JPH0241733B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to diazonium salt compounds and their use in the diazo type. Diazotype reproduction methods are well known in the art and have been described by Jaromir Kosar, John Wiley &
“Light Sensitive” by Sonc, Inc., NY1965
Systems” and E. Jahoda, 4th Edition
Andrews Paper & Chemical Co., Inc.
It is described in great detail in “Repsoduction Coating” by Port Washington, New York. Generally, diazotype reproduction printing is obtained by imagewise exposing a photosensitive diazo material to ultraviolet light and then developing the exposed diazotype material. There are several different methods convenient for developing a latent image placed on a photosensitive diazo material by light exposure including ammonia development, amine development, thermal development, and moisture (liquid) development. Photosensitive diazo materials are generally paper or films such as polyethylene terephthalate films,
It consists of a photosensitive diazo composition deposited on a support base, such as a cellulose acetate or polymeric resin coated base support. The photosensitive diazo composition may consist of a photosensitive diazonium salt compound mixed with a diazo reinforcing compound. In exposing the photosensitive diazonium compound to ultraviolet light through a translucent original with an opaque image area,
The unmasked portions of the diazonium salt are degraded by ultraviolet radiation, while the masked portions remain undegraded. The latent image created by imagewise exposure may then be developed by the methods described above. In the so-called "dry development" process, the photosensitive diazo composition would contain, in addition to the photosensitive diazonium salt, an azo color former or color former, and an acid color inhibitor. The development of the azo latent image is
This is accomplished by placing the exposed diazo material under an alkaline atmosphere that neutralizes the acid inhibitor and allows the undecomposed diazonium salt and color former to react. The latent image is thereby developed. In a moisture development process (also called a one-component process), the photosensitive diazo composition is
Contains essentially diazonium salts. After imagewise exposure, development of the latent image of the azo dye is accomplished by applying to the exposed diazo material a buffer solution containing an azo color former, where the azo color former is It then reacts with undecomposed diazonium salt to develop the latent image). Prior art diazonium compounds employed to prepare photosensitive diazo materials are generally used in the form of acid salts such as zinc chloride, cadmium chloride, tin chloride, sulfate and borofluoride salts. Acid salt derivatives are generally more stable than the parent diazonium compound. The parent diazonium compound will often spontaneously decompose under ambient conditions. For the preparation of diazo-sensitive paper materials, the diazonium compound and auxiliary chemicals are dissolved in water and the resulting diazo composition is applied from an aqueous medium to a paper substrate. Therefore, it is necessary that the diazonium salt be substantially soluble in water. From a practical point of view,
This requirement limits the selection to very few types of diazonium salts, and in particular to the zinc chloride or sulfate salts of the diazonium compounds. Diazonium sulfate salts are extremely soluble in water (as a result,
very difficult to isolate in solid form). Salts of zinc chloride have more limited water solubility and are easier to isolate in solid form. However, despite the stabilizing effect of zinc chloride, most diazonium chlorozincates are unstable when subjected to mild heating. In addition, such salts are easily ignitable, and once ignited, many burn violently, releasing lots of toxic smoke and vapors. The preparation of diazo materials, such as polymeric films and polymeric resin-coated papers carrying diazo compositions, includes
The diazonium and other ingredients are dissolved in a polar organic solvent such as an alcohol, ketone or glycol ether. The diazo composition is then applied from the solvent medium to the base support material. Therefore, it is necessary that the diazonium salt be dissolved in such a solvent. Diazonium polyfluoride salts are generally soluble in organic solvents, but most, like chlorozincate, are unstable when subjected to mild heat. They are also easily ignitable and burn violently, emitting toxic smoke and vapors when ignited. Because of the serious risks mentioned above, special precautions and procedures must be taken when handling or transporting prior art diazonium salt compounds and diazo compositions. The Code of December 31, 1976
Federal Registrations, 49, Transportation
Any solid material that is liable to cause a fire through friction or through retained heat from manufacture or processing under normal conditions typical of wheel transportation, or that is easily ignitable and ignites. Any solid material that burns so violently and persistently that it creates a significant transportation hazard when exposed to the environment, shall be labeled as a “flammable solid” and subject to all rules and regulations relating to transportation of hazardous materials. is requesting. In the case of international transport, the International Air Transport Association
(IATA) has imposed strict restrictions on
In addition, for transporting flammable solids by boat,
Intergovernmental Maritime Consultative
Orgamization (IMCO).
For example, IATA regulations require that flammable solids be
Requires packaging in individual suitable containers not exceeding 12 kg in total. IMCO requires that combustible solids be stowed on cargo ship decks within a specially located area. The above regulations not only make shipping and handling of prior art diazonium compositions more difficult, but also make them significantly more expensive than compounds that do not fall into the hazardous category. In addition to the flammability hazards associated with diazonium chlorosincate salts, their relatively low thermal stability gives them limited shelf life. Commercially available diazonium chlorosincate salts tend to slowly degrade over time, even at room temperature, and in doing so lose some of their basic organoleptic properties. In extreme cases of poor storage conditions,
For example, when diazonium salts are exposed to tropical climatic conditions, decomposition is greatly accelerated, rendering the diazonium totally unstable. For this reason, it has often been necessary to maintain diazonium compounds and compositions in a cooling zone. This adds substantially to storage costs,
It imposes severe restrictions on the level of product inventory. To reduce the risks associated with unstable diazonium, it has been proposed to mix it with solid diluents or stabilizers such as tartaric acid, citric acid, aluminum sulfate, boric acid and other organic or inorganic salts. However, diluents of up to 50% are often required to obtain a sufficient reduction in risk. Such methods reduce the rate of spread of combustion, but if the diazonium ignites,
However, it does not alter the flammability or thermal decomposition rate (which is inherent to a particular diazonium salt) of the diazonium salt. The diazonium salts of the present invention eliminate many of the problems associated with prior art diazonium compounds.
The diazonium salts of the present invention exhibit a large degree of thermal stability, nonflammability, and shelf life. These improved characteristics are also found in diazotype materials prepared from the diazonium salts of the present invention. Other advantages of the compounds, compositions and diazotype reproduction materials of the present invention will be described more fully below. The present invention is based on the formula (In the above formula, Ar represents aryl or substituted aryl; R ₁ is hydrogen, -SO ₃ H and -SO ₃ M
(wherein M means Na, K or NH ₄ ); R ₂ is hydrogen and the formula -
and R ₃ is selected from the group consisting _of hydrogen and alkyl). Preferred compounds of formula () above are somewhat bright yellow in color and absorb ultraviolet light and undergo photolysis to form colorless products. The term "photosensitive" as used herein refers to a compound or substance that is subject to photolysis. The term "hydrocarbyl" is used herein to mean a monovalent moiety obtained by removing a hydrogen atom from a parent hydrocarbon (e.g. containing 1 to 12 carbon atoms). as used throughout the book and claims. Examples of such moieties are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,
Alkyl having 1 to 12 carbon atoms, including nonyl, decyl, undecyl, dodecyl and their isomers; including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and analogs thereof; cycloalkyl having 3 to 8 carbon atoms; aryl having 6 to 12 carbon atoms including phenyl, tolyl, xylyl, naphthyl, biphenylyl, and analogs thereof; benzyl, phenethyl, phenpropyl,
Aralkyl having 7 to 12 carbon atoms, including phenbutyl, phenpentyl, phenhexyl and analogs thereof. As used herein, the term "substituted aryl" means
Aryl as defined above means one or more inert groups containing one or more hydrogen atoms, i.e. does not interfere with the desired function of the compound of formula () as a photosensitive component of a diazo type composition. It is substituted with a group that would be. Representative examples of such inert groups are amino, alkylamino, alkylcycloalkylamino, cycloalkylamino, halogen, hydrocarbyl, aryloxy, alkoxy, alkylthio, arylthio, tolylthio, morpholino, pyrrolidinyl,
Piperidino, piperazino, halo-substituted hydrocarbyl and similar groups. In compounds of formula () when Ar represents substituted aryl, inert substituents include amino, alkylamino, dialkylamino, alkylhydroxyalkylamino, dihydroxyalkylamino, alkoxy, phenoxy, cycloalkylamino, alkylcycloalkyl Amino, alkylaryl amino, alkylaralkylamino,
Diarylamino, tolylthio, morpholino,
Preferably, it is selected from the group consisting of pyrrolidino, piperidino, and piperazino. Most preferably, these preferred inert substituents are located para to the diazonium moiety. Among the latter preferred compounds (), the moieties
Ar is unsubstituted at the ortho and meta positions to the diazonium moiety, or at one or both of these positions, alkyl, alkoxy, phenoxy, halophenoxy, halogen and of the formula Ac-NH-, where Ac is carboxy It is further preferred that the group is substituted with a group selected from those (representing acyl). The term “aryroxy” used here is
It means a monovalent moiety having the formula aryl-O- (wherein aryl is as defined above). Examples of aryloxy are phenoxy, naphthoxy and analogues thereof. The term "alkoxy" is used herein to mean a monovalent moiety having the formula -O-alkyl, where alkyl is as defined above. Examples of alkoxy are methoxy, ethoxy, butoxy, pentyloxy, hepityloxy, decyloxy, dosyloxy and analogs thereof. The term "alkylamino" as used herein refers to an amino group in which one hydrogen is replaced with an alkyl group as described above. The term "dialkylamino" as used herein refers to an amino group in which two hydrogen atoms have been replaced with alkyl groups as described above. The term “alkylhydroxyalkylamino”
means an amino group in which one hydrogen atom is substituted with an alkyl group and one hydrogen atom is substituted with a hydroxyl-substituted alkyl group. The term "dihydroxyalkylamino" means an amino group in which both hydrogen atoms are replaced with hydroxy-substituted alkyl groups. The term "alkylarylamino" is used to mean an amino group in which one hydrogen atom is replaced with an alkyl group and another hydrogen atom is replaced with an aryl group. The term "diarylamino" means an amino group in which each hydrogen atom is replaced with an aryl group. The term "alkylaralkylamino" means an amino group in which one hydrogen atom is substituted with an alkyl group and another hydrogen atom is substituted with an aralkyl group. The term "carboxyacyl" as used throughout this specification and claims refers to an acyl group of a hydrocarbon carboxylic acid or an acyl group of a hydrocarbon carboxylic acid substituted with an inert group. Preferred carboxyacyl groups are acyl groups of hydrocarbon carboxylic acids, and acyl groups containing from 2 to about 18 in the structure.
is an acyl group of an inert group-substituted hydrocarbon carboxylic acid having 5 carbon atoms. A typical example of such a carboxyacyl group is the formula It has the following. In this formula, E is 1 to about 17
hydrocarbyl of 4 carbon atoms, with the hydrogen atoms replaced with inert substituents. Examples of acyl groups of hydrocarbon carboxylic acids when E is hydrocarbyl are (a) saturated or unsaturated, straight-chain or branched aliphatic carboxylic acids, such as acetic acid, propionic acid, butyric acid, isobutyric acid, Tert-butylacetic acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, acrylic acid, crotonic acid , undecylenic acid, oleic acid,
Acyl groups such as hexic acid, heptic acid, octonic acid; (b) saturated or unsaturated alicyclic carboxylic acids, such as cycloptanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid;
Acyl groups such as methylcyclopentenecarboxylic acid, cyclohexanecarboxylic acid, dimethylcyclohexenecarboxylic acid, dipropylcyclohexanecarboxylic acid; (c) saturated or unsaturated cycloaliphatic carboxylic acids, such as cyclopentaneacetic acid, cyclopentanepropionic acid , cyclohexanebutyric acid,
Acyl groups such as methylcyclohexaneacetic acid; (d) acyl groups such as aromatic carboxylic acids, such as benzoic acid, toluic acid, naphthoic acid, ethylbenzoic acid, isobutylbenzoic acid, methylbutylbenzoic acid;
(e) aromatic-aliphatic carboxylic acids, such as phenyl acetic acid, phenylpropionic acid, phenylvaleric acid,
Acyl groups such as cinnamic acid and naphthylacetic acid. The term "hydrocarbon carboxylic acid substituted with an inert group" means that one or more hydrogen atoms directly attached to a carbon atom are capable of reacting under the conditions described below for using the compounds of the invention (). is used herein to mean a hydrocarbon carboxylic acid substituted with an inert group. Examples of such substituents are halo-, nitro-, hydroxy-, amino-, cyano-, thiocyano- or alkoxy groups. halo, nitro, hydroxy,
Examples of amino-, cyano-, thiocyano-, and alkoxy-substituted hydrocarbon carboxylic acids include mono-,
Di- and trichloroacetic acid; α- and β-chloropropionic acid; α- and γ-promobutyric acid;
α- and δ-iodovaleric acid; mevalonic acid; 2-
and 4-chlorocyclohexanecarboxylic acid; shikimic acid; 2-nitro-1-methylcyclobutanecarboxylic acid; 1,2,3,4,5,6-hexachlorocyclohexanecarboxylic acid; 3-bromo-2-
Methylcyclohexanecarboxylic acid; 4- and 5
-Bromo-2-methyl-cyclohexanecarboxylic acid; 5- and 6-bromo-2-methylcyclohexanecarboxylic acid; 2,3-dibromo-2-methylcyclohexanecarboxylic acid; 2,5-dibromo-2-methylcyclohexanecarboxylic acid ;4,5
-dibromo-2-methylcyclohexanecarboxylic acid; 5,6-dibromo-2-methylcyclohexanecarboxylic acid; 3-bromo-methylcyclohexanecarboxylic acid; 6-bromo-3-methylcyclohexanecarboxylic acid; 1,6-dibromo-3 -Methylcyclohexanecarboxylic acid; 2-bromo-4-
Methylcyclohexanecarboxylic acid; 1,2-dibromo-4-methylcyclohexanecarboxylic acid; 3
-bromo-2,2,3-trimethylcyclopentanecarboxylic acid; 1-bromo-3,5-dimethylcyclohexanecarboxylic acid; homogentisic acid; o
-, m-, and p-chlorobenzoic acid; anisic acid; salicylic acid; p-hydroxybenzoic acid; β-
Resorcilic acid; gallic acid; veratrum acid; trimethoxybenzoic acid; trimethoxycinnamic acid; 4,4'-
dichlorobenzilic acid; o-, m-, and p-nitrobenzoic acid; cyanoacetic acid; 3,4- and 3,
5-Dinitrobenzoic acid; 2,4,6-trinitrobenzoic acid; Thiocyanoacetic acid; Cyanopropionic acid; Lactic acid; Ethoxyformic acid (ethyl hydrodiene carbonate); Butyloxyformic acid; Pentyloxyformic acid; Hexyloxyformic acid; Dodecyloxyformic acid; Hexadecyloxyformic acid etc. The term "cycloalkylamino" is used to mean an amino group in which one or more hydrogen atoms are replaced with a cycloalkyl group as described above. The term "alkylcycloalkylamino" means 1
It means an amino group in which one hydrogen atom is substituted with an alkyl group and one hydrogen atom is substituted with the above-mentioned cycloalkyl group. The term "halogen" is used herein in a general sense to include chlorine, bromine, fluorine, and iodine, and the term "halo" means chloro, bromo, fluoro, and iodo, respectively. The term "halofenoxy" means phenoxy in which a hydrogen atom is replaced with a halo group as described above. The term "alkylthio" means a monovalent moiety having the formula alkyl-S-, where alkyl is as defined above. Representative examples of alkylthio are methylthio, bentylthio, dodecylthio, and the like. The term "arylthio" is used herein to mean a monovalent moiety having the formula aryl-S-, where aryl is as defined above. Examples of arylthio are fenthio, naphthio, and the like. The compounds of formula () above are diazonium salts that are characterized by relative thermal stability and non-flammability. Compound () is useful as an active photosensitive diazo component in diazo-type photosensitive compositions. Compounds of formula () are less flammable and are more thermally stable than, for example, diazonium compounds having the formula: ArN ₂ X () In the above formula, Ar has the same meaning as above, and
X is Cl-, _SO4 =, _ZnCl4 =, _SnCl6 =, _CdCl4
=, BF ₄ −, etc., are anions that form soluble salts with ArN ₂ . The invention also consists of a method for the preparation of the compound () and its use in the diazotype copying materials of the invention. Compounds of the invention within the above formula () are:
It can be produced by reacting the diazonium compound of the above formula () with a compound of the following general formula. In the above formula, R ₁ , R ₂ , R ₃ are as defined above, and Y is hydrogen; or lithium, sodium, potassium, ammonium, etc.
Represents metal ions that form soluble sulfonate salts. The reaction is illustrated by the following schematic: In the above formula, Ar, R ₁ , R ₂ , R ₃ , X and Y are
has the meaning given above. The formula represents a metathesis reaction, which is carried out in an aqueous medium. It is preferred to first dissolve the diazo salt () in the reaction medium. Substituted phenyl sulfonate or acid (),
It is then introduced into the reaction mixture, preferably with stirring. The proportions of the reactants () and () used in the reaction may be stoichiometric, that is, equimolar proportions may be used. However, it is advantageous to use more than the amount of formula () required for complete reaction with the diazonium compound of formula ().
A slight molar excess of substituted phenyl sulfonate or acid is used in the reaction. The above reactions to obtain the compounds of the invention () are carried out over a wide range of temperatures and pressures (although neither are critical parameters of the reaction). Advantageously, the reaction is carried out at a temperature within the range of about -10°C to about 50°C, preferably at room temperature (approximately 26°C) and under atmospheric pressure. The reaction is generally complete in a few minutes, indicated by the precipitation of the desired product compound of formula () above in the reaction mixture. Precipitation usually occurs without further processing of the solution, although under certain conditions. of the formed diazo salt () by cooling the reaction mixture, seeding the solution, or adding some sodium chloride or such salt to reduce the solubility of the diazonium salt () in the reaction mixture. It is desirable to initiate precipitation.
Following precipitation, the desired diazonium salt of formula () is easily separated from the reaction mixture by common techniques such as by filtering, washing and recrystallization. A preferred method for the preparation of the new diazonium compounds () consists in reacting a substituted phenyl sulfonate of formula () with a diazonium salt () in an aqueous medium in the presence of a strong mineral acid such as sulfuric acid. Crystallization of the formed diazonium salt of formula () under such conditions is rapid, especially if the solution is cooled and some sodium chloride, sodium sulfate, etc. is added. It has been found that in the presence of strong acids, substituted phenylsulfo groups confer low water solubility to diazonium (). This is important in order to facilitate the economical production of a wide variety of stabilized diazo salts () by the metathesis reactions described herein. The proportion of strong mineral acid present in the preferred method of preparing the diazonium salts () of the invention is the water-insoluble proportion. Generally, the water-insoluble fraction is that amount necessary to establish a PH below 5 in the reaction medium. Those skilled in the art will recognize that the above method for preparing novel diazonium salt compounds of formula () does not include zinc or zinc compounds. The absence of zinc in the reaction medium is important for diazonium compound manufacturers with regard to environmental concerns in the disposal of waste solutions (as is the case in the conventional method by which diazonium zinc chloride is prepared). In the method described above, when X represents halogen, diazonium halide () is used as a double salt such as sulfate, chlorozincate, or borofluoride to prepare the diazonium salt ().
It will also be appreciated that it is not necessary to isolate the . Diazonium halide () solution is sufficient as reaction medium. The diazonium compound of formula () used as a reactant in the synthesis of the compound () of the present invention is a generally well-known compound, as is the method for producing it. Representative examples of such compounds of formula () are: 1-diazo-4-N,N-dimethylaminobenzene chloride, 1-diazo-4-N,N-dimethylaminobenzene chloride, 1- Diazo-4-N-morpholinobenzene chloride, 1-diazo-4-N-piperidinobenzene chloride, 1-diazo-4-N-piperazinobenzene chloride, 1-diazo-4-N-pyrrolidino Benzene chloride, 1-diazo-4-N-pyrrolidino-3-methylbenzene chloride, 1-diazo-4-N-pyrrolidino-3-methoxybenzene chloride, 1-diazo-4-N-morpholino-2,5-di Ethoxybenzene chloride, 1-diazo-4-N-morpholino-2,5-dimethoxybenzene chloride, 1-diazo-4-N-morpholino-2,5-dipropoxybenzene chloride, 1-diazo-4-N-morpholino -2,5-dipoxybenzene chloride, 1-diazo-4-p-tolylmercapto-2,5
-diethoxybenzene chloride, 1-diazo-4-p-tolylmercapto-2,5
-dimethoxybenzene chloride, 1-diazo-4-p-ethoxyphenyl-2,5
-diethoxybenzene chloride, 1-diazo-4-p-chlorophenoxy-2,5
-diethoxybenzene chloride, 1-diazo-4-N-N-diethylamino-3-
Chlorobenzene chloride, 1-diazo-4-N-N-diethylamino-2-
Ethoxybenzene chloride, 1-diazo-4-N-N-diethylamino-2-
Chloro-5-pchloro-phenoxybenzene chloride, 1-diazo-4-N-methyl-N-cyclohexyl-3-chlorobenzene chloride, 1-diazo-4-N-N dibutyl-3-chlorobenzene chloride, 1- Diazo-4-N-methyl-N-benzyl-3
-ethoxybenzene chloride, etc. Other diazonium compounds of formula () are described in U.S. Pat. No. 4,055,425 (columns 5 and 6) and Van
der Grinten, Photographic Journal, Vol.92B,
(1952), p. 46. The synthesis method for the compound of formula () is described in Azo and Diazo Chemistry, by
H. Zollinger, Interscience, New York, 1961
and The Aromatic Diazo Compounds, K.
H.Saunders, E.Arnold and Co., London,
(1969). Reactant compounds of formula () are also well known compounds, as are methods of their preparation. Representative examples of compounds of formula () are: 3-sulfobenzoic acid, 3-sulfobenzoic acid sodium salt, 3,5-disulfobenzoic acid, 3,5-disulfobenzoic acid potassium salt, 4-sulfophthal. acids, 4-sulfophthalic acid ammonium salt, 5-sulfophthalic acid 5-sulfoisophthalic acid sodium salt, 5-dimethylsulfoisophthalic acid sodium salt, etc. Preferred compounds () are 5-sulfoisophthalic acid sodium salt and 5-dimethylsulfoisophthalic acid sodium salt. They are the expression ()
preferred due to the exceptionally easy regeneration of the diazonium salt derivatives. When heated slowly, all diazonium salts decompose, first with the release of nitrogen and then with the formation of thermal decomposition products. Some diazonium salts decompose by self-propagating reactions once decomposition is initiated. In such cases, some local decomposition of any given amount will lead to decomposition of the entire amount. Most diazochlorozincate salts have a high rate of self-propagating degradation, placing those salts in the high risk category. The diazonium salt compounds of the present invention (), in contrast to prior art diazonium salts, exhibit decomposition after decomposition has occurred in localized portions of a given batch of compounds (e.g., initiated by excessive thermal exposure). Does not proliferate. It is not truly understood why the diazo compounds of the present invention do not propagate initiated decomposition and sustain combustion if ignited, but under the action of heat, nitrogen is released. It seems likely that not only is the carboxylic acid group destroyed, but carbon dioxide is released along with its well-known fire extinguishing effect. The diazonium salt compounds of the present invention () are useful as active ingredients in photosensitive diazo-type reproduction materials and are commonly used as coatings of photosensitive diazonium compositions on basic support materials. The diazotype copying materials of this invention may be prepared by coating an aqueous mixture of the diazo compositions of this invention onto a suitable base support material using conventional diazo coating equipment. This technology is well known; for example, US Pat. No. 3,923,528 and US Pat.
Please refer to No. 3996056. Representative examples of suitable basic supports include thermoplastic polymeric resin films, foils, including metal foils, fabrics, opaque papers, transparent papers, and the like. Preferred are commercially available diazotype papers. The diazonium salts () of the present invention have low water-solubility in strong mineral acid media, but are compatible with various color formers and ammonium tartrate, ammonium citrate, monosodium glutarate, ammonium formate, potassium citrate, sodium acetate, etc. It was also found that it has much higher solubility in weakly acidic media in the presence of salts such as . The reason for the solubility effect of these compounds is not well understood, but facilitates the utilization of diazonium salts in the preparation of aqueous coated diazotype materials as recognized by those skilled in the art. Surprisingly, it has been found that the diazonium salts () of the invention are also soluble in organic solvents. Since polymeric resin films and plastic coating base materials are commonly coated with non-aqueous photosensitive solutions as distinguished from aqueous solutions, diazonium salts can be easily coated onto such base supports. . There are advantages to such a use of diazonium compounds (). Special diazo salts have previously been proposed for use in photosensitive organic solvents. For example, diazohexafluorophosphate, diazohexafluoroarsenate,
and diazohexafluoroantimonate,
Easily soluble in organic solvents. However, such diazos suffer from inherent disadvantages. Diazo hexafluoroarsenate and antimonate salts are too toxic to find any commercial use;
Furthermore, since hexafluorophosphate is very insoluble in water, even the smallest amount of water is not tolerated during formulation. This increases the cost of the solvents used. In addition, this solvent must not contain even a small amount of water. Furthermore, many photosensitive systems for polymeric film coatings are based on mixtures of solvents and water, which reduce cost and fire hazards. Diazonium salts are soluble both in water and in solvents, making them particularly attractive for use in the production of polymeric films and plastic-coated basic support materials using commercially available low-cost solvents and/or water-solvent mixtures. suitable. As is well known in the art, a diazo composition for a two-component diazotyping process comprises at least one photosensitive diazonium compound, at least one azo color former, and the necessary acid to obtain a diazotyping copy. Consists of stabilizers. Additional ingredients for such diazo compositions include, for example: 1. Glycerol, polypropylene glycol, urea, etc. to reduce the required ammonia or amine concentration in the development environment. Development accelerator; 2 Thiourea, 1,3,6 to stabilize diazotype prints against bleaching under daylight exposure
- antioxidants, such as naphthalene trisulfonic acid sodium salt; 3. contrast-controlling compounds; and 4. solubilizing agents, such as caffein, which improve the compatibility of the various components in the photosensitive solution. Sometimes such ingredients perform one or more of these functions. Acid stabilizers are generally necessary components of the diazo compositions of the present invention. Any of the well-known acid stabilizers previously used in photosensitive diazo coating compositions may be used. Representative examples of such acid stabilizers include citric acid, tartaric acid, boric acid, mixtures thereof, and the like. In preferred diazo compositions of the present invention, the azo color former is applied to a diazonium compound () in an acid environment.
Prevent color development by mixing with When changing the PH from an acid to an alkaline PH, a coupling reaction occurs to form an azo dye as is known in the art. Azo color formers are generally aromatic compounds having phenolic hydroxyl groups, with or without other substituents. Color formers are generally colorless. Representative examples of azo color formers are: 1. resorcinol and its halogen and alkyl derivatives and ethers; 2. resorcylic acid and its amides and substituted amides with or without halogen substitution in the ring; 3. dihydroxynaphthalene monosulfones. acids and disulfonic acids; 4 dihydroxynaphthalenes; 5 beta- and alpha-hydroxynaphthoic acid amides and substituted amides; 6 compounds with active methylene groups such as aceto-aceto and cyanolaceto derivatives; 7 mono- and polyhydroxybiphenyls ; 8 polyhydroxybiphenyl sulfide; 9 pyrazolone derivative; 10 aminophenol derivative; etc. The photosensitive diazo coating composition of the present invention includes:
Contains any number of additional ingredients commonly used in the preparation of prior art photosensitive diazo coating compositions, such as, for example, solubilizers, fillers, stabilizers, promoters, solvents, antioxidants, contrast controlling compounds, etc. You may. The various components of the diazo compositions of the present invention may be in proportions that are (and were) commonly used in the preparation of prior art diazo photosensitive compositions in use prior to the present invention. .
These proportions are well known to those skilled in the art; see, for example, the Kosar disclosure cited above and U.S. Pat.
See Nos. 3923518 and 3996056. The diazo compositions of the present invention may be prepared by placing the ingredients together in a suitable reaction vessel. Preferably, the compositions of the invention are prepared in an aqueous medium for use as an aqueous coating mixture for preparing the diazotype reproduction materials of the invention. In one-component diazotype copying materials, the diazo composition layer contains the diazonium compound () and other auxiliary agents as mentioned above, but does not have an azo color forming component. An alkaline or neutral developer solution containing highly reactive color forming ingredients such as phloroglucinol and resorcinol and buffer salts such as sodium borate or sodium formate is applied to the diazotype material after image exposure to develop the print. Let's do it. The following examples describe techniques and methods of making and using the present invention and represent the best mode contemplated by the inventor, but are not limiting. It should not be interpreted as such. All parts specified are by weight unless otherwise stated. The tests conducted in the examples are as follows. Flammability test: width 1cm, length 10cm, and height 1/
A small fuse of 2 cm of powdered diazonium compound is lit with a match at the end. A diazonium compound is considered flammable if it ignites and a flame spreads along the entire length of the diazonium compound fuse. A diazonium compound is considered nonflammable if the diazonium compound does not ignite or the localized decomposition of the diazonium under the match does not spread along a portion of the length of the diazonium compound fuse. Example 1 (A) An aqueous solution of 1-diazo-4-N,N-dimethylaminobenzene chloride was cooled to 4°C,
- Mixing with a saturated solution of sulfoisophthalic acid sodium salt. The amount of 5-sulfoisophthalic acid sodium salt is a slight excess (10% to 20%) of the stoichiometric amount (calculated based on a 1:1 reaction between the reactants) required for the reaction with the chloride. )
It is. Add an amount of concentrated sulfuric acid equivalent to 0.1 mole per mole of diazonium salt. A saturated solution of sodium chloride is then added dropwise until precipitation of the diazonium salt begins. The pale yellow crystalline precipitate is filtered and air dried to yield 1-diazo-4-N,N-dimethylamino-benzenesulfoisophthalate. The thermal and combustion characteristics of sulfoisophthalate are described in 1-
Compare with diazo-4-N,N-dimethylaminochlorosincate and the corresponding borofluoride. The results are as follows:

[Table] Ride
(B) A white base paper suitable for a diazotype process, previously coated with an aqueous silica dispersion and a polyvinyl acetate emulsion in a manner well known in the art, is photosensitized with a liquid containing: Citric acid 20g Theophyllol 15g Thiourea 60g 2,7-dihydroxy 3,6-naphthalenedisulfonic acid sodium salt 10.5g Trihydroxydiphenyl 50% solution 8g 1-Diazo-4-N,N-dimethylaminobenzenesulfoisophthalate 15g Chloride Sodium 30 g Zinc chloride 50 g Water 1000 c.c. Printing on photosensitive paper under a transparent master carrying a black ink image and development with ammonia in the conventional manner gives isodensity black line copies and Brightness was obtained with the same photosensitive liquid using 1-diazo-4-N,N-dimethylaminobenzene chlorosincate in place of the corresponding sulfoisophthalate salt. Example 2 (A) 1-Diazo-4-N,N-dimethylaminobenzene chloride is cooled with ice and mixed with a solution of 5-sulfoisophthalic acid, sodium salt containing 0.2 moles of concentrated hydrochloric acid per mole of diazonium salt. react and follow the procedure of Example 1 above, precipitating the diazonium salt 1-diazo-4-N,N-diethylaminobenzenesulfoisophthalate upon addition of a saturated solution of sodium chloride;
Isolate by filtration. The product diazo was subjected to thermal and flammability tests as in Example 1 in comparison with the corresponding chlorozincate and borofluoride, the results of which are shown below:

[Table] Rate
(B) A white base paper suitable for the diazotype process is precoated and then sensitized with a liquid containing: 20 g citric acid 40 g thiourea 50 g urea 2,3-dihydroxy 6, naphthalene Sulfonic acid, sodium salt 15 g Dipropylene glycol 10 ml 1-Diazo-4-N,N-diethylaminobenzenesulfoisophthalate 11 g Zinc chloride 60 g Saponin 0.25 g Water 1000 ml Black ink Printing under a transparent master carrying an image and general Development with ammonia in the method gives isodensity blue line copies;
and gave a brightness similar to that obtained with similar photosensitive liquids using 1-diazo-4-N,N-diethylaminobenzene chlorosincate salt in place of the corresponding sulfoisophthalate salt. Example 3 (A) Following the procedure of Example 1 above, 1-diazo-
4-p-Tolylthio-2,5-diethoxybenzene chloride, 5-sulfoisophthalic acid, except using only stoichiometric amounts of reactants (calculated based on a 1:1 reaction) React with a saturated solution of sodium salt. Under these conditions virtually all of the product diazonium salt, 1-diazo-4-p-tolylthio-2,5-diethoxybenzenesulfoisophthalate, precipitates and is easily isolated. Comparing the sulfoisophthalate with the corresponding chlorozincate and borofluoride salts, we obtain the following results:

[Table] Mborofluoride
(B) A white base paper suitable for the diazotype process, previously coated with an aqueous silica dispersion and a sodium caseinate solution in a manner well known in the art, is sensitized with a liquid containing: citric acid. Acid 5g Caffeine 10g Potassium citrate 5g 1,3,6-1,3,7-naphthalene, trisulfonic acid, sodium salt 60g 1-diazo-4-p-tolylthio-2,5-
Diethoxybenzenesulfoisophthalate 10 g Photosensitive paper was printed under a black ink image transparent master and developed as a one-component diazotype material in a conventional manner using the following liquid color formers: Sodium formate 45 g Tartaric acid Sodium 2g Sodium benzoate 15g Phloroglucinol 3.5g Isopropylnaphthalenesulfonic acid, sodium salt 0.5g Water 1000ml The resulting black line copy is 1-diazo-4-p
-tolylthio-2,5-diethoxybenzene chlorosincate with a density and brightness equivalent to that obtained with a photosensitive liquid containing instead of the sulfoisophthalate salt. Example 4 (A) 1-Diazo-4-N-pyrrolidino-3-methylbenzene chlorosincate was cooled on ice and added in slight excess of the stoichiometric amount (calculated to react 1:1 with all the diazo). 30% of 5-sulfoisophthalic acid sodium salt (10% to 20%)
Mix with aqueous solution. Upon addition of a saturated solution of sodium sulfate, the diazonium salt 1-diazo-
4-N-pyrrolidino-3-methylbenzenesulfoisophthalate precipitates. The products were subjected to thermal and flammability tests similar to those in Example 1 and compared.
The results were as follows:

[Table] Tallate
(B) White 65g/pre-coated with an aqueous silica dispersion and polyvinyl acetate multipolymer emulsion in a manner well known in the art.
Light-sensitize the ^m2 clearing rag base paper with a liquid containing: p-toluenesulfonic acid 15g sulfosalicylic acid 3.5g ammonium citrate 20g thiourea 40g beta-resorcylic acid ethanolamide 17g 2,5- Dimethylmorpholinomethylphenol 25g Alpharesorcilic acid 2.5g 1-Diazo-4-N-pyrrolidino-3-methylbenzenesulfoisophthalate 50g Zinc chloride 20g 1,3,6-1,3,7-naphthalene trisulfone Acid, sodium salt 40 g Micronized silica 20 g Polyvinyl acetate emulsion 25 ml Saponin 0.25 g Water 1000 ml Printing under a transparent master and developing with ammonia in the conventional manner gave a sepia line copy of the original master. In view of the actinic radiopacity of the sepia image, such copies are particularly suitable for further reproduction onto standard diazotype materials. This copy is
It is as good as that obtained by substituting the corresponding chlorozincate salt for 1-diazo-4-N-pyrrolidino-3-methylbenzenesulfoisophthalate. Example 5 (A) Compound 1-
reacting diazo-4-morpholino-2,5-diethoxybenzene chloride and 5-dimethylsulfoisophthalic acid sodium salt together;
1-Diazo-4-morpholino-2,5-diethoxybenzene 5-dimethylsulfoisophthalate is produced. Repeat the steps again, but
5-dimethylsulfoisophthalic acid sodium salt as used above is replaced by 5-sulfoisophthalic acid sodium salt to obtain 1-diazo-4-morpholino-2,5-diethoxybenzenesulfoisophthalate. Thermal and flammability tests show the following results:

[Table]
Among the above salts, chlorozincate, 40%
Chlorozincate diluted with citric acid, and borofluoride were found to be flammable, whereas 5-dimethylsulfoisophthalate and 5-sulfoisophthalate were found to be nonflammable. (B) A polyethylene terephthalate film surface treated for adhesion promoting properties, such as Melinex 505 (ICI Americans Inc.), is coated with a layer of cellulose acetate propionate in a manner well known in the art, and then coated with a layer of cellulose acetate propionate as described below. Photosensitize with liquids: methanol 400ml ethylene glycol monomethyl ether
400ml Methyl ethyl ketone 100ml Formic acid 50ml Sulfosalicylic acid 15g Thiourea 10g Beta-resorcylic acid ethanolamide 10g 3-Hydroxyphenylurea 20g 1-Diazo-4-N-morpholino-2,5
-Diethoxybenzene-5-dimethylsulfoisophthalate 25 g The photosensitive film thus obtained was exposed through a transparent master and developed with ammonia in the usual manner to give a deep sepia shadow image of the original master. The copy film is particularly suitable for further copying on diazo type materials and is made of 1-diazo-4-N-morpholino-2,5-diethoxybenzene 5-
It was as good as that obtained with the corresponding diazoborofluoride salt in place of dimethyl sulfoisophthalate. Example 6 (A) Following the procedure in part (A) of Example 3 above, prepare 1-diazo-4-p- as used in Example 3.
tolylmercapto-2,5-diethoxybenzene chloride in equal proportions of 1-diazo-4-
The compound 1-diazo-4-morpholino-2,5-dibutoxybenzene-5-sulfoisophthalate is prepared by substitution with morpholino-2,5-dibutoxybenzene chloride. Thermal and flammability tests show the following results:

[Table] Among the above salts, chlorozincate salt was found to be flammable, sulfate salt and borofluoride were found to be slightly flammable, and 5-sulfoisophthalate salt was found to be nonflammable. I found out something. (B) A white base paper suitable for the diazotype process is sensitized with a liquid containing: citric acid 7.5 g caffeine 3 g urea 25 g thiourea 10 g dipropylene glycol 10 g 1,3,6-1,3, 7-naphthalenetrisulfonic acid sodium salt 70g 4-bromo-α-resorcylic acid amide 6g ammonium citrate 30g 1-diazo-4-morpholino-2,5-dibutoxybenzene 5-sulfoisophthalate
11 g Zinc chloride 25 g Amorphous silica 50 g Polyvinyl acetate emulsion 50 ml Saponin 0.5 g Water 1000 ml Printing under a transparent original and developing with ammonia in a conventional manner produces 1-diazo-4-morpholino-2,5-diethoxy Substituting the sulfate salt of benzene for the corresponding sulfoisophthalate salt gave a red copy of density and brightness equivalent to that obtained with the same photosensitive liquid. Example 7 (A) Following the procedure of Example 1 above, an aqueous solution of 1-diazo-4-N-methyl-N-cyclohexylamino-3-cyclobenzene chloride was cooled with ice and added per mole of diazonium salt. 1 by mixing with a solution of 0.5 molar equivalents of 5-sulfoisophthalic acid, sodium salt and methanesulfonic acid.
-Diazo-4-N-methyl-N-cyclohexylamine-3-chlorobenzenesulfoisophthalate is precipitated. Thermal and flammability tests show the following results in comparison with the corresponding chlorozincate and borofluoride salts.

[Table] Foisophthalate
The chlorozincate salts mentioned above were found to be flammable; the borofluoride and sulfoisophthalate salts were found to be non-flammable. (B) A blue colored 65 g/m ² clear rag pace paper was precoated with an aqueous silica dispersion of polyvinyl acetate emulsion, in a manner well known in the art, and then containing: Sensitized with liquid: citric acid 5 g 1,3,6-1,3,7-naphthalene trisulfonic acid, sodium salt 60 g ammonium citrate 30 g 1-diazo-4-N-methyl-N-cyclohexylamino-3 -Chlorobenzene sulfoisophthalate 35g Water 1000ml Print on photosensitive paper under a transparent master,
It was developed as a one-component diazotype material in the general manner using the liquid developer described below. Potassium borate tetrahydrate 35g Potassium citrate 15g Tripotasium phosphate 5g Sodium hyposulfate 2.5g Boric acid 2g Phloroglucinol 4.8g Resorcinol 2g Isopropylnaphthalenesulfonic acid, sodium salt 0.5g Water 1000ml A sepia copy of the original master. In view of the actinic radiopacity of the sepia image obtained, the copy is particularly suitable for further reproduction onto diazotype material. This copy is as good as that obtained by replacing the diazonium sulfoisophthalate salt with the corresponding diazochlorozincate. Example 8 (A) 1-diazo-4-N-morpholino-2,5
- An aqueous solution of dibutoxybenzene sulfate is cooled with ice and mixed with a saturated solution of 4-sulfophthalic acid in a slight excess of the calculated stoichiometric amount to react with all the diazo in a 1:1 reaction.
When seeding by adding crystals of sodium chloride, 1-diazo-4-N-morpholino-
2,5-dibutoxybenzenesulfoisophthalate precipitates. Upon separation of the generated precipitate,
It can be seen that the decomposition temperature range of this salt is 137°C to 142°C. Also, the salt is nonflammable. (B) A translucent natural tracing paper of 80 g/m ² is coated with a layer of cellulose acetate butyrate in a conventional manner and then sensitized with the following liquids: Ethyl alcohol 500 ml Ethylene glycol monoethyl ether
500ml p-Toluenesulfonic acid 10g Sulfosalicylic acid 10g Thiourea 15g Resorcinol monohydroxyethyl ether 15g Peter resorcylic acid, ethanolamide
10g 1-diazo-4-N-morpholino-2,5
-dibutoxybenzene-4-sulfophthalate
25 g The photosensitive tracing paper thus obtained was exposed through a transparent original with an ink line and developed with ammonia in the conventional manner to yield a deep sepia copy of the original. This copy is particularly suitable for further copying into diazotype materials, and the corresponding diazoborofluoride instead of 1-diazo-4-N-morpholino-2,5-dibutoxybenzene-4-sulfophthalate. As good as that obtained with salt.

Claims (1)

[Claims] 1 formula (wherein Ar represents aryl or substituted aryl; _R1 is selected from the group consisting of hydrogen, _-SO3H and _-SO3M , where M means Na, K or _NH4 ; R ₂ is hydrogen and the formula −COOR ₃
selected from the group consisting of; and
R ₃ is selected from the group consisting of hydrogen and alkyl). 2 Ar is amino, alkylamino, dialkylamino, alkylhydroxyalkylamino, dihydroxyalkylamino, alkoxy, phenoxy, cycloalkylamino, alkylcycloalkylamino, alkylarylamino, alkylaralkylamino, sialylamino, tolylthio, morpholino, pyrrolidino , piperidino,
2. Photosensitive diazonium salt according to claim 1, representing an aryl group substituted in the para position to the diazonium group by a chemical group selected from and piperazino. 3 The ortho and meta positions relative to the diazonium group are unsubstituted or alkyl, alkoxy, phenoxy, halophenoxy, halogen,
3. A photosensitive diazonium salt according to claim 2, which is substituted by a chemical group selected from: and having the formula Ac-NH-, where Ac represents carboxyacyl. 4. The photosensitive diazonium salt according to claim 1, which is 1-diazo-4-N,N-dimethylaminobenzenesulfoisophthalate. 5. The photosensitive diazonium salt according to claim 1, which is 1-diazo-4-N,N-diethylaminobenzenesulfoisophthalate. 6 1-Diazo-4-p-tolylthio-2,5-
The photosensitive diazonium salt according to claim 1, which is diethoxybenzenesulfoisophthalate. 7. The photosensitive diazonium salt according to claim 1, which is 1-diazo-4-N-pyrrolidino-3-methylbenzenesulfoisophthalate. 8. The photosensitive diazonium salt according to claim 1, which is 1-diazo-4-morpholino-2,5-diethoxybenzene-5-dimethylsulfoisophthalate. 9. The photosensitive diazonium salt according to claim 1, which is 1-diazo-4-morpholino-2,5-diethoxybenzene-5-sulfoisophthalate. 10 1-Diazo-4-morpholino-2,5-
The photosensitive diazonium salt according to claim 1, which is dibutoxybenzene-5-sulfoisophthalate. 11 The photosensitive diazonium salt according to claim 1, which is 1-diazo-4-N-methyl-N-cyclohexylamino-3-chlorobenzenesulfoisophthalate. 12 1-diazo-4-N-morpholino-2,
The photosensitive diazonium salt according to claim 1, which is 5-dibutoxybenzene-4-sulfophthalate. 13 formula (wherein Ar represents aryl or substituted aryl; _R1 is selected from the group consisting of hydrogen, _-SO3H and _-SO3M , where M means Na, K or _NH4 ; R ₂ is hydrogen and the formula −COOR ₃
and R ₃ is selected from the group consisting of hydrogen and alkyl) and an acid stabilizer. 14. The composition according to claim 13, further comprising an azo color former. 15. The composition of claim 14 further comprising a solubilized proportion of a compound selected from the group consisting of ammonium tartrate, ammonium citrate, monosodium glutamate, ammonium formate, potassium citrate, and sodium acetate. 16 consisting of a basic support and a coating on this support, said coating having the formula (wherein Ar represents aryl or substituted aryl; _R1 is selected from the group consisting of hydrogen, _-SO3H and _-SO3M , where M means Na, K or _NH4 ; R ₂ is hydrogen and the formula −COOR ₃
and R ₃ is selected from the group consisting of hydrogen and alkyl), an acid stabilizer and an azo color former. 17 A compound having the formula Ar-N=N-X () (wherein Ar represents aryl or substituted aryl and X is an anion that forms a soluble salt with _ArN2 ) and a compound having the formula (wherein R ₁ is selected from hydrogen, -SO ₃ H and -SO ₃ M (where M means Na, K or NH ₄ ); R ₂ is selected from the group of hydrogen and the formula -COOR ₃ R ₃ is selected from the group consisting of hydrogen and alkyl, and Y is selected from hydrogen and a metal ion forming a soluble sulfonate salt. (wherein Ar represents aryl or substituted aryl; R ₁ is selected from hydrogen, -SO ₃ H and -SO ₃ M, where M means Na, K or NH ₄ ; R ₂ is hydrogen and _R3 is selected from the group consisting _of hydrogen and alkyl. 18. The method of claim 17, wherein the reaction is carried out in an aqueous medium. 19. The production method according to claim 17, wherein the reactant compounds () and () react with each other in stoichiometric proportions. 20. The manufacturing method according to claim 17, wherein the reactant compound () is present in an excess amount over the amount necessary to sufficiently react with the reactant compound (). 21. The production method according to claim 17, which is carried out in the presence of a highly reactive mineral acid.