JPS6242160A - Photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE:To prevent the flawing on the surface of a photosensitive layer by the oscillation and impact to be received during transportation even if a lithographic printing plate having a photosensitive compsn. layer on a base is packed without using interleaving paper and to satisfactorily prevent the adhesion of the printing plates to each other even if the interleaving paper is not inserted therebetween by providing a fluorine surface active agent layer on one surface of the printing plate. CONSTITUTION:The fluorine surface active agent refers to an ordinary surface active agent of which the hydrogen bound with the carbon of the hydrophobic group is partly or fully substd. with fluorine in place of said hydrogen and among such surface active agents, the surface active agent having a perfluoroalkyl group in the molecule is more preferable. Any photosensitive compsn. of which the solubility of swellability with a developing soln. changes before or after exposure is preferable and is exemplified by photosensitive resins such as polyester having a photocrosslinkable group, polycarbonate or polysulfonate, among which the photosensitive layer contg. a diazo compd. and org. high-polymer binder is more particularly preferable. Such photosensitive compsn. is dissolved in a suitable solvent and is coated on the base in such a manner that the coating weight after drying is 0.1-5g/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive lithographic printing plate (hereinafter abbreviated as PS plate) which has significantly improved handling properties during plate-making operations.

[Conventional technology]

In recent years, major printing companies and newspaper companies have been rapidly adopting so-called automatic plate-making systems, which unmanned the conventional plate-making process of exposing a PS plate to light and then performing gumming after development. Improvements in technology and efficiency are being promoted. In such an automatic plate-making system, usually several tens to several thousand PS plates are stacked and set in the plate feeding section, which is the entrance of the automatic plate-making machine, and from here the PS plates are stacked and set.
The plates are sent one after another to the exposure section, but at that time, it is necessary to remove the thin sheet of paper or plastic (hereinafter referred to as the mount) inserted between each SP plate.
From the viewpoint of improving workability, it is desired to supply PS plates packaged without a liner.

If PS plates currently on the market are packaged without a mount and supplied to printing companies, vibrations and shocks during transportation and handling may cause numerous scratches on the surface of the photosensitive layer, which can cause printing problems. There is a problem with becoming. Also 500-100
When packaging a large quantity of 0 PS plates as a unit, if it is left in a high temperature place for a long time, the P plate will deteriorate due to its own weight and the pressure during packaging.
There is a problem in that the S plates adhere to each other, making it impossible to transport each of the 28 plates in an automatic plate making machine.

To address these problems, Japanese Patent Publication No. 5-i6570 discloses a method that protects printing plates from scratches caused by contact between printing plates or contact between printing plates and other objects during transportation or other handling. cutting, perforation, sorting,
In order to provide a photosensitive printing plate material that is easy to handle during processing steps such as counting or packaging, the photosensitive layer of the printing plate material or the back side of the support (referring to the side without the photosensitive layer) is easily peelable and It is described that a protective layer that does not adversely affect the photosensitive layer is provided. This protective layer is made of a material with a melting temperature of 320°C or lower, such as polyolefins such as polyethylene and polypropylene, nylon, polyvinylidene chloride, polyvinyl chloride, etc., which is extruded into a film form from a melt extruder and then printed in the molten state. It is provided by adhering to the photosensitive layer of the printing plate material or to the back surface of the support, or by hot-pressing a thermoplastic resin film capable of releasing 3:11 to the surface of the printing plate material.

However, in this method, the protective layer that is no longer needed when the printing plate material is used must be disposed of in the same way as the mount, and the above-mentioned problems still cannot be said to be sufficiently solved.

On the other hand, JP-A No. 60-73538 describes a photosensitive printing plate material in which a protective layer is provided on the back surface of a support and has the property of being removed during development by being dissolved or dispersed in a developer. There is.

However, this method has the disadvantage that it cannot be applied to photosensitive printing plate materials in which photosensitive layers are coated on both sides of the support. Furthermore, since the resin forming the protective layer is dissolved or dispersed in the developer, there is a drawback that the ability of the developer to remove non-image areas is reduced due to this influence.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a PS plate that can be suitably used in an automatic plate-making system, with the surface of the photosensitive layer not being damaged by vibrations or 1-f impact during transportation and handling even when packaged without a mount. Furthermore, the present invention is a PS plate in which the PS plates are stacked without inserting interleaving paper between the PS plates, and the PS plates do not stick together even if left for a long time at a temperature above room temperature and under pressure. The purpose is to provide

[Means for solving problems]

The inventors have discovered that the above problems can be solved by applying a fluorosurfactant to at least one surface of a lithographic printing plate, and have thus arrived at the present invention.

That is, the present invention provides a photosensitive lithographic printing plate having a fluorosurfactant layer on at least one surface of the lithographic printing plate having a photosensitive composition layer on a support.

The fluorine-based surfactant used in the present invention refers to a surfactant in which part or all of the hydrogen bonded to the carbon of the hydrophobic group of a conventional surfactant is replaced with fluorine. Those having a fluoroalkyl group in the molecule are preferred.

Next, examples of fluorine-based surfactants used in the present invention are illustrated.

(i) Ionic surfactant R,C00M,R,5O2N(R')2cl(2C○
0)A.

RrB NR' C2H-OS 03M, Rr
S03M.

R, CR20 (CR2), S O, M, M O3S
-Cto(C00CI-(, Rf.

CI (2COOCt421?,' R, B N R' (CR2), OP (OH)2 (wherein, R4 is a fluorocarbon group in which part or all of H in the alkyl group is replaced with F (C number is 3 to 20), B is CO, SO
2, R' is 11 or a lower alkyl group, M is H1 alkali, alkaline earth metal, etc., m is an integer from 1 to 10)
Anionic surfactant with the structure; RrBNHC2
HiNR', R”・HX.

A cationic surfactant with the structure R, BNHC2H, N'''R', ・X-1, where X is a halogen acid group, and the others are the same as above): R'> 2 (CH□)
Examples include amphoteric surfactants having a structure of , COO-.

(ii > nonionic surfactant R, OHlR, BN (, C, 8, 0) n) ((in the formula,
n is an integer of 1 to 20).

(iii > Polymer surfactants -CH, -CH(Co○Cf(2Rr)-).Next, typical specific examples of surfactants represented by the above general formula are Illustrate.

C5FzCOOH, C1P+5COOH, C5FzCO
Ot1. C1P+5COOHl.

CI(F2(CF2>, CD0K, CllF2(CF
, ), [:0 mouth, CHF2 (CF2) 11COO
K.

CF3 (CF,) 8 (CI+2) 5COONa
, CF3 (CF, > 6CHCH(CH2) 2゜-
3CO[1NCF,ll <CF,) 3CF (CF
'ri (CI+2), ocooN,, CFs (
CF, ), CD0NN,.

CaF + tsO2N (Bt) C1l 2COO
K, CaF + tsLH, CeF 1. ,sQs
N.

C, F, ff5O*Li, C-F, tSDJ,
C, F, -(CH-)sS mouth, N,.

C,F,-(C11□),SO,N,,CHF,(C
F2), PO(OH)2゜CaP+tSOJBtC21
140PO(Oil)z.

cc,p,,so□NBt[:H,C11,O) 2P
[1ON11. .

CtF+s("0NHCJJ"MezCH2j'H2C
O[1-.

CyF+5CDNIIC3tlsN”MezI-, Ca
P+tSOJHCatlsN”MeJ-.

CeP+tsOJEt([:H2>20P(OCOCa
Hs)2゜(:eF 1tsO2NI3t (Czll
nO) 1411. CsF 1tsO2NEtczl
ln (OC311s) 5ell.

CaF, 75O2NII (C2+1.11),
[l, CeF, tsclJEit <CI(,C
11zO). Hl(n-1~20).

These fluorinated surfactants are, for example, “Megafac”
(Dainippon Ink Chemical), “F-Top (Tohoku Fertilizer),”
It is easily available on the market under product names such as ``Surflon'' (Asahi Glass), ``Ftargient'' (Neos), ``Florado'' (Sumitomo 3M), ``Senflo 1'' (Kao Atlas/fcI), and ``Zonil'' (Dekopon Far East). can be done manually.

Among these, cationic type fluorosurfactants include FTOP EF132, Florado FC134,
As anionic type fluorinated surfactants, FTOP EF102, EF103, EF104, EF1
05, EF112, EF1238, EF1
23BSEF306A, EF501, Florado FC9
5, FC98, FCl26, FCl28, Mega 7 Atsuku F-110, F-113, F-120, F-812, F
-191S F-833, FTOP EF700 as an amphoteric type fluorine surfactant, Florard FC170S as a nonionic type fluorine surfactant
FC170C, FC430, FC431, FC, 17°
6. F-top EF121: EF122Δ, E F12
2B, EF122BA, EF, 122CSEF122A
3, EF126, EF 127, EF301, E F2
O3, EF303, EF304, EF305, Megafuck F-142D, F-144DSF-171, F-1
73, F-177, F-183, F-184, etc.

In the present invention, one type or a mixture of two or more of the above-mentioned fluorosurfactants can be used.

The present invention is characterized in that the fluorosurfactant layer is provided on at least one surface of a lithographic printing plate having a photosensitive composition layer on a support. and,
The above-mentioned fluorosurfactant layer can be formed by known methods such as roll coach ink, bar coating, spray coating, curtain coating, electrostatic coating, and spin coating. At this time, depending on its properties, the fluorine-based surfactant may be used alone or dissolved in an appropriate solvent such as water. It is applied by BC, but a resin or particulate filler (generally particle size l~100μ) is added to the solution.
degree) can be added. In the present invention, the thickness of the fluorosurfactant layer formed can be set arbitrarily, but is 1 to 1000 mg/+r+", more preferably 2 to 2
It is desirable to set it to 00 mg/m2. If it is less than 1mg/m2, the effect is small, while at 1000o+g/m
This is because if it exceeds 2, conveyance slips in an automatic plate making machine and development defects are likely to occur. The formed surfactant layer is preferably provided over at least one entire surface, but may be provided partially in a regular or irregular pattern. Further, the thickness may be uniform or non-uniform, and irregularities may be provided in a stacked manner.

Examples of at least one surface of the lithographic printing plate on which the fluorosurfactant layer is formed are as follows.

(b) When a photosensitive resin layer is installed on the support, either one surface or both surfaces of the support corresponding to the outer surface or back surface of the photosensitive resin layer (b) Photosensitive on both sides of the support If a resin layer is installed, the outer surface of one or both of the photosensitive resin layers (c) PV on the photosensitive resin layer in (a) and (b) above.
When a protective layer made of C or the like is formed, it is preferable to use the following as the photosensitive resin and support for the outer surface of one or both of the outermost layers.

0 Photosensitive composition The photosensitive composition may be one that changes its solubility or swellability in a developing solution before and after exposure, for example, if it has a -CII=CHC0- group in the main chain or side chain of the molecule. Those made of photosensitive resins such as polyester, polycarbonate or polysulfonate having photocrosslinkable groups, those containing 0-quinonediazide compounds, those containing an azide compound and an organic polymer carrier, diazo compounds and organic polymers Photosensitive layers containing a binder, addition-polymerizable unsaturated compounds, photopolymerization initiators, and organic polymer binders are listed. Among these, photosensitive layers containing a diazo compound and an organic polymer binder are listed. Particularly preferred are layers. These photosensitive compositions are dissolved in a suitable solvent and have a coating weight of 0.1 to 5 g after drying.
/m2 on the support.

Examples of the support include paper, plastic film, and metals such as aluminum, zinc, iron, and copper, and among these, aluminum is particularly preferred. When aluminum is used as a support, it is preferably surface-treated by graining, anodizing, or immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like. Also, U.S. Patent No. 2.714,066
As described in the specification, an aluminum plate that is grained and then immersed in an aqueous sodium silicate solution;
As described in U.S. Pat. No. 3,181,461, aluminum plates that have been subjected to two or more surface treatments sequentially are also suitable, such as an aluminum plate that is anodized and then immersed in an aqueous solution of alkali metal silicate. used for.

To prepare a lithographic printing plate using the photosensitive lithographic printing plate of the present invention, conventional methods can be used as they are. That is, the photosensitive layer in the non-image areas is removed by exposure through a transparent original having a line image and/or halftone image, and then treatment with a developer. Suitable light sources used during exposure include mercury lamps, xenon lamps, chemical lamps, metal halide lamps, strobes, and the like. Further, as a developer, an appropriate developer may be used depending on the composition of the photosensitive layer. For example, for a photosensitive layer consisting of a diazo compound and an organic polymer binder, U.S. Pat. No. 3.669.660
Same issue! Aqueous alkaline developers such as those described in No. 54.186.006 are used.

〔Effect of the invention〕

When the photosensitive lithographic printing plate of the present invention is used, PS plate and PS
Since it is possible to effectively prevent PS plates from adhering to each other without inserting interleaving paper between the plates, the automatic plate making system can be operated with high efficiency.

Next, the present invention will be explained in detail based on Examples, but the embodiments of the present invention are not limited thereby.

The percentages in the examples are by weight unless otherwise specified.

Example 1 An aluminum plate with a thickness of 0.3 mrn was degreased by immersing it in a 7% aqueous solution of tribasic sodium phosphate (liquid temperature 60°C) for 3 minutes, and then washed with water. While casting it, I rubbed it with a Nanron brush to make it grainy. Next, after washing with water, sodium silicate (S i 02/N
a-0=3.1-3.3 (molar ratio)) in a 5% aqueous solution (liquid temperature 70°C) for 30-60 seconds. Subsequently, it was thoroughly washed with water and dried.

A photosensitive liquid (I) having the following composition was applied to this aluminum plate and dried to obtain a photosensitive lithographic printing plate.

0 photosensitive liquid (1) 2-hydroxyethyl methacrylate copolymer (1) (as described in Example 1' in U.S. Pat. No. 4,123,276)...5. 00 gp-Diazodiphenylamine and paraformaldehyde condensate 2-methoxy-4-monohydroxy-5-benzoylbenzene sulfonate...0.50 g "Oil Blue #603" (Blue dye from Orient Chemical Industry ■)... ...0.10 g phosphorous acid
・・・・・・・・・・・・0.05 g2-methoxyethanol・・・100g The dry coating amount of the photosensitive layer is 2
．． It was 5g/m2.

A surfactant solution (I) having the following composition was applied onto the outer surface of the photosensitive composition of this photosensitive lithographic printing plate using an electrostatic air type spray gun to obtain a photosensitive lithographic printing plate B.

0 surfactant solution (r) Dainichi Ink Chemical Mega Fabric R-191...1.0g (perfluoroalkyl phosphate: R, SO□N (CH2) 20P (O
ll) 2) O Methanol・・・・・・・・・・・・50g Pure water・・・
The 50g surfactant layer formed had an irregular shape with a mixture of coated and non-coated areas. The average coating amount after drying was 80 mg/m2. 2 1000 sheets of each of the obtained photosensitive lithographic printing plates Δ and B were stacked without interleaving paper, and the weight was 300 kg/c.
After leaving it at 45℃ for 7 days under the pressure of
When plate-making was performed using Type 01, automatic plate-making was not possible for photosensitive lithographic printing plate A because the surface of the photosensitive layer and the back surface of the plate stacked on top of it stuck together. Photosensitive lithographic printing plate B could be automatically plate-made without any problems. Further, the printing performance of the lithographic printing plates obtained by developing these samples with a developer having the composition shown below was almost unchanged.

0 Developer composition Benzyl alcohol 30g Triethanolamine 10g Sodium tert-butylnaphthalene sulfonate 10g Sodium sulfite 2g Water
1000g Example 2 The photosensitive lithographic printing plate ASB obtained in Example 1 was 1003mm thick.
I cut them out to a size of x800mm, packed 20 of each into a cardboard box without interleaving paper, and after transporting them back and forth between Shizuoka and Sapporo by train and truck, I opened the box and inspected it. Photosensitive lithographic printing plate A had many fine scratches on the surface of the photosensitive layer, whereas photosensitive lithographic printing plate B according to the present invention had almost no scratches.

Example 3 An aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and a 400 mesh pumice stone-water suspension, and thoroughly washed with water. This plate was immersed in an aqueous solution of tribasic sodium phosphate (5%) at 70° C. for 3 minutes, then washed with water and dried. This support was coated with polyhydroxyphenyl naphthoquinone obtained by condensation polymerization of a7tone and pyrogallol as described in Japanese Patent Publication No. 43-28403.
1. Prepare a photosensitive solution by dissolving 1 part of 2-diazide-5-sulfonic acid ester and 2 parts of novolac type phenol formaldehyde resin in 20 parts by weight of 2-methoxyethyl acetate and 200 parts by weight of methyl ethyl ketone.
A photosensitive lithographic printing plate C was prepared by coating the above support and drying it.

A surfactant solution (Nu) having the following composition was coated on the back side of this photosensitive lithographic printing plate using a bar coater and dried at 100° C. for 2 minutes to obtain a photosensitive lithographic printing plate.

0 Surfactant solution (II) Fluorado FC-430 (non-ionic) manufactured by Jujutsu 3M = 2gr2-methoxyethanol...498g The surfactant layer is uniformly formed on the entire surface, The coating amount was 40 mg/m2.

When the obtained photosensitive planographic printing plates C and D were subjected to a transportation test in the same manner as in Example 2, photosensitive planographic printing plate C had many fine scratches on the photosensitive surface.
Almost no scratches were observed on the photosensitive lithographic printing plate according to the present invention. Next, this photosensitive lithographic printing plate was exposed in the usual manner and developed using Fuji Film developer DP-1 diluted 6 times with water. A similarly good lithographic printing plate was obtained.

Claims (1)

[Claims] A photosensitive lithographic printing plate comprising a fluorosurfactant layer provided on at least one surface of a lithographic printing plate having a photosensitive composition layer on a support.