JP2003072216A - Multicolor printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multicolor printing method, free from scumming and small in spoilage cost small, which has a wide printability range in the multicolor printing method by mounting a lithographic printing key plate. SOLUTION: In the multicolor printing method by mounting the lithographic printing key plate, at least one lithographic printing key plate is produced by treating a key plate negative, on which a resin allowing to elute with a developing solution is applied onto a support with a hydrophilic surface, with the developing solution so as to elute the resin in order to obtain the key plate under the condition that the difference between: the surface energy hydrogen bonding index component γ(H) represented by general formula (1):γ(H)=[ 1.159+2.159×cos(contact angle with H2 O)-cos(contact angle with CH2 I2 }/0.379]<2> of a key plate; and the surface energy hydrogen atom bonding index component γ(H) of the non-printing image part of a lithographic printing plate mounted on one and the same plate cylinder having the key plate mounted thereon, is set to be 10 dyn/cm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a multicolor printing method.
At least one version of a multicolor printing machine, in particular
Attach a lithographic printing plate with an image on the cylinder, and at least
Take a lithographic printing plate that has no image on one plate cylinder.
The present invention relates to a method for multi-color printing. Lithographic printing
Japanese Patent Laid-Open No. 3-1 discloses a multicolor printing method using a discarded plate
This is described in detail in JP75090. [0002] Japanese Patent Laid-Open No. 3-175090 discloses P
When the entire surface of the S-plate photosensitive layer is removed and discarded, the photosensitive layer
Cannot be removed completely, and printing stains have occurred.
is described. Furthermore, as a way to solve this,
Ink adherence prevention on the base where the light layer was not applied
Discarded versions with protective films are proposed. Only
While throwing away a protective film in advance like this
The plate has unnecessary ink attached at the start of printing.
The number of copies required to be completely removed (usually called black loss)
Has the disadvantage of increasing the
Not accepted. The reason why black loss increases is long
A protective film is usually used to prevent printing stains even when stored for a long period of time.
Much greater than the PS version gumming, and long-term
The solubility in dampening water during printing deteriorates due to storage
According. For this reason, there is no protective film on the market.
The base is supplied by the PS plate manufacturer, and this is just before printing.
It is used with the same hydrophilicity and gumming as the PS plate.
ing. As a disadvantage of such an uncoated plate for discarded plates,
Print stains easily occur due to various contamination during long-term storage
That is. Furthermore, handling until gumming is completed
Therefore, it is easy to be damaged. As a means for solving such a problem, a hydrophilic table is used.
Various water-soluble or alkaline on a substrate having a surface
Discarded plates with a resin that can be dissolved in a developer have been proposed.
The Specifically, JP-A-11-240267, JP-A-11-240267
No. 9-327900 discloses polyvinyl phosphone.
Acid, gum arabic, polyvinyl alcohol, polyvinyl
A water-soluble resin such as pyrrolidone is disclosed in JP-A-11-2402.
No. 66 includes polyurethane resin and polyurethane
Discarding plate for lithographic printing coated with alkali-solubilized resin
Is disclosed. In addition, a lithographic printing plate with an image and no image
Printing on a multi-color printing machine that simultaneously uses lithographic printing waste
Let's take a photolithographic printing plate for image formation and lithographic printing
It is possible to use a support that has the same physical properties as the printing plate.
Sometimes preferred because it allows the water effect on the non-image area to be the same
Yes. However, photosensitive lithographic printing plates for image formation offer other performance.
To fill, the same support as the lithographic waste plate is used.
Surface properties after development with lithographic printing plate
(Hydrophilicity, surface tension, etc.) are greatly different and water / ink
It is difficult to adjust the lance, causing dirt or water
There was a problem that caused printing defects such as scratches. [0005] The object of the present invention is to achieve multicolor
Lithographic printing with images on at least one plate cylinder of a printing press
Install the plate and have an image on at least one plate cylinder
A method for multicolor printing with no lithographic discard plate installed
However, there is no printing smudges, little black loss payment, and
To provide a multicolor printing method with a wide range of printability.
According to the present invention, printing stains occur even after long-term storage.
No scratches occur during handling until gumming
It is also possible to provide a discarded lithographic printing plate. [0006] The present invention provides a multicolor printing machine.
Take a lithographic printing plate with an image on at least one plate cylinder.
A lithographic plate with no image on at least one plate cylinder
In the method of multi-color printing by attaching the discard plate for printing,
At least one lithographic printing plate has a hydrophilic surface
A resin that can be eluted with a developer is coated on the support.
The plate precursor is treated with a developer and the resin is eluted to give
Represented by the following general formula (1).
The hydrogen bond index component γ (H) of the surface energy
Mounted on the same plate cylinder as the plate cylinder on which the discard plate was installed
Non-image area surface energy hydrogen bonding finger of lithographic printing plate
The difference from the number component γ (H) is within 10 dyn / cm
A multicolor printing method is provided. General formula (1) γ (H) = [{1.159 + 2.159 × cos (contact angle: H₂O) −cos (contact
Antenna: CH₂I₂)} / 0.379]² (Unit dyn / cm, contact angle is H₂O: 1.7 μL, CH₂I₂: 1.3 μL
(Value measured 30 seconds after dropping) [0008] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a lithographic seal used in the present invention.
The discard plate for printing plates will be described. The flat used in the present invention
Disposable plates for printing plates are obtained by treating the original plate for discarding plates with a developer.
Is obtained by eluting the resin on the support of the original plate.
is there. Here, the master for discarding plate is a support having a hydrophilic surface.
A resin that can be eluted with a developer is coated on the holder.
The (1) Support having a hydrophilic surface A support having a hydrophilic surface used in the present invention;
The aluminum and the aluminum coated composite
A support is preferred, and further 0.1 to 0.5% by weight of iron,
0.03-0.3 wt% silicon, 0.001-copper
0.03% by weight, and further 0.002-0.1% titanium
% 1S aluminum plate is preferred. The surface of the aluminum material increases the hydrophilicity.
It is desirable that the surface is treated for the purpose, alkali,
Preferably, 1-30 wt% sodium hydroxide, hydroxide
Water solution such as potassium hydride, sodium carbonate, sodium silicate
Immerse it in the liquid at a temperature of 20 to 80 ° C. for 5 to 250 seconds.
Etching may be performed. The etching bath contains aluminum
Umum ions may be added to about one fifth of the alkali. One
10 to 30 wt% nitric acid or sulfuric acid aqueous solution
Immerse for 5 to 25 seconds at a temperature of 70 ° C.
Perform neutralization and smut removal after ching. Also, the surface of the aluminum material is made hydrophilic.
As a method to give anodization after roughening treatment
The method of providing a film and applying a hydrophilic treatment can be mentioned.
The As a roughening method, for example, a generally known brush
Polishing method, ball polishing method, electrolytic etching, chemical etching
Methods, liquid honing, sandblasting, etc.
Combinations of these are mentioned, preferably brush polishing,
De-etching, chemical etching and liquid honing
Of these, the use of electrolytic etching is particularly important.
A roughening method including the above is preferred. Further, JP-A 54-
Brush polishing as described in Japanese Patent No. 63902
Thereafter, an electrolytic etching method is also preferable. In addition, the electric power used in the electrolytic etching is used.
As a bath, water containing acids, alkalis or their salts
A solution or an aqueous solution containing an organic solvent is used.
Among them, especially those containing hydrochloric acid, nitric acid or their salts
Dissolution is preferred. Brush polishing with Pamiston-water suspension
It is preferable to use a nylon brush and the average surface roughness
Is preferably 0.25 to 0.9 μm. The electrolytic solution used in the electrolytic etching process is
It is an aqueous solution of hydrochloric acid or nitric acid, and the concentration is 0.01 to 3
It is preferable to use in the range of wt%, 0.05 ~
More preferably, it is 2.5% by weight. Also this electrolyte
If necessary, nitrate, chloride, monoamines, dia
Mines, aldehydes, phosphoric acid, chromic acid, boric acid,
Corrosion inhibitors such as ammonium oxalate (or stabilization)
Agent), a grain uniformizing agent, and the like. Ma
In addition, an appropriate amount (1 to 10 g / liter) of Al
Minium ions may be included. Electrolytic etching is usually performed at 10 to 60 ° C.
At the temperature of the electrolyte. Exchange used at this time
If the current is a positive / negative polarity exchanged alternately,
Any of square wave, trapezoidal wave and sine wave can be used.
Use normal single-phase and three-phase alternating currents.
You can. The current density is 5 to 100 A / dm.²so,
It is desirable to process for 1 to 300 seconds. The aluminum alloy support of the present invention
The surface roughness is adjusted by the amount of electricity, 0.2-0.8μ
m. In addition, roughened aluminum
The plate can be desiccated with an aqueous acid or alkali solution if necessary.
Matt processed. Aluminized in this way
Um alloy consists of 10-50 wt% hot sulfuric acid (40-60
℃) and dilute alkali (sodium hydroxide, etc.)
Removal and etching of smut adhering to the surface (preferred
0.01 ~ 2.0g / m²In the range)
That's right. When removing smut and etching with alkali
In the case of subsequent immersion in acid (nitric acid or sulfuric acid) for cleaning.
Pickle and neutralize. After smut removal of the surface, anodic oxidation
A film is provided. The anodizing method is better known than before
Can be used, but sulfuric acid is most useful.
Used as electrolyte. Next, phosphoric acid also
It is a useful electrolyte. Further, JP-A-55-28400
The mixed acid of sulfuric acid and phosphoric acid disclosed in the publication is also useful.
is there. The sulfuric acid method is usually treated with a direct current.
However, alternating current can be used. Concentration of sulfuric acid 5-3
0% by weight, 20 to 60 ° C temperature range for 5 to 250 seconds
1-10 g / m on the surface after being treated²The oxide film is provided
It is done. This electrolyte contains aluminum ions.
It is preferable. At this time, the current density is 1 to 1.
20A / dm²Is preferred. In the case of the phosphoric acid method, 5 to 50% by weight of lithium is used.
Acid concentration, 30-60 ° C for 10-300 seconds, 1
~ 15A / dm²Processed at a current density of. Further, if necessary, US Pat. No. 2,7
No. 14,066 and US Pat. No. 3,181,461
Silicates (sodium silicate,
Potassium silicate) treatment, US Pat. No. 2,946,638
Potassium zirconate fluoride described in the specification
Processing, described in US Pat. No. 3,201,247
Phosphomolybdate treatment, British Patent 1,10
Alkyl titanes described in No. 8,559
Described in German Patent No. 1,091,433
Polyacrylic acid treatment, German Patent 1,13
No. 4,093 and British Patent No. 1,230,447
Polyvinylphosphonic acid treatment described in the specification, special
Phosphonic acid described in Japanese Patent Publication No. 44-6409
Processing, described in US Pat. No. 3,307,951
Phytic acid treatment, Japanese Patent Application Laid-Open No. 58-16893,
Parents described in JP-A-58-18291
For treatment with aqueous organic polymer compound and divalent metal salt
Therefore, a hydrophilic treatment can be performed. Silicate treatment is parent
It is especially preferred because of its high hydration capacity and simple processing.
Yes. Other hydrophilic treatment methods include US patents.
Siliques described in US Pat. No. 3,658,662
It can also be cited as an electrodeposition. Also graining treatment
And after anodizing, a sealing process can be performed. Take
Sealing treatment is hot water and hot aqueous solution containing inorganic or organic salt
It is carried out by immersion in water vapor bath or the like. (2) A developer to be coated on a hydrophilic support.
Dissolvable resin Next, the resin that can be eluted with the developer applied on the hydrophilic support.
The fat will be described. As a resin that can be eluted with a developer
A water-soluble resin can be mentioned. Water-soluble tree that can be used
Examples of fats include gum arabic, gelatin, and polyvinyl chloride.
Rualcohol and its derivatives, dextrin, steavi
Lack, stratane, alginate, polyacrylic acid
, Polyglycerol ester, polyvinylpyrrolidone,
Polyacrylamide and its derivatives, fibrin derivatives (eg
For example, methyl cellulose, hydroxypropyl cellulose
, Hydroxymethylcellulose, hydroxyethylcellulose
Roulose, carboxymethylcellulose), pullulan,
There are soy polysaccharides, among them gum arabic and dextst
Phosphorus, carboxymethylcellulose and soy polysaccharides are preferred
That's right. The application amount of the water-soluble resin is 0.2 to 2.0 g / m.²,
Preferably 0.4 to 1.0 g / m²It is. 0.2g / m²
If less, printing stains may occur due to long-term storage,
It becomes easy to be damaged by handling. on the other hand,
2g / m²If it is more, it takes a long time to dry after application,
It is difficult to elute later with water or aqueous solution, which is impractical.
Yes. The plate material produced in this way is used as a discarded plate.
Can be stored for a long time. Further, a water-soluble compound is placed on the hydrophilic support.
Painted and provided a resin layer that can be eluted with developer.
Is effective. As a water-soluble compound used for undercoating
For example, carboxymethylcellulose, dextri
, Gum arabic, 2-aminoethylphosphonic acid, etc.
Phosphonic acids having an amino group, may have a substituent
Phenylphosphonic acid, naphthylphosphonic acid, alkylphospho
Sphonic acid, glycerophosphonic acid, methylenediphosphonic acid
And organic phosphonic acids such as ethylene diphosphonic acid,
Phenyl phosphate, naphthyl phosphate, which may have a substituent,
Organophosphorus such as alkyl phosphates and glycerophosphates
Acid, optionally substituted phenylphosphinic acid, naphth
Tylphosphinic acid, alkylphosphinic acid and glyce
Organic phosphinic acids such as lophosphinic acid, glycine and β
-Amino acids such as alanine, and triethanol
Salts of amines with hydroxyl groups, such as hydrochloride of min
Preferred are water-soluble polymers having acid salts and sulfonic acid groups.
Among them, water-soluble polymers having sulfonic acid groups are used.
Particularly preferred. Water-soluble polymers having sulfonic acid groups are
Repeat at least one monomer unit having a sulfonic acid group.
A water-soluble polymer compound contained in the molecule as a repeating unit.
For example, Japanese Patent Publication No. 4-9296 (column 3, line 22 to
(4th column, 41st line). Sulfonic acid
As a monomer unit having a group, for example, p-styrene
Sulfonic acid, 2-acrylamido-2-methylpropane
Preferred are sulfonic acid, ethylene sulfonic acid, etc.
1 or 2 are appropriately selected and polymerized.
Or copolymerized with other monomers. Co-weight with other monomers
When combined, the partner monomer has a sulfonic acid group
Any monomer can be copolymerized with the monomer
Yes. Specific examples include, for example, methyl methacrylate / ether.
Tyl acrylate / 2-acrylamido-2-methyl group
Sodium lopansulfonate, methyl methacrylate /
Methyl acrylate / p-styrene sulfonate sodium
And sodium polystyrene sulfonate
The The molecular weight range of the water-soluble compound of the present invention is water-soluble.
There is no limit as long as there is, but if you give a general guide, weight average
A molecular weight range of about 1000 to 1000000 is appropriate.
Preferably 2000-100000, most preferably
Is in the range of 10,000 to 100,000. This subbing layer is composed of water, methanol, ethanol.
, Isopropyl alcohol, methyl ethyl ketone, etc.
Alternatively, the above compound is dissolved in a mixed solvent thereof,
It can be applied and dried on a support. Undercoat
The coating layer after drying is 10 to 500 mg / m²Is appropriate
Preferably 50 to 200 mg / m²It is. 1 undercoat
0mg / m²If it is less, the ability to prevent printing stains will be insufficient. under
Coating layer is 500mg / m²More, the resin layer applied later
The film strength is reduced and the ability to prevent scratches due to handling is low.
I will give you. A tree that can be eluted with a developer following the undercoat layer.
A fat layer is provided. Preferred as such a resin
Has an acid content of 0.1 to 3.0 meq / g, preferably 0.2
~ 2.0 meq / g, substantially insoluble in water (ie
Insoluble in neutral or acidic aqueous solution)
Although it is an organic polymer compound, it is soluble in an alkaline aqueous solution.
Those that can be deflated or swelled are preferred. Acid
If the content is less than 0.1 meq / g, dissolution is difficult and 3.0 m
If it exceeds eq / g, the strength of the membrane during high temperature and high humidity storage will be significant.
Become weaker. The molecular weight of the resin is dissolved and adjusted in the coating solvent.
There is no limit as long as it dissolves or swells in the aqueous solution of Lucari,
1000 to 1000000 in weight average molecular weight, preferably
Is 10,000 to 500,000. Low molecular weight membrane
If the strength is weak and the molecular weight is high, the solubility deteriorates. Particularly preferred resins include acrylic acid and meta
As an essential ingredient, Krylic acid, Crotonic acid or Maleic acid
A copolymer containing, for example, JP-A-50-118802
2-hydroxyethyl acrylate as described in
Or 2-hydroxyethyl methacrylate,
Lilonitrile or methacrylonitrile, acrylic acid
Or methacrylic acid and other copolymerizable if necessary
Multi-component copolymers with monomers, JP-A-53-120903
Terminal is a hydroxy group as described in
And a group containing a dicarboxylic acid ester residue
Acrylic acid or methacrylic acid, acrylic acid,
Or methacrylic acid and other copolymerizable if necessary
Multi-component copolymers with monomers, JP 54-98614
It has an aromatic hydroxyl group at the end as described in the publication
Monomers (eg N- (4-hydroxyphenyl) meta)
Acrylamide), acrylic acid or methacrylic acid
And multiple co-polymerization with other copolymerizable monomers as required
Polymer, described in JP-A-56-4144
Such as alkyl acrylate, acrylonitrile or
Multiple elements consisting of tacryonitrile and unsaturated carboxylic acid
Mention may be made of copolymers. In addition, acidic polyvinyl chloride
Local alcohol derivatives and acidic cellulose derivatives are also useful.
The Polyvinyl acetal and polyurethane
Resolubilized Japanese Patent Publication No. 54-19773, Japanese Unexamined Patent Publication No. 5
7-94747, 60-182437, 62-
The binders described in 58242 and 62-123453 are also used.
Useful, polyurethane-solubilized resin
However, the film strength is high, which is particularly preferable. The resin is dissolved in various known coating solvents.
Aluminium having a hydrophilic surface and an undercoat layer as a resin solution
The dry coating weight on the um support is 0.2 to 3.0 g / m.²When
Preferably, 0.3 to 1.5 g / m²To be
Can be applied and dried to obtain a lithographic waste plate
The Application amount is 0.2g / m²If it is less, scratches will be prevented
Insufficient capacity, conversely 3.0g / m²The above is the ability to prevent scratches
It is sufficient as a force, and the dissolution speed at the time of dissolution removal decreases.
Or reduce the processing capacity of the solution. Apply
The solid content concentration of the resin solution is preferably 1.0 to 50% by weight.
Preferably, 2.0 to 30% by weight is appropriate.
The As a method of applying a resin solution on a support, it has been publicly known.
Known methods, eg call coating, bar coating
Spray coating, curtain coating,
A method such as spin coating can be used. Painted tree
The fat solution is preferably dried at 50 to 150 ° C. Dry
The drying method starts with a low temperature and pre-drys, then at a high temperature.
It may be dried or may be directly dried at a high temperature. Various additives are added to the resin solution, such as coating.
Pigments to discriminate amounts, plasticizers to promote dissolution,
Coating surface quality improvement for low molecular acid compounds, fluorosurfactants, etc.
Add good agent, matting agent for surface matting, etc.
You can. In particular, dipicolinic acid, malic acid, sulfosa
Calcium such as lithylic acid, sulfophthalic acid, tricarballylic acid
Low molecular acid compounds containing a sulfonic acid group
Along with dissolution promotion, it prevents printing stains during long-term storage.
This is preferable. In addition, fluorine-based surfactant is applied
Not only the surface quality improvement effect but also the scratch resistance improvement effect
More preferable. Low molecular acid compounds are used for non-photosensitive resin layers.
1 to 20% by weight, fluorine surfactant is 0.1 to 5
Weight percent is added. Protrusions provided independently of each other on the resin layer
You may provide the mat | matte layer comprised by raising. mat
The purpose of the layer is to improve scratch resistance and the plate material during storage
It is to prevent the two from sticking to each other. Ma
As a coating method of the coating layer, JP-A-55-12974
Heat the powdered solid powder described in the publication.
Method of fusing, described in JP-A-58-182636
For spraying dried polymer-containing water
Any method can be used. Matt layer is tree
It can be dissolved in alkaline aqueous solution to remove the oil layer or
Or it can consist of a removable material.
desirable. When using a lithographic printing discard plate,
A resin having an aqueous surface and coated on a support
Elute with. As a developer, an ordinary lithographic printing plate
Use Lucari Developer as is or diluted as needed
For example, Japanese Patent Laid-Open No. 51-77401,
51-80228, 53-44202 and 55
Photosensitivity as described in each publication of 52054
Alkali developer for lithographic printing plate, pH = 8-1
3. Those containing 75% by weight or more of water can be used. Necessary
If necessary, the solubility in water is 10% by weight or less at room temperature.
Organic solvent (benzyl alcohol, ethylene glycol mono
Phenyl ether), alkaline agent (triethanolamine)
, Diethanolamine, monoethanolamine, phosphorus
Acid sodium, sodium carbonate), anionic surfactant
(Aromatic sulfonates, dialkylsulfosuccinates,
Alkyl naphthalene sulfonate, fatty acid salt, alkyl
Sulfate ester salt), nonionic surfactant (polyoxye)
Tylene alkyl ether, polyoxyethylene alkyl
Aryl ether, polyoxyethylene polyoxypro
Pyrene block polymer), antifouling agent (sodium sulfite)
Um, sulfopyrazolone sodium salt) and water softener
(Ethylenediaminetetraacetic acid tetrasodium salt, nitrile
Triacetic acid trisodium salt can be added. However, when an organic solvent or the like is contained,
Hygiene problems such as toxicity, odor, fire, gas explosion, etc.
Problems with integrity, workability problems such as generation of bubbles, and public waste
Because there are problems such as harm and costs, etc.
What does not contain an organic solvent is still more preferable. Such a real
As an aqueous developer that does not contain organic solvents,
Sho 59-84241, JP 57-192952 and
And Japanese Patent Application Laid-Open No. 62-24263
An image liquid composition can be used. In addition, water soluble
A material in which a soluble resin is dissolved can also be used. With this water-soluble resin
Even so, you can list those listed above. In addition,
This water-soluble resin composition may not be alkaline. This
Desensitizing gum process shown later if using an aqueous solution like
Can be omitted. Resin with developer solution
Elution treatment should be performed at the same time as the planographic printing plate in the same processor.
Alternatively, it may be performed separately. Development for making discarded plates
The solution is the same as or different from the developer used for preparing the lithographic printing plate.
May be. The lithographic printing discard plate of the present invention is disclosed in JP-A-54.
-8002, 55-115045, 59-58
In a manner similar to that described in each of the Gazette No. 431
The plate making process may be performed. That is, after elution treatment with a developer, washing with water
Desensitizing treatment, or desensitizing treatment as it is,
Or treatment with an aqueous solution containing an acid, or an aqueous solution containing an acid
After the treatment, a desensitization treatment may be performed. It should be noted that this type of lithographic printing discard plate elution process
In the case of alkaline aqueous solution is consumed according to the amount of treatment
Density decreases or the automatic processor is operated for a long time
Because the alkali concentration is reduced by air
In that case, Japanese Patent Laid-Open No. 54-62004
Use a replenisher to restore processing capacity as described in
Also good. In this case, U.S. Pat. No. 4,882,246
Replenishment is preferably carried out in the manner described. The plate making process as described above is disclosed in
-7054 and 2-32357.
It is preferable to use an automatic processor. Made
Desensitized gum applied as desired in the final step of the plate process
As Japanese Patent Publication Nos. 62-16834 and 62-2511
No. 8, No. 63-52600, JP-A No. 62-7595
No. 62-11693, 62-83194
Those described in the publication are preferred. Of desensitized gum
The coating amount is 0.005 to 0.2 g / m²Is preferred
0.02 to 0.15 g / m²Is more preferable. Small application amount
If not, scratches and print-in
Fingerprint stains are caused by handling with fingers attached
It's easy to do. Conversely, if the amount applied is large, the black loss increases.
Yeah. In the previous elution process, the applied resin is not treated.
Depending on the target, it may be completely eluted or partially eluted
Yes. If completely eluting, desensitize gum as above
Is preferably applied. Insensitive oil after partial elution
When applying denatured gum, the remaining resin and desensitized gum
The total is 0.005-0.2g / m²Like to be
Good. Also elute partially and apply desensitized gum.
When not clothed, the remaining resin is 0.005 to 0.2 g
/ M²Is preferable. A lithographic stamp made in this way
Disposable plates for printing are cyan, magenta, yellow
Attached to at least one plate cylinder of black and black
Used. Elution of resin with developer, conducted as necessary
About the discarded plate after the plate making process as mentioned above
Hydrogen bondability index of surface energy expressed by general formula (1)
The contact angle is measured for calculating the component γ (H). Contact
The antenna is measured for both non-image areas of discarded plates and lithographic printing plates.
And performed at a temperature of 25 ° C. and a relative humidity of 60%.
The In the present invention, the discard plate for lithographic printing is aforesaid.
Hydrogen bond finger with surface energy represented by general formula (1)
Number component γ (H) and surface energy of non-image part of planographic printing plate
The difference from Gee's hydrogen bond index component γ (H) is 10 dyn /
Within cm, preferably within 5 dyn / cm. They are,
For example, according to the above-mentioned method for producing a discarded plate, supporting the discarded plate
Body hydrophilization treatment conditions, primer applied on hydrophilic support
Elution amount of resin coated on hydrophilic support, etc.
This can be achieved by making adjustments. In the printing method of the present invention, it is used together with a discarded plate.
The lithographic printing plate used is not particularly limited and is a general one.
Although it can be used, JP 2000-39724 A
Photopolymerized lithographic printing plates as disclosed in
Yes. [0037] The present invention will be described more specifically with reference to the following examples.
However, the present invention is not limited to these. [Method for producing lithographic printing waste plate]
A waste plate for plate printing was prepared and used. 99.5 wt% Al
Minium with 0.01% copper and 0.03 titanium
% By weight, 0.3% by weight of iron and 0.1% by weight of silicon
JIS A1050 aluminum material thickness 0.30mm
Rolled plate made of 400 mesh pumiston (manufactured by Kyoritsu Ceramics)
20 wt% aqueous suspension and rotating nylon brush (6,
10-nylon) and the surface was grained
After that, it was thoroughly washed with water. This was treated with a 15% by weight aqueous sodium hydroxide solution.
Soaked in aluminum (contains 4.5 wt% aluminum)
The dissolution amount of um is 5 g / m²Etched to be
Then, it was washed with running water. Furthermore, neutralize with 1 wt% nitric acid,
Next, a 0.7 wt% nitric acid aqueous solution (aluminum 0.5 wt.
%)), Anode voltage 10.5 volts, cathode voltage
9.3 volt square wave alternating waveform voltage (current ratio r = 0.9)
0, described in the example of Japanese Patent Publication No. 58-5796
160 coulomb / dm using current waveform)²Anode anode
The electrolytic surface-roughening treatment was performed with the volume. 10 minutes at 35 ° C after washing with water
Immerse in an aqueous solution of sodium hydroxide by weight
The dissolution amount of um is 1 g / m²After etching to become
Washed with water. Next, it is immersed in a 30% by weight sulfuric acid aqueous solution at 50 ° C
After pickling and desmutting, it was washed with water. Furthermore, a 20% by weight aqueous solution of sulfuric acid at 35 ° C.
Using direct current in (containing 0.8% by weight of aluminum)
Then, a porous anodic oxide film forming treatment was performed. That is, electric
Flow density 13A / dm²Electrolysis is carried out by adjusting the electrolysis time.
Anodized film weight 2.7g / m ²It was. This support
After washing with water, add 3% by weight aqueous solution of sodium silicate at 70 ° C.
It was immersed for 30 seconds, washed with water and dried. Sodium silicate
The support before the treatment is the support A, and the support after the treatment is the support B.
And The aluminum support obtained as described above.
The holder is Macbeth RD920 reflection density for both support A and B
The reflection density measured by the meter is 0.30 and the centerline average roughness is
It was 0.58 μm. Next, as a primer,
Tacrylate / ethyl acrylate / 2-acrylami
Do-2-methylpropanesulfonic acid (Feed weight ratio 65 /
20/15) A part of the copolymer is sodium salt
And 1.0 wt% methanol / water = 90/10 solution
The coating amount after drying with a bar coater is 0.1 g / m²
It applied so that it might become. Next, as a resin that can be eluted with a developer,
The composition shown in Table 1 is methanol / methyl ethyl ketone /
1-methoxy-2-propanol / methyl methyl lactate =
Dissolved in a mixed solution of 30 g / 30 g / 25 g / 12 g,
The coating amount after drying using a bar coater is 1.5 g / m²
And apply at 110 ° C for 45 seconds.
Thus, lithographic printing discard plates 1 to 4 were produced. [0042] [Table 1] As a discarded plate for lithographic printing of a comparative example, a support
B: Arabic gum 0.5 g / m²Was applied. This is a lithographic
It is assumed that it is a discarded version 5 for printing. [Method for Producing Photosensitive Lithographic Printing Plate] Thickness 0.
30mm material 1S aluminum plate No. 8 nylon bra
Using an aqueous suspension of 800 mesh Pamiston
After the surface of the material was grained, it was thoroughly washed with water. 10% water
Etching by dipping in sodium oxide at 70 ° C for 60 seconds
After washing with running water, 20% HNO_ThreeNeutralized with washing, water
Washed. This is V_A= Sine wave crossing under the condition of 12.7V
300 coulomb in 1% nitric acid solution using a waveform current
/ Dm²Electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode. That
When the surface roughness was measured, 0.45 μm (Ra indication)
(Measurement equipment: Surfcom, Tokyo Seimitsu Co., Ltd.
Tip diameter 2 microns). Followed by 30% H₂
SO_FourImmerse in an aqueous solution and desmut for 2 minutes at 55 ° C.
And then 33 ° C, 20% H₂SO_FourGrained in aqueous solution
A cathode is placed on the surface and a current density of 5 A / dm²5
When anodized for 0 seconds, the thickness is 2.7 g / m²So
It was. The reflection density was 0.32. Process in this way
A polymer represented by U-1 (molecular weight)
Mn = 10,000) in water / methano so that the concentration becomes 2% by weight.
Solution = 5 g / 95 g was applied at 80 ° C., 3
Dried for 0 seconds. The thickness of this intermediate layer is 10 mg / m²So
It was. On top of this, a highly sensitive photopolymerizable composition P-1 having the following composition:
The dry coating weight is 1.5 g / m²Apply so that
A photosensitive layer was formed by drying at 00 ° C. for 1 minute. [0045] [Chemical 1] [0046]   (Photopolymerizable composition P-1)   Ethylenically unsaturated bond-containing compound (A1) 1.5 parts by weight   Linear organic polymer (polymer binder) (B1) 2.0 parts by weight   Sensitizer (C1) 0.15 parts by weight   Photopolymerization initiator (D1) 0.2 parts by weight   ε-phthalocyanine (F1) dispersion 0.02 parts by weight   0.03 part by weight of fluorine-based nonionic surfactant Megafac F177     (Dainippon Ink Chemical Co., Ltd.)   9.0 parts by weight of methyl ethyl ketone   7.5 parts by weight of propylene glycol monomethyl ether acetate   11.0 parts by weight of toluene [0047] [Chemical 2]On this photosensitive layer, polyvinyl alcohol (case)
3% by weight aqueous solution having a degree of conversion of 98 mol% and a degree of polymerization of 500)
The dry coating weight is 2.5 g / m²Apply so that
It was dried at 20 ° C. for 3 minutes to obtain a photosensitive lithographic printing plate. Feeling
The photolithographic printing plate is converted into an FD / YAG laser (CSI
100 μJ / cm with rate jet 4)²With an exposure amount of 40
Solid image and 1 to 175 lines / inch at 00 dpi
Development after scanning exposure of 99% halftone dot image (in 1% increments)
Liquid 1 and finishing gum liquid FP-2W (Fuji Photo Film)
Automatic processing machine (Made by Fuji Photo Film)
Standard processing with LP-850P2)
A plate printing plate was obtained. Preheat conditions are 1 plate surface temperature.
00 ° C, developer temperature is 30 ° C, immersion time in developer is about 1
5 seconds. Developer 1 has the following composition, pH 2
The conductivity was 11.5 at 5 ° C. and the conductivity was 5 mS / cm. [0049]   (Composition of Developer 1)   Potassium hydroxide 0.15g   Polyoxyethylene naphthyl ether (n = 10) 5.0 g   Kirest 400 (chelating agent) 0.1g   94.75 g of water The lithographic printing discard plates 1 to 4 are not exposed and are the same as above.
Development processing of lithographic printing discard plates 1 to 4
It was. [Hydrogen bond index component γ of surface energy
(H) Measurement] Water, CH₂Cl₂30 seconds after dripping
Non-image part of lithographic printing plate and lithographic printing without image
Discard plates 1 to 5 (1 to 4 are already developed, 5 is not treated
)) At 25 ° C. and a relative humidity of 60%.
Hydrogen of each surface energy based on general formula (1)
The connectivity index component γ (H) was determined. The results are shown in Table 2.
The [0051] [Table 2] [Examples 1-2 and Comparative Examples 1-3]
Many offset lithographic printing plates and lithographic printing plates made
Installed in the plate cylinder of a color rotary printing press, the newspaper of Sakata Ink Co., Ltd.
Ink and Toyo Alky dampening solution (manufactured by Toyo Ink)
20,000 pages at a speed of 100,000 sheets / hour
The situation (soil dirt, black loss payment) was evaluated. Also water / ink
A scale that changes the scale of the scale and does not cause soiling and water loss
The width was examined. The wider one is easier to print. Also against scratches
As a performance, scratches at the time of handling without interleaving paper were evaluated.
The results are shown in Table 3. [0053] [Table 3] From Table 3, Examples 1 and 2 are ground stain, black
The number of loss payment is small and the scale of water / ink adjustment is wide.
Multicolor printing is possible.
No printing stains even when stored, handling up to gumming
It is clear that scratches are unlikely to occur. [0055] According to the present invention, printing smudges do not occur and black
Multicolor printing with a small number of loss payments and a wide printable area
It becomes possible, and even if it is stored for a long time, printing stains will occur.
Less scratches during handling until gumming
Discrete plates for lithographic printing can also be provided.

Claims (1)

What is claimed is: 1. A lithographic printing plate having an image is attached to at least one plate cylinder of a multicolor printing machine, and a lithographic printing discard plate having no image is attached to at least one plate cylinder. In the multi-color printing method, at least one lithographic printing plate is treated with a developing solution for a printing plate precursor in which a resin that can be eluted with a developing solution is coated on a support having a hydrophilic surface. And a discarding plate obtained by eluting the resin, and the hydrogen bonding index component γ (H) of the surface energy represented by the following general formula (1) of the discarding plate and the discarding plate were attached. The difference between the surface energy of the non-image portion of the planographic printing plate mounted on the same plate cylinder as the plate cylinder and the hydrogen bond index component γ (H) is
A multicolor printing method characterized by being within 10 dyn / cm. General formula (1) γ (H) = [{1.159 + 2.159 × cos (contact angle: H ₂ O) −cos (contact angle: CH ₂ I ₂ )} / 0.379] ² (unit dyn / cm, contact angle (H ₂ O: 1.7 μL, CH ₂ I ₂ : 1.3 μL dropped and measured 30 seconds later)