JPH05303195A - Dampening waterless photosensitive planographic printing plat and its production - Google Patents

Abstract

PURPOSE:To obtain the protective layer having excellent scratching resistance to an ink repulsion layer and good gas permeability by constituting the protective layer of a continuous phase where discontinuous phases having good gas permeability coexist. CONSTITUTION:This dampening waterless photosensitive planographic printing plate has a primer layer, a photosensitive layer contg. at least one selected from a group consisting of a diazo compd., azide compd. and quinone diazide compd., the ink repulsion layer and the protective layer in this order on a substrate. The protective layer consists of the continuous phase where the discontinuous phase having the good gas permeability coexist. The discontinuous layers have the gas permeability better than that of the continuous layer and consist of, for example, air, silicone particulates, hollow resin particulates, etc., and consist more preferably of the air. The protective layer consisting of the continuous phase where the discontinuous phase coexist is formed by incorporating a foaming agent therein.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate requiring no fountain solution and a method for producing the same, and more specifically, a photosensitive lithographic printing plate requiring no fountain solution which is excellent in scratch resistance and does not cause burning blur and a method for producing the same. Regarding

[0002]

BACKGROUND OF THE INVENTION In the conventional printing method that requires dampening water, it is difficult to control the delicate balance between the dampening water and the ink, which causes emulsification of the ink or causes the ink to sprinkle in the dampening water, resulting in poor ink density. It had a big problem that it causes stains and scumming and causes a large amount of wasted paper. However, a dampening water-free photosensitive lithographic printing plate in which a primer layer, a photosensitive layer and an ink repellent layer are provided in this order on a support Has a number of advantages as it does not require fountain solution. JP 61-27547
No. 6, JP-A-62-14155, JP-A-62-279341, JP-A-3-1
Japanese Patent No. 22644 and the like disclose a technique for a fountain solution-free photosensitive lithographic printing plate containing a diazo, azide and quinonediazide in a photosensitive layer and having an ink repellent layer and a protective layer. Since the ink repellent layer is relatively susceptible to scratches, scratches are likely to occur during handling. Therefore, a protective layer having excellent scratch resistance is provided on the ink repellent layer for the purpose of preventing damage to the ink repellent layer. However, the conventional protective layer with excellent scratch resistance has poor gas permeability, and the nitrogen gas generated from the exposed photosensitive layer accumulates between the protective layer and the ink repellent layer, which causes light scattering and burning blurring. There was a drawback. On the other hand, although a protective layer with good gas permeability can prevent the occurrence of burning blur, it is insufficient in terms of scratch resistance to the ink repellent layer, and the ink repellent layer is easily scratched during handling of the printing plate, and There was a problem that dirt was generated. Therefore, a fountain solution-free photosensitive lithographic printing plate having a protective layer that does not cause these problems for a long time, has good gas permeability, and does not cause scratches on the ink repellent layer has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a protective layer having excellent scratch resistance to an ink repellent layer and good gas permeability. It is to provide a photosensitive lithographic printing plate that does not require fountain solution.

[0004]

The above object of the present invention is to provide a photosensitive layer and an ink repellent layer containing at least one selected from the group consisting of a primer layer, a diazo compound, an azide compound and a quinonediazide compound on a substrate. And a fountain solution-free photosensitive lithographic printing plate having a protective layer in this order, wherein the protective layer comprises a continuous phase in which a discontinuous phase having good gas permeability is mixed. Achieved by printing plates and by their method of manufacture.

The present invention will be described in more detail below.

The photosensitive lithographic printing plate not requiring fountain solution of the present invention has at least a primer layer, a photosensitive layer, an ink repellent layer and a protective layer on a substrate in this order.

The protective layer is composed of a layer having a discontinuous phase mixed uniformly or nonuniformly in the continuous phase. In the present invention, a polymer such as a polymer having good scratch resistance is used for the continuous phase. As the high molecular weight polymer preferably used in the present invention, those which provide a coating layer which is substantially transparent to actinic rays are preferable, and resins used in various film bases such as polyethylene terephthalate and polypropylene are also used. However, in the present invention, those which are soluble in water or the developing solution used are particularly preferable. Further, it is desirable to use a high-molecular polymer having appropriate softness and toughness, which does not cause cracks or the like during the drying process or handling after forming the coating layer and has excellent adhesion.

Specific examples of such high molecular weight polymers include polyvinyl alcohol; homopolymers of vinyl ether, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester and the like or copolymers containing them; soluble polyamide; ethyl cellulose, butyl. Examples thereof include cellulose derivatives such as cellulose.

The discontinuous phase has better gas permeability than the continuous phase, and is made of, for example, air, silicone fine particles, hollow resin fine particles, or the like. In the present invention, it is preferably made of air.

The protective layer comprising a continuous phase in which a discontinuous phase is mixed can be formed by containing a foaming agent. That is, by providing a protective layer containing a foaming agent on the ink repellent layer and drying at a high temperature, the organic foaming agent is decomposed, and as a result, a hollow phase composed of air is formed in the continuous phase.

Examples of the foaming agent used in the present invention include organic foaming agents, and examples of the organic foaming agent include nitroso compounds, sulfohydrazide compounds which are hydrazine derivatives of organic sulfonic acids, and azo compounds. These organic foaming agents are preferably used in a proportion of about 3 to 30% by weight of the protective layer, and the use in this range sufficiently achieves the object of the present invention.

Concretely, as the nitroso compound, for example, dinitrosopentamethylenetetramine (DPT or D
NPT), as a commercially available product, Unicel N made by DuPont (US)
D, NDX, Buyer (Germany) Porofor DNO, Eiwa Kasei Cellular D, BL, EX, GX, PP, Shiraishi calcium DPT, Sankyo Kasei cell microphone A, AMR,
AN is mentioned. Also, N, N'-dimethyl N, N'-
There are dinitrosoterephthalamide and hexamethylenetetramine.

The sulfohydrazide compound is, for example, p-toluenesulfonyl hydrazide (T.S.H.), and commercially available products are Sankyo Kasei's Celmic H, K, Eiwa Kasei's Unihole H, NH # 300, NH # 500, NH # 800, N
H # 1000 and AzobisBA manufactured by Kosei Co., Ltd. may be mentioned. In addition, benzenesulfonyl hydrazide, benzene monohydrazone, p, p'-oxybis (benzenesulfonyl hydrazide) (OBSH), as commercial products, Neocervon P # 1000, R # 700, P # 1000N manufactured by Eiwa Kasei, Cell Microphone manufactured by Sankyo Kasei S, others, benzene 1,3-disulfonyl hydrazide, diphenyl hydrazide, 3,3'-disulfone hydrazide diphenyl sulfone, toluene disulfonyl hydrazide, p-toluene sulfonyl hydrazone, p,
There are p'-thiobis (benzenesulfonylhydrazide), toluenedisulfonylhydrazone, p-toluenesulfonylazide.

As the azo compound, for example, azobisisobutyronitrile (AIBN), as commercially available products, Porofor N manufactured by Bayer (Germany), Azobis manufactured by Kosei Co., Vinyl Hall AZ-R, AZS manufactured by Eiwa Chemical Co., Ltd. cell microphone manufactured by Sankyo Chemical Co., Ltd. H
Is mentioned. In addition, azodicarbonamide (azobisformamide) (AC or ADCA), as commercially available products, Azobis CA manufactured by Photo Kasei, Vinylhol AC # 1, manufactured by Eiwa Chemical
AC # 2, AC # 3, AC # 6, AC # 9, Sankyo Kasei cell microphones C-22, CAP, CAP-124, CAP-14
9, CAP-195, CAP-250, and CAP-500. Further, diazoaminobenzene (DAB) and azocarboxylic acid diethyl ester (diethylazodicarboxylate) can be mentioned.

The decomposition temperature of the organic foaming agent is, for example, dinitrosopentamethylenetetramine (DP) which is a nitroso compound.
T or DNPT) is 125 to 205 ° C (including those containing an auxiliary agent). For example, p- of sulfohydrazide compounds
105-125 for toluenesulfonyl hydrazide (TSH)
℃, benzene sulfonyl hydrazide 90 ~ 95 ℃, p,
p'-oxybis (benzenesulfonyl hydrazide)
(OBSH) is 120 to 140 ° C, and 3,3'-disulfone hydrazide diphenyl sulfone is 145 to 155 ° C. For example, the azo compound azobisisobutyronitrile (AI
BN) 100-115 ° C, azodicarbonamide (azobisformamide) (AC or ADCA) 125-200 ° C
Is.

In the case of forming a protective layer comprising a continuous phase in which a discontinuous phase is mixed and a foaming agent, the photosensitivity of some photosensitive materials may be deteriorated by heat. It is desirable to pyrolyze the organic blowing agent at moderate temperatures. For that purpose, a substance that lowers the decomposition temperature of the organic foaming agent (hereinafter referred to as a thermal decomposition aid) may be contained in the protective layer together with the organic foaming agent.

Suitable examples of the thermal decomposition aid include urea and urea derivatives, and in the present invention, it is preferable to select and use at least one of them. The thermal decomposition auxiliary may be blended in a proportion of 30 to 60% by weight of the organic foaming agent. Examples of the urea derivative include aminoguanylurea and aminoguanidine carbonate. As commercial items, Sankyo Kasei Celton N, NP, M,
MR, Eiwa Kasei Cell Soest M ₃ , M ₄ , K ₄ , K ₅ , 10
1, A is mentioned.

Further, the protective layer comprising a continuous phase in which a discontinuous phase is mixed can be formed by dispersing polymer particles having good gas permeability in the continuous phase. In the present invention, it is preferable to use hollow resin particles as the polymer particles having good gas permeability.

The hollow resin particles are, for example, polystyrene, poly (1,6-hexanediaminediylterephthaloyl), polyvinyl acetate, polyethylene, polymethylmethacrylate, polyamide resin, polyvinyl acetate, polyester, polyacrylic ester, polyvinyl. Formed from resins such as formal, gum arabic, benzyl cellulose, ethyl cellulose, acrylonitrile-styrene copolymer, vinylidene chloride-acrylonitrile copolymer, hydroxymethyl cellulose phthalate, nitrocellulose, cellulose acetate, vinyl chloride-butyl acetate copolymer ..

Hollow resin particles are a general term for resins having small pores inside, and can be made from microcapsules containing a low boiling point solvent. The microcapsules can be produced by appropriately using a known technique, for example, an in situ polymerization method in which suspension polymerization is performed in the presence of a swelling agent. To make a good heat-expandable microcapsule,
It is necessary to consider the boiling point of the expander, the structure, the particle size, the particle size distribution, the softening point of the initiator and the film polymer, the elongation upon heating, the strength, the gas barrier property, and the like.

In the protective layer according to the present invention, the volume ratio of the discontinuous phase to the continuous phase is preferably discontinuous phase / continuous phase = 2/8 to 7/3, more preferably 4/6 to 6 /. It is 4.

The following are applied as the primer layer used in the present invention. (1) Epoxy Resin and Primer Layer Composed of Resin Composition Containing It A typical example of an epoxy resin is a reaction product of epichlorohydrin and a polyphenol such as bisphenol A. The epoxy resin may be mixed with other components to give a three-dimensional structure, or may be modified with other components. An example of its usage is as follows.

Thermosetting resin composition containing epoxy resin obtained by mixing one or more of thermosetting resins such as phenol resin, urea resin, melanin resin, amines, polyamides, acid anhydrides, etc. Room temperature or heat-curable resin composition containing an epoxy resin obtained by adding as a curing agent phenol, melamine, polyester, polyamide,
Epoxy resin obtained by precondensation with one or two or more of polysulfide, etc. Epoxy resin ester obtained by esterification with fatty acids These epoxy resins can be appropriately mixed and used, and further, vinyl resin, It can also be used as a mixture with an acrylic resin, an amino resin, an alkyd resin, a urethane resin, etc. within a range in which compatibility is allowed.

Upon curing of the curable fat containing these epoxy resins, a curing reaction accelerator such as p-toluenesulfonic acid or boron trifluoride monoethylamine can be appropriately added and used as necessary.

(2) Primer layer obtained by curing a layer made of a photodimerization type photocurable resin. As the photodimerization type photocurable resin, polyesters and polycarbonates containing a group shown below in the main chain or side chain of a polymer are used. And polyamides, polyacrylic acid esters, polyvinyl alcohol derivatives and the like. The molecular weight is not limited as long as it is soluble in a solvent, but it is generally advantageous to select it in the range of 1,000 to tens of thousands.

[0026]

[Chemical 1]

The photodimerizable curable resin preferably used in the present invention includes, for example, p-phenylene containing a photosensitive group in the polymer main chain as described in US Pat. Nos. 3,030,208 and 3,707,373. Photosensitive polymers such as photosensitive polyesters composed of diacrylic acid, diacrylic acid and diol, 2-propolydenmalonic acid such as cinnamylidene malonic acid and the like as described in US Pat. Nos. 2,956,878 and 3,173,787. Photosensitive polymers such as photosensitive polyesters derived from compounds and bifunctional glycols, US Pat. Nos. 2,690,966 and 2,75
2,373, 2,732,301 as described in each of the specification, polyvinyl alcohol, starch, cellulose and cinnamic acid esters of hydroxyl group-containing polymers such as cellulose and the like, a photosensitive polymer insolubilized by the action of actinic rays, etc. Is mentioned.

A pigment or dye may be added as a colorant to the above-mentioned photosensitive polymer. For example, phthalocyanine blue (C.I. 74160), carmine 6B (C.I.
I. 15850), rhodamine B lake (C.I. 45170) and the like are preferably used, but oil blue BO
It is also possible to use dyes such as (C.I.74350).
The addition amount naturally varies depending on the conditions such as the coating amount, but 1 to 50% by weight based on the polymer, and a particularly preferable range is 2 to
15% by weight.

It is preferable that the above-mentioned photosensitive polymer contains a sensitizer. Such sensitizers include, for example, U.S. Patent Nos. 2,610,120, 2,670,285, 2,670,286, and
2,670,287, 2,732,301, 2,835,656, 2,95
6,878, 3,023,100, 3,066,117, 3,141,770
Issue 3,173,787, Issue 3,357,831, Issue 3,409,593,
3,418,295, 3,453,110, 3,475,617, 3,5
61,969, 3,575,929, 3,582,327, 3,647,47
Those described in No. 0, No. 3,721,566, No. 3,737,319, etc. are included.

Specific examples of particularly useful sensitizers include 2-benzoylmethylene-1-methyl-β-naphthothiazoline, 5-nitroacenaphthene, β-chloroanthraquinone, 1,2-benzalanthraquinone and p. , P'-tetraethyldiaminodiphenyl ketone, p, p'-dimethylaminobenzophenone, 4-nitro-2-chloroaniline and the like. The use ratio of the sensitizer is preferably 0.5 to 1.5% by weight, and particularly preferably 2 to 8% by weight, based on the polymer.

(3) Primer layer having gelatin as a binder As the gelatin, so-called photographic gelatin obtained from bovine bone or hide by acid treatment or alkali treatment is mainly used. What is shown by the general formula of is used. In the present invention, any gelatin can be used as long as it is a natural polymer compound in which various amino acids are condensed.

[0032]

[Chemical 2] Examples of hardeners for hardening (that is, crosslinking) gelatin include inorganic hardeners such as chrome alum and aluminum alum, organic hardeners, and the like. Examples of organic hardeners include: Aldehyde type hardeners such as formaldehyde, glyoxal, succinaldehyde and glutaraldehyde, N-tyrole and acetal hardeners, epoxy hardeners, aziridine hardeners, mucohalogen acid hardeners, active halogen hardeners, dichloro. Examples include -s-triazine hardener, active olefin hardener, carbodiimide, isoxazolium salt hardener, methanesulfonate ester hardener, active ester hardener. The specific examples of the organic hardeners preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0033]

[Chemical 3]

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

The amino acids in gelatin that can be used in the hardening reaction differ depending on the type of hardening agent used, and the composition of amino acids also differs depending on the gelatin used. Therefore, the optimum addition amount of the hardener varies depending on the type of gelatin used and the type of hardener.
The hardener is preferably added in an amount of 1 to 200 mmol, more preferably 5 to 100 mmol, based on 100 parts by weight.

(4) Primer Layer Containing Diazo Resin and / or Photopolymerizable Photosensitive Composition Examples of the diazo resin and / or photopolymerizable photosensitive composition include polyester resin, vinyl chloride-vinyl acetate copolymer, and acrylic. Examples thereof include resins, vinyl chloride resins, polyamide resins, polyvinyl butyral resins, epoxy resins, acrylate-based copolymers, vinyl acetate-based copolymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene and polyvinyl acetate.

As the anchor agent constituting the primer layer, for example, a silane coupling agent, a silicone primer or the like can be used, and organic titanate or the like is also effective.

In the present invention, the primer layer contains a photosensitive composition as shown below. (1) Photosensitive Composition Containing Diazo Resin As the diazo resin used in the present invention, various kinds can be mentioned, but a diazo resin represented by a condensate of p-diazodiphenylamine and formaldehyde is preferable. It may be water-soluble or organic solvent-soluble, but is preferably Japanese Patent Publication Nos. 47-1167 and 57-
Water-insoluble and ordinary organic solvent-soluble substances as described in Japanese Patent No. 43890 are used. Particularly preferred is a diazo resin represented by the following general formula (1).

[0041]

[Chemical 7] [In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents a PF ₆ or BF _4, Y is -NH -, - shows S- or -O-. ]

Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazodiphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1 -Diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-
Hydroxyethylaminobenzene, 1-diazo-2,5
-Diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-
4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazodimethylaniline, 1-diazo -2,5
-Dibutoxy-4-morpholinobenzene, 1-diazo-
2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene,
1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N -Benzylaminobenzene,
1-diazo-3-chloro-4-N, N-diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro-4-N, N-dimethylamino-5- Methoxybenzene, 1-diazo-3-methoxy-4-pyrrolidinobenzene, 3-methoxy-4-
Examples thereof include diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine and 3- (isopropoxy) -4-diazodiphenylamine.

Examples of the aldehyde used as the condensing agent with the diazo monomer include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde and the like.

As the anion, a water-soluble diazo resin can be obtained by using chlorine ion, tetrachlorozinc acid, etc., and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 4 , 4 '
-Obtaining an organic solvent-soluble diazo resin by using biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, etc. You can Particularly preferably, a diazo resin composed of hexafluorophosphoric acid is used.

The diazo resin is a film-forming resin such as polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate. It is used as a mixture with a system copolymer, a phenoxy resin, a polyurethane resin, a polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate and the like, but it is particularly preferably used as a mixture with a polymer compound having a hydroxyl group.

Particularly preferably, the polymer compound is a monomer having an aliphatic hydroxyl group in the side chain, for example, a copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and another copolymerizable monomer. .. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, if necessary,
Epoxy resin, novolac resin, natural resin and the like may be added.

As the binder used in combination with the diazonium salt, various polymer compounds can be used, but it is preferable to use a monomer having an aromatic hydroxyl group as described in JP-A-54-98613. Polymers such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenylmethacrylate With other monomers,
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units as described in U.S. Pat.No. 4,123,276, natural resins such as shellac and rosin, polyvinyl alcohol, U.S. Pat.No. 3,751,257 Polyamide resin described in US Pat. No. 3,660,097, linear polyurethane resin described in US Pat. No. 3,660,097, phthalated resin of polyvinyl alcohol, epoxy resin condensed from bisphenol A and epichlorohydrin, cellulose acetate, cellulose acetate phthalate, etc. Cellulose is included.

Examples of alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. .. Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-formaldehyde resin such as those described in JP-A-55-57841.
Cresol / formaldehyde copolycondensation resin, JP-A-55
Examples of the copolymer resin include p-substituted phenol and phenol, or cresol and formaldehyde as described in JP-A-127553.

In addition to the above-mentioned materials, these photosensitive compositions may further contain dyes such as dyes and pigments, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides, and exposures, if necessary. A compound capable of generating an acid can be added. These binders account for 10 to 95% by weight in the solid content of the photosensitive composition,
Preferably, the content is 40 to 80% by weight. The diazo resin is contained in an amount of 5 to 80% by weight, preferably 15 to 60% by weight.

Other dyes, pigments and other dyes, oil sensitizers, plasticizers, surfactants and the like can be added to these photosensitive compositions.

(2) Photopolymerizable composition comprising addition-polymerizable unsaturated compound This composition preferably comprises (a) a monomer having at least two terminal vinyl groups, and (b) a photopolymerization initiator. And (c) a polymer compound as a binder.

As the vinyl monomer of the component (a),
It is described in Japanese Patent Publication Nos. 35-5093, 35-14719, and 44-28727. For example, acrylic acid or methacrylic acid ester of polyol, that is, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate.
Acrylate, trimethylolpropane tri (meth) acrylate, etc., bis (meth) acrylamides such as methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, or unsaturated monomers containing urethane groups, such as di- (2'-methacryloxyethyl) -2,4-tolylene diurethane, di- (2
Examples include reaction products of diol mono (meth) acrylate and diisocyanate such as -acryloxyethyl) trimethylene diurethane.

As the photopolymerization initiator of the above component (b),
The compound represented by the general formula (1) can be used, but other types can also be used.

For example, the above-mentioned J. There are carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes as described in Chapter 5 of "Light Sensitive Systems" by Kosar. More specifically, it is disclosed in British Patent No. 1,459,563.

The following can be used as the photopolymerization initiator. Benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-
Benzoin derivatives such as α-phenylacetophenone, benzophenone, 2,4-dichlorobenzophenone, o-
Benzophenone derivatives such as methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone, 2-
Chlorthioxanthone, thioxanthone derivatives such as 2-isopropylthioxanthone, anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, α, α-diethoxyacetophenone, Benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds, etc.

Further, as the binder of the component (c),
In addition to the binder resin used in the above item (1), various known polymers can be used. Details of specific binders are described in US Pat. No. 4,072,527.

The components (a), (b) and (c) are 20 to 80% by weight in the solid content of the photopolymerizable composition, and (b) is 0.
1 to 20% by weight and (c) are preferably contained in 20 to 80% by weight.

The photopolymerizable composition contains a thermal polymerization inhibitor,
A plasticizer, a dye, a pigment or the like can be contained.

An oil-sensitizing agent added to the photosensitive composition,
Additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, anchor agents (silane coupling agents, silicone primers, organic titanates), dyes such as dyes and pigments, etc. Depending on the photosensitive composition contained in the photosensitive coating liquid, the addition amount varies depending on the amount.
01 to 20% by weight, preferably 0.05 to 10% by weight are suitable.

The photosensitive layer according to the present invention contains at least one selected from the group consisting of diazo compounds, azide compounds and quinonediazide compounds.

As the photosensitive layer which can be used in the present invention, in the case of a positive type, a photopolymerizable adhesive layer or a photocrosslinking type photosensitive layer (containing a diazo compound and / or azide compound), a diazo resin, an azide compound and a binder resin are used. And the like. In the case of a negative type, a photosensitive layer made of a quinonediazide compound and a binder resin can be used.

As the above-mentioned diazo resin, various conventionally known ones can be used, but it is preferable to use a diazo resin represented by a condensation product of an aromatic diazonium salt and an active carbonyl-containing compound, especially formaldehyde. It is particularly preferable to use an organic solvent-soluble diazo resin. As a specific example, the resin represented by the general formula (1) used for the primer layer is preferably used.

The diazo resin represented by the general formula (1) preferably has a molecular weight of about 500 to 10,000. The content of the diazo resin in the photosensitive layer is preferably 1 to
70% by weight, more preferably 3 to 60% by weight.

Examples of the photo-curable azide resin include polyvinyl alcohol azidophthalic acid ester, azidobenzoic acid ester, styrene-maleic anhydride copolymer, and aromatic azide alcohol such as β- (4-azidophenol) ethanol. Ester and the like.

In a negative-type fountain solution-free photosensitive lithographic printing plate, an orthoquinonediazide compound is used. Examples of the compound include polycondensation resins of phenols and aldehydes or ketones and the following general formula (2): Alternatively, an orthoquinone diazide sulfonic acid ester or a carboxylic acid ester obtained by chemically condensing an orthoquinone diazide sulfonic acid or a carboxylic acid derivative represented by the general formula (3) can be mentioned.

[0066]

[Chemical 8] In the formula, X represents —SO ₂ Y or —COY, and Y represents a group that can be removed upon condensation of a halogen atom, an alkali metal or the like.

Specific examples of the compound represented by the above general formula (2) include 1,2-benzoquinonediazide (2) -4.
-Sulfonyl chloride, 1,2-benzoquinonediazide (2) -4-carbonyl chloride, 1,2-benzoquinonediazide (2)-, 5-sulfonyl chloride, 1,2
-Benzoquinonediazide (2) -5-carbonyl chloride and the like can be mentioned.

Specific examples of the compound represented by the above general formula (3) include 1,2-naphthoquinonediazide (2) -4.
-Sulfonyl chloride, 1,2-naphthoquinonediazide (2) -4-carbonyl chloride, 1,2-naphthoquinonediazide (2) -5-sulfonyl chloride, 1,2-
Naphthoquinonediazide (2) -5-carbonyl chloride and the like can be mentioned.

Examples of polycondensation resins of phenols and aldehydes or ketones include polycondensation products of pyrogallol and acetone as described in JP-B-43-28403, JP-A-55-76346. As described, a mixture of pyrogallol and resorcin and a polycondensation product of acetone, as described in JP-B-45-9610,
Phenol-formaldehyde-novolak resin or meta-cresol-formaldehyde-novolak resin, as described in Japanese Patent Publication No. 50-5083, para-substituted phenol-formalin resin (for example, para-cresol-formalin resin, para-t-butylphenol. Formalin resin, para-ethylphenol-formalin resin, para-propylphenol-formalin resin, para-isopropylphenol-formalin resin, para-n-butylphenol-formalin resin, para-octylphenol-formalin resin, etc.), Japanese Patent Publication No. 62-60407. As described above, an alkyl group having 3 to 12 carbon atoms or a phenyl group-substituted phenol and phenol or a methyl-substituted product thereof or a mixture thereof are used in a molar ratio of 1: 9-
A polycondensate of a mixture of phenols and formaldehyde containing 9: 1 (for example, a polycondensate of the above-mentioned para-substituted phenol and phenol, para-cresol, meta-cresol, etc.)
Etc.

The esterification rate of the orthoquinonediazide group with respect to the hydroxyl group of the polycondensation resin of phenols and aldehydes or ketones is preferably 15 to 100 mol%.
0 mol% is more preferable.

Further, as an orthoquinonediazide compound,
Orthonaphthoquinone diazide sulfonic acid ester of polyhydroxybenzophenone (for example, 1,2-naphthoquinone diazide (2) -5-sulfonic acid ester, 1,2-
Naphthoquinone diazide (2) -4-sulfonic acid ester and the like).

This polyoxybenzophenone is a compound obtained by substituting two or more hydrogen atoms of benzophenone with a hydroxyl group, for example, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or a derivative thereof, (For example, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a substituent of a carboxylic acid group) and the like. Preferred is trihydroxybenzophenone or tetrahydroxybenzophenone, and more preferred are 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone.

In this case, the esterification rate for the hydroxyl group is
30-100% is preferable.

In the present invention, the above compounds may be used alone as the orthoquinonediazide compound,
You may use it in combination of 2 or more types.

Among these orthoquinonediazide compounds listed above, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester of 2,3,4-trihydroxybenzophenone or 1,2-naphthoquinonediazide (2 ) -4-Sulfonic acid ester, 1,2-naphthoquinonediazide (2) -5-sulfonic acid ester of meta-cresol-formaldehyde-novolak resin or 1,
2-naphthoquinonediazide (2) -4-sulfonic acid ester or a mixture thereof is more preferably used.

The ratio of the orthoquinonediazide compound in the photosensitive layer is preferably 50 to 60% by weight, more preferably 20 to 50% by weight.

Examples of the binder resin used in the photosensitive layer include acrylic resin and novolac resin. All of the copolymerizable monomers can be used as the copolymerization constituent of the acrylic resin, and the following compounds having an unsaturated bond are used as the radical polymerization monomer.

(1) Monomers having a hydroxyl group; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2- (Meth) acrylate monomers such as hydroxyphenyl (meth) acrylate; N-
(Meth) acrylamide monomers such as methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (hydroxyphenyl)-(meth) acrylamide, N- (hydroxynaphthyl)-(meth) acrylamide; o-, (2) (meth) acrylic acid ester or amide monomers other than (1) such as m- and p-hydroxystyrene monomers; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Alkyl (meth) such as (meth) acrylate
Acrylates; N-phenyl (meth) acrylamide, o-, m-, p-methoxyphenyl (meth) acrylamide, o-, m-, p-ethoxyphenyl (meth)
(3) Monomers having a cyano group in the side chain such as acrylamide; (meth) acrylonitrile, 2-pentenitrile, 2-methyl-3
-Butene nitrile, 2-cyanoethyl acrylate, o
-, M-, p-cyanostyrene, etc .; (4) Monomers having a carboxylic acid in the side chain; (meth)
Acrylic acid, itaconic acid and its anhydride, maleic acid and its anhydride, crotonic acid, etc. (5) Vinyl ethers; propyl vinyl ether,
Butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (6) Styrenes; α-methylstyrene, methylstyrene, chloromethylstyrene, styrene, etc. (7) Vinyl ketones; methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, etc. (8) Monomers other than (1) to (7); olefins such as ethylene, propylene, isobutylene, butadiene, vinyl chloride, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, and the like. Any other monomer may be used as long as it can undergo radical copolymerization with these monomers.

In the present invention, in the photosensitive layer, in addition to each of the materials described above, a dye, a pigment, a coatability improver, a plasticizer, and
An oil sensitizer, a stabilizer and the like can be added. It is advantageous that the photosensitive layer of the positive-working photosensitive lithographic printing plate not requiring fountain solution further contains a known exposure visible image-imparting agent.

Examples of the above dyes include Victoria Pure Blue BOH, Oil Blue # 603, Oil Pink # 312, Patent Pure Blue, Crystal Violet, Leuco Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosine B, and Basic Fuchsin. , Malachite green, leucomalachite green, m-cresol purple, cresol red, xylenol blue, rhodamine B,
Examples thereof include triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes such as auramine, 4-p-diethylaminophenyliminonaphthoquinone, and cyano-p-diethylaminophenylacetanilide. Be done.

The dye is usually contained in the photosensitive layer in an amount of about 0.01 to about 10% by weight, preferably about 0.05 to 8% by weight.

Examples of the coatability improver include alkyl ethers (eg ethyl cellulose, methyl cellulose), fluorine-containing surfactants, nonionic surfactants (eg Pluronic L64 (manufactured by Asahi Denka Co.)) and the like.

Examples of the plasticizer for imparting flexibility and abrasion resistance to the coating film include butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate,
Dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrafurfuryl oleate,
Examples thereof include oligomers of acrylic acid or methacrylic acid.

The amount of these additives added varies depending on the intended purpose of use, but is generally preferably 0.01 to 30% by weight based on the total solid content.

The film thickness of the photosensitive layer used in the present invention is usually 0.
It is from 05 to 10 μm, preferably from 0.1 to 5 μm.

In the present invention, a silicone rubber layer is preferably coated as an ink repellent layer on the photosensitive layer. The silicone rubber used in the present invention is preferably a cotton-like or partially crosslinked polyorganosiloxane. The polyorganosiloxane has a molecular weight of usually 1,000 to several hundreds of thousands, and is appropriately crosslinked in the form of a liquid, wax or dough at room temperature.

The polyorganosiloxane is classified into a condensation type and an addition type depending on the method of crosslinking.

In the condensation type, since crosslinking is carried out by a condensation reaction, water, alcohol, organic acid and the like are released by the reaction. As a particularly useful condensation type silicone rubber,
Examples thereof include a mixture of a linear polyorganosiloxane having a hydroxyl group or an acetoxy group at both ends or a part of the main chain and a silicone cross-linking agent, or a mixture of a hydroxyl group and a silicone cross-linking agent, both of which are added with a condensation catalyst. It is more advantageous in terms of crosslinking speed.

Particularly preferred are those obtained by condensation-crosslinking linear dimethylorganopolysiloxanes having hydroxyl groups at both ends.

The main chain of the polyorganosiloxane has the following repeating units.

[0091]

[Chemical 9] In the formula, R ₁ and R ₂ are each an alkyl group which may have a substituent, an aryl group, an alkenyl group or a combination thereof, and in the present invention, a methyl group, a phenyl group, a vinyl group and a trifluoropropyl group are used. A methyl group is particularly preferable.

As the above-mentioned silicone crosslinking agent, --OCO
CH ₃ , -ONR (R '), -ON = CR (R'),-
So-called deacetic acid type, deoxime type, dealcohol type, deamino having a functional group represented by OR, —NR (R ′) or —OH (wherein R and R ′ are alkyl groups). Examples include condensation type and crosslinking type condensation type silicone crosslinking agents.

Examples of such a crosslinking agent are tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethylacetoxysilane, vinyltriacetoxysilane, and methyltrimethoxysilane. , Dimethyldimethoxysilane, vinyltrimethoxysilane, methyltris (acetoneoxime) silane, methyltri (N-methyl-N-acetylamino) silane, vinyltri (methylethylketoxime) silane, methyltri (methylethylketoxime) silane,
Or the oligomer etc. can be mentioned.

The amount of each of these crosslinking agents is preferably 0.5 to 30 parts by weight based on 100 parts by weight of the polyorganosiloxane.

Examples of the condensation catalyst include organic carboxylic acids, titanic acid esters, acetylacetone metal complexes, chloroplatinic acid, naphthenic acid and the like.

The addition type means that an unsaturated group in the main body, for example, a vinyl group (—CH═CH ₂ ) is added with an aqueous group in the crosslinking agent to crosslink. Specific examples include vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like mixed with a platinum catalyst (for example, chloroplatinic acid). The polyorganopolysiloxane has a repeating unit similar to the condensation type in the main chain.

For the silicone rubber layer used in the present invention, it is possible to use either or both of condensation type and addition type silicone rubbers. It is also possible to use a condensation and addition type one having a hydroxyl group and an unsaturated group in one polyorganosiloxane.

The thickness of the silicone rubber layer used in the present invention is usually 0.5 to 10 μm, preferably 1 to 5 μm.

In the present invention, an adhesive layer made of acrylic acid resin or the like may be provided between the photosensitive layer and the silicone rubber layer, and various reactive crosslinking agents, silane coupling agents, etc. may be provided in the adhesive layer. Can be included. The thickness of the adhesive layer is preferably 0.01 μm to 0.5 μm.

As the substrate used in the present invention, any substrate can be used as long as it has flexibility so that it can be set in an ordinary lithographic printing machine and can withstand the load applied during printing. There is no particular limitation.

For example, papers such as coated papers, metal plates such as aluminum plates (JIS H-16, H-18, etc.), or plastic films such as polyethylene terephthalate can be mentioned as examples.

Particularly, an aluminum plate or an aluminum foil and other composite materials are preferable, and an aluminum plate is particularly preferable from the viewpoint of printing durability. The thickness of the support is 50-400 μm,
It is preferably 100 to 300 μm.

From the viewpoint of storability, a substrate, particularly an aluminum plate, or an aluminum foil and another composite material can be surface-treated by a known method before use. Examples of such surface treatment include a method of treating the surface of an aluminum plate with a silicate (US Pat. No. 2,714,066), a method of treating with an organic acid salt (US Pat. No. 2,714,066), phosphonic acid and their derivatives. Method of processing (US Pat. No. 3,
220,832), a method of treating with potassium hexafluorozirconate (US Pat. No. 2,946,683), a method of anodizing and a method of treating with an aqueous solution of an alkali metal silicate after anodizing (US Pat. No. 3,181,461). ..

The photosensitive lithographic printing plate not requiring fountain solution of the present invention is
For example, it is manufactured as follows.

An ordinary coater such as a reverse roll coater, an air knife coater, a Meyer bar coater or a spin coater such as a whaler is used to coat and dry the composition solution to form the primer layer on the support, followed by crosslinking and curing. Let Next, the composition solution for forming the photosensitive layer is coated and dried, or after coating and drying, it is crosslinked and cured by light or heat.

A silicone rubber solution is coated on the above-mentioned photosensitive layer in the same manner and heat-treated at a temperature of usually 100 to 120 ° C. for several minutes to be sufficiently cured to form an ink repellent layer. A protective layer according to the present invention is provided on the silicone rubber layer by using a laminator.

Next, a method for producing a printing plate that does not require dampening water using the photosensitive planographic printing plate that does not require dampening water according to the present invention will be described.

A positive film, which is an original, is brought into vacuum contact with the surface of the positive plate material and exposed. As the light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, or the like, which generates abundant ultraviolet rays, is used.

Then, the positive film is peeled off, and development is performed using a developing solution. As the developing solution, a known developing solution for a plate material which does not require dampening water can be used, but an aqueous developing solution is preferably used.

The water-based developer is a developer containing water as a main component and is described in, for example, JP-A No. 61-275759, and contains 30% by weight or more of water, preferably 50% by weight. %
A developing solution containing an organic solvent and a surfactant in an amount of up to 98% by weight can be mentioned, and more preferably an alkaline agent is contained.

Examples of the organic solvent contained in the developing solution containing water as a main component include aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G (commercial products of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.). Name or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene etc.), halogenated hydrocarbons (triclene etc.), alcohols (methanol, ethanol, 1-butoxy-2-propanol, 3-methyl-) 3-methoxybutanol, β-anilinoethanol, benzyl alcohol, etc., ethers (methylcellosolve, ethylcellosolve, butylcellosolve, phenylcellosolve, methylcarbitol, ethylcarbitol, butylcarbitol, dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether) , Diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, dipropylene glycol butyl ether, tripropylene glycol methyl ether, polypropylene glycol methyl ether, etc., ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, 4-methyl- 1,3-dioxolan-2-one, etc., esters (ethyl acetate, propyl acetate, hexyl acetate, methyl acetate, propyl acetate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve acetate, cellosolve) Acetate, carbitol acetate, etc.) and the like.

As the surfactant added to the developing solution used in the present invention, anionic surfactants, nonionic surfactants, cationic surfactants and zwitterionic surfactants are used. The surfactants described in 206041 are used. These surfactants may be used alone or in combination of two or more.

The amount of the surfactant used in the present invention is 0.01 to 60% by weight, preferably 0.1 to 10% by weight.
Weight percent is suitable.

Further, the surfactant used in the present invention is preferably used together with an alkali agent, and examples of the alkali agent include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide and lithium hydroxide. Secondary or tertiary sodium phosphate or ammonium salt,
Inorganic alkali agents such as sodium metasilicate, sodium carbonate and ammonia, (2) mono-, di- or trimethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine ,
Organic amine compounds such as ethylenediimine may be mentioned.

The amount of the alkaline agent used is 0.05 to 20% by weight, preferably 0.2 to 10% by weight.

It is also possible to add a dye such as crystal violet or astrazonelet to the developing solution to dye the image area simultaneously with the development.

The development can be carried out, for example, by rubbing with a developing pad containing the above-mentioned developing solution or pouring the developing solution onto the plate surface and then rubbing it with a developing brush.

By the above development, a printing plate from which the photosensitive layer and the silicone rubber in the unexposed area have been removed, or a silicone rubber layer has been removed to expose the photosensitive layer and a printing plate in which the silicone rubber layer remains in the exposed area can get.

The photosensitive lithographic printing plate requiring no fountain solution used in the present invention may be of a type in which only the silicone rubber layer in the image area is removed after development, but preferably after development, A type in which the photosensitive layer is removed and the primer layer in the image area is exposed is preferable.

[0120]

EXAMPLES The present invention will be described in more detail with reference to examples.

Example-1 Synthesis of diazo resin-1 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. 1.35 g (45 mmol) of paraformaldehyde was slowly added to the reaction solution so that the reaction temperature did not exceed 10 ° C.

The reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, the precipitate is dissolved in 100 ml of pure water and 6.8 is added to this solution.
A cold concentrated aqueous solution in which g of zinc chloride was dissolved was added.

The formed precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water. To this solution was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and dried to obtain diazo resin-1.

Manufacture of aluminum plate a: An aluminum plate having a thickness of 0.24 mm was immersed in a 3% aqueous solution of sodium hydroxide and washed with water, and then the anode was stored in a 32% aqueous solution of sulfuric acid at a temperature of 30 ° C. under the conditions of 5 A / dm ² for 10 seconds. Oxidize,
Wash with water and add 2% sodium metasilicate solution at 85 ℃
It was immersed for 37 seconds, further immersed in water (pH 8.5) at a temperature of 90 ° C. for 25 seconds, washed with water and dried to obtain an aluminum plate a.

A primer layer composition having the following composition was applied to an aluminum plate a and dried at 85 ° C. for 3 minutes, and then 3 KW.
Front exposure of 1000 mJ / cm ² was performed using an ultra-high pressure mercury lamp. Further, it was dried at 100 ° C. for 4 minutes to form a primer layer having a thickness of 15 μm. (Primer layer composition) (1) Diazo resin-1 10 g (2) 2-hydroxyethyl methacrylate / methyl methacrylate (50/50 molar ratio) copolymer 100 g (3) Zinc oxide (white pigment) 20 g (4) Ket Yellow 402 (yellow pigment) 10 g (5) Methyl lactate 800 g

Next, a photosensitive composition having the following composition was coated on the primer layer and dried at 100 ° C. for 2 minutes to give a thickness of 0.3.
A photosensitive layer of μm was formed. (Photosensitive composition) (1) Diazo resin-1 50 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) methacrylamide, and methacrylic acid in a molar ratio of 40/57/3 50 Part (3) Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd. dye) 1 part (4) Methyl cellosolve 900 parts

Then, the following silicone rubber composition was applied on the above-mentioned photosensitive layer so that the dry weight was 1.8 g / m ² , and the temperature was 90 ° C.
And dried for 10 minutes. (Silicone rubber layer composition) (1) Dimethylpolysiloxane having hydroxyl groups at both ends (Molecular weight 82,000) 100 parts (2) Triacetoxymethylsilane 10 parts (3) Dibutyltin laurate 0.8 part (4) Isopar E (Esso Chemical Made) 900 parts

Next, a protective layer composition having the following composition was applied on the silicone rubber layer so as to have a thickness of 5 μ, and then,
The foaming agent in the protective layer was left to stand in an oven at 100 ° C. for 4 minutes to obtain a photosensitive lithographic printing plate not requiring dampening water. (Protective layer composition) (1) Polyvinyl alcohol (PVA) (GL-05 / Nippon Gosei Kagaku) 10 g (2) 4,4'-oxybis (benzenesulfonylhydrazide) (Sankyo Kasei) 1 g (3) Water 70 g (4) Methanol 30 g

On the positive photosensitive lithographic printing plate requiring no dampening water having the protective layer obtained as described above, a continuous weight type scratch strength tester (manufactured by Shinto Scientific Co., Ltd.) was used and the diameter was 0.1 mm. A load of 10 to 500 g was applied to the tip of the sapphire needle to scratch it.

When a positive film was brought into vacuum contact with the upper surface of the above plate material and exposed by using a metal halide lamp as a light source, no gas pocket was observed between the protective layer and the silicone rubber layer. It was

Next, after immersing in a developing solution having the following composition for 1 minute, the surface of the plate material was rubbed with a pad soaked with the developing solution to remove the silicone rubber layer and the photosensitive layer in the unexposed portion, A printing plate was obtained in which halftone dots of 2% to 98% were reproduced well.

Further, the image area of the above printing plate was able to be dyed vividly by applying a dyeing solution having the following composition to the cloth, lightly rubbing on the plate, and washing with water.

The waterless plate was mounted on a Heidelberg GTO printing machine without the dampening water supply device,
Black ink (made by Toyo Ink, TOYO KING ULT
When printed by RATUK Aquaress G), 100,000 prints without burnt-in blur were obtained. In addition, more than 300 g of scratches applied before printing appeared as scratches on the printed matter.

(Developer) β-anilinoethanol 0.5 part Propylene glycol 1.0 part p-tert-Butylbenzoic acid 1.0 part Potassium hydroxide 1.0 part Polyoxyethylene lauryl ether 0.1 part Potassium sulfite 2.0 parts Potassium metasilicate 3.0 parts Water 91 Part (Staining solution) Solfit (Kuraray Isoprene Chemical Co., Ltd., solvent) 10 parts Leodol TW-0120 (Kao Co., Ltd., surfactant) 0.5 part Benzyl alcohol 2.5 parts Victoria Pure Blue BOH 0.5 part Water 100 parts

Example-2 A fountain solution-free photosensitive lithographic printing plate was obtained in the same manner as in Example-1, except that the photosensitive composition and protective layer of Example-1 were changed as follows. (Photosensitive composition) (1) 2,5-diethoxy-4-morpholinobenzenediazonium fluoroborate 15 parts (2) 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) methacrylamide, methyl methacrylate, acrylo Copolymer resin in which the molar ratio of nitrile and allyl methacrylate is 20/10/50/10/10 50 parts (3) Pentaerythritol triacrylate 15 parts (4) Tetramethylolmethane tetraacrylate 20 parts (5) Victoria Pure Blue BOH ( Hodogaya Chemical Co., Ltd., dye) 1 part (6) Kayacure DETX (Nippon Kayaku Co., Ltd., photopolymerization initiator) 5 parts (7) Kayacure EPA (Nippon Kayaku Co., Ltd., photopolymerization accelerator) ) 2 parts (8) Methyl lactate 1900 parts

(Protective Layer Composition) (1) Silicone Fine Particles (Tospearl 103 / Toshiba Silicone) 10 g (2) Polyhydroxystyrene (Mw = 20,000) 10 g (3) Methylcellosolve 100 g Obtained fountain solution unnecessary The photosensitive lithographic printing plate was evaluated for scratches and blurring in the same manner as in Example 1. The results are shown in Table 1.

Example-3 [Synthesis of Hollow Capsule-1] 22.6 g of 20.4% isobam
A mixture of 54.5 g of water and 30.8 g of gum arabic with stirring and heating to 60 ° C. and using 20% sulfuric acid to adjust the pH.
Adjusted to 4.0. Then, 8.3 g of urea and 0.8 g of resorcinol were added and the solution was kept at 60 ° C.

This was placed in a Waring blender, 50 g of TMPTA (trimethylolpropane triacrylate), 12 g of Irgacure 151 (2,2'-1 dimethoxy-2-phenylacetophenone) and 1 g of Qu.
aniacure ITX (isopropylthioxanthone),
1 g of Quaniacure EPD (ethyl-p-dimethylaminobenzoate) and 6 g of 50% dibutyl succinate solution were added at 60 ° C. for 90 seconds at 90 V with stirring.

Then, the speed of the blender is reduced to 40V,
21.4 ml of 37% formaldehyde was added. Stirring was carried out at this speed for 2 hours at 60 ° C. Then transfer the emulsion to a metal beaker and add 0.6 g of ammonium sulfate.
It was dissolved in 12.2 g of water and added. Stir this emulsion with an overhead mixer for an additional hour at 60 ° C to give 10%
The pH was adjusted to 9.0 with sodium hydroxide solution. Finally, 2.8 g of sodium bisulfite was dissolved in the mixture with stirring and dried to obtain an average particle size of 12 μm.
Hollow capsule-1 of was obtained.

A fountain solution-free photosensitive lithographic printing plate was obtained in the same manner as in Example-1, except that the hollow capsule-1 (addition amount: 5 g) was used in place of the foaming agent. The obtained photosensitive lithographic printing plate not requiring fountain solution was evaluated for scratches and burning blur in the same manner as in Example-1. The results are shown in Table 1.

Comparative Examples 1 and 2 In the same manner as in Examples 1 and 2 except that the foaming agent or the silicone fine particles were not used in the protective layer in Examples 1 or 2, the protective layer in which discontinuous phase was not mixed was prepared. A photosensitive planographic printing plate having no dampening water was obtained. The obtained photosensitive lithographic printing plate not requiring fountain solution was evaluated for scratches and blurring in the same manner as in Example 1. The results are shown in Table 1.

The resin for the protective layer of Comparative Example 1 was converted to ethyl acrylate-methyl methacrylate-methacrylic acid (40/40 /
20) (Mw = 9,000). The results are shown in Table 1.

Comparative Example 3 A photosensitive lithographic printing plate unnecessary for fountain solution was obtained in the same manner as in Example 1 except that the protective layer composition was changed as shown below. The obtained photosensitive lithographic printing plate not requiring fountain solution was evaluated for scratches and blurring in the same manner as in Example 1. The results are shown in Table 1. (Protective layer composition) (1) Copolymer resin (Mw = 9000) with a molar ratio of ethyl acrylate, methyl acrylate, and methacrylic acid 40/40/20 (2) Water 70 g (3) Methanol 30 g

[0144]

[Table 1] As is clear from Table 1, the photosensitive lithographic printing plates requiring no fountain solution of the present invention and Examples 1 to 3 were found to have good scratch resistance and no blurring at all.

[0145]

As described above in detail, according to the present invention, it is possible to provide a photosensitive lithographic printing plate which is excellent in scratch resistance and does not cause blurring of printing, and which does not require a fountain solution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Komi Kojima, No. 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (72) Hiroshi Tomiyasu, No. 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd. In-house (72) Inventor Akio Kasakura 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (3)

[Claims] 1. A primer layer, a diazo compound, and
In a photosensitive lithographic printing plate requiring no fountain solution, which has a photosensitive layer containing at least one selected from the group consisting of an azide compound and a quinonediazide compound, an ink repellent layer and a protective layer in this order, the protective layer is gas permeable A photosensitive lithographic printing plate that does not require a fountain solution, characterized by comprising a continuous phase in which a good discontinuous phase of is mixed. 2. A continuous phase, in which the discontinuous phase having gas permeability according to claim 1 is mixed, is formed by adding a foaming agent to the protective layer according to claim 1. A method for producing a photosensitive lithographic printing plate which does not require fountain solution. 3. The dampening according to claim 1, wherein the continuous phase mixed with the discontinuous phase having gas permeability according to claim 1 is formed by dispersing polymer particles having gas permeability. A method for producing a waterless photosensitive lithographic printing plate.