US3911195A - Copy paper - Google Patents

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US3911195A
US3911195A US25887672A US3911195A US 3911195 A US3911195 A US 3911195A US 25887672 A US25887672 A US 25887672A US 3911195 A US3911195 A US 3911195A
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sheet
layer
paper
particles
polymer
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Joachim Schmidt
Martin Unruh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/10—Duplicating or marking methods; Sheet materials for use therein by using carbon paper or the like
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y10T428/249995—Constituent is in liquid form
    • Y10T428/249996—Ink in pores
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates to a multicopy paper in the form of sheets or tape for producing copies without the necessity of using carbon paper, and to a method of manufacturing the same.
  • Multicopy papers comprising a layer of colour pigment having an incomplete internal bond, which can be transferred from one paper to the surface of another paper, which is to carry the final copy, by application of strong local pressure, in particular by means of writing instruments, such papers utilising wax-like connecting materials. It is also known to produce the layer of colour pigments from powder particles of a synthetic resin, especially a resin based on polyvinyl chloride, which particles are locally combined at their points of contact.
  • multicopy paper of this type can be produced by distributing the synthetic resin powder particles, which have either been dyed in the mass or covered with colour pigment on their surface, in a liquid medium which causes them to swell, applying the homogeneous swelled mixture in the form of a layer on a support in a known manner and evaporating the liquid medium to produce a layer comprising the synthetic resin powder particles which are joined together at their areas of contact.
  • a covering layer of wax or some wax-like composition to this layer.
  • multi-copy paper of this type already produces reasonably acceptable results as regards resistance to smudging and the quality of the copies, it is still desirable to obtain further improvements in multicopy paper, especially in the case of such paper for use in data processing machines and modern addressing machines.
  • data processing machines operate with a low type touch pressure (line printing rods) because they function with only a slight rolling pressure on account of their high output of line printing per hour, which may nowadays be as much as 30,000 to 90,000 lines per hour.
  • a sheet of paper suitable for use as a multi-copy paper which sheet of paper comprises a support layer and a substantially uniform layer of finely particulate mutually adherent particles of a vinyl chloride polymer, the polymer having been produced by emulsion polymerisation, containing from 0.01 to 4.0 percent by weight of emulsifier, having a K-value in the range from to 80, the particles having an average size of 50p or less and having sieve residues, under standard DIN conditions, of not more than 34% by weight.
  • a sheet of paper suitable for use as a multi-copy paper which sheet of paper comprises a support layer and a substantially uniform donor layer of finely particulate mutually adherent particles of a vinyl chloride polymer, the polymer having been dyed prior to formation of the sheet.
  • the polymer is a homopolymer.
  • a process for producing a sheet of paper in accordance with the first aspect of the present invention comprises distributing finely particulate particles of a vinyl chloride polymer in a volatile organic liquid so that the particles swell and applying the resulting homogeneous distribution of swelled particles as a layer on a support layer, either directly or after suitable dilution, the layer being dried by evaporation of the organic liquid so as to produce a substantially uniform layer of finely dispersed mutually adherent particles.
  • a process for producing a sheet of paper in accordance with the advantageous embodiment of the first aspect of the present invention, which process comprises distributing finely particulate particles of vinyl chloride polymer in a volatile organic liquid, in which there is dissolved a dye or a material capable of dying. the polymer, so that the particles swell and applying the resulting homogeneous distribution of swelled particles as a layer donor on a support layer, either directly or after suitable dilution, the layer being dried by evaporation of the organic liquid so as to produce a substantially uniform layer of finely dispersed mutually adherent particles.
  • the polymer is a homopolymer.
  • the present invention also provides a multi-copy set of paper, which comprises a plurality of sheets of paper in accordance with either of the aspect of the present invention, with at least one coloured vinyl chloride polymer (preferably homopolymer) layer on a sheet arranged for transfer to another sheet on application of local pressure to the set of paper.
  • a multi-copy set of paper which comprises a plurality of sheets of paper in accordance with either of the aspect of the present invention, with at least one coloured vinyl chloride polymer (preferably homopolymer) layer on a sheet arranged for transfer to another sheet on application of local pressure to the set of paper.
  • Copying papers of the type proposed are provided with a donor layer and/or a receptor layer.
  • Papers having merely a donor or receptor layer are known as contact papers (C-papers) which copy on treated or untreated substrates, whereas papers having both a donor layer and a receptor layer are known as self copying papers (S-papers).
  • the layers are normally ap plied by a conventional doctor blade technique.
  • the receptor layer preferably comprises an optionally modified homopolymer or copolymer of ethylene.
  • the layer of vinyl chloride polymer preferably homopolymer, which may contain colour pigment or be dyed, is uniform in material and comprises a pure vinyl chloride polymer so that the additives customarily used in many of the known duplicating and copying papers,
  • wax for example wax, oil, fillers, thickeners and the like, may be omitted.
  • the term uniform in material means that apart from any colouring material present, the layer of vinyl chloride polymer comprises only one uniform material.
  • the material will be a product of a known emulsion polymerisation process of monomeric vinyl chloride, using conventional emulsifiers.
  • the PVDC/PVC copolymers such as GEONZOZ (The word Get-in is a Trade Mark).
  • the papers according to the invention may contain a very low proportion of colouring material.
  • the paper according to the invention differs from most of the known duplicating papers in that the substance transmitted in the writing process consists mainly of particles of synthetic resin powder which have a soft, ductile character, in other words, synthetic resin, and not mainly colour pigment particles.
  • the donor layer preferably comprises from about 75 to about l% by weight of homopolymer particles.
  • the colour pigment content, if present, is preferably not more than about by weight.
  • cationic dyes 1 cationic dyes 2 anionic dyes 3 metal complex dyes 4 nonionic dyes particularly cationic dyes as for example, basic dyes or in particular the free colour bases for example, of the dior tri-arylmethane, phenazine, keonimine, azodyes, etc., types at extremely low colour material concentra tions, extraordinarily intensive adherent and bright colouring of the polymer particles are obtained.
  • the dye is fixed to the PVC- particles so firmly that, with volatile organic solvents, it is dissolved out in such small quantities that free dye can scarcely be present, if at all.
  • Basic dyes contain in the dye molecule active, basic NH groups in a free or substituted condition.
  • this partial flocculating process it is possible to avoid the coating mixture going or colouring through as the flocculated dye particles are as known filtered by the paper fibres. It should be noted that according to this partial flocculating process, especially in organic solvents, one generally succeeds in obtaining insoluble elements in situ during the mixing process and, for example, to colour the PVC powder particles on their surface with extremely fine dye flocculation. Of course, this partial flocculating process is not limited to PVC powder particles.
  • dye bases dissolved in organic solvents not only colour the polymer powder particles intensively but also the paper. This is in connection with the acid content of a normal coating paper. It is known that. for example, dye bases such as tri arylmethane under the influence of acids produce dye salts intensively coloured and soluble.
  • Another feature of the present invention lies in the use of special vinyl chloride polymer material for the donor layer which may or may not contain colour pigment.
  • PVC powders obtainable commercially are polymers prepared in a known manner by emulsion, suspension or mass polymerisation. The most important properties of these known pure vinyl chloride polymers are laid down in the Standards Specification Sheet DIN 7746 of the association of Standards for Synthetic Resins of the German Standards Association (Distributors: Beuth-Vertrieb GmbH of Berlin and Cologne).
  • PVC powders containing emulsifiers of the type obtained by the emulsion polymerisation process are suitable for the production of the paper according to the invention, especially, in the form of PVC pastes or the PVC powders suitable for this purpose.
  • PVC powder containing emulsifier which has been selected in accordance with these factors is available commercially, it has hitherto only been used to a minor extent and has not been known for the purpose described here.
  • a PVC material which still contains, as residue from the emulsion polymerisation process, from 0.01 to 4.0% by weight of the emulsifier used in the process.
  • the amount of emulsifier should preferably be from 0. l to 2.0% by weight.
  • the emulsifier present surprisingly, has the effect of producing characters with very sharp contours, especially when using pigments/dyes which are liable to bleed (soluble or partly soluble), these dyes dissolving in the minute amounts of the emulsifier present.
  • the K- value of the PVC powder used is also important.
  • the PVC containing emulsifier used for producing the paper should have a K-value in the range of from 60 to 80 and preferably about 70. Determination of the K- value was carried out in accordance with the specifications of DIN 53 726 of the association for Standards of Synthetic Resins in the German Standards Association (Distributors: Benth-Vertrieb GmbH of Berlin and Cologne).
  • the particle size of the particles should be below about 50p. and preferably about i014. if the desired results are to be achieved.
  • the sieve residue according to the general DIN specification should be such that it can be classified as 3 or less, that is the sieve residue should be not more than about 34% by weight under the conditions indicated.
  • the pastes of swollen PVC powder or application mixtures used preferably have a PVC solids content of up to about 30% by weight, especially 5 to 20% by weight, and optionally contain up to about 25% of colour pigment, based on the PVC content.
  • the layer produced in this way consists of particles of synthetic resin powder which have been joined together at their surfaces of contact by swelling, this union of particles having been achieved without the aid of an additive or adhesive.
  • the layer therefore has a pseudo film structure and has an infinite number of potential points of breakage. In contrast to similar layers in some of the known duplicating papers, it is not brittle but elastic.
  • the liquid or volatile organic swelling and distributing medium used may be either a chemically uniform substance or mixtures of such substances which have a suitably low dissolving power for the polymer used for the donor layer, or a mixture of a solvent and a diluent which suitably reduces the dissolving power of the solvent. It is essential that formation of the layer should not be based on the known principle of flocculation precipitation of a dissolved substance by a non-solvent but that genuine swelling of the PVC material followed by drying of the synthetic resin powder particles which have only undergone swelling should take place.
  • the PVC particles used are subjected to swelling and not to gelatinisation.
  • this swelling process it is an important principle that only chemical substances or combinations of swelling agents of the type in which the synthetic resin material is relatively insoluble may be used so that they cannot be regarded as solvents in the real meaning of the word.
  • the effect of the medium does not go beyond the formation of envelopes of solvate round the molecules situated at the surface or in the interspaces of the polymer. Irreversible separation of the individual molecules therefore does not take place.
  • the swelling medium On removal of the swelling medium, the swelled material is restored to the state in which it existed before swelling.
  • the PVC particles can readily be adjusted to a specific degree of swelling by suitable choice of certain organic solvents, and hence the union of PVC powder particles and effciency of copying on the one hand and the resistance to smudging of the copying paper which is free from carbon on the other hand can be regulated.
  • Any number of other organic solvents can be placed in the swelling sequence shown above so that the extent of swelling can be finely graded and consequently it is possible, if desired, to use only one solvent as swelling agent, this solvent frequently being one which has a low or medium swelling action.
  • This very fine adjustment of the degree of swelling is generally achieved by using a combination of solvents which has a low, medium and high swelling action or by mixing these solvents with genuine PVC solvents.
  • the basic solvent used is frequently one which has a low swelling action.
  • the powder After introduction of the PVC powder, the powder swells to form a paste. A small pro portion of a substance which has a medium or high swelling action is then added.
  • the resistance to smudging and the union of particles can be assessed qualitatively, for example by a finger test. lfit is desired to obtain a very high resistance to smudging, the union of PVC particles must be produced with a higher proportion of substances which have a high swelling action or by adding a substance which has an exceptionally high swelling action, for example methyl ethyl ketone.
  • the proportion of substance which has a low swelling action can be varied in the direction of a higher degree of swelling and quantitative proportion.
  • Such solvent combinations of an organic solvent which has a low swelling action with a small quantity of an organic solvent which has a higher swelling action therefore, provides a convenient method of adapting the degree of swelling of the whole system to the particular requirements.
  • the system can be adjusted to a wide variety of highly differentiated degrees of swelling by mixing a low swelling, medium swelling or high swelling agent or a selected mixture of such agents with a true solvent such as tetrahydrofuran in proportions of for example up to 25%.
  • the degree of union between the particles can, therefore, be adjusted as desired by regulating the degree of swelling of the synthetic resin powder particles.
  • Swelling of the synthetic resin powder particles results in a substantial increase in their size and formation of a soft, plastic paste.
  • the swelled synthetic resin particles are very slippery and they readily give up their solvent.
  • pastes of swelled particles comprising a materially uniform substance of pure vinyl chloride polymer particles, that is they are free from the usual additives such as waxes, oils, binders, fillers, thickeners, etc. and yet have a suitable consistency for coating.
  • the paste may be carried out in a suitable manner, for example with a coating knife or a roll coater or by the aniline printing-process, and conveyor rates of about 300 m/minute with applications of, for example, about 0.5 to l .0 g/m of dry substance can be achieved.
  • the soft or deformable swelled PVC particles are apparently deformed or rolled out so that the particles of colour pigment if present are substantially included.
  • the degree of union between the PVC particles can be reduced by this deformation method, whereby even lighter transmission with sharper contours can be achieved and at the same time the paper produced has a higher resistance to smudging.
  • the content of colour pigment can be increased for a given degree of swelling because the deformation method results in high smudge resistance.
  • the coated web of paper may be dried by subjecting it to a blast of air at normal temperature (cold process), using a drying channel of 3 to 4 m in length.
  • a single layer which not only has a very smudge resistant free surface but which is distinguished by its very high mechanical resistance due to its special structure formation can easily be produced according to the invention by the method described above.
  • a layer formed according to the invention can react to the slightest writing pressure or rolling pressure so that the substance of the layer is completely lifted off and the particles are forced out of the ductile layer structure predominantly at the preformed potential points of breakage.
  • the uniform layer of pure vinyl polymer powder produced according to the invention is suitable for use with a large number of different plastic materials varying in their chemical structure as transfer media, it has been found that it is especially advantageous to use, as a receptor layer, a layer consisting of homopolymers or copolymers of a soft polyethylene which is preferably branched and has a low degree of crystallinity.
  • the polymer of the transfer layer may also be applied in the form of swelled particles. These swelled particles may be obtained by heating polyethylene homopolymers or copolymers in volatile organic solvents until true solution takes place and cooling the solution to room temperature.
  • the synthetic resin material used for producing the transfer or receptive layer preferably consists of low molecular weight polyethylene homopolymers or copolymers having a molecular weight of up to about l0,000, preferably up to about 5,000, and a density of from 0.9 to 0.93, preferably from 0.9] to 0.925.
  • a synthetic resin material which has a certain degree of hardness (penetration) to produce a transfer or receptive layer having a penetration according to DIN 51 579 of l to 34 and preferably 1 to 25.
  • polyethylene copolymers which can be introduced as separate component(s) and also as mixing components
  • the material used for the receptor layer comprises oxidized soft polyethylenes which contain carboxyl groups and which can be prepared by oxidizing branched polyethylenes of low crystallinity or by copolymerising ethylene with unsaturated monocarboxylic or dicarboxylic acids.
  • the acid number of these polyalkylenes which contain carboxyl groups is generally from S to I00 and preferably from to 70.
  • these synthetic resin materials are dissolved in organic solvents and applied in a known manner in amounts of about 1 to L5 g of dry substance per in in the case of C-paper and about 0.5 to 1.0 g of dry substance per m in the case of S-paper while the web of paper which is being coated is conveyed at the rate of about 300 m/min, for example.
  • the softfplastic, pasty consistency of the receptor coating can readily be adjusted to the most suitable coating viscosity and solids content by dilution with organic solvents as necessary.
  • the receptor layer based, on the chosen soft polyethylenes according to the invention is perfectly free from gloss and moreover, due to the increase in its specific surface area and to some extent due to its microporous structure, it can generally be printed on perfectly satisfactorily without the use of the special printing paste inks which were hitherto required.
  • the swelled particles of polyethylene used according to the invention not only have a high gliding capacity and only a slight tendency to penetrate the donor layer or substrate but they unite in a special way with the particles of selected types of PVC when brought into contact with them under pressure.
  • the foundation layer comprises uniform mutually adherent particles of pure vinyl chloride polymer powder without the addition of any colour pigment.
  • the layer there is a layer, of polyethylene which contains small amounts of colour pigment or dye of up to about 25% and preferably up to about based on the proportion of polyethylene. It must be regarded as surprising that such duplicating papers generally neither smudge nor show any weakness in the colour of the characters formed.
  • the organic solvents present cause the layer of PVC resin to swell, causing the formation of a slippery surface so that the layers unite superficially in response to the least possible application of layer substance.
  • the small amount of total substance applied in the layers (PVC layer and polyethylene layer), for example amounting to about 2 g/m is compressed by the pressure of type so that the PVC layer and covering layer penetrate in such a way that the colour pigment is uniformly distributed and becomes visible.
  • This particular embodiment of the invention provides excellent self-copying papers which are eminently suitable both for data processing machines and for addressing machines.
  • FIG. 1 shows a cross-sectional view through a paper according to the invention which is adapted to be used as S-paper, and
  • FIG. 2 shows a cross-sectional view through a paper according to the invention which is adapted to be used as C-paper.
  • the S-paper according to the invention comprises a layer 2 on a paper support I.
  • the layer 2 is substantially uniform in material and comprises a pure vinyl chloride polymer which has been prepared by emulsion polymerisation and which has the characteristic properties already defined above.
  • On this foundation layer there is a covering or transfer layer 3 which is composed substantially as optionally modified homopolymers or copolymers of ethylene.
  • the C-paper according to the invention comprises a layer 5 similar to the layer 2 of the S-paper applied to a paper support 4.
  • These C-papers also comprise, as one of their constituents, a receptive material which consists substantially of a suitable support 6 and of a receptor layer 7 applied to the upper surface thereof.
  • the composition of this receptor layer in C-paper may be similar to that of the covering layer 3 in S-paper.
  • ZAPON FAST BLACK RE is an azo dye.
  • the coupling component is -naphthol, with 2-hydroxy-4-nitroaniline. Two molecules of the azo couple with one atom of chromium.
  • ZAPON FAST RED BE is an azo dye.
  • the coupling component is with 2-hydroxy-e-nitro-aniline.
  • Two molecules of the azo couple with one atom of chromium.
  • ZAPON FAST RED 3B is a mixture.
  • the first component is azo dye
  • the coupling component is -naphthol substituted in the 6 and 8 position with SO Na, with 2-hydroxy-5-chloro-aniline. Two molecules of the azo couple with one atom of chromium.
  • the second component is Rhodamine B (possible alternative to ZAPON FAST BLACK RE).
  • VICTORIA BLUE RASE Bis a diphenylamine derivative The diphenylamine is connected to a carbon atom, to which is connected through a double bond, a naphthyl ring in the quinoloid form, with a group attached thereto.
  • the Neozapon equivalents to the Zapon dyes could be used. These are, we understand, of the same general formula as the corresponding Zapon dyes, but are sulphonated or sulphonated and then aminated.
  • Orasol dyes made by CIBA could be used.
  • EXAMPLE 1 I 1 of ethyl acetate (medium swelling action) were introduced into a high speed stirrer system rotating at the rate of between 500 to 2000 revs/min, and 22.0 kg of finely dispersed PVC pastes containing emulsifier were added. The mixture was stirred for about minutes with cooling until a homogeneous paste of swelled particles were obtained. 2.0 kg of carbon black pigment was then added. Stirring was then continued for about 30 minutes accompanied by cooling with water.
  • Coating of the substance on a paper support was then carried out in the usual manner.
  • the basic coating mixture prepared in this way is suitable for the production both of C-paper and S-paper.
  • EXAMPLE 2 The first process described in Example I was repeated but, instead of the swelling agent used therein, a mixture of 60.0 l of xylene (low swelling action) and 40.0 I of ethylene chloride (high swelling action) was used.
  • This swelling system may either be used as a mixture or the high swelling agent may be added separately to the system.
  • the quantity of PVC powder used in this case was 25.0 kg, and 6.0 kg of anthraquinone pigment was used colouring agent.
  • the colour mixture produced in this way is suitable for the production of both C-paper and S-paper.
  • EXAMPLE 3 The first process described in Example l was repeated but, instead of the medium swelling agent, a mixture of 70.0 1 of cyclohexane (low swelling agent) and 30 l of tetrahydrofuran (solvent) was used.
  • the quantity of PVC powder used in this case is 20.0 kg and 1.8 kg of an azo dye was used as colouring agent.
  • the colour mixture produced in this way is suitable for the production of both C-paper and S-paper.
  • EXAMPLE 4 The first process described in Example 1 was re peated but, instead of the medium swelling agent, a mixture of 82.0 1 of xylene (low swelling agent), l6.0 l of ethylene chloride (high swelling agent) and 2.0 l of tetrahydrofuran (solvent) was used.
  • the quantity of PVC powder used in this case was 22.0 kg.
  • 1.8 kg of an azo dye was used as colouring agent.
  • the colouring agents used for producing the duplicating papers according to the invention are advantageously of the type which, owing to the fineness of their particles or their pasty consistency, do not require to be triturated but can be distributed sufficiently finely simply by dispersion in high speed stirrer systems.
  • the colour is provided by dyeing of the vinyl chloride homopolymer.
  • the basic coating mixture may also be prepared by introducing the-PVC powder and colouring agent together into the swelling agent or mixture of swelling agents contained in the reaction vessel and then starting the stirring process.
  • EXAMPLE 5 The procedure described in the second part of Example l was repeated but 1.0 kg of carbon black pigment was added as colouring agent to the given quantities of trichloroethylene and soft polyethylene.
  • EXAMPLE 6 Use of a single organic swelling agent having a specific degree of swelling in association with one or more soluble cationic dyes liters of ethyl acetate (medium swelling agent) were introduced into a fast agitator running at from 500 to 2000 rpm and 22.0 kg of finely particulate emulsifier-containing PVC paste were added. Agitation was continued with simultaneous cooling for about 30 minutes until a uniform swollen paste had evolved. whereafter from 0.1 to 0.7 kg triarylmethane type dye was added.
  • the subsequent step of coating a paper support was conventional.
  • the resulting mixture was of use for the production of C-paper and S-paper.
  • This step possibly with an addition of l 2% based on the finished mixture, obviates the need for the centrifuging step.
  • EXAMPLE 7 Use of a mixture of organic swelling agents having different degrees of swelling in association with one or more cationic dyestuffs
  • the process of Example 6 was repeated except that the medium swelling agent was replaced by a mixture of 60 liters of xylene (low swelling agent) with 40 liters of ethylene chloride (high swelling agent).
  • Example I The process of Example I was repeated; however, after addition of the dye base and subsequent agitation of about 10 minutes, the mixture, instead of being centrifuged, was mixed with about 500-700 g of molybdatophosphoric acid H; [P (M 0 and agitated with cooling for about another to 30 minutes.
  • the addition of the molybdatophosphoric acid can be effected as a crystalline powder or from a solution, for example 0.7 kg of molybdatophosphoric acid in 5.00 liters ethyl acetate.
  • the dye base can be completely flocculated before the addition of the PVC powder ingredient, in which event a larger proportion of molybdatophosphoric acid would be used, for example 1.00 kg of molybdatophosphoric acid in 5.00 liters of ethyl acetate.
  • the subsequent step of coating 3 paper support was conventional.
  • the resulting mixture was of use in the preparation of C-paper and S-paper.
  • the invention is not limited to the Example just mentioned; for instance, the molybdatophosphoric acid addition could be made in a sequence other than theone just mentioned.
  • EXAMPLE 9 Use of a mixture of organic swelling agents having different degrees of swelling in association with one or more soluble cationic dyestuffs having one or more soluble metal complex dyestuffs liters of ethyl acetate were introduced into a fast agitator running at from about 500 to 2,000 rpm and 400 g of metal complex dyestuffs and 300 g of dye base, for example of the triarylmethane type, were added and dissolved with agitation for up to about 15 to 30 minutes. A further 80 liters of toluene were then added. After a short but thorough mixing, 30 kg of finely particulate emulsifier-containing PVC powder were added. Agitation with simultaneous cooling was effected for about 30 minutes until a homogeneous swollen paste had evolved. The subsequent step of coating a paper support was conventional.
  • the resulting mixture was of use in the preparation of C-paper and S-paper.
  • composition for the acceptor coating was made up as follows:-
  • the layers were applied by a conventional doctor blade technique.
  • a computer set according to the invention can yie d at least seven good copies and one wipeproof once-only paper insert (computer paper, once only copy paper, computer paper etc.)
  • a sheet of coated paper suitable for use as a multicopy paper comprising a support layer and a substantially uniform layer of finely particulate mutually adherent particles of a vinyl chloride polymer, the polymer having been produced by emulsion polymerisation, containing from 0.01 to 4.0 percent by weight of emulsifier, having a K-value in the range from 60 to 80, the particles having an average size of 50;; or less and having sieve residues under standard DIN conditions of not more than 34 percent by weight.
  • a sheet of coated paper suitable for use as a multicopy paper which sheet of paper comprising a support layer and a substantially uniform layer of finely particu late mutually adherent particles of a vinyl chloride homopolymer, the homopolymer having been produced by emulsion polymerisation. containing from 0.0l to 4.0 percent by weight of emulsifier, having a K-value in the range from 60 to 80. the particles having an average size of 50p. or less and having sieve residues under standard DIN conditions of not more than 34 per cent by weight.
  • a sheet of coated paper suitable for use as a mu]- ti-copy paper comprising a support layer and a substantially uniform donor layer of finely particulate mutually adherent particles of a polymer, the polymer having been dyed prior to production of the sheet.
  • a sheet of coated paper suitable for use as a multi-copy paper comprising a support layer and a substantially uniform donor layer of finely particulate mutually adherent particles of a vinyl chloride homopolymer, the homopolymer having been dyed prior to production of the sheet.

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US05258876 1970-10-23 1972-06-01 Copy paper Expired - Lifetime US3911195A (en)

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US05/551,499 US4098947A (en) 1970-10-23 1975-02-20 Copy paper

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GB5053070A GB1385179A (en) 1970-10-23 1970-10-23 Multi-copy papers
FR7220507A FR2188507A5 (enrdf_load_stackoverflow) 1970-10-23 1972-06-07

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US (1) US3911195A (enrdf_load_stackoverflow)
AT (1) AT321956B (enrdf_load_stackoverflow)
BE (1) BE794227A (enrdf_load_stackoverflow)
CA (1) CA997224A (enrdf_load_stackoverflow)
CH (1) CH565045A5 (enrdf_load_stackoverflow)
DD (1) DD106981A5 (enrdf_load_stackoverflow)
DK (1) DK133237C (enrdf_load_stackoverflow)
FI (1) FI55695C (enrdf_load_stackoverflow)
FR (1) FR2188507A5 (enrdf_load_stackoverflow)
GB (1) GB1385179A (enrdf_load_stackoverflow)
LU (1) LU65473A1 (enrdf_load_stackoverflow)
NL (1) NL7207337A (enrdf_load_stackoverflow)
SE (1) SE398323B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299411A (en) * 1978-12-29 1981-11-10 Appleton Papers Inc. Pressure-sensitive record material
US4593935A (en) * 1983-09-16 1986-06-10 Burroughs Corporation Conditionally self-copying stationery
US5689426A (en) * 1995-05-30 1997-11-18 Matthias D. Kemeny Computer-controlled master reproducer for depositing a master reproduction on a substrate, method for depositing the same, and master reproduction

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711375A (en) * 1951-08-24 1955-06-21 Ncr Co Pressure sensitive manifold sheet
US2976182A (en) * 1957-12-10 1961-03-21 Eastman Kodak Co Elastomeric vapor-permeable films and coatings
US3311582A (en) * 1964-06-24 1967-03-28 Rohm & Haas Delustering compositions and method of delustering fabrics
US3625736A (en) * 1967-10-27 1971-12-07 Fuji Photo Film Co Ltd Pressure-sensitive copying unit containing granular resinous material and method of making
US3779800A (en) * 1968-05-27 1973-12-18 Dow Chemical Co Coatings containing plastic pigments

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711375A (en) * 1951-08-24 1955-06-21 Ncr Co Pressure sensitive manifold sheet
US2976182A (en) * 1957-12-10 1961-03-21 Eastman Kodak Co Elastomeric vapor-permeable films and coatings
US3311582A (en) * 1964-06-24 1967-03-28 Rohm & Haas Delustering compositions and method of delustering fabrics
US3625736A (en) * 1967-10-27 1971-12-07 Fuji Photo Film Co Ltd Pressure-sensitive copying unit containing granular resinous material and method of making
US3779800A (en) * 1968-05-27 1973-12-18 Dow Chemical Co Coatings containing plastic pigments

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299411A (en) * 1978-12-29 1981-11-10 Appleton Papers Inc. Pressure-sensitive record material
US4593935A (en) * 1983-09-16 1986-06-10 Burroughs Corporation Conditionally self-copying stationery
US5689426A (en) * 1995-05-30 1997-11-18 Matthias D. Kemeny Computer-controlled master reproducer for depositing a master reproduction on a substrate, method for depositing the same, and master reproduction
US5890798A (en) * 1995-05-30 1999-04-06 Advanced Electro Mechanical, L.L.C. Computer-controlled master reproducer for depositing a master reproduction on a substrate, method for depositing the same, and master reproduction

Also Published As

Publication number Publication date
CA997224A (en) 1976-09-21
FI55695B (fi) 1979-05-31
SE398323B (sv) 1977-12-19
CH565045A5 (enrdf_load_stackoverflow) 1975-08-15
DD106981A5 (enrdf_load_stackoverflow) 1974-07-12
DE2302021A1 (de) 1973-08-02
BE794227A (fr) 1973-07-18
AT321956B (de) 1975-04-25
DE2302021B2 (de) 1976-08-12
GB1385179A (en) 1975-02-26
DK133237C (da) 1976-10-11
FR2188507A5 (enrdf_load_stackoverflow) 1974-01-18
DK133237B (da) 1976-04-12
LU65473A1 (enrdf_load_stackoverflow) 1973-07-06
FI55695C (fi) 1979-09-10
NL7207337A (enrdf_load_stackoverflow) 1973-07-24

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