CA1116852A - Production of pressure-sensitive carbonless record sheets using dioic acid hot melt systems and products thereof - Google Patents
Production of pressure-sensitive carbonless record sheets using dioic acid hot melt systems and products thereofInfo
- Publication number
- CA1116852A CA1116852A CA000315916A CA315916A CA1116852A CA 1116852 A CA1116852 A CA 1116852A CA 000315916 A CA000315916 A CA 000315916A CA 315916 A CA315916 A CA 315916A CA 1116852 A CA1116852 A CA 1116852A
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- Prior art keywords
- coating composition
- acid
- hot melt
- zinc
- dioic acid
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Classifications
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Paper (AREA)
Abstract
PRODUCTION OF PRESSURE-SENSITIVE CARBONLESS RECORD
SHEETS USING DIOIC ACID HOT MELT SYSTEMS AND
PRODUCTS THEREOF
Frederick W. Sanders Abstract of the Disclosure A process is provided for producing a pressure-sensitive carbonless record sheet comprising the steps of preparing a hot melt coating composi-tion, the hot melt coating composition having a melting point of from about 60°C to about 140°C. The hot melt coating composition comprises a chromo-genic material and a solid aliphatic dioic acid. The hot melt coating composition is heated to a temperature above its melting point and the heated coating composition is applied to a substrate, the coating composi-tion being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate. The coating composition is set by cooling the coated substrate. A pressure-sensitive carbonless record sheet comprising a substrate having a plurality of surfaces and at least one surface of which is coated with about 0.2 pounds to about 8 pounds per 3300 square feet of a set hot melt coating composition is produced. The set hot melt coating composition has a melting point of from about 60°C to about 140°C and comprises a chromogenic material and a solid aliphatic dioic acid.
A novel hot melt chromogenic coating composition having a melting point of from about 60 C to about 140°C and comprising a chromogenic material and a solid dioic acid is produced.
SHEETS USING DIOIC ACID HOT MELT SYSTEMS AND
PRODUCTS THEREOF
Frederick W. Sanders Abstract of the Disclosure A process is provided for producing a pressure-sensitive carbonless record sheet comprising the steps of preparing a hot melt coating composi-tion, the hot melt coating composition having a melting point of from about 60°C to about 140°C. The hot melt coating composition comprises a chromo-genic material and a solid aliphatic dioic acid. The hot melt coating composition is heated to a temperature above its melting point and the heated coating composition is applied to a substrate, the coating composi-tion being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate. The coating composition is set by cooling the coated substrate. A pressure-sensitive carbonless record sheet comprising a substrate having a plurality of surfaces and at least one surface of which is coated with about 0.2 pounds to about 8 pounds per 3300 square feet of a set hot melt coating composition is produced. The set hot melt coating composition has a melting point of from about 60°C to about 140°C and comprises a chromogenic material and a solid aliphatic dioic acid.
A novel hot melt chromogenic coating composition having a melting point of from about 60 C to about 140°C and comprising a chromogenic material and a solid dioic acid is produced.
Description
1 1 1 6~35~
Background of the Invention This invention relates to the production of a pressure-sensitive carbonless record sheet utilizing a hot melt system to form a coating com-position contain;ng a chromogenic material, which coating is set by cooling.
More particularly, it relates to production of a record sheet using a novel coating composition comprising chromogenic materials and solid aliphatic dioic acids. For purposes of this application the term l'chromogenic" shall be understood to refer to materials such as color developers, color precursors and color formers. Additionally, the term "CF" shall be understood to refer to a coating normally used on a record sheet and the term "CB" shall be understood to refer to a coating normally used on a transfer sheet.
Carbonless paper, briefly stated, is a standard type of paper wherein during manufacture the backside of a paper substrate ;s coated with what is referred to as a CB coating, the CB coating containing chromogenic material, generally one or more color precursors dissolved in a carrier oil and generally in capsular form. At the same time the front side of the paper substrate is coated during manufacture with what is referred to as a CF coating,which contains one or more color developers. Both the color precursor and the color developer remain in the coating compositions on the respective back and front surfaces of the paper in colorless form. This is true until the CB and CF coatings of adjacent sheets are brought into abutting relationship and sufficient pressure, as by a typewriter, is applied to rupture the CB coating to release the color precursor. At this time the color precursor contacts the CF coating and reacts with the color developer therein to form an image. Car-bonless paper has proved to be an exceptionally valuable image transfer medium for a variety of reasons only one of which is the fact that until a CB coating is placed next to a CF coating both the CB and the CF are in an inactive state as the co-reactive elements are not in contact with one another. Patents ~16~35~
relating to carbonless paper products are:
U.S. Patent 2,712,507 (1955) to Green U.S. Patent 2,730,456 (1956) to Green et al U.S. Patent 3,455,721 (1969) to Phillips et al U.S. Patent 3,466,184 (1969) to Bowler et al ~,:
U.S. Patent 3,672,935 (1972) to Miller et al A third generation product which is ;n an advanced stage of develop-ment and commercialization at this time and which is available in some business sectors is referred to as self-contained paper. Very generally stated self-contained paper refers to an imaging system wherein only one side of the-paper ~- needs to be coated and the one coating contains both the color precursor7 - generally in encapsulated form, and the color developer. Thus when pressure is applied, again as by a typewriter or other writing instrument, the color precursor capsule is ruptured and reacts with the surrounding color developer to form an image. Both the carbonless paper image transfer system and the self-contained system have been the subject of a great deal of patent activity.
A typical autogeneous record material system, earlier sometimes referred to as "self-contained" because all elements for making a mark are in a single sheet, is disclosed in U.S. Patent 2,730,457 (1956) to Green.
A disadvantage of coated paper products such as carbonless and - self-contained stems from the necessity of applying a liquid coating composition containing the color forming ingredients during the manufacturing process. In the application of such coatings volatile solvents are sometimes used which then in turn requires evaporation of excess solvent to dry the coating thus producing volatile solvent vapors. An alternate method of coating involves the application of the color forming ingredients in an aqueous slurry, again requiring removal of excess water by drying. Bothmethods suffer from serious disadvantages. In particular the solvent coating method necessarily involves the production of generally volatile solvent vapors creating both a health and a fire hazard in the surrounding environment. In addition, when using an aqueous solvent system the water must be evaporated which involves the expenditure of significant amounts of energy. Further, the necessity of a drying step requires s~
the use of complex an~l expensive app~ratus to continuously dry a substrate which has been coated with an aqueous coating compound. A separate but related problem involves the disposal of polluted l~Jater resulting from the preparationand clean up of the aqueous coating compositions. The application of heat not only is expensive, making the total product manufacturing operation less cost effective, but also is potentially damaging to the color forming ingredients which are generally coated onto the paper substrate during manufacture. The problems encountered in the actual coating step are generally attributable to the necessity for a heated dry;ng step following the coating operation.
Many of the particular advantages of the process and product of th;s invention are derived from the fact that a hot melt coating composition is used to coat the paper substrate. This is in contrast to the coatings used by the prior art which have generally required an aqueous or solvent coating.
For purposes of this apolication the term "100% solids coating" will sometimes be used to described the coating operation and should be understood to refer to the fact that a hot melt coating composition is used and, therefore, the drying step normally present in the manufacture of paper and in coating has been ; eliminated.
In this regard, it should be noted that spot application of aqueous and solvent systems has been known. See, for example, Vassiliades (U.S. Patent No. 3,914,511) and Miller et al. (3,672,935). MacCaulay (3,016,308), Staneslow et al. (3,079,351) and Shank (3,684,549) also disclose hot melt coatings. But to the best of our knowledge none of these hot melt coatings are CF coatings nor are they particularly effective as CB coatings.
The use of water insoluble hot melt coating compositions comprising 15%
to 100% of a water insoluble meltable color developer in the preparation of record (CF) sheets is disclosed in commonly assigned United States Patent No. 4,053,754.
By using a combination of solid aliphatic dioic acids and color developer, as in the instant invention, the amount of color developer needed in the coating ismarkedly reduced to as-low as 0.1% by weight of the CF coating without noticeable ~ ,- . . . .... . . .
loss in cnlor cleveloping power. These C~ coatings can be spot printed or coated.
Other advantages over the known prior art include sharpness of melting point of the coating composition and ability to accept water base inks, such as script inks and ball point pen inks, and pencil images. Paper coated with the solid aliphatic dioic acid compositions is more easily pulped than with, for example, paraffin or synthetic waxes.
The most preferred embod;ment of th;s invent;on relates to a process for the continuous product;on of manifold carbonless forms and more particu-larly to a process for utilizing solid dioic acid hot melt systems containing dispersed color developing material in this continuous production.
As can be appreciated from the above the continuous product;on of amanifold paper product would require simultaneous coating, simultaneous drying, s;multaneous printing and simultaneous collat;ng and finishing of a plurality of paper substrates. Thus, Busch in Canadian Patent No. 945,443 indicates that in order to do so there should be a minimuM wetting of the paper web by water during application of an emulsion coat. For that purpose a high solids content emulsion is used and special driers are described in Busch. ~owever, because of the complexit;es of the dry;ng stepS this process has not been commerc;ally poss;ble to date. More particularly, the dry;ng step involv;ng solvent evaporat;on and/or water evaporation and the ;nput of heat does not permit the s;multaneous or continuous manufacture of manifold forms. In addition to the drying step which prevents continuous manifold form production the necessity for the application of heat for solvent evaporation is a serious disadvantage since aqueous and other liquid coatings require that special grades of generally more expensive paper be employed and even these often result in buckling, distortion or warping of the paper since water and other liquids tend to strike through or penetrate the paper substrate. Addition-ally, aqueous coatings and some solvent coatings are generally not suitable for spot application or application to limited areas of one side of a sheet of paper.
They are generally suitable only for application to the entire surface area of asheet to produce a cont;nuous coat;ng.
Anoth~r problem ~hich h~s been com~only encountered in attempts to continuously manufacture manifold forms has been the fac~ ~hat a paper ~anufacturer ~ust design paper from a strength and durability standpoint to be adequate for use in a variety of printing and finishing machines.
This requires a paper manufacturer to evaluate the coating apparatus of the forms manufacturers he supplies in order that the paper can be designed to accommodate the apparatus and process e~hibiting the most demanding conditions. Because of this, a higher long wood fiber to short wood fiber ratio must be used by the paper manufacturer than is necessary for most coating, printing or finishing machines in order to achieve a proper high level of strength in his finished paper product. This makes the final sheet ~` product more expensive as the long fiber is generally more expensive than a ` short fiber. In essence~ the separation of paper manufacturer from forms ~ manufacturer, which is now common, requires that the paper manufacturer ;~ 15 overdesign his final product for a variety of machines, instead of specifi-cally designing the paper product for known machine conditions.
~ By combining the manufacturing, printing and finishing operations into -~ a single on-line system a number of advantages are achieved. First, the paper can be made using groundwood and a lower long fiber to short fiber ratio as was developed supra. This is a cost and potentially a quality improvement in the final paper product. A second advantage which can be derived from a combination of manufacturing, printing and finishing is that waste or re-cycled paper, hereinafter sometimes referred to as "broke", can be used in the manu-facture of the paper since the quality of the paper is not of an overdesigned high standard. Third, and most important, several steps in the normal process of the manufacture of forms can be completely eliminated. Specifically, drying ~; steps can be eliminated by using a non-aqueous, solvent-free coating system and - in addition the warehousing and shipping steps can be avoided thus resu~ting in a more cost efficient product.
Additionally, by using appropriate coating methods, namely hot melt coating compositions and methods, and by combining the necessary manufacturing and printing .. . ... . .
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steps, spot print-in~ and 5pot coatin~ can be realized. Both of these represent a significant cost savings, but nevertheless, one which is not generally available when aqueous or solvent coatings are used or where the manufacture, pr;nting and finishing of paper are performed as separate functions. An additional advantage of the use of hot melt coating compositions and the combination of paper manufacturer~ printer and finisher is that when the option of printing followed by coating is available significant cost advantages occur.
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S-talelnen-t o~ the Invent-ion ,. . ~
A process is providecl for producing a pressure-sensitive carbonless record sheet comprising the steps of preparing a hot melt coating composi-tion, the hot melt coating composition having a melting point of from about 60C to about 140C. The hot melt coating composition comprises a chromo-genic material and a solid aliphatic dioic acid. The hot melt coating com-position is heated to a temperature above its melting point and the heated coating composition is applied to a substrate, the coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate. The coating composition is set by cooling the coated substrate. A pressure-sensitive carbonless record sheet comprising a substrate having a plurality of surfaces and at least one surface of which is coated with about 0.2 pounds to about 8 pounds per 3300 square feet of a set hot melt coating composition is produced. The set hot melt coating composition has a melting point of from about 60C to about 140C and comprises a chromo-genic material and a solid aliphatic dioic acid. A novel hot melt chromogenic coating composition having a melting point of from about 60C to about 140C
and comprising a chromogenic material and a solid aliphatic dioic acid is pro-duced.
t~5 2 r)et(liled l)escription_of the Irlv_n ion The chromog~nic hot melt coating cor,~position of this invention is essentially a combination of one or more solid aliphatic dioic acids with one or more chromo-genic materials. The dioic acid acts as a hot melt binder in these compositions.The chromogenic materials and dioic acids are preferably miscible or partially miscible with each other in their molten form so that separation of the compo-nents of the composition substantially does not occur during application and setting of the chromogenic hot melt composition.
Other materials may be added, if desired, to the chromogenic coating composition to modify the melting point or other rheological properties or to modify its color or its color producing or physical properties. The use of volatile solvents, including organic solvents and water, in amounts large enoughto require a separate step for drying during setting of the hot melt compositionis to be avoided. Minor amounts of these solvents can be tolerated, and in some cases may be even beneficial. For example, a small amount of water, up to about 5% by weight based on the total weight of the coating composition, ~lill act as a plasticizer and rheology modifying material without requiring drying duringthe setting step.
- A preferred use of the chromogenic coating compositions of this invention is in the preparation of pressure-sensitive carbonless record sheets. Such papers can be used in manifold copy systems in combination with pressure-sensitive transfer sheets containing oil solutions of color precursors of the electron donor type. A preferred group of electron donor color precursors include the lactone phthalides, such as crystal violet lactone, and 3,3-bis-(l'-ethyl-2-methylindol-3"-yl) phthalide, the lactone fluorans, such as 2-dibenzyl-amino-6-diethylaminofluoran and 6-diethylamino-1, 3-dimethylfluorans, the lactone xanthenes, the leucoauramines, the 2-(omega substituted vinylene)-3,3-disubstituted -3-H-indoles and 1,3,3-trialkylindolinospirans.
The dioic acids useful in the practice of this invention are the solid aliphatic dicarboxylic acids. The preferred dioic acids have a carbon chain of about 3 to about 10 carbon atoms. The preferred range of dioic acid is from about 30'~ to about 99.9% by weight of the composition.
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They are water soluble compounds having a sharply defined, relatively high melting point. Ex~mples of the preferretl dioic acids are the following:
Name of AcidCarbons in ChainApproximate Melting Point C
Glutaric Acid 5 99 Pimelic Acid 7 106 S~iberic Acid 8 140 Azelaic Acid 9 107 Sebacic Acid 10 135 All of these acids are commercially available. For example, azelaic acid is available under the trade name "Emerox" from Emery Industries, Cin-cinnati, Ohio.
A particular advantage of the use of the dioic acids as the hot melt binder over the water insoluble hydrophobic waxes of the prior art, such as the hydrocarbon (paraffin) waxes, is that these acids are relatively polar.
This permits the use of chromogenic materials, particularly color developers, which are more polar in character than those previously used. Examples of such developers are phenolphthalein, certain metal salts and gallic acid. These polar color developers are at least partially miscible with the molten dio;c acids and thus form a homogenous blend of the melted developer and dioic acid.
In contrast to this, hydrophobic waxes, such as paraffin are not m;scible in the melted condition with the polar color developers and thus do not form homogenous blends with the polar color developers.
The solid aliphatic dioic acids of this invention are not reactive with electron-donor types of color precursors and thus have not been found to produce color in the absence of the chromogenic material of this invention.
Furthermore, the presence of these acids in the hot melt composition does not interfere with the reaction of the color prescursor and chromogenic material (developer) to form a color.
~ The chromogenic materials most useful are the color developers of the : 30 acidic electron-acceptor types. These developers include but are not limited to phenolic materials as other electron-acceptor types such as certain organic metal compounds and colloidal silica and acid clays have been found to be useful.
Metal compounds which have been found to be acceptable are zinc thiocyanate, zinc p-toluenesulfonic acid and zinc ammonium thiocyanate.
10.
,i 1 ~ 1t;8 5~
The preferred color dcvelopers are the phenolic co~pounds, novolak resins and their zincated compounds and resins. The phenolic compounds are solid àt normal room temperature. These preferred color developers include phenol-phthalein, salicylic acid. 3,5-di-tert-butyl salicylic acid, ammonium 5,5-S methylene disalicylic acid, salicylsalicylic acid, l-hydroxy-2-naphthoic acid, resorcinol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, 2-ethyl-hexyl gallate, tert-butyl phenol, p-phenylphenol, p-octylphenol, BisphenolA, sulfonyl d;phenol, p-phenylphenol novolak resin, p-octylphenol novolak resin (4% zinc), zincated p-phenylphenol novolak resin (4% zinc), zinc salicylate, the zinc salt of 3,5-di-tert-butyl salicylic acid and mixtures thereof. A
preferred combination of phenolic compounds or resins with zinc salts of organic acids, such as zinc thiocyanate produced intense blue images.
The preferred range of chromogenic material in the coating composition is from about 0.1% to about 35% by weight of the total composition. A most preferred range is from about 2% to about 25%. The optimum amount may vary somewhat depending on the particular chromogenic material used, the dioic acid used, the coat weight desired and the character and amount of any other ~ modifying material which may be added to the coating composition as desired.
- The chromogenic material may be supplemented with materials which act as color intensifiers and color stabilizers. These color intensifiers are materials-~ which in themselves produce little or no color in the presence of the electron ; donorcolor precursors. However, these same materials have been found to inten-sify colors produced by the color developers of this invention. Preferred color - intensifiers are arnmonium thiocyanate~ aluminum oxide and zinc compounds such as zinc oxide, zinc chloride, zinc nitrate, zinc gallate, zinc stearate, zinc neopentoate and zinc lineoleate.
Minor amounts of materials such as resins, waxes and liquid plasticizers may be added to the coating composition to modify the rheology of the composition and/or characteristics of the set coating. In general, these rheology modifying ;85~
rials can be non-poldr or ~olar. By polar it is meant that a certain amount of polarity is characteristic of these materials, the polar materials being characterized by the presence of functional groups selected from the group consisting of carboxyl, carbonyl, hydroxyl, ester, amide, amine, heterocyclic groups and combinat;ons thereof. The rheology modifying mater;als may vary in viscosity from liquids such as water to the low molecular weight polypropylene glycol ethers and esters. Other modifying materials which may be used are polyethylene glycols, polystyrenes, polyesters, polyacrylates, rosin, modified rosins, polyphenyls, fatty acids, fatty acid derivatives, oxazoline waxes, natural waxes, paraffin waxes microcrystalline waxes and fatty amides. These modifying materials may be present in an amount of from ; about 0% to about 10% by weight of the hot melt coating compos;tion. The preferred range is from about 0% to about 5% and the most preferred range is from about 0% to about 2% of the coating composition.
lS A desirable characteristic of the hot melt coating composition of this invention is a melting point of from about 60C to about 140C., although a more preferred melting point for the coating compositions is from about 70C
to about 100C. Also relative to the melting point, it is desirable for the coating composition of this invention to set rapidly after application to ~he .,:
particular substrate. More specifically, a practical melting range limitation or in other words range of temperature in which the liquid hot melt coating composition sets into a solid composition, is from about 0.1 C to about 15C.
The preferred setting time is from about 0.1 seconds to about 5 seconds while the most preferred setting time is from about 0.1 seconds to about 1 second.
While hot melt compositions having a melting range of more than 15C can be used, the time necessary for such a coating composition to set requires special apparatus and handling and makes use of these hot melt compositions commerciallyunattractive. Due to their sharply defined melting points, the dioic acids~of this invention have the particular advantage of keeping the melting range below 15C.
~16~52 The preferred hot melt coa-ting compositions of this invention have a low viscosity when in a molten state in order to facilitate ease of spreading on the substrate. In general, it is desirable that the hot melt coating compo-sition have a v;scosity of less than about 500 cent;poises at a temperature of approximately 5 above the melting point of a particular hot melt coating composition. In addition, it is preferred that the hot melt coating composition of this invention have a light color in order to be compatible with the final paper or plastic product being produced. This means that it is preferred for the hot melt to be white or colorless after application to the particular substrate being coated.
Pigment materials can be added to the coating composit;on as flattening agents to reduce the glossy appearance of the cured hot melt coatings and preserve the appearance of the substrate. Thus a bond paper which has been coated with the coating composition of this invention and which is then cured to a solid gives the impression of being an uncoated bond paper. Typical of the pigments which can be used are diatomaceous earth, calcium carbonate, tita-nium dioxide, barium sulfate, colloidal alumina, colloidal silica, acid clays and bentonite.
The chromogenic coating composition may be prepared by melting the dioic acid and stirring, grinding or melting in the color developer and other desired materials.
The chromogenic color developing coating composition can be applied hot to a substrate, such as paper or a plastic film by any of the common pap~r coating processes, such as roll, blade coating or by any of the common printing - 25 processes, such as planographic, gravure, or flexographic printing. The rheolo-gical properties, particularly the viscosity of the coating composition~ can be adjusted for each type of application by proper selection of the type and relative amounts of modifying materials. ~Ihile the actual amount of the hot melt coating composition applied to the substrate can vary depending on the particular final product desired, for purposes of coating paper substrates, the practical range of coat weights for the CF chromogenic coating compositions of this inven-tion are from about 0.2 pounds to about 8 pounds per 3300 square feet of , . .
;852 substrate, the preferred range being from about 0.2 pounds to about 5 pounds per 3300 sq~lare feet of substrate and the most preferred range being from about 0.2 pounds to about 2.5 pounds per 3300 square feet of substrate. Coat weights above the preferred range do not show any substantial improvement over those within the most preferred range.
These hot melt coating compositions can be set by any cooling means. Preferably a chill roll is used on the coating apparatus which cools the hot melt coating immediately after coating, but is also quite common to simply allow the coating composition to cool naturally by atmospheric exposure. As the temperature of the coating composition is substantially higher than room temperature and in light of the fact that the coating thickness is generally less than 50 microns it can be seen that when spread out over a coated substrate the hot melt material cools very rapidly. The actual exposure or chill time necessary for setting of the chromogenic coating composition is dependent on a number of variables, such as coat weight, the particular color developers and rheology modifying materials used, type of cooling means, temperature of the cooling means, specific substrate being coated and others.
In the preferred application of the process and products of this invention a manifold carbonless form is produced. In this process a continuous web is marked with a pattern on at least one surface. A non-aqueous, solvent free hot melt coating of chromogenic material is applied to at least a portion of at least one surface of the continuous web. The coated surface is then set by cooling. The continuous web having the set coating is then combined with at least one additional continuous web which has been previously or simultaneously coated with a hot melt material and set by cooling. A manifold carbonless form is then made by a variety of collating and finishing steps. Such a process and product are described in commonly assigned, United States Patent .~ 3 - 14 -111~;85Z
No. 4,112,138 entitled "Manifold Carbonless Form and Process for the Production Thereof (custom)" issued September 5, 1978.
In the most preferred application of the process and products of this invention a manifold form is continuously produced. In this most preferred embodiment a plurality of continuous webs are advanced at substantially the same speed, the plurality of continuous webs being spaced apart and being advanced in cooperating relationship with one another. At best one web of the plurality of continuous webs is marked with a pattern and at least one non-aqueous, solvent-free hot melt coating containing the chromogenic material is applied to at least a portion of at least one of the plurality of continuous webs. The hot melt material is then set by cooling. The continuous webs are then collated and placed in contiguous relationship to one another to create a manifold form. After the continuous webs are placed in collated, contiguous relationship they can be finished by any combination of the steps of combining, partitioning, stacking, packaging and the like. Such a process and product are described in commonly-assigned, United States Patent No. 4,097,619 entitled "Manifold Carbonless Form and Process for the Continuous Production Thereof (Standard)" issued on June 27, 1978.
The following examples illustrate preferred embodiments but do not limit the scope of the invention which is defined in the claims.
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E:x~mpl e 1 3 parts of sebacic acid and 1 part of 3,5-di-tert-but.yl salicylic acid were melted together and 0.2 part of solid ammonium thiocyanate was ground into the melt using a mortar and pestle to form a hot melt composition.
Using a blade heated to about 170C, the hot melt composition ~/as coated on paper and cooled to produce a coated paper having about 5 pounds of set coating per 3300 square feet of paper.
The set, coated paper was tested by placing the coated surface thereof in contact with the coated side of a CB paper coated with getatin m;crocapsules containing a marking oil made up of 180 parts of monoisopropylbiphenyl~ 5.3 parts of crystal violet lactone, 0.62 parts of 3,3-bis-(1-ethyl-2-methylindol-3-yl)-phthalide, 1.25 parts of 3-N-N-diethylamino-7-(N,N-dibenzylamino)-fluoran,0.95 parts of 2,3-(-1'-phenyl-3'methylpyrazolo )-7-diethylamino-4-spirophthalido-chromene and 122 parts of odorless kerosene. These sheet couples were imaged with an electric typewriter using the character "m" in a repeating block pattern, and the intensity and color of the images after an elapsed time of 10 minutes was recorded '~ ' An intense blue image was produced on the hot melt coated paper Example 2 3 parts of sebacic acid and 1 part of 3,5-di-tert-butyl salicylic acid were melted together as in Example 1. To this hot melt was added 0.5 parts of a second hot melt consisting of the following:
72.7 parts urea 7.3 parts polyvinyl pyrolidone 7 3 parts zinc oxide 7 3 parts ammonium thiocyanate 5.3 parts hydantoin The resultant coating composition was coated on paper and the coated paper was pressure irnaged as in Example 1 The coat weight was about 3 pounds per 3300 square feet of paper An intense brilliant blue image was formed 16.
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E ample 3 Into 8 parts of se~acic acid was ground 0.2 parts of ammonium thiocyanate and 0.1 parts of zinc oxide. The composition was coated on paper and the paper was pressure imaged as in Example 1. An intense violet-blue image was pro~uced.
Example 4 Example 3 was repeated additionally adding by grinding in 0.2 parts of urea to the hot melt coating compos;t;on. An intense blue ;mage was produced.
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Examples 5 through 12 A series of hot melt coating compositions were made in which the relative 0 amounts of color developer and dio;c acids were varied and different representa-tive d;oic acids were used. The color developer was a p-phenylphenol novolak resin. The hot melt composit;ons were prepared by melting together the ingre-- dients of each composition. The hot melt compositions were coated on paper and the papers were tested as ;n Example 1. The approximate melting point was determined for each composition by allowing a bead of molten composition to ` cool on the bulb of a thermometer and recording the temperature at which the bead became solid. The results are in Table 1 which follows:
TABLE I
Compositio~ of Hot Melt Approximate Description Example No. Color DeveloperDioic Acid Melting PointC of Imaqe 75 parts 25 parts azelaic 55~ Intense Blue 6 50 parts 50 parts azelaic 653 Intense Blue 7 25 parts 75 parts azelaic 804 Intense Blue 8 25 parts 75 parts glutaric 86 Moderate Blue 9 25 parts 75 parts pimelic 87 Intense Blue 25 parts 64 parts azelaic 60 Moderate Blue 7 parts pimelic ~4 parts glutaric 11 As Example 7 + 15 parts diatomaceous earth - Intense Grey-Blue 1. Color deve~oper is p-phenyl~henol novolak resin.
Background of the Invention This invention relates to the production of a pressure-sensitive carbonless record sheet utilizing a hot melt system to form a coating com-position contain;ng a chromogenic material, which coating is set by cooling.
More particularly, it relates to production of a record sheet using a novel coating composition comprising chromogenic materials and solid aliphatic dioic acids. For purposes of this application the term l'chromogenic" shall be understood to refer to materials such as color developers, color precursors and color formers. Additionally, the term "CF" shall be understood to refer to a coating normally used on a record sheet and the term "CB" shall be understood to refer to a coating normally used on a transfer sheet.
Carbonless paper, briefly stated, is a standard type of paper wherein during manufacture the backside of a paper substrate ;s coated with what is referred to as a CB coating, the CB coating containing chromogenic material, generally one or more color precursors dissolved in a carrier oil and generally in capsular form. At the same time the front side of the paper substrate is coated during manufacture with what is referred to as a CF coating,which contains one or more color developers. Both the color precursor and the color developer remain in the coating compositions on the respective back and front surfaces of the paper in colorless form. This is true until the CB and CF coatings of adjacent sheets are brought into abutting relationship and sufficient pressure, as by a typewriter, is applied to rupture the CB coating to release the color precursor. At this time the color precursor contacts the CF coating and reacts with the color developer therein to form an image. Car-bonless paper has proved to be an exceptionally valuable image transfer medium for a variety of reasons only one of which is the fact that until a CB coating is placed next to a CF coating both the CB and the CF are in an inactive state as the co-reactive elements are not in contact with one another. Patents ~16~35~
relating to carbonless paper products are:
U.S. Patent 2,712,507 (1955) to Green U.S. Patent 2,730,456 (1956) to Green et al U.S. Patent 3,455,721 (1969) to Phillips et al U.S. Patent 3,466,184 (1969) to Bowler et al ~,:
U.S. Patent 3,672,935 (1972) to Miller et al A third generation product which is ;n an advanced stage of develop-ment and commercialization at this time and which is available in some business sectors is referred to as self-contained paper. Very generally stated self-contained paper refers to an imaging system wherein only one side of the-paper ~- needs to be coated and the one coating contains both the color precursor7 - generally in encapsulated form, and the color developer. Thus when pressure is applied, again as by a typewriter or other writing instrument, the color precursor capsule is ruptured and reacts with the surrounding color developer to form an image. Both the carbonless paper image transfer system and the self-contained system have been the subject of a great deal of patent activity.
A typical autogeneous record material system, earlier sometimes referred to as "self-contained" because all elements for making a mark are in a single sheet, is disclosed in U.S. Patent 2,730,457 (1956) to Green.
A disadvantage of coated paper products such as carbonless and - self-contained stems from the necessity of applying a liquid coating composition containing the color forming ingredients during the manufacturing process. In the application of such coatings volatile solvents are sometimes used which then in turn requires evaporation of excess solvent to dry the coating thus producing volatile solvent vapors. An alternate method of coating involves the application of the color forming ingredients in an aqueous slurry, again requiring removal of excess water by drying. Bothmethods suffer from serious disadvantages. In particular the solvent coating method necessarily involves the production of generally volatile solvent vapors creating both a health and a fire hazard in the surrounding environment. In addition, when using an aqueous solvent system the water must be evaporated which involves the expenditure of significant amounts of energy. Further, the necessity of a drying step requires s~
the use of complex an~l expensive app~ratus to continuously dry a substrate which has been coated with an aqueous coating compound. A separate but related problem involves the disposal of polluted l~Jater resulting from the preparationand clean up of the aqueous coating compositions. The application of heat not only is expensive, making the total product manufacturing operation less cost effective, but also is potentially damaging to the color forming ingredients which are generally coated onto the paper substrate during manufacture. The problems encountered in the actual coating step are generally attributable to the necessity for a heated dry;ng step following the coating operation.
Many of the particular advantages of the process and product of th;s invention are derived from the fact that a hot melt coating composition is used to coat the paper substrate. This is in contrast to the coatings used by the prior art which have generally required an aqueous or solvent coating.
For purposes of this apolication the term "100% solids coating" will sometimes be used to described the coating operation and should be understood to refer to the fact that a hot melt coating composition is used and, therefore, the drying step normally present in the manufacture of paper and in coating has been ; eliminated.
In this regard, it should be noted that spot application of aqueous and solvent systems has been known. See, for example, Vassiliades (U.S. Patent No. 3,914,511) and Miller et al. (3,672,935). MacCaulay (3,016,308), Staneslow et al. (3,079,351) and Shank (3,684,549) also disclose hot melt coatings. But to the best of our knowledge none of these hot melt coatings are CF coatings nor are they particularly effective as CB coatings.
The use of water insoluble hot melt coating compositions comprising 15%
to 100% of a water insoluble meltable color developer in the preparation of record (CF) sheets is disclosed in commonly assigned United States Patent No. 4,053,754.
By using a combination of solid aliphatic dioic acids and color developer, as in the instant invention, the amount of color developer needed in the coating ismarkedly reduced to as-low as 0.1% by weight of the CF coating without noticeable ~ ,- . . . .... . . .
loss in cnlor cleveloping power. These C~ coatings can be spot printed or coated.
Other advantages over the known prior art include sharpness of melting point of the coating composition and ability to accept water base inks, such as script inks and ball point pen inks, and pencil images. Paper coated with the solid aliphatic dioic acid compositions is more easily pulped than with, for example, paraffin or synthetic waxes.
The most preferred embod;ment of th;s invent;on relates to a process for the continuous product;on of manifold carbonless forms and more particu-larly to a process for utilizing solid dioic acid hot melt systems containing dispersed color developing material in this continuous production.
As can be appreciated from the above the continuous product;on of amanifold paper product would require simultaneous coating, simultaneous drying, s;multaneous printing and simultaneous collat;ng and finishing of a plurality of paper substrates. Thus, Busch in Canadian Patent No. 945,443 indicates that in order to do so there should be a minimuM wetting of the paper web by water during application of an emulsion coat. For that purpose a high solids content emulsion is used and special driers are described in Busch. ~owever, because of the complexit;es of the dry;ng stepS this process has not been commerc;ally poss;ble to date. More particularly, the dry;ng step involv;ng solvent evaporat;on and/or water evaporation and the ;nput of heat does not permit the s;multaneous or continuous manufacture of manifold forms. In addition to the drying step which prevents continuous manifold form production the necessity for the application of heat for solvent evaporation is a serious disadvantage since aqueous and other liquid coatings require that special grades of generally more expensive paper be employed and even these often result in buckling, distortion or warping of the paper since water and other liquids tend to strike through or penetrate the paper substrate. Addition-ally, aqueous coatings and some solvent coatings are generally not suitable for spot application or application to limited areas of one side of a sheet of paper.
They are generally suitable only for application to the entire surface area of asheet to produce a cont;nuous coat;ng.
Anoth~r problem ~hich h~s been com~only encountered in attempts to continuously manufacture manifold forms has been the fac~ ~hat a paper ~anufacturer ~ust design paper from a strength and durability standpoint to be adequate for use in a variety of printing and finishing machines.
This requires a paper manufacturer to evaluate the coating apparatus of the forms manufacturers he supplies in order that the paper can be designed to accommodate the apparatus and process e~hibiting the most demanding conditions. Because of this, a higher long wood fiber to short wood fiber ratio must be used by the paper manufacturer than is necessary for most coating, printing or finishing machines in order to achieve a proper high level of strength in his finished paper product. This makes the final sheet ~` product more expensive as the long fiber is generally more expensive than a ` short fiber. In essence~ the separation of paper manufacturer from forms ~ manufacturer, which is now common, requires that the paper manufacturer ;~ 15 overdesign his final product for a variety of machines, instead of specifi-cally designing the paper product for known machine conditions.
~ By combining the manufacturing, printing and finishing operations into -~ a single on-line system a number of advantages are achieved. First, the paper can be made using groundwood and a lower long fiber to short fiber ratio as was developed supra. This is a cost and potentially a quality improvement in the final paper product. A second advantage which can be derived from a combination of manufacturing, printing and finishing is that waste or re-cycled paper, hereinafter sometimes referred to as "broke", can be used in the manu-facture of the paper since the quality of the paper is not of an overdesigned high standard. Third, and most important, several steps in the normal process of the manufacture of forms can be completely eliminated. Specifically, drying ~; steps can be eliminated by using a non-aqueous, solvent-free coating system and - in addition the warehousing and shipping steps can be avoided thus resu~ting in a more cost efficient product.
Additionally, by using appropriate coating methods, namely hot melt coating compositions and methods, and by combining the necessary manufacturing and printing .. . ... . .
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steps, spot print-in~ and 5pot coatin~ can be realized. Both of these represent a significant cost savings, but nevertheless, one which is not generally available when aqueous or solvent coatings are used or where the manufacture, pr;nting and finishing of paper are performed as separate functions. An additional advantage of the use of hot melt coating compositions and the combination of paper manufacturer~ printer and finisher is that when the option of printing followed by coating is available significant cost advantages occur.
1~16~35;~
S-talelnen-t o~ the Invent-ion ,. . ~
A process is providecl for producing a pressure-sensitive carbonless record sheet comprising the steps of preparing a hot melt coating composi-tion, the hot melt coating composition having a melting point of from about 60C to about 140C. The hot melt coating composition comprises a chromo-genic material and a solid aliphatic dioic acid. The hot melt coating com-position is heated to a temperature above its melting point and the heated coating composition is applied to a substrate, the coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate. The coating composition is set by cooling the coated substrate. A pressure-sensitive carbonless record sheet comprising a substrate having a plurality of surfaces and at least one surface of which is coated with about 0.2 pounds to about 8 pounds per 3300 square feet of a set hot melt coating composition is produced. The set hot melt coating composition has a melting point of from about 60C to about 140C and comprises a chromo-genic material and a solid aliphatic dioic acid. A novel hot melt chromogenic coating composition having a melting point of from about 60C to about 140C
and comprising a chromogenic material and a solid aliphatic dioic acid is pro-duced.
t~5 2 r)et(liled l)escription_of the Irlv_n ion The chromog~nic hot melt coating cor,~position of this invention is essentially a combination of one or more solid aliphatic dioic acids with one or more chromo-genic materials. The dioic acid acts as a hot melt binder in these compositions.The chromogenic materials and dioic acids are preferably miscible or partially miscible with each other in their molten form so that separation of the compo-nents of the composition substantially does not occur during application and setting of the chromogenic hot melt composition.
Other materials may be added, if desired, to the chromogenic coating composition to modify the melting point or other rheological properties or to modify its color or its color producing or physical properties. The use of volatile solvents, including organic solvents and water, in amounts large enoughto require a separate step for drying during setting of the hot melt compositionis to be avoided. Minor amounts of these solvents can be tolerated, and in some cases may be even beneficial. For example, a small amount of water, up to about 5% by weight based on the total weight of the coating composition, ~lill act as a plasticizer and rheology modifying material without requiring drying duringthe setting step.
- A preferred use of the chromogenic coating compositions of this invention is in the preparation of pressure-sensitive carbonless record sheets. Such papers can be used in manifold copy systems in combination with pressure-sensitive transfer sheets containing oil solutions of color precursors of the electron donor type. A preferred group of electron donor color precursors include the lactone phthalides, such as crystal violet lactone, and 3,3-bis-(l'-ethyl-2-methylindol-3"-yl) phthalide, the lactone fluorans, such as 2-dibenzyl-amino-6-diethylaminofluoran and 6-diethylamino-1, 3-dimethylfluorans, the lactone xanthenes, the leucoauramines, the 2-(omega substituted vinylene)-3,3-disubstituted -3-H-indoles and 1,3,3-trialkylindolinospirans.
The dioic acids useful in the practice of this invention are the solid aliphatic dicarboxylic acids. The preferred dioic acids have a carbon chain of about 3 to about 10 carbon atoms. The preferred range of dioic acid is from about 30'~ to about 99.9% by weight of the composition.
S~
They are water soluble compounds having a sharply defined, relatively high melting point. Ex~mples of the preferretl dioic acids are the following:
Name of AcidCarbons in ChainApproximate Melting Point C
Glutaric Acid 5 99 Pimelic Acid 7 106 S~iberic Acid 8 140 Azelaic Acid 9 107 Sebacic Acid 10 135 All of these acids are commercially available. For example, azelaic acid is available under the trade name "Emerox" from Emery Industries, Cin-cinnati, Ohio.
A particular advantage of the use of the dioic acids as the hot melt binder over the water insoluble hydrophobic waxes of the prior art, such as the hydrocarbon (paraffin) waxes, is that these acids are relatively polar.
This permits the use of chromogenic materials, particularly color developers, which are more polar in character than those previously used. Examples of such developers are phenolphthalein, certain metal salts and gallic acid. These polar color developers are at least partially miscible with the molten dio;c acids and thus form a homogenous blend of the melted developer and dioic acid.
In contrast to this, hydrophobic waxes, such as paraffin are not m;scible in the melted condition with the polar color developers and thus do not form homogenous blends with the polar color developers.
The solid aliphatic dioic acids of this invention are not reactive with electron-donor types of color precursors and thus have not been found to produce color in the absence of the chromogenic material of this invention.
Furthermore, the presence of these acids in the hot melt composition does not interfere with the reaction of the color prescursor and chromogenic material (developer) to form a color.
~ The chromogenic materials most useful are the color developers of the : 30 acidic electron-acceptor types. These developers include but are not limited to phenolic materials as other electron-acceptor types such as certain organic metal compounds and colloidal silica and acid clays have been found to be useful.
Metal compounds which have been found to be acceptable are zinc thiocyanate, zinc p-toluenesulfonic acid and zinc ammonium thiocyanate.
10.
,i 1 ~ 1t;8 5~
The preferred color dcvelopers are the phenolic co~pounds, novolak resins and their zincated compounds and resins. The phenolic compounds are solid àt normal room temperature. These preferred color developers include phenol-phthalein, salicylic acid. 3,5-di-tert-butyl salicylic acid, ammonium 5,5-S methylene disalicylic acid, salicylsalicylic acid, l-hydroxy-2-naphthoic acid, resorcinol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, 2-ethyl-hexyl gallate, tert-butyl phenol, p-phenylphenol, p-octylphenol, BisphenolA, sulfonyl d;phenol, p-phenylphenol novolak resin, p-octylphenol novolak resin (4% zinc), zincated p-phenylphenol novolak resin (4% zinc), zinc salicylate, the zinc salt of 3,5-di-tert-butyl salicylic acid and mixtures thereof. A
preferred combination of phenolic compounds or resins with zinc salts of organic acids, such as zinc thiocyanate produced intense blue images.
The preferred range of chromogenic material in the coating composition is from about 0.1% to about 35% by weight of the total composition. A most preferred range is from about 2% to about 25%. The optimum amount may vary somewhat depending on the particular chromogenic material used, the dioic acid used, the coat weight desired and the character and amount of any other ~ modifying material which may be added to the coating composition as desired.
- The chromogenic material may be supplemented with materials which act as color intensifiers and color stabilizers. These color intensifiers are materials-~ which in themselves produce little or no color in the presence of the electron ; donorcolor precursors. However, these same materials have been found to inten-sify colors produced by the color developers of this invention. Preferred color - intensifiers are arnmonium thiocyanate~ aluminum oxide and zinc compounds such as zinc oxide, zinc chloride, zinc nitrate, zinc gallate, zinc stearate, zinc neopentoate and zinc lineoleate.
Minor amounts of materials such as resins, waxes and liquid plasticizers may be added to the coating composition to modify the rheology of the composition and/or characteristics of the set coating. In general, these rheology modifying ;85~
rials can be non-poldr or ~olar. By polar it is meant that a certain amount of polarity is characteristic of these materials, the polar materials being characterized by the presence of functional groups selected from the group consisting of carboxyl, carbonyl, hydroxyl, ester, amide, amine, heterocyclic groups and combinat;ons thereof. The rheology modifying mater;als may vary in viscosity from liquids such as water to the low molecular weight polypropylene glycol ethers and esters. Other modifying materials which may be used are polyethylene glycols, polystyrenes, polyesters, polyacrylates, rosin, modified rosins, polyphenyls, fatty acids, fatty acid derivatives, oxazoline waxes, natural waxes, paraffin waxes microcrystalline waxes and fatty amides. These modifying materials may be present in an amount of from ; about 0% to about 10% by weight of the hot melt coating compos;tion. The preferred range is from about 0% to about 5% and the most preferred range is from about 0% to about 2% of the coating composition.
lS A desirable characteristic of the hot melt coating composition of this invention is a melting point of from about 60C to about 140C., although a more preferred melting point for the coating compositions is from about 70C
to about 100C. Also relative to the melting point, it is desirable for the coating composition of this invention to set rapidly after application to ~he .,:
particular substrate. More specifically, a practical melting range limitation or in other words range of temperature in which the liquid hot melt coating composition sets into a solid composition, is from about 0.1 C to about 15C.
The preferred setting time is from about 0.1 seconds to about 5 seconds while the most preferred setting time is from about 0.1 seconds to about 1 second.
While hot melt compositions having a melting range of more than 15C can be used, the time necessary for such a coating composition to set requires special apparatus and handling and makes use of these hot melt compositions commerciallyunattractive. Due to their sharply defined melting points, the dioic acids~of this invention have the particular advantage of keeping the melting range below 15C.
~16~52 The preferred hot melt coa-ting compositions of this invention have a low viscosity when in a molten state in order to facilitate ease of spreading on the substrate. In general, it is desirable that the hot melt coating compo-sition have a v;scosity of less than about 500 cent;poises at a temperature of approximately 5 above the melting point of a particular hot melt coating composition. In addition, it is preferred that the hot melt coating composition of this invention have a light color in order to be compatible with the final paper or plastic product being produced. This means that it is preferred for the hot melt to be white or colorless after application to the particular substrate being coated.
Pigment materials can be added to the coating composit;on as flattening agents to reduce the glossy appearance of the cured hot melt coatings and preserve the appearance of the substrate. Thus a bond paper which has been coated with the coating composition of this invention and which is then cured to a solid gives the impression of being an uncoated bond paper. Typical of the pigments which can be used are diatomaceous earth, calcium carbonate, tita-nium dioxide, barium sulfate, colloidal alumina, colloidal silica, acid clays and bentonite.
The chromogenic coating composition may be prepared by melting the dioic acid and stirring, grinding or melting in the color developer and other desired materials.
The chromogenic color developing coating composition can be applied hot to a substrate, such as paper or a plastic film by any of the common pap~r coating processes, such as roll, blade coating or by any of the common printing - 25 processes, such as planographic, gravure, or flexographic printing. The rheolo-gical properties, particularly the viscosity of the coating composition~ can be adjusted for each type of application by proper selection of the type and relative amounts of modifying materials. ~Ihile the actual amount of the hot melt coating composition applied to the substrate can vary depending on the particular final product desired, for purposes of coating paper substrates, the practical range of coat weights for the CF chromogenic coating compositions of this inven-tion are from about 0.2 pounds to about 8 pounds per 3300 square feet of , . .
;852 substrate, the preferred range being from about 0.2 pounds to about 5 pounds per 3300 sq~lare feet of substrate and the most preferred range being from about 0.2 pounds to about 2.5 pounds per 3300 square feet of substrate. Coat weights above the preferred range do not show any substantial improvement over those within the most preferred range.
These hot melt coating compositions can be set by any cooling means. Preferably a chill roll is used on the coating apparatus which cools the hot melt coating immediately after coating, but is also quite common to simply allow the coating composition to cool naturally by atmospheric exposure. As the temperature of the coating composition is substantially higher than room temperature and in light of the fact that the coating thickness is generally less than 50 microns it can be seen that when spread out over a coated substrate the hot melt material cools very rapidly. The actual exposure or chill time necessary for setting of the chromogenic coating composition is dependent on a number of variables, such as coat weight, the particular color developers and rheology modifying materials used, type of cooling means, temperature of the cooling means, specific substrate being coated and others.
In the preferred application of the process and products of this invention a manifold carbonless form is produced. In this process a continuous web is marked with a pattern on at least one surface. A non-aqueous, solvent free hot melt coating of chromogenic material is applied to at least a portion of at least one surface of the continuous web. The coated surface is then set by cooling. The continuous web having the set coating is then combined with at least one additional continuous web which has been previously or simultaneously coated with a hot melt material and set by cooling. A manifold carbonless form is then made by a variety of collating and finishing steps. Such a process and product are described in commonly assigned, United States Patent .~ 3 - 14 -111~;85Z
No. 4,112,138 entitled "Manifold Carbonless Form and Process for the Production Thereof (custom)" issued September 5, 1978.
In the most preferred application of the process and products of this invention a manifold form is continuously produced. In this most preferred embodiment a plurality of continuous webs are advanced at substantially the same speed, the plurality of continuous webs being spaced apart and being advanced in cooperating relationship with one another. At best one web of the plurality of continuous webs is marked with a pattern and at least one non-aqueous, solvent-free hot melt coating containing the chromogenic material is applied to at least a portion of at least one of the plurality of continuous webs. The hot melt material is then set by cooling. The continuous webs are then collated and placed in contiguous relationship to one another to create a manifold form. After the continuous webs are placed in collated, contiguous relationship they can be finished by any combination of the steps of combining, partitioning, stacking, packaging and the like. Such a process and product are described in commonly-assigned, United States Patent No. 4,097,619 entitled "Manifold Carbonless Form and Process for the Continuous Production Thereof (Standard)" issued on June 27, 1978.
The following examples illustrate preferred embodiments but do not limit the scope of the invention which is defined in the claims.
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E:x~mpl e 1 3 parts of sebacic acid and 1 part of 3,5-di-tert-but.yl salicylic acid were melted together and 0.2 part of solid ammonium thiocyanate was ground into the melt using a mortar and pestle to form a hot melt composition.
Using a blade heated to about 170C, the hot melt composition ~/as coated on paper and cooled to produce a coated paper having about 5 pounds of set coating per 3300 square feet of paper.
The set, coated paper was tested by placing the coated surface thereof in contact with the coated side of a CB paper coated with getatin m;crocapsules containing a marking oil made up of 180 parts of monoisopropylbiphenyl~ 5.3 parts of crystal violet lactone, 0.62 parts of 3,3-bis-(1-ethyl-2-methylindol-3-yl)-phthalide, 1.25 parts of 3-N-N-diethylamino-7-(N,N-dibenzylamino)-fluoran,0.95 parts of 2,3-(-1'-phenyl-3'methylpyrazolo )-7-diethylamino-4-spirophthalido-chromene and 122 parts of odorless kerosene. These sheet couples were imaged with an electric typewriter using the character "m" in a repeating block pattern, and the intensity and color of the images after an elapsed time of 10 minutes was recorded '~ ' An intense blue image was produced on the hot melt coated paper Example 2 3 parts of sebacic acid and 1 part of 3,5-di-tert-butyl salicylic acid were melted together as in Example 1. To this hot melt was added 0.5 parts of a second hot melt consisting of the following:
72.7 parts urea 7.3 parts polyvinyl pyrolidone 7 3 parts zinc oxide 7 3 parts ammonium thiocyanate 5.3 parts hydantoin The resultant coating composition was coated on paper and the coated paper was pressure irnaged as in Example 1 The coat weight was about 3 pounds per 3300 square feet of paper An intense brilliant blue image was formed 16.
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E ample 3 Into 8 parts of se~acic acid was ground 0.2 parts of ammonium thiocyanate and 0.1 parts of zinc oxide. The composition was coated on paper and the paper was pressure imaged as in Example 1. An intense violet-blue image was pro~uced.
Example 4 Example 3 was repeated additionally adding by grinding in 0.2 parts of urea to the hot melt coating compos;t;on. An intense blue ;mage was produced.
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Examples 5 through 12 A series of hot melt coating compositions were made in which the relative 0 amounts of color developer and dio;c acids were varied and different representa-tive d;oic acids were used. The color developer was a p-phenylphenol novolak resin. The hot melt composit;ons were prepared by melting together the ingre-- dients of each composition. The hot melt compositions were coated on paper and the papers were tested as ;n Example 1. The approximate melting point was determined for each composition by allowing a bead of molten composition to ` cool on the bulb of a thermometer and recording the temperature at which the bead became solid. The results are in Table 1 which follows:
TABLE I
Compositio~ of Hot Melt Approximate Description Example No. Color DeveloperDioic Acid Melting PointC of Imaqe 75 parts 25 parts azelaic 55~ Intense Blue 6 50 parts 50 parts azelaic 653 Intense Blue 7 25 parts 75 parts azelaic 804 Intense Blue 8 25 parts 75 parts glutaric 86 Moderate Blue 9 25 parts 75 parts pimelic 87 Intense Blue 25 parts 64 parts azelaic 60 Moderate Blue 7 parts pimelic ~4 parts glutaric 11 As Example 7 + 15 parts diatomaceous earth - Intense Grey-Blue 1. Color deve~oper is p-phenyl~henol novolak resin.
2. Hot melt composition is stiff and sticky at 55O.
3. Hot melt composition is too stiff to stir at 65 C.
4. Hot melt composition is a dry solid with a smooth non-sticky surface.
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Exameles_12 th ough 25 A series oF hot melt coating compositions were made in ~Ihich the relative amounts of azelaic acid were varied and different developers were used. The hot melt compositions were coated and tested as in Example 1. The results are given in Table II.
TABLE II
Example No. ComPosition of Hot Melt DescriPtion of Imaqe 12 0.1 part phenolphthalein Moderate Reddish elue 99.9 parts azelaic acid 13 0.5 parts salicylic acid Faint Purple 99.5 parts azelaic acid 14 1 part ammonium, 5,5'-methylene Pale Blue disalicylic acid 99 parts azelaic acid 1520 parts ammonium, 5,5'-methylene Moderate Blue disalicylic acid 80 parts azelaic acid 161 part tert-butyl phenol Moderate Blue 99 parts azelaic acid 1710 parts tert-butyl phenol Moderate Blue 90 parts azelaic acid 185 parts Bisphenol A Moderate Purple 9S parts azelaic acid 191 part sulfonyl diphenol Pale Purple 99 parts azelaic acid 2010 parts sulfonyl diphenol Pale Purple 90 parts azelaic acid 211 part gallic acid Blue 99 parts azelaic acid 2220 parts ethylhexyl gallate Intense Blue 80 parts azelaic acid 23 5 parts l-hydroxy, 2-naphthoic Moderate Purple acid 95 parts azelaic acid 24 5 parts zincated p-octyl-phenol Moderate Blue novolak resin (4% Zn) 95 parts azelaic acid 35 parts p-phenylphenol novolak Intense Blue resin 65 parts azelaic acid 18.
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Example 26 A hot melt composition was prepared by melting 6 parts of azelaic acid and adding 0.1 part of zinc carbonate, degassing the composition by applying ; a vacuum (about 25 mm absolute pressure) and adding 0.1 part of potass;um thiocyanate and 1 part of p-phenylphenol novolak resin. The hot melt coating composition was coated on paper and the coated paper was tested as in Example 1.Intense bright blue images were formed, which images were rès~stant to light ageing and water spotting.
`~ Example 27 -- 10 The hot melt composition of Example 7 was printed by means of a gravure offset press at a speed of 500 feet per minute on the obverse side of the CB
`~ paper of the type used in the pressure imaging of Example 1 Coat weights ranging from about 1 to about 4 pounds per 3300 square feet of paper were applied. A sheet of the printed paper was pressure imaged as in Example 1 with the printed hot melt side against the CB side of the second sheet.
Intense blue images were produced on the printed side of each of the papers tested regardless of coat weight.
_ample 28 Example 27 was repeated, however, instead of applying the hot melt composition to the obverse side of the CB paper, the hot melt coating was printed on the CB surface of the coated paper to form a self-contained paper.
Pressure imaging of the paper with a typewriter produced intense blue images.
From Examples 27 and 28 it can be seen that CF coatings of the hot melt type of the instant invention can effectively be printed in fluid hot melt form, set 2~ by cooling, and joined with a CB sheet to produce a carbonless copy system which upon application of pressure gives good transfer and a sharp developed image.
It is thus possible to utilize the hot melt CF coatings of this invention in thecontinuous production of manifold carbonless forms, especially ones in which theCF coatings are spot coated as a savings.
19.
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Exameles_12 th ough 25 A series oF hot melt coating compositions were made in ~Ihich the relative amounts of azelaic acid were varied and different developers were used. The hot melt compositions were coated and tested as in Example 1. The results are given in Table II.
TABLE II
Example No. ComPosition of Hot Melt DescriPtion of Imaqe 12 0.1 part phenolphthalein Moderate Reddish elue 99.9 parts azelaic acid 13 0.5 parts salicylic acid Faint Purple 99.5 parts azelaic acid 14 1 part ammonium, 5,5'-methylene Pale Blue disalicylic acid 99 parts azelaic acid 1520 parts ammonium, 5,5'-methylene Moderate Blue disalicylic acid 80 parts azelaic acid 161 part tert-butyl phenol Moderate Blue 99 parts azelaic acid 1710 parts tert-butyl phenol Moderate Blue 90 parts azelaic acid 185 parts Bisphenol A Moderate Purple 9S parts azelaic acid 191 part sulfonyl diphenol Pale Purple 99 parts azelaic acid 2010 parts sulfonyl diphenol Pale Purple 90 parts azelaic acid 211 part gallic acid Blue 99 parts azelaic acid 2220 parts ethylhexyl gallate Intense Blue 80 parts azelaic acid 23 5 parts l-hydroxy, 2-naphthoic Moderate Purple acid 95 parts azelaic acid 24 5 parts zincated p-octyl-phenol Moderate Blue novolak resin (4% Zn) 95 parts azelaic acid 35 parts p-phenylphenol novolak Intense Blue resin 65 parts azelaic acid 18.
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Example 26 A hot melt composition was prepared by melting 6 parts of azelaic acid and adding 0.1 part of zinc carbonate, degassing the composition by applying ; a vacuum (about 25 mm absolute pressure) and adding 0.1 part of potass;um thiocyanate and 1 part of p-phenylphenol novolak resin. The hot melt coating composition was coated on paper and the coated paper was tested as in Example 1.Intense bright blue images were formed, which images were rès~stant to light ageing and water spotting.
`~ Example 27 -- 10 The hot melt composition of Example 7 was printed by means of a gravure offset press at a speed of 500 feet per minute on the obverse side of the CB
`~ paper of the type used in the pressure imaging of Example 1 Coat weights ranging from about 1 to about 4 pounds per 3300 square feet of paper were applied. A sheet of the printed paper was pressure imaged as in Example 1 with the printed hot melt side against the CB side of the second sheet.
Intense blue images were produced on the printed side of each of the papers tested regardless of coat weight.
_ample 28 Example 27 was repeated, however, instead of applying the hot melt composition to the obverse side of the CB paper, the hot melt coating was printed on the CB surface of the coated paper to form a self-contained paper.
Pressure imaging of the paper with a typewriter produced intense blue images.
From Examples 27 and 28 it can be seen that CF coatings of the hot melt type of the instant invention can effectively be printed in fluid hot melt form, set 2~ by cooling, and joined with a CB sheet to produce a carbonless copy system which upon application of pressure gives good transfer and a sharp developed image.
It is thus possible to utilize the hot melt CF coatings of this invention in thecontinuous production of manifold carbonless forms, especially ones in which theCF coatings are spot coated as a savings.
19.
5~
The only re~luirenlent is that a hot melt coating or printiny operation (i.e., one in which the coating is maint2ine~ at above melting point of the coating) is followed by a cooling step to set the resulting coating As mentioned such a system is much less expensive and cumbersome, requ;res less floor space and requires less energy than systems which require expensive driers and/or solvent recovery systems.
While the method herein described constitùtes a preferred embodiment of the invention, it is to be understood that the invention is not limited to this precise method, and that changes may be made therein without depart1ng from the scope of the invention which is defined in the appended claims.
20.
The only re~luirenlent is that a hot melt coating or printiny operation (i.e., one in which the coating is maint2ine~ at above melting point of the coating) is followed by a cooling step to set the resulting coating As mentioned such a system is much less expensive and cumbersome, requ;res less floor space and requires less energy than systems which require expensive driers and/or solvent recovery systems.
While the method herein described constitùtes a preferred embodiment of the invention, it is to be understood that the invention is not limited to this precise method, and that changes may be made therein without depart1ng from the scope of the invention which is defined in the appended claims.
20.
Claims (17)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED
ARE DEFINED AS FOLLOWS:
1. A process for producing a pressure-sensitive car-bonless record sheet comprising the steps of:
(a) preparing a hot melt coating composition, said hot melt coating composition having a melting point of from about 60° C. to 140° C., said hot melt coating composition comprising from about 0.1% to about 50.0%, by weight, of a chromogenic material and from about 50% to about 99.9% of a solid alkane dioic acid, said chromogenic material being a color developer of the acidic electron acceptor type, said alkane dioic acid being a water soluble dicarboxylic acid having a carbon chain of at least 5 carbon atoms;
(b) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition;
(c) applying said heated coating composition to a substrate, said coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate, and, (d) setting said coating composition by cooling said coated substrate.
(a) preparing a hot melt coating composition, said hot melt coating composition having a melting point of from about 60° C. to 140° C., said hot melt coating composition comprising from about 0.1% to about 50.0%, by weight, of a chromogenic material and from about 50% to about 99.9% of a solid alkane dioic acid, said chromogenic material being a color developer of the acidic electron acceptor type, said alkane dioic acid being a water soluble dicarboxylic acid having a carbon chain of at least 5 carbon atoms;
(b) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition;
(c) applying said heated coating composition to a substrate, said coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate, and, (d) setting said coating composition by cooling said coated substrate.
2. The process of claim 1 wherein said substrate is paper.
3. The process of claim 1 wherein said coating composition additionally contains a color intensifier.
4. The process of claim 1 wherein said solid alkane dioic acid is selected from the group consisting of azelaic, glutaric, pimelic, suberic, adipic, and sebacic acids and mixtures thereof.
5. The process of claim 1 wherein said alkane dioic acid includes azelaic acid.
6. A process for producing a pressure-sensitive carbonless record sheet comprising the steps of:
(a) preparing a hot melt coating composition, said hot melt coating composition having a melting point of from about 60° C. to about 140° C., said hot melt coating composition including from about 0.1% to about 50%, by weight, of a chromogenic material and from about 50% to about 99.9%, by weight, of an alkane dioic acid, said chromogenic material being a color developer of the acidic electron acceptor type, said alkane dioic acid being a water soluble dicarboxylic acid having a carbon chain of at least 5 carbon atoms;
(b) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition;
(c) applying said coating composition to a paper substrate, said coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of paper substrate; and (d) setting said coating composition by cooling said coated paper substrate.
(a) preparing a hot melt coating composition, said hot melt coating composition having a melting point of from about 60° C. to about 140° C., said hot melt coating composition including from about 0.1% to about 50%, by weight, of a chromogenic material and from about 50% to about 99.9%, by weight, of an alkane dioic acid, said chromogenic material being a color developer of the acidic electron acceptor type, said alkane dioic acid being a water soluble dicarboxylic acid having a carbon chain of at least 5 carbon atoms;
(b) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition;
(c) applying said coating composition to a paper substrate, said coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of paper substrate; and (d) setting said coating composition by cooling said coated paper substrate.
7. The process of claim 6 wherein said solid alkane dioic acid is selected from the group consisting of azelaic, glutaric, pimelic, suberic, adipic, and sebacic acids and mixtures thereof.
8. The process of claim 6 wherein said color developer is selected from the group consisting of phenolphthalein, salicylic acid, 3,5-di-tert-butyl salicylic acid, ammonium 5,5'-methylene disalicylic acid, salicylsalicylic acid, 1-hydroxy-2-naphthoic acid, resorcinol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, 2-ethylhexyl gallate, tert-butylphenol, p-phenylphenol, Bisphenol A, sulfonyl-diphenol, p-phenylphenol novolak resin, p-octylphenol novolak resin, p-tert-butylphenol novolak resin, zincated p-octylphenol novolak resin (4% zinc), zincated p-phenyl-phenol novolak resin (4% zinc). Zinc salicylate, the zinc salt of 3,5-di-tert-butyl salicylic acid, zinc thiocyanate, zinc p-toluenesulfonic acid, zinc ammonium thiocyanate and mixtures thereof.
9. A pressure-sensitive carbonless record sheet comprising of a substrate having a plurality of surfaces, at least one of said surfaces being coated with about 0.2 pounds to about 8 pounds per 3300 square feet of a set hot melt coating composition, said set hot melt coating composition comprising from about 0.1% to about 50.0% of a chromogenic material and from about 50% to about 99.9% of a solid alkane dioic acid, said chromogenic material being a color developer of the acidic electron acceptor type, said solid alkane dioic acid being a water soluble dicar-boxylic acid having a carbon chain of at least 5 carbon atoms, said set hot melt coating composition having a melting point of about 60° C. to about 140° C.
10. The pressure-sensitive carbonless record sheet of claim 9 wherein the substrate is paper.
11. The record sheet of claim 9 wherein said solid alkane dioic acid is selected from the group consisting of azelaic, glutaric, pimelic, suberic, adipic, and sebacic acids and mixtures thereof.
12. The record sheet of claim 9 wherein said solid alkane dioic acid include azelaic acid.
13. The record sheet of claim 9 wherein said color developer is selected from the group consisting of phenol-phthalein, salicylic acid, 3,5-di-tert-butyl salicylic acid, ammonium 5,5'-methylene disalicylic acid, salicyl-salicylic acid, 1-hydroxy-2-naphthoic acid, resorcinol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, 2-ethylhexyl gallate, tert-butylphenol, p-phenylphenol, Bisphenol A, sulfonyldiphenol, p-phenylphenol novolak resin, zincated p-octylphenol novolak resin, p-tert-butyl-phenol novolak resin, zincated p-octylphenol novolak resin, zincated p-octylphenol novolak resin (4% zinc), zincated p-phenyl-phenol novolak resin (4% zinc), zinc salicylate, the zinc salt of 3,5-di-tert-butyl salicylic acid, zinc thiocyanate, zinc p-toluenesulfonic acid, zinc ammonium thiocyanate and mixtures thereof.
14. A hot melt chromogenic coating composition having a melting point of from about 60°C to about 140°C comprising from about 0.1% to about 50.0%, by weight, of a chromogenic material and from about 50% to about 99.9% of a solid aliphatic dioic acid, said chromogenic material being a color developer of the acidic electron acceptor type, and said alkane dioic acid being a water soluble dicarboxylic acid having a carbon chain of at least 5 carbon atoms.
15. The coating composition of claim 14 wherein said chromogenic material color developer is present in an amount from about 0.1% to about 35% by weight of said composition.
16. The coating composition of claim 14 wherein said aliphatic dioic acid is a water soluble dicarboxylic acid having a carbon chain of up to about 10 carbon atoms.
17. The coating composition of claim 14 wherein said aliphatic dioic acid is selected from the group consisting of azelaic, glutaric, pimelic and sebacic acids and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86999578A | 1978-01-17 | 1978-01-17 | |
| US869,995 | 1978-01-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116852A true CA1116852A (en) | 1982-01-26 |
Family
ID=25354575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000315916A Expired CA1116852A (en) | 1978-01-17 | 1978-11-07 | Production of pressure-sensitive carbonless record sheets using dioic acid hot melt systems and products thereof |
Country Status (14)
| Country | Link |
|---|---|
| JP (2) | JPS5497106A (en) |
| AU (1) | AU521717B2 (en) |
| BE (1) | BE872371A (en) |
| BR (1) | BR7808602A (en) |
| CA (1) | CA1116852A (en) |
| DE (1) | DE2901390A1 (en) |
| FI (1) | FI65189C (en) |
| FR (1) | FR2414408A1 (en) |
| GB (1) | GB2012795B (en) |
| IT (1) | IT1114352B (en) |
| MX (1) | MX149572A (en) |
| NO (1) | NO152541C (en) |
| SE (1) | SE439900B (en) |
| ZA (1) | ZA786238B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU595207B2 (en) * | 1985-06-13 | 1990-03-29 | North Broken Hill Limited | Coated front copy paper |
| JP4863248B2 (en) * | 2005-01-20 | 2012-01-25 | 九州日立マクセル株式会社 | Electric razor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS551195B2 (en) * | 1972-09-27 | 1980-01-12 | ||
| JPS5314006B2 (en) * | 1973-07-14 | 1978-05-15 | ||
| CH593147A5 (en) * | 1975-10-08 | 1977-11-30 | Ciba Geigy Ag | |
| US4063754A (en) * | 1976-05-07 | 1977-12-20 | The Mead Corporation | Process for the production of pressure sensitive carbonless record sheets using novel hot melt systems and products thereof |
-
1978
- 1978-11-06 ZA ZA00786238A patent/ZA786238B/en unknown
- 1978-11-07 SE SE7811479A patent/SE439900B/en not_active IP Right Cessation
- 1978-11-07 CA CA000315916A patent/CA1116852A/en not_active Expired
- 1978-11-14 AU AU41574/78A patent/AU521717B2/en not_active Expired
- 1978-11-29 BE BE192015A patent/BE872371A/en not_active IP Right Cessation
- 1978-11-30 FI FI783670A patent/FI65189C/en not_active IP Right Cessation
- 1978-11-30 JP JP14734678A patent/JPS5497106A/en active Granted
- 1978-12-01 NO NO784036A patent/NO152541C/en unknown
- 1978-12-14 MX MX176010A patent/MX149572A/en unknown
- 1978-12-14 FR FR7835236A patent/FR2414408A1/en active Granted
- 1978-12-28 BR BR7808602A patent/BR7808602A/en unknown
-
1979
- 1979-01-15 DE DE19792901390 patent/DE2901390A1/en not_active Withdrawn
- 1979-01-15 IT IT47646/79A patent/IT1114352B/en active
- 1979-01-15 GB GB791439A patent/GB2012795B/en not_active Expired
-
1985
- 1985-11-08 JP JP60250585A patent/JPS61154884A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FI783670A (en) | 1979-07-18 |
| GB2012795A (en) | 1979-08-01 |
| FR2414408A1 (en) | 1979-08-10 |
| SE439900B (en) | 1985-07-08 |
| ZA786238B (en) | 1979-10-31 |
| JPS6147717B2 (en) | 1986-10-21 |
| SE7811479L (en) | 1979-07-18 |
| FI65189B (en) | 1983-12-30 |
| MX149572A (en) | 1983-11-25 |
| FI65189C (en) | 1984-04-10 |
| NO152541B (en) | 1985-07-08 |
| DE2901390A1 (en) | 1979-07-19 |
| BR7808602A (en) | 1979-08-07 |
| NO152541C (en) | 1985-10-16 |
| JPS6117678B2 (en) | 1986-05-08 |
| BE872371A (en) | 1979-05-29 |
| IT1114352B (en) | 1986-01-27 |
| IT7947646A0 (en) | 1979-01-15 |
| JPS61154884A (en) | 1986-07-14 |
| JPS5497106A (en) | 1979-08-01 |
| AU4157478A (en) | 1979-07-26 |
| GB2012795B (en) | 1982-11-24 |
| NO784036L (en) | 1979-07-18 |
| AU521717B2 (en) | 1982-04-29 |
| FR2414408B1 (en) | 1985-04-05 |
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