JPH03172849A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To enhance uniformity in film thickness distribution and ink receptivity by incorporating a specified fluorinated surfactant in a photosensitive composition. CONSTITUTION:The fluorinated surfactant contained in the photosensitive composition is the copolymer of acrylate or methacrylate possessing a fluoroaliphatic group having >= 3 terminal fluorinated carbon atoms and having 3 - 20C and >=40wt.% F; polyoxyalkylene-acrylate or -methacrylate; and acrylate or methacrylate having a 10 - 22C hydrocarbon group each in a monomer weight proportion based on the copolymer of 10 - 50wt.% : 10 - 50wt.% : 40 - 70wt.%, thus permitting the obtained photosensitive layer to be free of nonuniformity of the film thickness and uniformized in the performance as a printing plate and enhanced in ink receptivity.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive composition containing a fluorosurfactant, and particularly to a photosensitive composition containing a fluorosurfactant dissolved or dispersed in an organic solvent. The present invention relates to a photosensitive composition that can obtain a uniform film thickness and improve ink receptivity by coating and drying it on a support.

[Prior Art and Problems to be Solved] Photosensitive compositions are generally made of aluminum, paper, plastic, or Sin which has been subjected to an appropriate surface treatment.

/ Si It is used by coating a solution or dispersion in an organic solvent on the surface of a support such as a wafer and drying it. When applying and drying this photosensitive composition, it is important to provide a uniform photosensitive layer on the support in order to exhibit the performance of the photosensitive composition.

In order to achieve the above-mentioned object, the present inventors have
As described in the specifications of JP-A-1270950 and JP-A-62-226143, by incorporating a specific fluorine-based surfactant into the photosensitive composition to be coated, the film thickness that occurs during the drying process is It has been found that the non-uniformity of the distribution can be resolved. However, although these techniques improve the non-uniformity, they are not necessarily sufficient and there remain problems such as insufficient ink receptivity.

Therefore, a further object of the present invention is to provide a photosensitive composition with improved uniformity of film thickness distribution and improved ink receptivity.

In order to achieve the above object, the present inventors further conducted extensive research on fluorosurfactants, and found that by incorporating a specific fluorosurfactant into the photosensitive composition to be applied, the drying process can be improved. It was discovered that the non-uniformity of the film thickness distribution that occurs can be further eliminated and the ink receptivity can be improved, and the present invention has been completed. That is, the present invention provides a photosensitive composition containing a specific fluorine-based surfactant, wherein the fluorine-based surfactant (i) has 3 to 20 carbon atoms and contains 40% by weight or more of fluorine. , an acrylate containing a fluoroaliphatic group (Rf group) in which at least three terminal carbon atoms are fully fluorinated or R
methacrylate containing an f group, (ii) poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate, and (iii) acrylate or RH containing a hydrocarbon group (RH group) consisting of 10 to 22 carbon atoms. a copolymer with a methacrylate containing groups, each monomer unit containing (iHo ~ 50% by weight, (ii) 10-50% by weight, based on the weight of the copolymer.
and (iii) 40 to 70% by weight.

The present invention will be explained in detail below.

The fluorosurfactant used in the present invention is (i) 3 to 2
Acrylates having 0 carbon atoms and containing 40% by weight or more of fluorine and containing a fluoroaliphatic group (hereinafter referred to as Rf group) having at least 3 terminal fully fluorinated carbon atoms; (ii) methacrylate;
Poly (oxyalkylene) acrylate or methacrylate and a hydrocarbon group consisting of lO~22 carbon atoms (
RH group) containing acrylate or methacrylate, in which each monomer unit is (i) 10 to 50% by weight, (ii) 10% by weight, based on the weight of the copolymer.
-50% by weight, and (iii) 40-70% by weight.

The fluoroaliphatic group Rf is a saturated and generally monovalent aliphatic group. It can be straight-chain, branched and, if sufficiently large, cyclic or combinations thereof (eg alkylcycloaliphatic groups). Fluoroaliphatic skeletal steels can contain chain oxygen and/or trivalent nitrogen heteroatoms bonded only to carbon atoms, which provide stable bonds between the fluorocarbon groups and provide free bonds in the Rf groups. Does not interfere with active properties. In order for the Rf group to exhibit a sufficient effect, 3 to
20, preferably 6 to 12 carbon atoms, and 40
It has at least 50% by weight of fluorine bonded to carbon atoms, preferably at least 50% by weight. At least three terminal carbon S atoms of the Rf group are fully fluorinated. R
The terminal f group is, for example, CF3CF, CF2-, and a suitable Rf group is a substantially fully or fully fluorinated alkyl group, such as CnF2h++ (n is an integer of 3 or more).

If the fluorine content of the R[ group is less than 40% by weight, the object of the present invention cannot be fully achieved. The effect is greater when the fluorine atom is localized at the end of the Rf group.

Although it is possible to increase the fluorine content even if the number of carbon atoms in the Rf group is 2 or less, the total amount of fluorine atoms becomes insufficient and the effect is weak. Even if the fluorine content in the copolymer is increased by increasing the ratio of a fully fluorinated Rf group-containing monomer having 2 or less carbon atoms to the copolymer, the fluorine atoms will not be localized. Because of this, the sufficient effect cannot be obtained.

On the other hand, when the number of carbon atoms in the Rf group is 21 or more, if the fluorine content is high, the resulting copolymer will have low solubility in a solvent, and if the fluorine content is low, the localization of fluorine atoms will be insufficient. , and the sufficient effect cannot be obtained.

The solubilizing portion in the copolymer is poly(oxyalkylene)
a group, (OR'), in which R' is an alkylene group having 2 to 4 carbon atoms, such as -CH2CH2-CH2C
H2CH2CH(CH3) CL-1 or CH(C11
3) CH(CH3)- is preferred. The oxyalkylene units in the poly(oxyalkylene) group may be the same as in poly(oxypropylene), or two or more different oxyalkylenes may be randomly distributed. , linear or branched oxypropylene and oxyethylene units, or blocks of linear or branched oxypropylene units and blocks of oxyethylene units. The poly(oxyalkylene) chain can include one or more chain bonds (e.g., mediated or included; if the chain bonds have a valency of three or more, it can contain branched oxyalkylene units). In order to obtain the desired solubility when this copolymer is added to a photosensitive composition, the molecular weight of the poly(oxyalkylene) group should be between 250 and 250.
0 is appropriate.

The ink receptivity improving moiety in the copolymer is a hydrocarbon group (RH group) consisting of 10 to 22 carbon atoms. The RH group is a linear or branched aliphatic hydrocarbon group or a cyclic hydrocarbon group, which may be a saturated compound or an unsaturated compound, and may also be a combination of an aliphatic group and a cyclic hydrocarbon group (e.g. , A may also be used. If the number of carbon atoms in the RH group is 9 or less, the effect of improving ink receptivity will be weak, while if it is 23 or more, the solubility of the copolymer in a solvent will decrease.
The group may be bonded to acrylic acid or methacrylic acid by a direct ester bond or mediated by one or more chain bonds (such as -CL-CII2-0--3-),
Or it may contain this.

The above-mentioned copolymers used in the present invention include, for example, a fluoroaliphatic group-containing acrylate or methacrylate, a poly(oxyalkylene)acrylate or methacrylate, such as a monoacrylate or diacrylate, and l
It can be prepared by free radical initiated copolymerization with acrylates or methacrylates containing hydrocarbon groups of from 0 to 22 carbon atoms or mixtures thereof. polyacrylate olicomer
The molecular weight of can be adjusted by adjusting the concentration and activity of the initiator, the monomer concentration and the polymerization reaction temperature, as well as by adding a chain transfer agent, such as a thionope such as n-octyl mercaptan. - For example, fluoroaliphatic group-containing acrylate, Rf-R' -D□C-
CH=CH2 (where R' is e.g. sulfonamidoalkylene, carbonamidoalkylene or alkylene), e.g. C8F, , SO□N(C=H9)CH
2CH202CCFl=CH2, poly(oxyalkylene) monoacrylate, CH2=C)IC(0)(OR'), OCH3,
When a hydrocarbon group-containing acrylate containing 10 to 22 carbon atoms, RH-02C-C)I=C)12, is copolymerized, a copolymer having the following repeating units is obtained.

The above fluoroaliphatic group-containing acrylate is disclosed in U.S. Pat.
．． 803.615, 2.642.416, 2, 826.564, 3.102.103, 3.282.905 and 3.304.278. It is stated in each specification. The poly(oxyalkylene) acrylates used in the preparation of the above copolymers, and other acrylates useful for this purpose, are commercially available hydroxypoly(oxyalkylene) materials, such as commercially available hydroxypoly(oxyalkylene) materials such as CPluronic (Asahi Denka Kogyo). ADEKABORIETHER (manufactured by Asahi Denka Kogyo ■)], “
Carbowax (Glyco Products) C
o,! I) ), “Triton” [
Triton (Rohm and Hearth)
and Haas) Co, Ltd.) and P, E, G, (Dai-Kogyo Seiyaku Flank) by reacting them with acrylic acid, methacrylic acid, acrylic chloride or acrylic anhydride in a known manner. Can be manufactured.

Separately, poly (oxyalkylene) diacrylate produced by a known method, CH2=C)lcO2(R' 0)-COCtl=CH
z, for example CHa=CHCO2(C2H40) r o
(Ca)+110) 22 (CJ40) l 0C
When OCH=CH2 is copolymerized with the fluoroaliphatic group-containing acrylate described above, a polyacrylate copolymer having the following repeating units is obtained.

+ + Other fluoroaliphatic group-containing terminal ethylenically unsaturated monomers suitable for producing the copolymer used in the present invention include:
U.S. Patent No. 2.592.069, U.S. Patent No. 2,995.5
No. 42, No. 3.078.245, No. 3.081.
No. 274, No. 3.291.843 and No. 3.32
No. 5.163, ethylenically unsaturated materials suitable for producing the terminal ethylenically unsaturated monomers containing fluoroaliphatic groups are described in U.S. Pat.
No. 4.791.

10 suitable for producing the copolymer used in the present invention
The hydrocarbon group-containing acrylate or hydrocarbon group-containing methacrylate consisting of ~22 carbon atoms is, for example, 10 to 2 carbon atoms.
They can be prepared by reacting aliphatic alcohols of 2 carbon atoms with acrylic acid, methacrylic acid, acrylic chloride or acrylic anhydride in a known manner. For example, by using stearyl alcohol, C
,,H3?0COCH=CH2 is obtained.

The copolymer used in the present invention comprises (i) a fluoroaliphatic group-containing acrylate or methacrylate, (ii) a poly(oxyalkylene)acrylate or methacrylate, and (iii) a hydrocarbon group consisting of >10 to 20 carbon atoms. A copolymer containing acrylate or methacrylate, wherein each monomer unit is (i) 10 to 50% by weight, (ii) 10 to 5.0% by weight, based on the weight of the copolymer.
% by weight, and (iii) 40-70% by weight.

If component (i) is less than 10% by weight, the uniformity of the film thickness distribution will not be sufficient, whereas if it is more than 50% by weight, the solubility in solvents will be too low, which is undesirable.

Component (ii) is a solubilized portion, and if it is less than 10% by weight, the solubility is insufficient, and if it is more than 50% by weight, (i)
) and (iii) components are reduced, resulting in insufficient effects.

If the component (iii) is less than 40% by weight, the effect of improving ink receptivity will be small, and if it is more than 70% by weight, the solubility in solvents will be too low, which is not preferable.

The molecular weight of the copolymer used in the present invention is 2.500 to 1
00,000, more preferably 6.000 to 100.00.
It is 000. If the molecular weight is less than 2.500, the effect will not be sufficient, and if it is more than 100.000, the solubility in solvents will decrease, which is not preferable.

In the copolymer used in the present invention, as a fluoroaliphatic group-containing monomer, fluoroaliphatic group-containing acrylate is added at 50 to 10% per fluoroaliphatic group-containing monomer unit.
It is preferable to use 0% by weight of poly(oxyalkylene) acrylate monomer units and 10% by weight or more of poly(oxyalkylene) acrylate monomer units based on the total weight of the copolymer. Particularly preferred are copolymers of (alkylene) acrylates and hydrocarbon group-containing acrylates. When the fluoroaliphatic group-containing methacrylate is 50% by weight or more based on the fluoroaliphatic group-containing monomer unit, the solvent solubility tends to decrease. Furthermore, if the poly(oxyalkylene) acrylate monomer is not mixed by 10% by weight based on the total weight of the copolymer, pinholes are likely to occur in the coating film.

The preferred usage range of the fluorosurfactant used in the present invention is 0.01 to 5% by weight based on the photosensitive composition (coating components excluding solvent), and the more preferred usage range is 0.01 to 5% by weight. It ranges from .05 to 3% by weight. If the amount of fluorosurfactant used is less than 0.01% by weight, the effect tends to be insufficient. On the other hand, if it is more than 5% by weight, the coating film may not dry sufficiently or the performance as a photosensitive material ( For example, it tends to have an adverse effect on developability.

Any photosensitive composition containing the fluorine-containing surfactant of the present invention can be used as long as its solubility or swelling property in a developer changes before and after exposure. Particularly preferred are diazo compounds, such as photosensitive compositions comprising diazo resin and shellac (Japanese Patent Laid-Open No. 47-24404
), poly(hydroxyethyl methacrylate) and diazo resins, diazo resins and soluble polyamide resins (U.S. Pat. No. 3.751.257), azide-sensitive futures and epoxy resins (U.S. Pat. No. 2.852.379), azide Photosensitive resins, such as photosensitive resins, diazo resins, and polyvinyl cinnamates, which have unsaturated double bonds in their molecules and which undergo a dimerization reaction and become insolubilized by irradiation with actinic rays, such as British Patent No. 843 No. 545, No. 966297,
derivatives of polyvinyl cinnamate as described in U.S. Patent No. 2.725.372, bisphenol A and divanylcyclohexanone as described in Canadian Patent No. 696.997; p-
Phenylene diethoxy acrylate and 1,4-di-β-
Photosensitive polyester obtained by condensation of hydroxynidoxin with clohexanone, U.S. Pat. No. 3,462,267
Prepolymers of diallyl phthalate as described in Kosho 35-8495
unsaturated esters of polyols, such as ethylene di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(
meth)acrylate, glycerol tri(meth)acrylate, ethylene di(meth)acrylate, 1.
3-7'0 pyrene di(meth)acrylate, 1,4-cyclo-hexanediol(meth)acrylate, 1゜4
-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1.3-
Propylene glycol di(meth)acrylate, 1.5
-Pentanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, molecular weight 50
~500 polyethylene glycol bisacrylates and methacrylates, unsaturated amides, especially amides of α-methylenecarboxylic acids and especially those of α,ω-diamines and ω-diamines with intermediate oxygen, such as methylene bis(meth)acrylamide and Diethylene triamine tris(meth)acrylamide, divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, etc. and a suitable binder, such as polyvinyl alcohol or a cellulose derivative containing a carboxy group in the side chain. As a negative working type photosensitive composition, a photosensitive composition consisting of a compound such as polyvinyl hydrogen phthalate, carboxymethyl cellulose, or a copolymer of methyl methacrylate heptamethacrylic acid becomes insoluble by the action of actinic rays. Useful. 0-
Diazo oxide photosensitive materials, phosphotungstate of diazo resin (Japanese Patent Publication No. 397,663), yellow blood salt of diazo resin (U.S. Pat. No. 3,113.023), and diazo resin and polyvinyl hydrogen phthalate (Japanese Patent Application No. 1983) -1881
A photosensitive composition comprising No. 2) etc. is useful as a positive working type photosensitive material. Also, U.S. Patent No. 3.0
No. 81.168, No. 3.486.903, No. 3.
Photosensitive compositions containing linear polyamides and monomers having addition-polymerizable unsaturated bonds, such as those described in specifications such as No. 512.971, No. 3, and No. 615.6'29, are also useful. It is.

Particularly useful photosensitive compositions include JP-A-47-244
A photosensitive composition comprising a diazo resin and shellac as shown in Japanese Patent Application No. 04, a composition comprising a diazo resin and a hydroxyethyl methacrylate copolymer as shown in JP-A-50-118802, and US Patent Box 3. .635.709
Examples include compositions made of esterified products of naphthoquinonediazide sulfonic acid and pyrogallol-acetone resin, and novola and tsuku resins shown in the specification of the above patent.

The photosensitive composition used in the present invention includes dyes for image identification, such as crystal violet, methyl violet, malachite green, tsuksin, para tsuksin, Victoria Blue BH [manufactured by Hodogaya Chemical Industry ■],
Victoria Pure Blue BOHC manufactured by Hodogaya Chemical Industry ■], Oil Blue #603 (manufactured by Ocento Chemical Industry A1), Oil Pink #312 (manufactured by Orient Chemical Industry ■), Oil Red 5B [manufactured by Orient Chemical Industry ■], Oil Green #502C manufactured by Orient Kagaku Kogyo ■], etc., in an amount of 0.3 to 15% by weight based on the total photosensitive composition.
It may be adjusted by weight%. Furthermore, compounds that interact with these dyes to generate photolytic products that change color tone, such as 0-natofquinonediazide-4-sulfonic acid halide described in JP-A-50-36209, JP-A-50-36209;
Trihalomethyl-2-pyrone and trihalomethyltriazine described in Publication No. 3-36223, JP-A-55-624
Various ○-naphthoquinonediazide compounds described in Japanese Patent Publication No. 44, 2-trihalomethyl-5-aryl-1,3°4-oxadiazole compounds described in JP-A-55-77742, etc. can be added. I can do it. These compounds can be used alone or in combination, and the amount added is 0.
．． 3 to 15% by weight is preferred. Furthermore, fillers can be added. Adding a filler not only makes it possible to further improve the physical properties of the coating film, but also makes it possible to make the surface of the photosensitive layer matte, which improves vacuum adhesion during image printing and eliminates so-called printing blur. It can be prevented. Such fillers include talcum powder, glass powder, clay, starch, wheat flour, corn flour, Teflon powder, and the like. Furthermore, various additives can be added depending on various other purposes.

The above photosensitive composition is generally coated on a support,
Used in photosensitive planographic printing plates, etc.

As the support, dimensionally stable plate-like materials are used, including those used hitherto as supports for printing plates. Such supports include paper, plastics (e.g. polyethylene, polypropylene, polystyrene, etc.)
Paper laminated with metal plates such as aluminum (including aluminum alloys), zinc, iron, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate , films of plastics such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with metals as described above, and aluminum plates are particularly preferred. Aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used, such as alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel. These compositions contain some iron and titanium as well as other negligible impurities.

The support is surface-treated as necessary. For example, in the case of a photosensitive lithographic printing plate, the surface of the support is subjected to a hydrophilic treatment. There are various types of such hydrophilic treatment. For example, in the case of a support having a plastic surface, so-called surface treatment methods such as chemical treatment, electric discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment (for example, U.S. Pat. box 2.76
No. 4.520, No. 3.497.407, No. 3.145
．． No. 242, No. 3.376, No. 208, No. 3.072.
No. 483, No. 3.475.193, No. 3.360.4
43, British Patent No. 788.365, etc.), and there are those in which a subbing layer is applied to the plastic after the surface treatment.

Various methods have been used for coating, such as a multi-layer method in which the first layer is made of plastic and a hydrophobic resin layer with good adhesion is applied, and the second layer is a hydrophilic resin layer. There is also a single layer method in which a layer of resin containing hydrophobic groups and parent wood groups is applied in the same polymer.

In the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorinated zirconate, phosphate, etc., or anodization treatment are performed. It is preferable. In addition, as described in U.S. Pat. No. 2.714.066, an aluminum plate that is grained and then immersed in a sodium silicate aqueous solution, U.S. Pat.
As described in No. 81.461, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

The above anodic oxidation treatment can be performed using, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution consisting of an aqueous solution or a non-aqueous solution of an inorganic acid such as boric acid, an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more of them. .

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve the adhesion with the photosensitive layer. It is done to improve.

Prior to graining the aluminum plate, if necessary, the surface may be pretreated to remove rolling oil from the surface and expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants, etc. are used.

For the latter, a method using an alkaline etching agent such as sodium hydroxide or potassium hydroxide is widely used.

Mechanical, chemical, and electrochemical methods are all effective as the graining method. Mechanical methods include the ball polishing method, blast polishing method, and brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush.
A method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Publication No. 31187 is suitable.
As the electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid, or a combination thereof is preferred.

Among these surface roughening methods, especially Japanese Patent Application Laid-Open No. 55-1379
A surface roughening method that combines mechanical roughening and electrochemical roughening as described in Japanese Patent No. 93 is preferred because it provides strong adhesion of the oil-sensitive image to the support.

Graining by the method described above is preferably carried out in such a range that the centerline surface roughness (Ia) of the surface of the aluminum plate is 0.2 to 1.0 μ.

The thus grained aluminum plate is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous base or acid solutions that dissolve aluminum. In this case, it is necessary that no film different from aluminum derived from the etching solution components is formed on the etched surface. Examples of preferred etching agents include basic substances such as sodium hydroxide, potassium hydroxide, trisodium phosphate, dibasic phosphate, tripotassium phosphate, and dipotassium phosphate; acidic substances such as sulfuric acid, persulfuric acid, and phosphoric acid,
Examples include hydrochloric acid and its salts, but salts of metals having a lower ionization tendency than aluminum, such as zinc, chromium, cobalt, nickel, copper, etc., are not preferred because they form an unnecessary film on the etched surface.

It is most preferable to use these etching agents in such a way that the concentration and temperature used are such that the dissolution rate of the aluminum or alloy used is 0.3 to 40 grams per minute of immersion time. There is no problem even if it exceeds or falls below.

Etching is performed by immersing the aluminum plate in the above etching solution or applying the etching solution to the aluminum plate, and the etching amount is 0.5 to 10 g/m.
' is preferably processed.

As the above-mentioned etching agent, it is desirable to use an aqueous base solution because of its high etching rate. In this case, since smut is generated, it is usually desmutted. The acids used for desmutting include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and hydrofluoroboric acid.

The etched aluminum plate is washed with water and anodized if necessary. Anodic oxidation can be performed by methods conventionally practiced in this field. Specifically, when a direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. or a combination of two or more thereof, the aluminum support An anodic oxide film can be formed on the surface.

The processing conditions for anodic oxidation vary depending on the electrolyte used and cannot be determined unconditionally, but generally the electrolyte concentration is 1 to 80% by weight, the solution temperature is 5 to 70°C, and the current density is 0. A suitable range is .5 to 60 amperes/dm, voltage of 1 to 100 V, and electrolysis time of 30 seconds to 50 minutes.

Among these anodizing treatments, especially British Patent No. 1.4
12,768 and U.S. Pat. No. 3,511.6.
The method described in No. 61, in which phosphoric acid is used as an electrolytic bath for anodic oxidation, is preferred.

The aluminum plate roughened as described above and further anodized may be subjected to a hydrophilic treatment if necessary. Preferred examples thereof include US Pat. No. 2,714.066 and US Pat. Alkali metal silicates such as aqueous sodium silicate solutions as disclosed in Japanese Patent Publication No. 36-22.063 and potassium fluorozirconate as disclosed in U.S. Pat. No. 4.153.
There is a method of treatment with polyvinylphosphonic acid as disclosed in US Pat.

The photosensitive composition containing the fluorosurfactant of the present invention is dissolved or dispersed in one or a mixture of the following organic solvents, applied to the above-mentioned support, and dried.

The organic solvent used has a boiling point of 40°C to 200°C, especially 60°C.
A temperature in the range of .degree. C. to 160.degree. C. is selected for its advantage in drying.

For example, alcohols such as methyl alcohol, ethyl alcohol, n- or iso-propyl alcohol, n-4 is iso-butyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone, methyl propyl ketone,
Ketones such as methyl butyl ketone, methyl amyl ketone, methyl hexyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, acetylacetone, benzene, toluene, xylene,
Hydrocarbons such as cyclohexane and methoxybenzene, ethyl acetate, n- or iso-propyl acetate,
n- or iso-butyl acetate 1, acetate esters such as ethyl butyl acetate and hexyl acetate, lactic acid esters such as methyl lactate and ethyl lactate, halides such as methylene dichloride, ethylene dichloride, and monochlorobenzene, isopropyl ether, n- Ethers such as butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran, ethylene glycol, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, diethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, etc. Hydrolic alcohols and their derivatives, special solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and the like are preferably used alone or in mixtures. The concentration of solid content in the coating liquid is 2 to 50% by weight.
is appropriate.

As the coating method, roll coating, dip coating, air knife coating, gravure coating, gravure offset coating, hopper coating, blade coating, wire doctor coating, spray coating, etc. are used, especially when the coating liquid amount is 10 to 100 m1/%. A range of is suitable.

Drying is done with heated air. Heating is 30
A temperature range of 200°C to 200°C, particularly 40 to 140°C is suitable. It is possible to implement not only a method in which the drying temperature is kept constant during drying, but also a method in which it is increased stepwise.

Also, good results may be obtained by dehumidifying the dry air. The heated air is 0.1 to 3
It is preferred to feed at a rate of 0 m/sec, especially 0.5 to 20 m/sec.

〔Effect of the invention〕

According to the present invention, the non-uniformity of the thickness of the photosensitive layer that conventionally occurs in the drying process is eliminated, the performance as a printing plate is made uniform, and the ink receptivity can be improved.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on examples. However, the present invention is not limited to these Examples. In addition, % in an example shows weight %.

Example 1 and Comparative Examples 1 to 8 A strip of aluminum having a thickness of Q, 3 mm and a width of 1,000 mm was transported and first heated to 1 mm of trisodium phosphate kept at 80°C.
Degreasing was performed by passing through a 0% aqueous solution for 1 minute. Next, the surface was grained using a nylon brush and a 400 meter Bamisu water suspension, and thoroughly washed with water. This board was immersed in a 25% sodium hydroxide aqueous solution at 45°C for 9 seconds to perform processing and notching, and after washing with water, an additional 20%
It was immersed in nitric acid for 20 seconds and washed with water. The amount of etching on the grained surface at this time was approximately 8 g/m. Next, this temporary was used as an electrolyte with 7% sulfuric acid at a current density of 15 A/dm2 for 3 hours.
After forming a DC anodic oxide film of g/rrr, it was washed with water and dried, followed by the following photosensitive liquid coating step.

The following photosensitive solution was prepared.

This was dried to form a photosensitive layer.

In this way, photosensitive lithographic printing plates (Example 1 and Comparative Example 1) provided with photosensitive layers containing various fluorosurfactants were prepared.
Table 1 below shows the results of evaluating the performance of 7) and a photosensitive lithographic printing plate (Comparative Example 8) provided with a photosensitive layer to which no fluorosurfactant was added.

Note ■: As described in Example 1 of US Pat. No. 3,635,709.

In Table 1, the uniformity of the photosensitive layer was determined by applying the above photosensitive liquid continuously on a grained aluminum strip at a rate of 30 g/m and then passing it through a hot air drying zone at 100°C for 1 minute. Visual judgment was made for color unevenness caused by such factors as well as line unevenness failures that occur during coating and drying.

From Table 1, it can be seen that in Example 1 in which the fluorine-based surfactant of the present invention was used, the uniformity of the thickness of the photosensitive layer was significantly improved compared to Comparative Example 8 in which the fluorine-based surfactant was not added. In addition, in Table 1, the ink receptivity was measured using an automatic processor 800U manufactured by Fuji Photo Film ■ after exposure through an image film.
The company's automatic developer DP-4 (1:8) was used to develop the product at 25°C for 40 seconds, and the company's gum (GP) was applied and printing was performed one week later. evaluated. From Table 1, it can be seen that Example 1 using the fluorine-based surfactant of the present invention has significantly improved ink receptivity compared to Comparative Example 8 where no fluorine-based surfactant was added.

Furthermore, it can be seen that in Comparative Examples 1 to 7 in which fluorosurfactants other than those of the present invention were used, the uniformity and/or ink receptivity of the photosensitive layer was poor.

After the photosensitive lithographic printing plate obtained in Example 1 was exposed in close contact with the original film, it was developed with a positive developer DP-4 (t: 8) manufactured by Fuji Photo Film 01.
It was found that the sensitivity and reproducibility of the original pattern were uniform and excellent.

When this was used for printing, it was found to have excellent stiffness resistance and uniform image strength.

Example 2 and Comparative Example 9 The band-shaped aluminum support provided with the anodic oxide film in Example 1 was passed through a 2.5% aqueous sodium silicate solution at 70°C for 30 seconds, washed with water and dried, and led to the coating process. .

Next, a photosensitive solution having the following composition was prepared.

Note that in Comparative Example 9, fluorine-based surfactant 1 was not used.

Continuously apply 40 g of the photosensitive solution to the aluminum strip.
-nf, the photosensitive layer is dried by passing through a drying zone supplied with hot air at 80°C for 1 minute and through a drying zone supplied with hot air at 100°C for 1 minute. Formed.

In Comparative Example 9, in which no fluorosurfactant was added, strong hazy unevenness occurred, but in Example 2, a photosensitive layer with a uniform thickness could be obtained.

The photosensitive lithographic printing plate cut into sheets after drying is a negative printing plate with excellent sensitivity and reproducibility, and the printing plate obtained from this plate has excellent rigidity resistance and uniform image strength. Ta.

After exposure and development, Fuji Photo Film 0 Chrysanthemum Gum (GU-2)
) was applied and printed one week later. Comparative Example 9 required 45 sheets for the ink to completely adhere, whereas Example 2 required 26 sheets, indicating good ink receptivity. there were.

Examples 3 to 7 Photosensitive lithographic printing plates and printing plates were prepared in the same manner as in Example 1, except that the following compounds were used as fluorosurfactants, and evaluated in the same manner. Similarly good results were obtained.

Example 3 Example 6 Example 4 Example 7 Example 5

Claims (2)

[Claims] (1) In a photosensitive composition containing a fluorine-based surfactant, the fluorine-based surfactant (i) has 3 to 20 carbon atoms and contains 40% by weight or more of fluorine, and has a terminal an acrylate or methacrylate containing a fluoroaliphatic group (Rf group) in which at least three carbon atoms are fully fluorinated; (ii) a poly(oxyalkylene) acrylate or methacrylate; (iii) 10 to 22 Hydrocarbon group consisting of carbon atoms (
RH group) containing acrylate or methacrylate, and each monomer unit is (i) 10 to 50% by weight, (ii) 10 to 5% by weight, based on the weight of the copolymer.
0% by weight and (iii) 40 to 70% by weight. (2) The molecular weight of the copolymer is 2,500 to 100,00
2. The photosensitive composition according to claim 1, wherein the photosensitive composition is 0.