JPS5931192A - Support for planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a support for a planographic printing plate excellent in latitude of developability and printing durability, by using an iron material with center line average roughness of 0.1-3mum as an iron material on which a cromium electrodeposition layer is formed. CONSTITUTION:As an iron material used as a base material, a plate shaped one which may be made of an iron alloy such as carbon steel or special steel other than pure iron and subjected to surface roughening treatment so as to bring the center line average roughness (Ra) thereof to 0.1-3mum is used. Surface roughening may be performed by either one of a mechanical method, a chemical method and an electrolytic method. A chromium electrodeposition layer having protruded parts formed on the iron material has, for example, polygonal crystal substance and/or the agglomerate thereof and pref. has a thickness of 0.01- 10mum and can be formed by a method wherein the iron material is subjected to electrolytic treatment in a plating liquid having the ratio of Cr<6+> ion concn. and sulfate ion concn. of 75-18 at current density of 100A/dm<2> or less and a temp. of 40 deg.C or less for 30sec or more.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a support for a lithographic printing plate, and more particularly to a support for a lithographic printing plate having a roughened surface and a chromium electrodeposited layer on an iron material.

It is disclosed in JP-A-56-1:50395 and JP-A-56-133396 that iron materials with roughened surfaces, such as iron foil manufactured by electroforming, are used as supports for lithographic printing plates.
No. 56-1505 So2 and No. 57-64597.

However, lithographic printing plates using these supports have drawbacks such as insufficient printing durability due to peeling of 11! Problems such as "one-hand development" in which development is done by soaking a sponge in developer and rubbing the plate without using an imager can easily cause damage to the image area.
That is, there is a problem that the latitude of development is limited.

Therefore, an object of the present invention is to provide a support for lithographic printing plates having sufficient performance in terms of developability latitude and printing durability.

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

The object of the present invention is to improve the centerline average roughness.1. La ) or 01
Chrome electric H”1 with protrusions on iron material with a length of ~38m
This is achieved by a lithographic printing plate tr=1 body characterized by having a layer.

The present invention will be explained in more detail.

In the present invention, the iron material includes pure iron and alloys of iron and other elements. Other elements that form alloys with iron include carbon, manganese, and nickel.

Specifically, the alloy is carbon 41'.1 (carbon (00
Cast iron has a higher carbon content (1.5% + 7%) than carbon bound, and special alloys containing other elements (such as manganese, nickel, chromium, cobalt, tungsten, molybdenum, etc.) Oki 1 (e.g. Mankan steel, nickel steel,
chromium steel, nickel-chromium steel, etc.). The above-mentioned carbon steel and [7] polar ζ moe (carbon 0.25% or less)
, mild steel (0,'25~0.5%), hard steel (carbon 0.5~0.5%),
1.0%), N! W? i! ! (carbon 1.0% or more) is included.

The iron material used in the present invention is a plate-like material (including a foil-like material) manufactured by a rolling method, a 4-gas casting method, etc.
can.

The iron material in the present invention has a center line average roughness of Ra or 0.
．． 1 to 3 μm, but here the center line average roughness R,
a) means assembled as shown in D-work N4768...1
It is the average of the absolute value of the deviation of each point on the curve from the center line at m, where the horizontal center line is the X axis and the vertical direction is the Y axis.
When the point on the roughness curve is expressed as the axis,
It is expressed in microns as Ra 4M, which is determined by the following formula for the measurement length em.

The diameter a of the iron material of the present invention is preferably 0.3 to 2 μm, and particularly preferably 0.3 to 1.5 μm from the viewpoint of water retention.

As a method for manufacturing iron materials with such center line average roughness,
Various conventionally known methods can be used, including mechanical methods, chemical methods, and electrolytic methods. Examples of mechanical methods include ball IJ1 polishing method, brush polishing method,
Examples include a polishing method using liquid honing. Chemical methods include etching with a solution containing sulfuric acid, phosphoric acid, nitric acid, @acid, oxalic acid, pyrophosphoric acid, ferrous chloride, hydrogen peroxide, etc. As a method using electrolysis, '[[t.

Examples include a method of etching by electrolytic solution and a method of plating by electrolysis. Examples of the electrolytic etching method include a method of etching using a solution containing phosphoric acid, sulfuric acid, perchloric acid, salt alcohol, nitric acid, pyrophosphoric acid, hydrofluoric acid, acetic anhydride, etc.4.

i! Methods for plating by solution include methods using acidic baths such as sulfate baths, chloride baths, boroptide baths, mixed salt baths (for example, sulfate chloride baths, sulfamic acid 21≧l iron baths). In producing the roughened iron material, the above-mentioned various methods can be appropriately selected and used depending on the composition of the iron phase, etc. Particularly preferred in the present invention is the method of plating with iK FW. It is.

The iron material in the present invention has an Ra of 01 to 3 μm, and especially a burry count T at a cutting line of 04 μm measured with a Belten belt meter type 35F.

is preferably 300 to 500. T here,
is the number of peaks per inch that cross the cut line set in the roughness profile R and then fall below the center line.

As long as the Ra of the above-mentioned roughened iron material is within the above-mentioned range, surface treatment may be applied to the roughened iron material prior to providing the chromium rrt, s layer having protrusions.

Examples of the surface treatment include methods of plating lead, nickel, copper, tin, chromium, etc. by electroplating, chemical plating, hot-dip plating, vapor phase plating, etc., phosphates, oxalates,
71. Film formation methods using chromate, etc. (methods using electrolysis may also be used), etc. Ru.

In addition, if the surface-surfaced iron material is as thin as a foil, for example, made by electric or pneumatic incubation, a metal plate, plastic film, etc. may be attached to the back surface directly or through an adhesive layer. May be combined. This bonding step may be performed before or after the step of providing the chromium electrodeposition layer having protrusions.

Surface treatment is applied to the roughened iron material mentioned above.
L.

Iron materials of the present invention also include materials in which metal plates or the like are bonded to the front and back surfaces.

The chromium electrodeposition layer having protrusions in the lithographic printing plate support of the present invention will be explained below.

Various types of chromium electrodeposited layer can be used as long as the lua of the lithographic printing plate support is maintained within the above-mentioned range.

A preferred shape of the protrusions of the chromium electrodeposited layer is, for example, an aggregate of curved, slightly agglomerated duct-shaped particles with small round protrusions, which are fused and flooded. For example, JP-A-55-1451 has virtually no corners.
No. 93, as well as angular crystals and/or collections thereof 821 and the applicant's Sho Jul 57
On June 18, 2003, the product described in the specification No. 57-2 (title of the invention "Support for lithographic printing plate") was disclosed. /or chromium having aggregates therein ``r#J, deposited layer on lithographic printing plate σ) Tolerance of printing durability and developability L (more excellent and preferable in Q). Alternatively, the hexahedral shape is preferably cubic.

The plate-like crystals are preferably polygonal, mainly 6) to 14-shaped plates, and the diameter of the polygonal cedar-shaped crystals is 0.5 to 5.
μm is preferable, and the EX size is O, f) 1 to 0.8
Preferably, the thickness is μm. The hexahedral crystals are preferably cube-shaped, particularly those with side lengths of 0.1 to 2 μm. The projected area ratio of the above-mentioned protrusions is preferably 20% or more. Here, the projection rate is a projection perpendicular to the direction of the support having the ↑electrodeposited layer of the present invention, that is, orthogonal projection, and the rate can be measured by microphotographs or the like.

The protrusions are preferably 0.3 to 5 microns thick, particularly preferably 05 to 4 microns thick, on the surface of the electrodeposited chromium layer.

The thickness of chromium T [4 layers is preferably 0.0 l-j10 μm, particularly preferably 0.01 to 4 μm.

This film thickness can be determined as an average value using a chromium plating layer with a known reference film thickness by means of a fluorescence X-ray analysis and a constant S41 from a pre-prepared test Qi.

The elemental composition of the chromium electrodeposited layer consists essentially of chromium and oxygen, and elemental analysis in the gamma direction shows that it consists essentially of chromium oxide (this oxide also includes hydrates) and metallic chromium. Chromium oxides include divalent, trivalent, and hexavalent chromium oxides. is mainly an oxide of trivalent chromium.

FIG. 1 is an electron micrograph of Table 11ri of the roughened iron phase before providing the chromium layer. Figures 2 to 4 are 7E microscopic photographs of the surface of a support according to Book@1v1, in which a chromium electrodeposition layer having plate-like protrusions 1ηζ is formed on a roughened iron material.

Next, four typical methods of providing a chromium conductive layer having protrusions on a roughened iron material will be described.

Curved, slightly agglomerated, solid particles with small round protrusions (h1) are rapidly coalesced into 1, 1 and 2.
A chromium electrodeposited layer with rounded protrusions is formed after immersing the beverage in a granulation tank containing a biflu slide.
/5042- in an amount of water having a ratio of 75 to 180 1λ·)11 (containing hydrochromic acid and sulfuric acid) for at least 30 seconds + rtl in one cup.

For specific conditions, please refer to t11'I55 145
It is described in detail in Publication No. 193.

A preferred method for providing a chromium electrodeposited layer having protrusions that are angular crystals and/or aggregates on a steel material is, for example, by cooling or heating the electrolytic solution 1 shown in dl to adjust the liquid temperature. , The solution treatment is carried out under the electrolytic conditions 1 shown in Table 2. This CIW liquid 1 is an electrodeposited chromium layer forming solution for forming a chromium layer of 6 on the surface L of the iron phase.

Table 1 Electrolyte solution l Chromic anhydride (Or, OB) l OO~5oog barium compound 1~10g Fluoride 9 example is water fluoride (HIF) O~20g nitric acid
Acid: 0 to log acetic acid Acid: 0 to 1 g Make the total amount to 11 with water.

Table 2 1B, solution condition 1 DC voltage 5-15 (V) Current density 5-50 A/d Soup wet 0-60'C negative
Polar iron material @
Electrode Lead Electrode Area ratio of cathode to 1 intimidation electrode 1: l~l: 1.5 Processing time 2~6 minutes This method was published by the applicant on June 18, 1982.
The invention is described in detail in the specification (title of the invention: ``Method for manufacturing a support for lithographic printing plate'') attached to the patent application (3) filed in Japan.

Another preferred method for providing a chromium electrodeposited layer having protrusions that are angular crystals and/or aggregates thereof on a steel material is [Or□+]/[so,'-] (where [ar ”
] is Or6+ ion srv, [so, t −] is S
O1! - represents the ion's degree. ) or 75-18
This is a method in which the electrodeposited plate (4) is applied to the iron material by dissolution treatment for 30 seconds or more in a plating solution of 0.0 m at a flow rate of 100A/d77/ or less and a temperature of 40°C or less. , [Cjr
” ] is preferably 0.2 to 4.5 mol/l, and preferably 0.5 to 4.5 mol/l.
Particularly preferred is 3 mol/l. [5n42-] is 0.0
1 to 0.046 mol/l is preferable, and 0.015 to 0.0
3 mol is particularly preferred. "Cr'+ supply source 7 is preferably chromic anhydride, and so, '- supply source is sum 1
1. Acid is preferred.

Hexavalent ROM ion concentration and I++! l, the ratio of acid ion 6i ([Or]/[so,'-]) is 75 to 180
and preferably i=tso is in the range of 130. The plating solution of the present invention may also contain fluorine compounds, strontium compounds, and the like. Examples of the fluorine compound include ammonium fluoride, sodium fluorosilicide, silica fluoride, chromium 7silicate, and the like.

Strontium compounds include strontium sulfate,
Examples include strontium chromate.

The amount of the fluorine compound added is 0.5 to 10 g/l, and the amount of the strontium compound added is 3 to 20 g/l.

The electrolytic conditions in the present invention include a current density of 100A
/drI? or less, preferably 10 to 30p, 7d
The range is 7. Furthermore, the plating bath temperature is preferably 0 to
40°C1, particularly preferably in the range of 10-30'C. Regarding the relationship between bath temperature and current density, it is preferable to increase the current density when the bath temperature is high and to decrease the current density when the bath temperature is low. Preferably bath temperature 22±4℃ and current 'H5I
This method is described in the specification attached to the patent application filed by the applicant on the same date as the present application (title of the invention: ``Method for manufacturing a lithographic printing plate support''). is described in detail.

It is also possible to perform appropriate pre-treatments and post-treatments before and after the step of providing the chromium electrodeposition layer (main treatment).

Examples of the pretreatment step include the following method. Table 3
An iron plate was used as a counter cathode electrode for electrolyte 2 shown in Table 4.
1 solution processing is performed under electrolytic conditions 2 shown in .

Table 3 Electrolyte solution 2 Chromic anhydride 80-200g Nitrogen
Acid (64%) 0.5-1 Make up to 11 with ml water.

Table 4 Electrolysis conditions 2 Night, flow WtFF, 4~xov Current V DL2~l Q A/dm7 liquid
Thirst 10℃～40℃Sun
Area ratio of iron material cathode and anode
1:1 Processing time: 30 seconds to 5 minutes In this way, water is sprayed onto the pre-treated Jul L and takk4Δ using a shower and washed, and then the main processing step is started.

Preferred methods for the post-treatment step include the following method.

After washing the iron material having the chromium electrodeposited layer with an acid or alkali aqueous solution as required, the surface is treated with a surface treatment solution of a permanganate aqueous solution.

Preferred permanganates used in the above surface treatment solution include lithium diormanganate, sodium permanganate, potassium permanganate, rubidium permanganate, potassium permanganate, barium permanganate, etc. There is. The content of manganate in the surface treatment liquid used is preferably 0.05 to 10% by weight, particularly preferably 11.0 to 5.0% by weight. i of treatment liquid
The bA degree is preferably 0 to 80°C, particularly preferably 20 to 80°C.
The temperature is 50°C. Regarding this method, the specification (
The title of the invention is ``Method for manufacturing a support for a lithographic printing plate,'' which describes the invention in more detail.

Another preferred method for the post-treatment step is the following method.

After washing the iron phase having the chromium electrodeposited layer with an acid or alkaline aqueous solution as necessary, a water-bathable polymer compound,
Also calcium and magnesium 1. The surface is treated with a surface treatment solution containing at least one selected from water-soluble salts of lead, barium, strontium, cobalt, manganese, nickel, and silicon.

The water-soluble polymer compound preferably has a solubility of 0.001% or more. Preferred water-soluble polymer compounds include, for example, natural polymer compounds such as arabicum, starch, textrin, sodium alginate, and gelatin, water-bathable cellulose thread compounds, such as water-soluble salts of carboxyalkylcellulose (alkyl is methyl,
ethyl, propyl, etc.), alkylcellulose such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydrodipropylcellulose, etc., polyacrylic acid or its water-soluble salt, polymethacrylic acid or its water-soluble salt, acrylic acid copolymer or a water-soluble salt thereof, a methacrylic acid copolymer or a water-soluble salt thereof, a styrene-maleic anhydride copolymer, a synthetic polymer compound such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, etc., including a water-soluble salt of a polymer compound. Examples 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, natural polymer compounds such as starch and dextrin and water-soluble cellulose compounds are preferred. Also, the molecular weight is 500
~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 organic acids such as calcium, magnesium, zinc, barium, strontium, cobalt, manganese, and nickel. and silicon salts. Typical organic acid salts include acetic acid, propionic acid, butyric acid, succinic acid, and K-benzene.
i acids, salts of carboxylic acids such as salicylic acid, and acetylacetonates. Representative inorganic acid salts are chloride, bromide, chlorate, bromate, iodide, iodate, nitrate, sulfate and phosphate. The water-soluble salts may be used alone or in combination of two or more.

As water-soluble salts, organic acid ends are particularly preferred, and calcium, magnesium, barium and zinc salts are particularly preferred. The coating weight of the layer containing the water-soluble polymer compound and the water-bathable salt formed by this method is 0.001
~l m9/d go is preferable, especially 005~0.5m
7 d, I is preferred. This method and the film formed are described in 1 "r1 June 1, 1957" by Mr.
In the specification attached to the patent application (6) dated August 8 (Title of the invention [Support for lithographic printing plate and method for producing the same)], there are numerous references to this invention.

An IB photosensitive lithographic printing plate can be produced by coating a photosensitive composition of Group I on a non-exploitable Ill support using, for example, an organic solution of W.

However, the photosensitive composition contains a photosensitive material 'ef as an essential component, and as a photosensitive material, 1 g of the photosensitive material is currently
! Those in which there is a difference in the M dissolution of the photosensitive composition layer with respect to liquids, those in which there is a difference in the adhesive force between molecules before and after Dew C, and the affinity of the photosensitive composition layer for water and oil due to Dew C You can use it to see if there is a difference or not.

Below, we will explain some typical examples. First, quinonediazide-type positive photosensitive materials such as conventionally known 0-naphthoquinonediazide compounds are mentioned.

The 0-quinonediazide compound is a compound having at least one 0-quinonediazide group, preferably an 0-benzoquinonediazide group or an 0-su7toquinonediazide group,
Known compounds of various structures, e.g. J. Kosar
Author: “Light-8 intensive Systems
J (John Wiley & 5one, Eng nc, 1
965, Publication 2, pages 339 to 353, M)' includes the compounds described in detail. Particularly suitable is an ester of a natural hydroxyl compound and 0-naphthoquinonediazide sulfonic acid. Preferred hydroxyl compounds include condensation resins of phenols and carbonyl group-containing compounds, particularly those which can be produced by condensation in the presence of an acidic catalyst. Rare.

The resin is praised. Examples of the phenols include phenol, resorcinol, cresol, and virocalol. Examples of the carbonyl group-containing compound include aldehydes such as formaldehyde and benzaldehyde, and ketones such as acetone.

Particularly preferred are phenol/formaldehyde)'[I]L cresol autoformaldehyde resin, pyrogallol/acetone tree 1]F7, and resorcinol/benzaldehyde resin.

Typical specific examples of 0-quinonediazide compounds include:
Ester of benzoquinone-(1,2)-diazide sulfonyl chloride or naphthoquinone-(II2)-diazide sulfonyl chloride with phenol-formaldehyde manure or ittalesol-formaldehyde resin, 1% U.S. Pat. No. 3,635.709 Naphthoquinone-(1,2)-diazide sulfonyl chloride and pyrogallol del described in JP-A-56-1044) (2) -5
-Condensation product of sulfonyl chloride and resorcinol-benzaldehyde resin, naphthoquinone-(1.2)-diazide-(
2) an ester compound of -5-sulfonyl chloride and a resorcinol-pyrogallol-acetone co-dC&7 compound;
Other useful 0-quinonediazide compounds include those prepared by esterifying a polyester having a hydroxyl group at the terminal with 0-naphthoquinonediazide sulfonyl chloride as described in JP-A-50-117503; A homopolymer of p-hydroxystyrene as described in 'i133Q5 or a copolymer of this with other copolymerizable monomers
Examples include those obtained by subjecting naphthoquinonediazide sulfonyl chloride to an esterification reaction.

Containing these O-quinonediazide compounds 1? c is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition.

Such a quinonediazide type positive photosensitive material can be used in combination with an alkali-soluble fat as a binder, if necessary. As the alkali-soluble 411 litf, those obtained by combining phenols and ketones or aldehydes in the presence of an acidic catalyst are preferred. Examples of the phenols include phenol, cresol and p-substituted phenol. Preferred examples of the aldehydes include acetaldehyde, formaldehyde, and loformaldepide. As the ketone force J, acetone is preferable.

Preferred alkali-soluble resins include, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, and phenol-cresol-formaldehyde resin as described in JP-A-55-57841. Condensate resistance IIIR% JP-A-11
1'' 55-12← Co-lk condensates of p-substituted phenol and phenol or cresol and formaldehyde, which are described in Japanese Patent No. 553, 1ii4,
resorcin-benzaldehyde ffV IIt7, condensates of polyhydric phenols and benzaldehyde such as pyrogallol-benzaldehyde resin, co-acrylic condensates of polyhydric phenols and acetone such as pyrogallol-resorcin-acetone resin, xylenol formaldehyde, etc. :
Seedling fat is mentioned. These σ) Alkaline 1-no-silicon soluble tree Jl
The content of i is 30 to 30% of the total solid content G of the M3 photosensitive composition.
It is preferably 90% by weight, particularly preferably 50 to 85% by weight.

As another photosensitive substance, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde may also be used. Particularly preferred are G: j, '%-' of a condensate of p-diazodiphenylamine and formaldehyde or a7toaldebide, for example, [Hegiyafluorophosphate, tetrafluoroboric acid 1'&. t, H. 'h 8a Subate or periodate and nVI 4 compounds and σ) antijl
Diazo resin inorganic salt which is a+ product and American 1r'1
°3rd.

Examples include diazo resin organic salts which are reaction products of the above condensate and sulfonic acids, as described in Patent Nos. 300 and 309. Furthermore, the diazo tree 11W is preferably used together with a binder. As such a binder, various polymeric compounds can be used, but preferably a monomer having an aromatic hydroxyl group, such as 8fN- (4
-Hydroxyphenyllacrylamide, N-(4-hydroxyphenylnometacrylamide, o-, m-, or p-hydroxystyrene, Q-, m-, or p-
Copolymers of hydroxyphenyl methacrylate, etc. and other medicinal substances, mainly containing hydroxyethyl acrylate units and hydroxyethyl methacrylic I/-) units as described in U.S. Pat. No. 4,123,276. Polymers containing repeating units, natural resins such as shellac and rosin, polyvinyl alcohol, U.S. Patent No. 3,
751,257, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, and epoxy resins condensed from polyvinyl alcohol A and epichlorohydrin.
Celluloses such as cellulose, acid m cellulose, and cellulose acetate phthalate are included.

Still another photosensitive material includes I in the main chain or side chain of the polymer.
Moritsu c. Polyvarnishes containing 1OH=OH-0- as hξ are also suitable, and those based on photosensitive polymers such as chills, polyamides, and polycarbonates are also suitable. for example,
Photosensitive polyester obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol, as described in JP-A-55-40415, US Pat. No. 2,956
Photosensitive polyesters derived from (2-properidinemalonic acid compounds and difunctional glycols such as cinnamylidenemalonic acid) as described in the specification of , 878, .

Furthermore, aromatic azide compounds in which the azide group is bonded to the aromatic ring directly or via a carbonyl group, a carbonyl thread, or a sulfonyl group are also used as other yC-sensitive substances. Examples include polyazidostyrene as described in U.S. Pat. The reaction product of the azidoarylsulfanyl chloride and the unsaturated hydrocarbon fiber polymer described in Japanese Patent Publication No. 43-210
No. 67, No. 44-229, No. 44-229154,
Examples include polymers having sulfonyl azide and carbonyl azide, as described in each publication of No. 45-24915.

Furthermore, as another photosensitive material, a former synthetic composition comprising an addition-polymerizable unsaturated compound is also used.

As shown in FIGS. 2 to 4, the support of the present invention has a complex surface shape in which a dense grained shape formed by a chromium adhesion layer with protrusions is present in a fine grained shape formed by the iron material. When used as a photosensitive lithographic printing plate, it has excellent pseudolithic properties with a layer containing many polymeric compounds having an oleophilic surface such as a photosensitive layer provided thereon, and has good printing durability. be. Further, since the developing property has a wide latitude, it is extremely rare for the image i'tls to be removed even in one-hand development 1, which is a more abrasive developer treatment than is necessary.

Furthermore, due to its surface shape, it has good water retention during printing,
Water management is easy, and it is extremely dirty. or,
The durability of the printed area against processing chemicals used during printing is also good.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

However, the embodiments of the present invention are not limited to these 7'L.

Example 1 Thickness O. Using a 1 mg carbon steel plate with the carbon plate as an anode, ferrous chloride 400 zo/l and calcium chloride 2 oom/l.

Using an electrolytic solution with a pH of 0.8 containing
Intense plating was performed to a thickness of 5 μm under the conditions of 0'c and a current density of 30 A/di, and the surface center line average roughness Ra was 05 μm.
An iron-plated steel plate of m was obtained.

Chromic anhydride 250 q/l, °
°Using an electrolyte containing 2.59/l of sulfuric acid, bath temperature: 20°C,
Chrome plating was performed under the conditions of a current density of 20 A/di and an electrolysis time of 1 minute.

The carbon steel plate that had undergone the main treatment step in this way was then washed with shower water, and then transferred to the next post-treatment step. In the post-treatment process, first, add 4% to 5% caustic soda aqueous solution.
IMl & ! for 1 minute at 0°C. Then, the sample was washed with shower water, and then immersed in an aqueous solution of carboxymethylcellulose sodium salt and calcium acetate (0.07@!t% each) at room temperature for about 1 minute, and then washed with shower water.

After finishing the post-treatment process, drying +i was performed with cold air.

Next, a photosensitive coating solution having the following composition was applied onto this support using a spin coater, and dried at 100°C for 4 minutes to prepare a lithographic printing plate material.

(n@photosensitive coating liquid composition) ・Naphthoquinone-<1,2)-diazide-(2) -5
- Esterified product of sulfonic acid chloride and m-cresol formaldehyde novolac 1IvHh (condensation rate 25 mol%) 3.5,9 m -Cresol formaldehyde novolak resin
8.0g・su7toquinone (1
,2)-Diazido-(2)-4-sulfonic acid chloride 0.15. Esterified product of lit p-octylphenol novolac resin and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride (condensation rate 50 mol%)
O, 12g skewer oil blue #603 (manufactured by Orient Kagaku Kogyo ■) o, 2g ethyl cellosolve 100. ! The coating weight after 1 drying was about 2.7 mm.

A positive original film and a step tablet for sensitivity measurement (A 2 manufactured by Eastman Kodak, 21 steps with a density difference of 0.15 each) were adhered onto the lithographic printing plate material obtained in this manner, and 2 KW metal halide was applied. I use a lamp (Idol Fin 2000 manufactured by Iwasaki Electric Co., Ltd.) as a light source.
I! The plate was heated for 80 seconds from a distance of I, and developed with a 4% aqueous sodium metasilicate solution at 25° C. for 45 seconds to obtain a lithographic printing plate.

In order to examine the adhesion between the support and the image area and the printing durability of the printing plate, a processing chemical resistance test and a printing test were conducted.

As a treatment chemical resistance test, durability against the isopropyl alcohol aqueous solution used in the Thalgren dampening device was investigated.

++lfi with density difference on the above grayscale stairs
The printing plate with the image formed thereon was immersed in a 35% aqueous solution of isopropyl alcohol for 10 minutes at room temperature, then washed with water and rubbed with absorbent cotton soaked in water. The degree of corrosion of the image area against chemicals was determined by comparing it with the image area.As a result, the printing plate showed good treatment chemical resistance with no erosion of the image area.The printing durability test was conducted using offset printing. (I applied the printing plate to a Hamada Star 900 CDX) and performed the printing process, and it took 44 hours before the image area was damaged and printing became impossible.
It was measured by the number of printed matter. As a result, +m
With the A printing plate, good prints up to 20,000 sheets could be obtained. In addition, the printing plate showed no stains during printing, and also had good water retention.

EXAMPLE An iron-plated steel sheet that had been iron-plated under the same conditions as in Example 1 was chromium-plated using FjL solution and electrolytic solution having the following composition.

Electrolytic solution Chromic anhydride +30jl/71 (1 barium oxide 3.B9/1 nitric acid (64
%) 1.2ml/73 ammonium hydrogen fluoride
51/1 acetic acid
0.2g/l barium fluoride 0.19/1 Electrolysis Conditions Current +f; Degrees 5A/d771" Liquid Humidity 5°C Cathode
Iron plated hM plate anode When processing lead plate h 5 minutes When preparing the electrolyte, first pref + i ? lt Pi
(), and then add the two fluorides to form an electrolytic solution.

Next, post-ripening 511 similar to Example 1 was carried out, washing with water,
Drying was performed.

A lithographic printing plate material was obtained by applying the same formulation as in Example 1 onto the thus obtained Wi plate support having a chromium layer on its surface.

This lithographic printing plate material was exposed and developed in the same manner as in Example 1 to obtain a lithographic printing plate, and this lithographic printing plate was subjected to treatment chemical resistance tests NR and 1-IJ J! in the same manner as in Example 1 above. Ii
A ll test was conducted. As a result, this printing plate was prepared in Example 1.
Similarly, it has good treatment chemical resistance, water retention, and printing durability.
Up to 70,000 good prints were obtained.

Comparative Example 1 An iron-plated steel sheet was iron-plated under the same conditions as in Example 1, using an electrolytic solution containing 250 g of chromic anhydride/is sulfuric acid and 2.5 g/l of sulfuric acid at a bath temperature of 45"C and a current density. 40A/d
Chromium plating with a thickness of 0.1 μm was carried out under the conditions of 77 L. was confirmed by electron micrographs.

Next, the same post-treatment as in Example 1 was performed, including washing with water and drying. Next, the same formulation as in Example 1 was applied in the same manner as in Example 1 to obtain a lithographic printing plate material.

This lithographic printing plate material was subjected to dew C1 development in the same manner as in Example 1 to obtain a lithographic printing plate, which was subjected to processing chemical resistance testing and printing tests in the same manner as in Example 1 above. As a result, this printing plate showed significant erosion of the image 17 and poor processing chemical resistance, and after about 90,000 sheets were printed, scratches occurred in the ID + IF area and the printing durability was poor. It was also defective.

Example 3 The same type of steel plate as in Example 1 was subjected to the main treatment process and post-treatment process in the same manner as in Example 1.

Next, a % Hikari J/E coating solution having the following composition was applied to this iron plate using a rotary coater and dried at 100'C for 4 minutes to obtain a lithographic printing plate material.

(Photosensitive coating liquid composition) Naphthoquinone-(1,2)-diazide-(2)-5-X
/l/yh condensate of acid chloride and resorcinol-benzaldehyde resin (produced by the method described in Example 1 of JP-A-56-1044)
3.5. ! ? Phenol and m-+p! Co-condensation of cresol and formaldehyde (molar ratio of phenol and cresol is 3) Weight (average molecular weight 1500) Bysu7
Toquinone-(1,,2)-diazide-(2)-4-sulfonic acid chloride 0.15g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.2.
)ilp -t-butyl formaldehyde novolac resin 0.15g methyl cellosolve 100g dry (j17
The coating weight of ', 19 was approximately z, 5'j/rrt.

A step tablet for sensitivity measurement (Black 2 manufactured by Eastman Kodak) and a positive original film were tightly placed on the planographic printing plate material obtained in this way, and a 2KW metal halide lamp (Iwasaki Electric (Idol Fin 2000 manufactured by Ajiri)) was used as the light source. A 4% sodium metasilicate aqueous solution was used at 25°C for 80 seconds at a distance of 1m.
It was developed at 181 seconds to obtain a lithographic printing plate.

In order to examine the adhesion between the support and the fi'lji line portion and the printing durability of the printing plate, a processing chemical resistance test and one or more printing trials were conducted. As a treatment chemical resistance test, Ultra Plate Cleaner (A, B), which is used as a cleaning solution to remove background stains that occur in the stretched image area during printing, was used.

Durability against C Chemical Co., Ltd. product was investigated.

The printing plate with the image with the difference in martyrdom on the gray scale steps mentioned above is added to the Ultra Plate Cleaner stock solution for 2 minutes at room temperature.
After immersion for 0 minutes, the sample was washed with water, and the degree of corrosion of the image area against the processing chemicals was determined by comparing it with the image area before immersion fa. As a result, the printing plate had no erosion in the image area, and the halftone dots were preserved up to a halftone dot with a business ratio of 2%, showing good resistance to processing chemicals. The printing durability test was conducted in the same manner as in Example 1, and the results showed that the printing plate produced good prints up to 250,000 copies.It also had good water retention and was easy to manage. .

Example 4 A steel plate of the same type as in Example 1 was plated with iron and chrome in the same manner as in Example 2, washed with water, and dried.

Next, a spreadable coating solution having the following composition was applied to this support using a rotary coater and dried at 85° C. for 3 minutes to obtain a lithographic printing plate material.

(Photosensitive coating liquid composition: Copolymer A 5.0.
lit/diazo resin B O
, 5g Julimar AC-1OL O
,05,9 (manufactured by Nippon Pure Chemical Co., Ltd.) Victoria Pure Blue BOH 0.1 g (Methyl Cellosolve manufactured by Hodogaya Chemical Co., Ltd.) 100 ml However, the above copolymer A has a molar ratio of p -Hydroxyphenylmethacrylamide/acrylonitrile/ethyl acrylate/methacrylic acid = 10/30/60/6 composition was dissolved in 4 L of methyl cellosolve, heated at 65°C for 10:11 in a nitrogen-substituted sealed tube, and after the reaction was completed. It was obtained by pouring the reaction solution into water with stirring and drying the resulting white precipitate at f4.Diazo resin "B +; t, M 5% diazo resin (trade name, K, H, 0) Co., Ltd. D
-012) Mix an aqueous solution with a 10% ammonium hexafluorophosphate aqueous solution, absorb and filter the resulting precipitate, and dry under reduced pressure at 30 to 40°C to obtain a fluorinated hexafluorophosphate. . The above-mentioned H (the market weight average molecular pupil of the union is 80
,000, and furthermore, when the molecular distribution of the above diazo resin was measured by gel emission chromatography (Gpe), trimers and below accounted for 93 mol% of the total.
Met.

The coating weight after drying was approximately 2.0 g/ba.

A negative original film was closely attached to the planographic printing plate material obtained in this way, and a 2 KW metal halide lamp (Iwasaki Electric Co., Ltd.) was used.
1m using Idolfin 2000 manufactured by Co., Ltd. as a light source.
The planographic printing plate was t'd by applying 158 IfiK light for 84 seconds at a distance of 150 ms and developing with a developer having the composition shown below.

(Developer composition) - Phenyl cellosolve 10og - Jetanolamine 5QgΦ Pionin A-44B 30so (Takemoto Yushi Co., Ltd. Shakan, Water 780.ji + Development conditions are 25°C and 45 seconds.

Support and iI! In order to examine the adhesion with the U image area, the latitude of developability, and the printing durability of the printing plate, we conducted a "one-hand development" process test in addition to the process using an automatic developing machine.
A printing test was also conducted.

Manual development was carried out by thoroughly soaking a sponge with the above-mentioned developer and lightly biting the exposed lithographic printing plate material placed in a dish with the sponge evenly for 2 minutes, followed by washing with water. As a result, the image area of the lithographic printing plate material was not damaged at all even by manual development. The printing test was conducted in the same manner as in Example 1. As a result, the planographic printing plate using the support of the present invention produced good printed matter up to 220,000 sheets.

Comparative Example 2 ``J!'' A steel plate of the same type as Example 1 was plated with iron and chrome in the same manner as in Comparative Example 1, washed with water, and dried.

Next, a photosensitive coating solution having the same composition as in Example 4 was applied to this support in the same manner as in Example 4, and dried to prepare a lithographic printing plate material. Next
A lithographic printing plate was prepared in the same manner as in Example 2, and a printing durability test was conducted. As a result, during manual development, the image area was significantly damaged and the nl was almost completely peeled off. Furthermore,
In printing, part of the image line peeled off after 80,000 copies were printed.13
1it, and it became impossible to print.

Example 5 A steel plate of the same type as Example 1 was plated with iron in the same manner as in Example 1, then plated along the surface to a thickness of 1.4 μm, and then chromium plated in the same manner as in Example 1. A lithographic printing plate was obtained by the same operation as in Example 1.1. -0 When this printing plate was printed on the same 4th printing plate, a good quality printed matter with no background stains was obtained.

Example 6 A plate of the same type as in Example 1 was plated with iron to the same 4゛1: as in Example 1, and then plated with nickel to a thickness of 2 μm,
Next, chromium plating of F:7 as in Example 1 was applied, and a J Pil 1 plate between the planographic plates was then etched by the same procedure as in Example 1.

When this Dlj version was printed in the same way, it showed dirt γ1. Good quality printed matter was obtained.

Example 7 A drawing board of the same type as in Example 1 was etched with a Baumey-40' diiron chloride solution, and the center line average pattern of the surface was I(, a
The surface was roughened to 0.7 μm.

Next, the same chromium plating as in Example 1 was applied, and the lithographic plate 1-IJ printing plate was yarned by the same operations as in Example 1.

When this printing plate was printed in the same manner, it was possible to obtain printed matter of good quality with no scumming.

[Brief explanation of drawings]

Figure 1 (Photograph) Nichrome 'tIK, scanning type microscopy of the surface of iron material with roughening grooves and ridges before installation (magnification 5000 times, tilt angle 300), 2nd to 4th leap Figures (All photos are taken from a scanning electron microscope of the surface of the support of the present invention) (Magnification: Figures 2 and 3 are 500
0 times, 4th threshold is 3611 Q times, tilt angle is 00 in Figure 2
, and all others are 300]. Agent Yoshimi Kuwahara Figure 2 Figure 3 Figure 4 I's Procedural Amendments 1982-19II l 3+, 1 1 1st 'FIij+ 'l'; Kazuo Wakasugi 1 Middle ('1) Kullj'i sum 5 phi 14'r R'+'jx+'
t i:fi 114643 lji25 name of name (ij lithographic printing plate support,) 1111116-・1ノ:ll'i°11i'1 which relationship 1 de'rIII Jiffi person 11 place
East j; [To ゛a1 inn 1〆West T+NiJ
No. 26 2I32・I'F (1271tJ -jJ
Ll6) J゛Shin, Nigyo Co., Ltd. 1st Generation Control Dan 1 month
Hon Ikotohiko 4, agent〒IC) 1 j1报：lTf -1 town! ;-1? i l
l! 1f Yamasa (+', Il1cho'
irr Jil Specification 1°, "Detailed Description of the Invention" Column 7, Contents of the Amendment The detailed description of the invention is amended as follows. (1) The description shall be amended as shown in the table below. (2) Delete page 30 of the specification, lines 9 to 12.

Claims (1)

[Claims] A support for a lithographic printing plate, comprising a chromium electrodeposited layer having protrusions on an iron material having a centerline average roughness (Ra) of 01 to 3 μm.