DE2550367A1 - 1-HYDROXY-1- (4-AMINOPHENYL-POLYMETHINE) NAPHTALANE COMPOUNDS, METHOD FOR THEIR PREPARATION AND USE OF THE SAME - Google Patents

Description

7550367

MOORE BUSINESS FORMS, INC. 1001 Buffalo Avenue, Niagara Falls, New York, U.S.A.

1-Hydroxy-1- (4-aminophenyl-polymethine) naphthalene compounds, Process for their manufacture and use thereof

1 (39822/1004

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1-hydroxy-1 - (4-aminophenyl-polymer thin) naphthalan compounds, Process for their manufacture and use thereof

The invention "originally relates to colorless chromogenic color precursors, which can be used in a particularly advantageous manner in the field of carbon-free copying technology. The compounds of the invention can, for. B. for the production of pressure-sensitive carbonless papers of the transmission or duplicating type in which a first marking component is disposed on a sheet of paper is to be implemented with a second marking component, which is usually on a sheet of paper placed on it is housed.

Carbon-free transfer papers that are sensitive to impact or pressure have recently found widespread use around the world. Usually such Papers printed and combined in multiple sets that are suitable for producing multiple copies. In doing so, caused pressure on the top sheet will mark a corresponding mark on each of the remaining sheets of the multiple set.

The top sheet of paper on which the stop or pressure is applied is usually on top of it Back side coated with microscopic capsules, which are one of the reactive components that create a mark contain. A receiver sheet placed in contact with such a back side of the top sheet is coated on its front side with a material that has a component capable of reacting with the capsule contents, so that when capsules break by applying pressure with a pen or a typewriter key, the original colorless or practically colorless contents of the broken capsules with a reaction partner for this on the receiver

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Receiving sheet reacts and a marking is formed on the receiving sheet, which is indicated by the pen or the typewriter key corresponds to the marked marking.

Transfer papers that respond to pressure are used in technology with the terms CB, CFB and CF referred to as abbreviations stand for "coated back", "coated front and back" and "coated front", d. H. so "back coated", "Front and back coated" and "front coated" mean, respectively. The CB sheet is therefore usually the top one Sheet and the one on which the impact pressure is directly applied j. the CFB sheets are the interleaves of which each forms a mark on its front and each of which shows the contents of the broken capsules of its own Back side transfers to the front side of the next following sheet; and the CF sheet is the last sheet and only on his Front side coated to create an image on it. The CF sheet is not coated on its back as usual, since no further transmission is desired.

Although it is customary to apply the capsules to the back and to apply the reaction partner for the capsule contents to the front of each sheet, the reverse procedure can also be used if desired. Furthermore, in some systems coatings need not be used at all and the reactant components can be housed in the sheets themselves, or one of these reactants can be housed in one of the sheets and the other can be present as a surface layer. Furthermore, both reactants can be incorporated into the liquids present in microcapsules. Numerous such systems of the most varied lyps in which such reactant components are used and which can be used for the production of multiple transfer papers are, for. Described as the US Patents Z 299,694, 2,712,507 3,016,308, 3,429,827 and 3,720,534.

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The most common type of carbonless pressure sensitive transfer paper and the type in which the compounds of the invention are preferably used is the z. B .. from the U.S. Patents 2,712,507 and 3,016,308 referred to in U.S. Patents 2,712,507 and 3,016,308, in which the reverse side of the sheet Microcapsules are applied, which contain a liquid, which consists of a solution of an initially colorless, chemically reactive, dye-forming color precursor compound, wherein a dry coating of a chemical reactant for the color precursor compound is on the face of a Receiving sheet is applied.

The active in the present special field of technology Numerous color precursor compounds useful in carbonless copier systems are known to those skilled in the art. Particularly referenced be z. B. to the color precursor compounds described in US Pat. No. 3,455,721, particularly in which columns 5 and 6 of this patent bridging paragraph. Other color precursors are e.g. B. in the United States patents 3 703 397 and 3 713 863. These color precursors are for reaction with a CF coating capable of containing an acidic material, e.g. B. the acid-leached clay of the bentonite type, as it is in the am United States patent application Ser. No. 125 075 is described, or the acidic reacting organic polymer material, as in U.S. Patent 3,455,721 referenced is described.

Many of the color precursor compounds known from the specified patents are capable of an acid-base reaction to enter with an acidic material. Other already known color precursor compounds are the spiro-dipyran compounds, how they z. B. in US Pat. No. 3,293,060, in particular from column 11, line 32 to column 12, line 21 will. The results from the specified patents

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known color precursors are usually initially colorless and capable of becoming strongly colored when them with an acidic layer, e.g. B. an acid-leached bentonite-type clay or an acidic polymeric material or the like.

The specified color precursors from the state of Technique are, in general terms, dissolved in a solvent and the solution obtained is enclosed in capsules, z. By the methods described in U.S. Patents 3,016,308 and 2,712,507 referenced. Other methods of encapsulating color precursor compounds are e.g. In U.S. Patents 3,429,327 and 3,578,605. In this context it deserves to be highlighted that the particular type of capsule is not critical as long as it is used to contain and enclose the Color precursor compound is enabled and by the application of pressure according to known, in the carbon-free copying technology usually method used can be broken. Typical, known for dissolving color precursor compounds suitable solvents are e.g. B. chlorinated biphenyls, vegetable oils (e.g. castor oil, coconut oil and cottonseed oil), Esters (e.g. dibutyl adipate, dibutyl phthalate, butyl benzyl adipate, Benzyl octyl adipate, tricresyl phosphate and trioctyl phosphate), Petroleum derivatives (e.g. petroleum fractions, kerosene and mineral oils), aromatic solvents (e.g. benzene and toluene), silicone oils, or combinations thereof. Those in US Pat. No. 3,005,463 are particularly suitable alkylated naphthalene solvents described.

With regard to the acidic coatings that convert the color precursors are capable of their strongly colored form, for example, reference is made to the relevant information in said U.S. Patents 3,622,364, 3,330,722, 3 38g 007 and 3,293,060, as well as to the noted U.S. Patent Application Ser. Fo. 125 075.

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In the specified color-forming systems are, as the skilled person readily recognizes the color precursor compounds as a rule in microcapsules which can be broken by the application of pressure contained in the backing layers of the sheets of carbonless multiple copy sets. It can also be seen that the acidic layers are usually applied as front side coatings, the color precursor material in one Solvent for the same from an adjacent backing layer onto the acidic layer forming the front side coating is transferred when the capsules containing the color precursor material break.

The object of the invention is to find new and improved compounds to indicate with chromogenic properties incorporated into a sheet of paper or on the surface of a sheet of paper can be applied to create multiple copy units, and which also provide improved mark generation zti make possible in reactive contact with one Dye-activating material with the achievement of brightly colored reaction products in those areas where a marking is desired.

According to the invention, the chromogenic compounds should be practical be colorless or only faintly colored and possess a wide variety of new and improved chromogenic properties and new, strongly colored substances on contact with color-activating substances Materials.

the

According to the invention should also / normally practically colorless chromogenic compounds colored reaction products when reactive Provide contact with Lewis acid materials.

Another object of the invention is the production and use of such compounds.

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The stated task is to use a compound class solvable, which are practically colorless chromogenic 1-hydroxy-1- (4-aminophenyl-p olyme thin) naphthalane color precursors of the following general formula:

where mean:

R either hydrogen atoms or short-chain alkyl radicals with 1 to 5 carbon atoms and

η is an integer from 1 to 3.

The compounds according to the invention are originally practically colorless, but can be converted into a strongly colored form are when brought into contact with a solid, a Lewis acid representing electron acceptor material, z. B. the with Bentonite-type acid-leached clay as disclosed in the referenced U.S. Patent Application Ser. No. 125 075 is described. Various other solid acidic materials that are generally capable of converting these compounds into their strongly colored form are, z. Described in U.S. Patents 3,622,364, 3,330,722, 3,389,007, and 3,293,060 referenced.

The fiction according to the specified haphthalane compounds Formula in which η = 1 can be prepared by reacting 1 mol of a p-aminobenzaldehyde compound with a hydroxy

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naphthalan compound in the presence of HOl and subsequent neutralization of the reaction product with a base according to the following reaction scheme:

CH = OH

+ 2 H ₀ O

GH-CH =

The specified hydroxynaphthalane compound can be produced by treating 1,8-naphthalide with ÖH, MgJ according to follow

the reaction scheme:

+ CH.MgJ

CH + MgJ (OH)

1,8-haphthalide can be produced from 1,8-naphthaldehyde acid and this in turn can be produced from acenaphthenquinone after those by Fuson and Munn in J.A.C.S. 71, 1870 (1949) loading

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procedures, whereby express reference is made to the entirety of this information.

According to the process of the invention is a p-aminobenzaldehyde compound can be used for the preparation of compounds of the formula given in which η = 1. For production of Compounds of the formula given in which η = 2 is a 3- (p-aminophenyl) propenal compound of the formula

R HHH

usable and for the preparation of compounds of the formula given, in which η = 3, a 5- (p-aminophenyl) pentadienal compound the formula

HHHHH IIIII

G = G-O = C-C = O

in each case instead of p-aminobenzaldehyde.

The following examples are intended to explain the invention in more detail.

example 1

100 g acenaphthenequinone was added to 500 ml of an aqueous solution having a content of 30 wt .- ^ EOH added and the resulting mixture was heated under constant stirring for about 10 minutes at 150 ⁰ C. The reaction mixture was then diluted with distilled water and filtered, and the filtrate was acidified with HGl. The white precipitate formed was separated by filtration and poured into an aqueous solution

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Solution containing 10 wt .- ^ Na ₂ CO-. contained ^ solved. The resulting solution was treated with activated charcoal and the process product was reprecipitated with Hol. The reprecipitated solids were filtered and 111 g of 1.8 ~ naphthaldehyde acid with a melting point of F = 165 "to 170 ^° C. were obtained.

Example 2

111 g of the 1,8-naphthaldehyde acid obtained according to Example 1 were dissolved in 3330 ml of a 30 % KOH solution and 110 ml of formalin were added to the resulting solution. The reaction mixture was ^{heated to about 60 °} C. and stirred at this temperature for about 3 1/2 hours. During the first hour of stirring, a further 55 ml of formalin were added. The reaction mixture was then filtered, cooled and acidified with concentrated HCl. The after acidification which formed white precipitate was collected on a filter and first 600 ml with a 5 follow NaHCO -.- solution and then washed with distilled water. The yield was 57 g. 52.4 g of this product were recrystallized several times from "high-boiling" ligroin, the yield of recrystallized 1,8-naphthalide being 42.5 g.

Example 3

9.2 g (about 0.05 mol) of 1,8-naphthalide obtained according to Example 2 became 700 ml anhydrous ether in a 1000 ml two-necked boiling flask, which was equipped with a reflux condenser and a drying tube was added. After the 1,8-naphthalide was completely dissolved in the ether, 16.5 ml of a 3 »18-Hiolaren aqueous solution of CHJVEgJ were added dropwise, while the solution was stirred. Immediately after

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A white precipitate began to form and the ether began to boil. The GEkMgJ was added at a rate such that controlled boiling was maintained in the flask. After all of the GHJOgJ was added, the reaction mixture was cooled using a The heating mantle was heated to reflux for about 30 minutes, after which 100 ml of water was added dropwise at such a rate to maintain a slow boil in the flask, the reaction mixture was transferred to a separatory funnel and the insoluble MgI (OH) was removed remaining ether layer was _{dried with Na 2} SO. and the ether was evaporated using a steam bath, leaving about 9 »0 g of an almost colorless oily product, which was a hydroxynaphthalane compound of the following formula:

Example 4

2.00 g (about 0.01 mol) of the Hydroxynaphthalanprodukt.es obtained according to Example 3 and 1.50 g (about 0.01 mol) of p-dimethylaminobenzaldehyde were dissolved in 10 ml of glacial acetic acid and the resulting solution then became HCl-G -as passed through for about 10 minutes until the color of the solution had turned an intense brown. The brown solution obtained was poured into 300 ml of water, an intensely blue solution of the dye being obtained. 3 »2 g

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1-Hydroxy-1 - (4-dimethylaminophenyl-polymethine) naphthalane color precursor compounds were precipitated by neutralizing the blue solution with an aqueous 15 " NH., Solution. The naphthalane color precursor compound obtained was dissolved in ethanol and reprecipitated with water After reprecipitation, filtration and drying, the yield was 1.0 g of a pale yellow solid of the following formula:

Example 5

0.50 g of the naphthalane product obtained according to Example 4 were mixed with 10.0 g of a mixture of isomeric diisopropylnaphthalenes des evidently in U.S. Patent 3,806,463 described type, known under the name "R-300-Solvent" (Commercial product of Kureha Corporation of America) and the resulting mixture was placed on a hot Plate gently heated until a clear Lc & ng (solution A) is obtained became. Solution Δ was then allowed to cool to room temperature (when a small amount of solution A was at a layer of acidic clay placed on a paper substrate, a purple color was formed).

1.63 g of terephthaloyl chloride were then added to 5.0 g of "R-3OO-Solvent" was added and the resulting mixture was also

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Heat gently on a hot plate until a clear solution (Solution B) was obtained. Solution B was then allowed to cool to room temperature.

After preparation of the solutions A and B were 50 g of an aqueous solution containing 2.0 wt -. ^A / o of a polyvinyl alcohol-s with 87 to 89% hydrolysis and a viscosity of 35 to 45 cps in a 4 $ aqueous solution at 20 ⁰ O, known under the name "Elvanol 50-42" (commercial product of EI duPont de Nemours), introduced into a semimicro-V / ring mixer, and then solutions A and B were mixed with one another at room temperature, whereupon the solution obtained to the "Elvanol ^n" solution in the mixer. The mixer was started and stirring was carried out at high shear for about 2 minutes until an emulsion with a particle size of the disperse phase of about 2 to 10 microns was obtained. In this emulsion The aqueous solution containing the "Elvanol® polyvinyl alcohol" formed the continuous phase and the solution containing the "R-300 solvent", the 1-hydroxy-1- (4-dimethylaminophenyl polymethine) naphthalene and terephthaloyl chloride contained, formed the disperse phase. The emulsion was then placed in a suitable vessel, e.g. B. a beaker, and stirred with a variable speed mechanical stirrer at 300 to 500 rpm while an aqueous solution containing 0.93 g of diethylenetriamine, 0.72 g of sodium carbonate and 10 ml of water was added. Stirring was continued at room temperature for about 24 hours until a stable pH of about 8.0 was observed. At this point in time, the particles of the disperse phase had been individually encapsulated in a polyamide shell.

The slurry containing the microcapsules and the "Elvanol" polyvinyl alcohol binder in the continuous Phase was then increased to a continuous 5 »9 kg

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(13 pound) -Neutralbasis post paper web void contacted with a coating weight of about 2.34 "to 3> O4 g / m ^ to the coated paper sheet was oven dried for about 30 to 45 seconds at a temperature of 110 ⁰ C. The dry layer on the paper was white The dry coating of microcapsules containing the 1-hydroxy-1- (4-dimethylaminophenyl-polymethine) naphthalane compound was then brought into contact with an acid-leached clay layer applied to the surface of another sheet of paper, and if on When a pressure mark was applied to the side of the sheet opposite the microcapsule coating, a corresponding, light purple-colored reproduction of this pressure mark immediately appeared on the acid-leached clay layer.

Correspondingly advantageous results were obtained if instead of the 1-hydroxy-1- (4-dimethylaminophenyl · - polymethine) naphthalane compound of the formula given, in which η = 1, compounds according to the invention in an analogous manner The 1-hydroxy ~ 1- (4-aminophenyl-polymethine) naphthalane compounds were prepared and used of the formula given, in which the amino nitrogen atom is either Wasserst off atoms or methyl, ethyl, propyl, butyl or pentyl groups or carries any mixtures of 2 of the radicals indicated, and in which η = 1, 2 or 3.

Correspondingly beneficial results have also been obtained using others in the art Solvents known to those skilled in the art for color precursor compounds, it has been found that any solvent which does not significantly impair color formation can be used, if the color precursor compound is brought into contact with a reactant.

It goes without saying that the compounds according to the invention are generally used for the production and generation of colored markings

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useful and their use is not limited to to use them in copier systems or in the form of a solution enclosed in microcapsules.

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Claims (10)

2SB0367 patent claims 1. Chromogenic 1-Hydroxy-1- (4-arainophenyl-polymethine) naphthaian compound of the general formula (GH = CH) where mean: R hydrogen atoms or short-chain alkyl radicals with 1 to 5 carbon atoms and η = an integer from 1 to 3 · ■
2. Naphthalane compound according to claim 1 of the formula CH = GH 3. Process for the preparation of a naphthalane compound according to claim 1, characterized in that 1 mol equivalent of a p-aminobenzaldehyde compound with 1 molar equivalent of one 609822 / 10OA ner p-aminobenzaldehyde compound with 1 molar equivalent of one Hydroxynaphthalane compound represented by the following formula implements. 4 · Process for the preparation of a naphthalane compound according to Claim 1, characterized in that 1 mol equivalent of a 3- (p-aminophenyl) propenal compound with 1 mol equivalent of a hydroxynaphthalane compound of the following formula implements. 5. Process for the preparation of a naphthalane compound according to Claim 1, characterized in that one molar equivalent of a 5- (p-aminophenyl) pentadienal compound with 1 molar equivalent of a hydroxynaphthalane compound of the formula 609822/1004 implements. 6. The method according to claim 3, characterized in that one as the p-aminobenzaldehyde compound, p-dimethylaminobenzaldehyde used. 7 · Use of a naphthalane compound according to claim 1 as Color precursor compound in a pressure responsive Recording system with a layer of microcapsules which contain a practically colorless color precursor compound, and a layer of an electron acceptor material. 8. Use of a naphthaian compound according to claim 2 as Color precursor compound in a pressure sensitive recording system comprising a layer of microcapsules containing the contain a practically colorless color precursor compound, and a layer of an electron acceptor material. 9. Use of a waphthalan compound according to claim 1 as A color precursor compound in a pressure sensitive recording system with a virtually colorless color precursor compound containing layer and a layer consisting of an electron acceptor material. 10. Use of a naphthalane compound according to claim 2 as A color precursor compound in a pressure sensitive recording system with a virtually colorless color precursor compound containing layer and a layer consisting of an electron acceptor material. 6 0.98 22/1004