JPS59192250A - Lithographic material and its manufacture - Google Patents

Abstract

PURPOSE:To prevent peeling of image areas and staining of a background, and to enable a large number of good prints to be made by forming a nonphotosensitive interlayer contg. a silane coupling agent in contact with a support and between the support and a photosensitive layer. CONSTITUTION:A nonphotosensitive interlayer contg. a silane couplng agent is formed in contact with a support and between the support and a photosensitive layer. The surface of the support is treated with a soln. contg. said agent, and the interlayer is formed on it, and the photosensitive layer is formed on the interlayer to obtain a printing plate material. The printing plate thus obtained is good in adhesive strength, and causes no peeling and no staining of the background, and permits formation of a large number of good prints. The silane coupling agent is a compd. obtained by combining at least two kinds of reactive groups and/or an atom directly or by the medium of a linking group, with tetravalent Si, and as the reactive group, an amino, vinyl group, or the like is desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lithographic printing plate material and a method for producing the same, and more particularly to a lithographic printing plate material having a non-photosensitive intermediate layer containing a silane coupling agent and a method for producing the same.

Lithographic printing is a printing method that uses water and ink on a lithographic printing plate, supplying ink to the image area and water to the non-image area.In order to obtain a large number of prints, it is necessary to bond the image area and the support. In addition, after exposing the lithographic printing plate material,
It is necessary that the image area has good stability (1w chemical resistance) against various chemicals used in the plate-making process in which a lithographic printing plate is obtained by performing a development process and further in the printing process. Furthermore, it is also necessary that no stains occur in non-image areas during the printing process.

Regarding the use of silane coupling agents in lithographic printing plate materials, a method is known in which a silane coupling agent is incorporated into a photosensitive layer coated on a support (for example, JP-A No. 52-52002). Public bulletin). However, the second lithographic printing plate has the disadvantage that scumming occurs during the printing process, and furthermore, when a printout material is added to the photosensitive layer to form a visible image by exposure, the visible image becomes unclear. There were also some drawbacks.

Accordingly, an object of the present invention is to provide a lithographic printing plate material suitable for a lithographic printing plate that can produce a large number of good-quality printed materials without causing scumming or peeling of image areas.

Another object of the present invention is to provide a lithographic printing plate material with excellent stability (chemical resistance) to chemicals used in each process and a method for producing the same.

Another object of the present invention is to provide a lithographic printing plate material suitable for a lithographic printing plate, which can prevent visible images from becoming unclear even when a printout material is added, and which can produce a large number of good-quality printed materials. The object of the present invention is to provide a manufacturing method thereof.

Other objects of the invention will become apparent from the description below.

As a result of intensive research to achieve the above object, the present inventors have discovered that the above object can be achieved using a lithographic printing plate material and a method for producing the same having the following configuration.

That is, the lithographic printing plate material of the present invention is a lithographic printing plate material having a photosensitive layer on a support, and a non-photosensitive layer containing a silane coupling agent adjacent to the support between the support and the photosensitive layer. A method for producing a lithographic printing plate material is to treat the surface of the support with a liquid containing a silane coupling agent. The above-mentioned silane camping agent refers to a compound in which at least two reactive groups and/or atoms are bonded to a tetravalent silicon atom either directly or via a linking group. Examples of reactive groups include amine 7 groups, vinyl groups, and epoxyethyl groups (C
IQ -, C1l -), an epholkoxy group, an alkyl group, an acyloxy group, and an ammonium compound residue. Examples of alkoxy groups include those having 1 to 4 carbon atoms, such as methoxy and ethoxy groups. Alkyl groups have 1 carbon atom, such as methyl and ethyl groups.
4 to 4 are listed. Examples of the acyloxy group include alkylcarbonyloxy groups having 2 to 4 carbon atoms such as an acetyloxy group and a butyryloxy group. Examples of ammonium compound residues include quaternary ammonium compound residues such as octadecyldimethylammonium chloride residues.

These groups may have a substituent, and examples of groups having a substituent include α-methylvinyl group, β-methoxyethoxy group, anilino group, bis(β-hydroxyethyl)amino7 group, etc. .

Examples of atoms bonded to the silicon atom directly or via a linking group include halogen atoms such as chlorine atoms.

Examples of the above-mentioned linking group include ethylene group, propylene group,
1 carbon atom, such as trimethylene group and tetramethylene group
to 5 carbon atoms, such as an alkylene group, a trimethyleneoxymethylene group, an ethyleneoxyethylene group, and a carbon atom number of 2 to 8.
alkyleneoxyalkylene groups, alkyleneamine groups having 2 to 8 carbon atoms such as trimethyleneamine/ethylene groups, ethyleneoxycarbonyl groups,
An alkyleneoxycarbonyl group having 2 to 5 carbon atoms, such as a trimethyleneoxycarbonyl group (however, the alkylene group is directly bonded to a silicon atom).

), alkyleneaminoalkyleneaminophenylene groups having 9 to 15 carbon atoms, such as trimethyleneaminoethyleneamine/methylenephenylene groups (however, the alkylene group is directly bonded to the silicon atom).

) etc. Furthermore, the aforementioned epoxyethyl group is bonded to a linking group, such as a β-(3,4-epoxycyclohexylethyl group), and is bonded to a silicon atom as an epoxychloroalkylalkyl group.

The silane coupling agent of the present invention further contains a silane-based compound such as hexaalkyldisilanzane.

Next, specific examples of silane coupling agents that can be used in the present invention will be shown.

Exemplary compound (1) NH2(CH2)zNH(C)12)3si
(OCt13)3(2) Nt12(Clh)2N1
1(C112)1Si(OCII3)2CH3 (3) N11゜(C1h)3Si(OC2Hs)3
(4) NH2CH2S1(OC2115)3(5)
Nt12(C112)2si(OC2Hs), 3(
6) Nll□(CH2)3si(OCH3)(7
) (110CH2CH2゜)2N(C1l□)3S
i(OCJs)s(9) CtL= CH5i(OC
H*>3(10) CI+□=C1l 5i(OC
H2CH20CH:+):+(11) C11z-C
IISi(OCOCIIs)3(12)Cl12”
CC00(CII2)3Si(OCII3)3 [CI+3 (13) CIl□= Cll5I(OC2+1.)
-(OCII3)31 ・lIC4 (15) CI! 2=CIISiCd3(16)C1
12=CC00(CH2)ssi(OCH2CH20C
1i3):+IL (19)CH3Si(OC112C1l+)3(20)
CH:+5i(OCII3)3(21)(CH,3)+
5iCl'! (23) (CH3)2SiCg3 (24) Ce (CH2)3Sl (OCII:1)
3(25)C/(CH2), 5i(OCH3)2CH
3 (26) Is(C112)3si(OCH3)2113 (27) Its(Cl12)3s+(OCHs):+B (29) (CI+3):+S+Nll5+(Cl1
3) Among the silane coupling agents mentioned above, preferred in the present invention are those in which 2 to 3 alkoxy groups are directly bonded to the silicon atom, and in addition, amine 7 groups are bonded to the silicon atom via a linking group. .

Particularly preferred silane coupling agents in the present invention are those represented by the following general formula.

(CH3λ (wherein R represents an alkyl group having 1 to 4 carbon atoms, an acyl group having 12 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 4 carbon atoms, a is an integer of 1 to 4, and b is 0 or 1, C is an integer from 1 to 3, d is 1 or 2, e
is 0 or 1, f is 2 or 3, and the sum of d, e, and f is 4. If d is 2, two N112((C1
12>aNl+, (C112) may be the same or different, and 2 to 3 ORs may be the same or different. ) In the above general formula, particularly preferred is the case where l< is an alkyl group and d is 1.

The silane coupling agents described above may be used alone or in combination of two or more.

The amount of silane coupling agent used is preferably 0.
0001-1 mg/d+n2.

The intermediate layer in the present invention may be composed of a silane coupling agent alone, or may be composed of a silane coupling agent in combination with a polymer compound.

As the polymer compound, a water-soluble polymer compound is preferable.
In particular, those having a solubility in water of 0.01% or more are preferred. Preferred water-soluble polymer compounds include, for example, gum arabic, starch, dextrin, sodium alginate, natural polymer compounds such as gelatin, water-soluble cellulose compounds, such as water-soluble salts of carboxyalkyl cellulose (alkyl is methyl, ethyl, propyl, etc.), alkyl cellulose such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc., polyacrylic acid or its water-soluble salt, acrylic acid copolymer or its water-soluble salt, methacrylic acid copolymer or its water-soluble salts, synthetic polymeric compounds such as styrene-maleic anhydride copolymer, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, etc. Examples of water-soluble salts of the polymeric 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.

When a silane coupling agent is used in combination with the above-mentioned polymer compound, the amount of the polymer compound is preferably 1/100 to 10 times the amount of the silane coupling agent.

The intermediate amount of film is 0.001 to 1 mg/d.
m2 is preferred, and 0.05 to 0.5+ng is particularly preferred.

A method for forming an intermediate layer on a support is to wash the support surface with an acid or alkaline aqueous solution as necessary, and then
A method of surface treatment using a surface treatment liquid containing a silane coupling agent is preferred.

The solvent for dissolving the silane force/mumbling agent and the polymer compound used as necessary may be water, methanol, ethanol, methyl cellosolve, or water and water-miscible solvents such as methanol, ethanol, acetone, methyl cellosolve, etc. , methyl cellosolve, nooxane, etc. are preferably used.

The concentration of silane coupling agent in the surface treatment liquid is 0.00
1 to 10% by weight is preferred, particularly 0.1 to 1.0% by weight
is preferred.

Further, a wetting agent such as a surfactant may be added to the surface treatment liquid as necessary.

Any method may be used, such as a method in which the support is surface treated with a surface treatment liquid, a method in which the surface treatment liquid is sprayed onto the support, a method in which the support is immersed in the surface treatment liquid. The temperature during surface treatment is preferably 0 to 80°C.

Examples of the support used in the present invention include paper, plastic, and metal. Examples of metals include aluminum, magnesium, zinc, chromium, iron, nickel,
and alloys of these metals. The support may be made of any of these materials at least on its surface.

That is, the surface of the support is combined with another base material, for example, paper, plastic, or other metal base material is pasted on the back side of a thin metal plate, metal is vapor-deposited on paper or plastic, or It may be plated or a metal plate plated with another metal.

Further, the surface of the support may be flat or roughened.

Various conventionally known methods can be used to roughen the surface of the metal support, including mechanical methods such as ball polishing and brush polishing, and chemical methods such as etching with an acid-containing solution. Examples include an electrochemical method, a method of etching using an electric field, and a method of etching using an electric field.

A preferred support in the present invention is aluminum. Among these, aluminum with a roughened surface is preferred, and aluminum whose roughened surface has been anodized is particularly preferred.

Other preferable supports in the present invention include those having a chromium-based coating layer, particularly those having a chromium-based coating layer on an iron material that is less likely to break when printed. Iron materials include pure iron as well as alloys of iron and other elements.

Other elements that form alloys with iron include carbon, manganese, and nickel.

Furthermore, iron rods obtained by electroforming as described in JP-A-56-150592 can also be used as the iron material in the present invention.

Chromium-based coating layers include a layer made of chromium, a layer made of chromium oxide, a layer with chromium oxide on top of chromium, a layer with a chromium layer on top of chromium oxide, and a layer with a mixture of chromium and chromium oxide. Examples include layers that exist.

Conventionally known methods can be used to form the chromium-based coating layer, such as the so-called chromium electromechanical method, which involves electrolyzing an iron material as a cathode in an aqueous solution containing chromic anhydride as the main component. The so-called chromic acid heat treatment method involves immersing the iron material in an aqueous chromate solution, or applying a thin layer of an aqueous solution containing chromic acid and a reducing agent to the surface of the iron material and baking it at about 120°C to form a thin layer of chromium oxide, such as anhydrous. A so-called electrolytic chromic acid treatment method in which a chromium oxide layer or a layer containing chromium oxide on chromium is formed by electrolyzing an iron material as a cathode in an aqueous chromic acid solution containing additives such as disulfonic acid and thiocyanate; Examples include vacuum evaporation method. These methods can also be used in combination, if necessary.

One of the preferable iron materials having a chromium-based coating layer is an iron material having a chromium electrodeposited layer.

The elemental composition of the surface side portion of the electrodeposited layer is substantially composed of chromium and oxygen, and the elemental composition ratio of chromium and oxygen in the portion is substantially at the same depth from the surface and in each portion of the surface. An example of this is iron material, which is uniform. The thickness of the chromium-based coating layer is preferably o, ooi to 10μ, particularly preferably 00OO5 to 4μ.

The surface shape of the chromium-based coating layer may be smooth, but
Preferably, the surface has irregularities. Examples of uneven surfaces include those described in JP-A-55-145193, which generally have a curved surface with small round protrusions; This patent application is filed by the present applicant on June 18, 1982, and has a substantially flat outer surface and a chromium electrodeposit layer having virtually no relatively sharp protrusion angles. Patent Application No. 57-105724 (title of invention “
An iron material having a chromium electrodeposited layer as described in "Support for Lithographic Printing Plate"), wherein the surface of the electrodeposition layer has a shape in which angular crystals are exposed, and the surface side of the electrodeposition layer has a shape in which angular crystals are exposed. The elemental composition of the part is substantially composed of chromium and oxygen, and the elemental composition ratio of chromium and oxygen in the part is substantially uniform at the same depth from the surface and in each part of the surface. Although these are listed as typical examples, the latter is particularly preferred.

The surface shape where the angular crystals of the chromium electrodeposited layer are exposed includes plate-shaped or hexahedral (for example, cubic rod-shaped) crystals, aggregates of these crystals, or the crystals. And/or a shape in which the mixture of aggregates is exposed is preferred. The plate-like crystalline material is preferably polygonal, mainly hexagonal, and the diameter of the polygonal surface is 0.5.
~5μm is preferable, and the thickness is 0.01~0.8μm.
"n" is preferable. As the hexahedral crystal, a cubic shape, particularly one with a side length of 0.1 to 2 μIII is preferable.

Regarding the manufacturing method of the iron material having the chromium electrodeposition layer having the above-mentioned uneven surface shape, the above-mentioned Japanese Patent Application Laid-Open No. 55-14
Publication No. 5163 and the present applicant June 1, 1982
Specification of Japanese Patent Application No. 57-1057243 filed on June 8th (Title of invention [Method for producing support for lithographic printing plate]), Specification of Japanese Patent Application No. 114642 of 1987 filed on June 30th, 1988 (
The method is described in detail in the title of the invention, ``Method for manufacturing a support for a lithographic printing plate.''

The lithographic printing plate material of the present invention can be obtained by forming a photosensitive layer made of a photosensitive composition on the above-mentioned intermediate layer.

Various types of photosensitive compositions that have been conventionally used in lithographic printing plate materials can be used as the photosensitive composition for the photosensitive layer, and representative ones will be described below.

Various types of photosensitive compositions that have been conventionally used in lithographic printing plate materials can be used as the photosensitive composition for the photosensitive layer, and representative ones will be described below.

(1) Photosensitive resin composition A photosensitive resin composition having an unsaturated double bond in the molecule, for example, U.S. Pat. Nos. 3,030,208 and 3
, 435,237 and 3,622,320, photosensitive groups -CII in the polymer main chain.
There is a polyvinyl cinnamate having a photosensitive group in the side chain of a photosensitive resin or polymer having =C11-C-.

(2) Photo/polymerizable photosensitive composition Monomer with double bond and baingu (high molecular compound)
A typical composition is disclosed in U.S. Pat. No. 2,76
No. 0,863, No. 2,791,504 and No. 3
, No. 801,328.

(3) Photosensitive composition containing a diazo compound A diazo compound, preferably a diazo resin represented by a condensate of an aromatic diazonium salt and formaldehyde, may also be used.

Particularly preferred are salts of condensates of p-diazophenylamine and formaldehyde or acetaldehyde, such as reaction products of hexafluoroborophosphates, tetrafluoroborates, perchlorates or iodates with said condensates. diazo resin inorganic salts and U.S. Patent No. 3,300
Examples include diazo resin organic salts, which are reaction products of the above condensate and sulfonic acids, as described in No. 309. Furthermore, diazo resins are preferably used together with binders. As such a binder, various polymeric compounds can be used, but preferably disclosed in JP-A-54-98
A monomer having an aromatic hydroxyl group as described in Japanese Patent No. 613, such as N-(4-hydroxyphenyl)
Acrylamide, N-(4-hydroxyphenyl)methacrylamide, 01m-, or p-hydroxystyrene, o-+l1l-.

or I]-Copolymer of hydroxyphenyl methacrylate chopsticks and other monomers, U.S. Pat. No. 4,123,276
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit, natural resins such as shellac and rosin, polyvinyl alcohol, US Pat. No. 257 Mei 4; Polyamide resin described in US Patent No. 3,660,
Celluloses such as linear polyurethane resins described in No. 097, polyvinyl alcohol heptatalate resins, epoxy resins condensed from bisphenol A and epichlorohydrin, cellulose acetate, and cellulose acetate heptatalates are included.

(4) Photosensitive composition containing an o-quinonediazide compound The o-quinonediazide compound contains at least one O-quinonediazide group, preferably an O-penzoquinonenoando group. Compounds having various known structures, such as J, Kosar-9[L
light-Sensitive SystemsJ(J
ohn Wiley & 5ons+Inc, 196
(Published in 1999), pages 339-353, which include compounds described in detail. Especially with various hydroxyl compounds
Preference is given to esters with 0-7-diacid sulfonic acid. Preferred hydroxyl compounds include:
condensation resin of 7-el and carbonyl group-containing compound,
In particular, resins obtained by condensation in the presence of an acidic catalyst are mentioned. Examples of the phenols include phenol, resorcinol, cresol, pyrogallol, etc., and examples of the carbonyl group-containing compound include aldehydes such as formaldehyde and benzaldehyde, and ketones such as acetone.

Phenol/formaldehyde resin, cresol/
Formaldehyde resin, pyrogallol acetone resin,
Resorcinol benzaldehyde +7 (fat is preferred.

Typical examples of 0-quinonenoanodo compounds include:
an ester of benzoquinone (1,,2)-diazide sulfonyl chloride or 7-toquinone-(1,2)-diazide sulfonyl chloride with a 7-ether formaldehyde resin or a cresol formaldehyde resin;
Sulfonic acid ester of tohyrol-acetone resin described in U.S. Pat. No. 3,635,709, JP-A-56-1044 The condensate of sulfonyl chloride and resorcinol-benzaldehyde resin described in JP-A-55-76346; 7toquinone-(1,2)-noazidoho(2)-
Ester compounds of 5-sulfonyl chloride and resorcinol-pyrogallol-acetone copolycondensate, and other useful 0-quinonediazide compounds are disclosed in JP-A-50-1
Polyesters having hydroxyl groups at the terminals are esterified with 0-su7toquinonediazide sulfonyl chloride as described in Japanese Patent Publication No. 17503, and
- Hydroxystyrene homopolymers or copolymers of this and other copolymerizable monomers are esterified with 0-su7toquinone diazide sulfonyl chloride.

Such a quinonediaside type photosensitive material can be used in combination with an alkali-soluble resin as a binder, if necessary. As the alkali-soluble resin, those obtained by combining phenols and ketones or aldehydes in the presence of an acidic catalyst are preferred. The 7 er/-ers include:
Examples include phenol, cresol and p-substituted pheno-fury. Examples of the aldehydes include acetaldehyde and formaldehyde, with formaldehyde being preferred. Acetone is preferred as the ketone.

Preferred alkali-soluble at+11 include, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensate resin as described in JP-A-55-57841, JP-A-55-57841; With polyvalent 7-ethers such as copolycondensate resins of p-substituted phenols and 7-emers or cresol and formaldehyde, resorcinol-benzaldehyde resins, pyrogallol-benzaldehyde resins, etc., as described in Japanese Patent No. 127553. Examples include condensates with benzaldehyde, copolycondensates of polyhydric phenol and acetone such as pyrogallol-resorcinol-acetone resin, and xyler-formaldehyde resins.

The photosensitive composition can include a purine-out material that forms a visible image upon exposure to light.

The printout material consists of a compound that generates an acid or a free radical when exposed to light, and an organic dye that changes its color tone by interacting with it. 0-su7toquinone diazido 4-sulfonic acid halide described in Publication No. 1988-3Cd09-2, JP-A-53-36
Trihalomethyl-2-pyrone and trihalomethyl-trianone described in JP-A No. 223, and o-su7toki/dido-4-sulfonic acid chloride and electron-withdrawing substituent described in JP-A No. 55-6244. and esterified or amide compounds with anilic acid, halomethyl-vinyl-oxadiazole compounds and diazonium salts described in JP-A-55-77742, and the like.

In addition, examples of the organic dyes include Victoria Pure Blue Boil (manufactured by Sakutogaya Chemical Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Oil Blue I 603 (manufactured by Orient Chemical Industry Co., Ltd.), Examples include Sugun Blue 11 (manufactured by BASF), Crystal Violet, Malachite Green, Tsukusin, Methyl Violet, Ethyl Violet, Methyl Orange, Brilliant Clean, Fungolet, Eosin, Rhodamine 6G, and the like. Further, various additives such as additives and plasticizers for improving coating properties can also be added to the photosensitive composition.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. Examples of solvents that can be used include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexane, methyl ethyl ketone, and the like. The coating amount of the photosensitive layer is preferably 0.5 to 5 g/2.

After exposing the lithographic printing plate material of the present invention, a lithographic printing plate can be obtained by processing it with a developer suitable for the photosensitive composition used.

By carrying out lithographic printing using the lithographic printing plate obtained from the lithographic printing plate material of the present invention, it is possible to obtain a large number of good-quality printed matter without the occurrence of background smearing, and also to support a support having a chromium-based coating layer. In some cases, it can also eliminate background stains. This printing plate also has good stability against chemicals used in processing and printing steps. Furthermore, when the above-mentioned printing material is added to the lithographic printing plate material of the present invention, the formation of a visible image is not hindered.

Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto. The results of the various tests are summarized in a table.

Example 1 An aluminum plate was roughened by electric field etching,
Then, an anodizing treatment and a sealing treatment using hot water were performed. This support was placed in a surface treatment solution having the following composition at 25°C for 60 minutes.
After being immersed for a second, it was washed with water and dried to form an intermediate layer. The film amount of the intermediate layer was 0.10+nH/dm2.

Surface treatment liquid composition (fl'J Compound (1) 20
0 gL5 water
ioo Subsequently, a photosensitive solution having the following composition was coated using a rotating coater and dried at 85° C. for 3 minutes to obtain a lithographic printing plate material of the present invention.

Esterified product of sodium diazide (1,2)-5-sulfonic acid chloride and m-cresol formaldehyde resin (combination ratio 25 mol%) 3.5゜m-
Cresol formaldehyde novolac resin 8. ogsu7toquinone-(1,2)-diazide(2)-4-sulfonic acid chloride 0.15g p-octylphenol novolak resin and 7toquinone-(1,2)-diazide(2)-5-sulfonic acid Esterified product with chloride (condensation rate 50 mol%) 0.12g Oil Blue 9603 (manufactured by Orient Chemical Industry Co., Ltd.)
0.2g methylceronlube
A positive original film was placed in close contact with the photosensitive surface of the 100 g lithographic printing original plate obtained in this way, and exposure was performed for 80 seconds from a distance of 1 m using a 2 KW metal halide lamp (Idolfin 2000, manufactured by Iwasaki Electric Co., Ltd.) as a light source. After that, the plate was developed with a 4% by weight aqueous sodium metasilicate solution at 25° C. for 45 seconds to obtain a lithographic printing plate.

The printout performance (exposure visible image quality) test of photosensitive planographic printing plates, the stability test for processing chemicals (chemical resistance) of planographic printing plates, and the printability test (print durability, stain generation) of planographic printing plates were conducted as follows. I did it like this.

Exposure Visibility Test It is judged whether the difference in tone between the exposed and non-exposed areas of the exposed printing plate under yellow light is clear or not.

Chemical Resistance Test A A developed planographic printing plate is immersed in a plate cleaner (Ultra Plate Cleaner Δ, B, C) for 60 minutes, washed with water, and then the degree of dissolution of the image area is determined.

Printing aptitude test Planographic printing plate offset printing machine (Hamada Star CI)
90 (manufactured by Hamada Printing Machinery Co., Ltd.) to judge the printing durability and occurrence situation.

Example 2 An aluminum plate was roughened by electric field etching, then anodized, and then metasilicate) l)
The pores were sealed using a rum aqueous solution.

This support was surface treated in the same manner as in Example 1 to achieve a film thickness of 0.
An intermediate layer of 13 g/da2 was provided.

Next, a photosensitive liquid having the following composition is spin-coated onto this intermediate layer (
It was coated using a reed and dried at 85° C. for 3 minutes to obtain a lithographic printing original plate.

Copolymer A 5. og diazo resin B O, 5g Jurimer AC-1OL (manufactured by Nippon Pure Chemical Industries, Ltd.) 001g Victoria Pure Blue ([1011) (Hodogaya Chemical Co., Ltd.)
Co., Ltd.) 001g methyl cellosolve
100 mQ (however, the above copolymer A
A composition of p-hydroxyphenylmethacrylamide/acrylonitrile/ethyl acrylate/methacrylic acid = 10/30/60/6 in molar ratio was dissolved in methyl cellosolve and heated at 65°C for 10 hours in a sealed tube purged with nitrogen. After the reaction was completed, the reaction solution was poured into water with stirring, and the resulting white precipitate was filtered and dried. Diazo resin B is 5% by weight of diazo resin (trade name = D-0) at room temperature.
12, EIIC Co., Ltd.) aqueous solution and a 10% by weight ammonium hexafluorophosphate aqueous solution, the resulting precipitate was collected by filtration, and dried under reduced pressure at 30 to 40°C. . The weight average molecular weight of the copolymer A is so, o
Furthermore, when the molecular weight distribution of diazo resin B was measured by delpermeation chromatography (GI'C), it was found that the proportion of trimers and below was 93 mol %. )
The coating weight after drying is 2.0. /ω2.

A negative original film was brought into close contact with the photosensitive surface of the lithographic printing plate precursor obtained in this way, and a 2Kl metal halide lamp (
After exposure was carried out for 42 seconds from a distance of 1 m using an Idol Fin 2000 (manufactured by Iwasaki Electric Co., Ltd.) as a light source, development was performed at 25° C. for 45 seconds with a developer having the composition shown below to obtain a lithographic printing plate.

Phenyl cellosolve 160g Noethanolamine 70g Bionin He-44B (manufactured by Takemoto Yushi Co., Ltd.) 50g Water 7
80 g An exposure visible image property test and a printability test were carried out in the same manner as in Example 1, except that the following chemical resistance test) B was carried out in place of the chemical resistance test) A in Example 1.

Chemical Resistance Test B A developed planographic printing plate is immersed in plate protective ink PI-2 (manufactured by Fuji Photo Film Co., Ltd.) for 24 hours, washed with water, and then the degree of dissolution of the image area is determined.

Example 3 A lithographic printing plate was prepared and tested in the same manner as in Example 1, except that the following surface treatment liquid was used instead of the surface treatment liquid in Example 1. The amount of film in the middle layer is 0.11! I1g/dI
02゜Surface Treatment Liquid Composition Example 4 A lithographic printing plate was prepared and tested in the same manner as in Example 1, except that a surface treatment liquid having the following composition was used instead of the surface treatment liquid in Example 1. Intermediate layer film amount 0.18mg/
dm2° Surface Treatment Liquid Composition Example 5 A lithographic printing plate was prepared and tested in the same manner as in Example 2, except that a surface treatment liquid having the following composition was used in place of the surface treatment liquid in Example 2. Intermediate layer film f40.14mg/
dm2° Surface Treatment Liquid Composition Example 6 A lithographic printing plate was prepared and tested in the same manner as in Example 1, except that a surface treatment liquid having the following composition was used in place of the surface treatment liquid in Example 1. Film amount of intermediate layer: 0. IIB/
dm2° Surface treatment liquid composition Example 7 An iron plate with a thickness of 0.15 m111 was subjected to gas honing treatment. (This step can be omitted if there are no foreign substances on the surface of the iron plate.) Next, as a pretreatment process, the iron plate is used as a counter electrode in the electrolytic solution shown below, and electrolytically treated under the electrolytic conditions shown below. did.

Electrolytic solution Chromic anhydride 100 Kg Nitrogen
Acid 4Δ/dm2
water 10
00 Viewing electrolysis conditions DC voltage 6v current density
4A/dII12 liquid temperature
25℃ Cathode Iron plate (1,2m2) Anode Iron plate as plate material (1,2+n2
) Treatment time: 1 minute The iron plate that had undergone the pretreatment process in this way was then washed with shower water, and then subjected to the next main treatment process. The composition of the electrolytic solution and the electrolytic conditions in this treatment step are shown below.

Electrolytic solution chromic acid anhydride 400 Kg sulfur
Acid 2.5 Kg
Pure water 10
00 Electrolysis conditions DC voltage 4■Current density
208/d "2 liquid temperature
5ge0 negative pole
Iron plate as a plate (1,2 "r12) Anode Lead plate (1,6+n2) Processing time 20 seconds After completing this treatment process, the iron plate was then washed with water in the shower.
It was immersed in a 5% by weight aqueous caustic soda solution at 40° C. for 1 minute, washed with water, and then subjected to the same surface treatment as in Example 1. The amount of film in the middle layer is 0.12mg/dm2
Met.

Next, a photosensitive layer was applied in the same manner as in Example 1 to prepare a lithographic printing plate material, and a test was conducted.

Example 8 A steel plate was treated by the method described in JP-A-55-145193 to provide a chromium electrodeposited layer, and then immersed in a 5% by weight caustic soda aqueous solution at 40°C for 1 minute and washed with water. Surface treatment was performed in the same manner as in Example 1, followed by washing with water and drying. The film amount was 0.13+ng/dm2.

Next, a lithographic printing plate material and a lithographic printing plate were prepared in the same manner as in Example 2, and tested.

Example 9 A lithographic printing plate material and a lithographic printing plate were prepared and tested in the same manner as in Example 7 except that the following electrolytic solution was used in the main processing step of Example 7.

The film amount of the intermediate layer was 0.13+og/dm2.

Electrolyte Chromic anhydride 430 KB Barium nitrate 3.8 Kg Nitric acid (64%) 1
．． 2 7 ammonium hydrogen fluoride 5 kg vinegar
Acid 0.2K
.

Barium heptafluoride 0.1 Kg water
1000
North Example 10 A lithographic printing plate material and a lithographic printing plate were prepared and tested in the same manner as in Example 7, except that the same surface treatment liquid as in Example 3 was used as the surface treatment liquid. The film amount of the intermediate layer was 0.1.2 mg/d+o2.

Example 11 A lithographic printing plate material and a lithographic printing plate were prepared and tested in the same manner as in Example 8, except that the same surface treatment liquid as in Example 4 was used. The amount of film in the middle layer is 0.18+
It was ng/dm2.

Example 12 A lithographic printing plate material and a lithographic printing plate were prepared and tested in the same manner as in Example 1, except that the same surface treatment liquid as in Example 5 was used. The amount of film in the middle layer is 0.15m
g/dm2.

Example 13 Instead of the support of Example 2, a surface average roughness of 30.9μ [n
Electric power g) Teppaku ni Saanen)? A lithographic printing plate material and A lithographic printing plate was prepared and tested. The amount of skin IIi in the middle layer is 0.
121111? / dm2teatsuta.

Comparative Example 1 A lithographic printing plate was obtained and tested in the same manner as in Example 1, except that the surface treatment step was omitted.

Comparative Example 2 A lithographic printing plate was prepared in the same manner as in Example 1, except that the surface treatment step of Example 1 was omitted and a photosensitive solution in which 0.28 of Exemplified Compound (1) was added to the photosensitive solution of Example 1 was used. I have created and tested it.

Comparative Example 3 A lithographic printing plate was obtained in the same manner as in Example 7, except that the surface treatment step was omitted.

Exposure visibility ○: Clear image baked under yellow light ×: Unclear image baked under yellow light Chemical resistance ○: Image area not dissolved ×: Image area dissolved printability (stains) ○: No stains generated ×: Printing Scratching occurred in the early stage Agent Yoshi Kuwahara Procedural amendment (method) % formula % 1. Indication of the case 1982 Patent Application No. 210483 2. Name of the invention Lithographic printing plate material and its manufacturing method 3. Amendment Relationship with the case of the person who filed the patent application Address of the patent applicant Tokyo Ina; 1-26-2 Nishi-Shinjuku, Shinjuku-ku Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 191 Address: 1-6 Sakura-cho, Hino-shi, Tokyo, Subject of amendment - 7. Contents of amendment: Engraving of the specification as shown in the attached sheet (no change in content)

Claims (2)

[Claims] (1) In a lithographic printing plate material having a photosensitive layer on a support, a non-photosensitive intermediate layer containing a silane coupling agent is provided adjacent to the support between the support and the photosensitive layer. Characteristic lithographic printing plate materials. (2) A method for producing a lithographic printing plate material, which comprises treating the surface of the support with a liquid containing a silane coupling agent and then providing a photosensitive layer.