JPH0262543A - Damping-waterless lithographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the damping-waterless planographic printing plate having good scratching resistance at the time of development and plate wear by superposing a primer layer, photosensitive layer and Si rubber layer on a base and incorporating at least one of prescribed compds. into the Si rubber layer. CONSTITUTION:The Si rubber essentially consisting of the linear org. polysiloxane which has a prescribed repeating unit and several thousands to several tens thousands mol. wt. and has an OH group in the main chain or main chain end is used for the Si rubber layer and the compds. expressed by the formulas I to III are incorporated as a crosslinking agent therein. In the formulas, Rf is a fluorine-substd. alkyl group; X is a bivalent org. group; R is an alkyl group; l is 0 or 1 integer. A packing material may be mixed therein in addition thereto. The thickness of the Si rubber layer is adequately 1 to 40mum and if necessary, a protective layer is provided atop the layer. The Si rubber layer is formed by a spin coating method. The damping-waterless planographic printing plate which has the good stratching resistance at the time of development and the good plate wear is obtd. according to this constitution.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a lithographic printing plate material that does not require dampening water.

More specifically, the present invention relates to a lithographic printing plate material that does not require dampening water and has good scratch resistance during development and printing durability.

[Prior Art] Conventionally, as a lithographic printing plate material that does not require dampening water (hereinafter referred to as "one plate material if necessary"), one in which a photosensitive layer and a silicone rubber layer are sequentially coated on a support is known. . If you use a lithographic printing plate that does not require dampening water (hereinafter referred to as a "printing plate" as necessary) obtained by exposing and developing this plate material, the print material will be can be obtained.

It is known that in order to improve the printing durability of such printing plates, it is sufficient to increase the coating strength of the silicone rubber layer. Conventionally, methods of adding various additives to increase film strength have been known, and are disclosed in JP-A No. 43-88103 and JP-A No. 55-55.
No. 1102411 contains various silane coupling agents,
JP-A No. 54-54702 discloses vinyltriacyloxysilane, JP-A 58-80744 discloses organic titanium compounds, JP-A 82-14158 discloses allyl isocyanurate compounds, JP-A 82-111254 discloses No. 2, discloses a technique for adding each aminosilane compound.

[Problems to be Solved by the Invention] However, although adding the various additives described above increases the film strength of the silicone rubber layer, it has the disadvantage that the ink repellency, which is an originally required property, decreases. be.

Therefore, an object of the present invention is to provide a lithographic printing plate material that does not require dampening water and exhibits excellent scratch resistance and good printing durability without reducing the ink repellency of the silicone rubber layer.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors have arrived at the present invention.

Namely, the lithographic printing plate material that does not require dampening water according to the present invention has a primer layer, a photosensitive layer, and a silicone rubber layer in this order on a support, in which the silicone rubber layer has the following general structure. Formula [1], [II] or [m]
It is characterized by containing at least one compound selected from the following compounds.

General formula [I1] Rf -X -(CH2) 5i
(In the ORh formula, Rf represents a fluorine-substituted alkyl group, such as a fluorine-substituted methyl group or ethyl group, or a divalent organic group, such as (CH2) nO (n is an integer of 1 or more), COO, The 0 sentence representing 6 groups such as SO2NR'(R' is an alkyl group such as a methyl group) is O or an integer of 1 or more.

[Function] When the compounds of the above general formulas [I to [m] are used in the silicone rubber layer of the present invention, unlike conventional additives, silicone
It not only increases the film strength of the rubber layer, but also has good ink repellency, has excellent printing durability, and produces many good-quality prints without stains.

[Specific Structure of the Invention] The support of the present invention is preferably flexible enough to be set in a normal lithographic printing machine and capable of withstanding the load applied during printing, such as aluminum, zinc, copper, steel, etc. Metal plates, metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. 1 paper, plastic films and glass plates, resin coated paper, paper covered with metal foil such as aluminum, hydrophilic Examples include treated plastic films and rubber. Among these, aluminum plates are preferred.

The primer layer of the present invention includes 1, for example, polyester resin,
Vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, phenol resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin.

Examples include polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like. Among them, epoxy resins and phenol resins are preferred. Furthermore, a silane coupling agent, a silicone primer, etc. can be used for the primer layer, and organic titanates and the like are also effective.

The photosensitive material used in the photosensitive layer of the present invention is not particularly limited, and examples thereof include quinonediazide-type positive photosensitive materials such as conventionally known 0-naphthoquinonediazide compounds. Suitable 0-naphthoquinone diazide compounds include naphthoquinone-(1,2)-diazide-(2)-sulfonic acid chloride and phenol or cresol-formaldehyde resins described in U.S. Pat. No. 3,048,120. There is an ester with. Other useful O-naphthoquinonediazide compounds include esters of pyrogallol-acetone resin and O-naphthoquinonediazide sulfonic acid chloride described in U.S. Pat.
Ester of polyhydroxyphenyl resin and 0-naphthoquinonediazide sulfonic acid chloride described in No. 5B-1044 and No. 5B-1045, JP-A-50
A homopolymer of p-hydroxystyrene as described in No. 113305 or a copolymer of this with other copolymerizable heptamers with 0-naphthoquinonediazide sulfonic acid chloride, especially Examples thereof include a reaction product of a polymer product of a styrene monomer and a phenol derivative and 0-quinonediazide sulfonic acid described in Publication No. 17481/1982, and an ester of polyhydroxybenzophenone and 0-naphthoquinonediazide sulfonic acid chloride.

A photosensitive composition containing such a quinone diazide type positive photosensitive material may optionally contain a binder. For example, a preferred example is a novolac resin soluble in an aqueous alkali solution. Examples of such novolac resins include phenol-formaldehyde resins,
Representative examples include cresol-formaldehyde resin, p-tart-butylphenol-formaldehyde resin, and phenol-modified xylene resin. The amount of the quinonediazide compound in the photosensitive layer is 10 to 50% by weight, more preferably 20 to 4Qii%.

In addition, the amount of the above-mentioned binder is 45 to 80% in the photosensitive composition.
The weight is the highest %, preferably 50~? It is Oii%.

Further, in the present invention, the following photosensitive substances can be used. For example, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde. Particular preference is given to salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as reaction products of hexafluorophosphates, tetrafluoroborates, perchlorates or periodates with said condensates. Certain diazo resin inorganic salts, U.S. Patent No. 3,300,
Examples include diazo resin organic salts, which are reaction products of the above condensate and sulfonic acids, as described in No. 309. Furthermore, diazo resins are preferably used together with binders. As such a binder, various polymer compounds can be used, but preferably, JP-A-54-98Ei13
monomers with aromatic hydroxyl groups as described in Hydroxystyrene, 0
-, copolymer of fat-1 or p-hydroxyphenyl methacrylate and other monomers, U.S. Pat. No. 4,123,
Polymers containing hydroxyethyl acrylate units or hydrodiethyl methacrylate units as a main repeating unit as described in US Pat. No. 278, natural resins such as shellac and rosin, polyvinyl alcohol, polyamide resins, linear polyurethane resins described in U.S. Pat. No. 3,880,097, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate. class is included.

Also, -CH=C as a photosensitive group in the main chain or side chain of the polymer.
Examples include those whose main component is a photosensitive polymer such as polyesters containing H-C-, polyamides of type 8, and polycarbonates. For example, JP-A-55-404
A photosensitive polyester obtained by the condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol, as described in US Pat. Examples include photosensitive polyesters derived from (2-properidene)malonic acid compounds such as cinnamylidenemalonic acid and difunctional glycols, as described in No. 1] 5fl, No. 878.

Further examples include aromatic azide compounds in which the azide group is bonded directly or via a carbonyl or sulfonyl group to an aromatic ring. For example, polyazidostyrene as described in U.S. Pat. No. 3,098,311; Polyvinyl-p-azidobenzoate, polyvinyl-p-7 didobenzal, the reaction product of 7-didoarylsulfanyl chloride and unsaturated hydrocarbon polyde-described in Japanese Patent Publication No. 45-9613, and also -2108? No. 44-229 Hakama, No. 44-22954 and No. 45-2
Examples include polymers having sulfonyl 7dide and carbonyl azide, as described in No. 4915.

Furthermore, a photopolymerizable composition comprising an addition polymerizable unsaturated compound may also be mentioned.

In addition to the above, the photosensitive layer contains dyes (for example, Victoria Pure Blue 80) 1 (manufactured by Hodogaya Chemical Co., Ltd.) and Oil Blue 1803 to make the image visible after exposure or development.
(manufactured by Orient Chemical Industry Co., Ltd.), alkyl ethers to improve coating properties (e.g., ethyl cellulose,
methyl cellulose), fluorine-based surfactants, nonionic surfactants (for example, Pluronic L64 (manufactured by Asahi Denka).

Plasticizers to impart flexibility to the coating (e.g.

Polyethylene glycol, tricresyl phosphate.

acrylic acid or methacrylic acid polymers), stabilizers (eg phosphoric acid, oxalic acid, tartaric acid, etc.).

The silicone rubber used in the silicone rubber layer of the present invention includes molecules ffi having the following repeating units.
Preferably, the main component is a linear organic polysiloxane having several thousand to hundreds of thousands of OH groups in the main chain or at the ends of the main chain.

Here, n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkyl group, a vinyl group,
aryl group, silanol group (O)l group), and H is 6
Preferably, 0% or more of the silanol groups (OH groups) are present in the main chain or at the end of the main chain, but preferably at the end.

,tJ? In the IrJJ silicone rubber layer, compounds represented by the above general formulas [I] to [m] are used as crosslinking agents.

Specific examples of the compound represented by the general formula [I] include the following.

Rf -X -CH2CHCH2 HOH Specific examples of the compound represented by the general formula [II] include the following.

Rf -X -CHzC,Hpn2 Specific examples of the compound represented by the general formula [ml] include the following.

Rf -X -(C)I2) 5t(ORhAn example of a method for synthesizing the compounds represented by general formulas [1] to [ml] is given below.

(Synthesis example of exemplified compound [I-3]) Ha → F+3CbCH2CH20CH2CHCH2+
HCtanNa0)l (Synthesis example of exemplified compound [I-3]) HaF+3CbCH2CH20CH3COCH3+ H20
→ F+3 (6cH2cH20CH2COCH2 (Synthesis example of exemplified compound [l11-1]) F+sfl near GO
OH+ H2N((:H?)3sj(OMe)x→ F
+5(,+C0N)1(C)I2)tsi(0)1
g) The amount of the compound represented by the 3 general formulas [I] to [III] is preferably 0.3 to 30 parts by weight, more preferably 1.0 to 15 parts by weight. In addition, general formulas [1] to [I1
The compounds represented by 1] can be used alone or in combination of two or more.

Further, it is preferable to use the compound of the present invention in combination with a conventionally used crosslinking agent, such crosslinking agents include:
Examples include:

(1) R-9i÷OR') (2) R-Si+OAc) (3) R-9i-+0N-OR' 2)2 Here, R has the same meaning as R explained above.

R' is an alkyl group such as a methyl group or an ethyl group.

In addition to the above-mentioned components, the silicone rubber layer of the present invention contains heavy machinery carboxylates of metals such as tin, zinc, cobalt, lead, calcium, and manganese, such as dibutyltin laurate, tin(II) octoate, and naphthenic acid. Catalysts such as cobalt or chloroplatinic acid may be added.

In addition, in order to improve the strength of silicone rubber and obtain silicone rubber that can withstand the frictional forces generated during printing operations,
Fillers can also be mixed.

Furthermore, the silicone rubber layer may contain additives that are conventionally used, such as silane coupling agents.
Furthermore, a small amount of photosensitizer may be included in the silicone rubber layer.

The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support has a thickness of 50 to 400μ, preferably 100μ
~300pLm, primer layer 0.1-100pL
11 is preferred, more preferably 1.0-15.

The photosensitive layer has a thickness of 0.05 to IO μm, preferably 0.1 to 2
The gm silicone rubber layer is 0.5 to 100 gm, preferably 1 to 40 gm.

In the present invention, a protective layer may be provided on the upper surface of the silicone rubber layer, if necessary.

The dampening water-free plate material of the present invention is manufactured, for example, as follows.

A primer layer is applied onto the support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coating device such as Whaler, and then dried and hardened.Next, a photosensitive layer is applied on the primer layer. The composition solution to be made up is applied, dried and optionally heat cured. If necessary, an adhesive layer may be provided on the photosensitive layer by the same method as described above.Next, a silicone rubber solution is applied on the photosensitive layer in the same manner, and the adhesive layer is usually 100 to 100 g.
Heat treatment is performed at a temperature of 20° C. for several minutes to fully cure and form a silicone rubber layer. If necessary, a protective film is provided on the silicone rubber layer using a laminator or the like.

To obtain a printing plate using the plate material obtained as described above, a positive film, which is an original, is vacuum-adhered to the surface of the plate material.
Expose. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used. A photo-insolubilized area is formed in the photosensitive layer by exposure.Next, the unexposed area is eluted and removed using a developer and developed, resulting in an image area (concave area).
form. As the developer, those known as those for plate materials that do not require dampening water can be used. product name) or gasoline,
kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.)
, or a halogenated hydrocarbon (such as trichlene) to which the following polar solvent is added is suitable.

Alcohols (methanol, ethanol, water, etc.), ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl calpitol, butyl calpitol.

Dioxane, etc.), ketone a (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, methylselonlubu acetate, selonlubu acetate, carpitol acetate, etc.), etc. Also, dyes such as Crystal Bioleft and Astrazone Red are added to the developer. It is also possible to dye the image area at the same time as development.

Development can be carried out by a known method, such as rubbing with a developing pad containing a developer as described above, or pouring a developer onto the printing plate and then rubbing with a developing brush. As a result, only the silicone rubber layer or the silicone rubber layer and the photosensitive layer in the image area are removed, and the surface of the photosensitive layer or primer layer is exposed, and that portion becomes an ink receiving area.

The depth of the ink receiving portion may be only the thickness of the photosensitive layer and the silicone rubber layer, or may be only the thickness of the photosensitive layer or the silicone rubber layer.

Note that, if necessary, it is also preferable to embed an ink receptive substance in the recess in order to reduce the depth of the ink receiving part (printing part).

[Effects of the Invention] According to the present invention, there is an effect that the silicone rubber layer exhibits excellent scratch resistance and good printing durability without reducing the ink repellency of the silicone rubber layer.

[Example] The present invention will be explained in further detail by giving examples below.

Note that "parts" means "parts by weight" unless otherwise specified.

Example 1 Phenol formaldehyde resol resin (Sumilite Resin PC-1) manufactured by Sumitomo Durez Co., Ltd. was applied to a thickness of 0.5 gm on an aluminum plate having a thickness of 0.24 part m.
A primer layer was formed by curing at 00°C for 3 minutes.

Apply a tetrahydrofuran solution with the composition below on this primer layer! σ and heat-treated at 125° for 0.35 seconds to form a photosensitive layer with a thickness of 2 gm.

A and Exhibit 1 (1) Phenol formaldehyde novolac resin with G average degree of polymerization of 5.6 and naphthoquinone-I, 2-diazide-
100 parts of a partially esterified product with 5-sulfonic acid chloride (esterification rate: 49%) (2) 30 parts of 4,4-diphenylmethane diisocyanate (3) 0.2 part of dibutyltin diacetate Next, the following was applied on the photosensitive layer. Silicone rubber layer composition dry weight 1.0
Apply it so that it becomes smooth.

It was dried at 120°C for 4 minutes to obtain a silicone rubber layer.

Silicone rubber layer composition: 6 parts of silane (3) 0.1 part of dibutyltin acetate (4) 5 parts of the following crosslinking agent of the present invention (MF-120 manufactured by Mitsubishi Metals) Surface of the silicone rubber layer obtained as described above A one-sided matted polypropylene film having a thickness of 12 parts m was laminated onto the plate to produce a plate material that did not require dampening water.

Developer composition Isopar H (manufactured by Esso Chemical Co., Ltd.) 50 parts Turfitz (manufactured by Clarei Soprene Chemical Co., Ltd.) 25 parts methanol
25 parts A positive film was vacuum-adhered to the top surface of the above plate material and exposed using a metal halide lamp. The laminate film was peeled off at zero order, and the unexposed areas of the photosensitive layer were rubbed with the developer using the above developer. The silicone rubber layer was removed to produce a lithographic printing plate that did not require dampening water.

Next, the above printing plate was attached to a Heidelberg GTO printing machine with the dampening water supply device removed, and a TOY manufactured by Toyo Ink Co., Ltd.
When printed with OKING ULTRA TUK Aquares G red ink, 250,000 prints were obtained that were clean and clean up to the final print, and were found to have excellent printing durability and ink repellency.

Example 2 In Example 1, the crosslinking agent of the present invention in the silicone rubber layer was changed to C6F+3-CH2CH201J2CHCH20H0).
I (MF-100 manufactured by Mitsubishi Metals Co., Ltd.) A printing plate was obtained in the same manner except that 2 copies were used, and 20,000 sheets of excellent prints without stains were obtained, and the printing durability and ink were excellent. It was found to have excellent repellency.

Example 3 In Example 1, the crosslinking agent of the present invention in the silicone rubber layer was replaced with 10 parts of F+:+C6GONH(CH2CH2(OCHsh (MF-150 manufactured by Mitsubishi Metals)).
A printing plate was obtained in the same manner, and when printing was performed, 50,000 sheets of excellent prints without stains were obtained, and it was found that the printing plate had excellent printing durability and ink repellency.

Examples 4 to 6 Printing was carried out in the same manner as in Examples 1 to 3, except that 0.5 part of γ-7 minopropyltrimethoxysilane was added to each silicone rubber layer. Like No. 3, it showed good printing durability.

Comparative Example 1 A printing plate was obtained and printed in the same manner as in Examples 1 to 3, except that the crosslinking agent of the present invention was not added and 5 parts of aminopropyltrimethoxysilane was added.

As a result, the ink repellency was poor, and scumming occurred in all printing plates after 5,000 sheets or less were printed due to an increase in the temperature of the printing plate during printing.

Comparative Example 2 Printing was carried out in the same manner as in Examples 1 to 3, except that the crosslinking agent of the present invention was not added and the following conventional additives were used instead.

(Conventional crosslinking agent) N+β-aminoethyl)aminomethylphenethyltrimethoxysilane 4 parts As a result, due to poor ink repellency, scumming occurred after printing 4,000 sheets or less.

Comparative Example 3 Printing was carried out in the same manner as in Examples 4 to 6 except that the crosslinking agent of the present invention was not added. Although no scumming occurred, streak-like stains due to scratches on the plate surface occurred after printing 15,000 copies, and the printing durability was poor.

Note that printing was performed in the same manner as in Examples 1 to 3 using a crosslinking agent other than that used in Examples 1 to 3 within the range described above, and the effects of the present invention were confirmed.

Claims (1)

[Scope of Claims] In a lithographic printing plate material that does not require dampening water and has a primer layer, a photosensitive layer, and a silicone rubber layer in this order on a support, the silicone rubber layer has the following general formula [I], [II], or [
At least one compound selected from the compounds shown in [III]
A lithographic printing plate material that does not require dampening water and is characterized by containing: General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] Rf-X-(CH_2)_lSi(OR
)_3 In the formula, Rf represents a fluorine-substituted alkyl group, X represents a divalent organic group, R represents an alkyl group, and l is an integer of 0 or 1 or more.