JPS6149656B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diazo photosensitizer composition, and more particularly to a diazo photosensitizer composition characterized by containing a photosensitive diazonium salt, an acid stabilizer, and an alkyl ketene dimer.

A one-component diazo wet copying method in which a one-component diazo photosensitive layer containing a photosensitive diazonium salt and an acid stabilizer is exposed and then developed with an alkaline aqueous solution containing a coupler to form an image, and a photosensitive diazonium salt; Two-component diazo copying in which an image is formed by exposing a two-component diazo photosensitive layer containing an acid stabilizer and a coupler to light and then developing it with a solution containing an alkaline agent such as an amine or a developer consisting of ammonia-steam vapor. This method is widely used as a low-cost copying method.

However, in this diazo copying method,
Since dye-forming components such as photosensitive diazonium salts or couplers and the diazo dye itself have a strong tendency to permeate into the paper substrate, the amount of dye-forming components used and the amount of dye actually formed during development may vary. The disadvantage is that the density of the image formed is still low compared to the amount. This trend is
This is particularly noticeable in wet development methods that use alkaline developers.

Furthermore, as mentioned above, the dye has permeated into the interior, and dyeing and insolubilization of the dye are not yet complete, so the formed dye image is prone to so-called bleeding, resulting in so-called image breakage. It tends to have the disadvantage that it is not good.

Furthermore, wet copying methods that use alkaline liquids often destroy the size of the paper substrate;
The above-mentioned bleeding phenomenon appears even more strongly, and the texture and strength of the copy paper also deteriorates.

The present inventors have discovered that when an alkyl ketene dimer is contained in a one-component or two-component diazo photosensitizer composition containing a photosensitive diazonium salt and an acid stabilizer as essential components, the alkyl ketene dimer is formed by exposure and development. significantly improves the density of dye images,
We have discovered that it is possible to eliminate blurring in images.

That is, an object of the present invention is to provide a diazo photosensitive composition that can significantly improve the density of the dye image formed or further increase the optical sensitivity of the diazo photosensitive layer.

Another object of the present invention is to provide a diazo photosensitive composition that eliminates bleeding in dye images formed and is capable of forming dye images with excellent contrast.

Still another object of the present invention is to effectively prevent the solubilization and desorption of dyes even when brought into contact with a developer containing an alkaline agent, and to destroy the size of a paper substrate coated with a photosensitizer. The object of the present invention is to provide a diazo photosensitizer composition that can significantly suppress deterioration in texture, texture, and strength.

These objects are achieved by the invention described above.

The alkyl ketene dimer used in the present invention is
General formula below In the formula, R is an alkyl group having 9 or more carbon atoms, particularly 12 to 20 carbon atoms.

It can be expressed as This alkyl ketene dimer is commercially available under the trade names of Aquapel (Hercules Powder Company) and Nippelsize (Nippon Oil & Fats), and is easily available. This alkyl ketene dimer is
Although it is widely used as an aid in resin processing or as a sizing agent for paper and textiles, the present invention uses this alkyl ketene dimer for a completely different purpose from that of a sizing agent. are also completely different.

In the present invention, by incorporating an alkyl ketene dimer into the diazo photosensitizer composition,
The exact reason for the marked increase in the density of the dye image formed is still not fully clear;
It is assumed that this is due to the following reasons. That is, this alkyl ketene dimer suppresses permeation of the photosensitive diazonium salt or coupler into the paper substrate in the process of applying the photosensitive agent composition to the paper substrate, and also adsorbs or absorbs the diazo dye formed during development. seems to have the property of retaining bonds.
Thus, the use of the diazo sensitizer composition of the present invention prevents the dye from spreading into the interior, ensuring that the dye is present only in the surface portion of the paper substrate and that the dye is retained on the surface of the alkyl ketene dimer particles. In connection with the presence of the dye in the form of relatively large particles, the density of the dye image formed can be significantly improved and, moreover, desorption of the dye can be effectively prevented.

Furthermore, whereas the sizing agents applied to conventional paper substrates generally cause size destruction when they come into contact with alkaline liquids, the alkyl ketene dimers used in the present invention rather sizing the paper substrates in such alkaline media. In this way, it is possible to suppress the deterioration of the texture and mechanical strength of the copy.

In the present invention, the blending amount of the alkyl ketene dimer mentioned above differs depending on whether it is a one-component photosensitizer or a two-component photosensitizer, and also differs depending on the type of photosensitive diazonium salt. However,
Generally speaking, 0.15 per photodegradable diazonium salt
It is preferably used in an amount of 10 to 10 times by weight, particularly 0.5 to 5 times by weight. That is, if the amount of the alkyl ketene dimer used is greater than the above range, the diazo photosensitive layer tends to become matte and have poor texture, while if it is less than the above range, it is within the above range. It appears that the effect of improving image density is significantly smaller than in the case where the image density is improved.

The diazo photosensitizer composition of the present invention is known per se, except for incorporating the alkyl ketene dimer described above, and any known components can be used according to any known formulation.

As the photosensitive diazonium salt, any diazonium salt can be used as long as it is photodegradable itself and can be coupled with a coupler under normal development conditions. Examples of diazo compounds constituting these diazonium salts include, but are not limited to, the following.

4-Diazo-N,N-dimethylaniline (abbreviation)
MA salt) 4-diazo-N,N-diethylaniline (abbreviation
EA salt) 4-Diazo-N-ethyl-N-β-hydroxyethylaniline (abbreviated as EH salt) 4-Diazo-N,N-bis-β-hydroxyethylaniline 4-diazo-N-methyl-N- β-hydroxyethylaniline 4-diazo-N-ethyl-N-β-hydroxypropylaniline 4-diazo-N-ethyl-N-(β-diethylamino)-ethylaniline 4-diazo-2-chloro-N, N-diethylaniline 4-diazo-2-methyl-N,N-diethylaniline 4-diazo-2-iodo-N,N-diethylaniline 4-diazo-2-trifluoromethyl-N,N-
Diethylaniline 4-diazo-N-ethyl-N-benzylaniline 4-diazo-N-methyl-N-benzylaniline (abbreviation methylbenzyl) 4-diazo-2,5-dibutoxy-N,N-diethylaniline 4-diazo -2,5-diethoxy-N-benzoylaniline (abbreviated as BB salt) 4-diazo-2,5-diethoxy-N-ethyl-N-benzoylaniline 4-diazo-2,5-dibenzyloxy-N-benzoylaniline 4-Diazo-2-chloro-5-methoxy-N-benzoylaniline 4-diazo-2,5-diethoxy-N-benzoyl-methylaniline 4-diazo-2,5-diethoxy-N-benzoyl-oxymethylaniline para Diazodiphenylamine 4-Diazo-2,5,4'-triethoxydiphenylamine 4-diazo-2,5,4'-triethoxydiphenyl-4,4'-bisdiazo-2,2',5, 5'-Tetrahydroxydiphenylmethane bisdiazo-8,8'-dichloro-5,5'-dimethoxybenzidine 4-diazo-2,5-dimethoxyphenyl-ethylsulfide 4-diazo-2,5-diethoxy −4′-methyl−
Diphenylsulfide 4-Diazo-2,5-dibutoxy-N-phenylmorpholin 4-Diazo-2,5-diethoxy-N-phenylmorpholin 4-Diazo-2-methoxy-N-thiomorpholin 4-Diazo -N-phenylpiperidine 4-diazo-N-phenylpyrrolidine 4-diazo-2,5-di-n-butoxy-N-phenylpiperidine 2-diazo-4-methylmercapto-N,N'-
Dimethylaniline 2-diazo-5-benzoylamino-N,N'-
Dimethylaniline 2-diazo-1-naphthol-5-sulfonic acid.

The diazo compounds mentioned above are used as relatively stable diazonium salts as sulfates or hydrochlorides, or are further used as zinc chloride, tin chloride, aluminum sulfate,
It is used as a double salt by et al. Further, stabilization methods such as allylsulfonate (diazonium salt of aromatic sulfonic acid) and diazosulfonate can also be used.

As the acid stabilizer, any organic or inorganic acid can be used, such as sulfosalicylic acid, p-toluenesulfonic acid, citric acid, tartaric acid, oxalic acid, sulfamic acid, maleic acid, phosphoric acid, and the like.

In the case of a two-component diazo photosensitizer composition, a coupler is contained in addition to the above-mentioned essential components. Such couplers are also well known per se, and any compound capable of coupling with the above-mentioned diazonium salts can be used. Suitable examples include, but are not limited to:

Pyrocatechol, resorcin, phloroglycin, pyrogallol, resorcin monoglycol ether, resorcin glycol ether, meta-aminophenol, para-aminophenol, diethylaminophenol, ortho(hydroxyethoxy)phenol, 2,5,6-trimethylphenol, 2-hydroxymethyl Phenol, β-(2-hydroxyphenyl)-propionic acid, 2-(ω-phenylaminomethyl)-phenol, β-(4-methyl-2-hydroxyphenyl)-
Glytaric acid, 2,5-dimethyl-6-(N-dimethylaminomethyl)-phenol, 1,3 dimethyl ether of pyrogallol, N-lauryl-para-aminophenol, N-acyl-meta-aminophenol, metahydroxy- Acetanilide, ortho-N-hydroxydiphenyl-mono-guanidine, para-N-hydroxydiphenyl-bi-guanidine, 2,5-dimethyl-4-morpholinomethylphenol, 2-methyl-5-isopropyl-4- Morpholinomethylphenol, 4-morpholinmethylresorcinol monomethyl ether, 3,3',5-trihydroxydiphenyl 3,3',5,5'-tetrahydroxydiphenyl, 2,2',4,4 '-Tetrahydroxydiphenyl, 2,4,4'-trihydroxydiphenyl-2'-
Sulfonic acid, 2,4,6,3',5'-pentahydroxydiphenyl, 2,2',4,4'-tetrahydroxydiphenyl sulfide, 2,3-dioxynaphthalene, β -naphthol, α-naphthol, 1,6-dioxynaphthalene, 2,7-dioxynaphthalene, 2,3-dihydroxynaphthalene-6-sulfonic acid, 2-naphthol-3,6-disulfonic acid, 2,7 -dihydroxynaphthalene-3-sulfonic acid, 2,8-dihydroxynaphthalene-6-sulfonic acid, 1,8-dihydroxynaphthalene-8-sulfonic acid, 1,8-aminonaphthol-5-sulfonic acid, 2, 7-dihydroxynaphthalene-3,6-disulfonic acid, 1,8-benzoylaminonaphthalene-2-sulfonic acid, 1,8-dihydroxynaphthalene-6-sulfonic acid, 2-hydroxy-3-naphthoic acid-N- β-hydroxyethylamide, 2-hydroxy-3-naphthoic acid-N,N-bis-β-hydroxyethylamide, 8-hydroxy-2-naphthoic acid-hydroxyethylamide, 1-(N-carboethoxy methylamino)-8-naphthol-4-sulfonic acid, 5-(para-nitro)-benzamido-1-naphthol, 1-hydroxynaphthyl-7-phenylguanidine 2-hydroxy-naphthyl-8-biguanidine, 1- Naphthol-3-(N-β-hydroxyethyl)-sulfonamide, 1-naphthol-3-(N-O-methoxyphenyl)-sulfonamide, bis-[5-oxy-7-sulfonaphthyl (2)〕
Amine, N,N-bis[1-oxy-3-sulfonaphthyl(6)]-thiourea 1-phenyl-3-methylpyrazolone(5), acetoacetic acid anilide, 1-phenyl-3-carboxy Pyrazolone, acetoacetate cyclohexylamide, acetoacetate benzylamide, cyanoacetanilide, cyanoacetomorpholine, 1-(3'-sulfoamide)-phenyl-3-methylpyrazolone-5, 1-(4'- carboxy-ethylphenyl)-3-dodecyl-pyrazolone-5, 8-hydroxy-1,2-naphthiimidazole, 2-methyl-4-hydroxybenzimidazole, 7-methyl-4-hydroxybenzothiazole, 1,7- Dimethyl-4-hydroxybenzotriazole, 3-hydroxythiophene-5-carboxylic acid, 1,3,4-cyclopentatrione.

These couplers can be used alone or in combination of two or more.

In addition to the above-mentioned essential components, the diazo photosensitive composition of the present invention may contain compounding agents known per se, such as wetting agents, stabilization aids, development accelerators, extenders, dispersants, dyes, etc. Each of these components is dissolved or dispersed in a solvent such as water to prepare a coating composition. Representative examples of this prescription are as follows.

(1) Two-component diazo photosensitive composition Diazonium salt 0.1 to 4.0% Coupler 0.1 to 5.0% Acid stabilizer 2 to 10.0% Alkyl ketene dimer 0.15 to 40.0% Development accelerator 2 to 10.0% Extender 0 to 10.0% Dispersant 1 to 1.0% Dye 0 to 0.003% Solvent Remaining amount (2) One-component diazo photosensitizer composition Diazonium salt 0.1 to 4.0% Acid stabilizer 2.0 to 10.0% Alkyl ketene dimer 0.15 to 40.0% Stabilizing agent 0 to 10.0% Extender 0 to 10.0% Dye 0 to 0.003% Solvent Remaining amount As the above-mentioned stabilizing aid, zinc chloride, thiourea, etc. can be used, and as the development accelerator, polyhydric alcohol such as glycerin, ethylene glycol, diethylene glycol, etc. can be used. can. Further, as the extender, dextrin, gum arabic, colloidal silica, polyvinyl acetate resin emulsion, starch, etc. are used. As the dye, a blue dye such as methylene blue or patent blue, or a fluorescent whitening agent is suitably used in order to clarify the photosensitive surface or further increase the whiteness of the background.

When producing these photosensitive compositions for coating,
Each component except the alkyl ketene dimer is dissolved or dispersed in water, and then an emulsion of the alkyl ketene dimer is added to this solution. Emulsions of alkyl ketene dimers can be prepared by melting the alkyl ketene dimer and pouring the melt into hot water with stirring, or by dissolving the alkyl ketene dimer in a water-miscible organic solvent such as methanol and adding the solution. It can be easily produced by pouring it into water.

It is important from the viewpoint of the formation of the photosensitive layer that the particle size of the alkyl ketene dimer to be added is below the so-called emulsion size, and is generally preferably in the range of 0.1 to 15 microns, particularly 0.2 to 8 microns.

As the substrate on which the photosensitive composition is coated, various papers such as ordinary tissue paper, art paper for copying paper, and coated paper are advantageously used. Processed or foamed synthetic paper, nonwoven fabric or woven fabric, metal foil, or a laminate thereof may be used.

The photosensitive composition can be applied by means known per se,
For example, the photosensitive composition can be applied by using a coating roller, an air knife coater, a bar coater, a blade coater, a reverse coater, a hard coater, spraying, dip coating, etc. The photosensitive composition coated on the substrate is dried by a known method per se. and use it as photosensitive paper.

The coating amount of the photosensitive composition of the present invention varies depending on the type of substrate and the development method, but generally speaking, the coating amount of the diazonium salt is 0.05 to 0.05.
It may be 0.2 g/m ² , particularly in the range of 0.09 to 0.15 g/m ² .

According to the present invention, by incorporating an alkyl ketene dimer into a photosensitizer composition, the amount of diazonium salt coated can be reduced to about 80% of the conventional amount, or the amount of diazonium salt in the composition can be reduced Even when the content is reduced, it is a remarkable advantage that it is possible to form a dyed image with a density equal to or higher than that when using a conventional diazo photosensitive composition. It is also a remarkable feature of the present invention that the sensitivity of the diazo-sensitive layer during exposure can be significantly increased in connection with the ability to form a dye image with high density while reducing the amount of diazonium salt used. This is a great advantage.

The diazo photosensitive composition of the present invention can be advantageously used in a diazo copying method using a wet developer.

For the two-component diazo photosensitizer composition mentioned above, a developer containing a well-known alkaline agent is used, and for the one-component diazo photosensitizer composition, a developer containing a well-known alkaline agent is used. and a water-soluble coupler are used. A typical example of its prescription is as follows.

(A) Two-component developer Alkaline agent 3 to 50% Wetness regulator 0 to 5% Anti-tarnish agent 0 to 10% Solvent Remaining amount (B) One-component developer Alkaline agent 1 to 5% Coupler 0.5 to 4 % Discoloration inhibitor 0 to 10% Water Remaining amount As the alkali agent mentioned above, in the case of a two-component system, organic bases such as monoethanolamine, diethanolamine, triethanolamine, morpholine, and guanidine are preferably used; In the case of component systems, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium tetraborate, potassium carbonate, etc. are used.

As the anti-wetting agent, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, and polyvinyl alcohol are preferably used in order to completely wet the paper substrate.

As the discoloration inhibitor, a weak reducing agent such as thiourea or sodium thiosulfate is used for the purpose of preventing discoloration during storage of copies.

The invention will be explained in detail in the following examples.

Example 1 As a one-component type diazo photosensitive paper 4-Diazo-2,5-diethoxy-N-benzoylaniline chloride zinc chloride double salt...12g Citric acid...8g Dextrin...20g Thiourea...5g Methylene Blue B-Conc. ...0.1g Alkyl ketene dimer (Akoben 12; manufactured by Dekk Harkyures Co., Ltd.) ...20g Add water to bring the total volume to 1, and apply this solution to base paper for photosensitive paper (manufactured by Sanyo Kokusaku Pulp Co., Ltd.; SK) using an air knife coater. Base paper 68Kg)
and dried to form a diazo photosensitive sheet. This photosensitive paper sheet is layered with a document sheet with an image on it and exposed to light from a mercury lamp to form a latent image of diazonium salt. After that, a developer with the following formulation is applied uniformly to the surface using a roller coating method. When it was deposited and developed, a copy having a clear blue-purple image with high contrast was obtained.

developer prescription 1-hydroxynaphthalene-4- Sodium sulfonate...14g Potassium carbonate...30g Sodium bicarbonate...10g Sodium thiosulfate...50g Borax...10g Nonionic surfactant ……0.01g Add water to bring the total volume to 1 Example 2 As a one-component type diazo second original photosensitive paper 4-Diazoorthochloro-diethyl Aniline chloride zinc chloride double salt...20g Tartaric acid...7g Boric acid...2g Dextrin...20g Methylene blue B-conc...0.1g Dodecyl ketene dimer...50g Add water to bring the total volume to 1.

This solution is applied to a translucent second original image base paper (Tracing Paper SZ, manufactured by Tomoekawa Paper Industries Co., Ltd.) in the same manner as in Example 1, and dried to obtain a wet diazo second original image sensitive paper. This second original photosensitive paper was used in Example 1.
The second original copy was developed in the same manner as in Example 1 using the same developer as that used in Example 1, and a clear image with high contrast was obtained.

Example 3 As a one-component type diazo photosensitive paper 4-Diazo-2,5-diethoxy-N-benzoyl-methyl-aniline chloride zinc chloride double salt...12g Citric acid...8g Dextrin...10g Polyvinyl acetate (Movinyl DC) ; manufactured by Hoechst Gosei Co., Ltd.) ...10 g Methylene Blue B-conc. ...0.1 g Alkyl ketene dimer (New Bell size; manufactured by Nihon Yushi Co., Ltd.) ...20 g Add water to bring the total amount to 1.

This solution was applied in the same manner as in Example 1, dried to form a diazo photosensitive sheet, and then copied in the same manner as in Example 1 to obtain a blue-purple copy with a clear image with high contrast. .

Example 4 As a one-component type diazo black line sensitive paper 4-Diazo-2,5-diethoxyphenylsulfide chloride zinc chloride double salt...15g Tartaric acid...5g Sulfamic acid...2g Aluminum sulfate...2g Zinc sulfate ...2g Polyvinyl acetate (Movinyl DC; manufactured by Hoechst Gosei Co., Ltd.) ...10g Patent Blue ...0.12g Decylketene dimer ...20g Add water to bring the total amount to 1.

This solution is applied to base paper for diazo photosensitive paper (manufactured by Sanyo Kokusaku Pulp Co., Ltd.; SK base paper 68 kg base) using an air knife coater, and dried to obtain diazo black line photosensitive paper. This photosensitive sheet was exposed in the same manner as in Example 1, and then developed in the same manner as in Example 1 using a developer with the following formulation. A copy with a clear black image with high contrast was obtained. Obtained.

Diazo developer for black lines Phloroglycin...8g Resorcinol...2g Sodium benzoate...30g Carbamic acid ethyl ester...10g Sodium thiosulfate...50g Sodium borate...5g Add water to bring the total volume to 1.

Example 5 As a two-component type diazo photosensitive paper 4-Diazo-2,5-dipoxy-N-phenylmorpholine chloride zinc chloride double salt
...15g 2-hydroxy-3-naphthoic acid-N-β-hydroxyethylamide ...12g Tartaric acid ...7g Boric acid ...2g Zinc chloride ...1g Rice starch ...5g Polyvinyl acetate ...5g Thiourea ... 2g Sorbitt...3g Hexadecylketene dimer (New Pel size)...15g Methylene Blue B-Conc...0.12g Add water to bring the total amount to 1.

This solution is applied to base paper for photosensitive paper (manufactured by Sanyo Kokusaku Pulp Co., Ltd.; SK base paper 68 kg base) to a coating weight of about 1.4 g/m ² using an air knife coater, and dried to form a diazo photosensitive paper sheet. A diazo copying machine with a built-in fluorescent lamp (manufactured by Sanda Kogyo Co., Ltd.;
When exposed using an ED-200 model and developed using a developer having the following formulation, a copy having a clear blue image with high contrast was obtained.

developer prescription Monoethanolamine ……200g Diethylene glycol ……200g Sodium acetate...20g ethylene glycol mono Methyl ether...100g Add water to bring the total volume to 1.

Example 6 As a two-component type diazo photosensitive paper 4-Diazo-N,N-diethylaniline Chloride zinc chloride double salt...15g 2,3-dihydroxynaphthalene-6- Sodium sulfonate...25g Tartaric acid...30g Thiourea...50g Zinc chloride...10g Magnesium chloride...40g Patent Pier Blue ……0.12g Tridecyl ketene dimer...25g Add water to bring the total volume to 1.

This solution was applied in the same manner as in Example 5, dried to form a diazo photosensitive sheet, exposed in the same manner as in Example 5, and developed with a developer having the following formulation. A copy with a blue-purple image was obtained.

developer prescription Diethanolamine...150g Morpholine...50g Cationogen L (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)...5g Ethylene glycol ……100g Add water to bring the total volume to 1.

Example 7 As a two-component type diazo photosensitive paper 4-Diazo-2,5-dipoxy- N-phenylmorpholine chloride Zinc chloride double salt...20g Bis-[5-hydroxy-7-sul Honaphthyl (2)] Amine ……30g Tartaric acid...30g Magnesium chloride...40g 1,3,6-naphthalenetri Sodium sulfonate...30g Methylene blue B-conc...0.1g Acopel 12 (Deitsuk Ha (manufactured by Kyures) ……25g Add water to bring the total volume to 1.

This solution was coated in the same manner as in Example 5 to form a photosensitive sheet, and when it was copied in the same manner as in Example 5, a clear copy with a high blue-purple contrast was obtained.

Claims (1)

[Scope of Claims] 1. A diazo photosensitizer composition containing a photosensitive diazonium salt, an acid stabilizer, and an alkyl ketene dimer. 2. The composition according to claim 1, wherein the alkyl ketene dimer is contained in an amount of 0.15 to 10 times the weight of the photosensitive diazonium salt. 3. The composition of claim 1, wherein the alkyl ketene dimer is contained in the form of emulsion particles. 4 The alkyl ketene dimer has the formula Claim 1 is a compound represented by the formula, wherein R is an alkyl group having 9 or more carbon atoms.
Compositions as described in Section. 5. The two-component diazo photosensitizer composition according to claim 1, further comprising a coupler capable of coupling with the photosensitive diazonium salt.