JPH043166A - Dampening waterless planographic printing plate material - Google Patents

Abstract

PURPOSE:To improve printing durability by processing a base with a silane coupling agent. CONSTITUTION:This printing plate material has a primer layer, a photosensitive layer and a silicone rubber layer in this order on a base and the base is processed with the silane coupling agent. Since the primer layer is provided between the base and the photosensitive layer, the adhesion of the primer layer to the base increases if the base is processed by the silane coupling agent. The peeling of the primer layer during the execution of developing and printing is prevented in this way and, therefore, the excellent printing durability is obtd. The faithful peeling of the image part or non-image part of the photosensitive layer at the time of development is possible and the degradation in developability is obviated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive lithographic printing plate material that does not require dampening water, and more particularly to a photosensitive lithographic printing plate material that does not require dampening water and has excellent printing durability.

[Background of the invention]

A dampening water-free lithographic printing plate material (hereinafter abbreviated as "1 plate material" as necessary) having a photosensitive layer and a silicone rubber layer on a support is coated with a dampening water-free lithographic printing plate material (hereinafter "printing material" as necessary). To obtain a manuscript (abbreviated as "plate"), a manuscript, such as a positive film, is placed on the surface of the plate material under vacuum. After exposure using a metal halide lamp and developing with a developer, only the silicone rubber layer and photosensitive layer or silicone rubber layer in the unexposed area are removed, and a printing plate in which a recessed image area is formed is obtained. I can do it.

In order to improve the plate-making performance of such printing plates, a primer layer has conventionally been provided between the support and the photosensitive layer.

However, if the adhesion between the primer layer and the support is weak, the primer layer will peel off during development or printing, making it impossible to print, resulting in a decrease in printing durability. I found out something.

Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate material that does not require dampening water and can improve printing durability.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventor has developed a photosensitive lithographic printing plate material that does not require dampening water and has a brimer layer, a photosensitive layer, and a silicone rubber layer on a support in this order. It has been found that the above object can be achieved by a photosensitive lithographic printing plate material that does not require dampening water and is characterized by being treated with a coupling agent.

[Function] Photosensitive planographic printing plate materials generally require dampening ice (hereinafter referred to as rPs plate materials) and photosensitive planographic printing plates that do not require dampening water, which is the subject of the present invention. Divided into materials.

PS plate materials have a structure in which a photosensitive layer is directly coated on a support, and after exposure and development, the surface of the support is exposed, and dampening water is retained on the exposed portion of the support surface. is printing. In such PS plate materials, since the adhesion between the photosensitive layer and the support affects the printing durability, surface treatments of the support have been attempted, one of which is a technique of treatment with a silane coupling agent. is also known.

However, when treated with a silane coupling agent, the adhesion between the photosensitive layer and the support becomes strong, so there is a problem that the image area or non-image area cannot be faithfully peeled off during development, resulting in poor development.

On the other hand, in the case of the plate material that does not require dampening water of the present invention, a primer layer is provided between the support and the photosensitive layer, so when the support is treated with a silane coupling agent, the primer layer and the support The primer layer will not peel off during development or printing, so it has excellent printing durability, and the image or non-image areas of the photosensitive layer can be peeled off faithfully during development. , developability does not deteriorate.

There are various methods for firmly adhering the primer layer and the support, but treatment with a silane cuff pulling agent is very effective in terms of printing durability.

The present invention will be explained in detail below.

The dampening water-free plate material of the present invention has a primer layer on the support,
A photosensitive layer and a silicone rubber layer are formed. The photosensitive layer and the silicone rubber layer may be one-year photosensitive silicone rubber layers, and an adhesive layer may be provided between the photosensitive layer and the silicone rubber layer.

(Support) Supports include metal plates made of aluminum, copper, zinc, iron, etc., plastic films or sheets made of polyester, polystyrene, polyethylene, polypropylene, etc., chloroprene rubber, coated paper, and sandwiched with aluminum foil. Paper, plastic film, etc. can be used. Particularly preferred is an aluminum plate.

The silane coupling agent used for treating the support is not particularly limited, but includes, for example, the following.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyltriethoxysilane tetraethoxysilane,
Methyldimethoxysilane, Methyljethoxysilane 2
Dimethylethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, trimethylchlorosilane dimethyldichlorosilane, methyltrichlorosilane, methyldichlorosilane,
dimethylchlorosilane, dimethylvinylchlorosilane,
Methylvinyldichlorosilane, triphenylchlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, chloromethyldimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, γ -chloropropylmethyldimethoxysilane, γ-chloropropylmethyljethoxysilane, γ-aminopropyltriethoxysilane, N-(
β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxybrobyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane Among these, γ-methacryloxypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane are preferred. Preferred are silane, γ-7minopropyltriethoxysilane, and N-(β-aminoethyl)-γ-7minobrobylmethyldimethoxysilane.

A common method for treating a support with a silane coupling agent is to dissolve it in a solvent such as water or alcohol that dissolves the silane coupling agent, and then uniformly treat the surface by spraying, dipping, coating, etc. .

In addition, when an aluminum plate is used as a support, surface roughening treatment such as graining treatment, anodizing treatment, etc. may be performed before, during, or after treatment with a silane coupling agent.

The thickness of the support is preferably 50 to 400 am, more preferably 100 to 300 am.

(Primer layer) The primer layer preferably contains a resin and, if necessary, a curing agent, various additives, a silane coupling agent, and an organic titanate agent.

Examples of resins include polyester resin, vinyl chloride, etc.
Vinyl acetate copolymer, acrylic resin, vinyl chloride resin,
Examples include polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

The primer layer used in the present invention is preferably crosslinked in order to improve solvent resistance to the coating solvent of the photosensitive layer and the organic solvent of the developer.

As the component to be crosslinked, polyvalent incyanate compounds, diazo resins, polyvalent epoxy compounds, compounds having two or more polymerizable ethylenically unsaturated double bonds, etc. are used.

Examples of polyvalent incyanate compounds include diphenylmethane-4,4'-diincyanate, hexamethylene diisocyanate, and Coronate E.

Examples include HL and EH (manufactured by Nippon Polyurethane Industries, Ltd., polyvalent incyanate compounds).

Examples of the diazo resin include 4-diasodiphenylamine, hexafluorosulfate-formaldehyde resin, 3-methoxy-diphenylamine-4-diazonium salt and 4,4'-
Examples include mesitylene sulfonate salt of a condensate of bis-methoxymethyl-diphenyl ether.

Examples of the polyvalent epoxy compound include bisphenol epoxy resin, bisphenol F diglycidyl ether, novolac glycidyl ether, hexahytomipthalic acid glycidyl ether, triglycidyl isocyanurate, and the like.

Examples of the compound having two or more polymerizable ethylenically unsaturated double bonds include trimethylolpropane triacrylate, tetramethylolmethane triacrylate, allyl acrylate, and 1.4-butanediol dimethacrylate. In addition, when using a compound having an ethylenically unsaturated double bond, a polymerization initiator or a photopolymerization initiator is used together.

Among the above crosslinking agents, diazo resins are preferred.

(Photosensitive layer) The structure of the photosensitive layer of the present invention is not particularly limited, and various photosensitive substances can be used. Typical examples will be explained below.

First, quinonediazide-type positive photosensitive materials such as conventionally known 0-naphthoquinonediazide compounds are mentioned.

Suitable 0-naphthoquinone diazide compounds include naphthoquinone-(1,2)-diazide-(2) sulfonic acid chloride and phenol or cresol-formaldehyde resins as described in U.S. Pat. No. 3,046,120. There are esters of Other examples of 0-naphthoquinonediazide compounds include 2, for example, U.S. Patent 3,
Ester of pyrogallol-acetone resin and 0-naphthoquinone cyacytosulfonic acid chloride described in No. 835,709, JP-A-55-76346, No. 56-
Ester of polyhydroxyphenyl resin and 0-naphthoquinonediazide sulfonic acid chloride described in No. 1044 and No. 5 [1-1045], JP-A-1983-11
A homopolymer of P-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in No. 3305 is ester-reacted with 0-naphthoquinonediazide sulfonic acid chloride, Japanese Patent Publication No. 1973-
17481, a reaction product between a polymer product of a styrene monomer and a phenol derivative and O-quinonediazide sulfonic acid, and a reaction product between a polyhydroxybenzophenone and O-quinonediazide sulfonic acid.
-Esters of naphthoquinonediazide sulfonic acid chloride and the like.

A binder may be added to the photosensitive composition containing such a quinonediazide type photosensitive substance if necessary6.
For example, suitable examples include novolac resins soluble in aqueous alkaline solutions. Typical examples of such novolac resins include phenol-formaldehyde resin, talesol-formaldehyde resin, p4ert-butylphenol-formaldehyde resin, and phenol-modified xylene resin.

The amount of quinonediazide compound in the photosensitive composition is 10-5
It is 0% by weight, more preferably 20 to 40% by weight. In addition, the amount of the above-mentioned binder is 45 to 45% in the photosensitive composition.
It is 80% by weight, preferably 50 to 70% by weight.

Further, as the photosensitive substance, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde is also used.

Particularly preferred are salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphates, tetrafluoroborates,
A diazo resin inorganic salt which is a reaction product of a perchlorate or a periodate and the above-mentioned condensate, and U.S. Pat.
Examples include diazo resin inorganic salts, which are reaction products of the condensate and sulfonic acids, as described in No. 309. The diazo resin is preferably used together with a binder. Various polymeric compounds can be used as such a binder, but monomers having aromatic hydroxyl groups such as those described in JP-A-54-98813, such as tho(4-hydroxyphenyl), are preferable. Acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m-1 or p-hydroxystyrene, o-
, m-, or p-hydroxyphenyl methacrylate, etc., and copolymers with other monomers, U.S. Pat. No. 4.123.2
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit as described in No. 7fi, Scherer
7, natural resins such as rosin, polyvinyl alcohol, polyamide resins described in U.S. Pat. No. 3,751,257, linear polyurethane resins described in U.S. Pat. No. 3,660,097, phthalates of polyvinyl alcohol. epoxy resins condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate.

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
15, photosensitive polyesters obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol; Examples include photosensitive polyesters derived from (2-properidene)malonic acid compounds such as denmalonic acid and difunctional glycols.

Further examples include aromatic azide compounds in which the azide group is bonded directly or via a carbonyl group or a sulfonyl group to an aromatic ring. For example, polyazidostyrene as described in U.S. Pat. Polyvinyl-p-7zidobendi7-topolyvinyl-P-azidobenzal, a reaction product of azidoarylsulfanyl chloride and an unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 45-9613, and also in Japanese Patent Publication No. 43-21067, 4
No. 4-229, No. 4422954 and No. 45-249
Examples include polymers containing sulfonyl azide and carbonyl azide as described in No. 15.

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

In the present invention, the photosensitive substance may include a! which does not impair the purpose of the present invention! Filler 1 Pigment or dye other than the invention,
Pigments, surfactants for improving coating properties and other customary additives and auxiliaries can be contained.

The thickness of the photosensitive layer is preferably 0.05 to 10 m, more preferably 0.1 to 2 m.

(Silicone rubber e) The silicone rubber used in the silicone rubber layer is a linear organic polysiloxane having the following repeating units, a molecular weight of several thousand to several tens of blades, and an OH group in the main chain or at the end of the main chain. Preferably, the main component is

(-5i -0 thick where n is an integer of 2 or more, R is an alkyl group having 1 to 0 carbon atoms, a halogenated alkyl group, a vinyl group, an aryl group,
Preferably, it is a silanol group (OH group) and 60% or more of H is a methyl group.

The silanol group (OH group) may be located either in the main chain or at the end of the main chain, but is preferably located at the end.

The silicone rubber useful in the present invention is obtained by the condensation reaction of such a silicone paste polymer with a silicone crosslinking agent as listed below.

(+) R-5i+CIR') (2) R-Si+0Ac) (3) R-Si(-ON-CR'?)2 Here, R has the same meaning as R explained earlier, and R' is a methyl group, It is an alkyl group such as an ethyl group, and Ac is an acetyl group.

These silicone rubbers are also available as commercial products, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd.

Other useful silicone rubbers can be produced by reacting the above-mentioned pace polymers with silicone oils having the following repeating units, or by reacting them with silicone base polymers in which about 3% of R is vinyl groups. addition reaction,
Alternatively, it can also be obtained by a reaction between the silicone oils.

(In the formula, R has the same meaning as R above, and l is 2 or more!
i! ! The number n is an integer of 0 or 1 or more. ) In order to obtain silicone rubber through such a crosslinking reaction, organic carboxylates of metals such as tin, zinc, cobalt, lead, calcium, and manganese, such as dibutyltin laurate and tin ( II) Catalysts such as octoate, naphthenic cobalt, etc., or platinic platinic acid are added.

Further, in order to improve the strength of the silicone rubber and obtain a silicone rubber that can withstand scratches that occur during printing operations, a filler may be mixed. Silicone rubber premixed with filler is commercially available as silicone rubber stock 4 or silicone rubber dispersion, and if it is preferred to obtain a silicone rubber film by coating as in the present invention.

RT V or L TV silicone rubber dispersion is preferably used. An example of this is
Syl OFF 23.5III manufactured by Toray Silicone
There are silicone rubber discs for paper coating such as X-257 and 5H237.

In the present invention, in addition to the above-mentioned components, a small amount of photosensitizer can be included in the silicone rubber layer.

The silicone rubber layer can further contain a silane coupling agent used in the treatment of supports in order to improve adhesion to the photosensitive layer.

The thickness of the silicone rubber layer is 0.1 to 10. Snow is preferred, and more preferably 0.5 to 2 μm.

Note that in the case of forming a photosensitive silicone rubber layer, a photosensitive layer is not necessary, and such a photosensitive silicone rubber may include γ-methacryloxypropyltrimethoxysilane or heptanocinnamoyldiethoxysilane at the terminal OH group of dimethylpolysiloxane. Examples include compounds obtained by dealcoholization condensation of polydiorganosiloxane, compounds obtained by adding a bisazide compound to polydiorganosiloxane, or compounds obtained by reacting acryloyl chloride or p-azidobenzoate.

A light-transmissive film layer can be formed on the silicone rubber layer. Here, light transmittance refers to, for example, active light (wavelength 30
0 nm to 500 n+s), the light transmittance is 50% or more.

Examples of resins used in the light-transmitting film layer include polyolefins such as polypropylene, polystyrene, polymethylpentene, and ethylene-butene copolymers, polystyrene, fluororesins, polyethylene terephthalate, nylon, polyvinyl alcohol, polycarbonate, polymethyl methacrylate, and polyimide. , polyacrylocotrile, and the like.

The light-transmissive film layer may be a single layer of the resin film described above, or may be a laminated film of two or more layers.

The thickness of one light-transmissive film layer is preferably 0.5 to 20 microns, more preferably 3 to 8 microns.

The light-transmitting film layer is preferably matted.

Next, a method for manufacturing the above plate material will be explained.

The support is treated with a silane coupling agent. Next, a brimer layer is formed on the treated support using a normal coater such as a reverse roll coater, an air knife coater, a Meyer percoater, or a rotary coating device such as a Whaler. Apply and dry a composition solution to form a photosensitive layer, and then apply and dry a composition solution to form a photosensitive layer.1.Next, if necessary, apply an adhesive layer on the photosensitive layer in the same manner, and after drying, apply silicone. The rubber solution is applied on the adhesive layer in the same manner and heat-treated at a temperature of usually +00-120°C for several minutes to fully cure and form a silicone rubber layer.Then, a light-transparent film is applied on the silicone rubber layer. Laminate.

Next, a method for manufacturing a printing plate that does not require dampening water using the plate material of the present invention will be described.

An original, for example, a positive film, is aligned with the surface of the plate material that does not require dampening water, is vacuum-adhered, and exposed. 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. After exposure, the light-transmitting film is peeled off and developed with an aqueous alkaline developer to form a four-part image area as described in one or more steps in which only the silicone rubber layer and photosensitive layer or silicone rubber layer in the unexposed area is removed. You can obtain a printed version.

(Effects of the Invention) According to the present invention, a photosensitive lithographic printing plate material that does not require dampening water and has excellent printing durability can be provided.

〔Example〕

The present invention will be explained in more detail below with reference to one example, but the present invention is not limited to these examples.

(Preparation of plate material samples a to d) After anodizing and sodium silicate treatment, 5 of the silane cuff pulling agent listed in Table 1 was added to a % methanol solution at 30°C.
A dispersed primer solution having the following composition A was applied onto an aluminum plate (a-cl) treated for 5 minutes so that the film thickness after drying was 5 mm.

Cobrimer liquid composition A> PF6 salt of a condensate of p-diazodiphenylamine and formaldehyde 10g Copolymer 100g Zinc oxide (white pigment) 20g Get Yellow 402 (grain color pigment) 10g
Methyl lactate 800° The obtained brimer was irradiated with ultraviolet light of 800 mJ/cm' using a high-pressure mercury lamp to be cured to form a brimer layer.

Next, a photosensitive solution having the following composition was applied so that the film thickness after application was 0.2 μm.

Photosensitive liquid composition> PFb salt 10g of a condensate of p-diazodiphenylamine and formaldehyde 2- and a copolymer of droxyphenyl methacrylamide/hydroxyethyl methacrylate-1/methacrylic acid (50/40/10 in molar ratio) 10g orange■
Methyl lactate
IGOOgNext, a silicone rubber liquid having the following composition was applied so as to have a dry film thickness of 2 layers, and then a 6 pts polypropylene film was laminated to prepare plate samples a to d.

Silicone rubber liquid composition> Polydimethylsiloxane with hydroxyl groups at both ends (molecular weight 37
,000) 9g triacetoxysilane 0.9g dibutyltin laurate 0.07g Isopar E (manufactured by Exxon) 90g (Preparation of comparative plate sample i) Silane cup for treating the support in the preparation of plate samples a to d Comparative plate material sample i was prepared in the same manner except that no ring agent was used.

(Preparation of plate samples a to h) A degreased aluminum plate was treated with the silane cuff pulling agent listed in Table 1 in the same manner as plate samples #4a to d, and the dispersed primer liquid with the following composition was dried. Later film thickness is 10g
It was applied so that the thickness was m.

Primer liquid composition> Copolymer of 2-hydroxyethyl methacrylate/methyl methacrylate (50150 molar ratio)
100g DETX (initiator 1 manufactured by Nippon Kayaku Cod) EPA (initiator manufactured by Nippon Kayaku ■) Zinc oxide (white pigment) g g 0g Get Yellow 402 (yellow pigment) 10g methyl lactate
1000g or less, plate material trial $
Plate material samples e-h were prepared in the same manner as in 4 a-d.

(Preparation of comparative plate material sample j) Comparative plate material sample j was prepared in the same manner as in the preparation of plate material samples eh, except that the silane coupling agent for treating the support was not used.

(Preparation of printing plate) The obtained plate material samples a to h and comparative plate material samples i and j were heated to 4Kw.
After image exposure using a metal halide lamp, the sample was immersed in 5DR-1 (manufactured by Konica ■) diluted 6 times with water for 40 seconds.
A printing plate was prepared by rubbing with absorbent cotton and developing, and the image area was dyed with a dyeing liquid having the composition shown below.

Dyeing solution composition> Victoria Pure Blue BOH 1 part by weight Nlufit (manufactured by Clarei Soprene Chemical Co., Ltd.) 20 parts by weight Rheodol T
Wo-120 (manufactured by Kao ■) 0.5 parts by weight Hensyl alcohol 5 parts by weight water 100 parts by weight (Evaluation) The printing durability was determined when the dyed plate was printed on a Heidelberg GTO printing machine.

The results are shown in Table 1.

As is clear from Table 1, the plate material samples of the present invention had excellent printing durability, whereas the comparative printing material samples had a primer layer that peeled off during printing and were found to have poor printing durability.

Claims (1)

[Claims] A dampening solution-free photosensitive lithographic printing plate material having a primer layer, a photosensitive layer, and a silicone rubber layer in this order on a support, characterized in that the support is treated with a silane coupling agent. Water-free photosensitive lithographic printing plate material.