EP0482409A1 - Papier rapide sans carbone - Google Patents
Papier rapide sans carbone Download PDFInfo
- Publication number
- EP0482409A1 EP0482409A1 EP9191117025A EP91117025A EP0482409A1 EP 0482409 A1 EP0482409 A1 EP 0482409A1 EP 9191117025 A EP9191117025 A EP 9191117025A EP 91117025 A EP91117025 A EP 91117025A EP 0482409 A1 EP0482409 A1 EP 0482409A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- image
- alkyl
- forming component
- composition
- carbonless
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
Definitions
- the present invention relates to carbonless copying systems, and more specifically, to compositions for use with coated front (CF) paper, which compositions provide enhanced image development speed for carbonless paper at below room temperature.
- CF coated front
- Standard carbonless copying systems or pressure sensitive copying paper include a plurality of substrates, e.g., paper sheets, arranged in a manifold, each sheet having one or more coatings on a surface thereof.
- the manifold is designed so that when external pressure caused by a typewriter, pen, or other instrument is applied to the outermost sheet, a colored image will be formed on at least one surface of each sheet of the manifold.
- the top sheet of the manifold to which the pressure is applied has a coating on its back surface.
- This coated back surface typically includes microcapsules containing an initially colorless chemically reactive color-forming dye precursor as the fill material.
- the front surface of the next sheet, which is adjacent to the back surface of the top sheet, is coated with a material containing a component, such as phenolic resin or reactive clay, that is capable of reacting with the colorless dye precursor contained in the microcapsules to produce a color.
- a component such as phenolic resin or reactive clay
- the sheets of the carbonless copying system manifold are designated in the art by the terms CB for "coated back,” CFB for “coated front and back,” and CF for "coated front.”
- the CB or transfer sheet is usually the top sheet of the manifold and the sheet to which the external pressure is applied.
- the CFB sheets are the intermediate sheets of the manifold, each of which is able to have an image formed on its front surface by a pressure, and each of which also transmits the contents of ruptured microcapsules from its back surface to the front surface of the next sheet.
- the CF or recording sheet is the bottom sheet and is coated only on its front surface so that an image can be formed on it.
- the coating containing the microcapsules on the back surface of the sheets and to have the coating containing the reactive component for the capsules on the front surface of each of the sheets, the reverse arrangement is also possible.
- one of the reactive ingredients may be carried in the sheets themselves, rather than applied as surface coatings.
- the component that reacts with the colorless dye precursor may also be microencapsulated.
- a carbonless copying system CF coating incorporating a resin which is a phenol/aldehyde condensation product produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; along with a binder and a pigment; provides faster imaging than standard CF coatings which contain HRJ-2456, especially at temperatures below room temperature.
- the present invention provides a coating composition for use in carbonless copying systems.
- the composition comprises a phenol/aldehyde condensation product produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a pigment, wherein the composition is capable of providing enhanced image development at temperatures below 40°F.
- the present invention also provides a carbonless copying system comprising a recording substrate; a first image-forming component which is a mixture of (1) a phenol/aldehyde condensation product resin formed by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source, (2) a binder, and (3) a pigment; and a complementary image-forming component, encapsulated in microcapsules and capable of reacting with the first image-forming component to produce a colored reaction product; the first image-forming component and the complementary image-forming component are arranged in juxtaposed contact with one another whereby the application of pressure in selected areas upon the carbonless system causes a colored image to form on corresponding areas of the recording substrate, wherein the system is capable of providing enhanced image development at temperatures below 40°F.
- a first image-forming component which is a mixture of (1) a phenol/aldehyde condensation product resin formed by the interaction of an alkyl-substi
- the present invention also provides a carbonless copying system comprising a recording substrate; a transfer substrate; a first image-forming component which is a mixture of (1) a phenol/aldehyde condensation product resin formed by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source, (2) a binder, and (3) a pigment and is carried by the recording substrate; a complementary image-forming component encapsulated in microcapsules carried by the transfer substrate and capable of reacting with the first image-forming component to produce a colored reaction product; and the first image-forming component is arranged in juxtaposed contact with the complementary image-forming component whereby the application of pressure in selected areas upon the carbonless system causes colored images to form on corresponding areas of the recording substrate.
- the system is capable of providing enhanced image development at temperatures below 40°F.
- the present invention also provides a method of using the carbonless copy system of this invention at temperatures below room temperature, including temperatures below 40°F.
- a coating composition for use in carbonless copying systems.
- the composition comprises a resin which is a phenol/aldehyde condensation product produced by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a pigment.
- the coating composition is applied to a coated front (CF) sheet in a carbonless copying manifold.
- the alkyl-substituted salicylic acid is substituted with at least one alkyl group containing three or more carbon atoms. More preferably, the alkyl group contains at least four carbon atoms, even more preferably, four to twelve carbon atoms.
- Particularly useful are salicylic acids of the formula I: where R is an alkyl group containing from four to twelve carbon atoms.
- the group R is preferably octyl or nonyl, especially tertiary-octyl (derived from di-isobutene) and nonyl (derived from propylene trimer).
- the group R may also be a dodecyl group.
- the preferred group is the nonyl group.
- the alkylphenol component preferably contains at least one alkyl group containing at least three carbon atoms, more preferably, four to twelve carbon atoms.
- the phenols are phenols substituted in the para-position with an alkyl group containing four to twelve carbon atoms, particularly tertiary-butyl, tertiary-octyl, nonyl (derived from propylene trimer) and dodecyl.
- the preferred material is the tertiary-octyl group.
- the alkyl substituted group in the para position is represented by R' in formula II below.
- the aldehyde is preferably formaldehyde, although the formaldehyde may be supplied, for example, from paraformaldehyde or a similar source of formaldehyde.
- the preferred metal source is zinc oxide.
- the phenol/aldehyde condensation product may be synthesized by combining and heating the alkyl-substituted salicylic acid, the alkyl-substituted phenol, the aldehyde, the metal source and water.
- EPA 0,338,808 discloses a general example of a suitable manufacturing process: 750 parts nonylsalicylic acid, 523 parts p-t-octylphenol, 199 parts 50% formaldehyde solution, 3 parts of Daxad 30 (a wetting agent of proprietary composition available from W.R. Grace & Co.), 69 parts water and 103 parts of zinc oxide are heated to reflux with agitation. After the reaction takes place, heating is discontinued and additional wetting agent is added. The mixture is cooled with agitation, and further diluted with water. The mixture is then filtered to obtain the phenol/aldehyde condensation product.
- Daxad 30 a wetting agent of proprietary composition available from W.R. Grace & Co.
- the resin dispersion which is a component of the coating composition of the invention may be HRJ-10176 or HRJ-10802, which are trademark names of resins manufactured and supplied by Schenectady Chemicals, Inc. of Schenectady, New York. Applicant has been informed by Schenectady Chemicals, Inc. that HRJ-10176 and HRJ-10802 are each within the scope of the description and/or the claims of the phenol/aldehyde condensation product of EPA 0,338,808.
- the resin component of the coating composition of the invention is preferably present in an amount ranging from 7 to 40 parts, more preferably from 10 to 20 parts, per 100 parts of the pigment and resin. Unless otherwise stated, "parts" in this invention are parts by weight.
- the pigment component of the coating composition of the present invention can be any of those pigments known to be useful in coating compositions for carbonless copying paper.
- the pigments can be selected from, for example, Ansilex (Kaolin product manufactured by Engelhard), Hydral (hydrated alumina manufactured by Alcoa), M-60 (calcium carbonate - 70% dispersion in water manufactured by Mississippi Lime Co.) and Exsilon (Kaolin product manufactured by Engelhard).
- the pigment is used in an amount preferably ranging from 60 to 93 parts, more preferably from 80 to 90 parts, per 100 parts of the pigment and resin.
- the binder component of the coating composition of the present invention can be any of those binders known to be useful in coating compositions for carbonless copying paper.
- the binders can be selected from, for example, Penford Gum (PG) 290, Penford Gum (PG) 380 (both manufactured by Pennick and Ford) and latex.
- the binder is used in an amount of preferably ranging from 5 to 25 parts, more preferably from 10 to 20 parts, per 100 parts of the pigment and resin.
- compositions of the present invention can include, for example, dispersing agents, such as, Tamol 850 (anionic polymer-type dispersing agent) and Colloid 230 (dispersing agent manufactured by Colloids, Inc.); ph adjustment agents, such as, ammonia 26°Be (alkaline pH adjuster); and cross-linking agents, such as, Sunrez 700m (a starch cross-linking agent manufactured by Sun Chemicals, Inc.).
- dispersing agents such as, Tamol 850 (anionic polymer-type dispersing agent) and Colloid 230 (dispersing agent manufactured by Colloids, Inc.)
- ph adjustment agents such as, ammonia 26°Be (alkaline pH adjuster)
- cross-linking agents such as, Sunrez 700m (a starch cross-linking agent manufactured by Sun Chemicals, Inc.).
- a carbonless copying system includes a recording substrate, a first image-forming component, and a complementary image-forming component.
- the first image-forming component in accordance with the invention is a mixture of a resin dispersion which is a phenol/aldehyde condensation product formed by the interaction of an alkyl-substituted salicylic acid, an alkyl-substituted phenol, an aldehyde and a metal source; a binder; and a pigment.
- the resin may preferably be HRJ-10176 or HRJ-10802.
- the complementary image-forming component is encapsulated in microcapsules and is capable of reacting with the first image-forming component to produce a colored reaction product.
- the first image-forming component and the complementary image-forming component are arranged in juxtaposed contact with one another whereby the application of pressure in selected areas upon the carbonless system causes a colored image to form on corresponding areas of the recording substrate.
- the complementary image-forming component is preferably a colorless dye precursor encapsulated in microcapsules.
- Representative colorless dye precursors that can be utilized as the complementary image-forming component include, for example, crystal violet lactone, benzol leucomethylene blue, rhodamine lactam, the p-toluene sulfonate of Michler's hydrol, and any of the various chromogenic compounds that are capable of changing from a colorless to a colored form on contact with an acidic substance.
- the microcapsules utilized for enveloping the dye precursor material may comprise a shell or wall of polymeric material, may have generally continuous walls and may range from about 0.1 to about 500 microns in diameter.
- the complementary image-forming component is carried by a transfer substrate which is in juxtaposed contact with the recording substrate.
- the image-forming component may be adhered to the transfer substrate by utilizing a known binder.
- the recording substrate and the transfer substrate are arranged adjacent to one another so that the first image-forming component and the complementary image-forming component are in juxtaposed, i.e., pressure sensitive, contact with respect to one another.
- pressure is applied to the transfer substrate at locations corresponding to areas containing the complementary image-forming component, microcapsules of the complementary image-forming component are ruptured and the contained dye precursor is released to contact and react with the first image-forming component on the recording substrate to form a standard colored image thereon.
- both the first image-forming component and the complementary image-forming component can be applied to the recording substrate.
- a transfer substrate can be utilized wherein the complementary image-forming component is carried on the transfer substrate and a first image-forming component is carried by the recording substrate.
- the external pressure is necessary to cause the microcapsules containing the complementary image-forming component to rupture may be applied to either the recording substrate itself, or in the embodiment utilizing the transfer substrate, to the transfer substrate.
- the carbonless copying system of the invention may also contain a plurality of intermediate substrates, or CFB (coated front and back) sheets, located between the transfer substrate and the recording substrate.
- CFB substrate sheets are coated on the front side of the recording substrate with the first image-forming component (corresponding to the component on the recording substrate) and are also coated on the back side with the complementary image-forming component (corresponding to the component on the transfer substrate).
- the intermediate sheets are capable of functioning as both recording and transfer sheets by forming the colored reaction products on their front side like the recording substrate, and they also enable the transfer of the complementary image-forming components to successive sheets, like the transfer substrate. This enables the formation of multiple copies of sheets, each sheet containing the standard colored images.
- the coating compositions of the examples were applied to the recording substrate by utilizing a hand drawdown with a wire round rod. A slurry was placed on the paper and the wire round rod was pulled across the surface of the paper by hand to spread the slurry coating. After the substrate was coated, the substrate was placed in a drying oven until the coating reached ambient humidity.
- Table 1 illustrates that the enhanced speed CF coating of the present invention (HRJ-10176 resin) provides for faster imaging than the standard CF coating (HRJ-2456 resin), both at room temperature and at 32°F.
- HRJ-10176 resin the enhanced speed CF coating of the present invention
- HRJ-2456 resin the standard CF coating
- the faster imaging is more pronounced at 32°F. It can be seen that, at 32°F, it takes 5 minutes for carbonless paper utilizing the resin of the invention to form an image having a % reflectance of 59.9.
- the % reflectance is 79.1 after 5 minutes, and it takes 20 minutes to form an image having a % reflectance of 58.7.
- both HRJ-10176 and HRJ-10802 provide faster imaging than conventional HRJ-2456 at room temperature and also at 32°F.
- the faster imaging is more pronounced at 32°F.
- a production sample (55 gal drum) of HRJ-10176 was used for testing in the lab (compared to a sample of HRJ-2456 and lab sample of HRJ-10176).
- the improved results achieved by the resin of the invention may be due to the fact that the resin of the invention is a condensation product of a salicylic acid.
- Salicylic acid may act as an enhancer to assist the dye in reacting with the resin.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60261990A | 1990-10-24 | 1990-10-24 | |
| US602619 | 1996-02-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0482409A1 true EP0482409A1 (fr) | 1992-04-29 |
Family
ID=24412094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP9191117025A Withdrawn EP0482409A1 (fr) | 1990-10-24 | 1991-10-07 | Papier rapide sans carbone |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0482409A1 (fr) |
| JP (1) | JPH04263986A (fr) |
| AU (1) | AU8606691A (fr) |
| CA (1) | CA2054032A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0584969A3 (fr) * | 1992-08-20 | 1995-01-25 | Moore Business Forms Inc | Composition de revêtement pour la formation d'un papier de copiage sans carbone et papier revêtu de celle-ci. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268878A2 (fr) * | 1986-11-05 | 1988-06-01 | MITSUI TOATSU CHEMICALS, Inc. | Copolymères d'acide salicylique et sels métalliques, préparation, révélateur de couleurs à base de ces sels de copolymères et feuilles pour l'enregistrement à base de ces agents |
| EP0338808A2 (fr) * | 1988-04-20 | 1989-10-25 | Schenectady International, Inc. | Résine alkyl salicylate pour papier de copiage sans carbone et son utilisation pour former des images |
| EP0361040A2 (fr) * | 1988-08-15 | 1990-04-04 | MITSUI TOATSU CHEMICALS, Inc. | Produits inodores de copolymères de l'acide salicylique modifiés par des métaux polyvalents, leurs procédés de fabrication, et leur utilisation comme agents révélateurs de couleur pour des papiers copiants sensibles à la pression |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50145739A (fr) * | 1974-05-15 | 1975-11-22 |
-
1991
- 1991-10-07 EP EP9191117025A patent/EP0482409A1/fr not_active Withdrawn
- 1991-10-23 JP JP3304039A patent/JPH04263986A/ja active Pending
- 1991-10-23 AU AU86066/91A patent/AU8606691A/en not_active Abandoned
- 1991-10-23 CA CA 2054032 patent/CA2054032A1/fr not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268878A2 (fr) * | 1986-11-05 | 1988-06-01 | MITSUI TOATSU CHEMICALS, Inc. | Copolymères d'acide salicylique et sels métalliques, préparation, révélateur de couleurs à base de ces sels de copolymères et feuilles pour l'enregistrement à base de ces agents |
| EP0338808A2 (fr) * | 1988-04-20 | 1989-10-25 | Schenectady International, Inc. | Résine alkyl salicylate pour papier de copiage sans carbone et son utilisation pour former des images |
| EP0361040A2 (fr) * | 1988-08-15 | 1990-04-04 | MITSUI TOATSU CHEMICALS, Inc. | Produits inodores de copolymères de l'acide salicylique modifiés par des métaux polyvalents, leurs procédés de fabrication, et leur utilisation comme agents révélateurs de couleur pour des papiers copiants sensibles à la pression |
Non-Patent Citations (3)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 12, no. 340 (M-740)(3187) 13 September 1988 & JP-A-63 099 983 ( MITSUI TOATSU CHEM INC ) 2 May 1988 * |
| PATENT ABSTRACTS OF JAPAN vol. 13, no. 115 (C-578)(3463) 20 March 1989 & JP-A-63 289 017 ( MITSUI TOATSU CHEM INC ) 25 November 1988 * |
| WORLD PATENTS INDEX LATEST Section PQ, Week 8826, Derwent Publications Ltd., London, GB; Class P75, AN 88-178& JP-A-63 115 782 (MITSUI TOATSU CHEM INC) 20 May 1988 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0584969A3 (fr) * | 1992-08-20 | 1995-01-25 | Moore Business Forms Inc | Composition de revêtement pour la formation d'un papier de copiage sans carbone et papier revêtu de celle-ci. |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2054032A1 (fr) | 1992-04-25 |
| AU8606691A (en) | 1992-04-30 |
| JPH04263986A (ja) | 1992-09-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): FR GB |
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| 17P | Request for examination filed |
Effective date: 19921019 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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| 18W | Application withdrawn |
Withdrawal date: 19940530 |