JPH05125031A - Aromatic diazo compound, its production and photosensitive composition produced therefrom - Google Patents

Abstract

PURPOSE:To provide a new compound having maximum absorption wavelength of UV spectrum at 372-382nm, free from absorption in visible range, having high sensitivity and excellent storage stability and solubility, and useful as a photosensitive agent, etc. CONSTITUTION:The compound of formula I [Z<1> is O-CH2, O-phi<1> (phi<1> is arylene or substituted arylene non-reactive with diazonium salt and nitrous acid), etc.; R<1> and R<2> are H, 1-8C alkyl or 1-8C alkyloxy; X<-> is anion; R<3> is alkyl, aralkyl, etc.], e.g. the compound of formula II. The compound of formula I can be produced by deacylating a compound of formula III (Ac is acyl, arylsulfonyl, etc.) and diazotizing with a diazotizing reagent such as nitrous acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive aromatic diazo compound having high sensitivity, good storage stability and easy synthesis, a method for producing the same, and a photosensitive composition using the same.

[0002]

BACKGROUND ART Conventionally, as a photosensitive substance added to a photosensitive coating layer of a photosensitive lithographic printing original plate or a photosensitive screen printing original plate, a diphenylamine-4-diazonium salt (4-phenylaminobenzenediazonium salt in academic terms) is used.
A condensate of solute with formaldehyde (commonly called diazo resin) has been used as a representative compound. The production of such polyfunctional diazo condensates is described in US Pat. No. 2,679,498,
No. 2922715, No. 2946683, No. 3050
No. 502, No. 3311605, No. 3163633,
No. 3406159 and No. 3277074. These diazo condensates have many advantages as a practical photosensitive material, but also have various problems to be improved.

The first problem is that these diazo condensates are relatively insoluble in organic solvents. As a counter ion of the diazonium group of these diazo compounds, halogen ions, when using inorganic ions such as phosphate ions, of course, benzene sulfonic acid, triene sulfonic acid or alkyl sulfonic acid such as an ion of a sulfonic acid, Solubility in organic solvents such as glycol ethers, alcohols and ketones is not sufficient. Such low solubility in organic solvents is a drawback when these diazo condensates are used as a photosensitizer for a photosensitive lithographic printing original plate.

Therefore, various studies have been made to improve these drawbacks. For example, Japanese Patent Publication No. 53-24449 discloses that when a special compound such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid is used as a counter ion of a diazonium group, the solubility in an organic solvent is increased. In addition, Japanese Patent Publication Sho-49-453
No. 23, JP-A No. 62-156656 discloses a similar improvement by using a special compound such as 4,4′-bismethoxymethyldiphenyl ether instead of formaldehyde as a condensing agent for diphenylamine-4-diazonium salt. It is clear what can be done. Further, in JP-A-2-3049, it is found that hexamethoxymethylmelamine is preferable as such a special condensing agent.

The second problem is diphenylamine-
The diazo condensate having a 4-diazonium salt as a basic structural unit also has an absorption in the visible region of 420 to 500 nm and absorbs light of this wavelength to decompose, so that it is difficult to handle under a white lamp. This represents an important manufacturing and use drawback.

As a method for solving the second problem and the first problem at the same time, a new polyfunctional diazo compound having a chemical structure basically different from that of the conventional diazo compound is also studied. Came to be. The new-type diazo compound thus obtained is the conventional diphenylamine-4.
The greatest feature is that a 4-dialkylaminobenzenediazonium salt is used as a basic structural unit instead of the diazonium salt. For example, in JP-A-54-30121 and JP-A-61-273538, two or more 4
A dialkylaminobenzenediazonium salt is linked by an ester bond to form a polyfunctional diazonium salt.
In Japanese Patent Publication No. 1-57332, 4-dialkylaminobenzenediazonium salt is bound in the form of polyalkylamine to form a polyfunctional diazonium salt. Although all of these new polyfunctional diazo compounds have excellent performance, they are generally not easy to manufacture. Further, the diazo compounds described in the above-mentioned two types of published patent publications which are polyfunctional with an ester bond have a drawback that the ester bond is easily hydrolyzed.

A third problem is that the diazo compound used in the photosensitive screen printing original plate has a high solubility in water as a necessary condition. With respect to this point, no studies have been reported to date about a diazo compound having a performance higher than that of a conventional diazo compound obtained by condensing a diphenylamine-4-diazonium salt with formaldehyde. In JP-A No. 2-11198, diphenylamine-4-diazonium salt and hydroxybenzoic acid are condensed with formaldehyde to obtain a highly water-soluble polyfunctional diazo compound. It was developed to improve the developability of the lithographic printing plate precursor with an alkaline aqueous solution, and has not been improved for screen printing.

[0008] The fourth problem is that the condensate of the currently used diphenylamine-4-diazonium salt of formaldehyde with light is not sufficiently sensitive to light. For this reason, it is difficult to shorten the practical exposure time with a photosensitive composition containing a currently used polyfunctional diazo compound as a photosensitizer. If the exposure time is shortened, the image after development tends to be colored brown. There are drawbacks.

[0009]

As described above, there are many unsolved problems in the prior art. The summary of the objects of the present invention, including these problems, is as follows. 1) Development of polyfunctional diazo compounds that can be handled under white light. 2) Development of a multifunctional diazo compound which has a large solubility in an organic solvent suitable as a sensitizer for a lithographic printing plate and is easily developed by a developing solution containing an alkaline aqueous solution as a main component. 3) Development of a highly water-soluble polyfunctional diazo compound suitable as a sensitizer for a screen printing original plate. 4) Development of multifunctional diazo compounds with high sensitivity to light. 5) Development of polyfunctional diazo compounds with simple synthetic methods and establishment of low-cost production methods for those compounds. 6) Development of a photosensitive composition that effectively utilizes the performance of the novel polyfunctional diazo compound obtained as described above.

[0010]

Means for Solving the Problems As a result of various studies, the present inventors have found a novel aromatic diazo compound optimal for achieving the above-mentioned objects 1) to 6) and completed the present invention.
The aromatic diazo compound according to the present invention based on this finding has as a main component a compound in which two or more atomic groups represented by the general formula (I) shown in the following "Chemical Formula 30" are bonded in one molecule.

[0011]

[Chemical 30]

[0012]

[Chemical 31]

[0013]

[Chemical 32]

Specific examples of X ⁻ in the general formula (I) shown in the above “Chemical Formula 30” are as follows. Cl ^-, Br ^-, HS
_{^{O 4 -, 1 / 2SO 4}} 2-, H 2 PO 4 -, 1 / 2HPO 4 2-, HSO 3 -, 1 / 2Z
^{_{nCl 2 Cl -, 1 / 2ZnCl}} 2 Br -, BF 4 -, PF 6 -, a benzenesulfonate anion, toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion, mesitylene sulfonate anion, naphthalenesulfonic acid anion, naphthalene disulfonic acid anion , 2-Hydroxy-4-methoxybenzophenone-5-sulfonate anion, methanesulfonate anion

As a specific example of Z ¹ in the above general formula (I), the ^one shown in the following "Chemical Formula 33" is preferable.

[0016]

[Chemical 33]

As specific examples of R ³ in the general formula (I) shown in the above "Chemical formula 30", those shown in the following "Chemical formula 34" and "Chemical formula 35" are preferable.

[0018]

[Chemical 34]

[0019]

[Chemical 35]

Representative examples of aromatic diazo compounds having two or more atomic groups represented by the general formula (I) shown in the above "Chemical Formula 30" bonded in one molecule (aromatics of the first to fifth types) The diazo compound) is shown below.

The first type of aromatic diazo compound is an aromatic diazo compound represented by the general formula (II) shown in the following "Chemical Formula 36".

[0022]

[Chemical 36]

[0023]

[Chemical 37]

[0024]

[Chemical 38]

[0025]

[Chemical Formula 39]

[0026]

[Chemical 40]

[0027]

[Chemical 41]

[0028]

[Chemical 42]

[0029]

[Chemical 43]

[0030]

[Chemical 44]

[0031]

[Chemical 45]

[0032]

[Chemical 46]

[0033]

[Chemical 47]

The second type of aromatic diazo compound is an aromatic diazo compound represented by the general formula (III) shown in the following "Chemical Formula 48".

[0035]

[Chemical 48]

[0036]

[Chemical 49]

[0037]

[Chemical 50]

[0038]

[Chemical 51]

[0039]

[Chemical 52]

[0040]

[Chemical 53]

[0041]

[Chemical 54]

The third type of aromatic diazo compound is a long chain molecule and has the general formula (IV) shown in the following "Chemical formula 55".
It is an aromatic diazo compound represented by.

[0043]

[Chemical 55]

[0044]

[Chemical 56]

[0045]

[Chemical 57]

The aromatic diazo compound of the fourth type is a long chain molecule like the third type, but the atomic group connecting the benzenediazonium is not uniform and two or more different " Which is an aromatic diazo compound represented by the general formula (V).

[0047]

[Chemical 58]

However, the general formula (V) shown in the above "Chemical Formula 58"
In the middle, the integer n to n ⁱ is 0 to 4, also n ¹ + n ² + n
³ + ... + n ⁱ = 2 to 20 and X ⁻ , R ⁵ , R ⁶
Each have the same meaning as X ⁻ , R ⁵ and R ^{6 in} formula (IV). Q ₂ ^{1 to} Q ₂ ⁱ are divalent groups belonging to Q ₂ of the formula (IV), and Q ₂ ^{1 to} Q ₂ ⁱ are not the same group but at least two kinds of different atomic groups. Represent.

A fifth type of aromatic diazo compound is 1
In the molecule, two or more atomic groups represented by the general formula (I) shown in “Chemical formula 1” and an atomic group represented by the general formula (VI) shown in the following “Chemical formula 59” are contained in the molecule. Is a compound having one or more

[0050]

[Chemical 59]

The above-mentioned fifth type aromatic diazo compound is represented by the following general formula (Chemical Formula 60), (Chemical Formula 61) and (Chemical Formula 62) as a derivative of the aromatic diazo compound of the first to fourth types. II '), (III'), (V ').

[0052]

[Chemical 60]

[0053]

[Chemical formula 61]

[0054]

[Chemical formula 62]

"Chemical 60", "Chemical 61", "Chemical 62"
In the general formulas (II ′), (III ′) and (V ′) shown in
E represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group,
The representative one is as follows. Alkyl · C ₁ ~C _20. Halogen, a hydroxyl group, a carboxyl group, an alkyl group substituted with C ₁ -C ₂₀ sulfonamide group. -Phenyl group, naphthyl group, and their alkyl substitution products. -Aryl group substituted with halogen, carboxyl group or sulfonamide group. An aralkyl group in which a benzyl group or an aryl group is substituted with a carboxyl group or a sulfonamide group.

Next, the production method of the aromatic diazo compound according to the present invention will be shown by production methods (I) to (IX). First, as the first method for producing an aromatic diazo compound (production method (I)) of the present invention, a compound represented by the following general formula (VI)
The p-aminoacylanilide represented by I) or a substituted product thereof and the polyglycidyl ether represented by the general formula (VIII) represented by the following "Chemical Formula 64" are reacted in an organic solvent, and further the general formula (VII) When R ^{7 of} is a hydrogen atom and the hydrogen atom remains after the reaction, the remaining hydrogen atom is replaced with R ³ , and the compound represented by the general formula (II _AC ), Further reacting an aqueous solution of one or a mixture of sulfuric acid, hydrochloric acid, phosphoric acid to substitute the acyl group (A _C ) which is a protecting group for an amino group with a hydrogen atom. To the aromatic amino compound represented by the general formula ( _IIa ) shown in Chemical formula 66, and diazotizing this aromatic amino compound with a diazotizing reagent such as nitrous acid to produce an aromatic diazo compound of the first type. Is characterized by.

[0057]

[Chemical 63]

[0058]

[Chemical 64]

[0059]

[Chemical 65]

[0060]

[Chemical 66]

As the second method for producing an aromatic diazo compound (production method (II)) of the present invention, p-aminoacylanilide represented by the following general formula (VII) or a substituted product thereof is shown. And the general formula (I
When a polyglycidylamino compound represented by X) is reacted in an organic solvent and R ^{7 in the} general formula (VII) is a hydrogen atom and the hydrogen atom remains after the reaction, The residual hydrogen atom is replaced with R ³ to give a compound represented by the following general formula (III _AC )
Furthermore, by reacting with an aqueous solution of one of sulfuric acid, hydrochloric acid, phosphoric acid or a mixture thereof, an acyl group (A
_C ) is replaced with a hydrogen atom, and the general formula shown in the following "Chemical Formula 70"
The aromatic amino compound represented by (III _a ) is prepared, and the aromatic amino compound is diazotized with a diazotizing reagent to produce a second type aromatic diazo compound.

[0062]

[Chemical 67]

[0063]

[Chemical 68]

[0064]

[Chemical 69]

[0065]

[Chemical 70]

As the third method for producing an aromatic diazo compound (production method (III)) of the present invention, aniline represented by the general formula (X) shown in the following "Chemical Formula 71" or a homologue thereof and The polyglycidyl ether compound represented by the general formula (VIII) represented by the formula "Chemical formula 72" is reacted in an organic solvent, and R ⁷ is a hydrogen atom in the general formula (X), and the hydrogen If the atom remains,
The residual hydrogen atom is replaced with R ³ , and a nitrosating reagent is reacted to synthesize an aromatic nitroso compound represented by the general formula (II _NO ) shown in the following “Chemical Formula 73”, and the nitroso group is converted to an amino group. To an aromatic amino compound represented by the general formula ( _IIa ) shown in the above "Chemical formula 66", which is diazotized to produce a first type aromatic diazo compound.

[0067]

[Chemical 71]

[0068]

[Chemical 72]

[0069]

[Chemical formula 73]

As the fourth method for producing an aromatic diazo compound (production method (IV)) of the present invention, an aniline represented by the general formula (X) shown in the following "Chemical formula 74" or a homologue thereof, and The polyglycidylamino compound represented by the general formula (IX) represented by the formula “Chemical formula 75” is reacted in an organic solvent, and further, in the general formula (X), R ⁷ is a hydrogen atom, and after the reaction, the hydrogen When the atom remains, the residual hydrogen atom is replaced with R ³ and reacted with a nitrosating reagent to give an aromatic nitroso compound represented by the following general formula (III _{NO 3} ) And reducing the nitroso group to an amino group to give _a compound represented by the general formula (III _a )
The aromatic amino compound represented by the formula (1) is diazotized to produce a second type aromatic diazo compound.

[0071]

[Chemical 74]

[0072]

[Chemical 75]

[0073]

[Chemical 76]

As the fifth method for producing an aromatic diazo compound (production method (V)) of the present invention, p-aminoacylanilide represented by the following general formula (XI) or a substituted product thereof is shown. In the general formula (VI
II _{n = 2} ), or one of the diglycidyl ethers represented by
Alternatively, one of the diglycidylamino compounds represented by the general formula (IX _{n = 2} ) shown in the following “Chemical Formula 79” is reacted in an organic solvent, and after the reaction, a hydrogen atom of —NH ₂ of the general formula (XI) is also reacted. In the case of remaining, the monoglycidyl ether represented by the general formula (XII) shown in the following "Chemical formula 80" is further reacted, and A _C is replaced with H by the same reaction as in the production method (II). Further, a diazotization reaction is further performed to produce a third type aromatic diazo compound which is a long chain molecule.

[0075]

[Chemical 77]

[0076]

[Chemical 78]

[0077]

[Chemical 79]

[0078]

[Chemical 80]

As the sixth method for producing an aromatic diazo compound (production method (VI)) of the present invention, a p-aminoacylanilide represented by the general formula (XI) shown in "Chemical Formula 77" or a substituted product thereof can be used. , The general formula (VI
II _{n = 2} ) and the diglycidyl ether
9) and a mixture of at least two diglycidylamino compounds represented by the general formula (IX _{n = 2} ) in an organic solvent. When the hydrogen atom of —NH ₂ remains,
Further reacting the monoglycidyl ethers represented by the above general formula in "of 80" (XII), the A _C is replaced with H by the same manufacturing method II reaction, further by performing the diazotization reaction, long chain It is characterized by producing a fourth type of aromatic diazo compound which is a molecule.

The seventh method for producing an aromatic diazo compound (production method (VII)) of the present invention is one atom group represented by the general formula (I) shown in the above "Chemical Formula 30" in one molecule. A compound having the above and reacting with a carbonyl reagent such as formaldehyde to give a polycondensation product is reacted with formaldehyde or a reagent generating the same in sulfuric acid or phosphoric acid.

As the eighth method for producing an aromatic diazo compound (production method (VIII)), the atomic group represented by the general formula (II _AC ) shown in the "Chem.
A compound having at least one compound and reacting with a carbonyl reagent such as formaldehyde to give a polycondensation product is reacted with a reagent generating a carbonyl reagent such as formaldehyde in an acidic solvent to give a compound represented by the general formula: The compound is characterized by synthesizing a compound in which one or more atomic groups represented by (II _AC ) are bonded in one molecule, and then performing a deacylation reaction and a diazotization reaction.

The ninth method for producing an aromatic diazo compound (production method (IX)) of the present invention is the above-mentioned p-aminoacetanilide represented by the general formula (XI) shown in "Chemical Formula 77" or a substituted product thereof. General formula (XIII) shown in "Chemical Formula 29"
The amino compound represented by the formula (1) is mixed in a desired ratio and the production methods (I), (II), (V) and (V
I) is reacted with a glycidyl compound in the same manner, then reacting the strong acid aqueous solution was replaced protecting group of an acylamino group of the (A _C) by H, characterized by further performing diazo reaction.

Further, the photosensitive composition according to the present invention contains 1 atomic group represented by the general formula (I) shown in the above "Chemical Formula 30".
It is characterized in that it contains an aromatic diazo compound whose main component is a compound having two or more bonded in the molecule and a binder, and further contains an auxiliary agent such as a coloring material or a stabilizer if necessary.

The contents of the present invention will be described below.

Specific examples of the compounds (formulas (1) to (24)) as the main components of the novel aromatic diazo compound obtained in the present invention are shown in the following "Chemical formula 81" to "Chemical formula 104". Is not limited to this.

[0086]

[Chemical 81]

[0087]

[Chemical formula 82]

[0088]

[Chemical 83]

[0089]

[Chemical 84]

[0090]

[Chemical 85]

[0091]

[Chemical formula 86]

[0092]

[Chemical 87]

[0093]

[Chemical 88]

[0094]

[Chemical 89]

[0095]

[Chemical 90]

[0096]

[Chemical Formula 91]

[0097]

[Chemical Formula 92]

[0098]

[Chemical formula 93]

[0099]

[Chemical 94]

[0100]

[Chemical 95]

[0101]

[Chemical 96]

[0102]

[Chemical 97]

[0103]

[Chemical 98]

[0104]

[Chemical 99]

[0105]

[Chemical 100]

[0106]

[Chemical 101]

[0107]

[Chemical 102]

[0108]

[Chemical 103]

[0109]

[Chemical 104]

As mentioned above, specific examples of the compound as the main component of the novel aromatic diazo compound obtained by the present invention are shown by the chemical structural formulas, but it is difficult to industrially produce a single product of these compounds with high purity. Is. For example, in the compound of the formula (1) shown in the above “Chemical formula 81”, m = 0,
Although it is difficult to industrially synthesize the diazo compound of the formula (1 _{m = 0} ) shown in Figure 1 with high purity, the compound of the formula (1 _{m = 0} ) is the main component, and If it is a mixture with a higher molecular weight diazo compound corresponding to 1 to 8, industrial production is possible.

[0111]

[Chemical 105]

The reason why such a mixture is obtained is that ethylene glycol diglycidyl ether is an important starting material for the production of the compound of formula (1), as described in the production method (I) or (III) of the present invention. However, it is difficult to industrially produce this diglycidyl ether with high purity. As described above, the compound of formula (1) is industrially obtained as a mixture. However, even if it is a mixture, all of these compounds are novel compounds corresponding to compounds in which two or more atomic groups represented by the general formula (I) are bonded in one molecule, and are suitable as a photosensitizer for a photosensitive composition. Is.

The polyfunctional diazo compounds of the present invention have various molecular structures as exemplified by the formulas (1) to (24), but these compounds have almost the same spectral characteristics due to diazonium. The maximum absorption wavelength λ max of the UV spectrum of the near-ultraviolet region of each of these aqueous solutions is in the range of 372 to 382 nm, and is 420 to 500.
There is no absorption in the visible region of nm.

This example is shown in FIG. 1 in comparison with a conventional polyfunctional diazonium compound having a basic structure of diphenylamine-4-diazonium salt. Therefore, the diazo compound according to the present invention can be handled under a white lamp,
This is a great advantage in the production of these diazo compounds or in the use as a photosensitizer. As a result, the object 1) described in [Problems to be solved by the invention] described above can be achieved by the present invention.

The objects 2) and 3) described in [Problems to be solved by the invention] are, as described above, the problem of the solubility of the diazo compound in an organic solvent or water. As described above, according to the present invention, various kinds of polyfunctional diazo compounds having various molecular structures can be obtained. Since the solubility of these various polyfunctional diazo compounds in organic solvents or water is naturally diverse, it is possible to provide a polyfunctional diazo compound having optimum solubility for lithographic printing or screen printing. it can.

Each of the diazo compounds of the present invention is more sensitive to light than the currently used "diazo resin". This is one of the most excellent properties of the diazo compound of the present invention, and was able to solve the fourth problem.
FIG. 2 shows the photolysis rate curves of the currently used "diazo resin" and the polyfunctional diazo compound according to the present invention in an aqueous solution at pH 3.

The fifth excellent characteristic of the diazo compound of the present invention is that it has good storage stability as compared with the currently used "diazo resin". The diazo compound is decomposed by reacting with the mixed water during storage. Example 1 of an experiment for promoting storage stability
FIG. 3 shows the result obtained in Example 2, which shows that the diazo compound of the present invention has high storage stability.

The novel aromatic diazo compound of the present invention can be easily produced by a combination of known synthetic reactions. The synthesis reaction in the first stage of these production steps is a reaction of an aniline homolog with a glycidyl ether or a glycidyl amino compound, as described in the production methods (I) to (VI) of the present invention. For example, the first-step synthetic reaction described in the production method (I) is shown in the following "Chemical formula 106".

[0119]

[Chemical formula 106]

It is generally known that the reaction of an epoxy compound with an amine produces two isomers, a secondary alcohol and a primary alcohol. The reaction shown in the following "Chemical Formula 107" is a typical example thereof, and when a group having a conjugated double bond such as a phenyl group or an ethylene group or an electron donating group is bonded to the epoxy ring, Easy to produce one alcohol (JKAddy, RMLaird, REParker, J.Chem.Soc., 1961 .1)
970).

[0121]

[Chemical formula 107]

Contrary to the example of this reaction, if an electron-withdrawing group is present near the epoxy ring, it is difficult to form the primary alcohol. Since the electron-withdrawing oxygen atom is present near the epoxy ring in glycidyl ether, the main product is the secondary alcohol in the reaction between glycidyl ether and amine, and the primary alcohol is difficult to form (L. Shechter , J.Wy
mstra, RP Kurkiy, Ind. Eng. Chem., 48 , 94 (1956).

Therefore, the formula (VII) shown in "Chemical Formula 106"
The main product of the reaction of the compound of formula (VIIIe) with the compound of formula (VIIIe) is a secondary alcohol of formula (I _ACE )
_However , the compound of the formula (I _ACEi ) shown in the following “Chemical Formula 108” of the primary alcohol is unlikely to occur.

[0124]

[Chemical 108]

As a result, in the novel aromatic diazo compound of the present invention, the main component is a compound in which two or more atomic groups (secondary alcohol) represented by the general formula (I) are bonded in one molecule.

Specific examples of p-aminoacylanilide represented by the general formula (VII) of the production method (I) or (II) of the present invention are shown in the following "Chemical formula 109" and "Chemical formula 110". However, the present invention is not limited to this.

[0127]

[Chemical 109]

[0128]

[Chemical 110]

Specific examples of the aniline represented by the general formula (X) or the homologue thereof described in the production method (III) or (IV) of the present invention are shown in the following "Chemical Formula 111". However, the present invention is not limited to this.

[0130]

[Chemical 111]

Two glycidyl ether atomic groups represented by the general formula (VIII) or glycidylamino atomic groups represented by the general formula (IX) described in the production method (I) or (II) of the present invention are contained in one molecule. Specific examples of the compound bound above are shown in the following formulas (46) to (61). However, the present invention is not limited to this. Generally, it is difficult to industrially produce a single compound of polyglycidyl ether or polyglycidyl amine with high purity. This is because the epoxy group of the glycidyl group is highly reactive, and during the synthetic reaction of the compound having these glycidyl groups, a sequential reaction occurs due to the epoxy ring, and a multimer is easily produced as a by-product. For example, when ethylene glycol is reacted with epichlorohydrin to produce ethylene glycol diglycidyl ether, a mixture represented by the formula (46) shown in the following "Chemical Formula 112" is obtained.

[0132]

[Chemical 112]

In the formula (46), m is an integer of 0-20.
As the glycidyl ether for synthesis of the novel diazo compound of the present invention, the compound represented by m = 0 of the formula (46) is good except for a special case, but it is possible to industrially synthesize such a single compound. Have difficulty. However, m
Even if a compound with = 0 as a main component and a compound with m of 1 to 8 are mixed, there is no inconvenience as a raw material for synthesizing the compound of the present invention. Further, specific examples thereof are shown in Formulas (47) to (61) shown in the following "Chemical 113" to "Chemical 127".

Diglycidyl obtained by condensing 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) containing formula (47) shown in the following "Chemical 113" as a main component with epichlorohydrin ether.

[0135]

[Chemical 113]

2,2-bis (4-hydroxy-3,5-dibromophenyl) propane (tetrabromobisphenol A) and epichlorohydrin containing the following formula (48) as a main component Diglycidyl ether obtained by condensation of.

[0137]

[Chemical 114]

A diglycidyl ether obtained by condensing bis (4-hydroxyphenyl) methane mainly composed of the formula (49) shown in the following "Chemical Formula 115" and epichlorohydrin.

[0139]

[Chemical 115]

A diglycidyl ether obtained by condensing dihydroxybenzene mainly containing the formula (50) shown in the following "Chemical Formula 116" and epichlorohydrin.

[0141]

[Chemical formula 116]

A diglycidyl ether obtained by condensing bis (4-hydroxyphenyl) sulfone containing formula (51) shown in the following "Chemical 117" as a main component and epichlorohydrin.

[0143]

[Chemical 117]

A diglycidyl ether obtained by condensing propylene glycol having the formula (52) shown in the following "Chemical 118" as a main component with epichlorohydrin.

[0145]

[Chemical 118]

A diglycidyl ether obtained by condensing 1,6-hexanediol containing formula (53) shown in the following "Chemical Formula 119" as a main component and epichlorohydrin.

[0147]

[Chemical 119]

A polyglycidyl ether obtained by condensing epichlorohydrin with glycerin containing the formula (54) shown in the following "Chemical Formula 120" as a main component. However, in equation (54)
C ₃ H ₅ (OH) ₃ represents glycerin, and n represents 2 or 3.

[0149]

[Chemical 120]

A polyglycidyl ether obtained by condensing pentaerythritol mainly containing the formula (55) shown in the following "Chemical 121" and epichlorohydrin. However, in the formula (55), C ₅ H ₈ (OH) ₄ represents pentaerythritol, and n represents an integer of 2 to 4.

[0151]

[Chemical 121]

A polyglycidyl ether obtained by condensing sorbitol containing formula (56) shown in the following "Chemical Formula 122" as a main component and epichlorohydrin. However, formula (56)
C ₆ H ₈ (OH) ₆ represents sorbitol, and n represents an integer of 2 to 6.

[0153]

[Chemical formula 122]

A polyglycidyl ether obtained by condensing a phenol-formalin condensate containing the formula (57) shown in the following "Chemical formula 123" as a main component and epichlorohydrin.
However, in the formula (57), PFR represents an atomic group obtained by removing n phenolic OH groups from a phenol / formalin condensed molecule, and n represents an integer of 2 to 10.

[0155]

[Chemical 123]

A diglycidylamino compound obtained by condensing ethylene urea containing formula (58) shown in the following "Chemical formula 124" as a main component and epichlorohydrin.

[0157]

[Chemical formula 124]

A diglycidylamino compound obtained by condensing 4-chloroaniline containing formula (59) shown in the following "Chemical Formula 125" as a main component and epichlorohydrin.

[0159]

[Chemical 125]

A polyglycidyl isocyanate obtained by condensing epichlorohydrin with isocyanuric acid containing the formula (60) shown in the following "Chemical Formula 126" as a main component.

[0161]

[Chemical formula 126]

Polyglycidylaminodiphenylmethane obtained by condensing 4,4'-diaminodiphenylmethane mainly composed of the formula (61) shown in "Chemical 127" below with epichlorohydrin.

[0163]

[Chemical 127]

In the molecule of the production method (VII) of the present invention, one or more atomic groups represented by the general formula (I) are contained in one molecule,
In addition, the chemical structural formula of a specific example of the compound that reacts with a carbonyl reagent such as formaldehyde to give a condensation polymer is shown in the following "Chemical Formula 128". However, the present invention is not limited to this.

[0165]

[Chemical 128]

A polyfunctional diazo compound obtained by polycondensing the compounds of formulas (62) and (64) shown in "Chemical Formula 128" with formalin is represented by the formulas shown in "Chemical Formula 101" and "Chemical Formula 102", respectively. (21) and the compound of formula (22).

One or more atomic groups represented by the general formula (II _AC ) in the production method (VIII) of the present invention are contained in one molecule,
Moreover, the chemical structural formula of a specific example of the compound which reacts with a carbonyl reagent such as formaldehyde to give a condensate is shown in the following "Chemical formula 129". However, the present invention is not limited to this.

[0168]

[Chemical formula 129]

A polyfunctional diazo compound obtained by condensation, deacetylation and diazotization with formaldehyde using the formulas (67) and (68) shown in the above "Chemical formula 129" gives the above-mentioned "Chemical formula 100" and "Chemical formula 100". 102 ”and the formulas (2
0) and the compound of formula (22).

The novel aromatic diazo compound of the present invention can be relatively easily prepared by a combination of known synthetic reactions as described above. Details of the synthesizing method will be described in Examples below, but the outline of each synthesizing step is as follows.

1) The reaction between the aniline homologue represented by the general formula (VII) or (X) and the glycidyl compound having the atomic group represented by the general formula (VIII) or (IX) is an exothermic reaction. When the temperature is higher than 0 ° C, a side reaction is likely to occur, so it is preferable to carry out external cooling to keep the reaction temperature at 20 to 40 ° C. 2-methoxyethanol as a reaction solvent,
1-Methoxy-2-propanol, 1,4-dioxane, dimethylacetamide, acetic acid, pyropionic acid, lactic acid or mixtures thereof are suitable. Above all, the reaction proceeds smoothly when acetic acid and lactic acid are used.

In the reaction of an amine with an epoxy compound, a carboxylic acid has a catalytic action for promoting the reaction (Takao Kakurai,
Tatsuya Noguchi, Yuka magazine 18 , 485 (1960), industrialization 63 , 294 (1960),
Koka 64, 398 (1961)), acetic acid is excellent as a solvent aniline homologues represented by the general formula (VII).

2) For deacylation of the compound represented by the general formula (II _AC ) into the compound represented by the general formula (II _a ), both alkaline hydrolysis and acidic hydrolysis can be applied. The acidic hydrolysis is more advantageous in relation to the steps before and after this reaction. As the acid used in this reaction, any of sulfuric acid, hydrochloric acid and phosphoric acid is suitable. There are many experimental examples of acidic hydrolysis of acetanilide homologues (eg JR Johnson, T. Sandborn, Organic Synthesis C
oll.Vol.I, 111), and those methods.

[0174] 3) General formula (for the II _a) compounds of the compound represented by having an atomic group represented by the general formula by diazotization (I), the 4-amino -N, of N- dimethylaniline Since the industrial operation method of the diazotization reaction has been published (PB report74026 P.2963 to 5), it can be carried out according to it.

4) The synthetic method of 4-nitroso-N, N-dimethylaniline can be carried out by synthesizing the compound represented by the general formula (II _NO ) and converting it into the compound represented by the general formula (II _a ) by reduction. And the reduction method thereof.

The novel aromatic diazo compound having as a main component a compound having two or more atomic groups represented by the general formula (I) in one molecule, which is obtained by the present invention, is excellent as a photosensitizer as described above. Has performance. Therefore, by using the novel aromatic diazo compound of the present invention as a photosensitizer, various photosensitive compositions having novel and excellent performance can be obtained. Among these various kinds of novel photosensitive compositions, the photosensitive lithographic printing original plate, the photosensitive screen printing original plate, and the colored image-forming photosensitive material have excellent performances, and therefore a detailed description thereof is given below. To do.
However, the present invention is not limited to these.

The present invention can produce a photosensitive lithographic printing original plate having excellent performance by using the novel aromatic diazo compound. For example, in the production of lithographic printing plates,
The diazo compound of the present invention and various natural or synthetic resins can be mixed and used. The resins must be sufficiently ink receptive, soluble in common organic solvents, compatible with the aromatic diazo compounds of the invention, and film-forming. Next, it is necessary to have abrasion resistance and appropriate elasticity.

Examples of these resins include cresol resin, polyester, polyamide, polyurethane, polyvinyl chloride, poly (meth) acrylate, polystyrene,
Polymers of α, β unsaturated carboxylic acids such as polyvinyl acetate, acrylates such as methyl acrylate, ethyl acrylate and 2-hydroxyethyl acrylate, alkyl methacrylates, acrylamides such as acrylamide and N-ethyl acrylamide, vinyl ethers And copolymers selected from polymerizable monomers such as vinyl esters and styrenes.

The content of the photosensitive diazo compound of the present invention in the photosensitive composition of the present invention varies depending on the kind of the support and the purpose, but it is preferably 1 to 50% by weight, more preferably 3 to 20% by weight. ..

In addition to the components described above, dyes, pigments, coatability improvers, plasticizers and the like can be added to the photosensitive composition used in the present invention, if necessary.

Examples of the dye include Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue # 603 (Orient Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet,
Brilliant green, ethyl violet, methyl green, erythrosine B, basic furosine, malachite green, oil red, m-gresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. , Triphenylmethane type, diphenylmethane type, oxazine type,
Xanthene type, iminonaphthoquinone type, azomethine type,
Alternatively, anthraquinone dyes can be used.

The dye is usually contained in the photosensitive composition in an amount of about 0.5 to about 5.
10% by weight, preferably about 1 to 5% by weight.

As the coatability improver, alkyl ethers (eg ethyl cellulose, methyl cellulose),
Fluorine-based surfactants (for example, Florard FC-43
0 (manufactured by Sumitomo 3M) and nonionic surfactants (for example, Pluronic L-64 (manufactured by Asahi Denka Co., Ltd.)), and a plasticizer for imparting flexibility and abrasion resistance of the coating film. As, for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Examples thereof include tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid, or methacrylic acid oligomer. Examples of the oil sensitizer for improving the oil sensitivity of the image area include JP-A-55-527. Examples thereof include half-esterified products of styrene-maleic anhydride copolymer with alcohol, and examples of the stabilizer include polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acids (acrylic acid, methacrylic acid). Acid, citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-
5-sulfonic acid, etc.) and the like. The amount of these additives added varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

A photosensitive lithographic printing plate is obtained by applying the above-mentioned photosensitive composition onto the surface of a support and drying it.

As the support, a plate of paper, plastic, aluminum or the like suitable for a lithographic printing plate is used.

As the coating solvent, methyl cellosolve, 1
Examples thereof include cellosolves such as methoxy-2-propanol, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in admixture of two or more.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating can be used. The coating amount is 0.2 to 10 g / m as solid content.
² is preferred.

The support on which the photosensitive composition is provided includes
An aluminum plate is particularly preferable. However, if the aluminum plate is used as it is without treatment, there are disadvantages that the adhesion of the photosensitive composition is poor and the photosensitive composition is decomposed. In order to eliminate this drawback, various proposals have been made in the past. For example, a method in which the surface of an aluminum plate is grained and then treated with silicate (US Pat. No. 2,714,066).
Method of treatment with organic acid salt (US Pat. No. 2,714,06
No. 6). Method of treatment with sulfonic acids and their derivatives (US Pat. No. 3,220,832). Method of treatment with potassium hexafluorozirconate (US Pat.
46,683). There are a method of anodizing, a method of treating with an aqueous solution of an alkali metal silicate after the anodizing (US Pat. No. 3,181,461) and the like.

In the present invention, the aluminum plate on which the photosensitive composition is formed is preferably one which has been grained, anodized and then sealed. As a method for graining, there are a brush polishing method, a chemical polishing method, an electrolytic etching method and the like after degreasing the aluminum plate surface.

The anodic oxidation treatment is performed by using a solution containing one or more kinds of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid and the like as an electrolytic solution and electrolyzing with an aluminum plate as an anode. The amount of anodized film formed is 1 to 50 mg
/ Dm ² is suitable, preferably 10-40 mg / dm ² . Here, the amount of the anodic oxide film is, for example, an aluminum plate with a phosphoric acid chromic acid solution (85% phosphoric acid aqueous solution 35 ml,
It can be determined by immersing 20 g of chromium (VI) oxide in 1 liter of water to form an oxide film, dissolving the oxide film, and measuring the weight change before and after film dissolution of the plate.

The sealing treatment includes boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment and the like. In addition, the aluminum support may be subjected to a subbing treatment with a water-soluble polymer compound or an aqueous solution of a metal salt such as fluorinated zirconic acid.

A photosensitive printing plate is obtained by applying the above-mentioned photosensitive composition to the aluminum support thus treated. When such a support is used, particularly, the storage stability of the photosensitive composition layer and the adhesiveness with the support are better, and a clear image is obtained after exposure and development, and it is clear in an extremely long printing process. It is possible to provide a printed matter having a clear image.

The photosensitive lithographic printing plate thus obtained can be used by a known method. Typically, a negative film is brought into close contact with a photosensitive printing plate, exposed to light, and developed with a weak alkaline aqueous solution containing a small amount (10 wt% or less) of an organic solvent to obtain a printing plate. The lithographic printing plate thus produced can be used in a sheet-fed, offset printing machine.

That is, by exposing through a transparent original image having a line image, a halftone image and the like, and then developing with an aqueous developer, a negative image is obtained with respect to the original image. Examples of the light source suitable for exposure include an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, and a strobe.

The developing solution used for the development treatment of the photosensitive lithographic printing plate obtained using the photosensitive composition of the present invention may be any known one, but preferably a specific organic solvent and an alkali are used. It contains an agent and water as essential components. Here, the specific organic solvent is capable of dissolving or swelling the non-exposed area (non-image area) of the above-mentioned photosensitive composition layer when it is contained in a developing solution, and is water at room temperature (20 ° C.). Refers to an organic solvent having a solubility of 10% by weight or less. Such an organic solvent only needs to have the above-mentioned characteristics and is not limited to the following, but if these are exemplified, ethyl acetate, propyl acetate, butyl acetate can be used. , Carboxylic acid esters such as amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol, methylamino alcohol; alkyl-substituted aromatics such as xylene Hydrocarbons: Halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, monochlorobenzene and the like. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developing solution is generally 1 to 2
It is 0% by weight, and particularly preferable is 2 to 10% by weight.

On the other hand, as the alkaline agent contained in the developer, (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium di- or triphosphate or Inorganic alkali agents such as ammonium salts, sodium metasilicate, sodium carbonate, ammonia, etc. (B) Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, di or triethanolamine, mono, Di or triisopropanolamine,
Examples thereof include organic compounds such as ethyleneimine and ethylenediamine. Preferred are (A) potassium silicate and sodium silicate, (B) organic amine compounds, and particularly preferred are (A) sodium silicate and (B) di- or triethanolamine. The content of these alkaline agents in the developer is usually 0.05 to 8% by weight.

Further, in order to further improve the storage stability, printing durability and the like, it is preferable to add a water-soluble sulfite salt to the developer, if necessary. As such a water-soluble sulfite, an alkali or alkaline earth metal salt of sulfite is preferable, and examples thereof include sodium sulfite, potassium sulfite, lithium sulfite and magnesium sulfite.
The content of these sulfites in the developer composition is usually 0.05 to 4% by weight, preferably 0.1 to 1% by weight.

Further, a certain solubilizing agent may be contained in order to assist the dissolution of the above organic solvent in water. As such a solubilizing agent, it is preferable to use a low molecular weight alcohol or ketone which is more water-soluble than the organic solvent used.
Moreover, an anion activator, an amphoteric activator, etc. can also be used. Examples of such alcohols and ketones include methanol, ethanol, propanol, butanol,
Acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, methoxyethanol, methoxypropanol, 4-
It is preferable to use methoxy-methylbutanol, N-methylpyrrolidone or the like. Examples of the activator include sodium isopropyl naphthalene sulfonate, sodium n-butyl naphthalene sulfonate, N-methyl-N.
-Pentadecylaminoacetic acid sodium salt, lauryl sulfate sodium salt and the like are preferable. These alcohols,
The amount of the solubilizing agent such as ketones used is not particularly limited, but generally it is preferably about 30% by weight or less based on the entire developer.

The photosensitive composition of the present invention has high sensitivity and high printing durability. Further, a weak alkaline aqueous solution enables rapid development. Moreover, since the range of optimum developing conditions (so-called developing latitude) is wide, the developing process is easy.

Another preferred use mode of the photosensitive composition of the present invention is as a photosensitive material for screen printing plates.

The diazo compound of the present invention and a water-soluble resin (for example, polyvinyl alcohol, polyvinyl alcohol having a styrylpyridinium group pendant, etc.) are mixed to obtain a screen printing photosensitive solution. Further, it is also possible to add a polyvinyl acetate emulsion or a vinyl monomer such as alcohol monoacrylate or diacrylate or triacrylate.

This photosensitive composition is applied to a synthetic resin such as polyester, nylon, or polyethylene, or a metal-vapor-deposited product of nickel or the like on the resin, or a screen mesh made of stainless steel or the like, and the composition of the present invention is applied and dried. The above process may be repeated to obtain a screen printing plate having a thickness of 10 to 400 μm.

The photosensitive composition of the present invention gives a screen printing plate having high sensitivity and high ink resistance.

Another preferable use mode of the photosensitive composition of the present invention is as a colored image-forming photosensitive material.

Examples of the transparent support used in the light-sensitive material of the present invention include transparent plastic films such as polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polycarbonate and cellulose triacetate.

Examples of the film-forming water-soluble polymeric substance which is insoluble by light and can be eluted and developed only with water include polyvinyl alcohol, gelatin, casein, gluarginic acids, gums, carboxymethyl cellulose, hydroxyethyl cellulose and other celluloses. Examples thereof include derivatives, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, and many others.

The colorant can be selected in a wide range as long as it is a pigment dispersible in water. Also, a water-soluble or alcohol-soluble dye or the like can be used.

In addition to the above-mentioned components, a stabilizer for preventing dark reaction and a colored layer which is insoluble by light are provided on the transparent support, and a leveling agent or a defoaming agent is added to improve the coating property. Agents, surfactants and the like can be added as necessary.

When the colored layer is provided, the above components are mainly dissolved or dispersed in water and mixed, but if necessary, soluble in water such as alcohols for the purpose of defoaming or improving coatability. It is also possible to use part of the organic solvent as a diluent.

The thickness of the colored layer is preferably as thin as possible from the viewpoint of resolution such as halftone reproducibility, but thicker is preferable from the viewpoint of dyeability, and the balance between the two is 2 to 5 μm.
Is the best. The colored layer may be directly coated on the transparent support, but it is effective to provide an intermediate layer between them in order to improve adhesiveness and the like. In particular, when a polyethylene terephthalate film is used as the support, the adhesiveness of the colored layer of the present invention becomes insufficient, so it is not necessary to provide an intermediate layer mainly with a synthetic resin such as polyester, polyvinylidene chloride or polyurethane. Particularly preferred.

The coating of the colored layer or the intermediate layer on the transparent support is not particularly limited as long as a uniform coating film free of pinholes and the like can be obtained by any conventionally known method.

The light source used for exposing the light-sensitive material of the present invention may be any one as long as it effectively insolubilizes the colored layer, and various mercury lamps, carbon arc lamps, xenon lamps,
A metal halide lamp, a chemical fluorescent lamp, etc. can be used.

Besides, it is widely used for forming a pattern by exposing and developing a photosensitive composition comprising the diazo compound of the present invention and a hydrophilic or hydrophobic binder resin. In addition, these photosensitive compositions may be used by further adding coloring materials such as dyes and pigments. These applications include photoresist materials, photomasks, calibration materials,
A second original map, etc. is possible.

[0214]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

Examples 1 to 9 show synthetic examples of the aromatic diazo compound of the present invention. Experiments for measuring the physical properties of the aromatic diazo compounds of the present invention are shown in Examples 10-12. Example 1
3 to 17 show examples of photosensitive compositions using the aromatic diazo compound of the present invention. Example 18 shows a basic experiment for confirming the chemical structure of the aromatic diazo compound of the present invention. As described in paragraphs “0131” to “0133”, the industrial products of the polyglycidyl compound, which is one of the main raw materials of the present invention, is a mixture, and it is difficult to obtain a pure single compound. .. Therefore, the aromatic diazo compound of the present invention is also obtained as a mixture except in special cases,
It is difficult to confirm its chemical structure like a single compound. Therefore, in Example 18, a basic experiment of the synthetic reaction of the present invention was conducted using a special glycidyl compound that was easily obtained as a single compound, and the chemical structure of the obtained compound was confirmed. From this experiment, the chemical structure of the main component of the aromatic diazo compound of the present invention could be confirmed.

Example 1 [Synthesis of aromatic diazo compound (11)] p was added to 90 g of acetic acid.
-Aminoacetanilide 15.0 g (0.1 mol) was dissolved and stirred at 25-30 ° C at an epoxy equivalent of 184 bisphenol A diglycidyl ether 4
0.5 g was added dropwise, and stirring was continued for 3 hours while maintaining the temperature of the reaction solution at about 30 ° C, and for 6 hours while maintaining at about 40 ° C. 50 g of 35% hydrochloric acid was added, and the mixture was heated and stirred at 75 ° C. for 8 hours for deacetylation. After cooling to about 50 ° C,
Add 350 g of methyl cellosolve, cool to 5 ° C. with good stirring, and add 7.3 g of sodium nitrite (0.1
(05 mol) was dissolved in 15 g of water and slowly added dropwise while keeping the temperature of the reaction solution at 5 ° C., and stirring was continued at the same temperature for 1 hour for diazotization, followed by cooling to 5 ° C. 10%.
The above-mentioned diazotization solution was injected while stirring in 2 kg of saline, the target substance precipitated in the form of particles was filtered off, this was dissolved in 250 g of methyl cellosolve, the insoluble material was filtered off, and this solution was cooled to 5 ° C. The mixture was poured into 1.5 kg of 10% saline while stirring, the precipitated target substance was filtered off, washed with a small amount of isopropyl alcohol, and dried under reduced pressure. The yield was 40 g, and the diazo compound aqueous solution had a U.V. V. The λ _max of the spectrum is 378 nm, and the extinction coefficient is 5 when the concentration is g / l and the optical path length is cm.
It was 4.7.

Example 2 [Synthesis of aromatic diazo compound (12)] 15.0 g (0.1 mol) of p-aminoacetanilide was dissolved in 180 g of acetic acid and stirred at 25 to 30 ° C to obtain an epoxy equivalent of 356. Powder of 78.3 g of tetrabromobisphenol A diglycidyl ether was added little by little, and the mixture was stirred at 25 ° C for 8 hours and at 45 ° C for 8 hours. To this was added 250 g of methyl cellosolve, 40 g of 95% sulfuric acid was added little by little, and the mixture was stirred at 75 ° C. for 8 hours for deacetylation. Add 450g of methyl cellosolve and dilute 3-5
After cooling to ℃ and stirring well, add nitrosyl sulfuric acid prepared by dissolving 7.7 g (0.11 mol) of sodium nitrite in 160 g of 95% sulfuric acid while keeping the liquid temperature at 3 to 5 ° C., and further for 1 hour. Continued stirring. This 5
It is poured into kg of ice water, the precipitated target is separated by filtration, and cooled with cold water.
It was washed twice, then with a small amount of isopropyl alcohol, and dried under reduced pressure. The yield was 84 g, the λ _max of the near-ultraviolet absorption spectrum of the methyl cellosolve solution of this diazo compound was 382 nm, the concentration was g / l, and the optical path length was cm.
The extinction coefficient when expressed by was 31.5.

Example 3 [Synthesis of aromatic diazo compound (17)] p was added to 80 g of acetic acid.
-Aminoacetanilide (15.0 g, 0.1 mol) was dissolved and stirred at 25 to 30 ° C, and powder of 23.5 g of tetrabromobisphenol A diglycidyl ether having an epoxy equivalent of 356 was added little by little for 3 hours.
Stir at about 30 ° C., further add 17.7 g of ethylene glycol diglycidyl ether having an epoxy equivalent of 115 at the same temperature, continue stirring at 40 to 45 ° C. for 6 hours, and add 50 g of 35% hydrochloric acid to 75 ° C. Deacetylation was carried out by stirring for 8 hours. After cooling to about 50 ° C,
After adding 40 g of water and cooling to 3-5 ° C, a solution of 7.6 g (0.11 mol) of sodium nitrite in 20 g of water was slowly added dropwise at 3-5 ° C, and stirring was continued for 1 hour after the addition. Diazotization was performed. While stirring 18.0 g (0.11 mol) of ammonium hexafluorophosphate in a solution of 150 g of water, the diazotized solution was added dropwise at 5 to 10 ° C, and after 30 minutes, 150 g of water was further added, and further for 1 hour. After stirring, the precipitated crystals were separated by filtration, washed 3 times with water, 2 times with isopropyl ether, and dried under reduced pressure. The yield was 55 g. The λ _max of the UV absorption spectrum of the 2-methoxyethanol solution of this diazo compound was 382 nm, and the extinction coefficient was 44.9 when the concentration was expressed in g / l and the optical path length was expressed in cm. In this diazo compound, X ^{− in the} formula (17) shown in “Chemical Formula 97” is PF ₆
^It is a polyfunctional aromatic diazo compound corresponding to-.

Example 4 [Synthesis of aromatic diazo compound (10)] p was added to 60 g of acetic acid.
-Cyanoethylaminoacetanilide 20.3 g (0.
1 mol) and, while stirring, at about 30 ° C., 18.5 g of polyglycidyl ether of a phenol-formaldehyde condensation resin having an epoxy equivalent of 175 is added and dissolved, and 30 to 35 ° C. for 4 hours and 40 to 45 ° C. for 8 hours. The reaction continued. Add 70 g of 40% sulfuric acid and add 1 at 75-80 ° C.
The mixture was heated and stirred for 2 hours to carry out a deacetylation reaction of an acetylamino group and a hydrolysis reaction of a cyanoethyl group to a carboxyethyl group. Add 100 g of water, cool to 3-5 ° C., and, with stirring, 7.3 g of sodium nitrite.
A solution of (0.105 mol) and 15 g of water was added at the same temperature to about 1
The solution was added dropwise over a period of time, and the mixture was stirred for another 30 minutes to complete the diazotization reaction. When the above diazotized solution was poured into 400 g of a 15% saline solution at 5 ° C. with stirring, the diazo compound was released in a paste form. When this paste was separated and kneaded with isopropyl alcohol, the diazo compound gradually changed to powder. The powdery diazo compound was filtered off, washed twice with isopropyl alcohol and dried under reduced pressure. The yield was 32 g. Λ of the absorption spectrum in the near-ultraviolet region of this diazo compound aqueous solution
_{The maximum} was 374 nm, and the extinction coefficient was 64. 1 when the concentration was expressed in g / l and the optical path length was expressed in cm. This diazo compound has considerably better storage stability in the presence of water than the conventionally used diphenylamine-based diazo compounds. An experiment on storage stability in an aqueous solution at pH 3 and 50 ° C. was conducted according to Example 12, and the results are shown in FIG.

Example 5 [Synthesis of aromatic diazo compound (19)] p was added to 70 g of acetic acid.
Dissolve 15.0 g (0.1 mol) of aminoacetoanilide and stir at 25-30 ° C. with stirring to give 10.5 triglycidyl isocyanurate with an epoxy equivalent of 100.
g in small portions, stirred at 25 ° C. for 12 hours, and further added with glycidyl methyl ether having an epoxy equivalent of 91.
6 g was added dropwise at 25 ° C., and the mixture was stirred at 30 ° C. for 12 hours. 50 g of 35% hydrochloric acid was added, and the mixture was stirred at 75 ° C. for 8 hours for deacetylation. Add 100 g of water and stir well, cool to 3-5 ° C, and add 7.6 g of sodium nitrite.
A solution of (0.11 mol) in 20 g of water was added to 3 to 5
The mixture was slowly added dropwise at 0 ° C, and stirring was continued at the same temperature for 1 hour after the completion of the addition to carry out diazotization. The diazotized solution was added to about 2 liters of isopropyl alcohol cooled to about 10 ° C. with stirring, the precipitated solid was filtered off, washed twice with isopropyl alcohol, and dried under reduced pressure. The yield was 26 g. Λ _max of absorption spectrum of this diazo compound in the near-ultraviolet region is 376 nm
The extinction coefficient was 78.9 when the concentration was expressed in g / l and the optical path length was expressed in cm.

Example 6 [Synthesis of aromatic diazo compound (1)] 80 g of acetic acid was added with N-.
Methylaniline 21.4 (0.2 mol) was dissolved in 25
At -30 ° C, 25.3 g of ethylene glycol diglycidyl ether having an epoxy equivalent of 115 was added dropwise, and the mixture was stirred at 25 ° C for 4 hours and at 40 ° C for 6 hours. 20% hydrochloric acid 13
0 g was added and the mixture was cooled to 5 ° C. At the same temperature, a solution of 14.5 g (0.21 mol) of sodium nitrite and 40 g of water was slowly added dropwise over 30 minutes for nitrosation. To this, 250 g of 20% hydrochloric acid and 150 g of water were added, and 33 g of zinc dust was slowly added while cooling from the outside to keep the temperature at 35 to 40 ° C., whereby the nitroso compound was reduced to a colorless transparent solution. Add 5 g of activated carbon, stir well, filter,
The filtrate is cooled to 5 ° C. and sodium nitrite 14.5 g
A solution of (0.21 mol) and 40 g of water is slowly added dropwise at the same temperature. After completion of dropping, the mixture was stirred for 1 hour to complete the diazotization reaction. While stirring well, 80 g of sodium chloride was slowly added for salting out, the precipitated zinc chloride double salt of diazonium salt was filtered off, washed once with 15% sodium chloride and once with isopropyl alcohol, and dried under reduced pressure. The yield was 36g. The absorption spectrum of the aqueous solution of this diazo compound in the near-ultraviolet region has a λ _max of 376 nm and a concentration of g /
The absorption coefficient was 84. 1 when the optical path length was expressed in cm. (This example is an example of the production method (III) of the production method of the aromatic diazo compound of the present invention.)

[0222] X in Example 7 equations shown in the synthesis of aromatic diazo compound (21)] "of 128" (62) ^- is HSO ₄ ^- ice diazo compound 26.6 g (0.05 mol) under a Was dissolved in 40 g of concentrated sulfuric acid, and 1.2 g (0.04 mol) of paraformaldehyde was slowly added thereto while being careful not to let the reaction temperature exceed 10 ° C. Then, stirring was continued at 5 to 8 ° C. for 2 hours. The reaction solution was added dropwise to 300 g of isopropyl alcohol cooled to 3 ° C at the same temperature, the generated precipitate was filtered off, washed with isopropyl alcohol at 3 to 5 ° C, and dried under reduced pressure. The yield was 18.1 g. Λ _max of the absorption spectrum of the aqueous solution of this diazo compound in the near ultraviolet
Was 377 nm, the extinction coefficient was 63.4 when the concentration was expressed in g / l and the optical path length was expressed in cm. (This example is a method for producing the aromatic diazo compound of the present invention (VI
I) is an example. )

Example 8 [Synthesis of aromatic diazo compound (22)] 33.4 g (0.05% mol) of the compound of the formula (68) shown in "Chemical formula 129".
Is dissolved in 150 g of 85% phosphoric acid, 0.8 g (0.027 mol) of paraformaldehyde is dissolved at 30 to 35 ° C., and the mixture is stirred at the same temperature for 18 hours to perform a condensation reaction with formaldehyde, and the temperature is raised to 80 ° C. Then, heating and stirring were continued for another 8 hours to carry out a deacetylation reaction.
200 g of water was added, the mixture was cooled to 3 to 5 ° C., and a solution of 7.6 g (0.011 mol) of sodium nitrite and 20 g of water was added to 3 to 5.
The mixture was slowly added dropwise with stirring at 5 ° C., and then the mixture was stirred for another hour to carry out diazotization. Add 5 g of activated carbon, stir and add 5 g of diatomaceous earth and filter,
The filtrate is a 20% aqueous solution of sodium tetrafluoroborate 1
After pouring into 50 g, the precipitated diazo compound was washed 3 times with isopropyl alcohol and dried under reduced pressure. Yield 26.2
It was g. This crystal is represented by the formula (2
2) is a compound in which X ⁻ is BF ₄ ⁻ . (This example is a method for producing the aromatic diazo compound of the present invention (VI
II) is an example. )

Example 9 [Synthesis of aromatic diazo compound (24)] p was added to 60 g of acetic acid.
-Aminoacetanilide 9.0 g (0.06 mol) and p
Dissolve 6.6 g (0.04 mol) of ethyl aminobenzoate, add 25.3 g of ethylene glycol diglycidyl ether having an epoxy equivalent of 115 at 25 to 30 ° C., and add at 6 ° C. at 40 to 45 ° C. for 3 hours at about 30 ° C. Stir for a while to react. 35 g of 35% hydrochloric acid was added, and the mixture was heated to 75-78 ° C to
The mixture was heated and stirred for 0 hour to deacetylate the acetylamino group and hydrolyze ethyl benzoate. 70g of water
Was diluted with water and cooled to 3 to 5 ° C., and a solution of 4.5 g (0.065 mol) of sodium nitrite and 10 g of water was added dropwise with stirring to diazotize. When the above diazotized solution was poured into 400 g of a 15% saline solution at 5 ° C. with stirring, the diazo compound was released in a paste form. This paste-like substance was separated, dissolved in 450 g of cold water, and added dropwise to a solution of 16.3 g of ammonium hexafluorophosphate and 200 g of water at 5 to 10 ° C. to release the hexafluorophosphate salt of diazonium in the form of paste. The paste was separated and kneaded in diisopropyl ether to give a powder. This was separated by filtration and dried under reduced pressure. Yield is 23
It was g. This compound has the formula (2
4) is a polyfunctional aromatic diazo compound in which X ⁻ corresponds to PF ₆ ⁻ . This compound belongs to the fifth type of aromatic diazo compound described in Paragraph No. “0049” and is one of the general formula (V ′) shown in “Chemical Formula 62”. The λ _max of the UV absorption spectrum of the 2-methoxyethanol solution of this compound was 382 nm, and the extinction coefficient was 27 when the concentration was expressed in g / l and the optical path length was expressed in cm. The solubility of this compound in 1-methoxy-2-propanol was 25% or more at room temperature.

Comparative Example 1 [Synthesis of Condensate of Diphenylamine-4-diazonium Salt and Formaldehyde] 14.5 g (0.05 mol) of diphenylamine-4-diazonium sulfate was added under ice cooling to give 5
It was dissolved in 0 g of concentrated sulfuric acid, and 1.2 g (0.04 mol) of paraformaldehyde was slowly added thereto at 5-8 ° C.
Stirring was continued for 2 hours at ℃. This mixed solution was added dropwise to 200 g of ice-cooled isopropyl alcohol at about 5 ° C,
The generated precipitate was filtered off, washed with cold isopropyl alcohol three times, and dried under reduced pressure. The yield was 11 g.

Comparative Example 2 Synthesis of 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate of diphenylamine-4-diazonium salt / formaldehyde condensate Diphenylamine-4-diazonium salt / formaldehyde synthesized in Comparative Example 1 5 g of the condensate was dissolved in 60 g of ice-cooled 1.5% diluted sulfuric acid, and 6 g of 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid was poured into a solution of 40 g of cold water while stirring, and a precipitate formed. Was filtered off, washed 3 times with cold water and dried under reduced pressure. The yield was 7.5g.

Example 10 [UV absorption spectrum of diazo compound of the present invention] The UV absorption spectra of the aromatic diazo compound of the present invention in the near ultraviolet region are almost the same. As a representative example, the UV absorption spectrum of an aqueous solution of the diazo compound (10) synthesized in Example 4 and the diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 1 at pH 3 was measured and shown in FIG. As is clear from the figure, the absorption spectrum of the diazo compound of the present invention is a sharp curve with λ _max of 374 nm, whereas the absorption spectrum of the diphenylamine-4-diazonium salt / formaldehyde condensate has a broad curve, and There is absorption in the visible region of 420 to 500 nm.

Example 11 [Measurement of Photolysis Rate of Diazo Compound of the Present Invention in Aqueous Solution] As a basic experiment for the sensitivity of the diazo compound of the present invention to light, the photolysis rate of the diazo compound of the invention was measured. Aromatic diazo compound (19) synthesized in Example 5 and diphenylamine-4-diazonium salt / formaldehyde condensate condensate synthesized in Comparative Example 1 were added to an aqueous solution having a pH of 3 (absorbance of an aqueous solution having an optical path length of 1 cm was 1.8) under ultrahigh pressure. FIG. 2 illustrates the absorbance at λ _max of the UV absorption spectrum of the aqueous solution irradiated with light from a mercury lamp, with the non-irradiation taken as 100%. From the figure, it can be seen that the diazo compound of the present invention has high sensitivity to light.

Example 12 [Measurement of Storage Stability of Aqueous Solution of Diazo Compound of the Present Invention] As a basic experiment for the storage stability of the diazo compound of the present invention, the decomposition rate in an aqueous solution under light shielding was measured. Aqueous solutions of the aromatic diazo compound (19) synthesized in Example 5 and the diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 1 at pH 3 (absorbance of an aqueous solution having an optical path length of 1 cm is 2.0). Is stored in a constant temperature bath at 55 ° C. in the dark, the absorbance at λ _max of the UV absorption spectrum of the aqueous solution is measured at regular intervals, and the absorbance when storage time is 0 is shown as 100% in FIG. .. From the figure, it can be seen that the storage stability of the diazo compound of the present invention is excellent.

Example 13 [Photosensitive lithographic printing original plate 1] Synthesis of copolymer (I) 300 g of methyl cellosolve was added to a 2000 ml four-neck separable flask and heated to 90 ° C under a nitrogen stream. A mixed solution of 162.3 g of acrylonitrile, 89.7 g of methyl methacrylate, 18.0 g of methacrylic acid, 30.0 g of glycerol monomethacrylate, and 0.60 g of benzoyl peroxide was added dropwise thereto over 2 hours.
After completion of the dropwise addition, 300 g of methyl cellosolve and 0.24 g of benzoyl peroxide were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After the reaction was completed, 900.0 g of methyl cellosolve was added to this and diluted. The reaction solution was poured into 15 l of water to precipitate the copolymer. The precipitate was filtered off and dried in vacuum at 80 ° C. to obtain a copolymer (I). A 0.24 mm thick aluminum plate is soaked in a 10% aqueous solution of sodium triphosphate kept at 80 ° C for 3 minutes to degrease it, and after sanding with a nylon brush, it is treated with sodium aluminate at 60 ° C for about 10 seconds. Etched and then desmutted with 3% aqueous sodium hydrogen sulfate. This aluminum plate was anodized in 20% sulfuric acid at 2 A / dm ² for 2 minutes and then treated with a 2.5% aqueous sodium silicate solution at 70 ° C. for 1 minute to produce an anodized aluminum plate. A photosensitive solution (1) having the following composition was applied to this aluminum plate using a whaler. Drying was performed at 100 ° C. for 2 minutes. Blending of Photosensitive Solution (1) Diazo Compound (11) (synthesized in Example 1) 0.53 g Copolymer (I) 6.0 g Oil Blue # 603 0.16 g (manufactured by Orient Chemical Industry Co., Ltd.) Acid 0.05 g Methyl Cellosolve 100 g Dry coating amount was 2.0 g / m ² . This photosensitive lithographic printing plate precursor was image-exposed with a 1 Kw metal halide lamp from a distance of 70 cm for 50 seconds. Developer DN-3C (manufactured by Fuji Photo Film Co., Ltd.) was diluted with water (1: 1), and this developer was used to develop at 25 ° C. for 1 minute to obtain a lithographic printing plate. This printing plate was applied to a 3200MCD printing machine (manufactured by Ryobi Co., Ltd.) to print on high-quality paper, and 120,000 or more sheets could be printed.

Example 14 [Photosensitive planographic printing original plate 2] An anodized aluminum plate was produced in the same manner as in Example 13. A photosensitive solution (2) having the following composition was applied to this aluminum plate using a whaler.
Drying was performed at 100 ° C. for 2 minutes. Blending of Photosensitive Solution (2) Diazo Compound (12) (synthesized in Example 2) 1.09 g Copolymer (I) 6.0 g Oil Blue # 603 0.16 g (manufactured by Orient Chemical Industry Co., Ltd.) Acid 0.16 g Methyl Cellosolve 100 g Dry coating amount was 2.0 g / m ² . This photosensitive lithographic printing plate precursor was imagewise exposed with a 1 Kw metal halide lamp from a distance of 70 cm for 65 seconds. Developer DN-3C (manufactured by Fuji Photo Film Co., Ltd.) was diluted with water (1: 1), and this developer was used to develop at 25 ° C. for 1 minute to obtain a lithographic printing plate. This printing plate was applied to a 3200MCD printing machine (manufactured by Ryobi Co., Ltd.) to print on high-quality paper, and 120,000 or more sheets could be printed.

Example 15 [Photosensitive lithographic printing original plate 3] An anodized aluminum plate was prepared in the same manner as in Example 13. A photosensitive solution (3) having the following composition was applied to this aluminum plate by using a whaler.
Drying was performed at 100 ° C. for 2 minutes. Blending of Photosensitive Solution (3) Diazo Compound (17) (synthesized in Example 3) 0.69 g Copolymer (I) 6.0 g Oil Blue # 603 0.16 g (manufactured by Orient Chemical Industry Co., Ltd.) Phosphorus Acid 0.05 g Methyl Cellosolve 100 g Dry coating amount was 2.0 g / m ² . This photosensitive lithographic printing plate precursor was imagewise exposed with a 1 Kw metal halide lamp from a distance of 70 cm for 65 seconds. Developer DN-3C (manufactured by Fuji Photo Film Co., Ltd.) was diluted with water (1: 1), and this developer was used to develop at 25 ° C. for 1 minute to obtain a lithographic printing plate. This printing plate was applied to a 3200MCD printing machine (manufactured by Ryobi Co., Ltd.) to print on high-quality paper, and 120,000 or more sheets could be printed.

Comparative Example 3 [Comparative sample of photosensitive lithographic printing plate precursor] An anodized aluminum plate was produced in the same manner as in Example 13. A comparative photosensitive solution (1) having the following composition was applied to this aluminum plate by using a whaler. Drying was performed at 100 ° C. for 2 minutes. Blending of Comparative Photosensitive Solution (1) Comparative Diazo Compound (2) 2-Methoxy-4-hydroxy-5-benzoylbenzenesulfonate of the diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 2 51 g Copolymer (I) 6.0 g Oil Blue # 603 0.16 g (manufactured by Orient Chemical Industry Co., Ltd.) Phosphorous acid 0.05 g Methyl cellosolve 100 g Dry coating amount was 2.0 g / m ² . .. This photosensitive lithographic printing plate precursor was image-exposed with a 1 Kw metal halide lamp from a distance of 70 cm for 90 seconds. Developer DN-3C (manufactured by Fuji Photo Film Co., Ltd.) was diluted with water (1: 1), and this developer was used to develop at 25 ° C. for 1 minute to obtain a lithographic printing plate. When this printing plate was printed on a high-quality paper using a 3200MCD printing machine (manufactured by Ryobi Co., Ltd.), 100,000 or more sheets could be printed. The photosensitive lithographic printing plate precursors prepared in Examples 13, 14, and 15 and the comparative sample prepared in Comparative Example 3 were used as Kodak Photographic step ta.
The exposure time for using blet no.2 to make a solid of 5 layers is as shown in "Table 1" below. Photosensitive lithographic printing plates 1 to 3 using the diazo compound of the present invention had higher sensitivity than the comparative sample.

[0234]

[Table 1]

As shown in the table, the photosensitive composition of the present invention has high sensitivity, can be rapidly developed with a weak alkaline developing solution, has good ink receptivity and printing durability, and is stable over time. An excellent photosensitive composition for a photosensitive printing plate can be provided.

Example 16 [Photosensitive screen printing original plate] Formulation of photosensitive liquid (4) Diazo compound (19) (synthesized in Example 5) 0.35 g water 4.65 g direct photo emulsion diazo type SP-1700H ( Murakami Screen) 45.00 g The photosensitive solution (4) obtained by the above formulation was applied to a 250 mesh monofilament polyester screen stretched on an aluminum frame using a bucket. Application and warm air drying at 40 ° C. for 10 minutes were repeated 4 to 5 times to obtain a photosensitive film having a thickness of 70 μm (including the thickness of the screen). This screen photosensitive plate was exposed for 2 minutes from a distance of 1 m by a 4 Kw ultra-high pressure mercury lamp (Oak Seisakusho). Image washout development was carried out as follows. This screen photosensitive plate was immersed in water at 25 ° C for 1 minute to elute most of the unexposed area, and water at 20 ° C was added at 6 kg / cm ^2.
The residual photosensitive film in the image area was completely removed by spraying from a distance of 30 cm with a spray gun at a water pressure of. Using the diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 1, a comparative sample of a photosensitive screen printing original plate was prepared in the same manner as described above. As a result of comparing the two plates, the plate using the diazo compound (19) of the present invention had higher sensitivity and was excellent in water and solvent resistance.
When printing was carried out using this plate, there was no destruction of the image lines, and printing with no change in printing reproducibility was performed throughout.

Example 17 [Colored image type photosensitive material] <Photosensitive film for obtaining a colored image> Blending of intermediate layer forming liquid Vinyl chloride-vinylidene chloride copolymer (40% liquid) (Kureha Chemical Co., Ltd., Kurehalon SOA) 10 0.000 Toluene 45.00 g Ethyl acetate 45.00 g Color layer forming liquid formulation Diazo compound (10) 10% aqueous solution (synthesized in Example 4) 9.00 g Polyvinyl alcohol Average degree of polymerization 1700, Saponification rate 88% 100.00 g Pigment dispersion liquid (phthalocyanine blue 20% solution) 4.00 g Water 100.00 g Isopropyl alcohol 10.00 g The intermediate layer forming liquid was applied on one side of a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm with a bar coater, and the temperature was 100 ° C. And dried for 1 minute to form an intermediate layer of about 1 μm. Then, a colored forming liquid was applied onto the coated film with a bar coater so that the coating film thickness after drying was 3 μm, and dried with a blow dryer at 80 ° C. for 1 minute to give a cyan-colored film-I. Obtained. Negative original (color-separated halftone negative for cyan plate) on the colored photosensitive surface of this film-I
And expose it for 2 minutes from a distance of 70 cm with a 1 Kw metal halide lamp, and then wash away the non-image area with normal temperature water jetted from a nozzle pressurized to 1 kg / cm ² , and drain at 50 ° C. A warm positive air dried positive image was obtained. The positive image of the cyan-colored diazo compound of the present invention shows that other diazo compounds (diphenylamine-
Compared to the one using 4-diazonium salt / formalin condensate, the residual color after photolysis was less colored, so that the pure color tone of the colorant was obtained.

Example 18 [Basic Experiment for Confirming Chemical Structure of Aromatic Diazo Compound of the Present Invention] As described in the paragraphs “0131” to “0133”, the main experiment of the aromatic diazo compound of the present invention was conducted. The industrial product of polyglycidyl compound, which is one of the raw materials, is a mixture, and it is difficult to obtain a pure single compound. Therefore, the aromatic diazo compound of the present invention is also obtained as a mixture. Further, the general formula (IV) described in "claim 4",
The aromatic diazo compound represented by the general formula (V) described in "Claim 5" and the general formula (V ') belonging to "Claim 6" is similar to an oligomer of a polymer compound produced by a polycondensation reaction. , A mixture of low-order polycondensates having different molecular weights. Thus, the aromatic diazo compound of the present invention,
Although it is a compound characterized by bonding two or more atomic groups having a basic structure represented by the general formula (I) in one molecule, it is not a single compound except in special cases, and it has a molecular weight of It is an assembly of different molecules. Therefore, it is difficult to confirm the molecular structure of each aromatic diazo compound of the present invention as if it were a single compound. However, since a means for binding two or more atomic groups represented by the general formula (I) in one molecule is a known reaction, if the chemical structure of the atomic group represented by the general formula (I) can be confirmed, the present invention Therefore, the chemical structure of the diazo compound was confirmed. Therefore, in this experiment, a compound of formula (69) shown in the following "Chemical Formula 130" was synthesized as a model compound of the atomic group represented by the general formula (I), and its chemical structure was confirmed.

[0239]

[Chemical 130] The compound of the formula (69) is a compound corresponding to the following “formula 131” in the general formula (I).

[0240]

[Chemical 131]

The compound of the formula (69) shown in the "Chemical Formula 130" was synthesized by a reaction similar to the method described in Examples 1, 2, 3 and 5. First, by reacting p-aminoacetanilide with glycidyl phenyl ether,
2 ”, the compound of formula (70) is deacetylated and diazotized, and the obtained diazo compound is reacted with NH ₄ PF ₆ to obtain the desired compound of formula (69).

This synthetic process is shown in the following “Chemical 132”.

[0243]

[Chemical 132]

During the above-mentioned synthesis step, the formula (70) is an important intermediate raw material of this synthesis step, and therefore its chemical structure was also confirmed. Further, compounds of formulas (71) to (73) shown in the following “Chemical Formula 133” of known chemical structure were also synthesized, and their physical properties were used as reference samples for confirming the structures of the compounds of formulas (69) and (70). And

[0245]

[Chemical 133]

Synthesis of Compound Represented by Formula (70) 0.1 mol of p-aminoacetanilide was dissolved in 60 g of acetic acid and 0.2 g of glycidyl phenyl ether was added at 25-30 ° C.
1 mol was added, and both reagents were reacted under the same conditions as in Example 1. When the above reaction solution was added dropwise to a solution prepared by dissolving 65 g of sodium carbonate in 1 kg of water while stirring, the reaction product separated as an oil. This oily substance was extracted with methylene chloride, and the methylene chloride extracted solution was washed with water four times with shaking, and magnesium sulfate powder for dehydration was added thereto for dehydration drying, and methylene chloride was distilled off to obtain 39.5 g. Crude crystals of the compound represented by the formula (70) were obtained. To this crystal, add 300 g of benzene, attach a Dean-Stark trap for dehydration, and heat and reflux the benzene to dehydrate 100 g.
The benzene was removed by distillation, the remaining solution was cooled to 40 ° C., 80 g of methylene chloride was added, and the mixture was slowly cooled with stirring to precipitate cotton-like crystals. The crystals were separated by filtration, washed with benzene three times and left under reduced pressure to obtain 35.5 g of crystals. When degassed in a vacuum dryer at 75 ° C for 5 hours,
It became a white powder with a melting point of 88-98 ° C. Since the molecule of formula (70) has two asymmetric carbon atoms bonded to an OH group, the compound represented by formula (70) has an asymmetric carbon atom configuration of SS, RR, SR. It is a mixture of different stereoisomers. Formula (7) synthesized in this experiment
Since the compound of 0) is also such a mixture, its melting point is unclear.

Synthesis of Compound Represented by Formula (69) 22.5 g (0.05 mol) of crystals of the compound represented by formula (70) obtained by the above-mentioned synthesis was dissolved in 30 g of acetic acid,
35 g of hydrochloric acid (24 g) was added, and deacetylation and diazotization were performed in the same manner as in Example 3 to obtain the obtained diazo compound.
PF ₆ of NH ₄ by reacting an aqueous solution of PF ₆ diazo compound of 19.0 g ^- yield the salt. This diazo compound was dissolved in a mixed solution of 20 g of acetone and 15 g of chloroform, filtered, 50 g of chloroform was further added to the filtrate, and the mixture was left in a cool and dark place. The extract was washed twice with, and left under reduced pressure in a cool dark place to obtain 12 g of pale yellow crystals of the target compound.

Compounds represented by formulas (71) to (73)
Synthesis of p-diethylaminobenzenediazonium sulfate was dissolved in water, insoluble matter was filtered off, the filtrate was added dropwise to an aqueous solution of NH ₄ PF ₆ , the resulting crystals were filtered off, and dissolved in approximately the same weight of acetone. The insoluble matter was filtered off, chloroform was added to the filtrate in an amount twice that of the above crystal, and the mixture was allowed to stand in a cool dark place to obtain a crystal of the compound represented by the formula (71). Using p-phenylaminobenzenediazonium sulfate in the same manner as in formula (73)
Crystals of the compound represented by N, N-diethylamino-p-phenylenediamine was acetylated with acetic anhydride in tetrahydrofuran, poured into cold water, neutralized with sodium carbonate and cooled with ice to obtain a crystal of the compound represented by the formula (72).

Compounds represented by formulas (70) and (69)
Structure confirmation (a) the structure confirmed electromagnetic wave frequency by proton NMR spectra using a proton NMR spectrometer 270MHz of, determine the NMR spectrum by dissolving compound of formula (69) - (72) in acetone -d _6. ¹ H NMR of compounds represented by formulas (70) and (69)
The spectra are shown in FIG. 5 and FIG. 6, respectively, and the following “Table 2” and “Table 3” are the respective analysis data. In addition, the formula (7
Spectra of compounds of known structure represented by 1) and (72) are shown in FIGS. 7 and 8.

[0250]

[Table 2]

[0251]

[Table 3]

In the uppermost spectrum curve of FIG. 5, δ is 2.0.
The spectrum curve in the middle row is the spectrum in which δ is 3.3 to 5.4. The five spectra with δ between 2.035 and 2.068 are ¹ H that are not substituted with D remaining in the solvent acetone-d ₆ , and the spectra between δ2.7 and 2.9 are under measurement. Due to H ₂ O dissolved in acetone-d ₆ .
Except for these spectra, all spectra in FIG. 5 were found to completely belong to all Hs in the formula (70) as shown below, and confirm that the formula (70) is correct. I was able to do it. In formula (70), there are two asymmetric carbon atoms having OH groups bonded. Therefore, equation (7
In the molecule represented by 0), there should be three types of stereoisomers having a configuration of SS, RR, SR centering on the asymmetric carbon atom. The isomers with the configurations SS and RR differ only in optical rotation, and the other physical properties are NM.
It is the same including R. On the other hand, the isomer SR has physical properties different from those of the former two and has different NMR. That is, NMR should identify the compound represented by formula (70) as two types of isomers. The attribution of spectra shown in "Table 4" below also makes this clear.

[0253]

[Table 4]

The spectrum curve in the upper part of FIG. 6 is an enlarged spectrum of δ between 3.8 and 5.2. δ is 1.9
The spectrum between ~ 2.1 and the spectrum between 2.7-2.9 are
Similar to the case of FIG. 5, the spectra of H and H ₂ O remaining in acetone-d ₆ , respectively, with a δ of 8 are due to careless contamination mixed with TMS. The spectrum is assigned as shown below and corresponds to all Hs in the formula (69).

[0255]

[Table 5]

7 and 8 show equations (71) and (7
2) ¹ H NMR (acetone-d ₆ , TMS). 5 to 6
Similarly, δ is 2.05 to 2.13 and 2.84 to 2.89, and the spectra of H remaining in acetone-d ₆ and H of H ₂ O are 8.0. The spectrum is displayed. The attribution of each spectrum is shown in "Table 6" and "Table 7" below.

[0257]

[Table 6]

[0258]

[Table 7]

CH ₃ CONH- of formula (72) having a known structure is replaced with PF ₆ N _2-
In the case where the compound of the formula (71) is substituted with ## STR3 ## to change the compound of formula (71), there are two characteristic changes in the effect of H on the NMR as shown in the following "Table 8".

[0260]

[Table 8]

Similarly, comparing the NMR of the compounds of formula (70) and formula (69), the results are shown in "Table 9" below.

[0262]

[Table 9]

As described above, the NMR chemical shift when the formula (70) is changed to the formula (69) is changed to the formula (71) from the structure-known formula (72).
The similarity to the chemical shifts in Eqs. Is one proof that Eqs. (70) and (69) are correct.

The formula (7) corresponding to the isomer of the formula (70)
Although it is possible that the compound represented by the formula (70 ′) shown in the following “Chemical 134” is difficult to form, it has already been introduced in the paragraph “0122”. ..

[0265]

[Chemical 134]

Formula (70) is a secondary alcohol and formula (70 ') is a primary alcohol. Alcohols ac
When dissolved in etone-d ₆ and measured by NMR, H of the OH group
NMR of the alcohol has been revealed to be a triplet in the primary alcohol and a doublet in the secondary alcohol (DJP
asto, CRJohnson, Organic Structure Determination,
Prentice-Hall, EnglewoodCliffs, NJ (1969). Figure 5
As is clear from FIG. 6, in the NMR spectra of the compounds represented by the formulas (70) and (69), the H of the OH group is a double line. Therefore, it became clear that both of these compounds were secondary alcohols, not primary alcohols of the formula (70 ').

(B) IR absorption spectrum KBr tablets of diazo compounds (69) and (71) were prepared and the IR absorption spectrum thereof was measured. The results are shown in "Table 10" below. In FIG. 9, the compound (6
The spectrum of 9) is shown.

[0268]

[Table 10]

(C) UV absorption spectrum UV absorption of a solution prepared by dissolving each of the diazo compounds (69), (71) and (73) in 2-methoxyethanol to a concentration of 4 × 10 ^-5 mol / l. The spectrum is shown in FIG.
Is. The maximum absorption wavelength (λmax), the absorbance (A) and the measured value of this absorbance and the molecular extinction coefficient (ε) calculated from the molecular weight of each compound represented by the formulas (69), (71) and (73) are as follows. As shown in "Table 11".

[0270]

[Table 11]

CL.1 instead of PF _{6 in} equations (71) and (73)
/ 2 ZnCl ₂ bonded compound aqueous solution
e, Kokado, Shimada, Nippon Kagaku Kaishi, 12 , 2272 (1
974) is like the following “Chemical Formula 135”, which agrees well with the value of ε in the equations (71) and (73) of this experiment.

[0272]

[Chemical 135]

[0273]

As described above in detail with reference to the embodiments, the present invention can exert the following effects. 1) It is possible to obtain a polyfunctional diazo compound that can be handled under white light. 2) It is possible to obtain a polyfunctional diazo compound which is suitable as a sensitizer for a lithographic printing plate precursor, has a high solubility in an organic solvent, and is easily developed by a developing solution containing an alkaline aqueous solution as a main component. 3) It is possible to obtain a highly water-soluble polyfunctional diazo compound suitable as a photosensitizer for a screen printing original plate. 4) A polyfunctional diazo compound having high sensitivity to light can be obtained. 5) It is possible to provide a development of polyfunctional diazo compounds having a simple synthetic method and a low-cost production method of those compounds.

[Brief description of drawings]

FIG. 1 is a UV absorption spectrum of a diazo compound synthesized in Example 4 and a diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 1.

FIG. 2 is a graph showing a change in absorbance at λ _max due to light irradiation of an aqueous solution of the diazo compound synthesized in Example 5 and the diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 1 at pH 3.

FIG. 3 An aqueous solution of the diazo compound synthesized in Example 5 and the diphenylamine-4-diazonium salt / formaldehyde condensate synthesized in Comparative Example 1 at pH 3 was shielded from light at 55 ° C.
3 is a graph showing the change in absorbance at λ _max when stored at.

FIG. 4 shows the pH of the diazo compound synthesized in Example 4, pH 3,5.
It is a graph which shows the storage stability in an aqueous solution at 0 degreeC.

FIG. 5 shows ¹ H NMR (270 M of the compound represented by the formula (70).
It is an Hz-sd- ₆ , TMS) spectrum.

FIG. 6 shows ¹ H NMR (270 M of the compound represented by the formula (69).
It is an Hz-sd- ₆ , TMS) spectrum.

FIG. 7 shows ¹ H NMR (270 M of the compound represented by the formula (71).
It is an Hz-sd- ₆ , TMS) spectrum.

FIG. 8 shows ¹ H NMR (270 M of the compound represented by the formula (72).
It is an Hz-sd- ₆ , TMS) spectrum.

FIG. 9 is an infrared absorption spectrum of a compound represented by the formula (69).

FIG. 10: Diazo compounds (69), (71), (73)
Is an ultraviolet absorption spectrum of the.

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[Procedure amendment]

[Submission date] August 19, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

[Chemical 59]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0268

[Correction method] Change

[Correction content]

[0268]

[Table 10]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display area C07D 251/34 A C08G 73/02 NTC 9285-4J C08K 5/23 KBC 7167-4J G03F 7/016 7/021 501 7/027 502 7/038 (72) Inventor Katsuhiko Sugao 563 Yonegasaki-cho, Funabashi-shi, Chiba Toyo Gosei Kogyo Co., Ltd. Sensitive Material Laboratory (72) Inventor Norieko Harada 563 Yonegasaki-cho, Funabashi, Chiba Toyo Gosei Kogyo Co., Ltd. Photosensitive Materials Laboratory

Claims (19)

[Claims] 1. An aromatic diazo compound containing as a main component a compound having two or more atomic groups represented by the general formula (I) represented by the following chemical formula 1 in one molecule. [Chemical 1] [Chemical 2] [Chemical 3] 2. The aromatic diazo compound according to claim 1, which is represented by the general formula (II) shown in the following "Chemical Formula 4". [Chemical 4] 3. The aromatic diazo compound according to claim 1, which is represented by the general formula (III) shown in the following "Chemical Formula 5". [Chemical 5] 4. The aromatic diazo compound according to claim 1, which is represented by the general formula (IV) shown in the following "Chemical Formula 6". [Chemical 6] 5. The aromatic diazo compound according to claim 1, which is represented by the general formula (V) shown in the following "Chemical formula 7". [Chemical 7] 6. The aromatic diazo compound according to claim 1, wherein in one molecule, two or more atomic groups represented by the general formula (I) shown in the above "Chemical formula 1" are added, and the following "Chemical formula 8" An aromatic diazo compound containing as a main component a compound having one or more atomic groups represented by the general formula (VI). [Chemical 8] 7. A p-aminoacylanilide represented by the following general formula (VII) represented by the general formula (VII) or a substituted product thereof, and a polyglycidyl ether represented by the general formula (VIII) shown below in the following "chemical formula 10". Are reacted in an organic solvent, and when R ^{7 in the} general formula (VII) is a hydrogen atom and the hydrogen atom remains after the reaction, the residual hydrogen atom is replaced with R ³ . Then, the general formula (I
I _AC ), and further reacting with an aqueous solution of one or a mixture of sulfuric acid, hydrochloric acid, phosphoric acid, and an acyl group (A
Replacing _C) a hydrogen atom, an aromatic amino compound represented by the general formula (II _a) shown in Tsugiki "Formula 12", wherein diazotized the aromatic amino compound with a diazo reagent such as nitrous acid Item 3. A method for producing an aromatic diazo compound, which comprises producing the aromatic diazo compound. [Chemical 9] [Chemical 10] [Chemical 11] [Chemical 12] 8. A p-aminoacylanilide represented by the following general formula (VII) represented by the general formula (VII) or a substituted product thereof, and a polyglycidylamino represented by the following general formula (IX) represented by the general formula (IX). When the compound is reacted with an organic solvent and R ^{7 in the} general formula (VII) is a hydrogen atom and the hydrogen atom remains after the reaction, the residual hydrogen atom is replaced with R ³ . Substituting the compound of the general formula (III
_AC ) and further reacting with an aqueous solution of one of sulfuric acid, hydrochloric acid, phosphoric acid or a mixture thereof to obtain an acyl group (A
_C ) is replaced with a hydrogen atom, and the general formula shown in the following "Chemical Formula 16"
And aromatic amino compound represented by (III _a), the production method of an aromatic diazo compound, characterized in that for producing an aromatic diazo compound of Claim 3 wherein the aromatic amino compound is diazotized diazo reagent .. [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] 9. An aniline represented by the general formula (X) or a homologue thereof represented by the following chemical formula 17 and a polyglycidyl ether compound represented by the general formula (VIII) represented by the following chemical formula 18. When the reaction is carried out in an organic solvent and R ⁷ is a hydrogen atom in the general formula (X) and the hydrogen atom remains after the reaction, the residual hydrogen atom is replaced with R ³ . By reacting with a nitrosating reagent, an aromatic nitroso compound represented by the general formula (II _NO ) shown in the following "Chemical Formula 19" is synthesized, and the nitroso group is reduced to an amino group.
A method for producing an aromatic diazo compound, which comprises producing the aromatic diazo compound according to claim 2 by diazotizing the aromatic amino compound represented by the general formula ( _IIa ) shown in (4). [Chemical 17] [Chemical 18] [Chemical 19] 10. An aniline represented by the general formula (X) shown in the following "Chemical formula 20" or a homologue thereof and a polyglycidylamino compound represented by the general formula (IX) shown in the following "Chemical formula 21". When the reaction is carried out in an organic solvent and R ⁷ is a hydrogen atom in the general formula (X) and the hydrogen atom remains after the reaction, the residual hydrogen atom is replaced with R ³ . By reacting with a nitrosating reagent, an aromatic nitroso compound represented by the general formula (III _NO ) shown in the following "Chemical Formula 22" is synthesized, and the nitroso group is reduced to an amino group.
Formula and aromatic amino compound represented by (III _a), the production method of an aromatic diazo compound, wherein this to produce an aromatic diazo compound of Claim 3 wherein diazotized shown. [Chemical 20] [Chemical 21] [Chemical formula 22] 11. A p-aminoacylanilide represented by the following general formula (XI) represented by the general formula (XI) or a substitution product thereof is represented by the general formula (VIII _{n = 2} ) shown in the following general formula (24). One type of diglycidyl ether or
When one of the diglycidylamino compounds represented by the general formula (IX _{n = 2} ) shown in 5 ”is reacted in an organic solvent and the hydrogen atom of —NH ₂ of the general formula (XI) remains after the reaction. Is further reacted with a monoglycidyl ether represented by the general formula (XII) shown in the following "Chemical Formula 26", and further reacted with an aqueous solution of one of sulfuric acid, hydrochloric acid, phosphoric acid or a mixture thereof to form an amino group Acyl group (A
A method for producing an aromatic diazo compound, which comprises producing an aromatic diazo compound according to claim 4 by substituting c) with a hydrogen atom and further carrying out a diazotization reaction. [Chemical formula 23] [Chemical formula 24] [Chemical 25] [Chemical formula 26] 12. The p-aminoacylanilide represented by the general formula (XI) shown in the above "Chemical Formula 23" or a substituted product thereof is represented by the formula (VIII _{n = 2} ) in the general formula shown in the above "Chemical 24". A mixture of at least two kinds of a glycidyl ether and a diglycidylamino compound represented by the general formula (IX _{n = 2} ) shown in “Chemical Formula 25” is reacted in an organic solvent, and the “Chemical Formula 23” is reacted even after the reaction. Of the general formula (XI) shown in
When the hydrogen atom of H ₂ remains, it is further reacted with the monoglycidyl ether represented by the general formula (XII) shown in the above “Chemical Formula 26”, and further, one of sulfuric acid, hydrochloric acid, phosphoric acid or its By reacting an aqueous solution of the mixture, the amino protecting group (Ac) is converted to H.
The method for producing an aromatic diazo compound according to claim 5, wherein the aromatic diazo compound is produced by substituting it with diazotized compound and further performing a diazotization reaction. 13. An atomic group represented by the general formula (I) is 1
A general formula characterized by reacting a compound having one or more in a molecule and giving a polycondensation product by reacting with a carbonyl reagent such as formaldehyde in sulfuric acid or phosphoric acid with formaldehyde or a reagent generating the same. A method for producing an aromatic diazo compound containing a compound having two or more atomic groups represented by (I) bonded in one molecule as a main component. 14. A general formula shown Tsugiki "Formula 27" (I _AC)
A compound having one or more atomic groups represented by the formula (1) in a molecule and reacting with a carbonyl reagent such as formaldehyde to give a condensation polymer is reacted with a carbonyl reagent such as formaldehyde in an acidic solvent to give a compound of the general formula An atomic group represented by the general formula (I), characterized in that a compound in which two or more atomic groups represented by (I _AC ) are bonded in one molecule is synthesized, and then a deacylation reaction and a diazotization reaction are performed. The manufacturing method of the aromatic diazo compound which has as a main component the compound which couple | bonded two or more in 1 molecule. [Chemical 27] 15. A p-aminoacylanilide represented by the following general formula (VII) represented by the following general formula (VII) or a substituted product thereof, and an amino compound represented by the following general formula (XIII) represented by the following general formula (29). Are mixed in a desired ratio, and a glycidyl compound is reacted in an organic solvent by the same operation method as the synthetic method according to claim 7, 8, 11 and 12, and then an aqueous solution of a strong acid is reacted to protect the amino group. A method for producing an aromatic diazo compound, characterized in that the group ( _AC ) is substituted with H and a diazotization reaction is further carried out to produce the aromatic diazo compound according to claim 6. [Chemical 28] [Chemical 29] 16. An atomic group represented by the general formula (I) is 1
Photosensitivity characterized by containing an aromatic diazo compound whose main component is a compound in which two or more are bonded in the molecule and a binder, and further containing an auxiliary agent such as a coloring material or a stabilizer if necessary. Composition. 17. All or part of the aromatic diazo compound contained in the photosensitive layer of a photosensitive lithographic printing original plate using an aromatic diazo compound as a photosensitive substance contains one molecule of an atomic group represented by the general formula (I). The photosensitive composition according to claim 16, which is an aromatic diazo compound having two or more bonded therein. 18. All or part of the aromatic diazo compound contained in the photosensitive layer of the photosensitive screen printing original plate using the aromatic diazo compound as a photosensitive substance is represented by the general formula (I).
17. The photosensitive composition according to claim 16, which is an aromatic diazo compound in which two or more atomic groups represented by are bonded in one molecule. 19. All or part of the aromatic diazo compound contained in the photosensitive layer of a colored image-forming photosensitive material using an aromatic diazo compound as a photosensitive substance contains one molecule of an atomic group represented by the general formula (I). The photosensitive composition according to claim 16, which is an aromatic diazo compound having two or more therein.