JP3223222B2 - Photosensitive printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative printing plate,
In particular, it relates to a negative type lithographic printing plate (hereinafter simply referred to as “PS plate”) that can be directly written with laser light.

[0002]

2. Description of the Related Art Negative PS plates have been widely known, including those using a diazo resin-containing photosensitive layer that cures when exposed to light, those using a photopolymerizable photosensitive layer, Examples include those using a photocrosslinkable photosensitive layer. Here, the terms photopolymerizable and photocrosslinkable refer to the property that polymerization and cross-linking of the organic layer is caused by active chemical species generated by light. To make a printing plate from such a PS plate, a P plate having these photosensitive layers is used.
An operation of placing a transparent negative film original on the S plate and exposing using ultraviolet light is performed. Even if the original is composed of characters, once the original is taken on film,
Since the operation of exposing the S plate is required, the operation is complicated. Therefore, using a kind of high-sensitivity polymerizable layer as the photosensitive layer, a laser beam with a narrow beam is scanned over the plate surface, and a character document, an image document, etc. are formed directly on the plate surface, without using a film document. Attempts have been made to make direct plate making. For example, by using the photosensitive composition described in JP-B-61-9621, JP-A-63-178105, JP-A-2-244050, etc., it is possible to directly form a plate without a film original.

[0003] However, such a conventional high-sensitivity photopolymerizable printing plate depends on the conditions when used as a printing plate. However, since the adhesion between the photosensitive layer and the support is not always strong, a large number of copies can be obtained at high speed. When used for printing, there occurs a problem that a solid image is missing or a thin line is cut off. If the rough surface of the support is roughened to enhance the adhesion between the photosensitive layer and the support, the durability of the image is certainly improved, but the hydrophilicity of the non-image area is reduced, and the printing becomes dirty. . Further, even if an attempt is made to improve the adhesion between the photosensitive layer and the support by using an undercoat layer such as a diazo resin, the process in which the diazo group is photolyzed and bonded to the support itself and / or the diazo group itself is performed. And the process of bonding the photosensitive layer is difficult to proceed, and requires a relatively large amount of exposure,
It is not compatible with systems that try to make plates directly by laser exposure. Accordingly, the present invention provides a photosensitive polymerizable photosensitive layer having high sensitivity, and during polymerization, the photosensitive layer and the support are photo-adhered to each other to exhibit a strong adhesive strength between the photosensitive layer and the support. It is an object of the present invention to provide a photo-sensitive PS plate having a portion having sufficient hydrophilicity, in particular, a laser-writable PS plate.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a functional group capable of causing an addition reaction by a radical is covalently inoculated on a surface of a support, and added. A reactive support was prepared and 4
It has been found that the above object can be achieved by coating a high-sensitivity photopolymerizable photosensitive layer having sensitivity to light of 00 to 1000 nm, and the present invention has been accomplished. That is, the addition-reactive functional group implanted on the support by covalent bonding is photo-adhered to the photopolymerizable photosensitive layer to exhibit strong adhesion between the photosensitive layer and the support. Since the addition-reactive functional groups are present at a density that does not reduce the hydrophilicity of the support, sufficient hydrophilicity is maintained in the non-image area.

Hereinafter, the present invention will be described in detail. In the present invention, the functional group bonded (implanted) to the surface of the support by a covalent bond is not particularly limited as long as the functional group can cause an addition reaction by a radical. For example, CH ₂ = CHC
OO- (CH ₂ ) _3- , CH ₂ = C (CH ₃ ) COO- (CH ₂ ) _3- , CH ₂ = CH-C (= C
_{H 2) -, CH 2 =} CH-S0 2 NH- (CH 2) 3 -,

[0006]

Embedded image

CH ₂ = CH-, HC≡C-, CH ₃ C≡C-,

[0008]

Embedded image

[0009] _{CH 2 = CHCH 2 O-, CH} 2 = CHCOO- (CH 2) 4 -, CH
_{2 = C (CH 3) COO-} (CH 2) 4 -, CH 2 = C (CH 3) COO- (CH 2) 5 -, CH
₂ = CHCH _2- , HO-CH ₂ -C≡C-, CH ₃ CH ₂ CO-C≡C-, CH ₂ = C
HS- (CCH ₂ ) _3- , CH ₂ = CHCH ₂ O- (CH ₂ ) ₂ -SCH _2- , CH ₂ = CHCH
₂ S- (CH ₂ ) ₃ -S-, (CH ₃ ) ₃ -CCO-C≡C-, CH ₂ = CHCH ₂ NH- (CH
₂ ) _3- , (CH ₂ = CH) ₂ -N- (CH ₂ ) ₂ -SCH _2- ,

[0010]

Embedded image

Can be mentioned as an example. As the support to which such an addition-reactive functional group is bound by a covalent bond, a sheet-like support having sufficient strength to be applied to a printing machine is used. As such a support,
For example, a metal plate, a polyester sheet, a polyimide sheet, reinforced paper, and the like can be given. For the purpose of obtaining a printing plate for high-speed printing of a large number of copies, it is preferable to use a metal plate as a substrate, and particularly to use an aluminum plate degreased by a conventional method. The aluminum plate used in the present invention is a plate-like body made of pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The alloy composition has a different atomic content of 10% by weight or less. Aluminum that is suitable for the present invention is pure aluminum, but completely pure aminium is preferably one that contains as little foreign atoms as possible because it is difficult to produce due to smelting technology. In addition, any aluminum alloy having the above-described heteroatom content can be said to be a material that can be used in the present invention. As described above, the composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. The preferred material is JI
SA 1050, 1100, 1200, 300
3, 3103, and 3005. The thickness of the aluminum plate used in the present invention is about 0.1 mm to about 0.5 mm.

The aluminum plate is subjected to a degreasing treatment, for example, a treatment with a surfactant or an alkaline aqueous solution, a graining treatment, an anodic oxidation treatment, and a hydrophilization treatment to remove rolling oil on the surface, if desired. The graining method includes
There are a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of chemically selectively dissolving the surface. As a method for mechanically roughening the surface, known methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. As an electrochemical surface roughening method, there is a method of performing electrolysis in a hydrochloric acid or nitric acid electrolytic solution by alternating current or direct current to roughen the surface. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as necessary.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte can be used as long as it can form a porous oxide film. Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used, and the concentration of the electrolyte is appropriately determined depending on the type of the electrolyte. The anodizing treatment conditions vary depending on the electrolyte used, and thus cannot be specified unconditionally. In general, the concentration of the electrolyte is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
° C, current density 5-60 A / dm ² , voltage 1-100
V and the electrolysis time are suitably in the range of 10 seconds to 50 minutes. Among these anodizing treatments, in particular, British Patent No. 1,
The method of anodizing in sulfuric acid at a high current density described in U.S. Pat. No. 412,768 and the method of anodizing in a low concentration of sulfuric acid as described in U.S. Pat. No. 4,211,619 are preferred. Most preferably, the current density is 5 to 20 A / dm ^{2 in} an electrolyte containing 5 to 20% by weight of sulfuric acid and 3 to 15% by weight of aluminum ions at a temperature of 25 to 50 ° C.
Anodizing with direct current. The amount of anodized film is
It can be 0.1 to 10 g / m ² .

As the hydrophilizing treatment, a treatment with an aqueous solution of an alkali metal silicate and a treatment with an aqueous solution of an organic phosphonic acid are preferred. The alkali metal silicate is 1 to 30% by weight, preferably 2 to 15% by weight, and the pH at 25 ° C is 10 to 1%.
3 to an aqueous solution, for example, at 0.5 to 120 ° C. at 0.5 to 120 ° C.
Soak for 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 raise the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, an alkaline earth metal salt or IVB
A group metal salt may be blended. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium 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 from 0.01 to 10% by weight, and the more preferred range is from 0.05 to 5.0% by weight. The attachment of the addition-reactive functional group to the support surface is preferably performed by a method using an organic silicone compound as a raw material. When the addition-reactive functional group is represented by R ₁ , the following formula (1): R ₁ Si (OR ₂ ) ₃ (1) (wherein —OR ₂ is a hydrolyzable alkoxy group or —OC
OCH ₃ groups. The support is treated with the organosilicone compound (1) represented by the formula (1), and a metal, metal oxide, hydroxide, or -OH group on the support surface, or a silanol group formed by a chemical conversion treatment of the support is used. To form a covalent bond with the surface of the support, and the following formula (2):

[0015]

Embedded image

The functional group represented by the formula (1) may be bonded (or implanted) to the surface of the support. In the formula, R ₃ represents a same or different alkyl group or a hydrogen atom as R ₂ , or a bond to another adjacent Si atom. Addition-reactive functional group (R ₁ )
Is bonded to two or more Si atoms at the center by the following formula (1a) or (1b):

[0017]

Embedded image

The organic silicone compound represented by the formula (1)
a) (1b) can also be used. Further, when the addition reactive functional group is a functional group bonded to the central Si atom via -O-,

[0019]

Embedded image

The organic silicone compound represented by the formula (1)
c) can also be used. 4 bonding to the central Si atom
When at least one of R ₁ is left without being hydrolyzed, it is applied to a support and used. When applying the organosilicone compound (1) on a support, it may be used alone or may be diluted with an appropriate solvent before use. Water and / or a catalyst can be added to bind the organosilicone compound (1) more firmly on the support. As the solvent, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and hexylene glycol are preferable.As the catalyst, acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid,
Alternatively, a base such as ammonia or tetramethylammonium hydroxide can be used.

The amount of the addition-reactive functional group on the support varies depending on the type of the addition-reactive functional group to be bound.
² per general 0.01 to 400 units 0 Å, preferably 0.05
It is appropriate that the number be from 40 to 40, more preferably from 0.1 to 5. Sufficient light adhesive strength and addition-reactive functional group content is less than ² per 0.01 pieces 100Å difficult to obtain. By coating the organic silicone compound (1) thickly, 10
It is possible to increase the amount of the addition-reactive functional groups per O @ ² substantially arbitrarily, but since the amount of the addition-reactive functional groups which expose the face on the outermost surface is at most 10 per 100 @ ^2, it is thickly applied. It is useless even if it passes. Addition-reactive functional group content is multi Ayamate, to hydrophilicity of non-image portions when used as a PS plate is not insufficient, the amount of addition-reactive functional groups per 100 Å ² has to be within 400 preferable. Therefore, when the addition-reactive functional group is bonded (planted) to the support surface using the organic silicone compound, the type and amount of the solvent for diluting the organic silicone compound and the water added for hydrolysis on the support surface are used. (If added), the type and amount of catalyst for promoting hydrolysis on the surface of the support (if added), a method of applying a solution of the organosilicone compound onto the support, after applying to the support Drying atmosphere, drying temperature,
It is necessary to change the process parameters such as the drying time in various ways and to control the amount of the addition-reactive functional group retained on the support surface so as to be within the above range.

The amount of the addition-reactive functional group retained on the surface of the support can be determined by measuring the surface after the treatment with the support by an appropriate method such as a fluorescent X-ray analysis method or an infrared absorption method. It can be determined by quantifying the amount of a certain Si atom, quantifying the amount of multiple carbon-carbon bonds, or the like. When a PS plate is formed using a support to which an addition-reactive functional group is bonded (addition-reactive support), the printing stain is reduced only by treating the support using only the organic silicone compound of the formula (1). May occur. That is, a photopolymerizable photosensitive composition is generally applied to a support to which an addition-reactive functional group is bonded to form a photosensitive layer, and imagewise exposure is performed on the photosensitive layer to cause image-wise interfacial photoadhesion. After that, when the unexposed portion is removed with a developing solution, a photopolymerized adhesive film according to the light pattern remains on the support. Then, when the ink and water are applied thereto, the ink adheres to the imagewise exposed portion where the photopolymerization and adhesion are performed, and the water adheres to the unexposed portion. So, if you use this as a printing plate,
When the above-mentioned organic silicone compound is used alone, excess organic functional groups are likely to be present in unexposed areas where water is to adhere. May be done. Therefore, in order to prevent this printing stain, an addition-reactive functional group (R ₁ )
In addition to this, it is preferable to fix a large number of OH groups to enhance the hydrophilicity. Preferably, in addition of the organosilicone compound (1) represented by the formula (1): R ₁ Si (OR ₂ ) ₃ in bonding the addition-reactive functional group to the support surface, the following formula (3): Si
(OR ₄ ) ₄ (where -OR ₄ is a hydrolyzable alkoxy group,
Alkoxyalkoxy, aryloxy or -OCOC
H ₃ and R ₄ may be the same or different from R ₂ . The organic silicone compound (3) represented by the formula (2) is used in combination, and the formula (2):

[0023]

Embedded image

At the same time as combining the reaction sites represented by

[0025]

Embedded image

It is preferable to bind a hydrophilic site represented by Here, in the formula, R ₃ is an alkyl group, represents a bond to a hydrogen atom, or adjacent another Si atom, R ₃
Is most preferably a hydrogen atom from the viewpoint of hydrophilicity. When R ₃ is other than a hydrogen atom, hydrophilicity can be enhanced by washing the surface with an alkaline solution, if necessary. The mixing ratio between the organosilicone compound (1) of the formula (1) and the organosilicone compound (3) of the general formula (3) depends on the binding (planting) efficiency of each compound to the support surface depending on the properties of the support. Because of the variation, a suitable range cannot be determined. However, specifically, the support treatment is performed by changing the ratio of the two in various ways, and the condition that the photo-adhesiveness based on the addition-reactive functional group R ₁ and the hydrophilicity derived from the partial structure (4) are compatible. Is determined experimentally and used. In any case, the density of the addition-reactive functional group should be within the above range. Specifically, the mixing molar ratio of the organic silicone compound (3) to the organic silicone compound (1) is 0.05 to 0.05.
200 is suitable, but preferably 0.2 to 100, and more preferably 1 to 40. Further, within this range, as the amount of the hydrophilic group derived from the organosilicone compound (3) of the formula (3) increases, the hydrophilicity of the non-image portion increases.
However, even when the density of the hydrophilic group is low, the density of the hydrophilic group can be improved by hydrophilizing the addition-reactive functional group.

The bonding of the addition-reactive functional group to the surface of the support can be broadly classified, in addition to the above-mentioned method (hereinafter referred to as SC method), which comprises using the organic silicone compound as it is, using an organic silicone compound. A method comprising using an organic-inorganic composite in which an addition-reactive functional group is fixed to an inorganic polymer containing -Si-O-Si- bonds obtained by hydrolysis and polycondensation (hereinafter referred to as SG). Called the law). When this organic-inorganic composite is applied to a support and dried, if the support is a metal or its oxide, the inorganic polymer portion adheres to the substrate, and the addition-reactive functional group remains on the support surface as it is .

In the case of the SC method, the position at which the addition-reactive functional group is bonded to the support is likely to be a position having specific properties on the support, and it is difficult to uniformly distribute the functional group on the support. It may be. That is, a covalent bond with the Si atom is formed only at a specific acid point or base point, and the distribution of the addition-reactive functional group is easily controlled by the distribution of acid points or base points on the support surface. Therefore, unevenness may occur in the optical adhesive strength and the non-image area hydrophilicity. In such situations, it is advantageous to follow the SG method. In detail, besides the SC method and the SG method, in addition to the intermediate method, for example, a part or all of OR ₂ in the organic silicone compound (1) of the formula (1): R ₁ Si (OR ₂ ) ₃ is hydrolyzed. It is also possible to use an organosilicone compound having two or three molecules bonded as a starting material. According to the method for attaching an addition-reactive functional group by the SG method,
The organosilicone compound (1) of the formula (1) is optionally mixed with the organosilicone compound (3) of the formula (3) in a desired mixing ratio, and the addition reaction is carried out in a liquid, if necessary in the presence of a catalyst. An inorganic polymer in which the central Si atom is connected by a -Si-O-Si- bond by causing hydrolysis at -OR ₂ and -OR ₄ without causing a reaction at the functional group R ₁ and performing a polycondensation reaction. This is applied to the surface of a support as a liquid composition containing and optionally dried to bind the addition-reactive functional group on the support. When the SG method is used, the distribution of the addition-reactive functional groups bonded and immobilized on the support surface is hardly influenced by the distribution of chemical properties such as acid sites and base sites on the support surface. When an organic silicone compound (3) is used in combination with the organic silicone compound (1) as a starting material, an addition-reactive functional group site represented by the above formula (2) and a hydrophilic group represented by the above formula (4) are used. Since the relative ratio to the site is substantially determined by the charge ratio of the organic silicone compound (1) and the compound (3), there is an advantage that the route for determining the prescription for obtaining the optimum surface is more orderly than the SC method.

Specific examples of the organosilicone compound (1) represented by the above formula (1) used in the present invention include the following. CH ₂ = CH-Si (OCOCH ₃ ) ₃ , CH ₂ = CH-Si (OC ₂ H ₅ ) ₃ , CH ₂ = CHSi (O
CH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) ₃ , CH ₂ = CHCH ₂ NH (CH ₂ ) ₃ Si
(OCH 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 = C (CH ₃ ) COO- (CH ₂ ) ₃ -Si (OCH ₃ )
_{3, CH 2 = C (CH} 3) COO- (CH 2) 3 -Si (OC 2 H 5) 3, CH 2 = C (CH 3) C
OO- (CH ₂ ) ₄ -Si (OCH ₃ ) ₃ , CH ₂ = C (CH ₃ ) COO- (CH ₂ ) ₅ -Si (OCH
₃ ) ₃ , CH ₂ = CHCOO- (CH ₂ ) ₄ -Si (OCH ₃ ) ₃ ,

[0030]

Embedded image

CH ₂ = CH—SO ₂ NH— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ ,

[0032]

Embedded image

HC≡C-Si (OC ₂ H ₅ ) ₃ , CH ₃ C≡C-Si (OC ₂ H ₅ ) ₃
,

[0034]

Embedded image

CH ₂ = CHCH ₂ O-Si (OCH ₃ ) ₃ , (CH ₂ = CHCH ₂ O) ₄ S
i, 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- (C
H ₂ ) ₂ -SCH ₂ -Si (OCH ₃ ) ₃ ,

[0036]

Embedded image

CH ₃ COCH = C (CH ₃ ) —O—Si (OCH ₃ ) ₃ . Specific examples of the organic silicone compound (3) represented by the formula (3) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra (n-propoxy) silane, tetra (n-butoxy) silane, and 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. In both cases where the SC method and the SG method are used to attach the addition-reactive functional group to the support surface, the type of solvent, the method of applying to the support, the drying method, and the like are common. In this case, it is necessary to prepare an inorganic polymer composition holding the addition-reactive functional group in advance. Preferred examples are shown below. SG by subjecting the organosilicone compounds (1) and (3) represented by the formulas (1) and (3) to polycondensation together with hydrolysis
Solvents that can be used to make the composition suitable for the process include methanol, ethanol, propanol, isopropanol,
Alcohols such as ethylene glycol and hexylene glycol. The amount of the solvent used is generally based on the total weight of the organic silicone compounds (1) and (3) used.
It is 0.2 to 500 times, preferably 0.5 to 50 times, and more preferably 1 to 3 times. If the amount used is less than 0.2 times, the reaction solution tends 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 added to hydrolyze the organosilicone compound is generally from 0.5 to 1000 mol, preferably from 1 to 100 mol, per mol of the organosilicone compound.
Mol, more preferably 1.5 to 10 mol. When the amount of water is less than 0.5 mol per mol of the organic silicone compound, the progress of the hydrolysis and the subsequent polycondensation reaction becomes very slow, and it takes several days for stable surface treatment to be possible. But not preferred. On the other hand, when the amount of water is more than 1000 moles per mole of the organic silicone 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. In many cases, it is difficult to perform the coating operation stably.

The reaction temperature for preparing a composition suitable for the SG method is usually from room temperature to about 100 ° C., but depending on the type of catalyst described below, a temperature below room temperature or above 100 ° C. may be used. it can. It is also possible to carry out the reaction at a temperature higher than the boiling point of the solvent, and 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 per mole of the organic silicone compound, based on the total amount of the organic silicone compound (1) and the organic silicone compound (3) optionally added.
Mol, preferably 0.002 to 0.7 mol, more preferably
0.003 to 0.4 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, the reaction temperature is preferably in the range of 40 ° C. to 100 ° C. However, when a strong acid such as sulfuric acid or nitric acid is used as a catalyst, The range of 10 ° C to 60 ° C is good. When phosphoric acid is used as a catalyst, the reaction can be performed at 10 ° C to 90 ° C. In many cases, heat is applied in the process of preparing the composition used in the SG method, and in the process of applying and drying the composition on the substrate, but if a volatile acid is used as a catalyst, it will volatilize and adhere to surrounding devices. And may corrode this.
When the present method is used in a step mainly using iron as a material, it is preferable to use nonvolatile sulfuric acid and / or phosphoric acid as a catalyst. As described above, the composition comprising the organic silicone compound represented by the formulas (1) and (3), the organic solvent, water, and optionally the catalyst is mixed at an appropriate reaction temperature, reaction time, and optionally When the reaction is performed under agitation conditions, a polycondensation reaction occurs along with the hydrolysis, and a polymer or a colloidal polymer containing a Si—O—Si bond is generated, and the viscosity of the liquid composition increases to form a sol. When preparing a sol using both the organosilicon compounds represented by the formulas (1) and (3), both organosilicon compounds may be loaded into the reaction vessel from the beginning of the reaction, or only one of them may be used. After the hydrolysis and polycondensation reaction have proceeded to some extent, the other organosilicone compound may be added to terminate the reaction. When the sol solution used in the SG method is left at room temperature, the polycondensation reaction continues to proceed, and may be gelled. Therefore, the sol liquid once prepared by the above method can be diluted in advance with a solvent to be used for dilution at the time of coating the support, so that gelation of the sol liquid can be prevented or delayed.

In both the SC method and the SG method, in order to bond a desired amount of an organosilicone compound or an addition-reactive functional group on a support, or to prepare an organosilicone compound or an addition-reactive functional group on the support. It is preferable to adjust the concentration by adding a solvent before applying these treatment liquids to the support in order to eliminate the distribution unevenness of the treatment liquid. Alcohols, especially methanol, are suitable as solvents for this purpose, but other solvents, organic compounds,
Inorganic additives, surfactants and the like 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, methyl lactate, ethyl lactate, acetylacetone, ethylene glycol and the like can be mentioned. Examples of the organic compound that can be added include an epoxy resin, an acrylic resin, a butyral resin, a urethane resin, a novolak resin, a pyrogallol-acetone resin, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, and polypropylene glycol. Examples of the inorganic additive include colloidal silica and colloidal alumina. ethylene glycol,
High-boiling solvents such as ethylene glycol monomethyl ether work to increase the stability of the solution diluted to the concentration applied to the support and ensure the reproducibility of the addition-reactive functional groups bound to the support. . Organic compounds such as a novolak resin and a pyrogallol-acetone resin have the same effect, but have the side effect of lowering the hydrophilicity of the surface of the resulting support, and the amount of addition needs to be finely adjusted.

When a sol solution or a liquid composition suitable for the SG method is applied to the surface of a support and then air-dried or heated and dried, the inorganic polymer formed of Si—O—Si bonds is gelled, and at the same time, the surface of the support is And covalently bond with The drying is carried out to evaporate the solvent, residual water and optionally the catalyst, but the step can be omitted depending on the purpose of use of the treated support. Also in the SC method, this drying step includes a solvent,
In addition to the meaning of volatilization of residual water and the like, it has the meaning of ensuring adhesion between the organic silicone compound and the support.
Therefore, depending on the purpose, after the drying is completed, the temperature may be further increased and the heating may be continued. It is preferred that the maximum temperature during drying and, optionally, subsequent heating be in a range in which the addition-reactive functional group R ₁ does not decompose. Therefore,
Drying temperature conditions that can be used are room temperature to 200 ° C, preferably room temperature to 150 ° C, more preferably room temperature to 120 ° C. Drying time is generally 30 seconds to 30 minutes, preferably 4 seconds.
The duration is 5 seconds to 10 minutes, more preferably 1 minute to 3 minutes.
As the method of applying the liquid composition (organic silicone compound or its solution or sol solution) used in the present invention, various types such as brush coating, dip coating, atomizing, spin coating and doctor blade coating can be used. The thickness is determined in consideration of the shape of the support surface, the required thickness of the processed film, and the like. When the support is a metal plate, when treating the metal surface, it is preferable that the surface is a clean surface free of oils and the like, except when the support is significantly contaminated by oils and the like. Can be used as is. If necessary, the metal surface may be roughened by mechanically roughening or electrolytic deposition, electrolytic etching, or the like. In addition, those in which a natural oxide film is formed on the metal surface or those whose surface is positively oxidized by anodic oxidation, contact oxidation or the like can be suitably used.
Of course, an oxide film different from the base metal may be provided on the surface by thermal spraying, coating, CVD, or the like. Not only oxides but also those provided with a surface layer different from the metal surface by, for example, a surface silicate treatment or a surface nitridation treatment can be used.

According to the above-described method, a functional group capable of causing an addition reaction by a radical can be bonded to a support by a covalent bond, so that a highly sensitive photopolymerizable material having sensitivity to light of 400 to 1000 nm can be further provided thereon. By coating the optical layer, a laser-sensitive high-sensitivity PS plate having excellent adhesion between the photosensitive layer and the support can be formed. That is, a laser beam with a narrowed beam is scanned on the plate surface, radicals are generated in a portion irradiated with the laser beam, and the radicals are used to polymerize the photosensitive layer, and the photosensitive layer is bonded to the support surface. An addition reaction is caused at the interface with the addition-reactive functional group, and a polymerization pattern as in a manuscript such as a character manuscript or an image manuscript is formed directly on the plate surface. A printing plate can be obtained by elution and removal.

According to the present invention, examples of the high-sensitivity photopolymerizable composition having sensitivity to visible light applied on a support having an addition-reactive functional group bonded thereto include, for example, the following (i) to (i). Compositions consisting of iv) are preferred,
The scope of the present invention is not limited thereto as long as it is a photopolymerizable photosensitive composition having high sensitivity to light of 1000 nm. (I) a polymerizable compound having an addition-polymerizable unsaturated bond, (ii) a linear organic polymer, (iii) a photoinitiator, and (iv) 400 to 1000 nm, preferably 400 to 75.
A sensitizer capable of absorbing 0 nm radiation and spectrally sensitizing the photoinitiator (iii). The photopolymerizable composition capable of being exposed to laser light may further contain a compound (v) selected from the group consisting of the following (a), (b) and (c), if necessary. (A) Compound having R ¹ R ² N— R ¹ and R ² are each represented by —OR ³ , —CO—R ³ , —CO—C ₆ H as a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a substituent. _{Four
^{- (B) n, -COOR 3}} , -NH-CO-R 3, -NH-CO-C 6 H 4 -
(B) _n ,-(CH ₂ CH ₂ O) _m -R ³ , a halogen atom (F, Cl,
Represents a substituted alkyl group having 1 to 18 carbon atoms having Br and I). Here, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and B represents a dialkylamino group, a hydroxyl group,
Represents an acyloxy group, a halogen atom, or a nitro group. n
Represents an integer of 0 to 4, and m represents an integer of 1 to 20. (B) a thio compound represented by the following general formula (5)

[0044]

Embedded image

(C) a compound represented by the following general formula (6)

[0046]

Embedded image

In the formula, R ⁴ represents an alkyl group or a substituted alkyl group, an aryl group or a substituted aryl group, and R ⁵ represents a hydrogen atom or an alkyl group or a substituted alkyl group. Also,
R ⁴ and R ⁵ represent a group of non-metallic atoms necessary for forming a 5- to 7-membered ring which may combine with each other to contain a heteroatom selected from oxygen, sulfur and nitrogen atoms. R ⁶ , R
⁷ , R ⁸ and R ⁹ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, Or a substituted or unsubstituted heterocyclic group, wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ are
Two or more groups may combine to form a cyclic structure. However, at least one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is an alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation.

Hereinafter, each component of the photopolymerizable composition that can be used in the present invention will be described in detail. The polymerizable compound having an addition-polymerizable unsaturated bond (component (i)) has at least one terminal ethylenically unsaturated bond.
, Preferably two or more compounds. For example, those having chemical forms such as monomers, prepolymers, that is, 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. An amide of a carboxylic acid and an aliphatic polyamine compound is exemplified. 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, 1,3-butanediol diacrylate, and 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, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (Acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

Examples of the methacrylate 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- (acryloxy ethoxy)
Phenyl] dimethylmethane and the like. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetramethacrylate. Examples of the crotonic acid ester include 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. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Further, a mixture of the above-mentioned ester monomers can be mentioned. Further, 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, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. As another example, two molecules per molecule described in JP-B-48-41708 are used.
A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a hydroxyl group-containing vinyl monomer represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Is mentioned. CH ₂ CC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ ) Also, as described in JP-A-51-37193. Urethane acrylates, JP-A-48-6418
No. 3, JP-B-49-43191, JP-B 52-304
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-90-90 can be used. Furthermore, Japan Adhesion Association magazine vol.20, No.7, pages 300-308 (1
984) as photocurable monomers and oligomers. In addition, these use amounts are generally 5 to 50% by weight based on all components.
(Hereinafter simply referred to as “%”), preferably 10 to 4
0%.

The linear organic high molecular polymer (component (ii)) that can be used in the present invention includes a linear organic high polymer compatible with an addition-polymerizable unsaturated bond-containing compound (component (i)). Any polymer may be used as long as it is a polymer. Preferably, a linear organic high molecular polymer having a group from which hydrogen is easily extracted by a sulfur radical is selected, and preferably, water or weak alkaline water soluble or swellable, which enables water development or weak alkaline water development. A linear organic high molecular polymer is selected. The linear organic high molecular polymer functions as a film-forming agent of the composition, and is selected and used depending on the type of a developer to be used, that is, a developer of water, weakly alkaline water, or an organic solvent developer. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Application Laid-Open No.
44615, JP-B-54-34327, JP-B-58
-12577, JP-B-54-25957, JP-A-5
4-92723, JP-A-59-53836 and JP-A-59-71048, namely, methacrylic acid copolymer, acrylic acid copolymer, acrylic acid copolymer, Examples include itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. In addition, an acidic cellulose derivative having a carboxylic acid group in a side chain is also included. In addition, those obtained by adding a cyclic anhydride to an addition polymer having a hydroxyl group are also 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 linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. Linear organic high molecular polymer (component (ii))
Is a group whose main chain or side chain is preferably a group whose hydrogen is easily extracted by a sulfur radical, preferably a group whose hydrogen can be extracted more easily than a methyl group of toluene when hydrogen is extracted by a methyl radical. Preferably, R ¹⁰ R ¹¹ C = CH—CHR ¹² —, —CHR ¹³ Ar ₁ ,

[0052]

Embedded image

--C ₆ H ₄ CHAr ₂ Ar ₃ or

[0054]

Embedded image

Having the following. Wherein R ¹⁰ , R ¹¹ ,
R ¹² and R ¹³ represent a hydrogen atom, an alkyl group, an alkenyl group or an optionally substituted aryl group, Ar ₁ , Ar ₂ and Ar
₃ represents an aryl group which may be substituted. These linear organic high polymers can be incorporated in any amount in the total composition. However, if the amount exceeds 90% based on the weight of the entire composition excluding the weight of the solvent, no favorable result is obtained in view of the strength of the formed image and the like. Therefore, the amount of the linear organic high molecular polymer is generally 20 to 90%, preferably 30 to 80%. The weight ratio of the photopolymerizable ethylenically unsaturated compound (component (i)) and the linear organic high molecular polymer (component (ii)) is generally 1/9 to 7/3, preferably 3/7 to 3/7. 5/5.

The photoinitiator (component (iii)) that can be used in the present invention includes benzyl, benzoin,
Benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, trihalomethyltriazine compound, ketoxime ester, and the like, US Pat.
No. 850,445, for example, photoreducing dyes such as rose bengal, eosin, erythrosine and the like, or a system using a combination of a dye and an initiator, for example, a complex starting system of a dye and an amine (Japanese Patent Publication No. 44-20189). JP, JP-B-45-37377, etc.), a system of hexaarylbiimidazole, a radical generator and a dye
Hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528, JP-A-54-155292, etc.), and dye-organic peroxide system (JP-B-62-1641, 1959-15
04, JP-A-59-140203, JP-A-59-1
No. 89340, U.S. Pat. No. 4,766,055, JP-A-62-174203 and the like, and a system of a dye and an active halogen compound (JP-A-54-15102,
JP-A-58-15503, JP-A-63-178105
JP-A-63-258903, JP-A-2-6305
No. 4), a system of a dye and a borate compound (JP-A-6
2-143044, JP-A-62-150242, JP-A-64-13140, JP-A-64-13141,
JP-A-64-13142, JP-A-64-13143
JP-A-64-13144, JP-A-64-1704
No. 8, JP-A-64-72150, JP-A-1-2290
03, JP-A-1-298348, JP-A-1-138
No. 204, JP-A-2-179463, JP-A-2-24
No. 4050).

The above hexaarylbiimidazole includes 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-bromophenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole, 2,2'-bis (o-
(Chlorophenyl) -4,4 ', 5,5'-tetra (m-
Methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'
-Tetraphenylbiimidazole, 2,2'-bis (o
-Nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like. Examples of ketoxime esters include 3-benzoyloximinobtan-2-one,
Acetoxy iminobutan-2-one, 3-propionyloxy iminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-
1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-
ON and the like.

Preferred sensitizers (component (iv)) that can be used in the present invention include the following. For example, cyanine dye, merocyanine dye,
(Keto) coumarin dye, (thio) xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, aminoketone dye, squarylium dye, pyridinium dye, (thia) pyrylium dye,
Porphyrin dye, triarylmethane dye, (poly)
It is a methine dye, an aminostyryl compound and an aromatic polycyclic hydrocarbon. Among these, preferred sensitizers are cyanine dyes, merocyanine dyes, (keto) coumarin dyes, (thio) xanthene dyes, (poly) methine dyes, and aminostyryl compounds.

Examples of cyanine dyes include those described in
No. 13140 is mentioned. Examples of the merocyanine dyes include those described in JP-A-59-89303, JP-A-2-244050, and JP-A-2-179643. Examples of (keto) coumarin dyes include Polymer. Eng. Sci, 23 : 1022 (198
3) and those described in JP-A-63-178105. Examples of (thio) xanthene dyes include those described in JP-A-64-13140 and JP-A-1-126302. Examples of (poly) methine dyes include Japanese Patent Application Nos. 3-152062 and 3-2320.
No. 37 and No. 3-264494. Examples of the aminostyryl compound include JP-A-55-50001, JP-A-2-69, and JP-A-2-6.
No. 3053 and JP-A-2-229802. The above compound (iv) capable of absorbing light of 400 nm to 1000 nm and spectrally sensitizing a photoinitiator can be suitably used alone or in combination in the photopolymerizable photosensitive composition of the present invention. , More preferably 400 nm ~
The following compounds are used which absorb light in the range of 750 nm and can spectrally sensitize the photoinitiator. As the cyanine dye, those according to the following general formula are particularly useful.

[0060]

Embedded image

In the formula, Z ₁ and Z ₂ are heterocyclic nuclei usually used for cyanine dyes, especially thiazole nuclei, thiazoline nuclei, benzothiazole nuclei, naphthothiazole nuclei, oxazole nuclei, benzoxazole nuclei, naphthoxazole nuclei. , Necessary to complete the tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthymidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus or indolenine nucleus Represents an atomic group. These nuclei include a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, and an acetyl group. , Acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group,
It may be substituted by a nitro group or the like. L _1, L
₂ and L ₃ represent a methine group or a substituted methine group. Examples of the substituted methine group include a lower alkyl group such as a methyl group and an ethyl group, and a methine group substituted with an aralkyl group such as a phenyl group, a substituted phenyl group, a methoxy group, an ethoxy group, and a phenethyl group.

When L ₁ and R ₁ , L ₃ and R ₂ and m = 3, L ₂ and L ₂ may be alkylene-bridged to form a 5- or 6-membered ring. R ₁ and R ₂ are a lower alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), a carboxy group, a sulfo group, a hydroxy group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, A substituted alkyl group such as a phenyl group (preferably an alkylene moiety having a C ₁ -C
₅ ), for example, β-sulfoethyl, γ-sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, 2-
[2- (3-sulfopropoxy) ethoxy] ethyl, 2
-Hydroxysulfopropyl, 2-chlorosulfopropyl, 2-methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2,2,3,
3'-tetrafluoropropyl, 3,3,3-trifluoroethyl; N of allyl group and other ordinary cyanine dyes
-Represents a substituted alkyl group used for the substituent. m
₁ represents ₁ , 2 or 3. X ₁ ^- represents a halogen ion.

Particularly preferred cyanine dyes are:

[0064]

Embedded image

As the merocyanine dye, those according to the following general formula are particularly useful.

[0066]

Embedded image

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent the groups listed for R ¹ and R ² , or an alkylthio group, an arylthio group, an amino group or a substituted amino group. X represents a nonmetallic atom group necessary to form a 5- to 7-membered ring. Z represents a nonmetallic atom group necessary for forming a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring. Among these, particularly preferred merocyanine dyes are as follows.

[0068]

Embedded image

Further, merocyanine dyes according to the following general formula are also particularly useful.

[0070]

Embedded image

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl 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. X represents a non-metallic atomic group necessary for forming a nitrogen-containing 5-membered heterocyclic ring. Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group,
Represents an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group, and may be bonded to Y to form a ring. Among these, particularly preferred merocyanine dyes are as follows.

[0072]

Embedded image

[0073]

Embedded image

As the (keto) coumarin dye, those according to the following general formula are particularly useful.

[0075]

Embedded image

In the formula, R _{1 to} R ₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted Represents an amino group. R _{1 to} R ₄ may form a ring composed of a nonmetallic atom together with the carbon atom to which it can be bonded. R ₅ is a hydrogen atom,
Alkyl group, substituted alkyl group, aryl group, substituted aryl group, heteroaromatic group, substituted heteroaromatic group, cyano group, alkoxy group, substituted alkoxy group, carboxy group,
Represents an alkenyl group or a substituted alkenyl group. R ₆ is R ₇
Or a -Z-R _7, R ₇ is selected from the range of the R _5. Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R
₅ and R ₆ may together form a ring composed of non-metallic atoms. X represents O, S, NH, or a nitrogen atom having a substituent. Y is an oxygen atom or = CG ₁ G ₂ , G ₁
And G ₂ may be the same or different and include a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, Represents an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G ₁ and G ₂ are not hydrogen atoms. Also G ₁ and G
₂ may form a ring composed of non-metallic atoms together with the carbon atoms that it can form. Among them, particularly preferred (keto) coumarin dyes are as follows.

[0077]

Embedded image

As the xanthene dye, those according to the following general formula are particularly useful.

[0079]

Embedded image

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, X represents a halogen ion, Y represents an alkyl group, Represents an aryl group, a hydrogen atom or an alkali metal.
Among these, particularly preferred xanthene dyes are as follows.

[0081]

Embedded image

As the (poly) methine dye, those according to the following general formula are particularly useful.

[0083]

Embedded image

In the formula, Z ¹ and Z ² each represent a nonmetallic atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring usually used in cyanine dyes. R ¹ and R ² each represent an alkyl group. Q ¹ and Q ² are combined to form a 4-thiazolidinone ring, a 5-thiazolidinone ring,
4-imidazolidinone ring, 4-oxazolidinone ring, 5
-An oxazolidinone ring, a 5-imidazolidinone ring or 4
-Represents an atomic group necessary for forming a dithiolanone ring.
L ¹ , L ² , L ³ , L ⁴ and L ⁵ each represent a methine group. m represents 1 or 2. i and h each represent 0 or 1. l represents 1 or 2. j and k each represent 0, 1, 2 or 3. X ^- represents a counter anion. Among them, particularly preferred (poly) methine dyes are as follows.

[0085]

Embedded image

[0086]

Embedded image

As the aminostyryl compounds, those according to the following general formula are particularly useful.

[0088]

Embedded image

In the formula, ring A is a benzene ring or a naphthalene ring
And these may have a substituent. X is divalent
Represents a divalent or divalent group. R¹Represents an alkyl group;^Two
And R^ThreeIs hydrogen, alkyl, alkoxy, or alkyl
A luthio group;¹And R ^TwoAre connected to each other
Good. l represents 0, 1 or 2. Particularly suitable among them
The aminostyryl compounds are as follows.

[0090]

Embedded image

As the component (v) which can be used in the present invention, those belonging to the group (a) include various amines, and specific examples are as follows.

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

Specific examples of the thio compound represented by the formula (5) belonging to the group (b) of the component (v) include compounds having R ⁴ and R ⁵ as shown in the following table. However, in the case of compounds 15 to 46, they represent a group formed by bonding of R ⁴ and R ⁵ .

[0097]

TABLE 1 Compound ^{No. R 4 R 5 1 -H -H} 2 -H -CH 3 3 -CH 3 -H 4 -CH 3 -CH 3 5 -C 6 H 5 -C 2 H 5 6 - _{C 6 H 5 -C 4 H 9} 7 -C 6 H 4 Cl -CH 3 8 -C 6 H 4 Cl -C 4 H 9 9 -C 6 H 4 -CH 3 -C 4 H 9 10 -C 6 H ₄ -OCH ₃ -CH ₃ 11 -C ₆ H ₄ -OCH ₃ -C ₂ H ₅ 12 -C ₆ H ₄ -OC ₂ H ₅ -CH ₃ 13 -C ₆ H ₄ -OC ₂ H ₅ -C ₂ H ₅ 14 −C ₆ H ₄ −OCH ₃ −C ₄ H ₉ ─────────────────────────────────── 15 − (CH ₂ ) ₃ −16 − (CH ₂ ) ₂ −S −17 −CH (CH ₃ ) −CH ₂ −S −18 −CH ₂ −CH (CH ₃ ) −S −19 −C (CH ₃ ) ₂ -CH ₂ -S-20 -CH ₂ -C (CH ₃ ) ₂ -S-21-(CH ₂ ) ₂ -O-22 -CH (CH ₃ ) -CH ₂ -O-23 -C (CH ₃ ) ₂ -CH ₂ -O-24 -CH = CH-N (CH ₃ )-25-(CH ₂ ) ₃ -S-26-(CH ₂ ) ₂ CH (CH ₃ ) -S-27-(CH _{2) 3 -O - 28 - (} CH 2) 5 - 29 -C 6 H 4 -O - 30 -N = C (SCH 2) -S - 31 - _{C 6 H 4 -NH- 32 -C 6} H 4 -NC 2 H 5 - 33 (1) 34 (2) 35 (3) 36 (4) 37 (5) 38 (6) 39 (7) 40 (8 41 (9) 42 (10) 43 (11) 44 (12) 45 (13) 46 (14) The formulas for R ⁴ and R ^{5 in} Table 1 above are as follows.

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image Specific examples of compounds belonging to the group (c) of the component (v) include those described in JP-A-2-179643. The concentration of the photoinitiator (component (iii)) that can be 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 are produced. The amount of the photoinitiator in the present invention is generally 0.01 to 60 with respect to the total of the polymerizable compound (component (i)) and the linear organic high molecular polymer (component (ii)).
%, Preferably 1 to 30%. The ratio of the photoinitiator (component (iii)) to the sensitizer (component (iv)) is generally based on 1 part by weight of the sensitizer (component (iv)). 0.05 to 30 parts by weight, preferably 0.1 to 10 parts by weight
Parts by weight, more preferably 0.2 to 5 parts by weight. When component (v) is added, the amount of addition is determined by the amount of the photoinitiator (component (ii)
i)) It is generally 0.05 to 50 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 0.2 to 10 parts by weight per part by weight.

The photopolymerizable photosensitive composition used in the present invention comprises, besides the above basic components, unnecessary compounds (component (i)) which can be polymerized during the production or storage of the photosensitive composition. It is desirable to add a small amount of a thermal polymerization inhibitor to prevent thermal polymerization. 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 amount of the thermal polymerization inhibitor added is generally 0.001 to 10%, preferably 0.01 to 10% by weight of the total composition.
1 to 5%. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. The amount of the higher fatty acid derivative added is generally 0.1 to about 20% based on the total weight of the composition,
Preferably it is 0.5 to 10%. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. Dyes and pigments are generally added in an amount of 0.1 to 0.1% by weight of the total composition.
10%, preferably 0.5-5%. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

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 concentration of the solid content in the coating solution is generally 2 to 50%, preferably 5 to 30%.
%. The amount of coating is 0.1 to 10 g /
m ² , preferably 0.5 to 5 g / m ² .

[0103] Hereinafter, addition-reactive functional group R ₁ as CH ₂ =
Organosilicon compound of formula (1) having CH-group (1)
An example in which the surface of an aluminum plate is treated with a liquid composition according to the SG method and a photosensitive composition is applied to form a laser-sensitive high-sensitivity PS plate will be described in more detail. Take Si (OC ₂ H ₅ ) ₄ and CH ₂ CHCHSi (OCOCH ₃ ) ₃ in a beaker, add acetic acid as a catalyst, and further add water as a hydrolyzing agent. Add ethanol as a solvent to this mixture,
Stir at room temperature to form a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirring mechanism and a reflux cooling device, and immersed in an oil bath at room temperature. Raise the bath temperature to 80-90 ° C with stirring. The solution becomes more viscous with the progress of the reaction. At this time, it is considered that a polymer represented by the following formula exists in the solution.

[0104]

Embedded image

The liquid composition thus obtained is diluted with an appropriate solvent and applied on a metal surface, and the solvent is volatilized by applying heat to obtain an addition-reactive support having a vinyl group and a hydroxyl group on the surface. The body is obtained. Laser light sensitive high sensitivity P
In order to construct the S plate, for example, trimethylolpropane tri (acryloyloxypropyl) ether is appropriately combined with a linear organic polymer, a photoinitiator, a sensitizer, a thio compound of the formula (5), a surfactant and the like. The photopolymerizable composition mixed at an appropriate ratio is applied to the surface of the vinyl-bonded metal and dried. Next, when the obtained PS plate is image-exposed, radical polymerization occurs in a place where light is applied, and a covalent bond is generated between the photosensitive layer and the metal surface at the same time as the photosensitive layer is solidified. In other words, the radical polymerized film forms a new covalent bond with the vinyl group implanted covalently on the metal surface, and adheres to the radical polymerized film. On the other hand, in places where light does not shine, polymerization of the coating film does not occur, and no covalent bond is formed between the coating film and the metal surface.
Only the part of the coating film which is not exposed to the light can be dissolved and removed.

In this way, a radical polymer film firmly bonded to the support is formed where light is applied, and the surface of the support is exposed where light is not applied, and OH groups and vinyl groups are attached to the surface. It comes out. In order to use this system as a printing plate, ink must be applied to the radical polymerized film portion and water must be applied to the non-image portion where the support surface is exposed, so that the image cannot be turned on / off. Must. The adhesion of the ink to the radical polymer film portion is not a problem as long as both are lipophilic. In order for water to spread to the non-image area and keep ink away, the non-image area must have sufficient hydrophilicity, and the balance between OH groups and vinyl groups on the metal surface is problematic. Becomes

[0107] is sufficiently high density of surface OH groups (Kaowodasu OH groups on the outermost surface 100 Å ² per example, more than 0.5 units), only the way in treated metal surfaces of the present invention is exposed, That part functions as a non-image part. Low density of surface OH groups (Kaowodasu OH groups on the outermost surface, for example, per 100 Å ^2, 0.01 units), vinyl groups becomes relatively large, if the lipophilic properties can no longer be ignored , A hydrophilic treatment of the vinyl group is required. This can be performed, for example, by a method of coordinating a vinyl group with a sulfate ion and then hydrolyzing it to convert it to an alcohol, a method of oxidatively cleaving a Si—C bond to convert it to silanol, or the like. Alternatively, a hydrophilic substance such as potassium silicate may be contained in the developer, and the hydrophilic substance may be obtained by depositing the hydrophilic substance on the non-image area. Using the addition-reactive functional group immobilized on the metal surface, a reaction contributing to adhesion can be performed in the image area, and a hydrophilic reaction or a hydrophilic treatment can be performed in the non-image area. It is easily understood that the plates offer a wide range of applications.

The increase in the adhesion between the photosensitive layer and the support in the image area has the effect of increasing the printing durability when this is used as a printing plate. . This improvement in printing durability can be observed when any of the organosilicone compounds of the formula (1) disclosed in the present specification is bonded to a support. When the radical polymerizable group in the polymer is acryl or allyl, an example in which the organosilicone compound (1) in which R ₁ is a methacryl group is bonded to a support can be given.

[0109]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited by these examples.

Example 1 A 0.30 mm thick aluminum plate was coated with a nylon brush and 40
The surface was sand-grained with an aqueous suspension of 0 mesh pumistone, and then thoroughly washed with water. After immersing in 10% sodium hydroxide at 70 ° C for 60 seconds and etching,
After washing with running water, the sample was neutralized and washed with 20% nitric acid, and then washed with water (the aluminum plate treated to this stage is hereinafter referred to as an ED substrate). The ED substrate was placed in a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed at an anode charge of 0 coulomb / dm ² . When the surface roughness was measured, it was 0.6 μ ( _Ra display). Subsequently, after immersing in a 30% sulfuric acid aqueous solution and desmutting at 55 ° C. for 2 minutes, the thickness of the anodic oxide film becomes 2.7 g / m ² in a 20% sulfuric acid aqueous solution at a current density of 2 A / dm ² . For 2 minutes (the aluminum plate treated up to this stage is hereinafter referred to as an AD substrate). Further, an AD substrate was immersed in a bath heated to 70 ° C. with a 2.5% by weight aqueous solution of No. 3 sodium silicate for 14 seconds, and then a substrate washed with air and dried was prepared (hereinafter, this substrate is referred to as an SI substrate). .

Next, a liquid composition (sol solution) (1) for the SG method was prepared according to the following procedure. 23.4 g of triacetoxyvinylsilane, 1 g of acetic acid and 3.6 g of ion-exchanged water were added to a 100 ml beaker, and 50 g of ethanol was further added, followed by stirring at room temperature for 5 minutes. The whole solution was transferred to a three-necked flask, a reflux condenser was attached, and the three-necked flask was immersed in an oil bath at room temperature. While stirring the contents of the three-necked flask with a magnetic stirrer, the bath temperature was raised to 80 ° C. in about 30 minutes.
Up. The reaction was further continued for 6 hours while maintaining the bath temperature at 80 ° C. to obtain a liquid composition (sol liquid) (1). In order to confirm whether this liquid composition can be used in the present invention, a piece of the ED substrate was dipped in the liquid composition for 5 seconds, pulled up, dried, and then measured for diffuse reflection IR spectrum. The formation of Si—O—Si bonds and the presence of surface vinyl groups and surface silanol groups were confirmed, indicating that the composition can be used as a liquid composition for metal surface treatment in the present invention. Further, three types of aluminum substrates of ED, AD and SI were coated with a wheeler at 180 rotations per minute, dried at 100 ° C. for 1 minute, and the amount of the coating was measured. / M ² . On the other hand, when the diffuse reflection IR spectrum was measured, the relative abundance ratio of vinyl groups and silanol groups in the surface treatment layer was almost 1: 1 for all three. From the above, it was confirmed that the sol liquid (1) provided a substantially constant treated surface regardless of the properties of the support.

Next, using the AD substrate and the sol solution (1), a laser-sensitive PS plate was prepared in the following procedure. The sol solution (1) was diluted with a mixed solution of methanol / ethylene glycol (weight ratio: 9/1), and was applied on an AD substrate with a wheeler so that the dry coating amount was 1 mg / m ² ,
Dry for 1 minute at ° C. On the aluminum plate thus treated, a highly sensitive photopolymerizable composition 1 having the following composition was applied to a dry coating weight of 2.0 g / m ² and dried at 80 ° C. for 2 minutes. Was formed. Photopolymerizable composition 1 Trimethylolpropane tri (acryloyloxypropyl) ether 2.0 g Linear organic polymer (B ₁ ) 2.0 g Sensitizer (C ₁ ) 0.13 g (λ _max ^THF 472 nm (ε = 7.4 × 10 ⁴ )) Photoinitiator (D ₁ ) 0.09 g Thio compound (E ₁ ) 0.08 g Fluorinated nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g

[0113]

Embedded image

A 3% by weight aqueous solution of polyvinyl alcohol (having a degree of saponification of 86.5 to 89 mol% and a degree of polymerization of 1000) was applied on the photosensitive layer so that the dry coating weight was 2 g / m ^2, and 100 ° C. And dried for 2 minutes, and the photosensitive lithographic printing plate A1
I got Comparative Example 1 A photosensitive lithographic printing plate B1 was obtained in exactly the same manner as in Example 1 except that the sol solution (1) was not applied. The photosensitive test of these photosensitive lithographic printing plates A1 and B1 was performed at a wavelength of 490.
The measurement was performed with visible light of ± 10 nm. A xenon lamp is used as the light source for the visible light, and a Kenko optical filter BP-
Monochromatic light obtained through 49 was used. Further, a heat treatment was performed at 100 ° C. for 5 minutes after exposure for the purpose of increasing the degree of film curing. For the photosensitivity measurement, use the Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd .;
Step tablets with up to 15 tiers) were used. Illuminance 0.0132mW / cm at the photosensitive film surface
^The photosensitivity was indicated by the number of clear steps of the PS step guide after exposure for 10 seconds at ² . The development is performed by using the following developer 1 for 2
The immersion was performed at 5 ° C. for 30 seconds.

(Developer 1) 1K potassium silicate 30g potassium hydroxide 15g compound (F) 3g water 1000g

[0116]

Embedded image

For the printing durability measurement, SORKZ manufactured by Heidelberg was used as a printing machine, and Clough G (N) manufactured by Dainippon Ink and Chemicals was used as the ink. In addition, the background stain on the non-image area, the stain on the blanket, and the like were visually evaluated. Table 2 shows the results.

[0118]

[Table 2] Table 2数 Number of G / S stages Printing durability Stain ──── ─────────────────────────── Example 1 Photosensitive lithographic printing plate A1 8.5 100 Comparative Example 1 Photosensitive lithographic printing plate B1 7 40 ○ ────────────────────────────── (○ な い no stain: the same applies to the following table)

In the table, the evaluation values of the printing durability were shown as relative values with the PS plate FNSA manufactured by Fuji Photo Film Co., Ltd. as 100. That is, FNSA was image-exposed with a PS film made by the company using a negative film for 1 minute from a distance of 1 m, and a water-based alkaline developer DN-3C made by the company was treated with tap water with a volume ratio of 1:
1 and a solution prepared by diluting the gum solution FN-2 manufactured by the company with tap water to a volume ratio of 1: 1 using an automatic developing machine P manufactured by the company.
After development processing in S-800H, the printing durability was determined as the number of printable sheets by using the same printing machine, and the printing durability of the printing plates of Example 1 and Comparative Example 1 was expressed as a relative value by setting this to 100. From the results in Table 2, it can be seen that by providing an addition-reactive functional group on the support surface and then forming a lithographic printing plate, it is possible to improve the printing durability without deteriorating the stain resistance. Understand.

Examples 2 to 5 Sols (2) to (5) were prepared in the same manner as in Example 1 from a mixture having the following compositions. However, sol liquid (4)
In (5) and (5), the reaction temperature was room temperature (26 ° C.), and the reaction time was 1 hour. Sol (2) Si (OC ₂ H ₅ ) ₄ 18.7 g 3-methacryloxypropyltrimethoxysilane 1.3 g Acetic acid 1.0 g Ion-exchanged water 7.2 g Ethanol 50 g Sol (3) Si (OC ₂ H 5) ₅ ) ₄ 18.7 g 3-methacryloxypropyltrimethoxysilane 1.3 g 1% phosphoric acid aqueous solution 4.2 g ion-exchanged water 3.0 g ethanol 50 g

Sol solution (4) Si (OC ₂ H ₅ ) ₄ 18.7 g 3-methacryloxypropyltrimethoxysilane 1.3 g Phosphoric acid 3.0 g Ion-exchanged water 7.2 g Methanol 50 g Sol solution (5) Si (OC ₂ H ₅ ) ₄ 18.7 g 3-methacryloxypropyltrimethoxysilane 2.5 g phosphoric acid 3.0 g ion-exchanged water 7.2 g methanol 50 g

The sol solutions (2) to (5) were applied to an AD substrate in the same manner as in Example 1, and the photopolymerizable composition 1 described in Example 1 was applied to an aluminum plate obtained by drying. Of 2.0 g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Further, in the same manner as in Example 1, a polyvinyl alcohol layer was applied, and photosensitive lithographic printing plates A2 to A
5 was obtained. Comparative Example 2 A photosensitive lithographic printing plate B2 was obtained in exactly the same manner as described above except that the sol solution was not applied. These photosensitive lithographic printing plates A2 to A5 and B2 were subjected to image exposure in the same manner as in Example 1,
A printing test was performed by heating and developing at 100 ° C. for 5 minutes. Table 3 shows the results.

[0123]

[Table 3] Table 3ゾ ル Used sol liquid G / S number of stages Example 2 Photosensitive lithographic printing plate A2 (2 ) 8.5 100 〃 3 〃 Ａ A3 (3) 8.5 100 ○ 4 〃 Ａ A4 (4) 8.5 120 〃 5 ５ A5 (5) 8.5 120 比較 Comparative example 2 〃 〃 B2 None 740 ○ 刷 Printing durability was the same as in Example 1 using FNSA. It is indicated by a relative value of 100 (the same applies to the following examples). From the results in Table 3, it can be seen that by providing the lithographic printing plate after adding the addition-reactive functional group to the support surface, it is possible to improve the printing durability without deteriorating the stain resistance. Understand.

Examples 6 to 9 Sols (6) to (9) were prepared in the same manner as in Example 1 from a mixture having the following compositions. However, the reaction temperature was room temperature (26 ° C.), and the reaction time was 1 hour. Sol (6) Si (OC ₂ H ₅ ) ₄ 18.7 g 3-acryloxypropyltrimethoxysilane 1.2 g Phosphoric acid 3.0 g Ion-exchanged water 7.2 g Methanol 50 g Sol (7) Si (OC ₂ H ₅ ) ₄ 18.7 g Allyltriethoxysilane 1.1 g Phosphoric acid 3.0 g Ion-exchanged water 7.2 g Methanol 50 g

Sol (8) Si (OC ₂ H ₅ ) ₄ 18.7 g Tetraallyloxysilane 1.3 g Phosphoric acid 3.0 g Ion-exchanged water 7.2 g Methanol 50 g Sol (9) Si (OC ₂ H 5 ) ₅ ) ₄ 18.7 g Triethoxyvinylsilane 1.0 g Phosphoric acid 3.0 g Ion-exchanged water 7.2 g Methanol 50 g

The sol liquids (6) to (9) were applied to an AD substrate in the same manner as in Example 1, and the photopolymerizable composition 1 described in Example 1 was dried and applied to an aluminum plate obtained by drying. Was applied at 2.0 g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Further, a polyvinyl alcohol layer was coated in the same manner as in Example 1, and the photosensitive lithographic printing plates A6 to A
9 was obtained. Comparative Example 3 A photosensitive lithographic printing plate B3 was obtained in exactly the same manner as described above except that the sol solution was not applied. These photosensitive lithographic printing plates A6 to A9 and B3 were subjected to image exposure in the same manner as in Example 1,
A printing test was performed by heating and developing at 100 ° C. for 5 minutes. Table 4 shows the results.

[0127]

[Table 4] Table 4ゾ ル Used sol liquid G / S number of stages Example 6 Photosensitive lithographic printing plate A6 (6 ) 8.5 110 ○ 〃 7 〃 Ａ A7 (7) 8.55 110 〃 ８ 8 〃 Ａ A8 (8) 8.5 100 〃 ９ 9 〃 ９ A9 (9) 8 100 比較 Comparative example 3 〃 Ｂ B3 None 740 ○ ───────────────────────────────────

From the results shown in Table 4, it is possible to improve the printing durability without deteriorating the stain resistance by forming a lithographic printing plate after adding an addition-reactive functional group to the support surface. You can see that there is.

Examples 10 to 12 Liquid compositions (solutions or suspensions) (1) to (3) of the SC method were prepared by the following procedures. Solution (1) 5 g of 3-methacryloxypropyltrimethoxysilane, 45 g of methanol, 0.005 phosphoric acid in a 100 ml beaker.
g and 0.05 g of ion-exchanged water were added, and the mixture was stirred at room temperature for 5 minutes and immediately diluted 100-fold with methanol. Solution (2) In a 100 ml beaker, 1 g of 3-methacryloxypropyltrimethoxysilane, ₄ g of Si (OC ₂ H ₅ ) 4, 45 g of methanol
g, phosphoric acid (0.005 g) and ion-exchanged water (0.05 g), and the mixture was stirred at room temperature for 5 minutes.
Diluted 0-fold. Suspension (3) In a 100 ml beaker, 5 g of 3-methacryloxypropyltrimethoxysilane, 45 g of methanol, 0.005 phosphoric acid.
g, and 2.5 g of ion-exchanged water, and the mixture was stirred at room temperature for 5 minutes and immediately diluted 100-fold with methanol. Example 1
The solution (1), (2) or the suspension (3) was applied to the same AD substrate as described above so that the dry coating amount was 1 mg / m ^2.
Dry at 0 ° C. for 1 minute. On the aluminum plate thus treated, a photopolymerizable composition 1 was applied in the same manner as in Example 1 to provide a photosensitive layer, and a polyvinyl alcohol layer was further applied in the same manner as in Example 1, and Lithographic printing plates A10-A
12 was obtained.

Comparative Example 4 A photosensitive lithographic printing plate B4 was obtained in exactly the same manner as in Examples 10 to 12 except that the solution or suspension of the organosilicone compound was not applied. These photosensitive lithographic printing plates A1
0 to A12 and B4 were exposed in the same manner as in Example 1;
A printing test was performed by heating and developing at 0 ° C. for 5 minutes. Table 5 shows the results.

[0131]

[Table 5] Table 5液 Liquid G / S stage used Printing property Stainability Example 10 Photosensitive lithographic printing plate A10 solution (1) 8.5 120 〃 〃 11 〃 〃 A11 solution (2) 8 110 〃 １２ 12 〃 Ａ A12 suspension (3) 8.5 110 例 Comparative example 4 〃 ４ B4 None 740 ──── ──── ────────────────────────────────

From the results shown in Table 5, it is possible to improve the printing durability without deteriorating the stain resistance by forming the lithographic printing plate after adding the addition-reactive functional group to the support surface. You can see that there is.

Examples 13 to 24 The sol solutions (1) to (9) described in Examples 1 to 9 or Example 1
The solution (1), (2) or suspension (3) described in Nos. 0 to 12 was applied to the same SI substrate as described in Example 1 so that the dry coating amount was 1 mg / m ^2, and 100 ° C. Dried for 1 minute. On the aluminum plate thus treated, a photopolymerizable composition 1 was applied in the same manner as in Example 1 to provide a photosensitive layer,
Further, a polyvinyl alcohol layer was applied in the same manner as in Example 1 to obtain photosensitive lithographic printing plates A13 to A24. Comparative Example 5 A photosensitive lithographic printing plate B5 was obtained in exactly the same manner as described above except that the sol solution or the solution or suspension of the organic silicone compound was not applied. These photosensitive lithographic printing plates A
After subjecting 13 to A24 and B5 to image exposure and heating at 100 ° C. for 5 minutes in the same manner as in Example 1, aqueous alkaline developer DN-3C manufactured by Fuji Photo Film Co., Ltd. was treated with tap water at a volume ratio of 1 to 1. : 1 and a solution prepared by diluting the gum solution FN-2 manufactured by the company with tap water at a volume ratio of 1: 1 using an automatic developing machine PS-800H manufactured by the company. Example 1
Table 6 shows the results obtained when the printing test was performed in the same manner as described above.

[0134]

[Table 6] Table 6液 Liquid G / S stage used Printing property Stain property Example 13 Photosensitive lithographic printing plate A13 Sol Liquid (1) 8.5 100 ○ １４ 14 〃 Ａ A14 〃 (2) 8.5 100 〃 １５ 15 〃 Ａ A15 〃 (3) 8.5 100 ○ １６ 16 〃 Ａ A16 〃 (4) 9.0 120 ○ 〃 17 〃 〃 A17 〃 (5) 8.5 120 ○ １８ 18 〃 〃 A18 〃 (6) 8.5 110 ○ １９ 19 〃 Ａ A19 〃 (7) 9.0 110 ○ ○ 20 〃 Ａ A20 〃 ( 8) 8.5 100 〃 21 〃 Ａ A21 〃 (9) 8 100 ２２ 22 ２２ Ａ A22 solution (1) 8 100 〃 〃 23 〃 Ａ A23 solution (2) 8 100 １００ 24 Ａ A24 suspension (3) 8.5 100 Comparative Example 5 〃 Ｂ B5 None 510 ○ ─────────────────────────── ─────────

From the results shown in Table 6, it is possible to significantly improve the printing durability without deteriorating the stain resistance by forming the lithographic printing plate after adding the addition-reactive functional group to the support surface. It can be seen that it is.

Examples 15 to 30 The sol solution (4) described in Example 4 was applied to the same AD substrate as in Example 1 so that the dry coating amount was 1 mg / m ^2.
Dry for 1 minute at ° C. On the thus treated aluminum plate, the photopolymerizable compositions 2 to 7 having the following compositions were applied so that the dry coating weight was 1.5 g / m ^2, and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Formed.

Photopolymerizable composition 2 Trimethylolpropane tri (acryloyloxypropyl) ether 2.0 g Linear organic polymer (B ₁ ) 2.0 g Sensitizer (C ₂ ) 0.13 g (λ _max ^THF 474 nm (ε = 7.4 × 10 ⁴ )) Photoinitiator (D ₁ ) 0.09 g Fluorinated nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g

[0138]

Embedded image

(Note) The linear organic high molecular polymer (B ₁ ) and the photopolymerization initiator (D ₁ ) are as described above.

Photopolymerizable composition 3 to 5 (unit: g) Photopolymerizable composition 345-pentaerythritol tetraacrylate 4.0 2.0 2.0 Linear organic high molecular polymer (B ₁ ) 2.0 2.0 2.0 Sensitizer (C ₂ ) 0.13 0.13 0.13 Photoinitiator (D ₂ ) 0.1 0.1 0.1 Thio compound (E ₂ ) 0.07 0.07 0.07 Fluorine nonionic surfactant 0.03 0.03 0.03 Methyl ethyl ketone 20 20 20 Propylene glycol monomethyl ether acetate 20 20 20 ───────────────────────────────────

[0141]

Embedded image

(Note) The linear organic high molecular polymer (B ₁ ) and sensitizer (C ₂ ) are the same as described above. Photopolymerizable composition 6 Pentaerythritol triacrylate 2.0 g Linear organic polymer (B ₁ ) 2.0 g Sensitizer (C ₂ ) 0.13 g Photoinitiator (D ₂ ) 0.1 g Thio compound ( E ₂₎ 0.07 g fluorine-based nonionic surfactant 0.03g methyl ethyl ketone 20g propylene glycol monomethyl ether acetate 20g (Note) linear organic high molecular polymer (B ₁₎ and sensitizer (C ₁₎
Is the same as above.

Photopolymerizable composition 7 Pentaerythritol tetraacrylate 2.0 g Linear organic high molecular polymer (B ₁ ) 2.0 g Sensitizer (C ₂ ) 0.13 g Photoinitiator (D ₃ ) 0.1 g Additive (I) 0.2 g Fluorinated nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g

[0144]

Embedded image

(Note) The linear organic high molecular polymer (B ₁ ) and sensitizer (C ₂ ) are the same as described above. On the photosensitive layer thus obtained, a polyvinyl alcohol layer was applied in the same manner as in Example 1 to obtain photosensitive lithographic printing plates A25 to A30. Comparative Examples 6 to 11 Comparative lithographic printing plates B6 to B11 were obtained in exactly the same manner as described above except that the sol solution was not applied. These photosensitive lithographic printing plates A25 to A30 and B6 to B1
Sample No. 1 was subjected to image exposure, heating and development at 100 ° C. for 5 minutes in the same manner as in Example 1, and a printing test was performed. For the photosensitive lithographic printing plates A26 to A30, a printing test in which no heat treatment was performed after image exposure was also performed. That is,
Image exposure was performed in the same manner as in Example 1, development processing was performed as it was, and a printing test similar to that in Example 1 was performed. The results are shown in Table 7.

[0146]

Table 7-1ゾ ル Used sol liquid Used Photopolymerizable composition Example 25 Photosensitive lithographic printing plate A25 (4) 2 Comparative Example 6 〃 Ｂ B6 None 〃 ──────────────────────────────────── Example 26 〃 〃 A26 (4) 3 〃 〃 〃 A26 〃 比較 Comparative Example 7 〃 Ｂ B7 None 〃 ２７ Example 27 〃 Ａ A27 (4) 4 〃 〃 Ａ A27 〃 〃 Comparative Example 8 〃 Ｂ B8 None 〃 ────────────────── Example 28 Example A28 (4) 5 〃 〃 〃 A28 〃 〃 Comparative Example 9 〃 Ｂ B9 None 〃 ─────────────────────────────────── ─ Example 29 〃 〃 A29 (4) 6 〃 〃 Ａ A29 〃 〃 Comparative Example 10 〃 〃 B10 None 〃 ───────────────────────── ─────────── Example 30 〃 Ａ A30 (4) 7 〃 〃 〃 A30 〃 比較 Comparative Example 11 〃 Ｂ B11 None 〃 ─────────────── ───────────────────── Table 7-2 ─────────────────────────加熱 Heating after exposure G / S stages Printing durability Stain 汚 れ────────── Example 25 Photosensitive planographic printing plate A25 Yes 7.5 110 Comparative Example 6 〃 Ｂ B6 Yes 740 ○ 例 Example 26 〃 Ａ A26 With 8.5 120 ○ 〃 〃 〃 A26 Without 8 110 ○ Comparative Example 7 〃 〃 B7 With 740 ○ ──────────────────────── ──────────── Example 27 〃 〃 A27 Available 8 110 ○ 〃 〃 〃 A27 None 8 100 ○ Comparative Example 8 〃 〃 B8 Available 6.530 ○ ──────── ──────────────────────────── Example 28 〃 〃 A28 Available 8.5 120 ○ 〃 〃 Ａ A28 None 8 110 ○ Comparative Example 9 〃 Ｂ B9 Yes 740 ○ ──────────────────────────────────── Example 29 〃 Ａ A29 Ah 8. 8.5 120 〃 〃 〃 〃 A29 None 8 100 Comparative Example 10 〃 Ｂ B10 Yes 740 ────────────────────────── ────────── Example 30 〃 〃 A30 Available 8 110 ○ 〃 〃 〃 A30 None 7.5 100 ○ Comparative Example 11 〃 〃 B11 Available 6.530 ○ ──────── ────────────────────────────

Example 31 and Comparative Examples 12 to 14 The sol solution (4) of Example 4 was applied to the AD substrate used in Example 1 so that the dry coating amount was 1 mg / m ^2, and 100 ° C.
For 1 minute. The photopolymerizable composition 1 (Example 3) used in Example 1 was placed on the aluminum plate thus treated.
1) and the following photopolymerizable compositions 8 to 10 (Comparative Examples 12 to
14) was applied to a dry coating weight of 1.5 g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Photopolymerizable composition 8 Trimethylolpropane triacrylate 0.9 g Linear organic polymer (B ₁ ) 10 g Photoinitiator (D ₁ ) 0.2 g Fluorine nonionic surfactant 0.03 g Methyl ethyl ketone 27 g Propylene glycol monomethyl Ether 10 g Photopolymerizable composition 9 Trimethylolpropane triacrylate 2.0 g Linear organic polymer (B ₁ ) 6.6 g Photopolymerization initiator (D ₁ ) 0.2 g Fluorine nonionic surfactant 0.03 g Propylene glycol monomethyl ether 30 g Photopolymerizable composition 10 Trimethylolpropane tri (acryloyloxypropyl) ether 2.0 g Linear organic polymer (B ₁ ) 2.0 g Sensitizer (C ₃ ) 0.13 g (λ ^{_{max MeOH 380nm (ε = 0.67 ×}} 10 4)) photoinitiator (D ₁₎ 0.09 g thio compounds (E ₁₎ 0.08 g fluorine Nonionic surfactant 0.03g Methyl ethyl ketone 20g propylene glycol monomethyl ether acetate 20g

[0148]

Embedded image

On the photosensitive layer thus obtained, Example 1
In the same manner as in the above, a polyvinyl alcohol layer was applied to obtain photosensitive lithographic printing plates A31 and B12 to B14. These photosensitive lithographic printing plates were image-exposed at 100 ° C. in the same manner as in Example 1.
Was heated and developed for 5 minutes to evaluate the image forming properties.
The results are shown in Table 8 below.

[0150]

[Table 8] Table 8画像 Used image forming sol Liquid Photosensitive Composition Example 31 Photosensitive Lithographic Printing Plate A31 (4) 1 G / S step 8.5, with printing durability Comparative Example 12 B12 (4) 8 No image formation Comparative Example 13 B13 (4) 9 No image formation Comparative Example 14 B14 (4) ) 10 No image formation ────────────────────────────────────

Example 32 and Comparative Examples 15 to 17 The sol solution (4) used in Example 4 was applied to the AD substrate used in Example 1 so that the dry weight was 1 mg / m ^2.
Dried at 00 ° C for 1 minute. On the thus treated aluminum plate, the photopolymerizable composition 1 (Example 32) used in Example 1 and the photopolymerizable compositions 8 to 10 (Comparative Example 1) were used.
5-17) was applied so that the dry coating weight was 1.5 g / m ^2, and dried at 80 ° C. for 2 minutes to form a photosensitive layer. On the photosensitive layer thus obtained, a polyvinyl alcohol layer was applied in the same manner as in Example 1, and a photosensitive lithographic printing plate A3 was prepared.
2 and B15-17 were obtained. Except that the sol solution (4) was not applied, photosensitive lithographic printing plates B18 to B21 were obtained in exactly the same manner as in Example 32 and Comparative Examples 15 to 17. Of these photosensitive lithographic printing plates, A32 and B18 were subjected to image exposure, heating and development at 100 ° C. for 5 minutes in the same manner as in Example 1, but the illuminance at the photosensitive film surface was 0.0132 mW / c.
Adjust the number exposure time in m ^2, PS in the planographic printing plate A32
When the number of clear steps of the step guide was set to 6.5, the number of clear steps of B18 was evaluated. In addition, photosensitive lithographic printing plates B15-17 and B19-
Sample No. 21 was sufficiently evacuated with a PS light manufactured by FUJIFILM Corporation, exposed from a distance of 1 m,
When the exposure time is such that each of B15 to B17 has 6.5 steps of clear steps after heating and developing for minutes, how many clear steps of each of B19 to B21 correspond to the exposure time evaluated. The printing durability was evaluated in the same manner as in Example 1. The following results are summarized in Table 9 below.

[0152]

[Table 9] Table 9を Used sol solution (4) Printing resistance of sol liquid (4) Photosensitivity When applied When not applied Degree of improvement Composition Printing plate G / S Printing durability Printing plate G / S Printing durability Name Number of steps Name Number of steps ──────── ──────────────────────────── Example 32 1 A32 6.5 100 B18 5 10 90 Comparative Example 15 8 B15 6.5 30 B19 5 10 20 Comparative Example 16 9 B16 6.5 30 B20 5.5 10 20 Comparative Example 17 10 B17 6.5 40 B21 5.5 20 20 ────────────────刷 The printing durability improvement in the table depends on whether the sol solution (4) is applied or not. Only the difference or the difference A. It can be seen that by applying the sol liquid (4) according to the present invention, the printing durability is remarkably improved, and a printing plate having sufficient printing durability that can be practically used can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-315153 (JP, A) JP-A-55-125631 (JP, A) JP-A-53-105377 (JP, A) 299350 (JP, A) JP-A-54-151024 (JP, A) JP-A-4-219756 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/00 503 B41C 1/05 G03F 7/028 G03F 7/11 503

Claims (1)

(57) [Claims] (1) The following formula (1): R ₁ Si (OR ₂ ) ₃ (1) (wherein R ₁ is a functional group capable of causing an addition reaction;
R ₂ is a hydrolyzable alkoxy group or —OCOCH ₃
Group. ) And the following formula (3): Si (OR ₄ ) ₄ (where OR ₄ is a hydrolyzable alkoxy group,
A oxyalkoxy group, an aryloxy group, or -OCO
CH ₃ group. And (2) a photosensitive printing plate having a photopolymerizable photosensitive layer provided on the surface,
The photopolymerizable photosensitive layer contains a photoinitiator and 400 to 1000 n.
A photosensitive printing plate comprising a sensitizer having an absorption wavelength at m.