JPS6273255A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve the sensitivity and the yellowing shade property of the composition, without giving bad effects to a developing allowability and an aptitude of a ball pen, by incorporating a specific o-naphthoquinone diazide compd. and a specific novolak resin to the titled composition, and by specifying <=0.45mm mol/g a molar ratio of the o-naphthoquinone diazide which is a photosensitive unit in the composition. CONSTITUTION:The titled composition is composed of the o-naphthoquinone diazide compd. (A) which is the o-naphthodiazidosulfonic acid ester of the polycondensate of a polyhydroxyphenol and a ketone or an aldehyde, and the novolak resin (B) obtd. by copolymerizing and condensing a mixture of a cresol and a phenol comprising a mixed cresol of m-cresol and p-cresol and a phenol in a molar ratio of (6.0:4.0)-(10.0:0.0) and the aldehyde. The molar ratio of the o-naphthoquinone diazide compd. which is the photosensitive unit in the composition composed of the components (A) and (B) is <=0.45mm mol/g. The compounding ratio of the o-naphthoquinone diazido compd. (A) and the novolak resin (B) is 1-99wt%, preferably 8-40wt% the component (A) on the total weight basis of the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition, and more specifically, a positive photosensitive composition that has excellent sensitivity and printing blur characteristics without adversely affecting development tolerance and ballpoint pen suitability. The present invention relates to a photosensitive composition suitable for use in plain medium printing plates and the like.

[Back Chain of the Invention] Photosensitive compositions consisting of various 0-nano-1 hequinone diazide derivatives and novolac resins are used in positive-working photosensitive lithographic printing plates, but conventionally used photosensitive compositions However, no material has been found that satisfies sensitivity and blurring characteristics without adversely affecting development tolerance and suitability for ballpoint pens.

For example, if the proportion of the photosensitive unit 0-naphthoquinonediazide in the photosensitive composition is reduced, sensitivity increases and printing blur characteristics can be improved, but the development tolerance during development becomes narrower. Furthermore, there was a drawback that the ballpoint pen suitability of the automatic registration mark drawing machine was significantly reduced, making it impractical.

In addition, in order to increase the sensitivity, for example,
No. 19 includes the addition of hydantoins and orthobenzoic acid sulfide, JP-A-55-73045 includes the addition of a condensation product of hydroxybenzophenone and formaldehyde, and JP-A-52-80022 includes the addition of a condensation product of hydroxybenzophenone and formaldehyde. It has been proposed to add 5-membered cyclic acid anhydrides such as phthalic anhydride and 79421 anhydride, but neither of these methods can provide sufficient sensitivity, or even if the sensitivity can be increased, the development tolerance during development will be significantly reduced. However, there were drawbacks such as the paper becoming narrower, or the suitability of the automatic registration mark drawing machine for ballpoint pens being significantly reduced, making it impractical.

In the above photosensitive composition, increasing the sensitivity is one of the most important issues in order to reduce the exposure ω required for image formation.

In addition, printing blur refers to a photosensitive printing original plate having a photosensitive layer made of a photosensitive composition on a support such as a surface-treated aluminum base, and a film original plate of the original is placed on the photosensitive layer of the photosensitive printing original plate. The photosensitive layer is exposed to light and corresponds to the brightness and darkness of the image on the original. [Depending on the strength of the tip of the knife, hardened and unhardened parts are formed, and the unhardened parts are dissolved and removed with a developer to form the image area. In a lithographic printing plate prepared by forming a non-image area, if the film base plate is exposed to light without being brought into close contact with the photosensitive layer made of the photosensitive composition when applying the film base plate, the photosensitive layer may be exposed to light. This is a phenomenon in which the formed image becomes blurred, and how reliably and quickly this contact is achieved is important from the point of view of work efficiency.

Furthermore, when performing so-called multi-sided printing in which a plurality of film originals are successively printed on a photosensitive lithographic printing plate in different positions, the positions of the originals may be marked on the photosensitive layer in order to align the film originals. At this time, an oil-based ballpoint pen is usually used as the writing instrument for marking, but if the solvent of the ink of the ballpoint pen is an organic solvent, especially a high boiling point solvent such as a glycol-based solvent, the ink may affect the photosensitivity of the photosensitive lithographic printing plate. The photosensitive layer made of the composition is eroded and dissolved. If the marked area is an image area, if development processing is performed as it is, the photosensitive layer of the mark trace in the image area may be removed, causing a malfunction in which the mark trace is reproduced on the printed matter during printing. For this reason, a photosensitive composition is desired that has the property of being resistant to erosion by ballpoint pen ink (hereinafter referred to as "ballpoint pen suitability").

Furthermore, development tolerance refers to the ability to maintain a certain level of stable reproducibility even in the case of a developer that dissolves and removes uncured areas during the preparation of the lithographic printing plate, even when the developing ability is reduced or the developer is in excess. It is one of the important properties practically required for photosensitive compositions.

As a result of intensive studies on photosensitive compositions used in lithographic printing plates, etc., the present inventors found that they contain a specific 0-naphthoquinonediazide compound and a specific novolac resin, and that 0-naphthoquinonediazide, which is a photosensitive unit occupied in both, contains a specific 0-naphthoquinonediazide compound and a specific novolak resin. A photosensitive composition in which the molar ratio of L2
The inventors have discovered that the characteristics satisfy the above characteristics and have come up with the present invention.

[Object of the Invention] Therefore, an object of the present invention is to provide a photosensitive composition that has excellent sensitivity and printing blur characteristics without adversely affecting development tolerance and suitability for ballpoint pens.

[Structure of the Invention] The above object of the present invention is to obtain an O-naphthoquinonediazide compound FA which is an O-naphthoquinonediazide sulfonic acid ester of a polycondensation resin of polyhydroxyphenol and a ketone or aldehyde; Cresol and p-
Mixing with cresol The molar ratio of cresol and phenol is 6.0: 4.0 to 10.0 + 0.0
a novolak resin [B] obtained by copolycondensing cresol phenols and aldehydes, and the 0-naphthoquinonediazide compound [A] and the novolak resin [B]
This is achieved by a photosensitive composition in which the molar ratio of 0-naphthoquinonediazide, which is a photosensitive unit, is 0.45 mmol/g or less in the combined composition.

Blank space below [Specific constitution of the invention] The 〇-naphthoquinonediazide compound [△] which is the 0-naphthoquinonediazide sulfone H ester of the polycondensation resin of polyhydroxyphenol and ketone or aldehyde used in the present invention is as shown below. It is a compound.

As the polyhydroxyphenol which is a monomer of the backbone polymer, catechol, (mebul)resorcin, hydroquinone, pyrogallol, 70-glucine, etc. are preferably used. Further, more preferred is pyrogallol. As the ketone or aldehyde, acetone, formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, etc. are preferably used, and acetone is more preferable.

A generally known method is applied to synthesize the polycondensation resin of polyhydroxyphenol and ketone or aldehyde. Polyhydroxyphenol is dissolved in ketone or aldehyde, or an appropriate solvent if necessary, and hydrochloric acid,
A polymer is obtained by causing polycondensation in a suitable acid such as phosphorus oxychloride or oxalic acid. As for the polycondensation conditions, a synthesis method in which a polycondensation reaction is carried out at a high temperature from the initial stage of polymerization is preferably used compared to known methods. For example, a catalyst such as hydrochloric acid, sulfuric acid, oxalic acid, or phosphorous oxychloride is added dropwise to a mixture of polyhydroxyphenol, a ketone or aldehyde compound, and an optional solvent such as dioxane, methanol, ethanol, tetrahydrofuran, or water. Preferably, a formulation is used in which the flow reaches a steady state at the same time.

The molecular weight of the polyhydroxy polymer compound obtained by these methods is 3, according to the number average molecular fJIMn (polystyrene standard) determined by the gel permeation method (GPC method).
00 x 102~2,00 x 103. , tJl
Average molecule ff1Mw FL&5.00 x102~4
．． 00 x 10' is preferably used, more preferably Mn is 4.00 x lo to 1.50 x lo, M
W is 7,00 x 102 to 3.00 x 101, preferably 1, Mn is 5.00 x 10" to 1.10 x 10
3. Mw is 8.00 x 102 to 2.00 xlo.

These polyhydroxyphenol polymerized O-naphthoquinonediazide sulfonic acid esters can be easily obtained by the following synthetic method.

A polyhydroxyphenol polymer is dissolved in a suitable solvent such as dioxane, 0-naphthoquinone diazidi-1-sulfonic acid chloride is added thereto, and alkali carbonate is added dropwise to the equivalence point to easily esterify it.
be synthesized.

The condensation rate of 0-naphthoquinonediazide sulfonic acid chloride with respect to OHM of this esterified product is preferably 5 to 60% (% relative to one OH group), more preferably 7 to 60%.
It is 50%.

Monovalent phenols, such as phenol and cresol, were used as monomers for the backbone polymer, and in the same manner as above (
When a 0-naphthoquinonediazide sulfonic acid ester of phenol or cresol polymer is used, sufficient sensitivity is obtained, and furthermore, development tolerance during development and suitability for ballpoint pens are also poor.

Novolac &1rFt [B] used in the present invention is m
- Mixture of cresol and p-cresol The mixing ratio of cresol and phenol is 6.0:4.0 to 10 in molar ratio.
It is a resin made by copolycondensing 0:0.0 of cresol phenols and aldehydes in the presence of an acid catalyst. Among these, preferred resins include m-cresol and p-cresol mixed novolac resins in which the molar ratio of cresol and phenol is 7.0:3.0 to 9.5 to 1:1 of cresol phenols. It is.

If the molar ratio of phenol to mixed cresol exceeds 4.0, although the sensitivity is markedly increased, the N capacity during development is narrow and suitability for a ballpoint pen is reduced, which is not preferable.

The molecular weight (polystyrene standard) of the novolak resin [B] of the present invention has a limb average molecular mMw of 3. OO×103 to 1,50×404 is preferable, more preferably 4
,00 × 1033 to 1,20 × 10”, more preferably 5,00 × 1033 to 1.00 ×
There are 103 cows. Further, the ratio Mw/Mn (degree of dispersion) of the number average molecule of the suspended average molecular can j~4W to the number average molecule of the novolac resin is preferably 2 to 14, more preferably +, J
l 3 to 9.

The present invention contains an O-naphthoquinonediazide compound [△1 and a novolac resin [B] which is a ester of (J) O-soft quinonediazide sulfonic acid of a polycondensation resin of polyhydrogen 1-1 xyphenol and ketone or aldehyde. -7゛-[Ratio of -7゛-[L ratio of J51j O-buftoquinone diazide sensitization If in the silk composition is 0.45]
It is less than mmol/al, but it is very good (from 0.25 to 0.25 mmol/al).
It is 45 mmol/Q.

If the molar ratio exceeds 0.45 mmol/g, it is unfavorable in terms of sensitivity and blurring characteristics.

The mixing ratio of the O-naphthoquinonediazide compound [A] and the novolak resin [B] in the present defense is 1 to 99% of the O-naphtho4-nondiazide compound [A] to the gold side of both materials.
The weight percentage is preferably 5 to 60% by weight, more preferably 8 to 40% by weight.

In addition to the above-mentioned components, the photosensitive composition of the present invention may contain an exposure-visible image imparting agent and a dye. As the exposure visible image imparting agent, a substance that generates an acid upon exposure is generally used, and as the dye, a compound that forms a salt with this acid is generally used.

As a compound that generates acid upon exposure to light, the following general formula ■
or trihaloalkyl or diazonium salt compounds represented by (■) are preferably used.

General formula ■ Xa is a trihaloalkyl group having 1 to 3 carbon atoms, W is N
, 51Se or P, 7 is 01N1S, Sg or P,
Y represents a chromophore group and a nonmetallic atomic group necessary for cyclizing W and 7.

(e) General formula HAr-N2-x Ar represents an aryl group, and X represents a counter ion of an inorganic compound.

The trihaloalkyl compound represented by the general formula (2) includes compounds represented by the following general formula (1), Iv, or V.

General formula ■ General formula ■ Xa General formula V It represents an aryl group or a heterocyclic group, and n represents 0, 1 or 2.

Specific example compounds include quaternary sadiazole compounds having a benzofuran ring such as /f as compounds of general formula (1);
2-trichloromethyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
Examples include 3,4-oxadiazole compounds.

In addition, as a compound of formula IV or -69, JP-A No. 5
1-(2,4-
Lame 1-xy4-styryl)-6-dolychloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6-+1-methoxystyryl-5-1-riazine compound, 2. /4-bis-(1-lichloromethyl)-6
-+1-dimethylaminostyryl-8-triazine compounds and the like.

On the other hand, the diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and a counter ion of an inorganic compound is recommended as the counter ion moiety. Specific examples include aromatic diazonium salts in which the anion moiety of the diazonium salt is at least one of fluorinated arsenic ions, arsenic fluoride ions, antimony fluoride ions, andymonium chloride ions, tin chloride ions, bismuth chloride ions, and zinc chloride ions. A salt, preferably a varadiazophenylamine salt.

m contained in the total photosensitive ISi composition of the exposure visible image imparting agent is 0.01 to 20T! ￥ω% is appropriate, preferably 0.1 to 20 ω%, more preferably 0.2 to 1
It is 0 weight ω%.

On the other hand, as the dye, any compound which generally forms a salt with an acid can be used, and examples thereof include triphthonylmethane dyes, cyanine dyes, diazo dyes 11, and styryl dyes. Specifically, Victoria Pure Blue 80. Ethyl violet, Crystalba, IA
Let, Brilliant Green, Paysic Tsukushin,
Eosin, FJnorphthalein, 4-Silenol Blue, Congo Red, Mackai 1-Green, Oil Blue #603, Ail Pink #312, Cresol Red, Auramine, 4,-1'l-di]bruaminophenyliminonaf 1 to quinone, leucomalachite green, leucolithal violet, and the like.

The amount of this dye added in the total composition of the photosensitive layer is about 0.01~
It is preferably 10% by weight, more preferably 0.05 to 8% by weight.

In addition, various additives can be added to the photosensitive composition of the present invention depending on various purposes.

For example, to improve the coating properties, surfactants such as cell [1-alkyl ether, knot surfactants, silicone compounds, etc.] may be used, and acid anhydrides, such as geltaric anhydride, may be used as sensitizers. , itaconic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, etc. It is also possible to add plasticizers such as phosphorus ester, phthal resistant ester, polyvinyl butyl ether, etc. as physical property improvers of the coating film. be.

The content of these additives varies depending on their type and purpose, but generally ranges from 0.01 to 1% by weight in the total photosensitive composition.
is appropriate.

The photosensitive composition of the present invention can be prepared by dissolving each component of the 0-naphthoquinone diazide compound [A] and the novolak resin [B] in a solvent, and applying and drying the solution on the surface of a suitable support. A photosensitive layer such as a ribbon type photosensitive lithographic printing plate or a photoresist can be formed. Examples of solvents that can be used include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethylformamide,
Examples include dimethyl sulfoxide, dioxane, acetylene, cyclohexanone, trichloroethylene, and methyl edyl ketone. These solvents can be used alone or in combination of two or more.

The coating method can be conventionally known methods such as spin coating, wire bar coating, dip coating, ]] near knife coating roll coating, plate coating, curtain coating, and the like.

Supports include metal plates such as aluminum, zinc, copper, and steel;
and metal plates, paper, plastic films and glass plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper coated with resin, paper covered with metal foil such as aluminum, and hydrophilized. Includes treated plastic films and the like.

Anodized aluminum is used as the base material in the positive photosensitive bamboo lithographic printing plate using the photosensitive composition of the present invention. Aluminum alloys including silicon, magnesium, iron, copper, zinc, manganese, chromium, bismuth, nickel, etc. are included.

The aluminum material used in the positive-type photosensitive bamboo lithographic printing plate using the photosensitive composition of the present invention is a plate-shaped (including foil-shaped) aluminum material manufactured by the soup rolling method, molten aluminum potting, etc. can be used. Aluminum materials manufactured by hot-dip aluminum plating are made by plating a metal plate such as a steel plate in a hot-dip aluminum bath to a thickness of 7.
A plate with an aluminum layer on μml.

The aluminum material is subjected to a graining treatment. Next, it is preferable that a surface treatment such as a desmutting treatment and, if necessary, a sealing treatment is performed.

Known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method.

Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing. Abrasives used in mechanical polishing include alumina, silicon carbide, chromium oxide, red iron, tungsten carbide, boron carbide, diamond, sand, silica, granite, limestone, artificial emery, steel balls, iron pieces, and aluminum. Examples include random, pumice stone, and magnesium oxide. Examples include etching by electrolysis. In producing a roughened aluminum material, the various methods described above can be used alone or in combination, depending on the composition of the aluminum material. Preferred is electrolytic etching yj
It is the law.

Electrolytic etching uses one or two of the inorganic acids listed in
This is done in a mixed bath. Among these, preferred are sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, or a mixture of two or more thereof, and particularly preferred is a bath containing nitric acid or hydrochloric acid as a main component. In addition, alcohol, anhydrous acid resistant,
Additives include organic acids such as unsaturated carboxylic acids, inorganic substances such as potassium dichromate, and hydrogen peroxide, as well as coid substances such as gelatin and starch, as well as glycerin, other viscous substances, and surfactants. It can be added to the bath as

These additives may be used alone or in combination of two or more. The electrolytic etching bath is prepared by adding the above-mentioned acids and, if necessary, the above-mentioned additives to water.

When performing electrolytic etching, degreasing and cleaning can be performed to remove oil, fat, rust, dirt, etc. from the surface of the aluminum material. Degreasing treatments include solvent degreasing that removes dirt using petroleum-based solvents or chlorinated hydrocarbons such as trichlorethylene and perchlorethylene, and solvent degreasing that uses nonionic surfactants and solvents such as trichloroethylene and chlorine. ■Mulsion degreasing using a solution emulsified with water, where alkaline chemicals are included 3! Examples include alkaline degreasing by boiling in II solution, electrolytic degreasing, and the like.

Examples of alkaline chemicals used in alkaline degreasing include helium hydroxide, sodium carbonate, sodium silicate, and sodium phosphate, and a Wi'lli activator can be added.

After graining, if necessary, desmutting is performed using an alkali or liquor solution to neutralize the material, followed by washing with water.

The aluminum material used in the present invention is then subjected to anodization treatment. As an electrolytic solution, a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. is used, and aluminum cum is electrolyzed with an anode.
An anodic oxide film is formed on the aluminum surface.

In the present invention, "using an aluminum material provided with an anodized film as a base material" means that the anodized aluminum material may be used as it is as a support for a lithographic printing plate, or the anodized aluminum material may be used as a support for a lithographic printing plate. This means that the material may be subjected to treatments such as surface treatment or lining. This surface treatment includes, for example, a pore sealing treatment performed after the anodizing treatment, undercoating with an aqueous solution of a water-soluble polymer compound or a metal salt, and the like. The sealing treatment includes boiling water treatment, steam treatment, sodium silicate treatment, dichromate solution treatment, and the like.

Moon hole treatment is performed immediately after anodizing treatment.

If the roughened aluminum material is as thin as foil,
A metal plate, plastic film, paper, etc. may be attached to the back surface directly or via an adhesive layer.

The water-soluble polymer compound mentioned above is preferably one having a solubility of 0.01% or more. Preferred water-soluble polymer compounds include natural polymer compounds such as gum arabic, starch, dextrin, sodium alginate, and gelatin, water-soluble cellulose compounds, such as water-soluble salts of carboxyalkyl cellulose, methyl, ethyl, propyl, etc.), alkylcelluloses such as methylcellulose, hydroxymethylcellulose, human [1xethylcellulose, hydroxypropylcellulose, etc.], polyacrylic acid or its water-soluble salts, polymethacrylic acid or its water-soluble salts, Synthetic polymer compounds such as acrylic copolymer or water-soluble salt thereof, methacrylic acid copolymer or water-soluble salt thereof, styrene-maleic anhydride copolymer, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, etc. Water-soluble salts of the compounds include sodium salts and potassium salts.

The above various water-soluble polymer compounds may be used alone or in combination of two or more. Among water-soluble polymer compounds, starch,
Natural polymer compounds such as dextrin and water-soluble cellulose compounds are preferred. Also, the molecular sum is 500 to 1
,000,000 is preferably used.

Water-soluble salts used with water-soluble polymer compounds are preferably those having a solubility of 0.01% or more, particularly inorganic acids or 11 ftI calcium, magnesium, zinc, barium, strontium, cobalt, manganese, and nickel. and silicon salts. Representative organic acids are salts of carboxylic acids such as acetic acid, propionic acid, butyric acid, succinic acid, benzoic acid, salicylic acid and acedelacetonate. Typical inorganic acid salts include chloride, bromide, chlorate, bromate, iodide, iodate, nitrate,
Sulfates and phosphates. The water-soluble salts may be used alone or in combination of two or more.

As water-soluble salts, organic acid salts are particularly preferred, and calcium, magnesium, barium and zinc salts are particularly preferred. The film of the layer containing the water-soluble polymer compound and water-soluble salt formed by this method is 0.001 to 1
mQ/d v' is preferred, especially 0.05 to 0.5
m(1/d v2 is preferred. In addition, the surface can be treated with an aqueous solution of fluorozirconate.

The photosensitive lithographic printing plate and photoresist to which the photosensitive composition of the present invention is applied can be used in the same manner as those conventionally used. For example, a transparent positive film is exposed to a light source such as an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, and then developed with an alkaline developer, leaving only the unexposed areas on the surface of the support, creating a positive-positive relief. A statue is formed.

Examples of alkaline developers include sodium hydroxide,
Examples include aqueous solutions of alkali metal salts such as potassium hydroxide, sodium carbonate, sodium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate.

The concentration of the alkali metal salt is preferably 0.1 to 10% by weight. Further, an anionic surfactant, an amphoteric surfactant, or an organic solvent such as alcohol can be added to the developer as required.

The following margin [Specific effects of the invention] As explained above, in the photosensitive composition of the present invention,
The composition contains a specific O-naphthoquinonediazide compound [A] and a specific novolak resin [B], and the molar ratio of O-naphthoquinodine azide, which is a photosensitive unit, in the composition is 0.4.
By applying 5 mmol/g or less and 1, it was possible to apply fN+ to a lithographic printing plate and provide excellent characteristics in terms of sensitivity, J, and printing blur without adversely affecting development tolerance and suitability for ballpoint pens. .

(Examples) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 After degreasing an aluminum plate with a thickness of 0.24 mm in a 5% sodium hydroxide aqueous solution, it was degreased in a 0.5 molar hydrochloric acid aqueous solution at a temperature of 25° C., a current density of 60 A/di2, and a treatment time of 30 An electrolytic etching process was performed for the stripes f1 for 2 seconds. Next, a desmut treatment was performed using a 5% aqueous solution of prinium to hydroxide, and then an anodic acid treatment was performed in a sulfuric acid solution. Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.

Subsequently, a photosensitive coating solution having the following composition was applied to the aluminum support so that the molar ratio of 0-naphthoquinonediazide photosensitive units to the combination of photoreceptor [I] and novolac resin III was 0.40 mmol. /g, coated using a rotary coater, and dried at 100°C for 4 minutes to obtain a photosensitive lithographic printing plate (A).

(Photosensitive coating liquid composition) 0-pututoquinone-(1,2)-diazide-<2)-5
- Ester compound of sulfonic acid chloride and pyrogallol/acetone polycondensation resin (number average molecular weight Mn=100
0, weight average molecule @Mw = 1500), (condensation rate 30
(mol%, hereinafter referred to as photoreceptor [T]) 1.35q Copolycondensation resin of phenol, m-1p-mixed cresol, and formaldehyde (molar ratio of phenol and stone-〇-mixed cresol is 2.0 + 8.0, Weight ffl average - IJIMw = 7500, dispersity Mw/Mn = 5, hereinafter referred to as "novolac resin [■]") 6.750p
Novolak resin synthesized from -tert-octylphenol and formaldehyde and naphthoquinone-(1,
2) Esterified product with -diazide-(215-sulfonic acid chloride) 0.164 Q Oil Blue #603
(manufactured by Oriental IL1) o, oa.

2-]-]lichloromedyru-5-β-(2'-benzofuryl)vinyl]-1.3. /1-J xadiazole
0.03 (1 ethyl cellosolve 6 g () memethicellosolve 33 Q The amount applied after drying is approximately 20
It was mQ/dv'.

The molecular weight and degree of dispersion of the pyrogallol acetone resin and copolycondensation resin were measured using GPC (gel permeation chromatography). The GPC measurement conditions are as follows.

Equipment: Hitachi Model 635, Separation Column: Showa Denko ■
Manufactured by 5hodex A 802, △ 803 and A30
A calibration curve was prepared by connecting three of No. 4 in series, temperature: room temperature, solvent: tetrahydrofuran, flow Q: 1.5 vQ/win, and using polystyrene as a standard.

Step tablets for sensitivity measurement (Ys 1 to No. 2 manufactured by Man Kogutsuk 21, 21 gray scales with a difference fi of 0.15 each) and burn-out characteristic evaluation Using a 4KW metal halide lamp (P.
Exposure was carried out for 35 seconds with strip A1 of W/Cv'.

Next, this sample was added to a 4% potassium metasilicate aqueous solution at 25°C.
When the plate was developed for 45 seconds, the non-image area was completely removed and a lithographic printing plate was obtained. Sensitivity step tablet 1
When measured on a gray scale, the 140th stage was completely developed (clear). Further, the 15% flat screen was reproduced as a clear image, and no blurred edges of the screen dots were observed.

Next, in order to examine development acceptability, we used a developer whose alkali concentration was diluted compared to the standard 4% potassium metasilicate aqueous solution, and the alkali 11! Prepare each developer with a higher concentration, and use the sample exposed for 35 seconds to test the developability (under-developability) for a developer with a decreased developing ability and the developer with an excessive developing ability. Developability (A-bar conductivity) was examined. In the investigation of under-developability, 1.9% potassium metasilicate aqueous solution was used at 25°C.
The film was developed for 45 seconds and the solubility of the non-image area was determined. The more diluted the developer dissolves the photosensitive layer in the non-image area, the better the underdevelopment@f1 will be. In addition, in the study of over-developability, a 7.2% potassium metasilicate aqueous solution was used to
℃ for 90 seconds, the number of solid steps (the lowest number of steps at which the photosensitive layer remains completely in the gray scale of the step tablet) was measured, and this and M
! Semi-development (496 potassium metasilicate aqueous solution, 25°C,
45 seconds), the difference in the number of solid steps was determined. This difference in the number of solid steps is small e11? -The closer to development, the less erosion of the unexposed area, and the better the over-developability. Good development tolerance means under-development, over-development↑
It means that both are good.

Next, in order to examine suitability for a ballpoint pen, a hole pen (I) was placed on the photosensitive planographic printing plate (A) before exposure and development.
) (manufactured by Sefra Nm Co., Ltd., ZEBRAN 5100 black), ballpoint pen (IT) (manufactured by 1-Nmbo Pencil Company G)
OL F blue) and ballpoint pen (■) (Draw lines on pylon 1 using three types of ballpoint pens: a fountain pen (Pilot 8S-Blue, manufactured by TL Co., Ltd.), leave it for 25 minutes, and then apply the standard development process described above without exposing it to light. Ballpoint pen suitability was evaluated by evaluating the degree of erosion of the photosensitive layer after the handwriting, each in 3 ranks.

Table 1 shows the results of sensitivity, printing blur characteristics, development tolerance, and ballpoint pen suitability obtained for 1Z-F.

Comparative Example 1 The following photoreceptor [nl] was used instead of photoreceptor [I] in the photosensitive coating solution of Example 1, and the amount added was 2.3 (), and the amount of novolac resin [I] added was 5.8 ( ], O-
The molar ratio occupied by naphthoquinonediazide photosensitive units is 0.
The concentration was set at 40 mmol/g. The other conditions were the same as in Example 1, and the photosensitive planographic printing plate (B) was prepared at 4F.

Photoreceptor [■] Naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride and m-talesol formaldehyde novolac resin (number average molecular weight Mn = 1000, weight average molecular & iMw = 3000) (condensation rate 25 mol%
) The application rate after drying was approximately 20 mLJ/dv'.

Next, using this photosensitive planographic printing plate (B), Example 1
In the same way as above, sensitivity, 1 development tolerance bamboo with burn-out blur, and suitability for ballpoint pens were examined. The results are shown in Table 1.

Comparative Example 2 Novolak resin [1] was added to the photosensitive coating liquid of Example 1.
A photosensitive t#t M1 printing plate (
C) was obtained.

Novolac resin rTI] @condensation resin of m-cresol and formaldehyde (weight average molecule m M W = 30 (to, dispersity Mw /
Mn=3> The coating weight after drying was about 20 UJ/df.

Next, using this photosensitive lithographic printing plate (C), Example 1
Similarly, sensitivity, print blur characteristics, development tolerance, and ballpoint pen suitability were examined. The results are shown in Table 1.

Comparative Example 3 Novolak resin [I] in the photosensitive coating liquid of Example 1
A photosensitive lithographic printing plate (D) was obtained in the same manner as in Example 1 except that the following novolac resin [I[1] was used instead of .

Novolac resin [I[[] Copolycondensation resin of phenol, m-, p-mixed cresol, and formaldehyde (molar ratio of phenol and m-, p-mixed cresol is 5.0: 5.0, weight average molecular fitMw =12,000, dispersion degree Mw /Mn
The coating type ω after drying was about 2 On+a/df.

Next, using this photosensitive lithographic printing plate (1'), the sensitivity, print blur characteristics, development tolerance, and suitability for a ballpoint pen were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 The amount of photoreceptor IT] added in the photosensitive coating liquid of Example 1 was set to 1.7 g, and the amount of novolac resin [I] added was reduced to 1.7 g, compared to the novolak resin [1 [1] used in Comparative Example 3. 6.4
Example 1 except that the molar ratio occupied by the 0-naphthoquinonediazide photosensitive unit was 0.50 mmol/g.
A photosensitive lithographic printing plate (E) was obtained in the same manner as above.

The coating weight after drying was approximately 20111 (1/d 1').

Next, using this photosensitive planographic printing plate (E), Example 1
Similarly, sensitivity, print blur characteristics, development tolerance, and ballpoint pen suitability were examined. The results are shown in Table 1.

Comparative Example 5 A photosensitive lithographic printing plate (F) was obtained in the same manner as in Comparative Example 4, except that 06 g of phthalic anhydride was further added as a sensitizer to the photosensitive liquid coating solution of Comparative Example 4.

The coating weight after drying was approximately 20 mO/dv''.

Next, using this photosensitive lithographic printing plate (F), Example 1
Similarly, sensitivity, blur characteristics, development tolerance, 3! and ballpoint pen aptitude were examined. The results are shown in Table 1.

1' bottom margin The burning blur characteristics in Table 1 were evaluated on the following three levels.

Mark D indicates good image reproducibility and no blurring is observed.

A slight blurring phenomenon is observed in the Δ mark.

The image marked with an X clearly shows a burning blur phenomenon and is at a problematic level.

Ballpoint pen aptitude was evaluated on the following four levels.

Mark A shows almost no erosion in the image area.

Mark D indicates slight erosion in the image area.

Mark D indicates erosion as above, and the grains of the support under the photosensitive layer are slightly exposed.

Mark D indicates significant erosion as above, and the grains of the support below the photosensitive layer are completely exposed.

It means that.

In terms of development tolerance, in under-development, the photosensitive layer in the non-image area is completely dissolved and removed at mark D.

Part of the Δ mark remains as above.

The X mark indicates that the same as above is hardly dissolved.

It means that.

In addition, in the over conductivity, the numerical value means the difference in the number of solid stages from standard development, and the - symbol means that the image area is severely eroded and the over development property is poor, where the number of solid stages can hardly be determined.

It can be seen that there are no major defects in development tolerance or ballpoint pen suitability, and that the composition is uniformly excellent overall.

On the other hand, photosensitive lithographic printing plates (B) to (F) of Comparative Examples 1 to 5
has a significant drawback in at least one of the properties listed in Table 1.

Example 2 The following photoreceptor [I11] was used instead of photoreceptor [I] in the photosensitive coating liquid of Example 1, and the amount added was 1.55 (1
, the amount of copolycondensation resin added was changed to 6.55 (], and the molar ratio occupied by 0-naphthoquinone diazide photosensitive units was changed to 0.4.
The concentration was set to 0 mmol/g. A photosensitive lithographic printing plate (G) was obtained in the same manner as in Example 1 in other respects.

Photoreceptor rllll] Ester compound of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride and resorcinol benzaldehyde polycondensation resin (number average molecular weight Mll =
900, weight average molecular weight Mw = 1.300) (
Condensation rate: 40 mol%) The coating amount after drying is approximately 201 (]/
It was dv'.

Next, using this photosensitive planographic printing plate (G), Example 1
Similarly, sensitivity, printing blur characteristics, development tolerance, and suitability for ballpoint pens were examined. The results are shown in Table 2.

Example 3 A photosensitive lithographic printing plate (H) was prepared in the same manner as in Example 1, except that a photoreceptor [IV] one step lower was used in place of the photoreceptor [I] in the photosensitive coating solution of Example 1. Obtained.

Photoreceptor [rV] Ester compound of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride and pyrogallol/acetone polycondensation resin (number average molecular weight Mn = 1,5
00, weight average molecular weight Mw = 2,500) (condensation rate 30 mol%) The coating weight after drying was about 20 tI1g/df.

Next, using this photosensitive lithographic printing plate (H), Example 1
Similarly, sensitivity, printing blur characteristics, development tolerance, and suitability for ballpoint pens were examined. The results are shown in Table 2.

Example 4 Same as Example 1 except that the following photoreceptor [V] and novolac resin [■] were used instead of photoreceptor [I] and novolac resin [I] in the photosensitive coating liquid of Example 1. A photosensitive planographic printing plate (1) was obtained.

Photoreceptor [V] Ester compound of naphthoquinone-<1.2)-diazide-(2)-5-sulfonic acid chloride and pyrogallol/acetone polycondensation resin (number average molecular weight Mn = 2,0
00, weight average molecule t? 1Mw -4,000> (condensation rate 30 mol%) Novolak 41 resin [IV1 +1111fFj small condensation resin of cresol and formaldehyde (■ 1 average molecular weight Mw = 5,000, dispersity Mw/
Mn = 4) The coated product after drying had a weight of about 20111 Mdf.

Next, using this photosensitive lithographic printing plate (I), Example 1
Similarly, sensitivity, printing blur characteristics, development tolerance, and suitability for ballpoint pens were examined. The results are shown in Table 2.

Example 5 In the photosensitive coating solution of Example 1, the following photoreceptor [■] and novolak resin [Vl] were used instead of the photoreceptor [I] and novolac resin [I], and the amount occupied by 0-naphthoquinonediazide photosensitive units was A photosensitive lithographic printing plate LJ) was obtained in the same manner as in Example 1, except that the following additions were made so that the molar ratio was 0.35 mmol/Q.

Photoreceptor [Vl] Esterified product of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride and pyrogallol/acetone polycondensation resin (number average molecule 1nvn = 1,1
00, weight average molecular faMw = 1,700) (condensation rate 30 mol%) 1.18 (1 phenol and m -,
Copolycondensation resin of p-mixed cresol and formaldehyde (molar ratio of J-nor and m-, p-mixed cresol is 3.0:7.0, weight average molecular weight Mw = 8.5
00, dispersity Mw /Mn = 6 > 6.920 The coated product after drying had approximately 20 tag/d 11'.

Next, using this photosensitive planographic printing plate (J), Example 1
Similarly, sensitivity, printing blur characteristics, development tolerance, and suitability for ballpoint pens were examined. The results are shown in Table 2.

Example 6 An aluminum plate having a thickness of 0.24 am was degreased in a 5% aqueous sodium hydroxide solution and then grained with a nylon brush. Next, a desmut treatment was performed with a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.

Subsequently, a photosensitive lithographic printing plate (K
) was obtained.

The coating feel after drying was approximately 20 NO/d1'.

Next, using this photosensitive lithographic printing plate (K), Example 1
Similarly, sensitivity, printing blur characteristics, development tolerance, and suitability for ballpoint pens were examined. The results are shown in Table 2.

It can be seen that the margin printing plates (G) to (K) are comprehensively uniformly excellent in sensitivity, printing blur characteristics, development tolerance, and suitability for ballpoint pens, and have no major defects.

Patent applicant Konishiroku Photo Industry Co., Ltd. lA’7

Claims (3)

[Claims] (1) O-naphthoquinonediazide compound which is o-naphthoquinonediazide sulfonic acid ester of polycondensation resin of polyhydroxyphenol and ketone or aldehyde [
A], a mixture of m-cresol and p-cresol The mixing ratio of cresol and phenol is 6.0:4.0 in molar ratio
A novolak resin [B] obtained by copolycondensing cresol phenols and aldehydes in a ratio of ~10.0:0.0, and the o-naphthoquinonediazide compound [A] and the novolak resin [B] are combined. The molar ratio of o-naphthoquinone diazide, which is a photosensitive unit, in the composition is 0.
A photosensitive composition characterized in that it has a concentration of 45 mmol/g or less. (2) The o-naphthoquinonediazide compound [A] is
Number average molecular weight Mn is 3.00×10^2 to 2.00×1
0^3, weight average molecular weight Mw is 5.00 x 10^2-4
．． The photosensitive composition according to claim 1, which is an o-naphthoquinonediazide sulfonic acid ester of a polycondensation resin of 00x10^3 polyhydroxyphenol and a ketone or aldehyde. (3) The novolak resin [B] is a cresol phenol in which the mixing ratio of m-cresol and p-cresol to phenol is 7.0:3.0 to 9.5:0.5 in molar ratio. A novolak resin that is copolycondensed with aldehyde and has a weight average molecular weight Mw of 3.00×
10^3 to 1.50 x 10^4, the weight average molecular weight Mw
and the number average molecular weight Mn of the resin (Mw/Mn) is 2
Claim No. (1) characterized in that
The photosensitive composition according to item or item (2).