taken by mechanical engineering, fiber flakes develop because the repulsive negative charges on the fibers are largely neutralized by the cationic substances and fiber -Bridging can be facilitated. The fiber flakes have different sizes and distributions in the paper sheet, depending on the materials used and mechanical engineering devices, and determine the homogeneity and surface quality of the base paper. The structure once created in the paper sheet can no longer be changed even by strong calendering.
Durch die in DE-OS 32 10 621, DE-OS 32 16 840, DE-OS 33 28 463 und schließlich DE-Patent 36 06 806 beschriebene kombinierte Verwendung von kationischen und anionischen wasserlöslichen Harzen wurde nun zwar eine Verringerung des Bädereindringens an den Schnittkanten erreicht, das Problem der Formation, die Oberflächengüte und die Gefügefestigkeit fanden jedoch wenig Beachtung. Diese beiden Punkte wurden lediglich in DE-Patent 36 06 806 in Verbindung mit einer sauren Leimung berücksichtigt.The combined use of cationic and anionic water-soluble resins described in DE-OS 32 10 621, DE-OS 32 16 840, DE-OS 33 28 463 and finally DE-Patent 36 06 806 has resulted in a reduction in bath penetration at the cut edges achieved, the problem of the formation, the surface quality and the structural strength received little attention. These two points were only taken into account in DE patent 36 06 806 in connection with acid sizing.
In neutral geleimten Papieren bewirkt die kombinierte Verwendung von anionischen und kationischen Harzen regelmäßig eine Verschlechterung der Formation. Außerdem geht sehr häufig die Gefügefestigkeit des Papierblattes zurück, weil bei unsauberer Prozeßführung isolierte Flocken aus anionischem und kationischem Harz entstehen, die ohne verfestigenden Effekt im Papiervlies eingelagert sind.In neutral sized papers, the combined use of anionic and cationic resins regularly results in a worsening of the formation. Also goes very often the structural strength of the paper sheet is reduced, because if the process is unclean, isolated flakes of anionic and cationic resin are formed which are embedded in the paper fleece without a solidifying effect.
Zur Umgehung dieser Flockungsprobleme wurde versucht, der Zellstoffsuspension nichtionische Polymere, z. B. Stärke, Polyvinylalkohol oder Guar, zuzusetzen. Dies führte zwar zu einer gewissen Verbesserung der Blattbildung und der Oberflächengüte; die Retention dieser Stoffe war jedoch deutlich schlechter, die Produktionsgeschwindigkeit mußte zurückgenommen werden, und bei Einwirkung der fotografischen Prozeßlösungen erwies sich die innere Festigkeit als erkennbar verringert. Die Kanten des beschichteten Schichtträgers spalteten unter Einwirkung der fotografischen Prozeßlösungen auf.To avoid these flocculation problems, attempts have been made to add nonionic polymers, e.g. B. starch, polyvinyl alcohol or guar. This did lead to a certain improvement in sheet formation and surface quality; however, the retention of these substances was significantly poorer, the production speed had to be reduced, and when the photographic process solutions were used, the internal strength was noticeably reduced. The edges of the coated substrate split under the influence of the photographic process solutions.
Nur bei sauer geleimten Papieren kann bislang gemäß DE-PS 36 06 806 mit einiger Sicherheit eine gute Blattformation und eine ausreichende Oberflächengüte erhalten werden. Eine saure Leimung ist jedoch in vielen Fällen nicht wünschenswert, weil dadurch die Empfindlichkeit fotografischer Schichten erniedrigt werden kann.According to DE-PS 36 06 806, good sheet formation and sufficient surface quality can only be obtained to date with acid-sized papers. Acid sizing is not desirable in many cases because it can decrease the sensitivity of photographic layers.
Aber selbst Papiere gemäß DE-PS 36 06 806 sind noch verbesserungsbedürftig. Nachteilig ist, daß bei Verwendung zweier unterschiedlich geladener Polyacrylamide zwangsläufig zwei Lösestationen und zwei Dosierstationen benötigt werden. Nachteilig ist auch, daß die Dosierung der beiden Komponenten nicht präzise aufeinander abgestimmt werden kann, weil einerseits der elektrochemische Charakter der beiden Polyacrylamidtypen in Lösung nicht stabil ist und andererseits das elektrochemische Verhalten der Fasern ständigen Schwankungen unterliegt. Daraus resultiert, daß die innere Festigkeit (Gefügefestigkeit) und die Blattstruktur Schwankungen unterliegen, die bislang weder zuverlässig erklärbar, noch kontrollierbar sind.But even papers according to DE-PS 36 06 806 are still in need of improvement. It is disadvantageous that when two differently charged polyacrylamides are used, two dissolving stations and two dosing stations are inevitably required. It is also disadvantageous that the dosage of the two components cannot be precisely coordinated with one another because, on the one hand, the electrochemical character of the two types of polyacrylamide is not stable in solution and, on the other hand, the electrochemical behavior of the fibers is subject to constant fluctuations. Out of it the result is that the internal strength (structural strength) and the leaf structure are subject to fluctuations that have so far been neither reliably explainable nor controllable.
Nachteilig am dargelegten Stand der Technik ist schließlich, daß keines der bislang beschriebenen Verfahren sowohl für "neutral" geleimte Papiere mit reaktiven Leimungsmitteln, als auch für "sauer" geleimte Papiere mit nicht reaktiven Leimungsmitteln geeignet ist. Bei einem Versuch der Übertragung z. B. der DE-PS 36 06 806 auf neutral geleimtes Papier treten vielmehr alle Schwächen der DE-OS 32 16 840 wieder zutage, und die beschriebenen nicht erklärbaren Schwankungen bei Gefügefestigkeit, Blattstruktur und Kanteneindringen werden ergänzt durch schlechte Formation und Oberflächengüte.Finally, it is disadvantageous in the state of the art that none of the processes described hitherto is suitable both for "neutral" sized papers with reactive sizing agents and for "acid" sized papers with non-reactive sizing agents. In an attempt to transfer z. B. DE-PS 36 06 806 on neutral sized paper rather all weaknesses of DE-OS 32 16 840 come to light again, and the described unexplainable fluctuations in structural strength, leaf structure and edge penetration are supplemented by poor formation and surface quality.
Es ist daher Aufgabe der vorliegenden Erfindung, ein Basispapier für fotografische Schichtträger zur Verfügung zu stellen, das die beschriebenen Nachteile nicht hat, und insbesondere hinsichtlich Formation, Oberflächengüte und innerer Festigkeit (Gefügefestigkeit) verbessert ist, ohne daß Kanteneindringen und andere wichtige Eigenschaften beeinträchtigt sind.It is therefore an object of the present invention to provide a base paper for photographic supports which does not have the disadvantages described, and in particular is improved with regard to formation, surface quality and internal strength (structural strength) without impairing edge penetration and other important properties.
Eine weitere Aufgabe der Erfindung ist es, ein Verfahren zur Herstellung eines Basispapieres für fotografische Schichtträger vorzuschlagen, nach dem die genannten Werte sowohl bei Anwendung der sog. sauren Leimung als auch der sog. Neutralleimung verbessert sind, und unerwünschte Schwankungen dieser Eigenschaften und des Kanteneindringens vermieden werden. Dabei gelten als unerwünschte Schwankungen auf den Mittelwert bezogene Schwankungen der Oberflächenzahl und das Kanteneindringens von mehr als ± 5 % sowie der inneren Festigkeit von mehr als ± 6 %.Another object of the invention is to propose a method for producing a base paper for photographic supports, according to which the values mentioned are improved both when using so-called acid sizing and so-called neutral sizing, and avoiding undesirable fluctuations in these properties and edge penetration will. Fluctuations in the number of surfaces and edge penetration of more than ± 5% and the internal strength of more than ± 6% are considered to be undesirable fluctuations based on the mean value.
Die Aufgabe wird dadurch gelöst, daß für die Laminatherstellung ein Basispapier verwendet wird, das neben den hydrophobierend wirkenden Leimungsmitteln wenigstens ein kationisches Harz und wenigstens ein amphoteres Polyacrylamid enthält.The object is achieved in that a base paper is used for the production of the laminate which, in addition to the sizing agents having a hydrophobic effect, contains at least one cationic resin and at least one amphoteric polyacrylamide.
Die Erfindung betrifft somit ein Basispapier für harzbeschichtete fotografische Schichtträger sowie ein Verfahren zur Herstellung eines Basispapieres, das wenigstens ein hydrophobierend wirkendes Leimungsmittel, wenigstens ein kationisches Harz und wenigstens ein amphoteres Polyacrylamid enthält.The invention thus relates to a base paper for resin-coated photographic supports and to a method for producing a base paper which contains at least one hydrophobizing sizing agent, at least one cationic resin and at least one amphoteric polyacrylamide.
Hydrophobierend wirkende Leimungsmittel im Sinne der Erfindung sind sowohl reaktive Leimungsmittel wie dimerisierte Alkylketene, epoxidierte Fettsäureamide oder Fettsäureanhydride als auch nichtreaktive Leimungsmittel wie höhere Fettsäuren (z.B. Stearinsäure) und Salze höherer Fettsäuren. Bei Verwendung eines nichtreaktiven Leimungsmittels werden dem Papierstoff außerdem mehrwertige Metallionen in Form eines Salzes wie Aluminiumsulfat oder Natriumaluminat zugesetzt, und der pH-Wert wird auf einen üblichen Wert zwischen pH = 4 und pH = 6 eingestellt. Im Einzelfall können mehrwertige Metallionen auch zusammen mit reaktiven Leimungsmitteln eingesetzt werden.For the purposes of the invention, hydrophobic sizing agents are both reactive sizing agents such as dimerized alkylketenes, epoxidized fatty acid amides or fatty acid anhydrides and non-reactive sizing agents such as higher fatty acids (e.g. stearic acid) and salts of higher fatty acids. When using a non-reactive sizing agent, polyvalent metal ions in the form of a salt such as aluminum sulfate or sodium aluminate are also added to the paper stock, and the pH is adjusted to a customary value between pH = 4 and pH = 6. In individual cases, polyvalent metal ions can also be used together with reactive sizing agents.
Ein besonders bevorzugtes dimerisiertes Alkylketen besteht zu wenigstens 50 % aus Behenylketen oder einem anderen Alkylketen mit mehr als 18 C-Atomen im Alkylrest. Der Kohlenwasserstoffrest des Ketens kann aber auch Ringstrukturen oder C=C-Doppelbindungen enthalten.A particularly preferred dimerized alkyl ketene consists of at least 50% behenyl ketene or another alkyl ketene with more than 18 carbon atoms in the alkyl radical. The hydrocarbon residue of ketene can also contain ring structures or C = C double bonds.
In weiteren Ausgestaltungsformen der Erfindung sind zwei oder mehr hydrophobierende Leimungsmittel im Papier enthalten. Dabei können reaktive mit nichtreaktiven Lei mungsmitteln kombiniert werden. Eine bevorzugte Kombination ist beispielsweise eine Kombination aus Alkylketendimer und Fettsäure, aber auch eine Kombination aus epoxidiertem Fettsäureamid und Fettsäure ist im Rahmen der Erfindung möglich.In further embodiments of the invention, two or more hydrophobizing sizing agents are contained in the paper. Thereby reactive with non-reactive Lei be combined. A preferred combination is, for example, a combination of alkyl ketene dimer and fatty acid, but a combination of epoxidized fatty acid amide and fatty acid is also possible within the scope of the invention.
Ein kationisches Harz ist jedes in der Papierherstellung als Naßfestmittel gebräuchliche Harz mit kationischen Gruppen. Solche Harze dienen üblicherweise zur Naßverfestigung und zur Retendierung von reaktiven Leimungsmitteln. Sie werden gemäß der Erfindung jedoch sowohl in Kombination mit reaktiven als auch mit nichtreaktiven Leimungsmitteln eingesetzt. In einer bevorzugten Ausführungsform ist das kationische Harz ein mit Epichlorhydrin modifiziertes Polyamin- oder Polyamidaminharz. Andere geeignete Harze sind Harnstoff/Formaldehydharze, Melamin/Formaldehydharze, Polyethylenimine und Polyethyleniminderivate.A cationic resin is any resin with cationic groups commonly used in papermaking as a wet strength agent. Such resins are usually used for wet strengthening and for the retention of reactive sizing agents. According to the invention, however, they are used both in combination with reactive and with non-reactive sizing agents. In a preferred embodiment, the cationic resin is an epichlorohydrin modified polyamine or polyamide amine resin. Other suitable resins are urea / formaldehyde resins, melamine / formaldehyde resins, polyethyleneimines and polyethyleneimine derivatives.
Die für den Erfindungserfolg maßgebliche dritte Komponente, das amphotere Polyacrylamid, ist ein Polyacrylamid, das sowohl anionische Gruppen als auch kationische Gruppen im Makromolekül enthält. Bei den anionischen Gruppen handelt es sich um Carboxyl- bzw. Alkalicarboxylat-Gruppen. Die kationischen Gruppen können beliebige kationische Gruppen sein. Bevorzugte kationische Gruppen sind jedoch quaternierte oder protonierte Alkalyaminoalkylen(meth)acrylat- oder Alkylaminoalkylen(meth)acrylamid-Gruppen, wobei eine Quaternierung vorzugsweise mit Dimethylsulfat oder Methylchlorid erfolgt und Salze der protonierten Form vorzugsweise schwefelsaure oder salzsaure Salze sind.The third component relevant to the success of the invention, the amphoteric polyacrylamide, is a polyacrylamide which contains both anionic groups and cationic groups in the macromolecule. The anionic groups are carboxyl or alkali carboxylate groups. The cationic groups can be any cationic groups. However, preferred cationic groups are quaternized or protonated alkalyaminoalkylene (meth) acrylate or alkylaminoalkylene (meth) acrylamide groups, with quaternization preferably taking place with dimethyl sulfate or methyl chloride and salts of the protonated form preferably being sulfuric or hydrochloric acid salts.
Die Einführung der kationischen Gruppierungen in ein Poly(meth)acrylamid geschieht in der Regel auf dem Wege einer Copolymerisation in Gegenwart entsprechender katio nischer Monomere, beispielsweise Dialkylaminoalkylen(meth)acrylat oder Dialkylaminoalkylen(meth)acrylamid in Form saurer Salze oder in quarternierter Form. Ein geeignetes kationisches Comonomer ist auch Dimethyldiallylammoniumchlorid. Kationische Gruppen können aber auch durch Umsetzung von Polyacrylamid nach Mannich oder Hoffmann oder durch Transaminierung mit Polyamin gebildet werden.The introduction of the cationic groupings into a poly (meth) acrylamide is usually carried out by copolymerization in the presence of the corresponding katio African monomers, for example dialkylaminoalkylene (meth) acrylate or dialkylaminoalkylene (meth) acrylamide in the form of acid salts or in quaternized form. A suitable cationic comonomer is also dimethyldiallylammonium chloride. Cationic groups can also be formed by reacting Mannich or Hoffmann polyacrylamide or by transamination with polyamine.
In ähnlicher Weise sind auch die anionischen Gruppen im amphoteren Polyacrylamid entweder das Ergebnis einer Copolymerisation in Gegenwart von z. B. (Meth)acrylsäure bzw. deren Salzen oder das Ergebnis einer Hydrolyse von Acrylamidgruppen oder copolymerisierten (Meth)acrylsäureestern.Similarly, the anionic groups in the amphoteric polyacrylamide are either the result of a copolymerization in the presence of e.g. B. (meth) acrylic acid or its salts or the result of hydrolysis of acrylamide groups or copolymerized (meth) acrylic acid esters.
Das Molekulargewicht des amphoteren Polyacrylamids liegt im Bereich von 100.000 bis 2.000.000, vorzugsweise zwischen 500.000 und 1 .500.000.The molecular weight of the amphoteric polyacrylamide is in the range from 100,000 to 2,000,000, preferably between 500,000 and 1,500,000.
Das Polyacrylamid (PAA) ist ein modifiziertes Polyacrylamid oder Polymethacrylamid, in dem das molare Verhältnis der Amidkomponente zur Summe der anionischen und kationischen Gruppen vorzugsweise im Bereich von 60 : 40 bis 95 : 5 liegt. Das Verhältnis der Zahl der kationischen Gruppen zur Zahl der anionischen Gruppen liegt zwischen 10 : 1 und 1 : 2. Das zum Einsatz kommende Poly(meth)acrylamid kann bis zu 10 Mol% eines vierten Comonomers (z. B. Acrylsäureester, Vinylester o. a.) enthalten. Die gemäß der Erfindung zum Einsatz kommende Menge beträgt 0,3 - 3 Gew.-% bezogen auf den Faserstoff.The polyacrylamide (PAA) is a modified polyacrylamide or polymethacrylamide in which the molar ratio of the amide component to the sum of the anionic and cationic groups is preferably in the range from 60:40 to 95: 5. The ratio of the number of cationic groups to the number of anionic groups is between 10: 1 and 1: 2. The poly (meth) acrylamide used can contain up to 10 mol% of a fourth comonomer (e.g. acrylic acid ester, vinyl ester or the like) contain. The amount used according to the invention is 0.3-3% by weight, based on the fiber material.
Überraschenderweise ergab sich, daß bei dem erfindungsgemäßen Zusatz der amphoteren Polyacrylamide zur Zellstoffsuspension die durch das kationische Harz verursach te Flockung deutlich vermindert ist oder gar ganz ausbleibt. Dieser Effekt zeigt sich sogar dann noch, wenn zusätzlich kleinere Mengen anionischer Verfestigungsmittel in die Papiermasse gegeben werden.Surprisingly, it was found that when the amphoteric polyacrylamides were added to the pulp suspension according to the invention, this was caused by the cationic resin te flocculation is significantly reduced or even completely absent. This effect can be seen even when small amounts of anionic strengthening agents are added to the paper pulp.
Entgegen der Befürchtung verstärkt sich bei erfindungsgemäßer Arbeitsweise auch nicht das Kanteneindringen der fotografischen Prozeßlösungen, und das bei nichtionischen Zusatzstoffen beobachtete Aufspalten der Kanten in fotografischen Prozeßlösungen trat nicht auf.Contrary to fear, the edge penetration of the photographic process solutions does not increase when the method of the invention is used, and the splitting of the edges in photographic process solutions observed with nonionic additives did not occur.
Wider Erwarten ist die Entwässerungsgeschwindigkeit nicht verschlechtert, und die entscheidenden Festigkeitswerte sind überraschenderweise besser als bei Verwendung von Kombinationen aus anionischen und kationischen Polyacrylamiden. Von besonderem Vorteil ist schließlich, daß die beschriebenen guten Ergebnisse mit kleinen Unterschieden sowohl bei neutral geleimten als auch bei sauer geleimten Papieren erhalten werden.Contrary to expectations, the drainage rate has not deteriorated and the decisive strength values are surprisingly better than when using combinations of anionic and cationic polyacrylamides. Finally, it is of particular advantage that the good results described are obtained with small differences both with neutral-sized and with acid-sized papers.
Erfindungsgemäß geleimte und verfestigte Papiere können alle sonst noch üblichen Papier-Zusatzstoffe wie Pigmente, Farbstoffe, Füllstoffe, optische Aufheller, Antioxidantien oder Anteile synthetischen Fasermaterials enthalten, ohne daß die erfindungsgemäßen Vorteile verloren gehen.Papers sized and strengthened according to the invention can contain all other usual paper additives such as pigments, dyes, fillers, optical brighteners, antioxidants or portions of synthetic fiber material without the advantages according to the invention being lost.
Im Rahmen des erfindungsgemäßen Verfahrens können die verschiedenen Komponenten in unterschiedlicher Reihenfolge und an verschiedenen dem Papierhersteller bekannten Stellen der Zellstoffsuspension zugefügt werden. Üblicherweise werden Fettsäure, Fettsäureanhydride und Aluminiumverbindungen unmittelbar nach der Mahlung der Zellstoffasern zugesetzt, während reaktive Leimmittel der Zellstoffsuspension relativ kurz vor der Zuführung zur Papiermaschine zudosiert werden.In the context of the method according to the invention, the various components can be added to the pulp suspension in a different order and at different locations known to the paper manufacturer. Fatty acid, fatty acid anhydrides and aluminum compounds are usually added immediately after the pulp fibers have been ground, while reactive sizing agents are added to the pulp suspension relatively shortly before being fed to the paper machine.
Das amphotere Polyacrylamid kann im Ablauf der Papierherstellung sowohl dem sog. Dickstoff als auch dem sog. Dünnstoff zugesetzt werden. Dabei kann die Reihenfolge der Zugabe der drei im Rahmen der Erfindung wichtigen Komponenten unterschiedlich sein. Jede Reihenfolge ist im Prinzip möglich. Im Hinblick auf die Erzielung optimaler Ergebnisse wird bei einer bevorzugten Ausführungsform der Erfindung das amphotere Polyacrylamid in der Reihenfolge vor dem kationischen Harz in die Faserstoffsuspension gemischt. Ansonsten gelten die dem Fachmann bekannten papiermacherischen Regeln.The amphoteric polyacrylamide can be added to both the so-called thick stock and the so-called thin stock in the course of the paper production. The order of addition of the three components important in the context of the invention can be different. In principle, any order is possible. In order to achieve optimal results, in a preferred embodiment of the invention, the amphoteric polyacrylamide is mixed into the fiber suspension in the order before the cationic resin. Otherwise, the paper-making rules known to the person skilled in the art apply.
Der erfinderische Gedanke wird an Hand der nachfolgenden Beispiele erläutert.The inventive idea is explained using the examples below.
Eine Mischung aus 90 Gew.-% Laubholz-Sulfatzellstoff und 10 Gew.-% Nadelholz-Sulfatzellstoff wurde bei einer Stoffdichte von 4 % bis zu einem Mahlgrad von 35 °SR gemahlen. Der Zellstoffsuspension wurden dann Leimungsmittel, amphoteres Polyacrylamid (PAA), kationisches Harz und Hilfsstoffe entsprechend Tabelle 1 zugesetzt und aus den auf etwa 1,2 Gew.-% verdünnten Suspensionen in bekannter Weise ca. 175 g/m² schwere Basispapiere gefertigt. Die Papiere wurden in gleichfalls bekannter Weise mit einer Lösung oberflächengeleimt, die 52 g/l oxidierte Stärke, 20 g/l NaCl und 1 g/l Weißtöner enthielt, und in-line geglättet.
Entsprechend Beispiel 1 wurden als Vergleiche die Proben 1.6 bis 1.8 ohne amphoteres PAA gefertigt mit den Abweichungen
Analog Beispiel 1 wurden ca. 175 g/m² schwere Basispapiere mit den in Tabelle 2 aufgeführten Zutaten hergestellt.
Entsprechend Beispiel 2 wurden die Proben 2.7 und 2.9 ohne amphoteres PAA gefertigt.
Analog Beispiel 1 wurden ca. 175 g/m² schwere Basispapiere mit den in Tabelle 3 angegebenen Zutaten hergestellt.
Entsprechend Beispiel 3.1 wurden die Proben 3.8 und 3.9 sowie entsprechend 3.6 die Proben 3.10 und 3.11 ohne amphoteres Polyacrylamid gefertigt.
Analog Beispiel 1 wurden ca. 175 g/m² schwere Basispapiere mit den in Tabelle 4 angegebenen Zutaten hergestellt.
Entsprechend Beispiel 4 wurden die Proben 4.7 bis 4.9 ohne amphoteres Polyacrylamid gefertigt.
Analog Beispiel 1 wurden zwei Papierproben unter Anwendung der technischen Lehre aus DOS 32 16 841 mit nachstehenden Zutaten gefertigt.
Analog Beispiel 1 wurden Papierproben unter Anwendung der technischen Lehre aus DOS 32 16 840 mit nachstehenden Zutaten gefertigt.
Analog Beispiel 1 wurden Papierproben unter Anwendung der technischen Lehre aus DE-0S 32 10 621 mit nachstehenden Zutaten gefertigt.
Das in den Beispielen aufgeführte Alkylketendimer ist ein Handelsprodukt, das aus einem marktüblichen Gemisch aus Stearinsäure und Palmitinsäure synthetisiert ist, also vorwiegend C₁₆-Alkylreste trägt. In weiteren Versuchen wurde festgestellt, daß die Ergebnisse prinzipiell ähnlich sind, wenn andere Ketendimere zum Einsatz kommen. Besonders gute Ergebnisse hinsichtlich Kanteneindringens und Gefügefestigkeit wurden erhalten, wenn gemäß DE 36 36 79 ein Ketendimer verwendet wird, das weniger als 40 % Kohlenwasserstoffreste mit weniger als 20 C-Atomen enthält. Ein bevorzugtes derartiges Ketendimer ist beispielsweise ein Behenylketendimer.The alkyl ketene dimer listed in the examples is a commercial product which is synthesized from a commercially available mixture of stearic acid and palmitic acid, that is to say predominantly carries C₁₆-alkyl radicals. In further experiments it was found that the results are basically similar when other ketene dimers are used. Particularly good results with regard to edge penetration and structural strength have been obtained if, according to DE 36 36 79, a ketene dimer is used which contains less than 40% hydrocarbon residues with less than 20 C atoms. A preferred such ketene dimer is, for example, a behenyl ketene dimer.
In weiteren Versuchen wurde festgestellt, daß der erfindungsgemäße Effekt nicht auf das den Beispielen zugrundegelegte Flächengewicht des Basispapiers und die angegebenen Zellstofftypen begrenzt ist. Der Effekt eines Zusatzes von amphoterem PAA ist unabhängig vom Flächengewicht, von der Faserart und von eventuellen weiteren üblichen Zusätzen, beispielsweise Füllstoffen.In further experiments, it was found that the effect according to the invention is not limited to the basis weight of the base paper on which the examples are based and the cellulose types indicated. The effect of adding amphoteric PAA is independent of the basis weight, the type of fiber and any other usual additives, for example fillers.
Die in den Beispielen verwendeten amphoteren Poly(meth)acrylamide sind wie folgt zusammengesetzt:The amphoteric poly (meth) acrylamides used in the examples are composed as follows:
PAA I ist ein copolymeres Polyacrylamid mit 15 Mol% Dimethylaminoethylacrylat, mit Dimethylsulfat quaterniert, das gemäß nachstehender Aufschlüsselung unterschiedliche Anteile an Acrylsäure und Natriumacrylat enthält:
PAA II ist ein copolymeres Polyacrylamid mit 7 Mol% Dimethylaminomethylmethacrylat in Form des schwefelsauren Salzes, das gemäß nachstehender Aufschlüsselung unterschiedliche Anteile an Acrylsäure und Natriumacrylat enthält:
PAA III ist ein copolymeres Polyacrylamid mit 10 Mol% Dimethylaminopropylacrylamid, mit Methylchlorid quaterniert, das gemäß nachstehender Aufschlüsselung unterschiedliche Anteile an Acrylsäure und Natriumacrylat enthält:
PAA IV ist copolymeres Polymethacrylamid mit 10 Mol% Diethylaminoethylacrylat in Form des salzsauren Salzes und mit 10 Mol% Methacrylsäure.PAA IV is a copolymeric polymethacrylamide with 10 mol% diethylaminoethyl acrylate in the form of the hydrochloric acid salt and with 10 mol% methacrylic acid.
Von den entsprechend den Beispielen und Vergleichsbeispielen gefertigten Papierproben wurde jeweils ein Teil unbeschichtet belassen und geprüft, ein anderer Teil wurde beidseitig in bekannter Weise mit Polyethylen beschichtet und in dieser Form einer Prüfung unterzogen. Im Rahmen der Erfindung wurden die nachstehend aufgeführten Prüfverfahren zur Bewertung herangezogen.A part of the paper samples produced in accordance with the examples and comparative examples was left uncoated and tested, another part was coated on both sides with polyethylene in a known manner and subjected to a test in this form. In the context of the invention, the test methods listed below were used for the evaluation.
Die Prüfung erfolgte an unbeschichteten Papierproben nach der in DE-OS 34 26 782 beschriebenen Prüfmethode. Die Oberflächenzahl kann nach vorliegenden Feststellungen als Formationsäquivalent gelten. Die Zahlenangaben in den nachfolgenden Tabellen sind jeweils Mittelwerte aus 5 Einzelmessungen.The test was carried out on uncoated paper samples according to the test method described in DE-OS 34 26 782. According to the available findings, the surface number can be regarded as a formation equivalent. The figures in the following tables are mean values from 5 individual measurements.
Die Gefügefestigkeit (innere Festigkeit) wurde nach TAPPI RC 308 mit einem Scott Bond Spaltfestigkeitsprüfer (Internal Bond Impact Tester Model B) bestimmt. Die Zahlenangaben in den nachfolgenden Tabellen sind jeweils Mittelwerte aus 5 Einzelmessungen.The structural strength (internal strength) was determined in accordance with TAPPI RC 308 with a Scott Bond gap strength tester (Internal Bond Impact Tester Model B). The figures in the following tables are mean values from 5 individual measurements.
Die mit Polyethylen beschichteten Papierproben wurden beschnitten und in der erforderlichen Mustergröße für 14 Minuten in ein handelsübliches Color-Entwicklerbad (T = 30 °C) getaucht. Nach Zwischenwässerung, Behandlung mit handelsüblicher Fixierlösung und Endwässerung wurden die Muster getrocknet und mit einer Meßlupe die Eindringtiefe (in mm) der Entwicklerlösung an der Schnittkante gemessen. Die Zone des Entwicklereindringens ist als mehr oder weniger bräunlich verfärbter Randstreifen im Durchlicht zu erkennen. Die Zahlenangaben in den nachfolgenden Tabellen sind jeweils Mittelwerte aus 6 Einzelmessungen.The paper samples coated with polyethylene were trimmed and immersed in the required sample size for 14 minutes in a commercially available color developer bath (T = 30 ° C.). After intermediate rinsing, treatment with a commercially available fixing solution and final rinsing, the samples were dried and the penetration depth (in mm) of the developer solution was measured at the cut edge using a measuring magnifier. The zone of developer intrusion is more than that or less brown discolored margins in transmitted light. The figures in the following tables are mean values from 6 individual measurements.
Routinemäßig wurden ferner Steifigkeit, Reißfestigkeit, Haftung der Polyethylenschichten und fotochemische Eigenschaften geprüft. Die Ergebnisse bewegen sich jedoch im bekannten Rahmen und wurden für die Bewertung der Erfindung nicht herangezogen.Rigidity, tear strength, adhesion of the polyethylene layers and photochemical properties were also routinely tested. However, the results are within the known framework and were not used to evaluate the invention.
Die Ergebnisse der beschriebenen Prüfungen sind in den Tabellen 5 und 6 zusammengestellt. Tabelle 5 beinhaltet die an erfindungsgemäß hergestellten Papieren der Beispiele 1 bis 4, Tabelle 6 die an den Vergleichsbeispielen 1 bis 7 erhaltenen Prüfergebnisse.The results of the tests described are summarized in Tables 5 and 6. Table 5 contains the papers of Examples 1 to 4 produced according to the invention, Table 6 the test results obtained on Comparative Examples 1 to 7.
Die in den Tabellen enthaltenen Prüfdaten sind wie angegeben jeweils Mittelwerte aus 5 bzw. 6 Einzelmessungen. Im Falle der erfindungsgemäßen Beispiele wurden in keinem Fall Schwankungen beobachtet, die bezogen auf den Mittelwert ± 5 % erreichten oder gar überschritten. Selbst bei Messungen an verschiedenen Rollen der erfindungsgemäßen Beispiele waren die Prüfwerte überraschend konstant. Bei den Vergleichsbeispielen lagen die Schwankungen teilweise bei ± 10 %, in keinem Fall jedoch unter ± 5 %.As stated, the test data contained in the tables are mean values from 5 or 6 individual measurements. In the case of the examples according to the invention, no fluctuations were observed which reached or even exceeded ± 5% based on the mean. Even when measured on different rolls of the examples according to the invention, the test values were surprisingly constant. In the comparative examples, the fluctuations were in some cases ± 10%, but in no case less than ± 5%.
Entscheidend für die Bewertung der Erfindung ist jedoch die hohe Oberflächengüte in Verbindung mit einer hohen Gefügefestigkeit. Die Oberflächengüte kommt in der niedrigen Oberflächenzahl zum Ausdruck, die selbst bei einer von Natur schlechten Mischung wie Beispiel 3 noch ein gutes Niveau erreicht. Die gute Gefügefestigkeit entspricht den hohen "Scott-Bond-Werten¨ der Tabelle 5. Es sind jeweils vergleichbare Systeme aus Tabelle 6 gegenüberzustellen.
Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88120390T ATE93977T1 (en) | 1988-02-16 | 1988-12-07 | BASE PAPER FOR PHOTOGRAPHIC COATINGS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3804776 | 1988-02-16 | ||
DE3804776A DE3804776A1 (en) | 1988-02-16 | 1988-02-16 | BASE PAPER FOR PHOTOGRAPHIC LAYER |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0328756A1 true EP0328756A1 (en) | 1989-08-23 |
EP0328756B1 EP0328756B1 (en) | 1993-09-01 |
Family
ID=6347501
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88120390A Expired - Lifetime EP0328756B1 (en) | 1988-02-16 | 1988-12-07 | Base paper for photographic supports |
Country Status (6)
Country | Link |
---|---|
US (1) | US5032226A (en) |
EP (1) | EP0328756B1 (en) |
JP (1) | JP2804064B2 (en) |
AT (1) | ATE93977T1 (en) |
AU (1) | AU612783B2 (en) |
DE (2) | DE3804776A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0415455B1 (en) * | 1989-09-01 | 1996-07-03 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
WO2018046794A1 (en) * | 2016-09-07 | 2018-03-15 | Kemira Oyj | Method for manufacture of paper, board or the like and use of the composition |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3804776A1 (en) | 1988-02-16 | 1989-08-24 | Schoeller F Jun Gmbh Co Kg | BASE PAPER FOR PHOTOGRAPHIC LAYER |
GB9215422D0 (en) * | 1992-07-21 | 1992-09-02 | Hercules Inc | System for sizing paper and cardboard |
JP3093965B2 (en) * | 1994-12-28 | 2000-10-03 | 日本製紙株式会社 | Printing paper and newspaper printing paper with improved water absorption |
AU3913197A (en) * | 1996-08-15 | 1998-03-06 | Hercules Incorporated | Amphoteric polyacrylamides as dry strength additives for paper |
CN1240010A (en) * | 1996-12-04 | 1999-12-29 | 金伯利-克拉克环球有限公司 | Method for making wet strength paper |
US5935383A (en) * | 1996-12-04 | 1999-08-10 | Kimberly-Clark Worldwide, Inc. | Method for improved wet strength paper |
DE69814359T2 (en) * | 1997-02-14 | 2004-03-25 | Bayer Corp. | METHOD AND COMPOSITIONS FOR PAPER PRODUCTION |
US6673205B2 (en) * | 2001-05-10 | 2004-01-06 | Fort James Corporation | Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products |
AU2003227212A1 (en) * | 2002-03-28 | 2003-10-13 | Nippon Paper Industries, Co., Ltd. | Bulky paper |
DE10222454B4 (en) * | 2002-05-22 | 2004-04-15 | Felix Schoeller Jr. Foto- Und Spezialpapiere Gmbh & Co. Kg | Ink-jet recording sheet with improved ozone resistance |
DE10309705B4 (en) * | 2003-03-06 | 2005-03-24 | Felix Schoeller Jr. Foto- Und Spezialpapiere Gmbh & Co. Kg | Ink-jet recording sheet with improved ozone and light stability |
JP4688014B2 (en) * | 2003-06-30 | 2011-05-25 | 荒川化学工業株式会社 | Paper additive and paper using the paper additive |
US7732525B2 (en) * | 2004-05-20 | 2010-06-08 | Ciba Specialty Chemicals Water Treatments Limited | Polymers for paper and paperboard coatings |
FI126610B (en) | 2015-01-27 | 2017-03-15 | Kemira Oyj | Particulate polymer product and its use |
CA3102917A1 (en) | 2018-07-12 | 2020-01-16 | Kemira Oyj | Method for manufacturing multi-layered fibrous web and multi-layered fibrous web |
Citations (4)
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DE3216840A1 (en) * | 1981-05-29 | 1982-12-16 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | WATER RESISTANT PHOTOGRAPHIC CARRIER |
US4533434A (en) * | 1981-09-11 | 1985-08-06 | Seiko Kagaku Kogyo Co., Ltd. | Process for sizing paper and process for making plasterboard base paper sized thereby |
US4654386A (en) * | 1985-09-04 | 1987-03-31 | Dic-Hercules Chemicals, Inc. | Ketene dimer-acrylamide polymer aqueous dispersion |
DE3606806C1 (en) * | 1986-03-03 | 1987-06-25 | Schoeller F Jun Gmbh Co Kg | Waterproof photographic paper carrier |
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US2884058A (en) * | 1955-05-02 | 1959-04-28 | American Cyanamid Co | Cellulose web of improved dry strength containing a polymer comprising carboxylic groups, amide groups, and quaternary ammonium groups and method for producing same |
JPS6017103B2 (en) * | 1981-03-24 | 1985-05-01 | 三菱製紙株式会社 | Support for photographic paper |
JPS57185432A (en) * | 1981-05-11 | 1982-11-15 | Fuji Photo Film Co Ltd | Support for use in photographic paper |
JPS5845730A (en) * | 1981-09-11 | 1983-03-17 | Seiko Kagaku Kogyo Co Ltd | Aqueous dispersion of substituted succinic anhydride, preparation thereof and papermaking sizing agent comprising said aqueous dispersion of said substituted succinic anhydride |
JPS5868744A (en) * | 1981-10-21 | 1983-04-23 | Fuji Photo Film Co Ltd | Backing for photographic paper |
JPS5895729A (en) * | 1981-12-03 | 1983-06-07 | Mitsubishi Paper Mills Ltd | Photographic material |
DE3328463A1 (en) * | 1983-08-06 | 1985-02-21 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | PHOTOGRAPHIC PAPER CARRIER |
JPH0678463B2 (en) * | 1984-06-04 | 1994-10-05 | 日本ピー・エム・シー株式会社 | Ketene dimer type aqueous dispersion |
DE3804776A1 (en) | 1988-02-16 | 1989-08-24 | Schoeller F Jun Gmbh Co Kg | BASE PAPER FOR PHOTOGRAPHIC LAYER |
-
1988
- 1988-02-16 DE DE3804776A patent/DE3804776A1/en active Granted
- 1988-12-07 AT AT88120390T patent/ATE93977T1/en not_active IP Right Cessation
- 1988-12-07 DE DE88120390T patent/DE3883742D1/en not_active Expired - Fee Related
- 1988-12-07 EP EP88120390A patent/EP0328756B1/en not_active Expired - Lifetime
-
1989
- 1989-02-08 AU AU29754/89A patent/AU612783B2/en not_active Ceased
- 1989-02-10 US US07/310,362 patent/US5032226A/en not_active Expired - Lifetime
- 1989-02-15 JP JP1033896A patent/JP2804064B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3216840A1 (en) * | 1981-05-29 | 1982-12-16 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | WATER RESISTANT PHOTOGRAPHIC CARRIER |
US4533434A (en) * | 1981-09-11 | 1985-08-06 | Seiko Kagaku Kogyo Co., Ltd. | Process for sizing paper and process for making plasterboard base paper sized thereby |
US4654386A (en) * | 1985-09-04 | 1987-03-31 | Dic-Hercules Chemicals, Inc. | Ketene dimer-acrylamide polymer aqueous dispersion |
DE3606806C1 (en) * | 1986-03-03 | 1987-06-25 | Schoeller F Jun Gmbh Co Kg | Waterproof photographic paper carrier |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0415455B1 (en) * | 1989-09-01 | 1996-07-03 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
WO2018046794A1 (en) * | 2016-09-07 | 2018-03-15 | Kemira Oyj | Method for manufacture of paper, board or the like and use of the composition |
US10787768B2 (en) | 2016-09-07 | 2020-09-29 | Kemira Oyj | Method for manufacture of paper, board or the like and use of the composition |
Also Published As
Publication number | Publication date |
---|---|
DE3804776A1 (en) | 1989-08-24 |
JPH025040A (en) | 1990-01-09 |
US5032226A (en) | 1991-07-16 |
EP0328756B1 (en) | 1993-09-01 |
ATE93977T1 (en) | 1993-09-15 |
DE3804776C2 (en) | 1990-02-01 |
JP2804064B2 (en) | 1998-09-24 |
AU2975489A (en) | 1989-08-17 |
AU612783B2 (en) | 1991-07-18 |
DE3883742D1 (en) | 1993-10-07 |
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