JPH10282679A - Negative type photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a negative type photosensitive planographic printing plate having high sensitivity to laser beam in the visible light region and satisfactory printing performance such as tone reproducibility, printing and stain resistances, using a photopolymerizable compsn. and capable of direct photomechanical process by forming a specified middle layer and a specified photopolymerizable photosensitive layer on a substrate. SOLUTION: The surface of a substrate is coated with a compsn. of a sol form contg. a compd. of a sol form prepd. by bringing a silane coupling agent having an addition polymerizable ethylenic double bond into hydrolysis and dehydration condensation and a compd. having at least one alkylene oxide chain and at least one (meth)acryloyl group in one molecule. Optionally after drying, the compsn. is cured in a gelatinous state by hydrolysis and dehydration condensation to form a middle layer on the substrate. A photopolymerizable photosensitive layer contg. a compd. having an addition polymerizable ethylenic double bond and a photopolymn. initiator is formed on the middle layer. The photosensitive layer is tightly bonded to the substrate by the middle layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a negative photosensitive lithographic printing plate using a photopolymerizable composition. In particular, it relates to a negative-working photosensitive lithographic printing plate that can be directly made using a photopolymerizable composition that is highly sensitive to laser light in the visible light region and has good printing performance such as tone reproducibility, printing durability, and stain resistance. It is.

[0002]

2. Description of the Related Art Conventionally, negative type lithographic printing plates are widely known and have various photosensitive layers. There are diazo resin-containing types, photopolymerization types, photocrosslinking types, and the like. In order to prepare such a lithographic printing plate, it is common to place a transparent negative film original (lith film) on these lithographic printing plates and to expose the image using ultraviolet light. It took time and effort. In recent years, with the development of image forming technology, a photopolymer having high photosensitivity to light in the visible region has been demanded. It is a photosensitive material suitable for non-contact type projection exposure plate making or visible light laser plate making, for example,
Photopolymer systems are the most sensitive and promising. As the visible light laser, 488, 514.5 nm light of an Ar laser, and second harmonic light (SHG-LD, 350 to
600 nm), 532 nm light of SHG-YAG laser, etc. are promising. Therefore, by using a kind of high-sensitivity photopolymerizable photosensitive layer as the photosensitive layer, a laser beam with a narrow beam is scanned over the plate surface to form a character document, an image document, etc. directly on the plate surface. Plate making can be performed directly without using a manuscript. For example, Japanese Patent Publication No. 61-96
21, JP-A-63-178105, JP-A-2-24
By using the photosensitive composition described in No. 4050, etc.,
Plate making is possible directly without using a film manuscript. However, such high-sensitivity photopolymerizable printing plates do not always have strong adhesion between the photosensitive layer and the support. Therefore, when used for high-volume printing at high speed, solid images may be missing or fine lines or highlights may be lost. The problem of thinning or flying occurs.

Therefore, in a high-sensitivity photopolymerization system, the photo-adhesiveness of the support and the photosensitive layer is an important factor, and many studies and developments have been made. For example, Japanese Patent Application Laid-Open No. 3-56177
JP, JP-A-7-159838, JP-A-8-3
In JP-A-20551 and the like, a functional group capable of causing an addition reaction by a radical is provided on the surface of the support by a covalent bond,
An attempt was made to impart adhesive strength to the photopolymerizable photosensitive layer.

[0004] Although these inventions certainly improve the adhesive strength, they are not yet practically sufficient, and there is a demand for further improvement in adhesiveness. Recent market trends include strong demands such as shortening the exposure time to improve the productivity of plate making operations and using low power as much as possible to extend the life of the laser. Higher sensitivity is an eternal issue. However, even when printing hundreds of thousands of sheets, the adhesion between the photosensitive layer and the support is sufficiently high, the tone reproducibility is the same as the printed matter at the start, and when the alkaline developer is used for a long period of time and the printing becomes fatigued, Even when the plate was stored for a long period of time, a highly sensitive photopolymerizable lithographic printing plate having no stain on the non-image area was in a very difficult situation.

[0005]

Therefore, according to the present invention, a high sensitivity and a high sensitivity can be obtained by the strong adhesion between the photosensitive layer and the support.
Excellent tone reproducibility that thin lines and highlights do not thin or fly even when a large amount of printing is performed.Excellent printing durability. It is an object of the present invention to provide a negative photopolymerizable lithographic printing plate which can be directly laser-writable without stain on a non-image area even when stored for a long time.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and have found that (a) a silane coupling agent having an ethylenic double bond capable of addition polymerization is hydrolyzed and dehydrated and condensed. However, a sol-like composition containing a compound still in a sol state and (b) a compound having at least one alkylene oxide chain and at least one acryloyl group or methacryloyl group in one molecule is provided on the surface of the support. The sol composition is further hydrolyzed and dehydrated and condensed to form a gel, and the resulting sol composition is cured into a gel. The above object was achieved by a negative photosensitive lithographic printing plate provided with a photopolymerizable photosensitive layer containing a compound having the formula (d) and a photopolymerization initiator (d). In other words, the exposed portion causes (a) a silane coupling agent having an ethylenic double bond and (b) each polymerizable group of a compound having an acryloyl group or a methacryloyl group in the intermediate layer by radicals generated by laser exposure. Reacts with the polymerizable monomer in the photopolymerizable photosensitive layer, and eventually the support and the photopolymerizable photosensitive layer are firmly adhered to each other by the intermediate layer, so that fine lines and highlights can be obtained even with high sensitivity and a large amount of printing. A photopolymerizable lithographic printing plate that does not shrink or fly and has excellent printing durability was provided. On the other hand, in the non-image portion, since one component of the intermediate layer has a hydrophilic alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain, the intermediate layer is easily removed with an alkaline developer to remove the alkylene oxide chain. Compared to the case where no component was used,
The removal of the gelled silane coupling agent in the intermediate layer by the alkaline developer is also improved, so that organic substances are less likely to remain in the non-image area. Thus, a negative-type photopolymerizable lithographic printing plate capable of direct laser writing, which is hardly stained during printing and easy to print, could be provided. That is, the present invention provides a compound obtained by hydrolysis and dehydration condensation of a silane coupling agent having an addition-polymerizable ethylenic double bond on a support, and an alkylene oxide chain and an acryloyl or methacryloyl group in one molecule. An intermediate layer obtained by applying and drying a composition containing a compound having
And a photolithographic printing plate having a photopolymerizable photosensitive layer containing a compound having an addition-polymerizable ethylenic double bond and a photopolymerization initiator.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [(A) Intermediate layer] The intermediate layer is obtained by hydrolyzing and dehydrating a silane coupling agent having an addition-polymerizable ethylenic double bond on the surface of an aluminum support described below.
However, a sol containing a compound and a compound having at least one alkylene oxide chain and at least one acryloyl group or methacryloyl group in one molecule (hereinafter abbreviated as “compound having an alkylene oxide chain”) in a sol state. The sol-like composition is applied by applying the sol-like composition, and the sol-like composition is further hydrolyzed and dehydrated and condensed to form a gel.

The preparation of a compound still in a sol form, which is one of the components of the sol composition, obtained by hydrolyzing and dehydrating a silane coupling agent may be carried out by a conventionally known method.

In general, -Si-O-Si obtained by hydrolyzing and dehydrating and condensing a silane coupling agent.
A sol-gel method (hereinafter referred to as “SG method”) comprising using an organic-inorganic composite in which an addition-reactive functional group is fixed to an inorganic polymer containing a bond is preferably applied.
About SG method [Latest technology of organosilicon polymer]
(Chapter 6 Research Trends of Sol-Gel Method and Silicon Polymer,
This is described in, for example, Yoshio Imai, CMC, 1996) and [Science of the Sol-Gel Method] (Miyao Sakubana, Agne Shofusha, 1988). Not necessarily.

In the intermediate layer according to the present invention, the inorganic polymer portion adheres to the surface of the support, and the addition-reactive functional group remains as it is and is fixed on the surface of the support. When the intermediate layer is coated by using the SG method, the distribution of the addition-reactive functional groups bonded and fixed on the support surface depends on the distribution of chemical properties such as acid sites and base sites on the support surface. It is preferable because it hardly occurs.

As the silane coupling agent used in the present invention, a compound represented by the following general formula (X) is effective. R ^a (R ^b ) SiR ^c (R ^d ) (X) (at least two of R ^{a to} R ^d represent an alkoxy group having 10 or less carbon atoms or an —OCOCH ₃ group, and the others represent addition polymerizable reactive groups. The addition-polymerizable reactive group in the general formula (7) includes an alkenyl group, an alkynyl group, and the like. Even when various linking groups are bonded between the Si element and the addition-polymerizable reactive group, I don't care. Examples of alkenyl groups include, but are not limited to, vinyl, propenyl, allyl, butenyl, dialkylmaleimide, and the like. Examples of the alkynyl group include, but are not limited to, an acetylene group and an alkylacetylene group. Examples of the silane coupling agent include [Silane Coupling Agent]
s] (Edwin P. Plueddemann, Pl
eum Press, 1982), but is not limited thereto.

Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra (n-propoxy) silane, tetra (n-butoxy)
Silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, tetrakis (2-methoxyethoxy) silane, tetraphenoxysilane, tetraacetoxysilane, and the like can be given, among which tetraethoxysilane is preferable. As the silane coupling agent having an addition-polymerizable ethylenic double bond reactive group, specifically,

[0013] _{CH 2 = CH-Si (OCOCH} 3) 3, CH 2 = CH-Si (OC 2 H 5) 3, CH 2 = CH-Si (OCH 3) 3, CH 2 = CHCH 2 -Si (OC _{2 H 5) 3, CH 2} = CHCH 2 NH (CH 2) 3 -Si (OC
_{H 3) 3, CH 2 =} CHCOO- (CH 2) 3 -Si (OCH 3)
_{3, CH 2 = CHCOO- (CH} 2) 3 -Si (OC
_{2 H 5) 3, CH 2} = CHCOO- (CH 2) 4 -Si (OCH 3)
_{3, CH 2 = C (CH} 3) COO- (CH 2) 3 -Si (O
_{CH 3) 3, CH 2 =} C (CH 3) COO- (CH 2) 3 -Si (O
_{C 2 H 5) 3, CH} 2 = C (CH 3) COO- (CH 2) 4 -Si (O
_{CH 3) 3, CH 2 =} C (CH 3) COO- (CH 2) 5 -Si (OC
_{H 3) 3, (CH 2} = C (CH 3) COO- (CH 2) 3) 2 -Si
_{(OCH 3) 2, CH 2} = C (CH = CH 2) -Si (OCH 3) 3, CH 2 = CH-SO 2 NH- (CH 2) 3 -Si (OC
H ₃ ) ₃ , CH ₂ ＣＨCH-ph-O-Si (OCH ₃ ) ₃ (where ph represents a benzene ring)

CH ₂ ＣＨCH-ph-CONH- (C
_{H 2) 3 -Si (OCH 3} ) 3, CH 2 = CH-ph-CH 2 NH- (CH 2) 3 -Si
_{(OCH 3) 3, CH 2} = CH-ph-CH 2 NH-C 2 H 4 NH (CH 2) 3
_{-Si (OCH 3) 3 · HCl} HC = C-Si (OC 2 H 5) 3, CH 3 C = C-Si (OC 2 H 5) 3, DMI- (CH 2) m -CONH- (CH 2 ) ₃ -Si
(OCH ₃ ) ₃ , (DMI: a dimethylmaleimide group, m = 1 to 2
_{0) CH 2 = CHCH 2 O} -Si (OCH 3) 3, (CH 2 = CHCH 2 O) 4 Si, HO-CH 2 -C = C-Si (OC 2 H 5) 3, CH 3 CH 2 CO _{-C = C-Si (OC 2} H 5) 3, CH 2 = CHS- (CH 2) 3 -Si (OCH 3) 3, CH 2 = CHCH 2 O- (CH 2) 2 -SCH 2 -Si
_{(OCH 3) 3, CH 2} = CHCH 2 S- (CH 2) 3 -S-Si (OC
_{H 3) 3, (CH 3} ) 3 CCO-C = C-Si (OC 2 H 5) 3, (CH 2 = CH) 2 N- (CH 2) 2 -SCH 2 -Si (O
_{CH 3) 3, CH 3 COCH} = C (CH 3) -O-Si (OCH 3)
₃ , but is not limited to these. The silane coupling agent may be used by mixing several compounds in an arbitrary ratio.

The alkylene oxide used in the present invention
The following compounds are effective as compounds having a chain.
is there. First, a compound having one alkylene oxide chain
The compound includes phosphorus represented by the following general formula (1)
There is a compound having an addition-polymerizable ethylenic double bond.
It is effective. R¹(R^Two) (R^Three) P = O (1) [(R¹, R^Two, R^ThreeAt least one of the following general formulas
Represents an addition polymerizable reactive group represented by (2);
Group, an OH group, an alkoxy group or an amine of the following general formula (3)
Represents a no group. ) CH_Two= C (R^Four) COO (CH_TwoCH (R^Five) O)_n-(2) (R^FourIs H or CH_ThreeRepresents R^FiveIs H, CH_Threeor
Is CH_TwoRepresents X. X is a halogen atom (for example, F,
Cl, Br, I). n represents 0 to 50. )
 R⁶-CH_TwoCH_Two-NH (R⁷)_Two−
 (3) (R⁶Is H, OH, C_1-6Alkyl group, acryloyl
Represents a group or a methacryloyl group. R⁷Is H or C_1-6
Represents an alkyl group. )] Is an addition-polymerizable ethyl
A phosphorus compound having a lenic double bond,¹~ R
^FourAre OH, CH_ThreeO, C_TwoH_FiveO, H
OC_TwoH_FourO, n-C_ThreeH₇O, i-C_ThreeH₇O, HO
C_ThreeH₆O, n-C_FourH₉O, i-C_FourH₉O, sec
-C_FourH₉O, t-C_FourH₉O, phenoxy, C₈H₁₇
O, CH_Two= C (CH_Three) COO (C_TwoH_FourO)_n, C
H_Two= CHCOO (C_TwoH_FourO)_n, CH_Two= C (CH
_Three) COOCH_TwoCH (CH_TwoCl) O, CH_Two= C
(CH_Three) COO (CH_TwoCH (CH_Three) O)_n, CH
_Two= CHCOO (CH_TwoCH (CH_Three) O)_n, ONH
_ThreeC_TwoH_FourOH, ONH (C_TwoH_Five)_TwoC_TwoH_FourOCO
C (CH_Three) = CH_Two, Vinyl group, propenyl group, ant
And a butenyl group. However
However, the present invention is not limited to these.

Specifically, the following compounds are mentioned, but not limited thereto. [Compound A] CH ₂ ＣC (CH ₃ ) COO (C ₂ H
₄ O) _n P = O (OH) ₂ n = 1; Unichemical Co., Ltd .; Phosmer M, Nippon Kayaku Co., Ltd .; Kayamar PM-1, Kyoeisha Oil & Fat Co., Ltd .; Light Ester PM, Shinnakamura Chemical Co., Ltd .; NK ester SA, n = 2; Unichemical Co., Ltd .; Phosmer PE2, n = 4-5; Unichemical Co., Ltd .; Phosmer PE, n = 8; Unichemical Co., Ltd .; Phosmer PE8 [ Compound B] [CH ₂ ＣC (CH ₃ ) COO (C ₂ H ₄
O) _n ] _m P = O (OH) _3-m n = 1, a mixture of m = 1 and 2; Daihachi Chemical Co., Ltd .; MR-
200 [Compound C] CH ₂ ＣＨCHCOO (C ₂ H ₄ O) _n P =
O (OH) ₂ n = 1; Unichemical Co., Ltd .; Phosmer A, Kyoeisha Yushi Co., Ltd .; Light ester PA [Compound D] [CH ₂ ＣＨCHCOO (C ₂ H ₄ O) _n ]
_m P = O (OH) _3- mn n = 1, a mixture of m = 1 and 2; Daihachi Chemical Co., Ltd .; AR-
200 [Compound E] CH ₂ ＣC (CH ₃ ) COO (C ₂ H
_{4 O) n P = O (} OC 4 H 9) 2 n = 1; Daihachi Chemical (Co.); MR-204 [compound _{F] CH 2 = CHCOO (C} 2 H 4 O) n P =
O (OC ₄ H ₉ ) ₂ n = 1; Daihachi Chemical Co., Ltd .; AR-204 [Compound G] CH ₂ ＣC (CH ₃ ) COO (C ₂ H)
_{4 O) n P = O (} OC 8 H 17) 2 n = 1; Daihachi Chemical (Co.); MR-208 [compound _{H] CH 2 = CHCOO (C} 2 H 4 O) n P =
O (OC ₈ H ₁₇ ) ₂ n = 1; Daihachi Chemical Co., Ltd .; AR-208 [Compound I] CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH)
(CH ₂ Cl) O) _n P = O (OH) ₂ n = 1; Unichemical Co., Ltd .; Phosmer CL [Compound J] CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH)
(CH ₃ ) O) _n P = O (OH) ₂ n = 5-6; Unichemical Co., Ltd .; Phosmer PP [Compound K] CH ₂ ＣＨCHCOO (CH ₂ CH (C
H ₃ ) O) _n P = O (OH) ₂

[Compound L] CH_Two= C (CH_Three) COO (C_TwoH
_FourO) P = O (OH) (ONH_ThreeC_TwoH_FourOH) n = 1; Unichemical Co., Ltd .; Phosmer MH [Compound M] CH_Two= C (CH_Three) COO (C_TwoH
_FourO)_nP = O (OH) (ONH (CH _Three)_TwoC_TwoH_Four
OCOC (CH_Three) = CH_Two) N = 1; Unichemical Co., Ltd .; Phosmer DM [Compound N] CH_Two= C (CH_Three) COO (C_TwoH
_FourO)_nP = O (OH) (ONH (C_TwoH_Five)_TwoC_TwoH
_FourOCOC (CH_Three) = CH_Two) N = 1; Unichemical Co., Ltd .; Phosmer DE [Compound O] CH_Two= CHCOO (C_TwoH_FourO)_nP =
O (O-ph)_Two (Ph: benzene ring) n = 1; Daihachi Chemical Co., Ltd .;
AR-260 [Compound P] CH_Two= C (CH_Three) COO (C_TwoH
_FourO)_nP = O (O-ph)_Two n = 1; Daihachi Chemical Co., Ltd .; MR-260 [Compound Q] [CH_Two= CHCOO (C_TwoH_FourO)_n]
_TwoP = O (OC_FourH₉) N = 1; Daihachi Chemical Co., Ltd .; PS-A4 [Compound R] CH_Two= CHP = O (OC_TwoH_FourCl)_Two n = 1; Daihachi Chemical Co., Ltd .; Vinylate-R [Compound S] [CH_Two= C (CH_Three) COO (C_TwoH_Four
O)_n]_TwoP = O (OH) n = 1; Daihachi Chemical Co., Ltd .; MR-200, Nippon Kayaku Co., Ltd .; Kayamar PM-2 [Compound T] [CH_Two= C (CH₃₎COOC_TwoH_Four(OC
OC_FiveH_Ten) O]_TwoP = O (OH) Nippon Kayaku Co., Ltd .; Kayamar PM-21 [Compound U] [CH_Two= CHCOO (C_TwoH_FourO)_n]
_ThreeP = On = 1; Osaka Organic Co., Ltd .; Biscoat 3PA Commercial products include the compounds shown above, but all
Not something.

As described in "Experimental Chemistry Course" and "Ultraviolet Curing System" by Kiyomi Kato, these phosphorus compounds can be used in the same manner as general acrylic monomers, such as acrylic acid or methacrylic acid and phosphoric acid. It is synthesized by a dehydration reaction with a compound or transesterification. Further, as the phosphorus compound, some compounds may be mixed and used in an arbitrary ratio. In the formula, the number of chain lengths n of ethylene oxide and propylene oxide becomes difficult to synthesize a pure product as the number of n increases in the synthesis, and the mixture becomes a mixture before and after. As specific numbers, n = 0, 1, 2, about 4 to 5,
About 5-6, about 7-9, about 14, about 23, about 40, about 50
However, the present invention is not limited to these.

The other compound having one alkylene oxide group may be a phosphorus-free addition-polymerizable ethylenic double bond represented by the following general formula (4), (5) or (6). Are effective. CH ₂ ＣC (R ⁸ ) COO (CH ₂ CH (R ⁹ ) O) _n Z ¹ (4) CH ₂ ＣC (R ⁸ ) COO (CH ₂ CH ₂ CH ₂ O) _n Z ² (5) [ ^{_{CH 2 = C (R 8)}} COO (R 10 O) n (R 11) l] m Z 3 (6) (R 8 are, .R ⁹ representing H or CH ₃ is, H, CH ₃ or CH ₂ Represents X. X represents a halogen atom, and n represents
Represents 1 to 50. Z ¹ and Z ² represent an H, C _1-6 alkyl group, an alkyl-substituted or unsubstituted phenyl group, an acryloyl group, a methacryloyl group, or an aromatic carboxylic acid residue. R ¹⁰ represents a C _2-3 alkylene group. R
¹¹ represents a C _1-3 alkylene group or a phenylene group substituted or unsubstituted with alkyl, and 1 represents 0 or 1. Z ³ represents a divalent or trivalent aliphatic hydrocarbon group C _3-6, m represents 2 when Z ³ is a divalent, Z ³ represents 3 when trivalent. )

Specific examples include, but are not limited to, the following compounds.

[0021]

Embedded image

These compounds may be used as a mixture of two or more kinds at an arbitrary ratio. In addition, these compounds and the above-mentioned phosphorus compounds can be mixed and used at an arbitrary ratio.

In preparing a sol composition to be coated on a support for forming an intermediate layer, a compound still in sol state obtained by hydrolyzing and dehydrating and condensing a silane coupling agent is combined with the above-mentioned various alkylene oxide groups. The compound has a weight ratio of 5000: 1 to 1: 500, preferably 1: 1.
000: 1 to 1: 100, more preferably 500: 1 to
1:20. The sol composition may be diluted with a solvent if necessary. Water and / or catalyst can also be added. Examples of the solvent include methanol, ethanol, propanol, isopropanol, ethylene glycol, hexylene glycol, THF, DMF, and the like. Alcohols are particularly preferable, but these organic solvents may be used as a mixture.

The amount of the solvent to be used is generally 0.2 to 500 times, preferably 0.5 to 100 times, more preferably 1 to 100 times, based on the total weight of the silane coupling agent and the compound having an alkylene oxide group used. It is up to 20 times.
If the used amount is less than 0.2 times, the reaction solution is apt to gel over time and becomes unstable, which is not preferable. If it is more than 500 times, the reaction takes several days, which is not preferable.
The amount of water to be added to the sol composition is generally 0.1 to 1000 mol, preferably 0.5 to 200 mol, more preferably 1.5 to 100 mol per mol of the compound constituting the sol composition. Is a mole. When the amount of water is less than 0.1 mol per 1 mol of the compound, the progress of the hydrolysis and the subsequent polycondensation reaction becomes very slow, and it takes several days until stable surface treatment becomes possible. Absent. On the other hand, if the amount of water is more than 1000 moles per mole of the compound, the resulting composition may cause poor adhesion when coated on a metal surface, and the composition may have poor stability over time and gel immediately. Therefore, it is difficult to perform a coating operation stably.

The reaction temperature for preparing a sol composition suitable for the SG method is usually from room temperature to about 100 ° C., but depending on the type of catalyst used, a temperature below room temperature or above 100 ° C. may be used. It can also be used. The reaction can be carried out at a temperature higher than the boiling point of the solvent. If necessary, a reflux condenser may be provided in the reactor. Examples of the catalyst used as necessary include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, malic acid, and oxalic acid, and bases such as ammonia, tetramethylammonium hydroxide, potassium hydroxide, and sodium hydroxide. Can be used. The catalyst is added in an amount of 0.001 to 1 mol, preferably 0.002 mol, per mol of the compound, based on the total amount of the silane coupling agent and the compound having an alkylene oxide group.
To 0.75 mol, more preferably 0.003 to 0.5 mol. Even if the amount of the catalyst added is more than 1 mol, there is no particular economical advantage as compared with the effect of the addition.

When a weak acid such as acetic acid or malic acid is used as a catalyst, it is generally advantageous to set the reaction temperature in the range of 40 ° C. to 100 ° C., although it depends on the solvent used. When a strong acid such as nitric acid is used as the catalyst,
A range of 0 ° C. is preferred. 1 when phosphoric acid is used as catalyst
The reaction can be performed at 0 ° C to 90 ° C. In many cases, heat is applied in the step of preparing the sol composition used in the SG method, and in the step of applying and drying the sol composition on a support,
When a volatile acid is used as a catalyst, it may volatilize and adhere to peripheral devices, causing corrosion. When the present method is used in a step mainly using iron as a raw material, it is preferable to use nonvolatile sulfuric acid and / or phosphoric acid as a catalyst.

When the addition-reactive functional group is coated on the surface of the support by using the SG method, the type and amount of the solvent for diluting the silane coupling agent and the compound having an alkylene oxide group, The amount of water to be added for decomposition (if added), the type and amount of catalyst for promoting hydrolysis (if added), and the sol composition of a silane coupling agent and a compound having an alkylene oxide group are applied to the substrate. It is necessary to change and control various process parameters such as the method of drying, the drying atmosphere after application to the substrate, the drying temperature and the drying time. Since the applied amount of the sol composition of the silane coupling agent and the compound having an alkylene oxide group is extremely small, it is difficult to measure by a gravimetric method. Therefore, the substrate surface after the treatment may be treated by an appropriate method, for example, a fluorescent X-ray analysis method.
It can be determined by measuring by a method such as an infrared absorption method and quantifying the amount of Si atoms on the surface, quantifying the amount of carbon-carbon multiple bonds, and the like. The coating amount of the sol composition of the silane coupling agent and the compound having an alkylene oxide group is 0.1 to 50 mg / m ² , preferably 0.5 to 20 as the amount of Si atoms on the surface.
mg / m ² , more preferably 1 to 10 mg / m ² .

As described above, a composition comprising a silane coupling agent, a compound having an alkylene oxide group, an organic solvent, water, and optionally a catalyst is mixed at an appropriate reaction temperature, reaction time, and optionally When the reaction is carried out under agitation conditions, a polycondensation reaction occurs together with the hydrolysis, and a polymer or a colloidal polymer containing -Si-O-Si- bonds is generated, and the viscosity of the liquid composition increases to form a sol. . When the sol liquid used in the SG method is left at room temperature, the polycondensation reaction may continue to proceed and gel. Therefore, it is possible to prevent or delay gelation of the sol liquid by previously diluting the sol liquid prepared by the above method with a solvent to be used for dilution at the time of coating on a support. it can. In order to coat an intermediate layer on a support by the SG method,
Further, in order to prevent the coating distribution unevenness of the intermediate layer on the support, it is preferable to adjust the concentration by adding a solvent before applying these treatment liquids to the support. Alcohols, particularly methanol and ethanol, are suitable as the solvent used for this purpose, but other solvents, organic compounds, inorganic additives and surfactants can also be added. Examples of other solvents include methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane,
Examples thereof include methyl lactate, ethyl lactate, acetylacetone, and ethylene glycol.

Examples of organic compounds that can be added include epoxy resins, acrylic resins, butyral resins,
Examples include urethane resins, novolak resins, pyrogallol-acetone resins, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polypropylene glycol and the like. Examples of the inorganic additive include colloidal silica and colloidal alumina. High-boiling solvents such as ethylene glycol and ethylene glycol monomethyl ether increase the stability of the solution diluted to the concentration applied to the support and guarantee the reproducibility of the addition-reactive functional groups bound to the support. There is work. Organic compounds such as a novolak resin and a pyrogallol-acetone resin have the same effect, but have a side effect of reducing the hydrophilicity of the surface of the obtained support, and it is necessary to finely adjust the addition amount.

The sol composition suitable for the SG method is applied on the surface of a support and then air-dried or heat-dried to give -Si-O
At the same time as the inorganic polymer consisting of —Si— bonds is gelled, it is covalently bonded to the substrate surface. The drying is performed to volatilize the solvent, residual water and optionally the catalyst, but the step can be omitted depending on the purpose of use of the treated substrate. Therefore, depending on the purpose, after the drying is completed, the temperature may be further increased and the heating may be continued. The maximum temperature during drying and, optionally, subsequent heating is preferably in such a range that the addition-reactive functional groups do not decompose. Therefore,
Drying temperature conditions that can be used are room temperature to 200 ° C, preferably room temperature to 170 ° C, more preferably room temperature to 140 ° C. The drying time is generally from 1 second to 30 minutes, preferably from 5 seconds to 10 minutes, more preferably from 10 seconds to 2 minutes. In the present invention, a method for applying a sol-based composition of a compound having a silane coupling agent and an alkylene oxide group to a support includes various methods such as brush coating, dip coating, atomizing, spin coating, and doctor blade coating. It can be used and is determined in consideration of the shape of the surface of the aluminum substrate, the required film thickness to be processed, and the like.

In carrying out the present invention, (1) graining treatment, (2) anodic oxidation treatment, (3) silicate treatment, and
(4) A photopolymerizable lithographic printing plate of the present invention is formed by forming a photosensitive layer composed of a photopolymerizable composition described below on a support obtained by performing an acid treatment and further coating an intermediate layer. Although it is formed, an organic undercoat layer may be provided as necessary before coating the photosensitive layer. Water-soluble resins, such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (eg, zinc borate), or those undercoated with a yellow dye, amine salt, etc. Are also suitable. Examples of the organic compound used in the organic undercoat layer include phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, and phenylphosphonic acid which may have a substituent. Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid,
Examples include amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxyl group such as hydrochloride of triethanolamine. These may be used in combination of two or more.

This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, and methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate having an intermediate layer coated thereon, and dried to provide a method. An aluminum substrate provided with an intermediate layer is immersed in a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof, and the organic compound is adsorbed. Thereafter, the organic undercoat layer is provided by washing and drying with water or the like. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight.
The immersion temperature is 20 to 90 ° C., preferably 25 to 5 ° C.
0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is ammonia,
Adjust the pH with basic substances such as triethylamine and potassium hydroxide, and acidic substances such as hydrochloric acid and phosphoric acid,
It can be used in a pH range of 1 to 12. Further, a yellow dye can be added for improving the tone reproducibility of the photopolymerizable lithographic printing plate. The coating amount of the organic undercoat layer after drying is suitably ² to 200 mg / m ² , preferably 5 to 200 mg / m ^2.
１００100 mg / m ² . The above coating amount is 2 mg / m
^If it is less than ² , sufficient printing durability cannot be obtained. Also, 20
The same is true even if it is larger than 0 mg / m ² . The aluminum support provided with the intermediate layer may be further subjected to a surface treatment such as immersion in an aqueous solution of potassium fluorozirconate, phosphate or the like.

[(B) Photopolymerizable Photosensitive Layer] The main components of the photopolymerizable photosensitive layer used in the present invention are a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, and an organic polymer. Various compounds such as a coloring agent, a plasticizer, and a thermal polymerization inhibitor are added as needed. The compound containing an addition-polymerizable double bond can be arbitrarily selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds. For example, monomers,
Prepolymers, that is, those having chemical forms such as dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaethritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol Tetraacrylate, sol Penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. The crotonic acid ester includes ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Another example is JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound having two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula (8) is added is exemplified.

CH ₂ ＣC (R ¹² ) COOCH ₂ CH (R ¹³ ) OH (7) (where R ¹² and R ¹³ represent H or CH ₃ ). Urethane acrylates as described in JP-A-48-641
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. Further, those described as photocurable monomers and oligomers in the Journal of the Adhesion Society of Japan, vol. 20, No. 7, pages 300-308 (1984) can also be used. In addition, the amount of these used is 5-70 weight% with respect to all components.
(Hereinafter abbreviated as%), preferably 10 to 50%.

As the photopolymerization initiator, various photoinitiators known in patents and literatures can be used depending on the wavelength of the light source used.
Alternatively, a combination system (photoinitiating system) of two or more photoinitiators can be appropriately selected and used. For example, when light near 400 nm is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used. Visible light of 400 nm or more, Ar laser, second harmonic of semiconductor laser, SH
Even when a G-YAG laser is used as a light source, various photoinitiating systems have been proposed. For example, US Pat.
Certain photosensitive dyes described in U.S. Pat. No. 0,445, a complex initiation system of a dye and an amine (JP-B-44-20189), and a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-37377) ), A system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528, JP-A-54-155)
No. 292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024).
No.), a system of 3-ketocoumarin and an activator (JP-A-52-1)
No. 12681, JP-A-58-15503), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-15503).
140203), a system of an organic peroxide and a dye (JP-A-5
9-140203, JP-A-59-189340),
System of a dye having a rhodanine skeleton and a radical generator
No. 244050), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-221110), and a system of a combination of titanocene and a xanthene dye and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group. JP-A-4-221958, JP-A-4-2197
No. 56) and a system of titanocene and a specific merocyanine dye (JP-A-6-295061). The use amount of these photopolymerization initiators is 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound. Can be used.

The photopolymerizable composition usually contains an organic polymer as a binder, and such an organic polymer has compatibility with a photopolymerizable ethylenically unsaturated compound. As long as the organic polymer is
It doesn't matter which one you use. 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 and used not only as a film-forming agent of the composition but also as a developer for water, weakly alkaline water or an organic solvent. 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 the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577,
JP-B-54-25957, JP-A-54-92723
JP-A-59-53836, JP-A-59-7104
No. 8, ie, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is.

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 Other addition-polymerizable vinyl monomers] copolymers are preferred. 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.
These organic high-molecular polymers can be mixed in an arbitrary amount in the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85%. Further, the weight ratio of the photopolymerizable ethylenically unsaturated compound and the organic polymer is preferably in the range of 1/9 to 9/1. A more preferred range is 2/8 to 8/2, and still more preferably 3/8.
7 to 7/3.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is inhibited in order to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. Suitable thermal polymerization inhibitors include haloid quinone, 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-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is about 0.01 to the weight of the whole composition.
% To about 5% is preferred. 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 photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition. Further, a coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the coloring agent include phthalocyanine pigments, azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of dye and pigment added is about 0.5% of the total composition.
% To about 5% is preferred. 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. The amount of these additives is preferably 10% or less of the total composition.

When the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl 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, methoxymethoxy Ethanol, 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, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 1 to 50% by weight.

A surfactant can be added to the photopolymerizable composition of the present invention in order to improve the quality of the coated surface. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably, 0.
It is 3 to 5 g / m ² . More preferably, 0.7 to 3 g /
m ² .

[(C) Support] The support used in the present invention is preferably a dimensionally stable metal containing aluminum as a main component, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, it is selected from an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or a plastic film or paper on which aluminum (alloy) is laminated or evaporated. In addition, Tokiko Sho 4
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-8-18327, or a composite sheet in which paper is sandwiched between aluminum on the upper and lower sides may be used.

In the following description, the above-mentioned substrates made of aluminum or aluminum alloy are collectively used as aluminum supports. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium, and the content of the foreign elements in the alloy is 10% by weight or less. In the present invention, a pure aluminum plate is preferable,
Since completely pure aluminum is difficult to produce due to refining technology, it may contain a slightly different element. As described above, the composition of the aluminum support applied to the present invention is not specified, and the material is conventionally known and used, for example, JIS A1050, JIS A1.
100, JIS A 3103, JIS A 3005
Etc. can be used as appropriate. The thickness of the aluminum support used in the present invention is approximately 0.1 mm.
About 0.6 mm. This thickness is the size of the printing press,
It can be appropriately changed according to the size of the printing plate and the user's request. The aluminum support is preferably subjected to a substrate surface treatment as described below as appropriate, but it does not mean that all the following treatments must be performed.

[(C) -1, Graining treatment] Graining methods include mechanical graining, chemical etching and electrolytic graining as disclosed in JP-A-56-28893. Further, an electrochemical graining method of electrochemically graining in a hydrochloric acid or nitric acid electrolytic solution, a wire brush graining method in which the surface of the aluminum support is scratched with a metal wire, and a graining of the aluminum support surface with a polishing ball and an abrasive. A mechanical graining method, such as a ball graining method for standing, or a brush graining method for graining the surface with a nylon brush and an abrasive, can be used, and the above graining methods can be used alone or in combination. Among them, the method of making the surface roughness usefully used in the present invention is an electrochemical method of chemically sanding in a hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100C.
/ Dm ^{2 to} 400 C / dm ² . More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm ² ~400C / dm ² Is preferably performed.

The aluminum support thus grained is chemically etched with an acid or an alkali. When an acid is used as an etching agent, it takes time to destroy a fine structure, which is disadvantageous in industrially applying the present invention. However, it can be improved by using an alkali as an etching agent. Alkali agents suitably used in the present invention include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. The preferred ranges of concentration and temperature are 1 to 50, respectively. %, 20 to 10
It is preferable that the temperature is 0 ° C. and the amount of Al dissolved is 5 to 20 g / m ³ . After etching, pickling is performed to remove dirt (smut) remaining on the surface.
As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. In particular, as a method of removing the smut after the electrochemical surface-roughening treatment, a method of contacting with 15 to 65% by weight of sulfuric acid at a temperature of 50 to 90 ° C as described in JP-A-53-12739 is preferred. And the alkali etching method described in JP-B-48-28123.

[(C) -2, Anodizing treatment] The aluminum support thus treated is preferably further subjected to anodizing treatment. The anodizing treatment can be performed by a method conventionally performed in this field. Specifically, when direct current or alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution by using sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or a combination of two or more thereof, the surface of the aluminum support is An anodic oxide film can be formed on the substrate.

The conditions of the anodic oxidation treatment vary depending on the electrolytic solution to be used, and thus cannot be unconditionally determined. In general, the concentration of the electrolytic solution is 1 to 80%, the liquid temperature is 5 to 70.degree. 0.5-60 amps / dm ² , voltage 1-100V,
An electrolysis time of 10 to 100 seconds is appropriate. Among these anodizing treatments, in particular, British Patent No. 1,412,7
No. 68, a method of anodizing at a high current density in sulfuric acid and a method of anodizing phosphoric acid as an electrolytic bath described in US Pat. No. 3,511,661 are preferred. . In the present invention, it is preferable that the anodic oxide film is ^{1~10g / m 2, 1g / m} 2
If the amount is less than the above, the plate is easily damaged, and if the amount is more than 10 g / m ² , a large amount of electric power is required for production, which is economically disadvantageous.
Preferably, it is 1.5 to 7 g / m ² . More preferably, it is ² to 5 g / m ² . Further, in the present invention,
After graining and anodic oxidation, the aluminum support may be subjected to a sealing treatment. Such a sealing treatment is performed by immersing the substrate in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

[(C) -3, Silicate treatment] The aluminum support is appropriately subjected to the above-described treatment such as graining and anodic oxidation, and then subjected to the method described in Japanese Patent Application No. 8-41690. The surface of the substrate may be subjected to a hydrophilic treatment with silicate. Hydrophilic treatment with a silicate in the present invention is the formation of a silicate coating, silicate coating to 40 mg / m ² as a Si element content, more preferably 4 to 30 mg / m ² formed. The coating amount can be measured by fluorescent X-ray analysis, and the Si element amount can be measured. The above-mentioned hydrophilic treatment is performed, for example, in Japanese Patent Publication No. 47-5.
As described in JP-A No. 125, a material obtained by subjecting an aluminum support to anodizing treatment and then immersing in an aqueous solution of an alkali metal silicate is preferably used. Alkali metal silicates such as those disclosed in U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734 (for example, aqueous sodium silicate solution) ) Law can be applied.
According to this method, an aluminum support having an anodized film formed thereon is added to an aqueous solution containing 1 to 30% by weight, preferably 2 to 15% by weight of alkali metal silicate and having a pH of 10 to 13 at 25 ° C. For example, 0.5 to
Soak for 120 seconds.

As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used to increase the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide.
In addition, alkaline earth metal salts or IV
A group B metal salt may be blended. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. Can be. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.01 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight.

Electrodeposition of 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, Japanese Patent Application Laid-Open No. 52-30503, and a surface treatment in which the above-described anodizing treatment and sodium silicate treatment are combined with an aluminum support subjected to electrolytic graining are also useful. The silicate-treated aluminum support may be further treated with an acidic solution as disclosed in Japanese Patent Application No. 8-250522. Examples of the acid used at this time include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid, benzenesulfonic acid and the like, and two or more of these may be used in combination. As the acid treatment liquid used in the present invention, an acidic aqueous solution having a pH of 0 to 6 is desirable. If the pH of the acid treatment liquid is lower than 0, handling is dangerous and production suitability is low. As an acid treatment condition at this time, for example, it is appropriate to carry out by immersing at a temperature of 10 to 80 ° C. for 1 to 300 seconds.

[(D) Oxygen barrier protective layer] The present invention (B)
If necessary, an oxygen-blocking protective layer (D) may be further provided on the photopolymerizable photosensitive layer. (D) Examples of the water-soluble vinyl polymer contained in the oxygen-barrier protective layer include polyvinyl alcohol and its partial esters, ethers and acetals, or a substantial amount of unsubstituted water so as to have the necessary water solubility. Copolymers containing vinyl alcohol units can be mentioned. Polyvinyl alcohol is hydrolyzed by 71 to 100% and has a polymerization degree of 30.
Those having a range of 0 to 2400 are exemplified. Specifically, Kuraray's PVA-105, PVA-110, PV
A-117, PVA-117H, PVA-120, PV
A-124, PVA-124H, PVA-CS, PVA
-CST, PVA-HC, PVA-203, PVA-2
04, PVA-205, PVA-210, PVA-21
7, PVA-220, PVA-224, PVA-217
EE, PVA-220, PVA-224, PVA-21
7EE, PVA-217E, PVA-220E, PVA
-224E, PVA-405, PVA-420, PVA
-613, L-8 and the like. Examples of the copolymer include 88-100% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, and these may be used alone or in combination.

The solvent used for coating the oxygen barrier protective layer of the present invention is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. . The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight. Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film may be added to the oxygen-barrier protective layer of the present invention. Examples of the water-soluble plasticizer include polyethylene glycol,
Examples include polypropylene glycol, propionamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth) acrylic polymer or the like may be added. The amount of clothing is 0.1% by weight after drying.
A range of １５15 g / m ² is appropriate. Preferably 0.5
〜１０10 g / m ² . More preferably, 1 to 5 g / m ²
It is.

The photosensitive lithographic printing plate thus obtained was
r laser (488 nm, 514.5 nm), the second harmonic of a semiconductor laser (SHG-LD, 350 to 600 n)
m), after being directly exposed by a YAG-SHG laser (532 nm) or the like, is subjected to development processing. 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, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium,
And inorganic alkali agents such as sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide. Also,
Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolan, diisopropanolamine, ethyleneimine And organic alkali agents such as ethylenediamine and pyridine.

These alkali agents may be used alone or in combination of two or more.
Used in combination above. Of the above alkaline aqueous solution
Of these, a developer in which the effects of the present invention are further exhibited is
An aqueous solution containing potassium metal silicate and having a pH of 12 or more.
You. The aqueous solution of alkali metal silicate is a silicate component
Some silicon oxide SiO_TwoAnd alkali metal oxide M _TwoO's
The ratio (typically [SiO_Two] / [M_TwoO]
) And the density can be adjusted according to the density.
For example, it is disclosed in JP-A-54-62004.
Una, SiO_Two/ Na_TwoWhen the molar ratio of O is 1.0 to 1.5 (that is,
[SiO_Two] / [Na_TwoO] is 1.0 to 1.5
And SiO_TwoSodium silicate having a content of 1 to 4% by weight
Aqueous solution, or described in JP-B-57-7427.
[SiO_Two] / [M] is 0.5 to 0.7
5 (ie [SiO_Two] / [M_TwoO] is 1.0 to 1.5)
And SiO_TwoIs 1 to 4% by weight, and
The gram amount of the total alkali metal present in the developer is
Containing at least 20% potassium, based on offspring
Alkali metal silicate consisting of
Can be

Further, when developing the photosensitive lithographic printing plate 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 also preferably applied in the present invention. For example, [SiO ₂ ] / [Na ₂ O] of a developer as disclosed in JP-A-54-62004 is used.
Of 1.0 to 1.5 (that is, [SiO ₂ ] / [Na ₂
O] is 1.0 to 1.5), an aqueous solution of sodium silicate having a SiO ₂ content of 1 to 4% by weight is used, and furthermore, depending on the throughput of the positive photosensitive lithographic printing plate. The molar ratio of SiO ₂ / Na ₂ O is continuously or intermittently 0.5 to
1.5 (that is, [SiO ₂ ] / [Na ₂ O] is 0.5 to
1.5) A method of adding an aqueous solution of sodium silicate (replenisher) to a developer, and further disclosed in JP-B-57-7427, where [SiO ₂ ] / [M] is 0.5 to 0. .
75 (that is, [SiO ₂ ] / [M ₂ O] is 1.0-1.
5), wherein a developer of an alkali metal silicate having a SiO ₂ concentration of 1 to 4% by weight is used, and [SiO ₂ ] / [M] of the alkali metal silicate used as a replenisher is 0.
25 to 0.75 (i.e., [SiO ₂ ] / [M ₂ O]
5 to 1.5), and both the developer and the replenisher contain at least 20% potassium, based on gram atoms of total alkali metal present therein. A development method 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 post-treated with a desensitizing solution containing gum arabic and starch derivatives. For the post-processing of the photosensitive lithographic printing plate of the present invention, these processings can be used in various combinations. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets. As a plate cleaner used for removing stains on the plate at the time of printing, a conventionally known plate cleaner for a PS plate is used. 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.

(Examples 1 to 15) The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The surface of an aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of pumice stone of 400 mesh, and then washed thoroughly with water. After being immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. This was subjected to electrolytic surface roughening treatment in an aqueous 1% nitric acid solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating current under the condition of V _A = 12.7 V. When its surface roughness was measured, it was 0.6μ.
(Ra display). Subsequently, the sample was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55 ° C. for 2 minutes.
In a sulfuric acid aqueous solution, anodic oxidation treatment was performed for 2 minutes so that the thickness of the anodic oxide film was 2.7 g / m ² at a current density of 2 A / dm ² . Subsequently, a substrate washed and air-dried was prepared.

Next, a liquid composition (sol liquid) of the SG method was prepared according to the following procedure. [Sol Solution] 130 parts by weight of methanol 20 parts by weight of water 16 parts by weight of 85% phosphoric acid 50 parts by weight of tetraethoxysilane 48 parts by weight of 3-methacryloxypropyltrimethoxysilane were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the contents were transferred to another container, and 24 parts by weight of the phosphorus compound in Table 1 and 3000 parts by weight of methanol were added to obtain a sol solution. This sol is mixed with methanol /
It was diluted with ethylene glycol = 9/1 (weight ratio), applied with a wheeler so that the Si on the substrate was 3 mg / m ^2, and dried at 100 ° C for 1 minute. On the substrate thus treated, a photopolymerizable composition 1 having the following composition was applied so as to have a dry coating weight of 1.4 g / m ² and dried at 80 ° C. for 2 minutes to obtain a photopolymerizable photosensitive layer. Was formed.

[Photopolymerizable Composition 1] Trimethylolpropane tri (acryloyloxypropyl) ether 1.5 g Allyl methacrylate / methacrylic acid (80/20 weight ratio) linear organic polymer polymer Mw = 40,000 (B ₁ ) 2.0 g 0.13 g of the following sensitizer (C ₁ ) (λmax THF 472 nm, ε = 7.4 × 10 ⁴ )

[0063]

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The following photoinitiator (D ₁ ) 0.09 g

[0065]

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The following thio compound (E ₁ ) 0.08 g

[0067]

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Fluorinated nonionic surfactant 0.03 g Methyl ethyl ketone 20.0 g Propylene glycol monomethyl ether acetate 20.0 g Polyvinyl alcohol (with a saponification degree of 86.
An aqueous solution of 5 to 89 mol% and a degree of polymerization of 1000) of 3% by weight was applied so that the dry application weight was 2 g / m ² ,
After drying at 0 ° C. for 2 minutes, a photopolymerizable lithographic printing plate was obtained. The printing plate was stored at 60 ° C. for 3 days. These plates were prepared using an Optronics XLP4000 high-definition laser plotter (air-cooled Ar laser 200 mW, 488 nm).
And halftone dots and solid areas were exposed at 4,000 dpi and 175 lines / inch at various energies. In order to further increase the degree of film curing, a post-heating treatment was performed at 110 ° C. for 12 seconds. Developed by Fuji Photo Film Co., Ltd. DP-
4 Using a developer obtained by diluting the developing solution 18 times with water and developing the printing plate of the example in 10 m ^{2 in} advance for 1 liter of the solution, using an 850NX automatic developing machine manufactured by the company at 30 ° C. for 15 seconds. The immersion was performed.

The plate energy at which 2% was reproduced at 4000 dpi and 175 lines / inch was determined as the sensitivity of the sample in the unit of mJ / cm ² . For printing durability evaluation, SOR-KZ manufactured by Heidelberg Co. was used as a printing machine, and dampening water was EU-3 (1: 1) manufactured by Fuji Photo Film Co., Ltd.
100) to which 10% of isopropanol is added,
Claf G (N) manufactured by Dainippon Ink and Chemicals, Inc. was used as the ink. In addition, the stainability of the non-image area was visually evaluated on a 10-point scale. Ten points are the least stained, and one point is the most easily stained. The highlight printing durability indicates the number of printed sheets on which a 2% halftone dot of 175 lines / inch is reproduced on a printed material.
Table 1 shows the results of extracting printed matter every 5,000 sheets and evaluating 2% halftone dots of 175 lines / inch. When the compound of the present invention was used, a negative-type photopolymerizable lithographic printing plate having excellent press life and stain resistance was obtained.

[0070]

[Table 1]

Comparative Example 1 Photopolymerizable lithographic printing plates were prepared and evaluated in the same manner as in Examples 1 to 15, except that the compounds shown in Table 1 used for preparing the sol solution were not used.
When the compound defined in the present invention was not used at the time of preparing the sol solution, the sensitivity was low, highlights were easily scattered, and the non-image area was stained.

Example 16 The other conditions were the same as in Example 1. After the support was subjected to anodizing treatment, a 2.5% by weight aqueous solution of No. 3 sodium silicate was added to a bath heated to 70 ° C. This substrate was immersed for 14 seconds, then washed with water and dried. The photosensitive solution was changed as follows, and a 5% by weight aqueous solution of polyvinyl alcohol (a saponification degree of 98 mol% and a polymerization degree of 700) was dried so as to have a dry coating weight of 2.4 g / m ² . A lithographic printing plate was prepared and evaluated in the same manner. [Photopolymerizable composition 2] Tetramethylolmethanetetraacrylate 2.0 g The above-mentioned linear organic high-molecular polymer (B ₁ ) 2.0 g The following compound (C ₂ ) (λmax THF 479 nm, ε = 6.9 × 10 ⁴ )

[0073]

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The following compound (D ₂ ) 0.20 g

[0075]

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The following IRGACURE907 (E ₂ ) (manufactured by Ciba-Geigy) 0.40 g

[0077]

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Compound in which ε-phthalocyanine is dispersed with B ₁ in propylene glycol monomethyl ether acetate 0.20 g Megafac F-177 (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.03 g Cupperon AL ( Nitroso compound, manufactured by Wako Pure Chemical) 0.015 g Propylene glycol monomethyl ether 7.5 g Methyl ethyl ketone 9.0 g Toluene 11.0 g Sensitivity 0.045 mJ / cm ² Sensitivity, highlight reproducibility printing 190,000 sheets, and stain 10 A negative-type photopolymerizable lithographic printing plate was obtained which was excellent in terms of printing durability and stain resistance, and was highly sensitive.

(Example 17) The other conditions were the same as in Example 16, and the same evaluation was conducted by changing only the sol liquid as follows. [Sol Solution] 130 parts by weight of methanol 15 parts by weight of water 13 parts by weight of 85% phosphoric acid 40 parts by weight of tetraethoxysilane 13 parts by weight of 3-methacryloxypropyltrimethoxysilane were mixed and stirred. An exotherm was observed in about 5 minutes. After the reaction for 60 minutes, the contents were transferred to another container, and 77 parts by weight of Unichemical Co., Ltd .;
By adding 00 parts by weight, a sol solution was obtained.

This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio), and the Si on the substrate was reduced to 5: 1.
mg / m ² was applied to a wheeler and dried at 100 ° C. for 1 minute. Example 1 was placed on the substrate thus treated.
Drying weight of photopolymerizable composition 2 of No. 6 was 1.5 g / m ^2.
And dried at 100 ° C. for 2 minutes to form a photopolymerizable photosensitive layer. Sensitivity of 0.045 mJ / cm ² , highlight reproducibility 210,000 printing plates, and stain resistance 10
A molybdenum photopolymerizable lithographic printing plate was obtained which was excellent in point, high sensitivity, and excellent in printing durability and stain resistance.

(Example 18) The other conditions were the same as in Example 17, and the same evaluation was performed by changing only the photosensitive solution as follows. [Photopolymerizable composition 3] Pentaerythritol tetraacrylate 1.5 g 2.0 g of the above-mentioned linear organic polymer (B ₁ ) 0.15 g of the following compound (C ₃ )

[0082]

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The following compound (D ₃ ) 0.20 g of CGI-784 (manufactured by Ciba-Geigy)

[0084]

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The following compound (E ₃ ) 0.40 g

[0086]

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Compound obtained by dispersing ε-phthalocyanine with B1 in propylene glycol monomethyl ether acetate 0.20 g Megafac F-177 (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g Cupron AL (Nitroso Compound, Wako Pure Chemical) 0.01 g Propylene glycol monomethyl ether 7.5 g Methyl ethyl ketone 9.0 g Toluene 11.0 g Sensitivity 0.04 mJ / cm ² Sensitivity, highlight reproducibility 210,000 sheets, and stain 10 points Thus, a negative-type photopolymerizable lithographic printing plate having high sensitivity and excellent printing durability and stain resistance was obtained.

(Example 19) The other conditions were the same as those of Example 17, and the same evaluation was performed by changing only the photosensitive solution as follows. [Photopolymerizable composition 4] Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku) 2.0 g Benzyl methacrylate / methacrylic acid / methyl methacrylate (60/30/10 molar ratio) copolymer, molecular weight 3.5 Ten thousand (B ₂ ) 2.0 g The following compound (C ₄ ) 0.15 g

[0089]

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Compound (D ₃ ) 0.20 g Compound (E ₃ ) 0.40 g Compound in which β-phthalocyanine is dispersed with B ₂ in propylene glycol monomethyl ether acetate 0.20 g Megafac F-177 (Dainippon) Ink Chemical Industry Co., Ltd. fluorine surfactant) 0.02 g cupron AL (nitroso compound, manufactured by Wako Pure Chemical) 0.01 g propylene glycol monomethyl ether 7.5 g methyl ethyl ketone 9.0 g toluene 11.0 g obtained in this manner Photopolymerizable lithographic printing plate was SHG-Y
AG laser (532 nm) Gu made by Rhinotype Hell
Exposure was performed using a tenberg platesetter. Subsequent processing was performed in the same manner as in Examples 1 to 15. As a result, the sensitivity was 0.10 mJ / cm ² , and the result of printing was 200,000 highlights even after the printing test. Further, the stainability was 10 points.

(Example 20) The other conditions were the same as in Example 19, and the same evaluation was performed by changing only the sol liquid as follows. [Sol liquid] 130 parts by weight of methanol 15 parts by weight of water 13 parts by weight of 85% phosphoric acid 40 parts by weight of tetraethoxysilane 20 parts by weight of 3-methacryloxypropyltrimethoxysilane 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 50 parts by weight of Nippon Kayaku Co., Ltd .; KAYAMER PM-21 and 3000 parts by weight of methanol were added to obtain a sol solution.

This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio) so that the Si on the substrate became 1
mg / m ² was applied to a wheeler and dried at 100 ° C. for 1 minute. Example 1 was placed on the substrate thus treated.
Drying weight of photopolymerizable composition 2 of No. 6 was 1.5 g / m ^2.
And dried at 100 ° C. for 2 minutes to form a photopolymerizable photosensitive layer. A negative photopolymerizable lithographic printing plate having a sensitivity of 0.04 mJ / cm ² , highlight reproducibility of 200,000 printing presses, and 9 stains and high sensitivity and excellent printing durability and stain resistance was obtained. Was.

(Example 21) The other conditions were the same as in Example 19, and the same evaluation was conducted by changing only the sol liquid as follows. [Sol Solution] 130 parts by weight of methanol 15 parts by weight of water 13 parts by weight of 85% phosphoric acid 40 parts by weight of tetramethoxysilane 5 parts by weight of 3-acryloxypropyltrimethoxysilane were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the contents were transferred to another container, and 45 parts by weight of Phosmer PE8 and methanol 3 were added to Unichemical Co., Ltd.
By adding 000 parts by weight, a sol solution was obtained.

This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio), and was applied with a wheeler so that the amount of Si on the substrate was 3 mg / m ^2.
And dried. On the substrate thus treated, the photopolymerizable composition 3 of Example 18 was dried at a coating weight of 1.5 g / m 2.
² and dried at 100 ° C. for 2 minutes to form a photopolymerizable photosensitive layer. Sensitivity of 0.04 mJ / cm ² , highlight reproducibility 200,000 printing presses, solid printing durability 20
A negative-type photopolymerizable lithographic printing plate was obtained which had a high sensitivity of 10,000 sheets, a stain resistance of 10 points, and excellent printing durability and stain resistance.

(Example 22) The other conditions were the same as in Example 19, and the same evaluation was conducted by changing only the sol liquid as follows. [Sol Solution] methanol 130 parts by weight of water 15 parts by weight of 85% phosphoric acid 13 parts by weight of tetraethoxysilane 50 parts by _{CH 2 = CH-Si (OCOCH} 3) 3 10 parts by weight of 3-methacryloxypropyl trimethoxysilane 5 parts by weight Were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the contents were transferred to another container, and 45 parts by weight of Nippon Oil & Fats Co., Ltd .; Blemmer PE200 and 3,000 parts by weight of methanol were added to obtain a sol solution. A negative type photopolymerizable lithographic printing plate having a sensitivity of 0.04 mJ / cm ² , highlight reproducibility of 190,000 printing plates, and a high sensitivity of 9 points of stain resistance and excellent printing durability and stain resistance was obtained. Was.

[0096]

As described above, according to the present invention,
A photosensitive polymerizable lithographic printing plate which can be laser-writable with high sensitivity, a high sensitivity, a high-lightness which does not fly even when a large amount of printing is performed, and a stain free from contamination can be provided.

Claims (1)

[Claims] 1. A compound obtained by hydrolyzing and dehydrating a silane coupling agent having an addition-polymerizable ethylenic double bond on a support, and an alkylene oxide chain and an acryloyl or methacryloyl group in one molecule. Having a photopolymerizable photosensitive layer containing an intermediate layer obtained by applying and drying a composition containing the compound having a compound having an ethylenic double bond capable of addition polymerization, and a photopolymerization initiator. A negative photosensitive lithographic printing plate characterized by the following.