FI69425C - FREQUENCY REFRIGERATION FOR ETC CARBON FRAME DUPLICERING FORMULA - Google Patents

Description

ΓΒ1 m ADVERTISEMENT 69425

IBJ (11) UTLÄGG Nl NGSSKRIFT J

C (45) Patent rr / önnctty P'tDit 10 00 1000 (51) Kv.lk. * / Lnt.CI. 'B 41 M 5/12 FINLAND — FINLAND (21) Patent application - Patentansökning 771370 (22) Application date - Ansökningsdag 29.04.77 (Fl) (23) Start date - Giltighetsdag 29.04.77 (41) Has become public - Blivit offentlig Qg]] ηη

National Board of Patents and Registration Date of publication and publication. -

Patent- och registerstyrelsen '1 Ansökan utlagd och utl.skriften publicerad 31 .10.85 (32) (33) (31) Privilege claimed - Begärd priority 07.05.76 07.05.76 USA (US) 684460, 684461 (71) Courthouse Plaza Northeast, Dayton, Ohio 45463, USA (72) Gerald Titus Davis, Chillicothe, Ohio, Dale Richard Shackle,

This invention relates to a method for producing a carbonless duplicating form, i.e., a multiple duplicating form, i.e., a multiple-form duplicating form, i.e., a method for producing a carbonless duplicating form.

Multiple forms have been in general use for several years for both commercial and private purposes. Historically, the standard commercial form has taken many forms. The most common is a multi-part form with a sheet of carbon paper fitted between the different sheets. This structure is quite cumbersome because carbon paper must be both fitted, removed, and discarded, in addition to the shortcomings such as staining that typically occur when using carbon paper. As a result of this obvious problem, a form was developed in which the carbon paper was pre-arranged between the various sheets forming the form and was easily accessible for removal and disposal. Removal and disposal were made even more convenient by attaching the carbon papers to each other from one side, usually the bottom edge, so that by simply jerking out the bottom of the form, all the carbon papers were removed. This system has been and continues to be used in many retail department stores. All of these systems have historically been plagued by one 69425 shortcoming, namely the use of carbon paper. Although carbon paper is suitable for some image transfer purposes, it is not the most popular product because it is quite cumbersome to use. It’s messy and doesn’t usually produce the high quality image you want. In addition, as it is generally known from the use of carbon paper, the more sheets of carbon paper used, the weaker the image on the last sheets of the form. This is especially true when using more than three or four sheets per form. Examples of patents generally relating to the use and manufacture of image transfer systems containing carbon papers and other dyes and pigments include the following: U.S. Patent Nos. 2,299,694, 2,374,862, 3,001,308, 3,020,170 and 3,079,351.

Given the shortcomings of carbon paper as an image transfer medium, many different products have been introduced to the market. One such product is commonly referred to as carbonless paper. In short, carbonless paper is a standard type of paper, during the manufacture of which the back side of the paper substrate is coated with a so-called With a CB coating containing one or more color precursors, usually in capsule form. At the same time, the front side of the paper tray is coated during manufacture with the so-called With a CF coating containing one or more color developers.

Both the color precursor and the color developer remain in colorless form in the coating compositions on the back and front of the paper, respectively. This is true until the CB and CF coatings are brought into contact with each other, and sufficient pressure, for example on a typewriter, is applied to them to break the CB coating so that the dye precursor is released. At this point, the color precursor comes into contact with the CF coating and reacts with the color developer therein to form an image. In this way, the image on the top sheet is transferred to the next sheet without the use of carbon paper. Carbonless paper has proven to be an exceptionally valuable image transfer medium for a variety of reasons, only one of which is that until the CB coating is placed closest to the CF coating, both CB and CF substrates are in an inactive state because the reactants are not in contact with each other. Patent publications for carbonless paper products include the following: U.S. Patent Nos. 2,712,505 and 2,730,456.

A third-generation product that is now quite well developed and commercialized and available in some areas of business is called self-sufficient paper. Generally speaking, the more self-sufficient paper refers to the image transmission system in which only one side of the paper is to be coated and the single coating contains both the color precursor, is usually encapsulated in the color developer. Thus, when subjected to compression, again with a typewriter or other writing medium, for example, the color precursor capsule ruptures and reacts with the surrounding color developer to form an image. Both the carbonless paper image transfer system and the self-contained image transfer system have been the subject of considerable patent activity. A typical autogenous recording system, formerly sometimes referred to as "self-contained" because the organs required to make the label are on a single sheet, is described in U.S. Patent No. 2,730,457.

In a particularly preferred embodiment of the present invention, the multiple paper product is manufactured continuously without the need for roll storage or the like. As will be apparent from the foregoing, continuous production of a multiple paper product requires simultaneous coating, drying, printing and matching of multiple paper substrates. Due to the complexity of the drying step, this has not been commercially possible so far. More specifically, the drying step, which includes evaporation of the solvent and / or evaporation of water and introduction of heat, does not allow the simultaneous or continuous production of multiple forms.

One disadvantage of coated paper products, such as carbonless and self-sufficient paper, is due to the need to layer a liquid coating composition containing color-forming ingredients during the manufacturing process. When coating such coatings, volatile solvents are sometimes used, which in turn requires evaporation of the over-solvent to dry the coating, during which volatile solvent vapors are generated. In an alternative coating method, the color-forming ingredients are deposited as an aqueous slurry, which in turn requires the removal of excess water by drying. Both methods suffer from serious drawbacks. In particular, the solvent coating process inevitably involves the development of generally volatile solvent vapors, which poses both a health and fire hazard to the environment. In addition, when using a water solvent system, the water must be evaporated, which involves the consumption of significant amounts of energy. Furthermore, the need for a drying step 69425 requires the use of complex and expensive equipment to continuously dry the substrate coated with the aqueous coating composition. A separate but related problem is the disposal of contaminated water. The use of heat, not only is expensive, so that the entire papermaking step becomes less economically efficient, may also damage the color-forming material components that are commonly deposited on the paper substrate during manufacture. The high temperatures in the drying step require special recipes for wall-forming compounds that allow the use of excess heat. The problems encountered in the actual coating step are usually due to the need for a heated drying step after the coating step.

The drying step, which includes evaporation of the solvent and / or evaporation of water as well as the use of heat, makes it impossible to produce multiple forms in the most economical and efficient way. In addition to the drying step which prevents the production of multiple forms, the need to use heat to evaporate the solvent is a serious drawback, as aqueous and other liquid coatings require the use of special, usually more expensive, grades of paper, often twisting, warping and twisting. liquids tend to strike, i.e. penetrate, through the paper tray. In addition, aqueous coatings and some solvent coatings are generally unsuitable for spot coating, i.e., coating on limited areas of one side of a paper sheet. They are generally only suitable for layering over the entire surface area of the sheet, so that a continuous coating is formed. Patents considered relevant in this regard include Canadian Patent Publication No. 945,443 and U.S. Patent Publication No. 3,914,511.

Another problem commonly encountered when attempting to continuously produce multiple forms on a continuous basis has been that the paper manufacturer must design the paper in terms of strength and durability to be good enough for use in a wide variety of printing and finishing machines. This requires the paper manufacturer to evaluate the coating equipment of the form manufacturers to whom he supplies paper so that he can design his paper to be suitable for the equipment and process in question under the most demanding conditions.

Therefore, the paper manufacturer must use a higher ratio of long wood fibers to short wood fibers than is necessary for most coating, printing or finishing machines to achieve the required high level of strength in its final paper product.

This makes the final sheet product more expensive because long fiber is usually more expensive than short fiber. Essentially, the fact that the papermaker is separate from the form maker, which is common today, requires the papermaker to redesign his end product for many different machines, rather than designing his paper product specifically for the conditions of a known machine.

Combining the manufacturing, printing and finishing steps into a single manufacturing facility provides a number of benefits. First, the paper can be made using wood chips and a lower ratio of long fiber to short fiber than outlined above. This represents an improvement in the cost and also in the quality of the final paper product. Another advantage that can be achieved by combining manufacturing, printing and finishing is that waste or recycled paper, which is sometimes sometimes referred to as the "home", can be used in papermaking because the quality of the paper is not at an over-designed high level. Third and most importantly, several steps of the normal mold making process can be completely omitted, specifically the drying steps can be omitted using an anhydrous, solvent-free coating system, and in addition many storage and shipping steps can be avoided to make the product more cost effective.

In addition, by using appropriate coating methods, namely, anhydrous, solvent tower coating compositions and methods, and combining the necessary manufacturing and printing steps, dot weight and dot coating can be performed. Both represent significant cost savings, and yet savings that are generally not achievable when aqueous or solvent coatings are used or when paper is manufactured, printed and finished in geographically separate manufacturing facilities. An additional advantage of using solvent-free, anhydrous coating compositions and combining the paper manufacturer, printer and finisher is that when the option of coating after printing is available, significant cost advantages are obtained. More specifically, when printing is performed prior to coating, from about 10% to about 30% less encapsulated color-forming ingredients need to be used to achieve the same satisfactory image transferability of 6,694,425. This advantage is achieved because, when the paper is transferred to the mold manufacturer when coated, the paper inevitably loses some of its encapsulated color-forming agents when pressed, in compression of the material due to fracture. This disadvantage is eliminated when the paper is first printed and then only coated.

Many particular advantages of the method and product of this invention are due to the use of an anhydrous, solvent-free coating composition to coat the paper substrate. This differs from coatings used in the prior art, which have generally required the use of an aqueous or solvent coating. For purposes of this application, the phrase "100% solid coating" is sometimes used to describe a coating delivery and means that an anhydrous, solvent-free coating composition is used and thus the normal drying step normally encountered in papermaking and coating may have been omitted.

The present invention relates to both a continuous and roll-interrupted method of making a carbonless duplicating form having one or more surfaces coated with a capsule-shaped color-forming symptom, the method being characterized by (a) providing a continuous paper substrate having a front surface and a back surface; depositing the printing ink on the front surface of the continuous paper substrate, the printing ink being deposited in a pattern corresponding to the printed image, (c) depositing the first anhydrous, solvent-free coating in the form of a melt suspending agent containing a capsule-shaped color-generating agent on the back surface of the continuous paper substrate; to form a continuous paper substrate by exposing the coated surface to a hardener, (e) combining the printed, coated continuous paper substrate with about 1-5 other continuous paper substrates to form a plurality of paper substrates in which the other continuous paper substrates each having a front surface and a back surface, and the second anhydrous, solvent-free coating is deposited in the form of a color-melt-containing melt-suspending agent on the front surface of at least one of the other continuous papermakers and cured therein to react with the second anhydrous, solvent-free coating. f) matching the continuous paper trays; (g) contacting the coordinated paper trays to form a duplicating form; and (h) finalizing the duplicating form.

The method according to the invention is directed to the complete production of carbonless amplification forms in a single processing and manufacturing plant. The term "carbonless" as used herein is to be understood as a general term encompassing all types of image transfer paper or paper system that do not require the use of carbon paper. Carbonless paper is explained herein as having a Upper Surface and a Lower Surface that correspond to these surfaces as they would appear to a person using the paper. One, both, or neither of the surfaces of the carbonless paper may be coated with a color-forming agent in the form of microcapsules, droplets, or other carrier dispersed in the binder. The capsule-shaped material is preferably microencapsulated. Coloring agents include color precursors, color enhancers, color inhibitors, and the like, and combinations thereof.

The carbonless amplification forms of the invention comprise about 2-6 private sheets and preferably about 2-4 private sheets per form.

The apparatus that can be used in the method of the invention comprises an apparatus conventionally used in papermaking and form printing. As a plurality of continuous webs travel to their final finishing or packaging station during the matching or finishing step, the webs must be transported at substantially the same speed, and the other process variables must be adjusted individually. For example, if the private paper webs are different in color to indicate the second or third copy, the 8 69425 coordination must be coordinated so that the colors of the forms are in the correct order. In addition, it is preferred, although not essential, that the size of the private continuous webs be substantially the same. In the production of carbonless paper forms, it is essential that the CM / CF coatings are against each other; and finally it is necessary to distinguish between carbonless and self-sufficient so that the two sides coated with the self-sufficient coating mixture do not collide with each other. For the purposes of this application, arranging these different sheets in the appropriate order is sometimes referred to below as coordinating the sheets, webs, or substrates.

A particular advantage of the method according to the invention is that the printing step and the marking step can be performed before the coating step.

It can be seen that in this way, less encapsulated material then needs to be deposited on the paper, because about 10-30% of the encapsulated material, which normally breaks or is otherwise destroyed during the printing step, is not needed because the web has already been printed before coating.

The continuous webs consist of paper trays. The continuous webs can be supplied in any of a variety of shapes and sizes. The primary and most common shape is the shape of the roll. Although the exact dimensions of the roll are not critical, the dimensions of the standard roll are approximately 7.5 cm to 185 cm wide and approximately 150 m to about 9000 m in total length. This particular size has been found to be suitable for most printing and coating equipment. In this way, the substrate is printed and coated and then stored for later use together with other, compatible printed and coated substrates to produce a final, multiple carbonless form. After storage of the private, treated substrates, they are placed in a matching and finishing device to complete the manufacturing process. According to an alternative embodiment, the continuous web may be supplied as a substrate line forming process. In this particular application, the process of making a multiple carbonless form is the final step in the papermaking process.

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The continuous web is paper, and as mentioned above, the overall quality of the paper may be somewhat lower than previously considered valid, and as a result some ground may be used in the manufacture of this paper and in addition the paper may have lower levels of long fibers and short fibers. relationship between. This cost-saving advantage of the lower overall quality of the paper is achieved because the paper can be made specifically for use with known coating and printing equipment.

A particular advantage offered by the process of the present invention is that the printing or marking operation can be completed before the coating step. It is clear, therefore, that less encapsulated material needs to be deposited on the paper, because about 10-30% of the encapsulated material, which normally breaks or is otherwise destroyed during printing, does not need to be used when the web has already been pre-printed when coated. This differs from what has been possible in the past, due to the fact that in the past it was necessary to carry out a drying step after each coating step, which generally required the use of a considerable amount of heat and thus a significant amount of energy consumption. This represents a significant advantage over cost and convenience over all methods previously presented or explained.

As described above, in the preferred process of the present invention, private substrates are subjected to a printing or marking step prior to the coating step. While this is the most affordable, it is not critical. In this application, the phrase "marking" is generally used to mean printing, writing, striking, or any other marking of a continuous web, whether the marking is visible or not. In the preferred process of the present invention, the top surface of each individual web in said plurality of continuous webs is marked with printing ink to provide the printed information normally present in business forms. Sometimes, however, only one surface, normally the top surface of the uppermost continuous web, is marked in this way. The current content of the label and the number of labeled webs depend on the form being made and can be conveniently set during the manufacturing step.

In a preferred embodiment of the present invention, the marking step is performed by depositing a marking liquid, preferably a printing ink, on one or more surfaces of the continuous webs with a suitable printing device. The primary printing method is offset, although any other approved printing method may also be used. The choice of printing method is limited only by the hardware, so it depends on the printing possibilities of the respective manufacturer. The inks used in this printing step are any inks commonly used in the printing industry today. The ink only needs to be selected from a group or type that is compatible with the coating process and mixture.

In order to produce multiple carbonless forms by the process of this invention, it is necessary that at least one coating composition be deposited on at least one surface of at least one continuous web before the webs are fitted together into a multiple form. In a preferred embodiment of the present invention, each continuous web of the plurality of continuous webs, except the top, has a CF coating containing a color developer on the upper surface and a CB coating containing a color precursor encapsulated on the lower surface. Another suitable embodiment is a self-contained image transfer system in which both the color developer and the color precursor are deposited on one surface of each continuous web, preferably the top surface, again except for the top web, which does not require a coating material at all, regardless of the carbonless transfer system used.

Depending on the particular coating method and mixture used, depositing a self-sufficient mixture on a continuous web may require either one or two separate deposition steps. Although the deposition step can be performed by a variety of known methods, the preferred deposition methods and coating compositions are melt suspending agents and radiation curable resins.

One of the particularly significant advantages of both of these primary coating methods is that the drying step of the coating is not necessary. Instead, the drying step is replaced by a curing or maturing step, in which case heat, waste of time or high temperatures are not necessary. Thus, the coating compositions used in the process of this invention can best be described by designating them as solvent towers, anhydrous coating compositions, or otherwise expressed as "100% solid coatings."

The coating process of the present invention uses a melt suspending agent, preferably waxes, resins or the like, in combination with microcapsules, which microcapsules contain a color precursor or a combination of color precursors. The most suitable melt suspending agents are low molecular weight polar waxes. The melt-suspending agent procedure described below is sometimes referred to hereinafter as the melt-activating system. The melt activation system has been found to be most suitable for use as a CB coating on carbonless papers, although to a lesser extent it may also act as a CF coating containing a color developer or color developer combination. This preferred procedure involves microencapsulating a dye precursor by one of a number of known microencapsulation methods, most of which require the use of a cross-coupling agent with a wall-forming compound to initiate an interfacial reaction that results in the formation of microcapsules. -compound.

The color-generating coating composition used in the melt embodiment of the present invention is essentially a dispersion of the color-generating agent in the melt system. The color generating agent may be either soluble or insoluble in the melt system, and the color precursors are preferably in micro-encapsulated and dispersed form. Fillers can also be added to the melt to modify the properties of the final coated substrate. The use of solvents that require heat to remove during curing of the coated film is avoided.

When using the melt embodiment of this invention, the most useful color precursors are electron donors such as lactone phthalides such as crystal violet lactone and 3,3-bis- (1'-ethyl-2-methylindol-31-yl) phthalide, lactone fluorans such as 2-dibenzylamino-6-diethylaminofluorane and 6-diethylamino-1,3-dimethylfluorans, lactone xanthene L, leucoauramines, 2- (omega-substituted vinylene) -3,3-disubstituted 3-H-indoles and 1,3,3-trialkylindolinospirans If desired, mixtures of these color precursors can be used. The primary melt process of this invention uses oil solutions of microencapsulated and color precursors. These oil solutions preferably contain color precursors from about 0.5% to about 20.0% by weight of the oil solution, and the most suitable range is from about 2% to about 7%.

Melt suspending agents commonly used in the practice of this invention include waxes and resins. A preferred group of compounds which are useful melt suspending agents comprises e.g. resin-purified, oxidized mineral waxes such as montan waxes, amide waxes such as bis-stearamide wax, stearamide wax, behenamide wax, fatty acid waxes, hydroxylated fatty acid waxes, hydroxy stearate waxes, oxazoline waxes, and amine waxes thereof. The melt suspending agent is characterized in that it has a penetration hardness of less than or equal to about 0, a list of about 20 ° C, a melting point of about 60 ° C to about 140 ° C, a narrow melting range, a viscosity the melt is low, has a certain amount of polarity, and has a faint color. Any wax or 13,69425 wax blend having the above properties can be successfully used as a suspending agent in the practice of this invention.

These waxes are all suitable to act as a suspending agent for the color-generating agent and other ingredients of the coating composition and at the same time are compatible with the color-generating properties of the color-generating agent. These substances can be solidified to solidification by cooling.

The primary group of melt suspending agents includes the following waxes: 2-n-heptadecyl-4,4-bis-hydroxymethyl-2-oxazoline, N, N'-ethylene bis-stearamide, N- (2-hydroxyethyl) -12-hydroxystearamide, glyceryl monohydroxystearate and ethylene glycol monohydroxystearate.

Other waxes of this type that have generally been shown to be effective include modified mineral type waxes, synthetic waxes and waxes of vegetable origin and mixtures thereof. These waxes must have a high melting point and high hardness, which eliminates the transfer of the wax to the developing sheet, thus improving image clarity, increasing the clogging temperature, and reducing packaging problems. Some of the most suitable waxes for use in the process and product of this invention are crude crude montan waxes relative to the resin. These waxes are made from bitumen-rich lignite feedstock, which is extracted with organic solvents to form crude montan wax. The resin is removed from the montan wax by extraction with organic solvents and then oxidation with chromic acid to give acidic waxes.

Another type of suitable melt suspending agent is a non-polar hydrocarbon wax such as Be Square 170/175 (melting point range 76-79 ° C).

From the Bareco Division of Petro li te Corporation, which contains a small amount of dispersing agent. The dispersing agent may be, for example, turmeric oil.

The primary waxes of the invention have a penetration hardness of about 0.1 to about 20 as measured by a wax penetration test having the ASTM code of D 1321-61T. The range of 0.1-20.0 represents a practical range of penetration hardness. A more suitable range is from about 0.1 to about 3 and a more suitable range is from about 0.1 to about 1 as the same needle penetration rate. The needle penetration number is obtained by a test procedure, 14 69425, which empirically evaluates the consistency of petroleum-derived waxes by measuring how deep a constant needle penetrates them.

This method is applicable to waxes with a penetration number not exceeding 250. The penetration number of petroleum wax is the number which indicates, in tenths of a millimeter, the depth at which the standard needle penetrates the test wax under the specified conditions. These specified conditions are usually as follows: the test sample is thawed, heated for approx.

17 ° C above its melting point, pour into a tank, and then cool in air, under controlled conditions. The sample is then conditioned at the test temperature, in a water bath. Penetration is measured with a penetrometer that presses a standard needle into the sample for 5 seconds at a load of 100 g.

Another characteristic of a suitable melt suspending agent according to the invention is that it has a melting point of from 60 to about 140 ° C. Preferably, the waxes or resins of the invention have a melting point in the range of about 70 to about 100 ° C. With regard to the melting point, it is essential that the coating composition according to the invention hardens rapidly after it has been deposited on the respective substrate. More specifically, the practical limits of the melting range, i.e., the limits of the temperature range in which the liquid melt mixture cures to a solid mixture, are from about 1.0 ° C to about 15 ° C. A suitable curing time is from about 0.5 seconds to about 5 seconds, and a most suitable curing time is from about 0.5 seconds to about 2 seconds. Although melting intervals in excess of 15 ° C can be used, the time required to cure such a coating composition requires special equipment and treatment and makes the use of such melt compounds commercially probable.

The melt waxes and resins of the invention must also have a low viscosity in the molten state to facilitate application to the substrate. In general, it is desirable for the melt suspending agent to have a viscosity of less than 120 centipoise at about 5 ° C above the melting point of the relevant melt suspending agent. In addition, the color of the melt wax according to the invention, i.e. the melt suspending agent, should preferably be light so as to be compatible with the final paper or plastic product to be manufactured. This knows that the melt should preferably be white or transparent after it has been deposited on the appropriate substrate to be coated.

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The primary waxes, resins and other melt suspending agents of the invention are preferably polar. By polar is meant that a certain amount of polarity is characteristic of the primary waxes, and these polar mixtures are characterized by the presence of functional groups selected from the group consisting of carboxyl, carbonyl, hydroxyl, ester, amide, amine. and heterocyclic groups and combinations thereof. An alternative but less desirable embodiment of the invention comprises the use of non-polar hydrocarbon waxes which must be used in conjunction with a dispersing agent.

Additives that can be included in melt CB coating compositions are typically a opacifying agent such as titanium dioxide or kaolin, a stiffening agent such as arrowroot starch, and wax modifying agents such as polyvinyl acetate, isophthalic polyester, or any main waxing agent, and any major wax. quality.

The method by which the microcapsules are dispersed in the melt-suspending agent is also important, as it is necessary to use a method which prevents significant agglomeration of the microcapsules. In the preferred method, the microcapsules are formed into an aqueous slurry containing approximately 40% solids and then spray dried to a free flowing powder. The free-flowing microcapsules are then agitated in the molten phase of a suspending agent such as wax, wax mixture, resin or a mixture thereof to form a uniform dispersion of the microcapsules in a continuous molten phase. This melt can then be deposited or printed by gravure printing, knife coating, flexography, or other means on a continuous web. The melt system hardens substantially immediately after being deposited on the web and forms an excellent marking sheet.

In the most preferred embodiment of the invention, a dispersing agent is added to the microcapsules before they are combined with the melt suspending agent. The primary group of dispersing agents are anionic dispersing agents, many of which are commercially available. The preferred group of anionic dispersing agents are the sodium salts of condensed naphthalenesulfonic acids, the sodium salts of polymeric carboxylic acids, the free acids of complex organic phosphate esters, sulfated castor oil, poly-16,69425 (methyl vinyl ether / hydrazide) / maleic acid. The most suitable dispersing agent is sulfated castor oil. The dispersing agent is added to the microcapsules from about 0.1% to about 10% based on the dry weight of the microcapsules. An even more suitable range of addition is from about 0.5% to about 5.0% based on the dry weight of the microcapsules, and the most suitable range is from about 1.0% to about 3.0% based on the dry weight of the microcapsules.

In a preferred embodiment of the invention, a dispersing agent is added to the microcapsules before the microcapsules are combined with the melt suspending agent. In some cases, the dispersing agent and the wall-forming agent are the same agent and that portion of the wall-forming agent that is not used for the actual wall-forming of the capsules remains in the melt-coating dispersion as a dispersing agent. Although, as described above, many well-known commercially available dispersants can be used in the process and product of the invention, one group of secondary dispersants that may be present as an additional wall-forming agent includes hydroxypropylcellulose, acacia, gelatin, polyvinyl alcohol, carbyvinyl alcohol, carbinyl alcohol and mixtures thereof.

Although the dispersant can be added at any stage of the process of the invention prior to curing the coating composition, for best results, the dispersant must be added to the microcapsules before they are combined with the melt dispersant. The amount of dispersing agent used in each case depends on several variables, e.g. the particular type of microcapsules used, the particular type of melt suspending agent, the consistency of the aqueous slurry of the microcapsules, the viscosity of the melt suspending agent, and the desired final coated product. For the purposes of this application, the practical range of addition amount, based on the weight of the microcapsules, is from about 0.1 parts by weight to about 10.0 parts by weight. An even more suitable range of addition is from about 0.5 parts by weight to about 5.0 parts by weight, and the most suitable range is from about 1.0 parts by weight to about 3.0 parts by weight.

The color-generating coating composition can be deposited on a substrate such as paper or plastic film by any of the conventional paper coating methods as mentioned above, such as roll or knife coating, or by any conventional printing methods such as gravure or flexographic printing. The rheological properties of the coating composition, in particular its viscosity, can be set for each deposition method by correctly selecting the type and relative amounts of melt-suspending medium. Although the actual amount of melt coating dispersion deposited on the substrate may vary depending on the particular end product desired, a useful CB coating surface weight of about 1.5 to about 12 kg per 1000 square meters of substrate has been found to be useful for coating paper substrates. A suitable range for the basis weight of the CB coating is from about 3.7 kg to about 7.5 kg per 1000 square meters of substrate, and the most suitable range is from about 4.5 to about 6 kg per 1000 square meters of substrate. If the CB coloring agents and a color developer (CF) are combined in the same, i.e., self-contained, color-generating coating composition, useful basis weights range from about 3 to about 13.5 kg per 1000 square meters of substrate, preferably from about 4.5 to about 9 kg per 1000 square meters of substrate. and preferably about 6 to about 7.5 kg per 1000 square meters of substrate.

These melt coating dispersions, i.e. melt coating compositions, which terms may alternatively be used, can be cured by any means of cooling. Preferably, a coating roll is used in the coating apparatus which cools the melt coating immediately after deposition, but it is also quite common to simply allow the coating mixture to cool naturally when exposed to the atmosphere. Since the temperature of the coating composition is substantially higher than room temperature and considering that the thickness of the coating is generally less than 50 microns, it is apparent that when applied to the substrate, the melt cools very rapidly. The exposure or cooling time required to cure the color-generating coating composition in each case depends on numerous variables such as the basis weight of the coating, the melt suspending agent used in each case, the type of cooling device, the temperature of the cooling device, and so on.

The choice of wall-forming agent and melt-suspending agent is important because some microcapsules whose walls are hydroxyethylcellulose when made by a certain patented method, or certain polyamides, tend to precipitate even in polar waxes. Impacting is detrimental because it prevents the color-generating agent from being uniformly distributed on the CF sheet. This adversely affects image shift and its consistency and intensity.

The encapsulation method and the encapsulated color-generating agent used are not within the scope of this invention. Instead, many different encapsulated color-generating agents that can be used have been described in the patent literature. Such color-generating agents have been encapsulated in gelatin wall-forming agents (see U.S. Patent Nos. 2,730,456 and 2,800,457), including gum arabic, polyvinyl alcohol, carboxymethylcellulose, 190-form as a resorcinol-formaldehyde wall-forming agent (see U.S. Pat. (see U.S. Patent 3,914,511) and hydroxypropylcellulose and mixtures thereof. Microencapsulation has been performed by a variety of known methods, e.g. coacervation, interfacial polymerization, polymerization of one or more monomers in an oil, various melting, dispersing and cooling methods, and spray drying methods. Compounds that have proven advantageous for use as wall-forming compounds in these various microencapsulation methods include, e.g. hydroxypropylcellulose, carboxymethylcellulose, gelatin, melamine-formaldehyde, polyfunctional isocyanates and its prepolymers, polyfunctional acid chlorides, polyamines, polyols, epoxides and mixtures thereof.

Particularly suitable for use in accordance with the present invention are microcapsules composed of hydroxypropylcellulose (HPC) materials. This is because such microcapsules are easily dispersed in most melt materials. If necessary, a small amount of dispersing agent may also be added, as described above, to improve dispersion. In addition, HPC capsules have good permeability, strength and temperature properties.

Another suitable coating method according to the present invention comprises the use of radiation curable resins. As with the melt-activation system, radiation-curable resins can be used as either a CF or CB coating, but are preferably used as a CF coating system. The main principle of a radiation curable activation system is that a developing agent such as a novolak resin is dissolved in a liquid, radiation curable material that can be cured by exposure to radiation such as ultraviolet or electron radiation. The liquid mixture containing the developing agent and the liquid, radiation-curable agent is then deposited as a thin film on a continuous web, which is then exposed to ultraviolet light to cure the coating.

A radiation curable color-generating coating composition suitable for use in the method of the invention is essentially a dispersion of a color-generating agent in a liquid, radiation-curable material. The color-generating agent may be either soluble or insoluble in said liquid, radiation-curable agent, and the color developing agents are preferably in microencapsulated or dispersed form. Insoluble, color-generating color developing agents such as acid clays used in the manufacture of carbonless recording sheets are included as solid particles dispersed in the coating composition. Most organic color developing agents are soluble in the radiation curable material of the invention.

The coating composition may contain additives that act as photoinitiators. The addition of these substances depends on the particular method of curing the color-generating coating. Fillers can also be added to modify the properties of the cured film. The use of unreacted solvents which require heat to remove during drying or curing of the laminated film is avoided.

The most suitable color-generating color developing agents for use in the radiation-curing embodiment of the present invention are acidic electron acceptors, and include e.g. acid clays such as attapulgus clay and stilton clay, phenolic substances such as 2-ethylhexyl gallate, 3,5-di-tert-butylsalicylic acid, novolak-type phenolic resins and metal-modified phenolic substances such as 3,5-di-tert-butyl zinc salt of salicylic acid and zinc-modified novolak-type resins. The most suitable color-generating color developers are the novolaks of p-phenylphenol, p-octylphenol and p-tert-butylphenol. Mixtures of these color developing agents can be used if desired. In a liquid color-generating mixture, they may be present in an amount of from about 25% to about 75% by weight of the color-generating mixture. A suitable range is from about 35% to about 65%, and a most suitable range is from 40% to about 55%.

69425 20 Radiation-curable materials useful in the practice of this invention include e.g. free radical polymerized ethylenically unsaturated organic compounds. These compounds must contain at least one ethylene end group per molecule. They are liquid and act as dispersing agents for the coloring agent and other ingredients of the coating composition. They can be cured into a solid resin by exposing them to ionizing or ultraviolet radiation. Curing occurs by polymerization.

The primary group of radiation-curable compounds are polyfunctional, ethylenically unsaturated, organic compounds having more than one (two or more) terminal ethylene groups per molecule. Due to the polyfunctional nature of these compounds, they are cured by radiation by polymerization involving crosslinking to form a hard, dry and non-stick film.

This primary group of radiation-curable compounds includes e.g. polyesters and polyhydric alcohols of ethylenically unsaturated acids such as acrylic acid and methacrylic acid. Examples of these polyfunctional compounds are the polyacrylates and methacrylates of trimethylolpropane, pentaerythritol, dipentaerythritol, ethylene glycol, triethylene glycol, propylene glycol, glycerol, sorbitol, enopentyyliglykoli and 1,6-hexane diol, hydroxy-terminated polyesters, hydroxy-terminated epoxy resins and hydroxy-terminated polyurethanes, and polyphenols such as bisphenol A. An example of the hydroxy-dimensional of the polyurethane polyacrylate found to be useful in the present invention is di (2'-acryloxyethyl) -4-methylphenylene diurethane.

This group also includes polyallyl and polyvinyl compounds such as diallyl phthalate and tetrallyloxyethane, and divinyl adipate, butanedivinyl ether and divinylbenzene. If desired, mixtures of these polyfunctional compounds and their oligomers and prepolymers can be used.

The second group of radiation-curable compounds consists of monofunctional ethylenically unsaturated organic compounds having one terminal ethylene group per molecule. Examples of 21,694,25 such monofunctional compounds are C 8 -C 18 alcohol esters of acrylic and methacrylic acid as well as styrene, substituted styrenes, vinyl acetate, vinyl ethers and allyl ethers and esters. In general, these compounds are liquid and have a lower viscosity than polyfunctional compounds, so that they can be used to lower the viscosity of the coating composition to facilitate its deposition by any desired method. These compounds are radiation curable and react with ethylenically unsaturated polyfunctional organic compounds during radiation curing to give a hard, dry, flexible film. Compounds having only one terminal ethylene group can be used alone as a radiation curable. However, the radiation-cured film obtained therefrom can be quite soft and flexible and may be slightly too sticky for commercial use. The most suitable radiation curable agent is a mixture containing one or more polyfunctional compounds and one or more monofunctional compounds. By appropriately selecting these compounds, a color-generating coating composition having the desired coating properties can be prepared for any type of coating application, and a hard, flexible, non-stick radiation-cured film can be obtained. In general, the most suitable films are obtained by using a radiation curable material having from about 33% to about 67% polyfunctional compounds and from about 33% to about 67% monofunctional compounds.

Preferably, a photoinitiator is added to the coating composition if the mixture is to be cured by ultraviolet radiation. There are many different photoinitiators available that are well suited to the system described in this invention. Preferred photoinitiators include benzoin alkyl ethers such as Vicure 30 (an alkyl benzoin ether mixture manufactured and sold by Stauffer Chemical Co., Westport, Connecticut), benzoin butyl ether (Vicure 10, Stauffer), benzoin methyl ether, and α, α-diethoxy. Other photoinitiators used include benzophenone, 4,4'-bis- (dimethylamino) benzophenone, ferrocene, xanthone, thioxanthan, α, α-azobisisobutylnitrile, decabromodiphenyl oxide, pentabromo-monochloro-cyclohexane, pentabromo-monochlorocyclohexane, 1200 series (manufactured and sold by Monsanto Chemical Co., St. Louis, Missouri), benzoin ethyl ether, 2-ethyl anthroquinone, 1- (chloroethyl) naphthalene, decyl chloride, chlorenedianhydride, naphthalene sulfonyl chloride, and 2-bromoethylethyl ether . Zinc 22 69425 oxide combined with a small amount of water is also a good substitute for a photo-initiation system. The amount of photoinitiator added may be from about 0.2% to about 10% by weight of the coating composition, with the most suitable range being from about 3% to about 8% by weight.

Photoinitiation enhancers can also be added to ultraviolet curable coating compositions. Photoinitiation enhancers improve the initiation efficiency of photoinitiators. Preferred enhancers are chain transfer agents such as tertiary alcohol amines and substituted morpholines such as triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine and N-methylmorpholine. The amount of photoinitiation enhancer to be added may be from about 0.2% to about 0.2%. to the weight of the coating composition, preferably from about 3% to about 8% by weight.

Fillers can be added as opacifiers, especially in color-developing coating compositions, to reduce the gloss of the cured resin film and to maintain the pre-coating appearance of the substrate. Thus, a bond paper coated with a coating composition of the present invention, which is then cured into a solid film, appears as an uncoated bond paper.

The primary fillers are colloidally precipitated or "smoked" silicic acids. Typical silicas that can be used are those under the trade name LoVel 27 (precipitated silicic acid manufactured and sold by PPG Industries, Inc., Pittsburgh, Pennsylvania), Syloid 72 (hydrogel silicic acid manufactured and sold by WR Grace & Co. KG). , Davison Chemical Division, Baltimore, Maryland) and Cab-o-sil ("smoked" silicic acid manufactured and sold by Cabot Corporation, Boston, Massachusetts). All of these silicas are known to initially give a bluish color with color precursors such as crystal violet lactone. However, this color fades quickly as it ages.

When a recording sheet made by the method of the present invention is used, the developed color does not fade easily. The theory is that the filler, due to its large surface area, gives the cured resin film more porosity, thus promoting a faster and more complete transfer of the oil solution of the color precursors from the transfer sheet to the surface of the recording sheet. The amount of fillers may be up to about 15% by weight of the coating composition and the most suitable range is from about 10% to about 15% by weight.

23 69425 The method of mixing the ingredients of the coating composition is not critical. The ingredients can be added one at a time or they can be added all at once, and stirred until they are uniformly mixed. Good results are obtained when the ingredients of the radiation-curable material and the color-generating material are heated with stirring to facilitate mixing of these ingredients. The photoinitiator, photoinitiation enhancer and filler, if used, are best added when the coating composition is at room or slightly higher temperature. Preferably, the microcapsules are also added at room temperature.

The color-generating coating compositions may be deposited on a substrate such as paper or plastic film by any conventional paper coating method such as roll, air sweep or knife coating, or by any conventional printing method such as offset, gravure or flexographic printing. The rheological properties of the coating composition, in particular its viscosity, can be set for each deposition method by appropriately selecting the relative amounts of liquid radiation-curable compounds. Although the amount of color-generating coating compositions to be deposited on the substrate may vary depending on the desired end product, the practical range of coating basis weight for paper substrates in the case of CF color-generating coating compositions of this invention is about 0.3 to about 12. about 0.7 to about 6 kg per 1000 square meters of substrate and with a most suitable range of about 1.5 to about 4.5 kg per 100 square meters of substrate. If the CF and CB dye-generating agents are combined into a single, i.e., self-sufficient, dye-generating coating composition, useful coating basis weights range from about 3 to about 13.5 kg per 100 square meters of substrate, preferably from about 4.5 to about 9 kg per 1000 square meters of substrate. and preferably about 6 to about 7.5 kg of substrate per 1000 substrates per square meter.

These coating compositions can be cured by any free radical-initiated chain reaction of the ethylene end groups of the radiation-curable compounds via a sustained addition polymerization reaction. These free radicals can be prepared by a variety of chemical methods, e.g. thermal or ultraviolet cleavage of a molecular species and any ionizing radiation using alpha particles, beta-24 69425 rays (high energy electrons), gamma rays, X rays or neutrons. The exposure time required to cure the color-generating coating composition in each case depends on a number of variables such as the basis weight of the coating, the thickness of the coating, the particular radiation curable material, the type of radiation, the radiation source, the radiation intensity and the radiation source. In most cases, curing is essentially blinking, with curing times ranging from about 1 millisecond to about 2.0 seconds. A suitable curing time is from about 0.1 second to about 1.0 second, and a most suitable curing time is from about 0.3 seconds to about 0.6 seconds.

In the preferred curing method, the coating composition is exposed to ultraviolet radiation having a wavelength of about 2,000 Å to about 4,000 Å. For uitraviolet curing to work, the mixture must contain suitable ultraviolet-absorbing photoinitiators that generate polymerization-initiating free radicals when exposed to radiation. A typical source of ultraviolet radiation suitable for this type of curing process is a Hanovia 200 watt medium pressure mercury lamp. The curing efficiencies of coating compositions depend on parameters such as the nature of the radiation curable material, the atmosphere in contact with the coating, the quantum efficiency of the absorbed radiation, the thickness of the coating, and the inhibitory effects of the various substances in the composition.

The curing of these coating compositions by ionizing radiation does not require a special radiation absorbing agent (photoinitiator). Exposure of the coating composition to a source of high energy electrons results in spontaneous curing of the mixture to a hard, non-stick coating. Any of a number of commercially available high energy electron beam or linear cathode type high energy electron sources are suitable for curing these mixtures. Parameters such as the atmospheric environment and the inhibitory effects of the various substances contained in the mixture play an important role in determining the curing efficiency of these mixtures.

A particular advantage of the coating step of the method according to the invention is that it allows the use of spot coating. Dot coating means that less than 100% of the surface area of a private sheet, whether CF, CB, self-adhesive or other sheet, needs to be coated. For example, the area of the paper that normally forms the double-sided margin of the printed portion of the page need not be coated. This, of course, represents a significant cost advantage in terms of savings on the encapsulated material. The encapsulated material is one of the more expensive materials used to make forms. Thus, by eliminating certain portions of the web surface that do not need to be coated, significant cost savings are apparently achieved. The use of dot printing can range from simply omitting the coating of the marginal portion of the paper to making a form in which only a single line is actually coated. At the same time, forms such as computer lists can be made in which only every other line is coated. Thus, it is apparent that from about 10% to about 95% of the surface area of the paper may be left uncoated. In most cases, it would be most convenient to simply not print the marginal areas of the paper, which would save about 10% to about 30% of the cost of the encapsulated material.

At the end of the coating delivery and the proper curing delivery, the web, i.e. the substrate, is wrapped in a roll sleeve and stored. The private roll is held in storage and then combined with a predetermined number of other coated or uncoated webs during the matching delivery. In this application, the phrase matching means the step in the method according to the invention in which a plurality of private coated or uncoated webs are arranged in order, i. CB coating closest to CF coating, etc. The phrase matching device refers to the machine or other device that provides the desired order of multiple private webs.

Before, during or after the matching operation, a leasing step is performed. The adhesive is layered or the gluing device is usually used only after several private webs have been removed from the warehouse and processed, i. reconciled.

The adhesive is deposited on one or more sides of these plurality of private webs, or alternatively, the adhesive may be deposited on all or a portion of one or more private webs. Any of the prior art adhesives and adhesives normally used in the paper industry are useful in the sizing device of this invention. Alternative interfaces - ______ - ΊΤ .........

26 69425 methods are e.g. the use of binding devices such as adhesive tapes, staples, V-shaped embryos, etc. other rarer devices. Although the bonding step has been described above as generally occurring after the coating step or steps and before the matching and finishing steps, it can be performed at any stage of the method according to the invention. More specifically, in a preferred embodiment of the method according to the invention, the liquid adhesive is deposited with a gluing device before the matching step, and the private webs are joined during the finishing step. Thus, in the preferred embodiment, the adhesive is deposited prior to bonding, but the webs themselves are not actually placed in contact with each other until the finishing step. In another embodiment of the present invention, the gluing device may be omitted altogether and the private webs may not be joined together but may only be arranged in a proper sequential order relative to each other.

In yet another embodiment of the invention, the gluing device may be located in a functional sequential order after the matching device. In another embodiment, the coordinated and finished sheets can be bound, i.e. joined together, after the finishing step. The sequential order and the device used in each case for the gluing device, the matching device and the finishing device is a matter of personal choice and depends on the desired end product. The specific order in which these steps take place is of no particular significance.

Bonding. After, during or before delivery, continuous substrates are transported to the joints. The matching device arranges the private different webs in the correct position relative to each other. This may involve arranging colors if the customer's copy or original is white, the customer's copy is green and the archive copy is red, or alternatively it may involve arranging private sheets so that CB and CF coated sheets come into contact when the final form is made. . If carbonless type carbonless paper is used, the coated surface of the paper is the top surface of each sheet. All this is done by pre-arranged programming of the matching device.

After coordination, the lorakakes are finished in any of a number of different steps. The finishing delivery may comprise the step of stapling the sheets together, the step of dividing the sheets into suitable

Claims (4)

27 69425 sizes, the appropriate stacks of the sheet stacking step and the sheet packaging step, as well as any other steps that may be desired. A method of making a carbonless duplicating form having one or more surfaces coated with a capsule-shaped color generating agent, characterized in that (a) a continuous paper substrate having a front surface and a back surface is provided, (b) a printing ink is deposited on the front surface of a continuous paper substrate. a printed image, (c) depositing a first anhydrous, solvent-free coating in the form of a melt suspending agent containing a capsule-shaped color-generating agent on the back surface of a continuous paper substrate, (d) curing the first coating to form a printed coated, continuous paper substrate by applying a coated surface; a printed, coated continuous paper tray with about 1-5 other continuous paper trays to form a plurality of paper trays, each of the other continuous paper trays each having a front surface and a back surface, and a second anhydrous, solvent-free coating layer applying to the front surface of at least one of the other continuous paper webs in the form of a melt-suspending agent containing a color-forming agent and curing it in which the second anhydrous, solvent-free coating is capable of reacting with the first anhydrous, solvent-free coating, (f) matching the continuous paper trays; to create a duplication form and (h) finalize the duplication form · A method according to claim 1, characterized in that the finishing steps comprise (a) integrally coordinating the paper trays in contact with each other into a single duplicating tray, (b) dividing the single duplicating tray into a plurality of sheets, each sheet being suitable for use as a carbonless amplification form, (c) the sheets are stacked and (d) the stacked sheets are packaged. 1. For use in the preparation of carbon black duplicating formulas, for example with the aid of a capsule-shaped chromium-containing material, kännetecknat av fig man (a) a commercial and a continuous papermaking agent, whether or not used as a batch, and the triccine head is frosted with a tracer-shaped body, the tracer staple applicator and the shape of the tracer image, (b) a batch of a single batch of beans, (b) a batch of batches of beans, ca 1-5 ytterligare continuous papersunderlag för att skapa ett flertal pappersunderlag, varvid vart och ett av de ytter ligand kontinuerliga pappersunder-lagen har en främre yta och en bakre yta, och en andra vattenfri, lösningsmedelsfri beläggning i form av ett smältsuspendingsmedel, sombegreper et chromogent material appliceras ochr-papas on the basis of the framre ytti hos vilken andra, vattenfria, lösningsmedels-fria beläggning är reagtiv med den första, vattenfria, lösningsmedelsf ria beläggningen, final authorization of the formulation.