JPS58136484A - Copying paper coated partially - Google Patents

Abstract

1. Process for the production of pressure-sensitive duplicating paper containing a paper substrate, the surface of which is partly coated with a dye-producing layer of a microencapsulated solution of a dye former in an organic solvent, characterized in that the water-face microcapsules provided with a meltable coating or water-face mixtures of a finely divided meltable powder with the microcapsule powders are electrostatically applied to a paper substrate and then fixed by heat treatment.

Description

[Detailed description of the invention]

The present invention relates to a partially coated copy paper and a method for making a first copy paper in which microcapsules with a fusible coating are electrostatically deposited onto a paper substrate and then fixed. @Ruru. The sensitive copying paper preferably consists of two or more sheets loosely placed on top of each other, and in each case the top sheet contains on its back a feed material 1 to 1, and in each case the bottom sheet contains Contains a receptor layer on top. That is, in each case the feeder layer and the receiver layer are in contact with each other. The feeder layer contains microcapsules whose core substance is a solution of a dye-former (dy-formar) in an organic solvent, and the receiver layer spreads the dye-former (d-!-). Contains a substance that causes a gap) to form a dye. During recording, the capsule ruptures under the high pressure of the recording device and the core material emerges onto the receiver layer, so that a copy is produced. The receiver layer usually contains binders and pigments, as well as active absorbents such as kaolin, athanolite, montmorillonite, etc.
, bentonite, acid clay or phenolic resin, t-
Contains. Dyes, such as those that are acid-activable on the hull layer, and acid-reactive components can be used in the receiver layer. Another method of developing these photosensitive copying papers is the 6-component 1 photocopying paper, in which one side of each sheet of paper is simultaneously coated with a dye precursor, generally micro-coated. It is available in capsule form. For example, when pressure is applied by a tie writer or other recording device, the capsule containing the dye precursor ruptures, and the dye precursor reacts with the vehicle around it (U.S. 4Sa). Coaching of paper substrates for the production of cartonless copying paper systems
Fi, on all surfaces according to known prior art. The contents are German published specifications 1,934,457 and 1,9
mS, 64% is generally applied using an aqueous coach 4 fu composition as described in 64 g. The methods described so far have the disadvantage that after application of the coating composition the water has to be evaporated, which requires a considerable expenditure of energy. The drying requirements require the use of complex and expensive equipment for continuous drying of substrates Q coated with aqueous coating compounds. Another related problem in that regard is the problem of waste water removal resulting from the manufacture and purification of aqueous coating compositions. If volatile organic solvents are used during the preparation of the coating, the excess solvent must also be evaporated to dry the coating. In this way, solvent vapors are generated which are particularly harmful. Therefore, the German Published Application 1.91% 001 tlj proposes a method for electrostatic VC deposition of dry microcapsules onto wet-laid paper. Although this method eliminates some of the drying, only full surface coach-in can be performed according to the proposed royal authority. Furthermore, a binder active in aqueous solution is required for capsule assembly fixation. In most cases, only a portion of the reproduction system is fully used, making full surface coating uneconomical. Various methods are therefore known for partially applying coating compositions onto a paper substrate. Thus, according to the prior art, aqueous or T'ig medium-containing coachine (paper substrates) can be partially applied in gravure or flexographic printing (see German Published Specification &! 441,001). and U.S. Pat. 3111 and 8.8454
9 as well as in German Publication No. I Specification λ1914 & Bisuf 1911, it has been shown that microcapsules can be absorbed in wax and coating of paper substrates can be carried out using this type of thermolysis system. It has been proposed. Although the method proposed by Nire et al. omits the actual removal of the solvent, a relatively large amount of wax is required to obtain satisfactory reproduction copies with a maximum microcapsule content of 4.0 wt. The waxy coachine changes the properties of the paper because it has to be applied. The present invention provides that dry microcapsules coated with fusible coachine r are either electrostatically deposited onto a paper substrate and fixed therein by means of a hot section m, resulting in a partially coated curl. This is based on the recognition that it is possible to obtain copy paper without printing. Accordingly, the present invention provides a partially coated uncured copying paper array K produced by electrostatically depositing microcapsules provided with a fusible coating onto a paper substrate and subsequently applying a heat treatment. Contains information on their manufacturing methods. According to the invention, the microcapsules VCFi are coachined such that they melt upon short heat treatment, so that the microcapsules stick to the paper substrate. The term @heat treatment 1 is to be understood as an action of heat that, on the one hand, is not so high as #1 that the microcapsules are damaged, but on the other hand, it must not be so low that melting does not occur. A suitable temperature f is, for example, 50-1! ! 0°C, suitable Ktf'i 60-120°C. The thermal energy generated at these temperatures corresponds to the energy rC used in typical dry copying when toning powder is stobindered. The duration of action also depends on this thermal energy, in that the higher the energy, the shorter the treatment time. A person skilled in the art can quickly determine this energy value by a simple test. It depends on the fusibility of the coating, its cohesive strength and the coating's setting time. For example, processing times can range from about 6 to 30 seconds. As a heat source, the heater can use common add-on components, an infrared radiator or a microwave device. Suitable materials for the exterior of the capsule include VcFi such as wax compositions, thermoplastics or hot melt adhesives, all of which are generally heated at temperatures of from 60 to 120°C, preferably from 70 to 90°C. has a softening temperature. The following 4 are examples of wax compositions:・
Mother rough-in wax #i1 ester waxes, ethylene wax fields, stearate IN and carna/soda waxes. For F1% moss, polymers and copolymers of ethylene, vinylidene, and vinyl acetate, as well as partially saponified ethylene vinyl acetate-1 compounds are suitable for use as F1% moths. As the adhesive, for example, Bolioid@f:fl can be used. Suitable exterior materials include the following four:
Carnapa Wax S+ and Partially Saponified Ethylene Vinyl Acetate Copolymer-0 The above materials are stirred in an aqueous Kuragusel dispersion in the form of an aqueous finely divided dispersion* or an emulsion and then this mixture is By spray-drying it into a lump-free powder, it is
It is advantageously coated with said material. The capsule drying operation is based on known prior art techniques. Other known drying techniques can also be used for the production of capsule powders. and then remove the solvent. If a sufficiently moldy and finely divided powder of the outer packaging material is present, it can optionally be mixed with the microcapsule powder.
That's enough. Generally, the amount of sheathing material is approximately 5 - SO layer weight 1 for microcapsules, preferably Fi.
lo~3・weight-. The packaged micromagnetic pellets are then applied by electrostatic methods to any form of paper substrate, set and subjected to heat treatment. ! - A common wood-containing or wood-free type of paper with a layer weight of 4G-10 (l) can be used as the paper substrate. The electric field between the two electrodes produces an ionic charge R1, which is added to the electrostatic field K. The sheathed microcapsules are charged. The nine microcapsules thus charged are deposited on the paper substrate when this is placed on one of the electrodes. The process of electrolytic deposition of particles is described in many publications [Jgms: Utters%ak].
s protection-ga* Ukar dam RdahayA
kavs Mat dalalmhgriaeha
m Stmskgkaehgidmvhg, Ckaw
+ia-I turtle gavnimwr-Tegh*ik
l 1. 11159 M1] and belongs to the prior art. The implementation of the deposition method for dry capsule material is shown in Figures t1 to 11. 1111 illustrates the principle of deposition of a capsule in an electrostatic field caused by a corona discharge at the point electrode I and by the ionic charge RIc generated by it between the electrode I and the receiver electrode. The air stream in which the capsule material 4 is distributed is directed through the injection nozzle 3 into the discharge area between the electrodes 1 and the snow. The receptor electrode is covered by a paper sheet 5, on which the capsule material is deposited. When the capsules arrive at the spraying location 6, they are electrically charged by the charge carriers present in them, and due to the force effect of the electric field according to the formula K = f, E, known as charge carriers. exposed. In this equation, KFi represents the force, q represents the charge 1, and se represents the field strength tube in the direction of the El-1 acceptor electrode, both the field and the ion impulse are maintained by a DC source 7. This is caused by the voltage between the electrodes I and I. The capsule is pressed onto the surface of the paper, which is placed under a countercurrent electrode (Q) by a force KK. A vlU*vcs current is continuously passed through the paper layer 1 to the electrode!. Preparation for operation of the method according to the invention The condition is sufficient permeability of the paper to electric fiK. Generally, this condition is such that the resistivity of the paper is 10"Okm+, rp*, hereinafter preferably 14).
4-10” Oh horse, wind and more preferably toh-t
o”aoh turtle is satisfied. Under the above conditions, a uniformly thick layer of capsule material is deposited on a sheet of paper. 1- intentionally deposits capsules on a portion of the paper substrate surface If the receiver electrode is designed such that it is present on the surface of the insulating part 1 and the conductive part 9, the ionic charge R emitted from the corona is
The charge carriers and their KfIP capsules are distributed in the field 6 and are deposited in a concentrated manner only on the conductive part of the electrode. The preliminary condition is that the paper 5 covering the Mukotaki electrode will not fall below a certain resistivity.If the resistance of the paper is too low, the capsule will be deposited in the middle part.
The preferred resistance range is produced such that the structure of the deposited l1ilFi conductor portion can be reproduced in a non-narrowly limited manner. This resistance range is explained in more detail above. Figure 3 illustrates a more practical and related variant of the method, in which the capsule material is deposited on a continuously moving unilateral paper substrate. The material is fed through the funnel-shaped container 10Q, which is advantageously vibrated to assist in ejecting the material. Fi vibration screen 4 for this purpose! Can be used. The paper web 1lF1 is drawn continuously on a drum 12 which is equipped with a rotating aT function, as indicated by the arrow ' in the drawing. Drum! are the insulating layer 13 and the conductor layer! The paper is covered with a covering layer of 4, which, however, is not continuous but has a pattern provided for capsule deposition. For the production of such conductive layer patterns, i
iw matter and omniscient methods (e.g. printed circuits or #i-
Coated coated plate can be used separately. Conductive partials of coating layer-I
The iIV is then electrically connected to the carrier roller. As you can see from the explanation of the point electrode! It is replaced by a line electrode II in the diagram, which is fastened parallel to the drum ob* face. corona discharge

[On the ninth day of generation, Jet-4I is several hv from the power supply. If you keep it, it will receive a voltage of TEHV. This is because discharge areas are obtained whose polarity is essentially distributed. To fix the deposited nine-cell material, one piece is passed through a stopper machine, where it is fabricated and melted by an electric wire. According to FIG. 4, a photoconductor layer can also be used on the periphery of the drum in order to reduce the deposition time. In the dark, the photoconductor layer is an insulator, and upon exposure to light, it is a conductor. Using the exposure device 2, non-limiting deposits are obtained by partial radiation passing through the paper. This method has the advantage that the coater distribution can be calculated in a very simple and fast manner. Fi, for example, oxidation in a suitable photoconductor! 1i lead, cadmium sulfide and selenium. Is the photoconductor 21 in Figure 5? It describes a modified method in which the drum is exposed from inside. The photoconductor is placed on a conductive transparent grounded carrier 8tt. This carrier, which can consist of an evaporated film, is applied to a transparent hollow cylinder 28, which is internally illuminated by rungs 24. Partially transparent pattern 28
This allows partial exposure of the photoconductor surface, where the photoconductor acts as a conductor in the exposed skin areas and as a silver-strength agent in the unexposed areas. A large number of microcapsules used for the present method are known, as are methods for making them. Therefore, the long-known microcapsules
’ and they can be used for coacelvage painting,! 9 can be prepared by complex core cell paging from gelatin and other organic and inorganic I anions from gelatin/and arabicium. Various methods of this type
) Written by Capsule Technology and Microcapsules (Caps
%is Ta5ks・lψIand Miarma＊a
mlas1mtim) , /Jesus r-me-ku 4rage shoin 11th place is written in the snow. In contrast, microcapsules are used in which the material is a polymer, a polycondensation product, and a polyaddition product. The table below shows G. Nogukster (8ggtgr) 11 microcaggcellization, methods and applications (Mietra@aap
aslt-tio%Proaeaama asd Ap
pliaati*v+m). J, I:, /4f”rT (Va*dmgaar
), published in 1999, which indicates the types of capsule polymers known from the prior art. Microcapsules made from special 4-lyacrylates and having 9 Il, such as those described in German Patent Application No. 217,845 & 11-31 GpK, can also be used for the method of the present invention. Furthermore, the phenol compound 1114% of the urea-formalde rm compound can be optionally combined with the above-mentioned carboxylic polymer for TL use. The microcapsules preferably used in this method include
-kk* is prepared from polyaddition products of 4 dyne cyanate #I and voriagine. Isocyanates used for the preparation of the microcarbohydrates include: V4:)'914
For example, xylylene-1,4-rein cyanate, silylene-1.1-1/isocyanate, trimethylene-V isocyanate group%, middle-sameethylene-V isocyanate, Gropyre 2-1. ! -t/incyanate, butylene-1,! -V isocyanate, ethylidene-rein cyanate, cyclohelium 1. ! -f/incyanate, sil-1, 4-8/incyanate, / 8L isocyanate prepolymers, addition product of sameethylenezoisocyanate and dP+hentriol, 1 .4-) Addition product of toluylene-V incyanate and catechol to toluylene diincyanate and 4&? addition products of toluylene diinocyanate and trimethylol, or suitable monositinates similar to the compounds mentioned above. Other modified nine aliphatic isocyanates are hexamethylene-1,6-V isocyanate% m-dF silylene-rein cyanate, 4. 4-y incyanato-
V cyclo to middle name ethylene - 1. Based on isophoro yN isocyanate.・-One conductor of rain cyanates 11tftKL9 Polyincyanates are included, and their manufacturing FiF Institute Report Specification 1
．． 10L3-4 and Lm 4 &1 Hatanaka and K l'
(Publication specification LlsI&OI? and L911.O8I
disclosed inside. Before using them for micro-encapsulation, overcharged 4-lisocyanates [, 1 to 100% of isocyanate]
Ni and Mitomiura Al;-ru I in amounts of a01 to as mol
It can also be modified by reaction with a, ethanediol, trimethylol group, or carunic acid, such as (Shun, alevin, and heptapacylic acid). The following groups may be present as reactive groups on the isocyanate group: 4 dicalyl, -chlorokylene, gloviolactone or cyclobutane, (1,
8) Group. Therefore, for example, polyisocyanatopolyuretones are produced by converting middle nameethylene-1,6-rein cyanate into a biuret group-containing compound using an organophosphorus catalyst, and converting the initially generated cal 1M ciide group into a biuret group-containing compound. By further reacting with the incyanate group, uretone 2
7 groups are produced from K, so they can be used. Additionally, these incyanates can be used in combination with tIL%/-& as well as other aliphatic and aromatic incyanates. Depending on the reaction conditions, the resulting modified polyisocyanate may contain significant amounts of triisocyanurate and symmetric triazine-trione as structural elements, and this layer The products of are also suitable as force cell photoforming agents. Particularly suitable are the polyisocyanates corresponding to formula 1. V amines suitable for reaction with the above incyanates include = Ir aliphatic primary or secondary V- and 49 RtFs, 1Ftf ethylene cyan - (1, g), bis (1-7i nogro
-Ain, hyplazone, hydrazone-ethanol-(division), bis-C2-methylainoethyl)-methylain, l, 4-8'ainocyclohenakasan, 3-amino-1
-Methyl-InoproJan, N-and ethyl ethylene, N-Methyl-Anopro-Jan, 1.4-YAono-butan% 1
1-diamine-hequinane, ethylene-(1,
1) (diethylene-triamine), bis-(A/, A
/'-diζnoethyl)-ethylenecyamino-(1,1)
Also mentioned as V amines in this connection are (), ethylenetetrane (), and salts thereof. 1@lVc of the dye forming agent is triphenylmethane compounds, y-phenylmethane compounds, medium-santhene compounds,
Examples of nitriphenylmethane compounds include thiarin compounds and sub-μpyran compounds. Examples of nitriphenylmethane compounds include the following. 6-zomethylaoonophthalide (
Crystal Violet Rataton, hereinafter txC,V,
) and 1゜1-bis-(CV methylaζ
(nophenyl)-fumeri (malachite). V Feni J&t HKFi of methane compound, 4*4'
-ex-y methyl ryodennopenihydrylpennu ether, N-halo-enylleucolatan, N-! -Natural leucoline, N-M, 4,5-totalophenyl μicoladen, and N-8,4-V-phenylquicofin. The rim of the middle nandene compound contains romaine-β-anilinoctam, -1in-β-(p-nitroaniline)-
Lactam, romaine-/-(-chloroanili/)-
lactam, dimethylamine-8-methoxyfluorane, methylamine-3-methoxyfluorane, 7
-yethylthione-3-methyl-fluorane, -Vethylamine-3-chloro-fluorane, y-tzethylthione-3-chloro-methylfluorane, 7-dinithylamine-11.41'methylfluorane Orane, τ-V ethylγi-1.1-s/methylfluorane, 71F ethyladeny-(m-acetyl-methylaine)-fluorane, mer V ethyla-2-3-(vpenV lua1y)
-Fluoran, mer V ethyla-kenno 3-(methylbenzolaine)-fluoran,! -V Ethylua Ken-1-
(taloloethylmethyla-ken)-fluorane, di-Vethyl-aty-s-(s/chloroethyl-ryoken)-f,
Included are fluorane and T-zoethylane-S-(S/ethylane)-fluorane. The rim of the thiazino compound contains N-benzoylroy 3fi+
Included are lene blue, 0-chlorobenzoyl leucomethylene true, cy-nitro-rubenzoyl leucomethylene true, and the like. The PIK of the compound S-methyl-2,! '-Spirotic Susu-benzo(/,)-Chromes) and the like are included. Solvents for dissolving these color formers include the following: chlorinated diphenyl, chlorinated chlorinated roughin, cottonseed oil, silicone oil, phthal-ester, Phosphate esters, sulfonate esters, monocoolobenzenes, S-hydrogenated terphenyls, naphthalenes in alkali, hydrogenated +y phenyls in alkali, aryl ethers, arylalkyl ethers, benzene, etc. These can be conveniently used alone or in combination. Diluents, such as kerosene, kerosene, fluorine compounds, and fluorine fluoride compounds, are often added to the solvent. Polyaddition method KF for producing Kj remicrocagucel
i, dye former, and incyanate are first dissolved in the primary solvent, and this organic phase t-4! ikS
It contains a colloid and optionally an emulsifier to emulsify it into a continuous aqueous phase. The aqueous solution of Liayne is added to the emulsion in a stoichiometric amount relative to the Iliisocyanate in the organic phase. In order to emulsify and stabilize the resulting emulsion,
Colloidal and emulsifying agents are added to the aqueous phase. The list of such products that act as storage colloids includes carboxymethyl cellulose, gelatin, and 4-bis-nilate. Included are the emulsifiers FlfjKFi, diethylated 91-pene V-ru in water and cibiphenyl in water, and the reaction products of nonylphenol with different amounts of #ed ethylene and sorbitan 111vj acid esters. ! Ikukal 17ru can be produced with continuous K or) paddle chibu. Dispersion equipment that produces a certain shear rate is commonly used. Examples of such devices include blade/four-sketches and bird-screen stirrers, colloid oils, *mosyxizers, supersonic dispersers, nozzles, steel nozzles, and sgeladon machines. Depending on the strength of the agitation during mixing, the resulting microcrystalline particles do not agglomerate, but have a uniform particle size distribution. Weight ratio of core material to outer material rio:s
. ~io: 6 at t. The following is a more detailed explanation of the embodiments developed by the present invention group. Actual mM(a) (Manufacture of icrocagcel) Microcapsules according to German Publication No. 2-31LI01 I
Manufactured according to F1. In accordance with this Example 1/IA, a 3s-aqueous Viclocagcel dispersion was prepared consisting of a polyaddition product of NTt/tritrione and Vamine in capsules of sameethylene diisocyanate. The contents of the capsule are a mixture of Zoin Gropil
The solution was a solution of 21% by weight of crystal violet ratatone and 1% by weight of N-benzoylleucomethylene blue in a 0:0 weight ratio. The average capsule diameter is t'
It was S Peng. Example) (Manufactured at the end of the packaged 9-microcell cell cost) 3 parts by weight of 4091 aqueous non-ionic? Liethylene dispersion t-100 parts by weight of the above aqueous microcuff"-41
The mixture was stirred in a liquid dispersion (Holme-PEon, Hoechst). This mixture was then spray-dried (110'C air @ vertical inlet, go'c air 1iyIt outlet) to obtain a powder without agglomerates. The average particle size was 7.0 mm in diameter, and the powder mixture produced was applied to a paper substrate. (Production of packaged microcapsule powder) Microcapsule dispersion-) Spray-dried as in (4). 100 parts by weight of the produced capsule powder was heated to 100 parts by weight of a partially saponified powdery ethylene-vinyl copolymer (Lawα# (%, Bayer AG)). Powder dispersion used for deposition onto substrates.Act IAIpH(t) (Preparation of packaged nine microcapsule powder) Microcapsule dispersion (・) was spray-dried as (&) to give 40% by weight. Karna d wax t!sO
40 parts of trichloroethane were dissolved with heating in 40 parts of trichloroethane, and 160 parts by weight of dry microcapsules mixed into this droplet was removed under vacuum from a trichloroethane tube. A good free-flowing Kagushichilu powder was obtained which was coated with Karna Shichido wax. The resulting powder mixture is used for deposition onto a paper substrate. Practical Example A material coated with Kana A9 wax (Example C Yama) was used for paper tool Ff4. The average size of the capsule is Ss, and the material is rotated in the air and blown into the discharge space between the point electrode and the plate-like countercurrent electrode in accordance with the intention. It was divided into an insulating field 8 and a conductive field 9, the conductive field being interconnected and connected to the power source. The paper which was covered with a sheet of paper which received this electrical force 17 layers had a resistivity of 1...□km, and the spacing between the skin point and the plate was 101:lII. A voltage of 5 ohV was present between the electrodes connected to the power source, and zero points were rarely found at the anode. If a voltage t was first applied and then applied to the discharge space, a regular capsule layer formed in a fraction of a second on the paper points placed on the conductive part of the countercurrent electrode. After this process, K
was removed from the coated paper tube carrier and placed into a heating device where it was heated for 10 seconds. The wax skin of the force t cell melts on the paper surface, resulting in force! It stuck to the cell layer. A practical sensitive copying paper was obtained. The capsules were used in the same manner according to the implementation guidelines α, & and #. A practical sensitive copying paper was obtained.

[Brief explanation of the drawing]

Figure 1 shows the principle of capsule deposition in an electrostatic field. The intent shows how to deposit the capsules on a portion of the paper substrate. Figure 1 illustrates a practical related variant. Figure 4 shows a photoconductor layer used in place 9 of the gold-covering layer [
It shows. Figure 5 shows a variation in which the photoconductor is exposed from inside the drum. Patent author: Bayer AttachenrSellschaft FIG, I FIG, 2 FIG, 4

Claims (1)

[Scope of the Claims] L is produced by electrostatically depositing a microcube on a paper substrate having a fusible coating and heating the surface thereof. Partial KIJ
Microforce f*kf in organic solvent of II group generator
A pressure-sensitive copying paper containing a paper substrate coated with a GK material-forming layer of Ill liquid. 1. 4IfI, characterized by the weight of the coach-in r being heavy to heavy based on the micro-cabinet.
1l fill of IF #1 car Copy paper described in item 1. Micro illumination with coach-in r of z possible
As a copying paper according to claims 1 and 2, the method is to electrostatically apply a layer on a paper substrate, set it, and then deposit it on a paper substrate. ,lo-11
4. Process according to claim 3, characterized in that a wax composition, a thermoplastic or a heat-melt adhesive having a softening temperature of 0 DEG C. is used. 4. As a fusible coating for microphone capsules, the softening temperature f? 5. A method according to claim 4, characterized in that a wax composition, an adhesive or a heat-melt adhesive is used. 6. Claim 1, characterized in that carnapa wax and/or partially saponified ethylene-vinyl acetate copolymers are used as coachine r! ~
The method described in any of Section 4. 7. If the layer weight of the paper substrate is 4 (1-2OOf/-, 6, it is considered as a t-patent. The method described in claims 3 to 6). The method according to any one of claims 3 to 7, wherein the image is smaller than 1O1loh foundation.
m. Demerit is a patent. The method according to claim 8. Scope of claims @ 3~, which is based on tIIFI, that heat treatment is performed by heating to ~150°C
The method described in Section 9.