JP2000019726A - New photosensitive polycondensation product containing diazonium group, manufacture thereof and photosensitive composition composed of this product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a product excellent in photosensitivity, resolution and printing aptitude by containing a compound containing a specific diazonium group, and specific xylene resin at a specific ratio. SOLUTION: This product contains xylene resin at the ratio of 0.15-2.0, preferably 0.3-1.5 of xylene conversion unit per unit of diazonium salt. A compound containing a diazonium group is diphenylamino-4-diazonium salt, 3-methyl or methoxydiphenylamino-4-diazonium salt expressed by a formula I. Xylene resin is low molecular weight initial condensation resin expressed by a formula II. The compound contains the diazonium group with average molecular weight of M=140-400 and with oxygen content of 8-25%, reacted m-xylene under acidic state with formaldehyde or paraformaldehyde. In the formula I, R1-R3 represent hydrogen atom or alkyl group with 1-3 in the number of carbon atoms, and X represents anion of diazonium salt. In the formula II, R1 represents methyl group, and R2 represents methylol group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel photosensitive polycondensation product comprising an aromatic diazonium salt and a xylene resin, a method for producing the same, and a method for dissolving a solvent in a photosensitive layer by replacing the polycondensation product with a salt. The present invention relates to a photosensitive composition containing a diazonium group modified to be soluble. More specifically, a novel photosensitive polycondensation product containing a diazonium group used in the production of lithographic printing plates and printed wiring boards, a method for producing the same, and a photosensitive composition containing and using this polycondensation product About.

[0002]

2. Description of the Related Art A diazonium group-containing polycondensate is produced by a condensation reaction between an aromatic diazonium salt, for example, a diazonium compound having a basic skeleton of diphenylamine-4diazonium salt and an active carbonyl compound, generally formaldehyde. Is known. This type of condensation product is disclosed in U.S. Pat.
No. 2,674,415.

It is known that the same diazonium compound is produced by a condensation reaction of a diphenyl methoxy group, in particular, an alkoxy group-containing aromatic compound represented by dimethoxymethyldiphenyl ether. Condensation products of this kind are described in the patent publication, Showa 49-45323.

It is known that the same diazonium compound is reacted with an aromatic dialdehyde or dimethylol adduct to produce the compound. Condensation products of this type are described in Patent Publication, 1983, 58-55925, U.S. Pat. No. 3,867,147.

The preparation of similar diazonium resins is described in US Pat. Nos. 2,679,498, 3050502, 3311.
605, 3163633, 3406159, 32
No. 77074 and 3867147.

A conventionally known diazonium resin is modified with a mineral acid such as phosphoric acid and sulfuric acid, a Lewis acid such as BF _{6 and} PF ₄ , an organic sulfonic acid, and an organic phosphonic acid to form a photosensitive material and a photosensitive material. Alone or as a water-soluble composition,
It is known that it is preferably used in combination with a resin soluble in an alkaline aqueous solution or a solvent. Such a diazonium group-containing condensate photosensitive material and photosensitive composition are disclosed in U.S. Pat. No. 2,714,066, 32353.
No. 83, No. 2,826,501, British Patent Specification, No. 10
No. 74392, JP-A No. 54-98613, No. 56-121031, No. 59-3874, No. 58-654
No. 30, etc., and many others are described.

A photosensitive diazonium group-containing polycondensate of this type is disclosed, for example, in US Pat. No. 3,235,383 with a formaldehyde condensate and a patent publication, Showa, 49-45323, US Pat. Specification,
No. 3867147, DEC, 20222444, DE-
A, Condensation products such as dimethoxymethyl diphenyl ethers described in US Pat. No. 2,739,774 are only used on a large scale for industrial use.

Other compounds described in the above publications include higher aliphatic and aromatic aldehydes, ketones,
Quinone or a different carbonyl group, ie alkyl aldehyde, anthraquinone-β-aldehyde, and the like.

The reactivity of all these higher carbonyl compounds is inferior to that of formaldehyde. This means that the reaction is carried out under severe conditions or the reaction time is long. Promote the formation of by-products,
In particular, it results in highly crosslinked insoluble condensation products.

The conventionally produced formaldehyde condensation products have the disadvantage that, despite their widespread use on a large industrial scale, their composition and properties can only be used within very restricted ranges. Have.

Known low molecular weight condensates include a diazonium mineral acid, a double metal salt represented by zinc chloride, a Lewis acid, a modified salt such as an organic sulfonic acid, and a water-, alkali-, or solvent-soluble resin. Even if the contained photosensitive composition is used as a coating film on various supports, for example, a surface-treated aluminum plate, the exposure product does not have sufficient ink receptivity.

Known diazonium resins having excellent photosensitivity and heat stability, such as a condensation product of 3-alkoxy-4-diazodiphenylamine with formaldehyde or dimethoxymethyldiphenyl ether, can be used for ink receptivity and photocurability. , And stability over time,
Not enough for every requirement under the conditions of use.

Heretofore, a common disadvantage of the diazonium resins used industrially is that these resins do not contain metal salts, such as chlorides, phosphates, sulfates, Lewis salts,
Alternatively, they are very difficult to separate as salts of organic sulfonic acids, and these salts often do not dissolve well in organic solvents.

In such a diazonium resin,
Generally, by increasing the molecular weight (mainly the degree of polymerization), it is possible to increase sensitivity and improve solvent solubility (lipophilicity). However, controlling the molecular weight in the condensation reaction is not only difficult in terms of synthesis, but also complicates the reaction conditions and increases the molecular weight, thereby increasing the content ratio of the highly cross-linkable by-products. On the other hand, the solubility in the organic solvent or the like becomes significantly reduced or the resolution is reduced.

The difficulty of the condensation was reduced during the production by producing a cocondensation product using a diazonium salt and formaldehyde, which is a carbonyl compound, and a second component capable of being cocondensed. These products and their use are described in U.S. Pat.
No. 47. These condensation products are used for high-grade photosensitive materials, especially for printing plates. However,
Its preparation is more complicated than the preparation of simple formaldehyde condensation products. This is because a three-component condensation reaction that is difficult to control or a two-stage reaction is required.

The present inventor has conducted detailed and extensive studies to overcome the above-mentioned disadvantages of known diazonium resins. As a result, a novel diazonium group-containing polycondensation product that dissociates and dissolves easily in a strongly acidic medium, promptly re-polycondensates with a diazonium compound, and has high sensitivity, good solvent solubility, and good ink adhesion. I found

[0017]

The object of the present invention is a novel photosensitive polycondensation product containing a diazonium group, which is excellent in photosensitivity, resolution and printability, in the production of lithographic printing plates and printed boards, a process for producing the same, and a photosensitive composition. It is to provide things.

[0018]

DISCLOSURE OF THE INVENTION Compared with known polycondensation products containing a diazonium group, 1) high sensitivity, improved heat and stability over time, 2) inexpensive and easy to produce, 3) solvent dissolution Novel polycondensation product containing diazonium salt with excellent properties, photocurability, ink receptivity, etc., its production method,
And to provide a photosensitive composition.

[0019]

The diazonium salt-containing compound of the present invention and a xylene resin which is a low-molecular-weight initial condensation resin are used. 15 ~
2.0, preferably in a ratio of 0.3 to 1.5, wherein the compound having a diazonium group is represented by the general formula (1):

[0020]

Embedded image

[Wherein R ¹ , R ² and R ³ are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or
X represents an alkoxy group having 1 to 6 carbon atoms, and X represents an anion of a diazonium salt], diphenylamino-4-diazonium salt, 3-methyl, or methoxydiphenylamino-4diazonium salt;
Alternatively, it is an alkyl or alkoxyphenylamino-4-diazonium salt, and the xylene resin is represented by the general formula (2):

[0022]

Embedded image

[Wherein, R ₁ represents a methyl group, R ₂ represents a methylol group, R ₃ represents a methylene group, a methylene ether group, an acetal group, ｛-CH ₂ O-,-(-CH
₂ O-) _{n- ,} -CH _2- } represents a bonding group, and represents n = 1,2], and is a low molecular weight initial condensation resin represented by the formula: When reacted with formaldehyde, the average molecular weight is M = 140-
400, preferably a 170 to 370, oxygen Motoritsu {100- (C% + H% ) = O 2%} 8 to 25 percent, preferably, it contains a diazonium group which is 9 to 20% according to Achieved by the photosensitive polycondensation product of Item 1.

Examples of suitable diazonium compounds are those derived from the following amines:

4-aminodiphenylamine, 4-amino-3-methoxydiphenylamine, 4-amino-2
-Methoxydiphenylamine, 4'-amino-2-methoxydiphenylamine, 4'-amino-4-methoxydiphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethyldiphenylamine, 4'-amino-3-methyldiphenylamine,
4'-amino-4-methyldiphenylamine, 4-amino-3-ethoxydiphenylamine, 4'-amino-2-methoxy-5-methyldiphenylamine, 4-amino-3-methoxy-6-methyldiphenylamine, 4'-amino-3,3'-dimethyldiphenylamine, 4'-amino-3 ', 4 dimethoxydiphenylamine.

Hydrochlorides and phosphates are commonly used as anion of the diazonium salt, and particularly preferred is sulfate.

Xylene resin (literature, formaldehyde,
-A Chemistry and Applications-, Asakura Shoten, pp. 609 to 616) is used as an alternative to carbonyl compounds, in which the oxygen-containing bonding group is once cleaved and recombined with a new methylene bond. As a result, despite the high reactivity, no highly crosslinked by-products or insoluble products are formed.

If the average molecular weight is lower than 140, the condensation efficiency becomes poor and a high molecular weight condensation product cannot be obtained. On the other hand, if the molecular weight is larger than 400, the oxygen content of the xylene resin decreases, and the solubility in an acid medium and the reactivity such as cleavage and recondensation decrease.

The method for producing a photosensitive polycondensation product according to claim 1 according to the present invention is characterized in that a diazonium salt is subjected to a condensation reaction with a low molecular weight xylene resin in a strongly acidic medium.

Xylene resin is used as a strongly acidic condensation medium.
It is sufficiently soluble in 6-98% sulfuric acid and 90% or more methanesulfonic acid, but at room temperature (room temperature).
Then, as a side reaction, a by-product by sulfonation and dehydration carbonization easily occurs, and a desired condensate cannot be obtained. The synthesis operation must be performed under a mild condensation environment while carefully keeping the liquid temperature of the medium at 0 ° C. or lower, which is similar to the production of a formaldehyde condensation product.

The novel process for producing diazonium condensation products according to the present invention uses 85-93% phosphoric acid, 80-95% sulfuric acid or a mixture thereof as the condensation medium.
A small amount of water, methanol, acetic acid, N-methyl-pyrrolidone and the like can be added.

In particular, 85-93% phosphoric acid is a condensing agent whose condensation is carried out very slowly. The strongly acidic condensation medium is
Use the least amount that does not interfere with stirrability, mixing, and dissolution. The condensation temperature is -5 to 60C, preferably 5 to 60C.
Perform at 40 ° C

This makes it possible to increase the molecular weight easily and conveniently under mild condensation conditions with the same degree of polymerization as that of the commonly used diazonium resin, without producing a condensation resin having excessively high molecular weight. .

This is because a 6-membered aromatic ring is present in the linking group connecting the diazonium compound, and as a result, the molecular weight of the linking group increases, that is, the average molecular weight of the novel diazonium polycondensate increases. Because. Also, this is because the diazonium salt works to improve the solvent solubility of the oil-soluble salt, that is, the salt when the Lewis acid and the organic sulfonic acid are substituted.

The photosensitive composition according to the present invention contains a diazonium group, and the anion of the diazonium salt of the photosensitive polycondensation product according to claim 1, is converted into an inorganic acid, a Lewis acid or an organic sulfonic acid. It is characterized by comprising a salt-substituted diazonium group-containing polycondensation product.

This novel polycondensation product can be separated and produced in the form of a salt of the following acid, or added to a component for forming a photosensitive layer in the form of being replaced with another salt, and used for the production of a photosensitive composition You can do it.

[0037] For example, Japanese Patent Publication No. 47-1167, 49
-45322, 49-48001 and U.S. Pat. No. 3,219,447.

Hydrohalic acids, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid,
(Pentavalent phosphorus), orthophosphoric acid, iso- and heteropolyacids such as phosphotungstic acid, phosphomolybdic acid,
Aliphatic or aromatic phosphonic acids or their half esters, halogenated Lewis acids such as arsonic acid, phosphinic acid, trifluoroacetic acid, amidosulfonic acid, selenic acid, borofluoric acid, hexafluoride Phosphoric acid, perhalic acids such as perchloric acid, and aromatic sulfonic acids such as methanesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, sulfosalicylic acid, naphthalene-1, or 2-sulfonic acid, 2,6- The third
Butylnaphthalenesulfonic acid, 1,2, naphthoquinone-1-diazido-4-sulfonic acid, 2-hydroxy-benzophenone-5-sulfonic acid, 2-hydroxy-4methoxybenzophenone-5-sulfonic acid, and the like.

Of these, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid is particularly preferred as the oil-soluble salt.

In general, it has been found that polycondensates having a low diazonium salt content are hardly soluble in water. It is difficult to uniformly separate it as a salt of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and it is not sufficient in a photosensitivity and curability test on an aluminum plate.

It was also found that polycondensation products having a large content of diazonium salt can only obtain low molecular weight condensation products. This, after separation as 2-hydroxy-4-methoxybenzophenone-5-sulfonate,
Photosensitivity and curability tests on an aluminum plate show low sensitivity, low curability, image deterioration and run-off, and insufficient water resistance and developability.

An advantage of the condensation products prepared by the process according to the invention is that they can be easily separated in the form of salts. For example, the condensation product is an aqueous solution of a crude condensation mixture, or
By adding the above-mentioned acid or a soluble salt thereof from the alcohol solution, precipitation can be easily performed, and the corresponding salt can be separated.

For example, the novel condensation products can be very easily separated from the aqueous solution in the form of salts by addition of inorganic salts such as sodium chloride, Lewis acids and organic sulfonic acid solutions. Further, the water-soluble salt can be separated as an oil-soluble salt by adding a Lewis acid or an organic sulfonic acid in an alcohol solution, stirring and filtering.

As the alcohol, a monohydric alcohol,
For example, methanol, ethanol, n-, isopropanol, primary, secondary and tertiary butanol can be mentioned. Particularly preferred is n- or isopropanol. This is because alcohol having a lower molecular weight than ethanol evaporates faster, absorbs heat from the surrounding atmosphere due to heat absorption during evaporation, and the removal operation becomes complicated due to generation of water droplets due to condensation.

Alcohols having a higher molecular weight than butanol have low dissolving power for salts and low dissolving power for the strong acid used in the reaction, making it difficult to take out the desired salt and requiring time for drying.

Further, a hydrocarbon suitable for the alcohol solution, for example, hexane, cyclohexane, diethyl ether, petroleum ether, or a chlorofluorocarbon solvent, for example,
0 to 50, preferably 5 to 30% of trifluoroethane and the like can be added and mixed, and used.

The polycondensation products according to the invention have the following advantages over known diazonium salt polycondensation products: These have the advantage that they can be easily separated from the condensation medium and isolated in pure form.

The photosensitive composition produced by using the novel condensation product, particularly a printing plate, has high photosensitivity and strong oil sensitivity of the cured image film. Furthermore, there is an advantage that it can be easily manufactured using easily available and inexpensive raw materials.

The use of the novel condensation product has the advantage over the known diazonium resins that, when using the same light source, it is possible to meet the requirements with a short exposure time. This effect increases in proportion to the content of the xylene resin. Generally, the increase in molecular weight by the aromatic ring component is more effective than the increase by other groups.

As the content of the xylene resin increases, the resin characteristics of the novel condensation product become clear, but the sensitivity characteristics of the diazonium salt decrease in proportion to the content of the diazonium salt in the molecule of the novel condensation product. .

As a characteristic of the xylene resin, as the molecular weight increases, the oxygen content tends to decrease, and for this reason, the solubility in a strongly acidic medium decreases.
Therefore, the dissociation and recondensation reactions in a strongly acidic medium are suppressed, and the characteristics of the target novel polycondensation product are limited.

Useful xylene resins have the above-mentioned ranges, that is, the average molecular weight is M = 140 to 400, preferably 170 to 370, and the oxygen content, 8 to 25%,
Preferably, a condensation product having the above advantages can be obtained by selecting an initial condensation xylene resin suitable for the required performance from the range of 9 to 20%.

In order to prepare a photosensitive composition using the novel polycondensed diazonium salt of the present invention, the diazonium polycondensation product is separated as the above-mentioned various salts, and then the other layer components are mixed with a suitable solvent. And coated on a predetermined coating surface with the obtained solution.

Numerous substances such as a resin capable of crosslinking with a diazonium group, an image strengthening agent, a coloring agent and an antioxidant can be added to the photosensitive composition. An example is described below.

A method for producing a lithographic printing plate using a known diazonium resin will be described. In this case, suitable supports include paper, plastic, zinc, copper, aluminum,
A metal plate such as stainless steel is useful. Particularly, an aluminum plate is suitable for a lithographic printing plate.

In the case of a lithographic printing plate, in order to prevent harmful interactions between the surface of the support and the diazonium compound, the surface of the support must be coated before the application of the photosensitive composition.
Passivated. This passivation promotes a tight bond between the exposed portions of the photosensitive layer that will become the image areas and the support, and in the non-image areas helps to provide a hydrophilic surface during the printing process.

The silicate treatment described in US Pat. No. 2,714,066 is a suitable passivation treatment for aluminum supports, and as an example of another passivation treatment, US Pat. No. 2,946,638, 365
No. 8662, anodizing an aluminum plate in phosphoric acid or sulfuric acid. Further, a method of performing the silicate treatment and the like are described.

The photosensitive layer is dried at room temperature or at a higher temperature. The material of this type of photosensitive layer and the photosensitive composition are those of the diazonium resin alone described in U.S. Pat. No. 2,714,066, that is, those in which no carrier is added, and those in which the diazonium resin is a water-soluble anion. For example, U.S. Pat.
No. 2,335,382, in which a water-soluble polymer such as polyvinyl alcohol, partially saponified polyvinyl acetate (acetyl content: ４０40%), polyacrylamide or the like is added, and an anion is added. Solvent-soluble salts, such as Lewis acids, organic sulfonates, and alkali- and solvent-soluble resins, such as U.S. Pat. No. 2,826,501, British Patent No. 1,074,392, and patent publications And high molecular compounds having a hydroxyl group as described in JP-A-52-7364 and 1983-209733, for example, those in which a copolymer of a monomer represented by the following general formula (3) and another monomer is added. Can be

General formula (3):

[0060]

Embedded image

In the general formula (3), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, and n represents an integer of 1 to 10. ｝ As the other monomer of the copolymer, for example, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic esters, methacrylic esters, acrylamides, allyl compounds, vinyl ethers, vinyl esters And styrene crotonic esters.

The present invention is not limited to the above copolymerizable monomers, but may be any copolymer as long as it is a compound having a curing action by a photocrosslinking reaction. In addition, water-insoluble polymers, such as phenolic resins, epoxy resins, urea, and melamine resins, polyvinyl acetal,
Polyurethane and polysulfonyluethane, etc.
It may be added in an amount not exceeding 0% by weight to improve image enhancement. Other additives, such as colored or non-colored pigments, dyes, plasticizers, wetting agents, sensitizers, stabilizers, antioxidants, pH adjusters, etc. can also be added to the photosensitive composition. .

All additives are selected that are compatible with the diazonium condensation product and that absorb as little light as possible within the wavelength range important for the photolysis of the diazonium compound.

Generally, the following amounts are added and used. In the case of an acid salt, for example, in the case of a divalent sulfuric acid salt, an amount of 0.01 to 4.00 mol, preferably 0.02 to 3.0 mol is used per 1 mol of a diazonium group. You. The amount of the Lewis acid as the oil-soluble salt and the amount of the organic sulfonic acid are 0.01 to 3.0, preferably 0.2 to 3.0.
2.5 moles are used.

The addition of a water-soluble, water-dispersible, emulsifying, or alkali-water-soluble or solvent-soluble polymer which is cured by a photocrosslinking reaction with a diazonium group-containing condensate is carried out by adding a diazonium group-containing polycondensation compound, Hit
It does not exceed 20 parts by weight, preferably 0.5 to 15 parts by weight.

When a water-soluble and water-insoluble polymer is added to the photosensitive composition, a colored or non-colored dye and a pigment are generally added to the polymer in an amount of 5 to 5%.
An amount of 0% by weight or less can be added.

The plasticizer, humectant, sensitizer, stabilizer, antioxidant, and pH adjuster are
An amount of not more than 30% by weight, preferably not more than 15% by weight, can be added to the photosensitive composition.

In preparing the photosensitive composition solution, the solvent for dissolution is water, alcohol such as ethanol, propanol, glycol ethers such as ethylene glycol monomethyl ether, dimethyl based on the components of the composition. Formamide and diethylformamide can be added in a range not exceeding 90% by weight. Two or more kinds of the above solvents may be mixed.

In the case of these oil-soluble salts, the above-mentioned alcohols, ethers and amides, which are good solvents for the compounds, or solvents or ethers slightly dissolving these compounds, for example, dioxane, tetrahydrofuran, esters, for example, , Acetate, butyl acetate, ethylene glycol methyl ether acetate, ketones,
For example, by adding methyl ethyl ketone, cyclohexanone, and a chlor solvent such as ethylene dichloride, the coating properties can be improved.

When the photosensitive composition is used, it is used by being coated on a support suitable for each application, for example, on a lithographic printing plate, an aluminum plate whose surface has been hydrophilized. The coating amount of the photosensitive layer of the photosensitive composition provided on the support is preferably 0.1 to 7 g / m ² , more preferably 0.1 g / m ² .
5 to 3.0 g / m ² .

Next, the original image is exposed on the obtained photosensitive layer. For image exposure, it is radiatively exposed in the long wavelength UV region and in the short wavelength visible region. For image formation such as plate making, a light source usually used, for example, a carbon arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like is used. It is also possible to emit an analog signal wave with a laser beam.

After the exposure, the film is developed with an appropriate developing solution.
dry. If necessary, post-processing, for example, retouching, erasing, non-image desensitization, or image enhancement, for example,
Practical application of resin coating and burning treatment. As the developer, water, an aqueous solution of a mixture of an alkali and a wetting agent can be used. Further, an organic solvent, an organic sulfonic acid, a mixture of a penetrant and the like, an acid, for example, phosphoric acid,
Alternatively, an aqueous solution of the salt can be added for use. Alkali compounds include caustic soda, caustic potash, and
As organic amines, for example, monoethanolamine, diethanolamine, triethanolamine, and salt compounds, for example, sodium silicate, potassium phosphate, and the like can be used.

The developer further contains other components, for example,
It is possible to add a wetting agent, a hydrophilic agent, a coloring agent, and a penetrating agent having a surface activity for uniformly and rapidly developing. The development is performed by a known method, for example, by immersing, coating, or spraying a printing plate in a developer.

The production of the novel diazonium polycondensation products and the photosensitive compositions according to the invention produced using them are described by way of examples. In order to demonstrate the properties of the diazonium salt used, the average molecular weight and oxygen content of the xylene resin reacted in a number of examples, and the diazonium salt and xylene units of the xylene resin in terms of the structure of the product (in xylene conversion) ) Is described. This molar ratio was calculated from the average molecular weight.

In the description of these examples, it is impossible to state the exact structure of the condensate according to the present invention, and the exact structure is unknown. This is because the xylene resin itself is a mixed product of a complex structure, and in the polycondensation reaction,
This is because it is a mixed product having a complicated structure. Furthermore, it does not require the performance due to the purity of the condensate, each one, one structure.

However, these examples showed a comparison of solubility and sensitivity as a performance that enables reproducibility of the characteristics of the mixture as a mixture of the structures. As already mentioned, to characterize the condensation product, the conditions of the condensation, in particular,
The addition ratio of the used substances is important.

[0077]

Next, the present invention will be described in more detail by way of examples. The examples include the description necessary for the preparation of the condensation product, but the invention is not limited thereby. In the examples, the parts by weight and the parts by volume are mutually
g and ml, percentages are by weight unless otherwise indicated, temperature is in ° C., and molecular weight is in M. In the examples, a crude condensate is generally referred to as a crude condensate mixture after the condensation reaction has ended, which generally contains a condensation medium. The production method of a typical novel diazonium salt-containing polycondensate and examples of evaluation of a photosensitive composition will be described in detail below.

Example 1 3-methoxydiphenylamine-4-diazonium sulfate (96 in 85% phosphoric acid, 50 parts by weight)
%), 20 parts by weight (M = 274, 0.073 mol) were dissolved at room temperature. Into this solution, xylene resin, 17 parts by weight, (Lignite Co., Ltd., Xylenol resin, X
-5: average molecular weight = 300, oxygen content = 9-11, 0.1.
(056 mol) was added slowly. After 30 minutes, the mixture was condensed at 40 ° C. for 12 hours. The obtained viscous crude condensation product was poured into 500 ml of water to obtain a diluted solution. This solution was converted into chlor salt by salt exchange with 500 ml of a saturated saline solution. In this case, the resulting precipitate is filtered and dried to obtain the condensation product 3
1.2 g were obtained.

The 2% aqueous solution was a clear yellow-brown solution. This means that the diazonium group, 1
Per unit ratio of xylene resin in terms of xylene,
Represents a homogeneously reacted polycondensation product of 0.78. This diazonium polycondensation product is a 7.5% aqueous polyvinyl alcohol solution (Nihon Gosei, GL05: average molecular weight = 500), 1
Very good solubility was shown at a concentration of 1 g per 100 parts by weight. Apply to a grained aluminum plate, after exposure,
Developed in running water. The coating film physical properties (sensitivity, degree of curing) were good.

Example 2 3-methoxydiphenylamine-4-diazonium sulfate (96 in 85% phosphoric acid, 50 parts by weight)
%) And 20 parts by weight were dissolved at room temperature. To this solution, a xylene resin, 17 parts by weight, (Lignite Co., Ltd., xylenol resin, X-4: average molecular weight = 370, oxygen content = 9 to 11, 0.046 mol) were gradually added.
The mixture was condensed at 40 ° C. for 18 hours. The viscous crude condensation product is converted to an isopropyl alcohol solution (liquid temperature, 1
(0 ° C.) and poured into 500 ml with stirring. A precipitate formed on the powder. The precipitate formed is filtered, washed with isopropyl alcohol, re-filtered, dried and dried.
2.5 g of a condensation product in which the diazonium groups are sulfates were obtained.

The 2% aqueous solution was a clear yellow-brown solution. This indicates a uniformly reacted polycondensation product having a diazonium group in the condensation product and a unit ratio of xylene skeleton unit of xylene resin per unit of 0.63. This diazonium polycondensation product is a 7.5% aqueous solution of polyvinyl alcohol (Nippon Gohsei, GL05: average molecular weight = 50).
0), very good solubility was shown at a concentration of 1 g per 100 parts by weight. Similarly, the coating film physical properties (sensitivity, degree of curing) were good.

Example 3 85% phosphoric acid, 35 parts by weight and 98%, sulfuric acid 10
20 parts by weight of 3-methoxydiphenylamine-4diazonium sulfate (96%) were dissolved in the mixture of parts by weight at room temperature. Xylene resin, 1
7 parts by weight, manufactured by Perignite Co., Ltd., xylenol resin,
X-4: average molecular weight = 370, oxygen content = 9 to 11,
0.046 mol) was added slowly. This mixture was condensed at 17 ° C. for 12 hours. The obtained viscous crude condensation product is treated with isopropyl alcohol (liquid temperature, 10
C) and poured into 500 ml with stirring. A precipitate formed on the powder. The resulting product was filtered, washed with isopropyl alcohol, re-filtered and dried to obtain 32.5 g of a condensation product in which the diazonium group was a sulfate.

The 2% aqueous solution was a clear yellow-brown solution. This indicates a uniformly reacted polycondensation product having a diazonium group in the condensation product and a unit ratio of xylene skeleton unit of xylene resin per unit of 0.63. This diazonium polycondensation product is a 7.5% aqueous solution of polyvinyl alcohol (Nippon Gohsei, GL05: average molecular weight = 50).
0), very good solubility was shown at a concentration of 1 g per 100 parts by weight. Similarly, the coating film had good physical properties (sensitivity and curing degree).

Example 4 Diphenylamine-4diazonium sulfate (96%), 18 (M = 24) in 85% phosphoric acid and 50 parts by weight
4, 0.072 mol) by weight at room temperature. Into this solution, xylene resin, 17 parts by weight, (Lignite Co., Ltd., Xylenol resin X-4: average molecular weight = 37)
0, oxygen content = 9-11, 0.046 mol). The mixture was condensed at 40 ° C. for 18 hours. The viscous crude condensation product was poured into 500 ml of an isopropyl alcohol liquid (liquid temperature, 10 ° C.) with stirring. A precipitate formed on the powder. The resulting product is filtered, washed with isopropyl alcohol, re-filtered,
After drying, 30.5 g of a condensation product in which the diazonium group was a sulfate was obtained.

The 2% aqueous solution was a clear yellow-brown solution. This means that the diazonium group, 1
The unit ratio of the xylene skeleton unit of the xylene resin per unit area is 0.63, indicating a uniformly reacted polycondensation product. This diazonium polycondensation product is a 7.5% aqueous solution of polyvinyl alcohol (Nippon Gohsei, GL05: average molecular weight = 50).
0), very good solubility was shown at a concentration of 1 g per 100 parts by weight. Similarly, the coating film had good physical properties (sensitivity and curing degree).

Example 5 85% phosphoric acid, 35 parts by weight, and 98% sulfuric acid, 10%
18 parts by weight of diphenylamine-4diazonium sulfate (96%) was dissolved at room temperature in the mixture of parts by weight. 17 parts by weight of a xylene resin (manufactured by Lignite Co., Ltd., xylenol resin X-4: average molecular weight = 370, oxygen content = 9 to 11, 0.046 mol) were gradually added to this solution. This mixture was condensed at 17 ° C. for 12 hours. The obtained viscous crude condensation product was poured into 500 ml of isopropyl alcohol (liquid temperature, 10 ° C.) while stirring. A precipitate formed on the powder. The precipitate formed was filtered, washed with isopropyl alcohol, filtered again, and dried to obtain 32.0 g of a condensation product in which the diazonium group was a sulfate.

The 2% aqueous solution was a clear yellow-brown solution. This indicates a uniformly reacted polycondensation product having a diazonium group in the condensation product and a unit ratio of xylene skeleton unit of xylene resin per unit of 0.63.
This diazonium polycondensation product is a 7.5% aqueous polyvinyl alcohol solution (Nihon Gosei, GL05: average molecular weight = 50).
0), very good solubility was shown at a concentration of 1 g per 100 parts by weight. Similarly, the coating film had good physical properties (sensitivity and curing degree).

Example 6 85% phosphoric acid, 50 parts by weight of 3-methoxydiphenylamine-4-diazonium sulfate (96%)
20 parts by weight were dissolved at room temperature. Hexylene resin, 12 parts by weight in this solution, (Lignite Co., Ltd., xylenol resin X-2: average molecular weight = 210, oxygen content = 18-2)
0, 0.057 mol) was added slowly.
The mixture was condensed at 40 ° C. for 18 hours. The thick viscous condensation product was poured into 500 ml of water and diluted and dissolved. This solution was salt-exchanged with 500 ml of 3% potassium hexafluorophosphate (KPF ₆ ) -dissolved water to convert it into oil-soluble hexafluorophosphate. In this case, the resulting precipitate was filtered and dried to obtain 37 and 5 g of a condensation product.

The 1% ethylene glycol monomethyl ether solution was a clear yellow tea solution. This represents a polycondensation product which reacted uniformly with a diazonium group in the condensation product and a unit ratio of 0.78 per m-xylene resin in terms of xylene. This diazonium polycondensation product is prepared by dissolving 6 g of the resin of the general formula (3) in ethylene glycol monomethyl ether solution, and adding 1 part to 100 parts by weight.
Very good solubility was shown at a concentration of g. It was applied to a surface-treated aluminum plate, exposed and developed. The coating film physical properties (sensitivity, degree of curing) were good.

Example 7 85% phosphoric acid, 35 parts by weight, and 98% sulfuric acid, 10%
20 parts by weight of 3-methoxydiphenylamine-4diazonium sulfate (96%) were dissolved in parts by weight at room temperature. Into this solution, xylene resin, 12 parts by weight,
(Lignite Co., Ltd., xylenol resin, X-2:
Average molecular weight = 210, oxygen content = 18-20: 0.05
7 mol) was added slowly. This mixture is kept at 17 ° C
For 12 hours. 2 viscous crude condensation products
3 g of 3-methoxy-4-hydroxybenzophenone 5
Isopropyl alcohol in which sulfonic acid is dissolved, 10
It was added in 00 ml and stirred to obtain a powdery precipitate. In this case, the resulting precipitate is filtered and dried to obtain a condensation product.
39.3 g were obtained.

The 2% ethylene glycol monomethyl ether solution was a clear yellow-brown solution. This represents a polycondensation product which reacted uniformly with a diazonium group in the condensation product and 0.78 units of xylene resin per xylene resin. The diazonium polycondensation product was prepared by adding 6 g of a resin of the general formula (3) to an ethylene glycol monomethyl ether solution, and 1 g per 100 parts by weight
And showed very good solubility. Similarly, the coating film had good physical properties (sensitivity and curing degree).

Example 8 In 50% by weight of 85% phosphoric acid, 20 parts by weight of 3-methoxydiphenylamine-4-diazonium sulfate were dissolved at room temperature. Xylene resin, 17
Parts by weight, (Lignite Co., Ltd., xylenol resin,
X-6: average molecular weight = 230, oxygen content = 18-20:
0.074 mol) was added slowly. This mixture was condensed at 40 ° C. for 12 hours. The viscous crude condensation product was dissolved in 25 g of potassium hexafluorophosphate in water, 1000 m
and poured into it with stirring. A powdery precipitate formed. After filtration, the resulting product is rewashed in 1000 ml of water or isopropyl alcohol (liquid temperature, 10 ° C.), refiltered and dried, and 42.5 g of diazonium group is hexafluorophosphate. A condensation product was obtained.

The 2% ethylene glycol monomethyl ether solution was a clear yellow tea solution. This represents a uniformly reacted polycondensation product having a diazonium group in the condensation product and a unit ratio of 1.01 per unit of xylene skeleton unit of the xylene resin. This diazonium polycondensation product showed extremely good solubility at a concentration of 1 g per 100 parts by weight of a solution of the resin of the general formula (3) in 6 g of ethylene glycol monomethyl ether. Similarly, the coating film had good physical properties (sensitivity and curing degree).

Example 9 85% phosphoric acid, 35 parts by weight and 98% sulfuric acid, 10%
20 parts by weight of 3-methoxydiphenylamine-4diazonium sulfate were dissolved at a liquid temperature of 17 ° C. in the mixture of parts by weight. Xylene resin, 17
Parts by weight, (xylene resin, manufactured by Lignite Co., Ltd., X-5: average molecular weight = 300, oxygen content = 9 to 11: 0.0)
57 mol) was added slowly and stirred. This mixture was condensed at 25 ° C. for 12 hours. The viscous crude condensation product is treated with isopropyl alcohol (liquid temperature, 10 ° C), 5
In 00 ml, 2-hydroxy-4-methoxy-benzophenone-5 sulfonic acid, 23 g (0.74 mol) was added, and the mixture was poured into a sufficiently dissolved solution with stirring.
A precipitate formed on the powder. The precipitate formed was filtered, washed again with isopropyl alcohol, dried again by filtration, and 44.2 g of diazonium group was converted to an organic sulfonate.
To be precise, a condensation product was obtained which was 2-hydroxy-4-methoxy-benzophenone-5-sulfonate.

The 2% ethylene glycol monomethyl ether solution was a clear yellow solution. This means that the condensation product has a diazonium group, a unit ratio of xylene skeleton unit of the xylene resin per unit ratio of 0.78, and a weight of the uniformly reacted 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid oil-soluble salt. Represents a condensation product.
This diazonium polycondensation product has 6 g of the general formula (3)
A solution of the resin in ethylene glycol monomethyl ether,
Very good solubility was shown at a concentration of 1 g per 100 parts by weight. Similarly, the coating film had good physical properties (sensitivity and curing degree).

Next, the photosensitive composition of the present invention will be described, but the present invention is not limited thereto. Example 10 A 2S aluminum plate having a thickness of 0.15 mm was immersed in an 8% aqueous solution of sodium tertiary phosphate kept at 80 ° C. for 3 minutes to degrease it. Etch with acid soda for about 10 seconds, then anodize the aluminum plate in 20% sulfuric acid at 2 A / dm ² for 2 minutes in a 3% aqueous solution of sodium hydrogen sulfate, then 1. sodium silicate at 70 ° C;
Anodized aluminum plate (A) was prepared by treating with a 5% aqueous solution for 1 minute, and the following photosensitive composition containing a diazonium condensation product described in Examples, 6, 7, 8, and 9 was used.
It was applied to the surface. Drying was performed at 100 ° C. for 3 minutes.

0.7 g of the 2-hydroxyethyl methacrylate copolymer (copolymer resin described by the general formula (3)) 0.2 g of diazonium resin produced in Examples 6, 7, 8 and 9 oil Blue # 603 (Hodogaya Chemical Industry) 0.03 g Ethylene glycol-2-methyl ether 30 g Citric acid 0.02 g

The dry coating amount was 2.0 g / m ² .
This photosensitive lithographic printing plate was image-exposed with an amount of 80, counted from a distance of 1 m, using a 3 kw idle fin exposure machine,
After immersion development for 1 minute at room temperature with the following developing solution, the surface was rubbed lightly and the unexposed portions were removed to obtain a lithographic printing plate.

Developer (A) 40% aqueous sodium silicate solution 5 g Sodium isopropylnaphthalenesulfonate 5 g Benzyl alcohol 15 g Monogen Y-100 3 g (Na salt of lauryl alcohol sulfate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 972 g

When these printing plates were printed using a Heidel printing machine, the oil sensitivity of the image area was good, the ink was deposited normally, and printing of 100,000 or more was possible. After leaving the unexposed printing plate in an environment of 45 ° C. and 75% humidity for one week (corresponding to one year of natural aging), the plate was made under the same conditions as above, and there was no change in sensitivity. , Moreover, inking of ink during printing,
There were no stains on the non-image area and no decrease in the number of prints (printing durability).

Comparative Example 1 The same operation as in Example 10 was carried out except that the photosensitive composition in which the diazonium resin was a 2-hydroxy-4-methoxy-benzophenone-5-sulfonate of a commercially available formalin condensed resin (1) had the following formulation: Was done.

2-Hydroxyethyl methacrylate copolymer 0.7 g Commercially available diazonium resin (1) 0.2 g Oil blue # 603 0.03 g Ethylene glycol-2-methyl ether 20 g Citric acid 0.02 g Dimethylformamide 5 g 5 g of ethylene dichloride

It was not sufficiently and uniformly dissolved in a solution of ethylene glycol-2-methyl ether alone. Further, plate making was performed under the same conditions as described above. As a result, the exposure in sensitivity was 15 counts, which was larger than that in Example 10. Then, when this printing plate was printed by a Heidel printing machine, paper printing and ink deposition were insufficient until about the twentieth sheet, and spots where the comb was lost were found. Further, after the unexposed printing plate was left in an environment of 45 ° C. and 75% humidity for 1 week (corresponding to one year of natural aging), plate making and printing were performed. However, the exposure amount required 15 counts, which was still large.

Comparative Example 2 A photosensitive composition in which the diazonium resin was a commercially available dimethoxydiphenyl ether condensed resin (2) was subjected to the same operation as in Example 10 except that the following formulation was used.

2-Hydroxyethyl methacrylate copolymer 0.7 g Commercially available diazonium resin (2) 0.2 g Oil blue # 603 0.03 g Ethylene glycol-2-methyl ether 20 g Citric acid 0.02 g Dimethylformamide 5 g 5 g of ethylene dichloride

Sufficient for 2-methoxyethanol alone solution,
It did not dissolve uniformly. Further, when this printing plate was printed by a Heidel printing machine, the ink was insufficiently printed on the 15th sheet, and the ink was not properly deposited. After leaving the unexposed printing plate in an environment of 45 ° C. and 75% humidity for one week (corresponding to one year of natural aging), the plate was made under the same conditions as described above. Exposure in sensitivity required 10 counts, which was large. In addition, the inking of the ink at the time of printing cannot be said to be sufficient, and a sensitization treatment was required.

Test evaluation results

[Table 1]

* Composition liquid: The above photosensitive composition was prepared using the diazonium condensed resin synthesized in Examples 6 to 9. And the above-mentioned comparative product shows the composition used in the comparative example. * ◎ Good ○ Normal, △ Slightly dissatisfied, ● Some parts are missing.

* Solubility: Dissolution in ethylene glycol monomethyl ether (2 g / 100 ml) * Sensitivity: Slight amount of exposure required (3-stage solid / 15-stage tablet) * Lipophilicity: Ink adhesion at initial printing Pass / fail: cyan ink, (DIC Graf-G); solid density, 1.5
(Density meter; KRD-3200, color filter, STATUS, TEA, manufactured by Koyo Chemical Industry)

Example 11 The copper surface of a plastic plate on which a thin copper foil was laminated was cleaned with an abrasive and washed with acetone, and then the photosensitive composition of Example 10 was coated. Layer weight 2 g /
It was adjusted to m ^2. The plate was exposed under a negative image representing a circuit diagram for one minute (a metal halide lamp of 5 KW) at a distance of 1 m between the lamp and the vacuum copying frame. The development was carried out using a developer having the following composition. After one minute of immersion development, the surface was rubbed lightly with a sponge and washed with water to finish.
In that case, the unexposed layer portions were dissolved.

Developer (b) Ethylene glycol monophenyl ether 25 g Alkyl benzene sulfonate 8 g n-propyl alcohol 20 g 40% sodium silicate aqueous solution 20 g Monogen Y-100 5 g Water 922 g

Next, the exposed portion of the copper was etched away with a 40% aqueous ferric chloride solution to obtain a copied circuit board. The sensitivity, curability and iron chloride etching solution resistance were good.

Claims (3)

[Claims] 1. A diazonium group-containing compound and a low molecular weight initial condensation resin, m-xylene resin (m-xylene, formaldehyde condensation resin, hereinafter referred to as xylene resin). Xylene conversion unit formed, 0.15
2.0, preferably in a ratio of 0.3 to 1.5,
The compound containing a diazonium group is represented by the general formula (1): [Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a 1 to 6 carbon atoms.
And X represents an anion of a diazonium salt], a diphenylamino-4-diazonium salt, 3-methyl or methoxydiphenylamino-4diazonium salt, or an alkyl or An alkoxyphenylamino-4diazonium salt, wherein the xylene resin has a general formula (2): [Wherein, R ₁ represents a methyl group, R ₂ represents a methylol group, R ₃ represents a methylene group, a methylene ether group, and
Acetal _{group, {- CH 2 O -,} - ( over CH ₂ O over) _{n over,}
—CH ₂ —} represents a bonding group, and represents n = 1, 2, and is a low-molecular-weight initial condensation resin represented by the formula below, which is obtained by reacting m-xylene with formaldehyde or paraformaldehyde under acidic conditions. The molecular weight is M = 140-400, preferably 170-370, and the oxygen content 含 100−
(C% + H%) = O ₂ %｝ is 8 to 25%, preferably
A novel photosensitive polycondensation product containing a diazonium group, which is 9 to 20%. 2. The method of producing a photosensitive polycondensation product according to claim 1, wherein a diazonium salt is subjected to a condensation reaction with a low molecular weight xylene resin in a strongly acidic medium. For producing a polycondensation product. 3. The diazonium according to claim 1, wherein the anion of the diazonium salt of the photosensitive polycondensation product containing a diazonium group is salt-substituted with a Lewis acid or an organic sulfonic acid, and modified to be solvent-soluble. A photosensitive composition comprising a group-containing polycondensation product.