JP2001125255A - Photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate satisfactory in sensitivity, printing durability and preservation stability. SOLUTION: This photosensitive lithographic printing plate is obtained by applying a coating liquid containing a linear polymer binder, a compound having an ethylenically unsaturated bond capable of being additionally polymerized and a urethane group and a solvent to a support having a hydrophilic surface to form a photopolymerizable layer and drying this by heating a temp. of 90-140 deg.C for 10 seconds or longer. It is preferable that the obtained photosensitive lithographic printing plate is cooled to 50 deg.C or lower after the drying and then a protecting layer containing a water-soluble oxygen blocking material is formed on the photo-polymerizable layer by application and the formed protecting layer is dried by heating.

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, and more particularly to a photosensitive lithographic printing plate excellent in sensitivity, printing durability and storage stability.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive lithographic printing plate, a lithographic printing plate comprising a support having a hydrophilic surface and a lipophilic photosensitive resin is used.
The S plate is widely used, and usually, a desired printing plate is obtained by dissolving and removing a non-image portion after mask exposure (surface exposure) through a lith film. In recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread. Then, various new image output methods corresponding to such digitization technology have come into practical use. As a result, computer-to-plate (CTP) technology, which scans highly directional light such as laser light in accordance with digitized image information and directly manufactures a printing plate without passing through a lithographic film, has become widespread. Obtaining a photosensitive lithographic printing plate adapted to the above is an important technical issue.

One of the methods for obtaining such a photosensitive lithographic printing plate capable of being scanned and exposed is a photopolymerizable composition having a very high photosensitive speed as a photosensitive resin layer provided on a hydrophilic support. Many layers have been proposed and further provided with an oxygen-barrier protective layer, and some of them have been put on the market.
The photopolymerizable composition used basically comprises an ethylenically unsaturated compound (hereinafter also referred to as an addition polymerizable compound), a photopolymerization initiator, and a binder resin. In image formation, a photopolymerization initiator absorbs light, generates an active radical, causes addition polymerization of an ethylenically unsaturated compound, and causes insolubilization of a photosensitive layer. However, a lithographic printing plate made from the above-described photosensitive lithographic printing plate may not have practically satisfactory performance in some cases.

[0004]

An object of the present invention is to provide a photosensitive lithographic printing plate having sufficient sensitivity, printing durability and storage stability.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a photopolymer layer containing an addition polymerizable compound having a urethane group has a thickness of 90 to 140.
The present inventors have found that a photosensitive lithographic printing plate which has been dried by heating at ℃ is excellent in sensitivity, printing durability and storage stability, and completed the present invention.

That is, the present invention is a photosensitive lithographic printing plate as described below. (1) A coating solution for a photopolymerization layer, comprising: i) a linear polymer binder, ii) a compound having an ethylenically unsaturated bond and a urethane group capable of addition polymerization, and a solvent on a support having a hydrophilic surface. And the temperature of the photosensitive lithographic printing plate is 9
A photosensitive lithographic printing plate obtained by heating and drying under the condition of maintaining at 0 to 140 ° C. for 10 seconds or more. (2) After the heating and drying, the temperature of the photosensitive lithographic printing plate is set to 50
The photosensitizing method according to (1), wherein the photosensitive layer is obtained by applying a protective layer containing a water-soluble oxygen-blocking substance onto the photopolymerized layer after cooling to a temperature of not more than ° C and drying by heating. Sexographic printing plate.

It is not clear why the photosensitive lithographic printing plate of the present invention is excellent in sensitivity, printing durability and storage stability. Is heated and dried at a temperature of 90 to 140 ° C. for 10 seconds or more, whereby some change in the coordination state such as a hydrogen bond is formed between the urethane groups of the addition-polymerizable compound. It is considered that the curing of the resin layer is accelerated and the sensitivity and printing durability are improved.

In the case where a protective layer containing a water-soluble oxygen-blocking substance (hereinafter, also referred to as an oxygen-blocking layer) is applied thereon after providing the above-mentioned photopolymerizable layer, a photosensitive lithographic plate may be used. By performing the process after cooling the printing plate to a temperature of 50 ° C. or less, the printing plate can be formed without coating unevenness. When the oxygen-barrier layer is formed in a state where the temperature of the photosensitive lithographic printing plate exceeds 50 ° C., coating unevenness occurs, and the oxygen-barrier property deteriorates.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive lithographic printing plate of the present invention will be described in detail. First, the conditions for heating and drying the photopolymer layer, which is a particularly important component in the production of the photosensitive lithographic printing plate of the present invention, will be described. In the production of the photosensitive lithographic printing plate of the present invention, the heating and drying after applying a photopolymerizable layer coating solution described below on a support described below is performed at a temperature of the photosensitive lithographic printing plate of 90 to 140 ° C for 10 seconds or more. It is performed under the conditions that are maintained.

[0010] The temperature of the photosensitive lithographic printing plate in the heating and drying is not particularly limited as long as it is 90 to 140 ° C, but is preferably 100 to 135 ° C, more preferably 1 to 135 ° C.
05-130 ° C. The temperature of the photosensitive lithographic printing plate can be substantially specified by measuring the temperature of the support. The method of measuring the temperature of the support is not particularly limited, but i) a method of directly attaching a thermocouple temperature sensor to the back surface of the support, and ii) a method of measuring from the back surface of the support with a non-contact radiation thermometer. Iii) a method of attaching a thermotape that changes color according to the highest temperature to the back surface of the support, drying the thermotape, and then confirming the discoloration of the thermotape;
And the like.

The measuring method i) is effective when preparing a photosensitive lithographic printing plate in batches, such as in an experiment for preparing a small amount of a sample. Is difficult to apply because the support web is constantly moving on the production line. In the case of industrial mass production as described above, the methods ii) and iii) are effective. Note that the method iii) only shows the highest temperature, but it is a measure of the superheat drying process on the production line. The most accurate temperature measurement method is the method ii).

The non-contact radiation thermometer used in the measurement method ii) is not particularly limited, but may be CT-3100, RT50, RT50- manufactured by HORIBA, Ltd.
LX, RT-60-1, RT-60-2, IT-340
S, IT-540N, IT-540S, IT-540
E, 530 01, 530 03, 530 04, and the like.

In the heating and drying of the photopolymerizable layer in the production of the photosensitive lithographic printing plate of the present invention, the time for keeping the temperature of the photosensitive lithographic printing plate within a predetermined temperature range is not particularly limited as long as it is 10 seconds or more. Not limited. However, when mass production is performed on an industrial production line, the time is preferably as short as possible. Specifically, it is preferably within 3 minutes, more preferably within 2 minutes, and further preferably within 1 minute. From the above, the actual temperature and the holding time of the photosensitive lithographic printing plate during the heating and drying are appropriately selected depending on the production equipment and the like.

When the above-mentioned heating and drying is performed in an oven or the like, it is necessary to set the temperature of the heating and drying means such as an oven to be higher than the predetermined temperature range of the photosensitive lithographic printing plate.

Next, the photopolymerizable layer coating solution used in the production of the photosensitive lithographic printing plate of the present invention will be described. The coating solution for the photopolymerization layer used in the production of the photosensitive lithographic printing plate of the present invention comprises: i) at least one kind of linear high molecular polymer binder; ii) an ethylenically unsaturated bond capable of addition polymerization and a urethane group. It contains at least one compound having a photopolymerization initiator and a solvent.

A compound having an addition-polymerizable ethylenically unsaturated bond and a urethane group First, among the components contained in the photopolymerizable layer coating solution, particularly important addition-polymerizable ethylenically unsaturated bond and a urethane group are described. The addition-polymerizable compound having a urethane group contained in the photopolymerizable layer coating solution for explaining the addition-polymerizable compound having the following is not particularly limited, but may have two or more ethylenically unsaturated bonds and two Those having the above urethane groups are preferred. An example of such an addition polymerizable compound having a urethane group is disclosed in
JP-A-128716 and JP-A-6-35189.

The addition-polymerizable compound having a urethane group described in JP-A-57-128716 is an acrylate or methacrylate of a polyvalent hydroxy compound having at least two urethane groups in a molecule, and its ester is Reaction product of polyisocyanate obtained by reaction of glycerol dimethacrylate or glycerol diacrylate with polyhydroxy compound having 2 to 6 OH groups and diisocyanate, or reaction product of glycerol dimethacrylate or glycerol diacrylate with diisocyanate It is something that is. The polyhydric hydroxy compounds preferably have 2 or 3 and particularly preferably 2 OH groups. The following formula:

[0018]

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Wherein R 'is O, B, CR ₂ or SO ₂ , and Q is a phenylene group or a group: C _q H _2q and C _q H _{2q -1.}
R is a hydrogen atom or a methyl group, Z is O or NR, n is an integer of 0 to 20, and m is 1
P is an integer of 2 to 20; q is an integer of 2 to 10; r is an integer of 4 to 20;
Is an integer of 2 to 10, v is an integer of 0 to 4,
p, q and s are at least 2 greater than v, and r is at least 4 greater than v].

In general, diisocyanates have the formula OCN
-X-NCO (wherein X is a hydrocarbon group, preferably a saturated aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms). Typically, the reaction product of glycerol dimethacrylate is preferred over the reaction product of glycerol acrylate. The polyvalent isocyanate obtained by reacting the polyvalent hydroxy compound with the diisocyanate has an average of 2 to 40, preferably 2 to 20 methane groups per molecule. Among the polyhydric hydroxy compounds used for producing such an addition polymerizable compound having a urethane group, a representative compound saturated with a polyether polyhydric hydroxy compound or the like, that is, a formula: HO- [C _p H _2p-v
Compounds of the formula (OH) _v -O-] _m H are preferred. The value of p is preferably 2 to 10, particularly preferably 2 to 4. When unsaturated polyhydric hydroxy compounds are used, they are used in an amount of 4 to 1 per unit of the polyhydroxy compound (also referred to as polyol).
It preferably has zero carbon atoms.

For certain purposes, such as certain mechanical properties and high sensitivity, it is also preferred to use polyester polyols. These can be synthesized in a known manner from dicarboxylic acid units and polyol units or from hydroxycarboxylic acid units. In this regard, q = 3 ~
Hydroxycarboxylic acids having 6 are preferred. Polyester diols from hydroxy carboxylic acids, typically from a lactone is produced by ring-opening using the molecules of H- active compound _{HO-C s H 2s -Z-} H. In this formula, s has a value of 2 to 6, and Z is advantageously oxygen.

The number of units in the polyester diols and polyether diols depends on the nature of these compounds and the remaining units of the molecule, the nature of the binder components described below and the particular application. Addition polymerizable compounds having relatively long polyoxyethylene chains in the molecule are very hydrophilic and are developed very quickly with aqueous developers. Even when a binder having low hydrophilicity is used, such an addition-polymerizable compound having a polyether group is generally very suitable. Conversely, in the case of an addition polymerizable compound containing a polyoxyalkylene group having a higher alkylene group or a polyester group, if the material is to be developed without adding an organic solvent to the developer, a more hydrophilic binder may be used. Need to be used. In many cases, m = 2-25, especially 3-15
Are preferred.

Examples of suitable diisocyanates are tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and tolylene diisocyanate. Or a reaction product of 2 mol of diphenylmethane diisocyanate and 1 mol of polytetrahydrofuran.

Examples of suitable diols are ethylene glycol, propylene glycol, 1,4-butanediol,
2-ethyl-1,6-hexanediol, 1,10-decanediol, 1,4-bis-hydroxymethylcyclohexane, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 200 to about 1500, and 4,4'-dihydroxy Diphenyl ether, 4,4'-dihydroxy-diphenyl-sulfide, 4,4'-dihydroxy-diphenylmethane,
4,4'-dihydroxy-diphenylpropane or 4,
It is the reaction product of 4'-dihydroxy-diphenyl sulfone with 0 to 40 moles of alkylene oxide, polypropylene glycol, polytetrahydrofuran, polybutylene glycol, thiodiethylene glycol or dithiotriethylene glycol.

Examples of suitable polyester components are polycaprolactone, polybutyrolactone, polyethylene terephthalate, polypropylene adipate, polybutylene adipate and polyethylene butylene sepassate.
Polyester polyols having a molecular weight in the range of about 500-3000 are generally very suitable.

Apart from this preferred diol, compounds having 2 to 6 fatty hydroxy groups can generally also be used. Examples of addition polymerizable compounds are glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Suitable polyhydric hydroxy compounds include polyester polyols such as lactone polyesters described in U.S. Pat. No. 3,169,945, terminal hydroxy group-containing polyester condensation polymers described in U.S. Pat. No. 3,641,199, and U.S. Pat. No. 3,931,117. The polyesters include hydroxy group-containing polyesters, polyethers having terminal hydroxy groups and polyester block copolymers, caprolactone polyols and polysiloxane polyols described in the specification.

The preparation of polymerizable diurethanes or polyurethanes is described, for example, in US Pat. No. 3,297,745, West German Patent Application Nos. 2064079 and 2822190.
It is carried out by a method known per se described in the specification. For the production of glycerol diester, 1 mol of glycidyl acrylate or glycidyl methacrylate is first reacted with 1 mol of acrylic acid or methacrylic acid. Then 1 mol of this reaction product is reacted with 1 equivalent of polyisocyanate. In this step, the polyisocyanate, preferably the diisocyanate, is monomeric or the reaction product of a monomeric excess of the diisocyanate with the polyol component. In the latter case, the polyol component is reacted in advance with the desired excess of diisocyanate. In this case, in principle, a mixture of polymer homologs is obtained. The non-uniformity of the molecular weight of the monomers obtained therefrom results in highly viscous and markedly amorphous products.

As the addition-polymerizable compound having a urethane group described in JP-A-6-35189, a reaction product of a monoisocyanate or a diisocyanate and a partial ester of a polyhydric alcohol is advantageously used. Such monomers are disclosed in DE-A-20 64 079, DE 23 61 041 and
No. 8 22 190 is described in each specification.

Particularly preferred are addition polymerizable compounds that contain at least one photooxidizable group and at least one urethane group in the molecule.
Suitable photo-oxidizable groups are, in particular, thio groups, ureido groups, amino groups, and enol groups, which may be members of a heterocycle. Examples of such groups are triethanolamino, triphenylamino, thiourea, imidazole, oxazole, thiazole, acetylacetonyl, N-phenylglycine and ascorbic acid groups. Preferred are primary, secondary, especially It is an addition polymerizable compound containing a tertiary amino group.

Examples of compounds containing a photo-oxidizable group include EP-A-28
Nos. 7,818, 353,389 and 364,735. Preferred among the compounds described therein are those which, in addition to the tertiary amino group, also contain ureido and / or urethane groups. Compounds of the following general formula [I] in which the nitrogen bond is saturated with a substituted or unsubstituted hydrocarbon group should be regarded as a ureido group.

[0031]

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The addition polymerizable compound having a urethane group contained in the photopolymerizable layer coating solution of the present invention is described in JP-A-57-128716 and JP-A-6-35.
In addition to those described in JP-A-189, reaction products of an isocyanate compound and an alcohol represented by the following general formula (II) may be mentioned.

[0033]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group;
Is a hydrogen atom or a group represented by the following general formula (III)

[0035]

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And at least one of them is a hydrogen atom, and X is an alkyl group, an aryl group, an alkoxy group, -OH or a group represented by the following general formula (III)

[0037]

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Wherein at least one of X and Y is a group represented by the general formula (III), and n, a,
b, c, d, e, and f represent 0 or a positive number)

Specific examples of the isocyanate compound include the following.

[0040]

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[0041]

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[0042]

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[0043]

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Specific examples of the alcohol represented by the general formula (II) include the following.

[0045]

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The above isocyanate compound and the compound represented by the general formula (I)
Representative examples of the reaction product with the alcohol represented by I) have the following structure.

[0047]

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Other examples of the addition polymerizable compound having a urethane group contained in the photopolymerizable layer coating solution of the present invention include urethane acrylate UA-306 manufactured by Kyoeisha Chemical Co., Ltd.
H, UA-101T, UA-101I, UA-306
T, UA-306I and the like are preferably used.

Next, the linear polymer binder contained in the photopolymerizable layer coating solution used in the present invention will be described.
Any linear polymer binder may be used as long as it is an organic polymer having compatibility with the photopolymerizable addition polymerizable compound. Preferably, an organic high molecular polymer which is soluble or swellable in water or weakly alkaline water which enables water development or weakly alkaline water development is selected. The organic high molecular polymer is selected not only as a film forming agent for the photopolymerizable layer of the photosensitive lithographic printing plate obtained by the method of the present invention but also according to the use as a water, weakly alkaline water or organic solvent developer. used. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such organic high-molecular polymers include addition polymers having a carboxylic acid group in a side chain, such as JP-A-59-44615,
4-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048. , Methacrylic acid copolymer,
There are acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like.

In these carboxylic acid group-containing copolymers, various (meth) acrylic acid esterified products, that is, methyl (meth) acrylate, Ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyacrylate, etc., and various (meth) acrylamide compounds, that is, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) Acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide,

[0051]

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And the like.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers.
In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamides and polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. Further, a polyurethane resin can be used.

Of these, particularly preferred are (meth) acrylic acid ester copolymers and carboxyl groups having a content of 0.1%.
It is a polyurethane resin containing 4 meq / g or more.

As the binder used in the present invention, a polyurethane resin binder is preferable because it is considered that the interaction with the addition polymerizable compound having a urethane bonding group is improved.

Iii) Photopolymerization initiator The photopolymerization layer coating solution used in the production of the photosensitive lithographic printing plate of the present invention has no direct causal relationship with the function and effect of the present invention, but the photopolymerization initiator is essential. It contains. As the photopolymerization initiator contained in the photopolymerization layer coating solution used in the present invention, various photopolymerization initiators known in patents and literatures, or two or more photopolymerization initiators may be used depending on the wavelength of the light source used. A combined system of initiators (photopolymerization initiation system) can be appropriately selected and used. In the present invention, a photopolymerization initiator used alone and a system using two or more photopolymerization initiators are collectively referred to simply as a photopolymerization initiator or a photoinitiator. For example, when light near 400 nm is used as a light source, benzyl, benzoyl ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used.

In addition, visible light of 400 nm or more, an Ar laser, a second harmonic of a semiconductor laser, SHG-YAG
When a laser is used as a light source, various photopolymerization initiators have been proposed, for example, US Pat. No. 2,850,44.
No. 5, certain photoreducing dyes, such as rose bengal, eosin, erythrosine, or a combination of a dye and a photopolymerization initiator, such as a complex initiation system of a dye and an amine (Japanese Patent Publication No. Sho 44) -20189)),
A combination system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. 45-37377), and a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Application Laid-Open No. 54-1979).
155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), and a system of a cyclic triazine and a merocyanine dye (JP-A-54-15102).
No. 4), a system of 3-ketocoumarin and an activator (Japanese Unexamined Patent Publication No.
112681, JP-A-58-15503), a system of biimidazole, a styrene derivative and a thiol (JP-A-5959 / 1983).
-140203), a system of an organic peroxide and a dye (JP-A-59-1504, JP-A-59-140203, JP-A-59-189340, JP-A-62-174203)
No., JP-B-62-1641, U.S. Pat.
055), a system of a dye and an active halogen compound (JP-A-6
3-178105, JP-A-63-258903, JP-A-2-63054, etc., and a system of a dye and a borate compound (JP-A-62-143044, JP-A-62-150).
No. 242, JP-A-64-13140, JP-A-64-1
No. 3141, JP-A-64-13142, JP-A-64-13142
No. 13143, JP-A-64-13144, JP-A-64
-17048, JP-A-1-229003, JP-A-1
-298348, JP-A-1-138204).
A system of a dye having a rhodanine ring and a radical generator (Japanese Patent Application Laid-Open (JP-A) Nos. 2-179643 and 2-244050);
System of titanocene and 3-ketocoumarin dyes
No. 221110), a system in which titanocene is combined with a xanthene dye and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (Japanese Patent Laid-Open No. 4-22)
1958, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-29506)
No. 1) and a dye system having titanocene and a benzopyran ring (JP-A-8-334897).

Preferred photopolymerization initiators (systems) are combinations using cyanine, merocyanine, xanthene, ketocoumarin and benzopyran dyes as dyes and titanocene compounds and triazine compounds as photopolymerization initiators. . Preferable examples of the cyanine dye include those having the following structures, but are not particularly limited.

[0059]

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(Where Z is¹And Z^TwoIs benzimidazo
Or naphthoimidazole ring required to form
Represents a group of metal atoms, which may be the same or different. R
^{twenty four}, R ^{twenty five}, R²⁶And R²⁷Are each substituted
Represents a good alkyl group. X^-Represents a counter anion,
n is 0 or 1. )

Table 1 below shows specific examples of cyanine dyes.

[0062]

[Table 1]

The merocyanine dyes preferably have the following structure, but are not particularly limited.

[0064]

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(Where Z is¹, Z^TwoIs a cyanine dye
5- and / or 6-membered nitrogen-containing heterocycles commonly used in
Represents a group of nonmetallic atoms necessary for forming a ring. R²⁸, R
²⁹Each represents an alkyl group. Q¹And Q^TwoIs a combination
To form a 4-thiazolidinone ring,
Dinone ring, 4-imidazolidinone ring, 4-oxazolidy
Non-ring, 5-oxazolidinone ring, 5-imidazolidino
Atoms required to form a ring or 4-dithiolanone ring
Represents a group. L¹, L^Two, L^Three, L^FourAnd L^FiveAre each
Represents a tin group. m represents 1 or 2. i and h are it
Represents 0 or 1, respectively. l represents 1 or 2. j, k
Represents 0, 1, 2, or 3, respectively. X ^-Is ani
Indicates ON. )

[0066]

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(Wherein R ³⁰ and R ³¹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group A represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl- or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom, and X forms a nitrogen-containing 5-membered heterocyclic ring. Y represents a substituted phenyl group,
Represents an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group; To form a ring. )

Specific examples of the merocyanine dyes are shown below.

[0069]

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[0070]

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Examples of the xanthene dyes include rhodamine B, rhodamine 6G, ethyl eosin, alcohol-soluble eosin, pyronin Y, and pyronin B.

The ketocoumarin dyes preferably include those having the following structures, but are not particularly limited.

[0073]

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Wherein R ³² , R ³³ and R ³⁴ each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ³⁴ and R ³⁵ each represent an alkyl group, at least one of which has 4 carbon atoms. Represents up to 16 alkyl groups, and R ³⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, a cyano group, a carboxyl group, or a group of an ester derivative or an amide derivative thereof;
R ³⁸ is a heterocyclic residue having a total number of carbon atoms of 3 to 17 —CO
Represents -R ^39, may be R ³³ and R ^34, R ³⁵ and R ³⁶ are bonded to each other to form a ring. Here, R ³⁹ is a group shown below. )

[0075]

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The following are specific examples of ketocoumarin-based dyes.

[0077]

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The benzopyran-based dye preferably has the following structure, but is not particularly limited.

[0079]

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[0080] (wherein, R ³ to R ⁵ are independently of each other, represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. Further, R ³ ~
R ⁵ may form a ring consisting of a non-metallic atom together with the carbon atoms to which they can each be attached. R ⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁵ is a radical or -Z-R ⁷ is represented by R ^7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group or arylene dicarbonyl group. R ⁷ and R ⁸ may together form a ring composed of a nonmetallic atom.
A represents O, S, NH or a nitrogen atom having a substituent. B is a group

[0081]

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And G ₁ and G ₂ may be the same or different and each represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group. Group, arylsulfonyl group or fluorosulfonyl group. However, G ₁ and G ₂ are not simultaneously hydrogen atoms. G ₁ and G ₂ may form a ring composed of a non-metal atom together with a carbon atom. )

The following are specific examples of benzopyran-based dyes.

[0084]

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Examples of the triazine compound as a photopolymerization initiator include the following compounds.

[0086]

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Wherein Hal represents a halogen atom.
Y ² is _{-C (Hal) 3, -NH 2} , -NHR 21, -N (R
²¹⁾ ₂ represents -OR ^21. Here, R ²¹ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.
R ²⁰ represents —C (Hal) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ).

The following are specific examples of the triazine compound.

[0089]

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Preferred photopolymerization initiators include titanocene compounds. Examples of titanocene compounds include, for example, JP-A-59-152396 and JP-A-61-61396.
Known compounds described in JP-A-151197 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl (hereinafter referred to as A-1), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetra Fluorophenyl-1-yl, di-cyclopentadienyl-Ti
-Bis-2,4,6-trifluorophenyl-1-yl,
Di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-
Ti-bis-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,
4,5,6-pentafluorophenyl-1-yl (hereinafter A
-2), di-methylcyclopentadienyl-Ti
-Bis-2,3,5,6-tetrafluorophenyl-1-
Yl, di-methylcyclopentadienyl-Ti-bis-
2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium (hereinafter referred to as A-3) and the like are listed. be able to.

The content of these photopolymerization initiators in the photopolymerization layer coating solution used in the present invention is usually low. In addition, when the number is inappropriately large, undesired results such as blocking of the effective light beam occur. The amount of the photopolymerization initiator in the present invention is preferably used in the range of 0.01% by weight to 70% by weight based on the total of the binder component and the addition-polymerizable compound component. More preferably, 1% to 50% by weight gives good results.

Auxiliary agents such as amine compounds and thiol compounds may be added to the photopolymerization initiator, and particularly preferred are amine compounds and amino acids represented by the following general formula.

[0094]

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(In the formula, R ^{8 to} R ¹⁸ each represent an alkyl group.)

[0096]

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(In the formula, R ^{19 to} R ²² represent alkyl or alkoxy, R ²¹ and R ²² may form a ring, and R ²³ represents a heterocyclic ring or alkylthio.)

[0098]

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(Wherein R ²⁸ and R ²⁹ are the same or different,
It represents a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a heterocyclic group. R ²⁶ , R ²⁷
Are the same or different, a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group,
Represents a substituted thio group. R ²⁶ and R ²⁷ are bonded to each other to form a ring, and —O—, —NR ²⁴ —, —O—CO—, and —
NH-CO -, - S-, and / or, -SO ₂ - represents an alkylene group having from 2 carbon atoms which may contain a linking backbone of the ring 8. R ²⁴ and R ^{25 each} represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. )

Further, dialkyl benzoates such as ethyl p-diethylaminobenzoate, bisaminobenzophenones such as 4,4'-bis (dimethylamino) benzophenone, and bisaminobenzyls such as 4,4'-bis (diethylamino) benzyl ,

[0101]

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N-phenylgulin and N-phenylglycine sodium salt are exemplified.

In the production of the photosensitive lithographic printing plate of the present invention, the heating and drying temperature after the application of the photopolymerizable layer coating solution is 90 to 140 ° C., which is slightly higher than the conventional production method. It is preferable to use a photopolymerization initiator having relatively excellent thermal stability.

The solvent contained in the coating solution for the photopolymerization layer used in the present invention is not particularly limited, but may be acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether. Ethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, Butoxy methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
3-methoxypropyl acetate, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture.

The photopolymerizable layer coating solution used in the present invention prevents unnecessary thermal polymerization of the addition polymerizable compound during the production or storage of the composition for the photopolymerizable layer in addition to the above basic components. For this purpose, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include:
Hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-
Nitrosophenylhydroxylamine cerium salt,
N-nitrosophenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% based on the weight of all components of the photopolymerizable layer composition of the photosensitive lithographic printing plate of the present invention. Also, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photopolymerization layer in a drying process after coating. Good. The amount of the higher fatty acid derivative added is based on the weight of all components of the photopolymerizable layer composition of the photosensitive lithographic printing plate of the present invention.
About 0.5% to about 10% is preferred.

Further, a coloring agent may be added for the purpose of coloring the photopolymerizable layer. Examples of the colorant include phthalocyanine pigments (CI Pigment Blue 15: 3, 15: 4,
15: 6), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of the dye or pigment added is preferably about 0.5% to about 5% based on the weight of all components of the photopolymerizable layer composition of the photosensitive lithographic printing plate of the present invention.

In addition, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. These addition amounts are 10% by weight of all components of the photopolymerizable layer composition of the photosensitive lithographic printing plate of the present invention.
% Or less is preferable. A surfactant can be added to the photopolymerization layer coating solution used in the present invention in order to improve the coating surface quality.

The concentration of the solid content in the photopolymerizable layer coating solution as described above is suitably from 1 to 50% by weight. The coverage of the photopolymerizable layer in the photosensitive lithographic printing plate of the present invention is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after coating and drying. More preferably 0.3 to 5 g / m ^2, more preferably from 0.5 to 3 g / m ^2.

In the photosensitive lithographic printing plate of the present invention, a dimensionally stable plate is used as a support for applying the above-mentioned photopolymerizable layer coating solution. Examples of the dimensionally stable plate include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), zinc, copper, etc. Metal plates, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, plastic films such as polyvinyl acetal, Paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited may be used. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of a metal, particularly aluminum, the surface may be subjected to graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or surface oxidation treatment. Preferably, the treatment has been performed. Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. After anodizing the aluminum plate as described in JP-B-47-5125,
Those immersed in an aqueous solution of an alkali metal silicate are preferably used. The anodizing treatment may be, for example, an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or an electrolytic solution in which two or more kinds are combined. It is carried out by passing a current through an aluminum plate as an anode.

Electrodeposition of a silicate as described in US Pat. No. 3,658,662 is also effective. Further, Japanese Patent Publication No. 46-27481 and Japanese Patent Application Laid-Open No. 52-5860.
No. 2, JP-A-52-30503, which is obtained by subjecting a support subjected to electrolytic graining to a surface treatment combining the above-described anodic oxidation treatment and sodium silicate treatment is also useful. Further, those obtained by sequentially performing mechanical roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable. Furthermore,
A sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-7-159983 is also preferably used. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the composition of the photopolymer layer provided thereon, and to improve the adhesion of the photopolymer layer. It is performed for the purpose of improving the quality.

On the photopolymerization layer provided on the support,
In order to prevent the polymerization inhibition effect due to oxygen in the air, a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol, polyvinylpyrrolidone, and acidic celluloses may be provided. Regarding the method of applying such a protective layer, for example, US Pat. No. 3,458,31
No. 11 and JP-A-55-49729, the method of the present invention is particularly effective when the photosensitive lithographic printing plate is cooled to a temperature of 50 ° C. or less so that the coating is free from uneven coating. Can be formed. When the oxygen-barrier layer is formed in a state where the temperature of the photosensitive lithographic printing plate exceeds 50 ° C., coating unevenness occurs, and the oxygen-barrier property deteriorates.

The photosensitive lithographic printing plate of the present invention is directly image-exposed with an Ar laser, a YAG-SHG laser or the like for image formation. After performing image exposure, development processing is performed. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate,
Inorganic alkali agents such as potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine,
Diisopropylamine, triisopropylamine, n-
Organic alkali agents such as butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are used alone or in combination of two or more.

Among the above-mentioned alkaline aqueous solutions, the developing solution in which the effect of the present invention is further exhibited is an aqueous solution containing an alkali metal silicate and having a pH of 12 or more. The aqueous solution of alkali metal silicate is silicon oxide Si which is a component of silicate
Ratio of O ₂ and alkali metal oxide M ₂ O (generally [SiO ₂ ] /
[Expressed in the molar ratio of [M ₂ O]) and the concentration can be adjusted. For example, the molar ratio of SiO ₂ / Na ₂ O as disclosed in JP-A-54-62004 can be adjusted. Is 1.0
1.5 (that is, [SiO _2] / [Na ₂ O] is 1.0 to 1.5)
And an aqueous solution of sodium silicate having a content of SiO ₂ of 1 to 4% by weight or [SiO ₂ ] / [M] of 0.5 as described in JP-B-57-7427. ~ 0.75
(That is, [SiO ₂ ] / [M ₂ O] is 1.0 to 1.5), the concentration of SiO ₂ is 1 to 4% by weight, and the developer contains Aqueous solutions of alkali metal silicates containing at least 20% potassium, based on gram atoms of metal, are preferably used.

Further, when the photosensitive lithographic printing plate is developed using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is added to the developing solution.
It is known that a large amount of photosensitive lithographic printing plates can be processed without replacing the developing solution in the developing tank for a long time. This replenishment system is preferably applied to the photosensitive lithographic printing plate obtained by the method of the present invention. For example, as disclosed in JP-A-54-62004, the molar ratio of SiO ₂ / Na ₂ O in a developer is 1.0 to 1.5 (that is, [SiO ₂ ] / [Na ₂ O] is 1). .0 to 1.5), wherein SiO ₂
Of an aqueous solution of sodium silicate having a content of 1 to 4% by weight, and the molar ratio of SiO ₂ / Na ₂ O is continuously or intermittently 0.5 depending on the throughput of the photosensitive lithographic printing plate. ~ 1.5
A method of adding an aqueous solution (replenisher) of sodium silicate (i.e., [SiO ₂ ] / [Na ₂ O] is 0.5 to 1.5) to a developer, and further disclosed in Japanese Patent Publication No. 57-7427. ing,
[SiO ₂ ] / [M] is 0.5 to 0.75 (that is, [SiO ₂ ] /
[M ₂ O] is 1.0 to 1.5) and the concentration of SiO ₂ is 1
４4% by weight of an aqueous solution of an alkali metal silicate is used as a developer, and [SiO ₂ ] / [M] of the alkali metal silicate used as a replenisher is 0.25 to 0.75 (ie,
[SiO ₂ ] / [M ₂ O] is from 0.5 to 1.5), and both the developer and the replenisher are at least based on gram atoms of all alkali metals present therein. 20
% Of potassium is preferably used.

The photosensitive lithographic printing plate thus developed is described in JP-A-54-8002 and JP-A-55-1504.
No. 5, No. 59-58431, etc., a rinsing solution containing washing water, a surfactant and the like,
It is treated with a desensitizing solution containing gum arabic and starch derivatives. In the post-processing of the lithographic printing plate produced from the photosensitive lithographic printing plate of the present invention, these processes can be used in various combinations.

After development or, optionally, post-treatments such as the desensitizing treatment described above, the entire surface is exposed by the method described above, and the lithographic printing plate thus obtained is subjected to an offset printing machine. Multiplied and used for printing many sheets.
At the time of printing, a conventionally known plate cleaner for a PS plate is used as a plate cleaner used for removing stains on a plate. For example, CL-1, CL-2, CP, CN-
4, CN, CG-1, PC-1, SR, IC (manufactured by Fuji Photo Film Co., Ltd.) and the like. Preferably, CP and CN-4 are mentioned.

[0119]

[Examples 1-3, Comparative Examples 1-3]

(Preparation of a photosensitive lithographic printing plate) An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and a 400-mesh aqueous suspension of pumicestone, and then washed thoroughly with water. 70 ° C in 10% sodium hydroxide aqueous solution
After etching by immersion in water for 60 seconds, rinse with running water
It was neutralized and washed with a 0% aqueous nitric acid solution, and then washed with water. This was subjected to electrolytic surface roughening treatment with a 1% aqueous nitric acid solution at an anode electricity of 160 coulomb / dm ² using a sine wave alternating current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μm (Ra display). Subsequently, after immersing in a 30% sulfuric acid aqueous solution and desmutting at 55 ° C. for 2 minutes, the current density was 2 A / d in a 20% sulfuric acid aqueous solution.
The thickness of the anodized film was anodized for 2 minutes so that 2.7 g / m ² in m ^2. Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure.

[Sol Solution] Unichemical Co., Ltd .: Phosmer PE 24 parts by weight Methanol 130 parts by weight Water 20 parts by weight 85% phosphoric acid 16 parts by weight Tetraethoxysilane 50 parts by weight 3-methacryloxypropyltrimethoxysilane 48 parts by weight

Were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the content was transferred to another container and 3,000 parts by weight of methanol was added to obtain a sol solution. This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio), applied with a wheeler so that the amount of Si on the substrate was 3 mg / m ^2, and dried at 100 ° C. for 1 minute. A coating solution of a photopolymerization layer having the composition shown below was applied to the thus treated aluminum plate using a wire bar so that the dry coating weight was 1.50 g / m ² .

After a thermocouple temperature sensor was attached to the back surface of the aluminum plate with an adhesive tape, it was dried in a high-temperature hot air drying oven ETAC HT220 manufactured by Kusumoto Kasei Co., Ltd. to form a photopolymerized layer. Table 2 shows the drying conditions at this time and the temperature of the aluminum plate support measured by the attached temperature sensor.

(Photopolymerization Layer Coating Solution A) Reaction product of 2 mol of hexamethylene diisocyanate with 3.33 g of 2 mol of hydroxyethyl methacrylate and 1 mol of 2-hydroxyethylpiperidine Methyl methacrylate 63 mol%, methacrylic acid 37 mol % 1.00 g copolymer (average molecular weight 28,000, acid value 3.82 meq./g) ethyl eosine 0.123 g IRGACURE 784 0.512 g (titanocene-based initiator manufactured by Ciba / Geigy) propylene glycol monomethyl ether 29. 62 g butanone 16.03 g

After the formation of this photopolymerization layer, it was once cooled to 50 ° C. or less, and 3% by weight of polyvinyl alcohol (86.5-89 mol% of saponification degree, polymerization degree of 1000) was formed on the photopolymerization layer. The aqueous solution was applied so as to have a dry application weight of 2 g / m ² and dried at 100 ° C. for 90 seconds.

This plate was used for Cymbolic Sci.
using an FD-YAG laser-platesetter Plate Jet4 manufactured by Ences Inc., with an exposure amount of 260 (plate light intensity 0.17 mJ / cm ² ), 1,000 DPI, de
After performing halftone dot image exposure at 100 lines / inch under the fault conditions, a digital plate processor LP-850P manufactured by Fuji Photo Film Co., Ltd. was supplied to a developer LP-D manufactured by Fuji Photo Film Co., Ltd. ) Was charged and developed, and the developability was evaluated. Table 2 shows the case where the image portion was obtained as the image was exposed, and the case where the image portion was not obtained as the image exposure was x. Further, the plate after coating and drying was stored under the condition of 50 ° C.-40% for 3 days, then exposed and developed in the same manner, and the developability after forced storage with time was similarly evaluated. Further, using each of the obtained printing plates, printing was performed on high quality paper with a commercially available ink using a KOR-D type printing machine manufactured by Heidelberg. Table 2 shows the number of printings for each printing plate.

[0126]

[Table 2]

Examples 4 to 6, Comparative Example 4 A photosensitive lithographic printing plate was obtained in the same manner as in the above Examples and Comparative Examples, except that the coating solution for the photopolymerization layer was changed to the following composition (B). Similarly, after performing image exposure using Plate Jet 4, the same development processing as in Examples 1 to 3 was performed to obtain a printing plate. Table 3 shows the results of the evaluation of the developability, and the results and the number of printings of each printing plate when the printing plate was similarly printed.

(Coating solution B for photopolymerization layer) Urethane acrylate monomer 1.5 g UA-306H manufactured by Kyoeisha Chemical Co., Ltd. (reacted product of 2 mol of pentaerythritol triacrylate and 1 mol of hexamethylene diisocyanate) Binder having the following structure B-1 2.0 g Compound 1 having the following structure 0.15 g IRGACURE-784 0.20 g Compound 2 having the following structure 0.50 g Copper phthalocyanine pigment (organic polymer dispersion) 0.5 g Megafax F-177 ( Dainippon Ink and Chemicals, Inc. 0.02 g Fluorosurfactant, manufactured by N-Nitrosophenylhydroxyl 0.015 g Amine aluminum salt (manufactured by Wako Pure Chemical Industries) Propylene glycol monomethyl ether 27.5 g Methyl ethyl ketone 19.0 g

The structural formulas of the above-mentioned binder B-1, compound 1 and compound 2 are shown below.

[0130]

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(Comparative Examples 5 to 6) Examples 1 to 3 and Comparative Example 1
After coating the photopolymerizable layer coating solution shown in the following composition (C) on an aluminum plate support having been subjected to the same surface treatment as that used in Examples 1 to 3, and dried under the drying conditions shown in Table 3, Similarly to Examples 1 to 3, a layer made of polyvinyl alcohol was provided, laser-exposed as in Examples 1 to 3, and then developed to obtain printing plates of Comparative Examples 5 and 6. Evaluation of developability was performed in the same manner, and the results were used.
Table 3 shows the number of endurable prints when printing under the same conditions and methods as
Shown in

(Photopolymer Layer Coating Solution C) Trimethylolpropane triacrylate 1.5 g Binder 2.0-1 g Compound 1 0.15 g IRGACURE 784 0.20 g Compound 2 0.50 g copper Phthalocyanine pigment (organic polymer dispersion) 0.5 g Megafac F-177 (Dainippon Ink Chemical Industry Co., Ltd., fluorine surfactant) N-nitrosophenylhydroxyl 0.015 g Amine aluminum salt (Wako Pure) Propylene glycol monomethyl ether 27.5 g Methyl ethyl ketone 19.0 g

[0133]

[Table 3]

(Example 7, Comparative Example 7) [0134] The photopolymerizable layer coating solution B used in Example 4 and Comparative Example 4 was replaced with the photopolymerizable layer coating solution D shown below, and the results were the same as those in Example 4 and Comparative Example 7. Example 4 A photosensitive lithographic printing plate prepared in exactly the same manner as in Example 4 was used.
Was evaluated in exactly the same way. Table 4 shows the results.

(Photopolymerization Layer Coating Solution D) Urethane methacrylate monomer 1.5 g U-4H (a reaction product of 2 mol of glycerol dimethacrylate and 1 mol of hexamethylene diisocyanate) manufactured by Shin-Nakamura Chemical Co., Ltd. Binder having the following structure B-2 2.0 g Compound 1 0.15 g IRGACURE 784 0.20 g Compound 2 0.50 g Copper phthalocyanine pigment (organic polymer dispersion) 0.5 g Megafax F-177 (Dainippon Ink & Chemicals, Inc.) 0.02 g (manufactured by KK, fluorine surfactant) N-nitrosophenylhydroxyl 0.015 g amine aluminum salt (manufactured by Wako Pure Chemical Industries) propylene glycol monomethyl ether 27.5 g methyl ethyl ketone 19.0 g

[0136]

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[0137]

[Table 4]

From the above results, it was found that the photosensitive lithographic printing plates of Examples 1 to 7 had a urethane group as an addition polymerizable compound, and the photopolymerization layer was dried by heating at 90 to 140 ° C. As a result, both the developability and the printing durability were excellent. In particular, the photosensitive lithographic printing plate of Example 7 had better printing durability than those of the other Examples. This seems to be due to the use of the polyurethane resin as the binder component. On the other hand, the photosensitive lithographic printing plates of Comparative Examples 1, 4, and 7 had good developability, but poor printing durability. In this method, a compound having a urethane group is used as an addition polymerizable compound.
It is considered that the curing was not performed in the range of 0 to 140 ° C., so that the curing of the photopolymerization layer was not sufficient. Also,
The photosensitive lithographic printing plate of Comparative Example 2 was poor in developability and could not be prepared. This uses a compound having a urethane group as an addition polymerizable compound. However, since the maximum temperature during heating and drying of the photopolymerized layer is higher than 140 ° C. and higher than a predetermined range, the curing is excessive and the non-image area Is not dissolved by the developer. Further, the photosensitive lithographic printing plates of Comparative Examples 5 and 6 were:
Developability immediately after coating was good, but printing durability was poor. In Comparative Example 5, the heat drying of the photopolymerization layer was 90 to 140.
It is considered that the curing was performed in the range of ° C., but the curing of the photopolymerization layer was not sufficient because a compound having a urethane group was not used as the addition polymerizable compound. In Comparative Example 6, the addition-polymerizable compound having no urethane group was not used, and the heat drying of the photopolymerization layer was also performed at 90 to 140 ° C.
It is considered that the curing of the photopolymerization layer was not sufficient because the photopolymerization was not performed in the range of the above.

[0139]

The photosensitive lithographic printing plate of the present invention uses a photopolymerizable layer having a urethane group as an addition polymerizable compound, and is heated and dried after the application of the photopolymerizable layer to reduce the temperature of the photosensitive lithographic printing plate. By carrying out the reaction at a temperature of 90 to 140 ° C., the sensitivity, printing durability and storage stability were excellent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA11 AA12 AA14 AB03 AC08 AD01 BC13 BC42 BC65 BC66 BC83 CB14 CB22 CB43 CC03 DA04 DA36 EA10 FA17 2H096 AA06 BA05 CA20 EA04 EA23 GA08 LA30

Claims (2)

[Claims] 1. A photopolymerizable layer comprising, on a support having a hydrophilic surface, i) a linear polymer binder, ii) a compound having an addition-polymerizable ethylenically unsaturated bond and a urethane group, and a solvent. A photosensitive lithographic printing plate obtained by applying a coating solution and heating and drying the photosensitive lithographic printing plate under conditions that the temperature of the photosensitive lithographic printing plate is maintained at 90 to 140 ° C. for 10 seconds or more. 2. After the heating and drying, the temperature of the photosensitive lithographic printing plate is cooled to 50 ° C. or less, and then a protective layer containing a water-soluble oxygen-barrier substance is applied on the photopolymerized layer, The photosensitive lithographic printing plate according to claim 1, obtained by heating and drying.