JPS6135959B2 - - Google Patents

Description

[Detailed description of the invention]

This issue concerns recording of information or copying materials for documents. More particularly, the present invention provides a record comprising a sensitive layer containing a chromogenic compound reactive with a phenol derivative and a phenol derivative, especially in the form of a complex product which decomposes into a phenol derivative reactive with said chromogenic compound. , or relating to copying materials. Belgian patent No. 849049 describes a copying material consisting of a color-forming compound and a phenylurethane, and a method for implementing this material. Upon application of energy (heat or contact with a liquid or gas), the phenyl urethane decomposes, liberating phenol, which reacts with the color-forming compound to produce a colored trace. When using a photosensitive color-forming compound, the material containing the photosensitive color-forming compound and phenyl urethane is exposed to light that has passed through the base paper (original), and then developed by supplying energy to liberate the phenol. , this phenol reacts locally with the color-forming compound that is destroyed during exposure, thereby regenerating the document. Similarly, French Patent No. 2368736 and No.
No. 2,368,737 discloses a diazo-sensitive layer consisting of a diazonium compound, a precursor of a coupler which converts into an active coupler in the presence of an acid, and a photosensitive acid generator. The implementation of such a sensitive layer is carried out by UV irradiation, which generates an acid (which also decomposes the diazonium compound), which activates the coupler. When passed through ammonia vapor, the coupler reacts with undecomposed diazonium compounds. Such methods and such sensitive layers have a number of drawbacks. This diazo-type material must be stored completely protected from sunlight (with ultraviolet rays).
This avoids activation of the coupler. If the surrounding medium is alkaline, Katsupura will
Reacts immediately with nearby diazonium salts. Therefore, the problem of long-term storage of such materials remains unsolved. Furthermore, the above method does not give satisfactory results because the diazonium salt also decomposes upon exposure to ultraviolet light. Therefore, the exposure time to ultraviolet light is shortened to avoid excessive destruction of the diazonium salt, but in this case the coupler is hardly activated and only a very faint image is obtained. Alternatively, if the exposure time is increased to destroy many of the diazonium salts, there will be nothing left to react with the coupler. This also results in an extremely thin image. Furthermore, when the photosensitive acid luminescent agent is a diazonium salt itself, acid is generated only to the extent that the diazonium salt is destroyed. It can therefore be seen that this method is extremely limited and does not produce well-colored images. Furthermore, the patent clearly states that the image background is stabilized by complete irradiation of the material with ultraviolet light. I do not understand why UV irradiation in some cases gives colored images (without destroying the diazonium salt) and in other cases this same UV irradiation results in decomposition of the diazonium salt without generating active couplers. . The latter case is less reliable, since the complete irradiation with ultraviolet radiation for stabilizing the ground is carried out after passing through the ammonia vapor. It is also known from experience that ammonia penetrates through the entire material during this operation. Therefore, when the entire area is irradiated with ultraviolet rays, coloration tends to occur in the ground area in the reaction medium.
This has also been confirmed in the examples of FR 2 368 737, the control sample (without acid anhydride) corresponding to the teaching of FR 2 368 736. Therefore, in this case, it was confirmed that the image area and the ground area have substantially the same optical density. In other words, the image on the control sample is substantially invisible. It has been discovered that some derivatives of dihydroxy-2,3-naphthalene react with certain chromogenic compounds to produce colored images. The recording or copying material of the invention is characterized in that the complex product is selected from dihydroxy-2,3-naphthalene derivatives of the formula: In formula (), G represents a hydrogen atom, and Z represents any one of the following formulas: When Z represents a group of formula (a), X ₁ and A
has one of the following meanings: (i) A independently represents a _group , and in this case, X ₁ in formula () represents the formula

It is a triorganosilyl group having the formula: R ₁ , R ₂ and R ₃ are the same or different alkyl groups or phenyl groups having a maximum of 6 carbon atoms. Preferred examples are methyl or phenyl groups. (ii) A forms a valence bond together with the X ₁ group of formula (). (iii) A is represents. In the formula, n is 1, 2 or 3,
R ₁ and R ₂ have the above meanings, and Y ₁ forms a valence bond together with the X ₁ group in formula (). When Z represents a group of the following formula (b), Y ₁ forms a valence bond together with X ₁ in formula (), T is a hydrogen atom, Na, K or Li atom, or EH ⁺ (E is ammonia or an aromatic or aliphatic primary , representing a secondary or tertiary amine) or (P represents 1, 2 or 3, and G is the same as above.) The silicon derivative of the present invention can be represented by any of the following formulas. In the formula, G, R ₁ , R ₂ , R ₃ and n have the above meanings. Preferred compounds are those in which R ₁ to _{R 3} are methyl or phenyl groups, and n is an integer of 1 or 2. Among these, compounds in which R ₁ , R ₂ , and R ₃ are all methyl groups are particularly preferred. The following are examples of other silicon derivatives. The phosphorus derivative of the present invention can be represented by any of the following formulas. In the formula, R represents a hydrogen atom, Na, K, or Li atom, or EH ⁺ , and E represents ammonia or a primary, secondary, tertiary aromatic, or aliphatic amine. especially,
E represents ammonia, tertiary aliphatic monoamine, or tertiary aliphatic polyamine. The group supported on the nitrogen atom is an alkyl, hydroxyalkyl, or alkylene group having up to 6 carbon atoms. For example, in addition to ammonia, trimethylamine, triethylamine, triethylenediamine, hexamethylene tetramine, etc. can be used. G
and P are as described above. The various phosphorus compounds can be divided into three groups, in which phosphorus compounds are made from simple phosphorus compounds with one, two or three reactive groups. Group 1 Group 1 is obtained from phosphorus compounds with one reactive group. R has the above meaning (linear or branched alkyl group having up to 8 carbon atoms, or ammonium group), p is an integer of 0, 1, 2 or 3, and G has the above meaning has. When there are multiple G groups in the same molecule, the G groups are the same. When OR is [−O ⁻ ,X ⁺ ]− group,
All R groups are the same and the G group is a hydrogen atom or a sulfonate group. The compounds of formula (f) generally exist in the form of mixtures of products differing only in the value of p and in the composition and can be separated by crystallization, preferably R has 1 to 4 carbon atoms.
linear or branched alkyl group, or [-
O ⁻ , X ⁺ ]− group. Second Group A second group of phosphorus compounds is derived from difunctional phosphorus derivatives. R' has the same meaning as a hydrogen atom or R group, and G has the above meaning. When there are multiple G groups in the same molecule, the G groups are the same. When one of the OR′ groups is a [−O ⁻ ,X ⁺ ]− group, all R′ groups are the same. The G group is therefore a hydrogen atom or a sulfonate group. In these formulas, p
and R' have the above meanings. When p is zero, the organophosphorus compound of formula (h) has the following formula: Compounds (g), (h), and (i) are generally present in a mixture in various proportions, and these compounds can be separated by crystallization. In this group, compounds in which R represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a [-O ^- , X ⁺ ]- group as defined above are preferred. Third Group The third group of phosphorus derivatives is derived from trifunctional phosphorus derivatives. These compounds therefore have one of the following formulas. G is a hydrogen atom, a sulfonic acid, or a sulfonate group, and preferred compounds are G=H,
This corresponds to p=0. It has been confirmed in practice that the said derivative of dihydroxy-2,3-naphthalene decomposes upon supply of thermal energy or upon contact with certain liquids or gases, liberating phenols which react with color-forming compounds. . The color-forming compound used in the sensitive layer of the present invention may be any color-forming product that reacts with phenol. Preferred are indoline spiropyran, benzothiazole spiropyran, triphenylmethane derivatives, ferric salts, diazonium salts, non-photosensitive silver salts, and the like. Generally, color-forming compounds and dihydroxy-2.3
- The weight ratio of naphthalene derivatives is between 0.01 and 10, preferably between 0.05 and 3. The sensitive layer of the invention can be prepared in a manner known per se with binders, such as polyvinyl alcohol, polyvinyl esters, allyl esters, polyvinyl chloride homopolymers or copolymers, or any other binders known to the expert. It can contain. The sensitive layer of the present invention can be deposited on any suitable support, such as paper, transparent or opaque plastic films, glass, metal, and the like. Implementation of the sensitive layer of the invention can be carried out in various ways: The first method is to supply thermal energy to decompose the dihydroxy-2,3-naphthalene derivative to generate dihydroxy-2,3-naphthalene; It consists of reacting this with a color-forming compound to form a colored trace. Color-forming compounds are photosensitive (e.g. diazo compounds)
Then, it is possible to copy documents: After irradiating sunlight through transparent base paper, the area irradiated by sunlight changes (the diazo compound is destroyed). When passed through a thermal processing machine, dihydroxy-2.
The 3-naphthalene is liberated and reacts locally with the intact color-forming compound. When the color-forming compound is not photosensitive, it is sensitized with a photosensitizer and the document is copied, or thermal recording is performed using a heating point, i.e. dihydroxy-2,3-naphthalene is liberated at the heating point. (It is clear that thermal recording can also be carried out with photosensitive color-forming compounds such as diazo compounds). In this thermal phenomenon method, a decomposition catalyst for dihydroxy-2,3-naphthalene derivatives can be added to the sensitive layer to lower the liberating temperature of said derivatives. The following compounds are listed as these catalysts. ammonia. Bases such as soda and potash. Aliphatic amines, preferably tertiary aliphatic amines of the following general formula: (R ₁ , R ₂ , and R ₃ have 1 to 10 carbon atoms) For example, tertiary alicyclic polyamines such as hexamethylene tetramine and triethylene diamine. For example mono-, di- or triethalamines,
Hydroxylamines (or amino alcohols) such as 2-amino-1-butanol, tri(hydroxymethyl)aminomethane, and the like. Organic and inorganic ammonium salts such as carbonates, acetates, bicarbonates, formates, oxalates, benzoates, etc. Morpholine, N-methylmorpholine, 2,6-
Morpholine derivatives such as dimethylmorpholine, N-aminoethylmorpholine, etc. Products that generate ammonia on heating, or co-products, especially urea, thiourea, and derivatives thereof; ammonium salts that decompose on heating, such as, for example, ammonium carbonate, ammonium benzoate, etc.: by reaction under heating; Ammonia-generating product pairs, such as those described in French Patent No. 1403004 (ammonium salts of strong acids + metal compounds), or for example the paired products described in French Patent No. 1418156 (strong acids and weak salts of bases + salts of weak acids and strong bases). Generally, the purpose of the thermal decomposition catalyst is to generate a base or alkaline medium under heating to favor the decomposition of the 2,3-dihydroxynaphthalene derivatives used in the present invention. The list of products generally includes products that generate bases by mutual reaction under heating, products that decompose to generate bases under the action of heat, and mixtures of products consisting of bases and excess volatile acids. Then, it is possible to add something that liberates the volatile acid by the action of heat and leaves the base in the photosensitive layer. Mention may be made, for example, of sodium, potassium or trichloroacetic acid salts of amines (piperidine, tertiary amines, ethanolamine), formates of sodium, amines, etc., among others. Volatile acids include trichloroacetic acid, formic acid, glycolic acid,
Malonic acid, lactic acid, etc. can be mentioned. For more information on these products and their implementation, see French Patent No. 1249913, or Patent of Addition No. 78619 to this patent. In the case of thermal recording, this can be done using a heated bed or other means known to the expert.
A colored image therefore appears where the material is heated. Another method of implementing the material of the invention for reacting a chromogenic compound with a dihydroxy-2,3-naphthalene derivative consists in contacting the sensitive layer of the invention with a fluid, which fluid may be a liquid or a gas. to make colored traces appear. Among the fluids in which this reaction occurs, mention may be made, in particular, of the following: Ammonia (gas) or ammonia (liquid), bases such as soda, potash, etc., aliphatic amines, preferably tertiary aliphatic amines of the following general formula: (R ₁ , R ₂ , and R ₃ have 1 to 10 carbon atoms) For example, tertiary alicyclic polyamines such as hexamethyl tetramine, triethylene diamine, and the like. Hydroxylamines (or amino alcohols) such as mono-, di-, or triethanolamine, 2-amino-1-butanol, tri(hydroxymethyl)aminomethane, and the like. Organic or inorganic ammonium salts such as carbonates, bicarbonates, formates, oxalates, benzoates, etc. Morpholine, N-methylmorpholine, 2.6
- Morpholine derivatives such as dimethylmorpholine, N-amino-ethylmorpholine and the like. It is clear that gaseous fluids can only be used for copying to develop previously irradiated materials by known methods which are outside the scope of the present invention. When the fluid is in liquid form, markings can be made on the material of the invention using dots or inked roller needles of known type. The ink is replaced with a phenol derivative liberating liquid. Copying using the material of the invention is done by liquid phenomenon. 40°C gently to accelerate the reaction and dry the material.
This may be heated to a temperature above .degree. C. and below the phenol liberation temperature. A particularly important application of the present invention is all types of diazo types; diazo products are known to react particularly with phenol couplers to produce colored marks. The reaction of the coupler with the diazo compound takes place under heat or in the semi-moist phase or in the gas phase using ammonia. Diazo type materials have the disadvantage of becoming less stable over time. Therefore, it is difficult to preserve diazo-type materials for more than three months under normal storage conditions, and the present invention provides a significant improvement to diazo-type materials. The diazo type materials of the present invention can be stored for very long periods of time, up to several years. In the special case of the diazo type, there is no need to use a binder to connect the diazo compound and the coupler. Dihydroxy-2,3-naphthalene derivatives are prepared by the following method: Method for producing silyl ethers Organosilicon compounds of naphthalene diol-2,3- corresponding to formulas () and (a) are used in organosilicon chemistry. Obtained by conventional methods. Silyl ether of formula (a), where G=H or G=SO ₃ H It is obtained by reacting dihydroxy-2,3-naphthalene with an organosilicon compound which produces the triorganosilyl group described below in an almost stoichiometric manner in an anhydrous inert solvent. Preferably a chlorosilane of the formula Cl.Si.R _{1.R 2.R 3} is chosen. Silyl ethers of formula (b) (c) and Dihydroxy-2,3-naphthalene with formula _Cl2 .
Obtained by reaction of Si・R ₁・R ₂ with dichlorosilane in an anhydrous solvent. The two compounds (b) and (c) are in equilibrium with each other, and compound (b) can be distilled, but at ambient temperature it changes to compound (c). Silyl compound of formula (d) (e) Dihydro-2,3-naphthalene and formula

Dichlorosiloxane of [formula], or expression

It is obtained by reacting with dichlorodisilylalkane of the formula in an inert solvent. Silyl derivatives in which G is a sulfonate group These derivatives are prepared by combining compounds (a) to (e) with a suitable amine in solution or in an aqueous suspension.
Alternatively, it can be obtained by reacting in an inert organic solvent solution under mild temperature conditions (generally up to 100°C). It is preferably carried out at room temperature. Method for producing phosphorus compounds Phosphorus esters of dihydroxy-2,3-naphthalene can be prepared by preparing dihydroxy-2,3-naphthalene, such as polyphosphoric acid, phosphoric anhydride, or formulas POCl ₃ , PCl ₃ ,
POCl ₂ (OR), PCl ₂ (OR), or POCl (OR) ₂
It can be obtained by reacting with monofunctional, difunctional, or trifunctional phosphorus derivatives such as. Production of a phosphorus compound of the formula (f) in which G is a hydrogen atom or an SO ₃ H group and R is an alkyl group. ClPO
Obtained by reacting (OR) ₂ with a monofunctional phosphorus compound (R is an alkyl group). Depending on the proportions of the reagents used in the practice, mixtures of compounds corresponding to formula (f) but with different p values are obtained. Compounds (f) corresponding to a single value of p can be isolated by recrystallization. Production of a phosphorus compound of the formula (f) in which G is a hydrogen atom or a sulfonate group and OR represents a [-O ^- , X ⁺ ]- group. The corresponding compound is the compound (f) as defined above.
(G represents a hydrogen atom or a sulfonic acid group) and ammonia, soda, potash, etc. or a suitable amine in a solution, an aqueous suspension, or a solution in an inert organic solvent under mild temperature conditions ( Generally, the reaction is carried out at a temperature of 100°C or lower), preferably at room temperature. Production of phosphorus compounds of formulas (g), (h), (i) where G is a hydrogen atom or SO ₃ H group and R is an alkyl group Various esters (g), (h), (i)
is obtained by reacting naphthalene diol-2,3- of the formula () with a difunctional phosphorus compound of the following formula. R represents an alkyl group. Compounds (g), (h), and (i) can be obtained in various proportions depending on the proportion of reagents and the method of introducing these reagents. Formula (g) in which G is a hydrogen atom or a sulfonate group and OR represents a [-O ^- , X ⁺ ]- group, (
h), Production of the phosphorus compounds of (i) These compounds are the compound (g) as defined above,
(h), (i) (G is a hydrogen atom or a sulfonic acid group; R is an alkyl group) and ammonia, soda, potash, etc. or a suitable amine in a solution, an aqueous suspension, or an inert organic solvent. It is obtained by reacting in a solution under mild temperature conditions (generally below 100°C). It is preferably carried out at room temperature. Such organic phosphorus compounds are obtained in the same manner by reacting naphthalene diol-2,3- with phosphorus oxychloride POCl ₃ . In the first stage, equations (g), (h),
Create a compound similar to compound (i), but with a chlorine atom in place of the OR group in the formula. In the second step, a base or amine is reacted,
The desired organophosphorus compound is obtained. G is a hydrogen atom or a sulfonic acid group,
Formulas (g), (h), (i) where OR′ is a hydroxyl group
Preparation of phosphorus compounds of formulas (g), (h)(i)
(wherein G is a hydrogen atom or a sulfonic acid group, and R is an alkyl group). After hydrolysis, compound (g), (
h), (i) can be isolated from these mixtures by appropriate recrystallization treatments. naphthalene diol-2.
These phosphorus compounds can similarly be obtained by reacting 3- with phosphorus oxychloride POCl ₃ . In the first step, compounds similar to those of formulas (g), (h), and (i) are created, but in that formula, a chlorine atom replaces the OR group. In the second step, the phosphorus compound obtained in the first step is hydrolyzed in the cold to obtain the formula (g) in which OR is a hydroxyl group, (
h) to obtain the compound (i). Production of organic phosphorus compounds of the formula (j) or (j') in which G is a hydrogen atom or a sulfonic acid group.The phosphorus ester of the formula (j) or (j') is prepared by combining phosphoric anhydride and naphthalene diol of the following formula. Obtained by reaction with -2.3-. G is a hydrogen atom or a sulfonic acid group. Production of organophosphorus compounds of formula (j) or (j') in which G is a sulfonate group. These compounds contain at least one sulfonate group.
Obtained by reacting a compound of formula (j) or (j') with ammonia or an amine in an aqueous solution or an inert organic solvent solution under mild temperature conditions (generally below 100°C) . It is preferably carried out at room temperature. The present invention will be further explained based on the following examples, but the present invention is not limited to these examples. In all of these examples, the identification of various compounds was performed using microanalysis, infrared analysis, nuclear magnetic resonance spectroscopy,
This was done by mass spectrometry. Example 1 The following naphthalene-dioxo-2,3-dimethylsilane was It is made in equilibrium with its dimer of the formula below. 1 g of triethylamine is added to a solution of 64.1 g of dihydroxy-2,3-naphthalene in 500 ml of toluene and 56.8 g of dichlorodimethylsilane are added over a period of 2 hours under reflux (110 DEG C.). Heating is then continued for 2 hours until the evolution of hydrochloric acid has ceased, the mixture is cooled, the triethylamine hydrochloride is filtered off and the solvent is removed by distillation, giving 80 g of a white precipitate corresponding to the dimer (melting point: 190° C.). The dimer is distilled to obtain a monomer that is liquid at room temperature, and this monomer converts into a dimer very slowly. Next, make the following recording materials.

[Table] Information is recorded on this material using a point heated to about 120°C, resulting in a blue mark on a white background. Example 2 Naphthalene dioxo-2,2-diphenylsilane of the following formula was Synthesize in equilibrium with its dimer of the following formula: 64.1 g of dihydroxy-2,3-naphthalene, 500 ml of toluene, and 1 ml of triethylamine were placed in a flask, heated under reflux, and 111.4 g of dichlorodiphenylsilane was added over 2 hours. Maintain under reflux for an hour.
After cooling, the precipitate of triethylamine hydrochloride was filtered, the solvent was distilled off, and the precipitate was dissolved in acetonitrile (2
After recrystallization in propionitrile, washing with 50 g of chloride twice), 135 g of the compound corresponding to the dimer (melting point: 169 DEG -170 DEG C.) are obtained. Distillation yields a monomer that is liquid at ambient temperature, but slowly converts to a dimer. Dangoummeau is the product below.
Disperse with a mill.

Table: The sensitive layer is deposited on a paper support at a rate of approximately 6 g/m ² . When thermal recording is carried out as in the previous example, the resulting trace is blue-black on white. Example 3 A compound of the following formula is synthesized by the method described in Example 1. Then make the following homogeneous mixture:

Table: After coating on a paper support at a rate of about 4 g/m ² , thermal recording is carried out as in Example 1, the trace obtained is maroon on a light background. Examples 4 to 11 Trimethylsilyl diethers of dihydroxy-2,3-naphthalene having the following formulas are synthesized. Dihydroxy-2.3 in 150ml of cyclomethane
- Add 200 ml of bistrimethylsilyl acetamide to a suspension of 64.1 g of naphthalene over a period of 1 hour. Boil for 6 hours and then distill the reaction mixture to obtain 118 g of silyl diether (boiling point: 124° C.). Next, make the following composition. Dihydroxy-2,3-naphthalene trimethylsilyl diether 2 g Citric acid 1 g Thiourea 2 g 4-Diazo-2,5-dibutoxy phenyl morpholine borofluoride 3 g Methyl ethyl ketone 200 g This composition was coated on a paper support. After drying, ^the paper is exposed to sunlight through ^the base paper. The image develops under the following conditions summarized in the table below.

【table】 Example 12 Make the following solution:

[Table] This solution is deposited at a rate of 15 cm ³ /m ² on a polyester support coated with a layer of cellulose acetate. The support is irradiated with sunlight through the base paper, and then the same phenomenon method as in Examples 4 to 11 is carried out (Example
The back layer 11 is in this case applied as a lower layer on top of the cellulose acetate). The results obtained are identical, the images being slightly more purple than the corresponding Examples 4-11, respectively. Example 13 The naphthalene-dioxy-2,3-diphenylsilane in Example 12 was converted into a stoichiometric equivalent of naphthalene-dioxy-2,3-diphenylsilane made in Example 3 with the following formula:
-Replace with dimethylsilane: Obtain the same results as in Example 12 (same phenomenon method, same coloring). Example 14 The synthesis of naphthalene dioxy-2,3-bis(dimethylsilyl)-1,2-ethane of the following formula is carried out: In a flask, 64.1 g of dihydroxy-2,3-naphthalene, 500 ml of toluene, 2 triethylamine
ml of bis(chlorodimethylsilyl)ethane in 50 ml of toluene.
Add over time. It is then maintained under reflux for 3 hours to ensure complete release of hydrochloric acid. Cool, filter triethylamine hydrochloride, remove toluene, and vacuum distillate to obtain 93.5 g of naphthalene-dioxy-2,3-bis(dimethylsilyl)-1,2-ethane fraction (boiling point 0.9140°). . Then make the next solution. Naphthalene dioxy-2,3-bis(dimethylsilyl)-1,2-ethane 11.5 g Citric acid 5 g Thiourea 10 g Methyl ethyl ketone 1 Paradiethyl amino benzenediazonium borofluoride 12 g It is deposited on a paper support at a rate of 15 cm ³ /m ² . After irradiation with sunlight through the base paper, it is developed in the manner described in Examples 4 to 11, respectively. The same coloration as in Example 12 is obtained in each case. It was observed that the ammonia phenomenon (as in Example 5) was much faster than in the previous examples. The sensitivity of such materials of the diazo type is almost the same as that of corresponding materials without fixed couplers. Examples 15-17 The synthesis of phosphorus products of the following formula is carried out: 64.1 g of dihydroxy-2,3-naphthalene are added to 500 ml of benzene containing 81 g of triethylamine. Phosphorous oxychloride in this solution under boiling
68 g of POCl ₃ are added over 2 hours and kept under reflux for 1 hour until the evolution of hydrochloric acid has ceased. Ice-cold, 20ml water
Add and pass. The precipitate is washed four times with 100 ml of ice water and then three times with 100 ml of acetonitrile. When this is recrystallized in DMF, 74g of white solid
is obtained, which corresponds to the desired formula. The following solution is then made: 16 g of the phosphorus product 1 g of dimethyl formamide 5 g of citric acid 10 g of thiourea 20 g of 4-diazo-2,5-diethoxyphenylmorpholine borofluoride This solution is then mixed in a proportion of 15 cm ³ /m ² onto a paper support. After irradiation with sunlight through the base paper, this material is processed in various ways. The results are shown in the table below.

【table】

[Table] Example 18 Synthesis of 2,3-naphthyl hydrogen phosphate of the following formula: Dihydroxy-2,3-naphthalene in flask
Add 80.1 g, 2 ml of triethylamine, and 250 ml of freshly distilled phosphorus oxychloride POCl ₃ and heat slowly. This ensures dissolution and is kept under reflux for 4 hours to ensure complete release of hydrochloric acid. The mixture is cooled, triethylamine hydrochloride is filtered and distilled to give a white solid corresponding to the formula: The compound is cooled to 0° C. and hydrolyzed very slowly at this temperature with 220 ml of water. The aqueous phase is extracted with ethyl acetate (4 times 100 c.c.). The desired compound is obtained by distilling off the solvent (this is 160
melts while decomposing). The following solution is deposited on a paper support at a rate of 3 g/m ² . Polyethylene (dispersion liquid: BASF Epotal)
181D) 25 g Triethylenediamine 2.5 g Water 25 g After drying, apply the following lower layer at a rate of 15 cm ³ /m ² using a solution of the following composition:

[Table] After irradiating sunlight through the base paper, the diazo type material is heated in a heating machine (120°C for 8 seconds). The resulting image was blue-purple, and no unpleasant odor was observed during the phenomenon. The same results were obtained when the same material was processed in a similar manner in dry and semi-wet baking machines. It turns out that the underlayer used promotes the liberation of the coupler and at the same time guarantees a favorable alkaline medium for the reaction. Example 19 A paper support is coated with the following sublayers at a rate of 5 g/m ² . Loadpass S051 (polystyrene emulsion from Lorne Poulenc) 70 g Geophane 207D (polyvinylidene chloride from BASF) 30 g Hexamethylenetetramine 5 g This underlayer is then coated with the same underlayer as in Example 18. The same results can be obtained under the same conditions. Example 20 The following sublayer is applied to a paper support at a rate of 5 g/m ² .

【table】

[Table] After irradiation with sunlight through the base paper, this material is processed at 100° C. for 8 seconds to obtain a deep blue-purple coloration. Example 21 The following composition is dispersed in a ball mill: 50 g sodium bicarbonate 200 g ammonium sulfate 35 g polyvinyl acetate (Roadpath H from Lorne Poulenc) 250 g toluene This dispersion is then applied to the back side of a paper support at 10 g/m ²
Apply at the rate of The following layers are then applied to the front side of the support:

[Table] After irradiation with sunlight, the phenomenon was carried out using a heating printing machine at 120°C for 8 seconds, and the appearance of a blue-purple image was confirmed. Example 22 Make the following composition:

Table: The mixture is homogenized and then deposited on a paper support at a rate of 3 g/m ² . A thermal recording paper which exhibits extremely good stability during storage and which develops at about 130°C is obtained. Example 23 The following compositions are mixed in a Dungmor mill:

Table: The composition is applied at a rate of 6 g/m ² onto a paper support. When recorded at a point heated to 140°C, a blue-marine trace is obtained on a bright background. Example 24

【table】

[Table] Apply 5 g/m ² of this solution to a paper support.
When recorded at the point heated to 140°C, a dark maroon colored trace is obtained. Examples 25-26 Make 2,3-naphthylhydrogen ammonium phosphate salts of the following formula: 2,3-naphthyl hydrogen phosphate dissolved in 10 ml of water
1 ml of ammonia (d=0.92) dissolved in 10 ml of water was slowly added to 2.22 g (prepared in Example 18) while cooling to 0°C to precipitate the ammonium salt. After filtering this, soaking it in water and drying it,
2.2 g of a white solid corresponding to the desired formula are obtained. 2,3- of triethylene diamine of the following formula
Make naphthyl phosphate similarly: When a solution of 2.22 g of 2,3-naphthyl hydrogen phosphate dissolved in 15 ml of isopropanol was slowly added to 1.34 g of triethylenediamine dissolved in 15 ml of isopropanol while cooling to 0°C, the amine salt precipitated and was filtered. , washed with cold isopropanol and dried to give 3.3 g of a white solid corresponding to the desired formula. The following solution is then prepared: 2,3-naphthyl phosphate of triethylene diamine 12 g Water 1 This solution is deposited on a paper support at a rate of 20 cm ³ /m ² . Then apply the following lower layer in a proportion of 20 cm ³ /m ² : 5 g citric acid 10 g thiourea 15 g paradiethylaminobenzene diazonium chlorzincate 10 g ammonium acetate 10 g water After irradiating the material through the base paper, heat the material at 120°C for 10 seconds.
When the phenomenon occurs in a heating machine, a blue-purple copy is obtained. The same result is obtained for the phenomenon in the presence of ammonia. 2,3- of triethylene diamine in the first layer
Make the same solution as above using 2,3-naphthyl hydrogen phosphate ammonium salt instead of naphthyl phosphate and urea instead of ammonium acetate in the second layer (the weight of each new component is equal to that of the previous component). weight). If you do it under the same conditions as before, you will get the same result. Although the terms naphthalene diol-2,3 and dihydroxy-2,3-naphthalene are used interchangeably herein, they have the same meaning. Example 27

[Table] This solution is deposited on a paper support at a rate of 0.5 g/m ² . After drying, apply a second layer of the following solution (1 g/m ² ): Paradiethylaminobenzene diazonium chlorozincate 0.3 g Citric acid 0.12 g Thiourea 0.25 g Water 25 cm ³ After irradiation with sunlight through the base paper, When heated to 100°C, a blue-purple image is obtained. Example 28 On a support made of polyethylene glycol terephthalate, sold under the name Terphane and coated with a surface layer, the following solution is deposited at a rate of 0.5 g/m ² :

[Table] After irradiating sunlight through the original paper to be copied, 100
Development by passing through water vapor at 0.degree. C. gives a deep purple image. In general, developing the materials of the invention with water vapor is possible when using rapidly coupling diazonium salts known to the specialist. Example 29

[Table] This solution is deposited on a paper support at a rate of 0.5 g/m ² . After drying, apply the following lower layer at a rate of 1 g/ ^m2 : 4-diazo-2,5-dibutoxyphenylmorpholine chlorzincate 0.35 g lactic acid 0.75 g Thiourea 0.5 g Water 25 cm ³ copies After exposing the base paper to sunlight,
When the phenomenon occurs at 120°C, a blue image is obtained.

Claims (1)

[Scope of Claims] 1. A color-forming compound that is reactive with a phenol derivative, and a color-forming compound that is easily decomposed by the action of heat and/or an alkaline or neutral liquid and that is reactive with the color-forming compound. A recording or copying material comprising a sensitive layer containing a phenol derivative, in particular in the form of a complex product which results in a phenol derivative capable of producing colored images, wherein said complex product is a naphthalene diol-2,3- of the formula Recording or copying material characterized in that it is selected from derivatives: [In the above formula, G represents a hydrogen atom, and Z represents one of the groups of the following formula: When Z represents a group of (a): A independently represents a group R ₃ , in which case X ₁ in formula () is a triorganosilyl group having the formula [formula], and R ₁ , R ₂ and R ₃ are the same or different and are an alkyl group or phenyl group having a maximum of 6 carbon atoms, or A forms a valence bond together with the X ₁ group of formula (), or A is formula (In the formula, n is 1, 2 or 3, R ₁ and R ₂ have the above meanings, and Y ₁ forms a valence bond together with the X ₁ group in formula ().) represents the group of When Z represents the group (b): Y ₁ forms a valence bond together with X ₁ of formula (), T is a hydrogen atom, Na, K or Li atom or EH ⁺ (in the formula E represents ammonia or aromatic or aliphatic primary, secondary or tertiary amine) or (P represents 1, 2 or 3). ] 2 Z represents a group (a) and R ₁ , R ₂ , R ₃ groups are
Material according to claim 1, characterized in that it represents methyl or phenyl. 3. Material according to claim 1, characterized in that Z represents a group of formula (b), T represents an EH ⁺ group and E is ammonia. 4. The material according to claim 1, characterized in that Z represents a group of formula (b) and T represents a hydrogen atom.