JP2668592B2 - Photosensitive lithographic printing plate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photosensitive lithographic printing plate in which a photosensitive resin composition layer is provided on the surface of a surface-treated aluminum having a surface provided with chemical reactivity.

(Conventional technology and problems to be solved) Conventionally, a technology for functionalizing a metal surface has been widely known.

For example, a protective film may be applied for physical protection or chemical protection, or a functional film may be added to impart chemical properties (coloring, light absorption, reflection, antireflection, photoconductivity, etc.). There is a technique of painting. These surface treatment techniques are common in that a specific chemical substance is provided on the surface, and can be implemented by various methods.

On the other hand, methods for imparting chemical functions such as chemical reactivity to the surface are limited. For example, a method is known in which a perovskite layer is provided on the surface of an electrode so that the surface has an oxidative reactivity, but this chemical reactivity is derived from a surface compound, the reaction proceeds catalytically, and the surface itself reacts. And it does not change. In other words, there are few methods for imparting chemical reactivity derived from a functional group to a surface to obtain a state in which the surface itself can be involved in a chemical reaction. Furthermore, there are few methods of obtaining a surface with the intended distribution of functional groups, each of which has drawbacks.

For example, the method of imparting a functional group to the surface by plasma treatment has a drawback that a vacuum is required, control of process parameters is complicated, and it is difficult to perform surface treatment with good reproducibility. Also, this treatment is often limited to polymer films and difficult to apply to metal surfaces.

In addition, the surface treatment with the silane coupling agent, the problem of poor adhesion based on poor wettability to the hydrophilic surface, the reaction control such as condensation dehydration on the surface to be treated is complicated,
The problem that the surface is likely to be contaminated by a catalyst, etc., and the part where the silane coupling agent adheres to the surface of the inorganic substrate is microscopically over-organic, it cannot be applied to applications requiring a lipophilic / hydrophilic balance on the surface. It has drawbacks.

Further, there are reports that a hydrophilic functional group is generated on the surface of silicone rubber by heavy ion implantation, but this is not general because the device is expensive and the applicable material is limited.

Therefore, the present invention has the following requirements: A functional group is added to a metal surface to make it chemically reactive.

At this time, the type of the functional group and the density of the functional group can be controlled.

Must be a wet process. That is, do not use vacuum, plasma, gas phase ions, or the like.

 Able to perform reproducible surface treatment.

Able to control the wettability or lipophilic / hydrophilic balance of the treated surface.

It is to provide a surface treatment method that simultaneously satisfies the above requirements.

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, an organometallic compound having a desired organic functional group and a group that undergoes polycondensation at the same time as hydrolysis is added in a liquid in the presence of a catalyst, if necessary. Thus, a desired organic functional group is hydrolyzed without causing a reaction and is subjected to a polycondensation reaction to form a liquid composition containing an inorganic polymer in which the metal part of the organometallic compound is connected to metal-oxygen-metal. The inventors of the present invention have found that the above object can be achieved by applying the composition on a metal surface and then drying it, if necessary. That is, the metal-oxygen-
Since the inorganic polymer containing a metal bond is in close contact with the processing substrate and the desired functional group remains on the processing substrate surface, a desired function can be obtained.

 Hereinafter, the present invention will be described in detail.

Specific examples of the organometallic compound that can be used in the composition of the present invention are represented by the following general formula (1).

A _m M (OR) _n (1) wherein M represents a metal, A represents an organic functional group, and R represents a hydrogen, an alkyl group or a function capable of being substituted with an alkyl group in a liquid, preferably in an organic solvent. M and n are positive integers representing 1 ≦ m + n ≦ 6, and when m is 2 or more, A may be the same,
It can be a mixture of different types.

The organometallic compound represented by the general formula (1) may be used alone, or a mixture of several kinds may be used. In addition, the following formula (2) having no organic functional group A
May be mixed.

M (OR) _n (2) In the formula, M and R have the same meanings as in the formula (1), and n is a positive integer satisfying 1 ≦ n ≦ 6.

In formulas (1) and (2), those in which some or all of the ORs are replaced by halogen atoms can also be suitably used as the organometallic compound for preparing the composition according to the present invention. More specifically, by the action of water, alcohols, etc., the general formulas (1) and (2)
All of the precursor organometallic compounds capable of producing the compound represented by the formula (1) can also be used. Typical examples of halogen atoms are F, Cl, Br
And I.

Further, in the general formulas (1) and (2), an organic metal compound in which a part or all of the OR causes a hydrolysis and polycondensation reaction to have a metal-oxygen-metal bond in the molecule is also used. It can be used in the present invention.

The organometallic compounds of the general formulas (1) and (2) are mixed and subjected to hydrolysis and polycondensation reactions to form a polymer or colloidal polymer containing a metal-oxygen-metal bond. When the metal surface is treated with the liquid composition, in addition to the functional group A derived from the compound (1), the OH group derived from the compound (2) or, in some cases, the compound derived from the compound (1).
The OH group and the OH group derived from the compound (2) are implanted on the metal surface. This OH group is nothing but the one in which the OR group in the general formula (2) or the general formulas (1) and (2) is hydrolyzed to an OH group.

The density of the organic functional groups A on the treated surface can be controlled by changing the concentration of the liquid composition according to the invention, as well as by changing the relative amounts of the compounds (1) and (2).

In the general formulas (1) and (2), the metal M is Li, N
a, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, rare earth metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb,
Mo, Hf, Ta, W, Ru, Rh, Pd, Ir, Pt, B, Al, Ga, I
Any of n, Tl, Si, Ge, Sn, Pb, P, As, Sb, and Bi may be used, and Al, Si, and Ti are preferable in view of raw material availability.

A is a functional group fixed covalently to the treated surface, and may be any functional group as long as it is stably present in the form of the formula (1). The chemical reactivity of the treated surface can be controlled by the type and amount of A.

Representative examples of A include hydrogen, an alkyl group, an aryl group, an alkenyl group, a propargyl group, an alkoxy group, an epoxyalkyl group, a silyl group, a siloxy group, and a hydroxyl group. It may be substituted with one or more functional groups as shown below. Halogen group, alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, acyl group, alkoxycarbonyl group, carbamoyl group, carboxy group, alkenyl group,
Propargyl group, amino group, alkylamino group, acylamino group, ureido group, carbamate group, diazonio group, diazo group, azo group, mercapto group, alkylthio group, sulfonyl group, sulfo group, cyano group, isocyanato group, thioisocyanato group, sulfamoyl Group, nitro group, silyl group, siloxy group. A more specific example of A is shown below.

_{H-, HO-, CH 3 -,} C 2 H 5 -, n-C 3 H 5 -, i-C 3 H 5
_{-, n-C 8 H 17} -, n-C 12 H 25 -, n-C 18 H 37 -, CH 2 Cl
−, CF ₃ CF _{2 3} , HOCH ₂ CH ₂ CH ₂ −, CH ₂ = CHCOOCH _{2 3} , CH ₂ = C (CH ₃ ) COOCH _{2 3} , C
H ₂ = CH-C-CH ₂ , _{HSCH 2 -, HSCH 2 3,} H 2 NCH 2 -, H 2 NHCH 2 3, H 2 N
CH _{2 3} , H ₂ NCH _{2 2} NHCH _{2 3} , NCCH _{2 3} , NC
CH _{2 2} , OCNCH _{2 2} , OCNCH _{2 3} , ClCH
_{2 3} , _{CH 2 BrCHBr-, CF 3 CH 2} 2, HOCH ₂ −, BrCH = CBr−, CF ₃ CH _{2 3} CH ₂ CH ₂ −, HO-CH ₂ -C≡C-, _{(CH 3 3, ClCH 2 CH} 2 SCH 2 -, (CH 3) 2 CHO-, HOCH 2 CH 2
SCH ₂ −, H ₂ NCH ₂ CH ₂ NHCH ₂ −, _{NCSCH 2 CH 2 SCH 2 3,} CH 2 = CHCH 2 OCH 2 2 SCH 2 -, CH
₂ = CHCH ₂ SCH _{2 3} S-, H ₂ NCH _{2 2} SCH _{2 2} −, CH ₂ = CHCH ₂ NHCH _{2 3} , N ₂ NCH _{2 2} NHCH _{2 2} NHCH _{2 3} , R in the general formulas (1) and (2) represents hydrogen, an alkyl group or a functional group capable of being substituted with an alkyl group in an organic solvent, and may be a single group or a group having several groups. The alkyl group may be any of linear, branched, cyclic and the like, and typical examples thereof are CH ₃ —, C ₂ H _{5
-, n-C 3 H 7} , i-C 3 H 7, n-C 4 H 9, sec-C 4 H 9, t-C
₄ H ₉ , It is. Functional group R capable of being substituted with an alkyl group in an organic solvent
Are halogen atoms such as Cl and Br, organic acid residues and the like. As an organic acid residue , But those having a large number of carbon atoms can also be used. The substitution between the functional group R and the alkyl group includes those where the R and the alkyl group are substituted as they are, and those where the -OR is substituted with an -O-alkyl group.

Further, -OR is not limited to a monodentate type, and may be a polydentate alkoxide such as diol or triol, or a polydentate organic acid residue such as oxalic acid or succinic acid.

The following are specific examples of the compound represented by the general formula (1).

_{H 2 N (CH 2) 2} NH (CH 2) 3 -Si (OCH 3) 3 CH 2 = CH-Si (OCOCH 3) 3 CH 2 = CH-Si (OC 2 H 5) 3 H 2 N (CH _{2) 3 -Si (OC 2 H} 5) 3 OCNCH 2 CH 2 CH 2 -Si (OCH 3) 3 _{HSi (OCH 3) 3 CH 2} ClSi (OCH 3) 3 CH 3 Si (OCH 3) 3 HSCH 2 Si (OCH 3) 3 CH ₂ CHCHSi (OCH ₃ ) ₃ CH ₂ CHCHCH ₂ Si (OC ₂ H ₅ ) ₃ HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (CH ₂ = CH) ₂ Si (OC ₂ H ₅ ) ₂ NC (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ CH ₂ = CHCH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ CH≡CSi (OC ₂ H ₅ ) ₃ CH = CHSi (OCOCH ₃ ) ₃ (C ₅ H ₇ O ₂ ) ₂ Ti (OC ₃ H ₇ ) ₂ (C ₅ H ₇ O ₂ ) ₂ V (OC ₃ H ₇ ) examples of _{2 (C 5 H 7 O 2} ) 2 Ba (OC 2 H 5) compound represented by the ₂ general formula (2) include the followings.

Si (OCH ₃ ) ₄ Si (OC ₂ H ₅ ) ₄ Si (OCOCH ₃ ) ₄ Si (OC ₃ C ₇ ) ₄ Si (OC ₄ C ₉ ) ₄ In _{Ti (OC 3 C 7) 4} Ti (OC 4 H 9) 4 Zr (OC 3 C 7) 4 V (OC 2 H 5) 5 W (OC 2 H 5) 6 formula (1) and (2) Examples of the organic solvent for polycondensing the organometallic compound represented by hydrolysis together with the compound are as follows.

Methanol, ethanol, n- and i-propanol, 1- and 2-butanol, isobutyl alcohol,
Amyl alcohol, pentanol, fusel oil, hexanol, heptanol, octanol, cyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, hexane, heptane, octane, decane, petroleum ether, petroleum benzyl,
Ligroin, gasoline, kerosene, cyclohexane, benzene, toluene, o-, m- and p-xylene, styrene, cresol, tetralin, decalin, turpentine,
Chloroform, carbon tetrachloride, methylene chloride, ethylene chloride, ethylidene chloride, trichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene,
Trichloropropane, isopropyl chloride, dichloropropane, butyl chloride, amyl chloride, hexyl chloride, ethylene bromide, tetrabromoethane, chlorobenzene, o-dichlorobenzene, trichlorobenzene, bromobenzene, chlorotoluene, diethyl ether, isopropyl ether , Dibutyl ether, diisoamyl ether,
Hexyl ether, methylphenyl ether, ethylphenyl ether, butylphenyl ether, ethylbenzyl ether, 1,4-dioxane, 2-methylfuran,
Tetrahydrofuran, tetrahydropyran, 2-ethoxytetrahydropyran, cineol, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone,
Methylhexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, diacetone alcohol, phorone, isophorone, cyclohexanone, methylcyclohexanone, acetophenone, ethyl formate, propyl formate, butyl formate, isobutyl formate,
Amyl formate, methyl acetate, ethyl acetate, propyl acetate,
Isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate, amyl acetate, isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, 2-ethylbutyl acetate, hexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, Butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, amyl butyrate, isoamyl butyrate, methyl acetoacetate, ethyl acetoacetate, isoamyl isovalerate, methyl lactate, ethyl lactate, butyl lactate, amyl lactate, benzoic acid Methyl, diethyl oxalate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, Tylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, Ethylene glycol monophenyl ether, ethylene glycol monophenyl ether acetate, ethylene glycol benzyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol butyric acid monoester, ethylene glycol propionic acid diester, Glycol acid diesters, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol isobutyl ether,
Diethylene glycol monobutyl ether acetate,
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol acetate,
Diethylene glycol dibutyl ether, propylene glycol, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether,
Trimethylene glycol, triethylene glycol dimethyl ether, butanediol, pentanediol, hexylene glycol, 3-methoxy-3-methoxybutanol, formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, valeric acid, lactic acid, pyridine , Picoline, quinoline, isoquinoline, dimethyl sulfoxide,
Triethyl phosphate, dimethylformamide, γ-butyrolactone, γ-valerolactone, 6-hexanolactone, methyl salicylate, ethyl salicylate, butyl salicylate, diethyl adipate, ethyl carbonate, butyl sulfide, acetylacetone, acetonylacetone, mono-,
Di- and triethanolamine, N, N-dimethylformamide, glycerin.

Particularly preferred are methanol, ethanol, i-
Propanol, hexane, cyclohexane, benzene,
Toluene, 1,4-dioxane, tetrahydrofuran, methyl ethyl ketone, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, acetylacetone, N, N-dimethylformamide and monoethanolamine.

The organic solvent may be used alone or in combination of two or more kinds.

When the organometallic compounds represented by the general formulas (1) and (2) are hydrolyzed in an organic solvent, it is possible to use the water contained in the organic solvent as a hydrolyzing agent as it is. In order to control the preparation of the liquid composition according to the present invention so as to be completed within a certain time, it is generally preferable to add 0.5 to 1,000 mol of water per mol of the organometallic compound. When the amount of water is less than this range, the hydrolysis and subsequent polycondensation reaction proceed very slowly, and it may take several days before the metal surface treatment becomes possible. On the other hand, if the amount of water is more than this range, the resulting composition may cause poor adhesion even when applied to the metal surface, and the composition may have poor stability over time and often gel immediately. In addition, it becomes difficult to perform the coating operation stably.

In addition to acting as a reaction substance for hydrolysis, water can also serve as a solvent for the treatment liquid of the present invention. The liquid composition according to the method of the present invention can be prepared in an aqueous medium under the conditions that the hydrolysis rate of the compounds represented by the general formulas (1) and (2) is sufficiently slow and does not easily gel.

The reaction temperature is usually from room temperature to about 100 ° C., but the reaction can be performed at a temperature higher than the boiling point of the solvent by providing a reflux condenser.

The reaction temperature determines the time required for the hydrolysis and polycondensation reactions. If the reaction takes several days at room temperature, the reaction is completed in several hours at 80 ° C., so it is set appropriately according to the purpose.

As the catalyst used as necessary, acids such as hydrochloric acid and acetic acid, or bases such as ammonia and tetramethylammonium hydroxide can be used. The amount of catalyst added is
Generally, it is about 0.01 to 0.1 mol per mol of the organometallic compound represented by the general formulas (1) and (2). However, 0.1 mol or more may be more suitable. The amount of the catalyst to be added is suitably at most 1 mol, and it can be avoided that the catalyst is added excessively and wasted.

The catalyst can be added not only by adding the catalyst itself but also by adding a catalyst solution. For example, instead of adding hydrochloric acid as it is, an anhydrous methanol solution of hydrochloric acid may be added. Also, tetramethylammonium hydroxide can be used, for example, as an aqueous solution or an ethanol solution.

A composition comprising one or more organometallic compounds represented by the general formulas (1) and (2), an organic solvent, water, and optionally a catalyst, is reacted at an appropriate reaction temperature, reaction time,
And if appropriate reacting by selecting appropriate stirring conditions,
A polycondensation reaction occurs with hydrolysis, and a polymer containing a metal-oxygen-metal bond or a colloidal polymer is produced,
The viscosity of the liquid composition increases, and the liquid composition turns into a sol.

The sol thus obtained is polymerized into a gel, which is
Heating to 400-1000 ° C. produces a glass, which is well known as the sol-gel method.

It is also known that an oxide film can be applied if the glass forming reaction is performed on another substrate.

In the method according to the present invention, an inorganic polymer consisting of a metal-oxygen-metal bond present in the sol is bonded to the surface of the metal to be treated and covalently fixed to the inorganic polymer. The purpose is to implant the organic reactive group on the surface of the metal to be treated, but not to provide another compound layer or material layer on the metal surface.

The sol liquid or liquid composition used in the present invention, when applied to a metal surface and then air-dried or heat-dried,
The inorganic polymer composed of the metal-oxygen-metal bond gels and simultaneously adheres to the metal surface. The drying is performed to volatilize the solvent, residual water and, in some cases, the catalyst. However, depending on the intended use of the treated substrate, the step may be omitted. In order to increase the adhesion between the inorganic polymer portion in the liquid composition according to the present invention and the surface of the metal to be treated, a temperature can be positively applied. The drying step in this case can be continuously performed even after volatilization of the solvent, water and the like. The maximum drying temperature must be lower than the decomposition temperature of the organic functional group (A in the formula (1)) implanted on the metal surface. Normal,
Temperatures from room temperature to 200 ° C, preferably from room temperature to 150 ° C, are used.

The type, shape, surface pretreatment state, and the like of the substrate having a metal surface that can be treated by the method of the present invention are arbitrary. For example, it can be applied to pure metals such as aluminum, iron, copper, titanium, and zirconium, as well as alloys of these.

The shape of the metal substrate may be any of a plate shape, a pipe shape, a linear shape, and the like.

As a method for applying the liquid composition (sol solution) used in the present invention, any of brush coating, dip coating, atomizing, spin coating, doctor blade coating and the like can be used, and the shape of the metal surface and the required Is determined in consideration of the processing film thickness and the like.

The metal surface is preferably a clean surface on which no oily substance or the like is attached, but it can be used as it is, unless it is significantly contaminated by the attachment of the oily substance or the like. If necessary, the metal surface may be roughened by mechanically making it uneven, or by electrolytic deposition, electrolytic etching or the like.

A metal oxide having a natural oxide film formed on its surface or a metal oxide whose surface has been positively oxidized by anodic oxidation, catalytic oxidation, or the like can be suitably used. It is of course possible to use an oxide film formed on the surface by thermal spraying, coating, CVD, etc., which is different from the bare metal.

Not only oxides, for example, surface silicate treatment,
A method in which a surface layer different from the metal surface is provided by a surface nitriding treatment or the like is also included in the method of the present invention.

The liquid composition used according to the present invention comprises a composition comprising one or more organometallic compounds represented by the general formulas (1) and (2), an organic solvent, water, and optionally a catalyst. It is obtained as a result of reacting by selecting an appropriate reaction temperature, reaction time, and, in some cases, appropriate stirring conditions. Any liquid composition may be used as long as the hydrolysis and polycondensation reactions proceed to a state where the effect of fixing the group can be obtained.

Whether the liquid composition achieves the object of the present invention is determined by actually applying the liquid composition on a metal surface, measuring a reflection infrared absorption spectrum, a Raman spectrum, and the like. It can be determined by confirming the presence and confirming the adhesion between the inorganic polymer layer and the metal surface by a tape peeling test after drying.

The degree of progress of the reaction can also be known by spectroscopically confirming the hydrolysis reaction and the polycondensation reaction. Regarding the progress of hydrolysis, for example, when an infrared absorption spectrum method is used, the vibration absorption spectrum based on -OR in the general formula (1) decreases, and the vibration absorption spectrum based on -OH groups increases. I can judge. The subsequent polycondensation reaction can be confirmed, for example, by the fact that a vibrational absorption peak derived from a metal-oxygen-metal bond appears in the infrared absorption spectrum and becomes stronger. Further, when the NMR spectrum is measured, it is observed that the spectrum width of A in the general formula (1) is widened by the progress of polycondensation, which also enables the reaction to be confirmed.

The liquid composition used in the present invention can be suitably used to achieve the object of the present invention when any one of such spectral information is confirmed.

More simply, the viscosity of the liquid composition during preparation is monitored, and if a significant increase in viscosity is observed compared to the viscosity before the start of the reaction, it is determined that the liquid composition according to the present invention has been prepared at that time. it can.

Depending on the composition and reaction conditions,
It is preferably from 0.2 centipoise to about 10 poise. If the viscosity is too low, it will be difficult to monitor the progress of the polymerization, and if the viscosity is too high, not only it will be difficult to coat the metal, but the film may peel off after drying, which is not preferable.
When the liquid composition is applied to the surface of the metal to be treated, it can be diluted with a suitable solvent, a liquid such as water, and used. Alternatively, a part of the solvent used at the time of preparing the solution can be volatilized and concentrated for use. Although it varies depending on the coating method, the target coating thickness, etc., it is easy to use a liquid viscosity at the time of coating of about 0.2 centipoise to about 10 poise.

Judging by the molecular weight of the inorganic polymer in the liquid composition, there is a method of determining the number average molecular weight from the freezing point depression of the liquid composition obtained by stopping the reaction by trimethylsilylation treatment, and the result is 1,000 to several. You only need to confirm that it is in the order of 10,000.

The metal surface treated by the method of the present invention has the intended functional groups in the intended amount and exhibits various chemical functions.

Generally, the surface free energy γ of a substance can be separated into a dispersive force component γ ^d and a polar component γ ^p , but in order to maximize the interaction between different substances and obtain good adhesion, the γ ^{d of} each other can be obtained. , Γ ^p should be close to the same value. Since γ ^d and γ ^p of the metal surface treated by the method according to the present invention can be determined by the kind of A of the organometallic compound represented by the general formula (1) and its relative amount, it is attempted to coat the surface. It is also possible to match γ ^d and γ ^p of the other party, and good adhesion can be obtained.

By implanting a thermally reactive organic functional group on a metal surface according to the method of the present invention, a coating film having a group capable of reacting with the organic functional group is formed on the metal surface, and heat is applied thereto. It can be firmly and chemically adhered only to the places where heat is applied.

When the functional group A in the general formula (1) is photoreactive, a photo-induced adhesion effect can be obtained between the metal surface treated according to the method of the present invention and another photoreactive material. You can

If the functional group implanted on the metal surface is a general radical polymerizable group, apply a monomer or oligomer that can be polymerized or copolymerized with this to the metal surface together with the initiator, and according to the type of the initiator. By applying an external stimulus, a chemical bond can be formed between the surface and the applied body. If the initiator is a thermal initiator, heat is applied, and if it is a photoinitiator, light is applied from the outside.
It is needless to say that when such an external stimulus is applied to the imagewise, a latent image corresponding to the external stimulus is formed as a chemical bond between the metal surface and the coating film.

Since the intended functional group is implanted on the metal surface treated by the method according to the present invention, it can be bonded to any substance having a reactive group capable of chemically reacting with the functional group. On the contrary, when trying to bring something into contact with the substrate, the reactive group of itself or the reactive group introduced into itself by some method is combined with an organic functional group capable of performing a suitable chemical reaction. The organometallic compound of the general formula (1) contained as A is selected, a liquid composition is formed by the method according to the present invention, the metal surface is treated with this, and the substance having the reactive group is applied.
What is necessary is just to cause an intended chemical reaction.

Therefore, the method according to the present invention can be used in a wide range of applications, for example, when a weathering coating film is provided on a building material, when fixing a functional chemical such as a fungicide, when fixing a bio-based substance such as an enzyme. In this case, when a functional chemical product is applied to a piping material or the like, it can be used to provide a functional group suitable for the purpose and to obtain a strongly covalently bonded complex.

It goes without saying that not only the adhesion but also the releasability, surface slippage and surface friction can be freely changed by the method according to the present invention.

As a functional chemical product suitably used on the metal surface thus obtained, there is a photosensitive resin layer for a lithographic printing plate (PS plate).

As the composition for such a photosensitive resin layer, any composition can be used as long as its solubility or swelling property in a developer changes before and after exposure. Hereinafter, representative examples will be given.

(1) Photosensitive resin layer composed of diazo resin and binder: US Pat. No. 2, as a negative-working photosensitive diazo compound.
Diphenylamine-p-diazonium salt, which is a reaction product of a diazonium salt disclosed in each of JP-A Nos. 63631/631 and 2,667,415 with an organic condensing agent having a reactive carbonyl group such as aldol and acetal, and formaldehyde (A so-called photosensitive diazo resin) is preferably used. Other useful condensed diazo compounds are described in JP-B-49-48001, JP-B-49-45322, and JP-B-49-4532.
It is disclosed in each gazette of No. 3. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts and can therefore be applied from aqueous solutions. Further, these water-soluble diazo compounds are reacted with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups or both by a method disclosed in Japanese Patent Publication No. 47-1167, A substantially water-insoluble photosensitive diazo resin, which is the reaction product, can also be used.

Further, as described in JP-A-56-121031, it can be used as a reaction product with hexafluorophosphate or tetrafluoroborate.

Examples of reactants having a phenolic hydroxyl group are diphenolic acids such as hydroxybenzophenone, 4,4-bis (4'-hydroxyphenyl) pentanoic acid, resorcinol, or diresorcinol, which are further substituted May be provided. Hydroxybenzophenone includes 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone or 2,2 ′,
4,4'-tetrahydroxybenzophenone is included.
Preferred sulfonic acids include, for example, aromatic sulfonic acids such as sulfonic acids such as benzene, toluene, xylene, naphthalene, phenol, naphthol and benzophenone, or soluble salts thereof, for example, ammonium and alkali metal salts. Sulfonic acid group-containing compounds are generally lower alkyl groups, nitro groups, halogens,
And / or may be substituted with another sulfonic acid group. Preferred examples of such compounds include benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, sodium mesitylenesulfonate, naphthalene-2-sulfonic acid, 1- Naphthol-2
(Or 4) -sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, m- (p'-anilinophenylazo) benzenesulfone Sodium acid, alizarinsulfonic acid, o-toluidine-m-sulfonic acid and ethanesulfonic acid, and ammonium salts and alkali metal salts thereof. Also useful are the sulfonic esters of alcohols and their salts. Such compounds are usually readily available as anionic surfactants. Examples include lauryl sulfate, alkylaryl sulfate, p-nonylphenyl sulfate, 2-
Examples thereof include ammonium or alkali metal salts such as phenylethyl sulfate and isooctylphenoxydiethoxyethyl sulfate.

These substantially water-insoluble photosensitive diazo resins are mixed as a precipitate by mixing the water-soluble photosensitive diazo resin with the above-mentioned aromatic or aliphatic compound in a water-soluble amount, preferably in a substantially equal amount. Be separated.

Further, diazo resins described in British Patent No. 1,312,925 are also preferable.

In addition, JP-A-1-102456, 1-102457 and 1
Also, diazo resins such as those described in JP-A-254949, JP-A-1-255246 and JP-A-2-66 can be used.

The most preferred diazo resin is 2-methoxy-4 which is a condensate of p-diazodiphenylamine and formaldehyde.
-Hydroxy-5-benzoylbenzenesulfonate, hexafluorophosphate, dodecylbenzenesulfonate.

The content of the diazo resin is appropriately 3 to 50% by weight, preferably 5 to 20% by weight in the photosensitive resin layer. When the amount of the diazo resin decreases, the photosensitivity naturally increases, but the stability over time decreases. The optimal amount of diazo resin is about 8-20% by weight.

On the other hand, various polymer compounds can be used as the binder. In the present invention, those containing groups such as hydroxy, amino, carboxylic acid, amide, sulfonamide, active methylene, thioalcohol, and epoxy are preferable. Such preferred binders include British Patent No.
No. 1,350,521, shellac, a polymer containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit as described in British Patent No. 1,460,978 and U.S. Pat.No. 4,123,276. U.S. Pat.No. 3,751,257
No. 1, the polyamide resin described in
No. 074,392, phenolic resins and polyvinyl acetal resins such as polyvinyl formal resins, polyvinyl butyral resins, U.S. Pat.
Includes linear polyurethane resin described in 3,660,097, phthalated resin of polyvinyl alcohol, epoxy resin condensed from bisphenol A and epichlorohydryl, and amino group such as polyaminostyrene and polyalkylamino (meth) acrylate. Examples include polymers, cellulose acetate, cellulose alkyl ether, cellulose derivatives such as cellulose acetate phthalate, and the like.

Further, JP-A-54-98614, JP-A-61-267042, and JP-A-62-5.
8242, 61-128123, 62-123452, 62-1234
The polymer compounds shown in JP-A-53 and JP-A-63-113450 are also preferably used.

The composition comprising a diazo resin and a binder may further contain a pH indicator as described in British Patent 1,041,463, a phosphoric acid described in U.S. Pat.No. 3,236,646, a dye, etc. Agents can be added.

(2) Photosensitive resin layer comprising an o-quinonediazide compound: A particularly preferred o-quinonediazide compound is an o-naphthoquinonediazide compound, for example, US Pat. No. 2,766,
No. 118, No. 2,767,092, No. 2,772,972, No. 2,85
No. 9,112, No. 2,907,665, No. 3,046,110, No. 3,0
No. 46,111, No. 3,046,115, No. 3,046,118, No. 3,
No. 046,119, No. 3,046,120, No. 3,046,121, No.
No. 3,046,122, No. 3,046,123, No. 3,061,430, No. 3,102,809, No. 3,106,465, No. 3,635,709,
It is described in a large number of publications, including each specification of the above-mentioned 3,647,443, and these can be suitably used.
Of these, o-naphthoquinonediazidosulfonic acid ester or o-naphthoquinonediazidocarboxylic acid ester of an aromatic hydroxy compound, and o-naphthoquinonediazidosulfonic acid amide or o-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound are particularly preferred. In particular, a product obtained by subjecting a condensate of pyrogallol and acetone described in U.S. Pat.No. 3,635,709 to an ester reaction with o-naphthoquinonediazidosulfonic acid, and a terminal hydroxy compound described in U.S. Pat.No.4,028,111. O-naphthoquinone diazide sulfonic acid or o-naphthoquinone diazide carboxylic acid obtained by subjecting a polyester having a group to an ester reaction, a homopolymer of p-hydroxystyrene as described in British Patent No. 1,494,043, or Other co-owners A copolymer of may monomer o- naphthoquinonediazide sulfonic acid or o-
Ester reaction of naphthoquinonediazidocarboxylic acid, o-naphthoquinonediazidesulfonic acid or a copolymer of p-aminostyrene and another copolymerizable monomer as described in U.S. Pat.No. 3,759,711. An amide reaction of o-naphthoquinonediazidocarboxylic acid is very excellent.

These o-quinonediazide compounds can be used alone, but are preferably used in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak-type phenol resins, and specifically include phenol formaldehyde resin, o-cresol formaldehyde resin, m-cresol formaldehyde resin, and the like. Further, as described in U.S. Pat.
More preferably, a condensate of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as butylphenol formaldehyde resin, and formaldehyde is used. The alkali-soluble resin is contained in an amount of about 50 to about 85% by weight, more preferably 60 to 80% by weight, based on the total weight of the composition constituting the photosensitive resin layer.

The photosensitive composition comprising the o-quinonediazide compound may further contain a dye and a plasticizer, if necessary, for example, as described in British Patent No.
1,401,463, 1,039,475, U.S. Pat.
Additives can be added, such as components that provide printout performance as described in each of the above-cited references.

(3) Photosensitive resin layer comprising an azide compound and a binder (polymer compound): For example, British Patent Nos. 1,235,281 and 1,495,861 and JP-A-51-32331 and 51-36128. In addition to the composition comprising an azide compound and a water-soluble or alkali-soluble polymer compound described in Japanese Patent Laid-Open Publication No. 50-51
No. 02, No. 50-84302, No. 50-84303, No. 53-12984 and the like, and a composition comprising a polymer containing an azide group and a polymer compound as a binder is included.

In addition, Japanese Examined Patent Publication No. 49-44601, Japanese Unexamined Patent Publication No. 52-89914 and 59
A composition containing a polyvinyl acetal resin having an azide group described in each of JP-A-208552 can also be used.

(4) Photopolymerizable photopolymer resin layer: Typical examples include a photosensitive composition containing an ethylenically unsaturated addition polymerizable compound, a polymer which is soluble in an organic solvent and can form a film, and a photopolymerization initiator. . Specifically, it is described in JP-A-61-282836.

(5) Photocrosslinkable photopolymer resin layer: For example, polyester compounds disclosed in JP-A-52-96696, British Patents 1,112,277, and 1,313,390
And polyvinyl cinnamate-based resins described in JP-A Nos. 1,341,004 and 1,377,747.

A particularly preferred composition is a photosensitive composition containing a photocrosslinkable polymer having a maleimide group in a side chain. The details are described in JP-A-62-78544.

(6) Electrophotographic photosensitive resin layer: The electrophotographic photosensitive resin is mainly composed of a photoconductive compound and a binder, but is required for the purpose of improving sensitivity, obtaining a desired photosensitive wavelength range, and the like. Depending on the case, known pigments, dyes, chemical sensitizers, and other additives can be used. The photosensitive resin layer can be composed of a single layer or a plurality of layers having separate functions of charge generation and charge transport. A lithographic printing plate can be obtained by forming a toner image on a photosensitive resin layer by a known electrophotographic process, and using this as a resist layer to decoat a non-image portion. For example, Japanese Patent Publication No. 37-17162,
No. 38-6961, JP-A-56-107246, 60-2541
No. 42, JP-B-59-36259, JP-B-59-25217, JP-A-56-146145, JP-A-62-194257, and JP-A-57-147656.
No. 58-100862, No. 57-161863, and many other publications, all of which can be preferably used.

The thickness of the photosensitive resin layer is 0.1 to 30 μm, preferably 0.5 to 30 μm.
It can be used at -10 μm.

The amount of the photosensitive resin layer provided on the metal surface is about 0.1 to
It is about 7 g / m ² , preferably 0.5-4 g / m ² .

Next, an example of compatibility between adhesion and releasability will be described in detail below, taking application to a PS plate as an example.

As the substrate, an aluminum plate degreased by an ordinary method is used. In some cases, the surface may be roughened with a brush or an electric current. If necessary, an oxide film layer may be provided on the surface by an anodic oxidation method, and if necessary, the surface may be immersed in a No. 3 sodium silicate treatment bath to form a silicate layer on the surface.

This aluminum plate is treated with a liquid composition according to the present invention prepared from an organometallic compound of the general formula (1) having a radical-polymerizable group as A, on which a radical-polymerizable photosensitive composition is also applied. Apply to form a film. Light is applied to the imagewise to cause the interface light bonding as in the image. When the unexposed portion is removed with a developer, a photopolymerized adhesive film remains on the aluminum plate according to the light pattern. When ink and water are applied thereto, the ink adheres to the photopolymerized adhesion film portion and the water adheres to the unexposed portion, respectively, and can be used as a printing plate.

In this example, if there is an excess of organic functional groups in the unexposed areas to which water should adhere, other inks of water also adhere,
It is observed as a stain on printing. In order to prevent this, a large number of OH groups are fixed on the metal surface of the substrate in addition to the functional group A to enhance the hydrophilicity, or by utilizing the reactivity of the functional group A itself to make it hydrophilic such as an alcohol group. Or conversion to a base.

The OH group on the metal surface can be increased by using a large amount of an organometallic compound of the general formula (1) and / or an organometallic compound of the general formula (2). In the organometallic compound of the general formula (2), the OR group is converted into an OH group by hydrolysis, and most of the OR group is used for a metal-oxygen-metal bond. Will exist as

In other words, how to select the functional group A, the general formula (1) and (2)
The resilience of the unexposed portion to ink and the affinity for water can be enhanced by the combination of the organometallic compounds represented by

Hereinafter, the surface of an aluminum plate is treated with a liquid composition according to the present invention using an organometallic compound of the general formula (1) having a CH ₂ CHCH— group as an organic functional group A, and a photosensitive composition is applied. An example of configuring the PS version will be described in more detail.

Add Si (OC ₂ H ₅ ) ₄ and CH ₂ = CHSi (OCOCH ₃ ) _{3 to the} beaker.
Then, acetic acid is added as a catalyst and water is further added as a hydrolyzing agent. Ethanol is added to this mixed solution as a solvent, and the mixture is stirred as it is 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 mechanism, and immersed in an oil bath at room temperature. While stirring, raise the bath temperature to 80-90 ° C.

The viscosity of the solution increases with the progress of the reaction. At this time, it is considered that the following reaction is disturbed in the solution.

Although it is described here that the polycondensation extends in one direction among the four functional groups bonded to Si, it is considered that the condensed chain actually extends in several directions at the same time. In addition to polycondensation of the same type, heteropolycondensation reaction of different types is considered to occur at a statistical frequency, so it is impossible to describe it completely as a reaction formula.

When the hydrolysis and polycondensation reactions proceed to some extent in this way, it is considered that the polymer represented by the following formula exists in the solution.

Actually, there are various kinds of chemical species having different Si—O—Si chain lengths and functional group contents. When the average composition is expressed as a chemical formula, (CH ₂ = CH _a SiO _b OH _c However, b + 1/2 (a + c) = 2 to be approximated. reaction -OC ₂ H ₅ group or -OCOCH ₃ group in the middle also zero considered not have been omitted. a in this formula, b, the value of c Is the amount of water, including the relative ratio of the organosilicon compound used as the raw material,
It depends on many experimental parameters such as the type and amount of the solvent, the type and amount of the catalyst, the reaction temperature, the reaction time, etc. On the contrary, a, b, arbitrarily designed by aligning these conditions
A final product with a value of c can be obtained.

The liquid composition thus obtained is applied on a metal surface.

It is known that there is some oxide film on the metal surface unless the surface is clean in an ultra-high vacuum, and the surface partially contains OH groups. When the liquid composition is applied to the metal surface, the single bond around the Si, which has a degree of freedom of rotation, rotates, and the highly inorganic part as a whole faces the metal surface, and the above-mentioned chemical species in the liquid Adhere to the metal surface. The driving force at this time is considered to be an interaction between the oxide or surface OH group on the metal surface and the Si—O—Si network or silanol group in the liquid composition.

When heat is applied after applying the liquid composition to the surface, the application solvent, catalyst residue, and the like can be volatilized quickly.
It is believed that the heating also promotes the formation of chemical bonds between the metal surface and the inorganic polymeric portion in the liquid composition. Although the details of the mode of bonding are unknown, dehydration condensation between OH groups on the metal surface and OH groups on the inorganic polymer will predominate.

In the case of the present specific example, the surface-treated metal substrate thus obtained has vinyl groups and hydroxyl groups, and most of them are considered to be protruding from the metal surface to the outside.

When a photopolymerizable photosensitive resin layer is applied to the treated metal surface to form a PS plate, a system containing a monomer having a C モ ノ マ ー C double bond is preferably used.

Allyl group -CH ₂ CH = CH ₂ , acrylate group at terminal Polymerizable monomers and binders containing such are commercially available and easily available. A mixture of these and a photo-radical generator in an appropriate ratio is applied to the surface of the vinyl-fixed metal and dried to form one PS plate.

Next, when the PS plate thus obtained is image-exposed, vinyl polymerization occurs in the place exposed to light, and the coating film hardens, and at the same time, a covalent bond is formed between the coating film and the metal surface. In other words, the vinyl polymer film forms a new covalent bond with the vinyl group covalently planted on the metal surface and is in close contact with the vinyl group.

On the other hand, in places where light is not applied, polymerization of the coating film does not occur, and no bond is formed between the coating film and the metal surface,
If it is dipped in an appropriate developing solution, only the coating film portion not exposed to the light is dissolved and removed.

In this way, a vinyl polymer film that firmly adheres to the substrate is formed in the place exposed to the light, and the substrate surface is exposed in the place not exposed to the light, and OH groups and vinyl groups are exposed on the surface. .

In order to use this system as a printing plate, ink must be applied to the vinyl polymer film portion and water must be applied to the non-image portion where the substrate surface is exposed, so that the image cannot be turned on / off. I won't. The application of the ink to the vinyl 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

If the density of surface OH groups is sufficiently high, only the metal surface treated by the method of the present invention is exposed, and that part can behave as a non-image part.

When the density of surface OH groups is low and the number of vinyl groups is relatively large, and the lipophilic property cannot be ignored, a hydrophilic treatment of the vinyl groups is required.

This can be performed by, for example, a method of coordinating a vinyl group with a sulfate ion and then hydrolyzing it to convert it to an alcohol, or a method of oxidatively cleaving a Si-C bond to convert it to silanol.

The functional group fixed to the metal surface can be used to cause a reaction that contributes to adhesion in the image area and a hydrophilic reaction in the non-image area, so that various treatments can be performed according to the method of the present invention. It is readily understood that a range of offers is provided.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 23.4 g of triacetoxyvinylsilane in a 100 ml beaker
Add 1 g of acetic acid and 3.6 g of ion-exchanged water, and then add 50 g of ethanol
Was added and stirred at room temperature for 5 minutes.

The entire 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.

At a stage of 30 minutes after the bath temperature of 80 ° C. was reached, a piece of the aluminum plate whose surface was roughened was immersed in the reaction mixture 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 and silanol groups were confirmed, indicating that the composition can be used as a liquid composition for metal surface treatment.

The metal surface treatment was successfully performed even after 10 hours at the bath temperature of 80 ° C. However, after 11 hours, the liquid became too viscous, and the rotation of the magnetic stirrer was reduced to about 1 rotation per second. In this case, the dip coating was unfavorable because coarse and dense streaks were formed on the metal surface, but if a drop of the liquid composition was dropped onto the metal surface and the glass rod was rolled and roller-coated, uniform treatment could be performed. It was

When the composition was further kept in a bath at 80 ° C., the entire liquid composition gelled after 12 hours. The effective use time of the liquid composition in this example was about 11 hours at 80 ° C.

Example 2 23.4 g of triacetoxyvinylsilane in a 100 ml beaker
After adding 3.6 g of ion-exchanged water and 50 g of ethanol, the mixture was stirred at room temperature for 5 minutes.

The entire solution was transferred to a three-necked flask and subjected to hydrolysis and polycondensation reaction under the same conditions as in Example 1.

At a stage of 30 minutes after the bath temperature of 80 ° C. was reached, a piece of an aluminum plate having a roughened surface was immersed in a reaction mixture for 5 seconds, pulled up, dried, and then measured for diffuse reflection IR spectrum. Si
Although the formation of -O-Si bonds and the presence of surface vinyl groups and surface silanol groups were confirmed, the absorption intensity was about 2/3 of that at the same reaction time as in Example 1. The hydrolysis itself was completed at this point, as no IR peak from the acetoxy group was detected. Although the degree of polycondensation was slightly behind that of Example 1, it could be used as a metal surface treatment liquid at this stage.

The metal surface treatment was successfully performed even after 10 hours at the bath temperature of 80 ° C. After 11 hours, dip coating was not preferred because of the formation of streaks on the coating film surface, but roller coating was possible.

Even after a lapse of 22 hours from the achievement of the bath temperature of 80 ° C., the gelation of the liquid composition did not occur, and the metal surface could be uniformly treated by roller application.

At this stage, when 50 ml of ethanol was further added and stirred, the liquid composition returned to a uniform liquid composition having reduced viscosity, so that dip coating could be performed again.

When the liquid composition was taken out of the bath and its storage life was observed, gelation did not occur even after aging at room temperature for 1 year, and no precipitate appeared.

NMR 3 days after preparation of the liquid composition for metal surface treatment
As a result, no signal derived from the acetoxy group, which was observed as the strongest peak in the raw material triacetoxyvinylsilane, was not observed at all from the liquid composition. Further, it was recognized that the signal corresponding to the vinyl group became wider than that of the raw material, and was shifted by about 0.3 ppm in the direction of the peak from tetramethylsilane added as an internal standard. These results indicate that the electron-absorbing acetoxy was eliminated around the covalently bonded chelium atom, and that the vinyl group had mobility due to the formation of an inorganic polymer chain of silicon atoms. Indicates that has decreased.

An aluminum plate having a roughened surface, an aluminum plate having an anodic oxide film formed on the surface, and an aluminum having a silicate layer formed thereon by sodium silicate treatment No. 3 After processing the three metal surfaces of the plate and measuring the diffuse reflection IR spectrum, the amount of vinyl groups fixed on the surface was almost the same for all three, and there was no significant difference.Similarly, silicon wafers, copper plates, etc. Processing was successful. Even after one year of aging at room temperature, no change was observed in the processability.

Example 3 and Comparative Example 1 50 g of CH ₂ = CHSi (OCOCH ₃ ) ₃ , 1.1 g of acetic acid, 7.7 g of distilled water and 100 g of ethanol were placed in a beaker, and stirred at room temperature to form a uniform solution. Next, this solution was transferred to a three-necked flask equipped with a stirrer and a reflux condenser, and immersed in an oil bath.
The reaction was carried out for 7 hours while maintaining the bath temperature at 80 ° C. while stirring to prepare a liquid composition (sol liquid).

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied at 10 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional group (CH ₂ = CH-) obtained as described above
The following liquid composition 1 for a photosensitive resin layer was applied to an aluminum substrate having a surface thereof with a wheeler and dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A1. The coating weight after drying was 1.5 g / m ² .

Liquid composition for photosensitive resin layer 1 Trimethylolpropane triacrylate 15 g Poly (allyl methacrylate / methacrylic acid) copolymer 80/20 copolymer 50 / g 50 g 2,4-bis (trichloromethyl) -6- (4 ′ -Methoxynaphthyl) -S-triazine 1.5 g Propylene glycol monomethyl ether 1500 g F-177 (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 1 g Oil-soluble dye (Victoria Pure Blue BOH) 1.5 g Sol solution Was obtained in the same manner as described above, except that no photosensitive lithographic printing plate B1 was applied.

These photosensitive lithographic printing plates A1 and B1 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed from a distance of 1 m for 3 minutes, and placed in various environments as shown in Table 1. Thereafter, the results of the tape peeling test are shown in Table 1. From these results, it can be seen that the photosensitive lithographic printing plate A1 coated with the sol liquid has a clearly improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B1.

Example 4 and Comparative Example 2 57.4 g of Si (OC ₂ H ₅ ) _{4 in a} beaker, CH ₂ SiCHSi (OCOCH ₃ )
₃ 4.6 g, water 7.2 g, ethanol 100 g and acetic acid 2 g were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional group (CH ₂ CHCH-) obtained as described above
Liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having
And dried for 2 minutes to obtain a photosensitive lithographic printing plate A2. The coating weight after drying was 1.5 g / m 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 and B2 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m and placed in various environments as shown in Table 2. After that, the results of tape peeling test are shown in Table 2. From these results, it can be seen that the photosensitive lithographic printing plate A2 coated with the sol solution clearly has an improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B2.

Example 5 and Comparative Example 3 57.4 g of Si (OC ₂ H ₅ ) _{4 was} added to a beaker. 2.3 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, a 0.3 mm-thick aluminum plate was degreased with an alkali, and then anodized in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² , to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The organic functional groups (CH ₃ -and CH ₂
= CH-) on the surface of an aluminum substrate,
The liquid composition 1 for a photosensitive resin layer described above was applied with a wheeler and dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A3. The coating weight after drying was 1.5 g / m ² .

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 A3 and B3 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 3. Then, the results of the tape peeling test are shown in Table 3. From these results, it can be seen that the photosensitive lithographic printing plate A3 coated with the sol solution clearly has an improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B3.

Example 6 and Comparative Example ₄ 57.4 g of Si (OC ₂ H ₅ ) _{4 was} placed in a beaker, and CH ₂ CHCHCH ₂ Si (OC
₂ H _{5) 3} 4.1g, water 14.4 g, taking ethanol 100g and acetic acid 2g, and a uniform solution was stirred at room temperature. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The organic functional group obtained as described above (CH ₂得 CHCH
Liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having _2- ) on the surface using a wheeler.
It was dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A4. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B4 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A4 and B4 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 4. Then, the results of the tape peeling test are shown in Table 4. From these results, it can be seen that the photosensitive lithographic printing plate A4 coated with the sol solution clearly has an improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B4.

Example 7 and Comparative Example 5 57.4 g of Si (OC ₂ H ₅ ) _{4 was} added to a beaker. 3.8 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, a 0.3 mm-thick aluminum plate was degreased with an alkali, and then anodized in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² , to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional groups (CH ₃ − and CH ₂ — obtained as described above
= CH-) on the surface of an aluminum substrate,
The liquid composition 1 for a photosensitive resin layer described above was applied using a wheeler and dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A5. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B5 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A5 and B5 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 5. Then, the results of the tape peeling test are shown in Table 5. From this result, it can be seen that the photosensitive lithographic printing plate A5 coated with the sol liquid has clearly improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B5.

Example 8 and Comparative Example 6 57.4 g of Si (OC ₂ H ₅ ) _{4 in a} beaker, CH ₂ CHCHCH ₂ NH (CH ₂ )
₃ Si (OCH ₃ ) ₃ 4.4 g, water 14.4 g, ethanol 100 g and acetic acid 2
g was taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The organic functional group (CH ₂ = CHCH ₂ NH) obtained as described above
The liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having (CH ₂ ) ₃ −) on the surface using a wheeler and dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A6. Obtained. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B6 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A6 and B6 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 6. After that, the results of tape peeling test are shown in Table 6. From these results, it can be seen that the photosensitive lithographic printing plate A6 coated with the sol solution clearly has an improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B6.

Example 9 and Comparative Example 7 beaker _{Si (OC 2 H 5) 4} 57.4g, 4.6 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, a 0.3 mm-thick aluminum plate was degreased with an alkali, and then anodized in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² , to prepare a substrate.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The organic functional groups (CH ₃ and CH ₂ =
The liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having C (CH ₃ ) COO (CH ₂ ) _3- ) on the surface using a wheeler, and dried at 100 ° C. for 2 minutes to expose the composition. A lithographic printing plate A7 was obtained. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B7 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A7 and B7 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed from a distance of 1 m for 3 minutes, and placed in various environments as shown in Table 7. Then, the results of the tape peeling test are shown in Table 7. From this result, it can be seen that the photosensitive lithographic printing plate A7 coated with the sol liquid has clearly improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B7.

Example 10 and Comparative Example 8 beaker _{Si (OC 2 H 5) 4} 57.4g, CH 2 = CHCOO (CH 2) 3 S
i (OCH ₃ ) ₃ 4.6g, water 14.4g, ethanol 100g and acetic acid 2g
And stirred at room temperature to form a homogeneous solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The sol solution is applied to this substrate using a
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The organic functional group obtained as described above (CH ₂ CHCHCOO
The liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having (CH ₂ ) ₃ −) on the surface with a wheeler and dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A8. Obtained. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B8 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A8 and B8 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 8. Thereafter, the results of the tape peeling test are shown in Table 8. From these results, it can be seen that the photosensitive lithographic printing plate A8 coated with the sol solution clearly has an improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B8.

Example 11 and Comparative Example 9 57.4 g of Si (OC ₂ H ₅ ) _{4 was} added to a beaker, 9.4 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The sol solution is applied to this substrate using a
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional group obtained as described above Liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having
For 2 minutes to obtain a photosensitive lithographic printing plate A9. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B9 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A9 and B9 were sufficiently evacuated using a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 9. After that, the results of tape peeling test are shown in Table 9. From this result, it can be seen that the photosensitive lithographic printing plate A9 coated with the sol liquid has clearly improved adhesion between the photosensitive resin layer and the substrate as compared with the photosensitive lithographic printing plate B9.

Example 12 and Comparative Example 10 beaker _{Si (OC 2 H 5) 4} 57.4g, CH≡CSi (OC 2 H 5) 3 3.
8 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate.

The sol solution is applied to this substrate using a
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having an organic functional group (CH≡C-) obtained on the surface thereof as described above using a wheeler, and heated at 100 ° C. for 2 minutes. It was dried to obtain a photosensitive lithographic printing plate A10. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B10 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A10 and B10 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and were placed in various environments as shown in Table 10. After that, the results of the tape peeling test are shown in Table 10. From this result, the photosensitive lithographic printing plate A10 coated with the sol liquid
Indicates that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B10.

Example 13 and Comparative Example 11 57.4 g of Si (OC ₂ H ₅ ) _{4 in a} beaker, and CH ₂ （CHSi (OCH ₃ )
₃ 3.0 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional group (CH ₂ CHCH-) obtained as described above
Liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having
For 2 minutes to obtain a photosensitive lithographic printing plate A11. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B11 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A11 and B11 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed from a distance of 1 m for 3 minutes, and placed in various environments as shown in Table 11. After that, the results of tape peeling test are shown in Table 11. From this result, the photosensitive lithographic printing plate A11 coated with the sol liquid was used.
Indicates that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B11.

Example 14 and Comparative Example 2 57.4 g of Si (OC ₂ H ₅ ) _{4 was} added to a beaker. 3.2 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional groups (CH ₃ and CH ₂ =
The liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having CH-) on the surface using a wheeler.
It was dried at 100 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate A12. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B12 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A12 and B12 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed to a distance of 1 m for 3 minutes, and placed in various environments as shown in Table 12. Thereafter, the results of the tape peeling test are shown in Table 12. From this result, the photosensitive lithographic printing plate A12 coated with the sol liquid
Indicates that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B12.

Example 15 and Comparative Example 13 57.4 g of Si (OC ₂ H ₅ ) ₄ and (CH ₂ CHCH) ₂ Si (OC ₂
H ₅ ) ₂ 3.4 g, water 14.4 g, ethanol 100 g and acetic acid 2 g were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The sol solution is applied to this substrate using a
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional group (CH ₂ = CH-) obtained as described above
Liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having
For 2 minutes to obtain a photosensitive lithographic printing plate A13. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B13 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A13 and B13 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 13. After that, the results of the tape peeling test are shown in Table 13. From this result, the photosensitive lithographic printing plate A13 coated with the sol
Indicates that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B13.

Example 16 and Comparative Example 14 57.4 g of Si (OC ₂ H ₅ ) ₄ and CH ₂ ＣC (CH ₃ ) COO were added to a beaker.
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ 5.0 g, water 14.4 g, ethanol 100 g and acetic acid 2 g were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, a 0.3 mm-thick aluminum plate was degreased with an alkali, and then anodized in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² , to prepare a substrate. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The sol solution is applied to this substrate using a
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

The organic functional group (CH ₂ = C (C
H ₃ ) COO (CH ₂ ) _3- ) On the surface of an aluminum substrate, the liquid composition 1 for a photosensitive resin layer described in Example 3 was applied with a wheeler and dried at 100 ° C. for 2 minutes to form a photosensitive lithographic plate. Printing plate A
I got 14. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B14 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A14 and B14 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed for 3 minutes from a distance of 1 m, and placed in various environments as shown in Table 14. Table 14 shows the results of the tape peeling test. From this result, the photosensitive lithographic printing plate A14 coated with the sol liquid was used.
Indicates that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B14.

Example 17 and Comparative Example 15 57.4 g of Si (OC ₂ H ₅ ) _{4 was} added to a beaker, 4.4 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional groups (CH ₃ − and CH ₂ — obtained as described above
= CHCOO (CH ₂ ) _3- ) on an aluminum substrate having the surface thereof coated with a liquid composition 1 for a photosensitive resin layer described in Example 3 using a wheeler, and dried at 100 ° C for 2 minutes to form a photosensitive lithographic printing plate. A
Got 15 The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B15 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A15 and B15 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed to a distance of 1 m for 3 minutes, and placed in various environments as shown in Table 15. After that, the results of the tape peeling test are shown in Table 15. From these results, the photosensitive lithographic printing plate A15 coated with the sol liquid was used.
Shows that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B15.

Example 18 and Comparative Example 16 57.4 g of Si (OC ₂ H ₅ ) _{4 was} added to a beaker, 6.0 g, 14.4 g of water, 100 g of ethanol and 2 g of acetic acid were taken and stirred at room temperature to obtain a uniform solution. Next, this solution is transferred to a three-necked flask equipped with a stirrer and a reflux condenser, immersed in an oil bath, and allowed to react for 7 hours while maintaining the bath temperature at 80 ° C. with stirring to form a liquid composition (sol liquid). did.

On the other hand, an aluminum plate having a thickness of 0.3 mm was degreased with an alkali, and then subjected to anodizing treatment in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² to prepare a substrate. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The coating amount of the sol liquid on this substrate was dried using a wheeler.
It was applied so as to be 1 mg / m ² and dried at 170 ° C. for 10 minutes.

Organic functional group obtained as described above Liquid composition 1 for a photosensitive resin layer described in Example 3 was applied to an aluminum substrate having
After drying for 2 minutes, a photosensitive lithographic printing plate A16 was obtained. The coating weight after drying was 1.5 g / m ² .

A photosensitive lithographic printing plate B16 was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates A16 and B16 were sufficiently evacuated with a PS light manufactured by Fuji Photo Film Co., Ltd., and then exposed from a distance of 1 m for 3 minutes, and placed in various environments as shown in Table 16. After that, the results of tape peeling test are shown in Table 16. From this result, the photosensitive lithographic printing plate A16
Indicates that the adhesion between the photosensitive resin layer and the substrate is clearly improved as compared with the photosensitive lithographic printing plate B16.

Example 19 and Comparative Example 7 The following composition: Si (OCOCH ₃ ) ₄ 39.6 g HSCH ₂ Si (OCOCH ₃ ) ₃ 12.6 g Acetic acid 0.6 g Distilled water 7.2 g Ethanol 100 g A sol solution was prepared in the same manner. However, the reaction temperature was 70 ° C. and the reaction time was 8 hours.

On the other hand, an aluminum plate having a thickness of 0.3 mm was grained with a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then washed thoroughly with water. This was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, neutralized and washed with 20% nitric acid, and then subjected to electrochemical roughening described in JP-A-53-67507. Chemical formula, V _A
= 12.7V, V _C = 9.1% using sine wave alternating waveform current of 9.1V
Electrolytic surface roughening treatment was performed in a nitric acid aqueous solution at an anode electricity amount of 160 coulomb / dm ² . Subsequently, it was immersed in a 30% aqueous nitric acid solution, desmutted at 55 ° C. for 2 minutes, and then anodized in a 7% aqueous sulfuric acid solution to a thickness of 2.0 g / m ² .
Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

The following liquid composition 2 for a photosensitive resin layer was applied to an aluminum plate obtained by applying and drying a sol liquid on this substrate in the same manner as in Example 3 using a wheeler, and dried at 80 ° C. for 2 minutes. Thus, a photosensitive lithographic printing plate C was obtained.

Liquid composition for photosensitive resin layer 2 Hexafluorophosphate of condensate of 4-diazodiphenylamine and formaldehyde 1.0 g Polymer (a) 5.0 g Malic acid 0.05 g FC-430 (Fluorine surfactant manufactured by 3M USA) 0.05 g oil-soluble dye (Victoria Pure Blue BOH) 0.1 g 2-methoxyethanol 60 g methanol 20 g methyl ethyl ketone 20 g Note) Polymer (a) is a vinyl copolymer described in Example 3 of JP-B-55-34929. It is united.

A photosensitive lithographic printing plate D was obtained in exactly the same manner except that the sol solution was not applied.

These photosensitive lithographic printing plates C and D were image-exposed with a PS film manufactured by Fuji Photo Film Co., Ltd. using a negative film from a distance of 1 m for 1 minute, and an aqueous alkali developer DN- manufactured by Fuji Photo Film Co., Ltd. was used.
After immersing 3C in a solution diluted to a volume ratio of 1: 1 with tap water for 5 minutes, the surface of the photosensitive resin layer in the image area was lightly rubbed with a claw, and the lithographic printing plate C was scarcely scratched. On the other hand, the lithographic printing plate D was easily scratched.

Further, the lithographic printing plates C and D were image-exposed in the same manner as described above, and the same developer 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 were used. Developing machine PS-8
After a development process at 00H, a printing test was performed on a Heidelberg GTO printing press. The planographic printing plate C showed a printing durability of 100,000 sheets, while the lithographic printing plate D showed a printing durability of 80,000 sheets. There was only power. In addition, in each of the lithographic printing plates C and D, no background stain occurred in the non-image portion.

Examples 20 to 26 and Comparative Example 18 A sol solution was prepared in the same manner as in Example 3 from a mixed solution having the composition shown in the table on the next page. These sols ~
Was applied to the same substrate as in Example 19 by the same method as in Example 3 and dried, and the following liquid composition 3 for photosensitive resin layer was applied to the obtained aluminum substrate in the same manner as in Example 19. After drying, photosensitive lithographic printing plates E1 to E7 were obtained.

Liquid composition 3 for photosensitive resin layer 3 ○ trimethylolpropane triacrylate 20 g ○ poly (allyl methacrylate / methacrylic acid) copolymer 80/20 copolymer 50 g ○ 2,4-bis (trichloromethyl) -6 -(4'-Methoxynaphthyl) -S-triazine 2 g ○ Behenamide 1 g ○ Propylene glycol monomethyl ether 1500 g ○ F-177 (Fluorine surfactant manufactured by Dainippon Ink Co., Ltd.) 1.5 g ○ Oil solubility Dye (Victoria Pure Blue BOH) 1.5 g On the other hand, a photosensitive lithographic printing plate F was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates E1, E2, and F were subjected to image exposure and development in the same manner as in Example 19, and a printing test was performed. As a result, the lithographic printing plate F exhibited a printing durability of 180,000 sheets. Against
The lithographic printing plates E1 and E2 had a printing durability of 220,000 sheets.

In addition, the photosensitive lithographic printing plates E1 to E7 and F were subjected to a tape peeling test in the same manner as in Example 3. As a result, F was partially immersed in water for 3 days after exposure and at 200 gf / cm ² in boiling for 7 hours after exposure. In contrast, E1 to E7 did not peel off.

Example 27 and Comparative Example 19 The following composition: CH ₂ CHCH—Si (OCOCH ₃ ) ₃ 11.6 g Si (OCOCH ₃ ) ₄ 39.6 g Acetic acid 0.6 g Distilled water 7.2 g Ethanol 100 g A sol solution was prepared in the same manner as in 3.

This sol solution was applied to the same substrate as in Example 19 except that it was not treated with an aqueous sodium silicate solution and dried in the same manner as in Example 3, and the obtained aluminum substrate was used for the photosensitive resin layer shown below. The liquid composition 4 was applied and dried in the same manner as in Example 19 to obtain a photosensitive lithographic printing plate G.

However, the dry coating amount of the photosensitive resin layer was 1 g / m ² .

Liquid composition for photosensitive resin layer 4 N [2- (methacryloyloxy) ethyl] -2,3-dimethylmaleimide / methacrylic acid = 65/35 (weight ratio) copolymer 5 g ・ Propylene glycol monomethyl ether 80 g ・ Methyl ethyl ketone 80 g ・ Megafac F-177 (Dainippon Ink and Chemicals, fluorine nonionic surfactant) 0.03 g ・ Plasticizer 10% dispersion of copper phthalocyanine pigment (CL Pigment Blue15) Liquid 1.0 g A photosensitive lithographic printing plate H was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates G and H were exposed in the same manner as in Example 19, and an aqueous alkali developer DP-4 manufactured by Fuji Photo Film Co., Ltd. was diluted with tap water to a volume ratio of 1: 7. Using a solution prepared by diluting the production gum solution FP with tap water to a volume ratio of 1: 1,
When development was carried out in the same manner as in Example 19, the lithographic printing plate H had slight scratches on the image area during development, whereas the lithographic printing plate G had no scratches and the image was firm.

When these lithographic printing plates G and H were subjected to a printing test in the same manner as in Example 19, the lithographic printing plate G had a printing durability of 60,000 sheets, whereas the lithographic printing plate H had a printing durability of 40,000. There was only one.

Examples 28 to 32 and Comparative Example 20 A sol was prepared from the mixture shown in the following table in the same manner as in Example 3.

These sol solutions were applied to the same substrate as in Example 27 in the same manner as in Example 3, and dried on an aluminum substrate, and a photosensitive resin layer similar to that in Example 27 was applied to the same substrate as in Example 27. Coating (after drying) was performed in such a manner that the coating amount (after drying) was 1.5 g / m ² , followed by drying to obtain photosensitive lithographic printing plates I1 to I5.

A photosensitive lithographic printing plate J was obtained in exactly the same manner as described above except that the sol solution was not applied.

When a printing durability test was performed on the photosensitive lithographic printing plates I1 and J in the same manner as in Example 27, J showed a printing durability of 50,000 sheets, whereas I1 showed a printing durability of 100,000 sheets. Was.

In addition, as a result of performing a tape peeling test on the photosensitive lithographic printing plates I1 to I5 and J in the same manner as in Example 3, although J was immersed in water for 3 days after exposure and then peeled off at 100 gf / cm ² by boiling for 7 hours On the other hand, I1 to I5 did not peel off.

Example 33 and Comparative Example 21 the following _{composition: CH 2 = CH-Si (} OOCH 3) 3 7.0g HSCH 2 Si (OCOCH 3) 3 7.6g Si (OCOCH 3) 4 37.0g acetic acid 0.6g distilled water 7.2g A sol solution was prepared from a mixed solution containing 100 g of ethanol in the same manner as in Example 1. However, the reaction temperature was 70 ° C. and the reaction time was 8 hours.

The same substrate as in Example 19 was dipped in this sol solution and dried to obtain an aluminum substrate, and the following liquid composition 5 for photosensitive resin layer was applied and dried in the same manner as in Example 19 to obtain a flat plate. Printing plate K was obtained.

However, the dry coating amount of the photosensitive resin layer was 2.0 g / m ² .

Liquid composition 5 for photosensitive resin layer β-cinnamyloxyethyl methacrylate / methacrylic acid = 90/10 weight ratio copolymer (acid value 61, molecular weight from GPC
48,000) 5 g PF ₆ salt of a condensate of P-diazodiphenylamine and formaldehyde 0.2 g diethyl phthalate 0.5 g F-177 (Dainippon Ink and Chemicals, Inc .: Fluorine nonionic surfactant) 0.02 g Methyl ethyl ketone 30 g Ethylene glycol monomethyl ether 10 g Propylene Glycol monomethyl ether 55 g Deionized water 5 g On the other hand, a photosensitive lithographic printing plate L was obtained in exactly the same manner as described above except that the sol solution was not applied.

These photosensitive lithographic printing plates were exposed and developed in the same manner as in Example 19 to perform a printing test.
Printing capacity was 300,000 sheets, while planographic printing plate L was 25
There were only 10,000 copies.

Claims (1)

(57) [Claims] 1. A liquid composition containing an inorganic polymer obtained by hydrolyzing and polycondensing an organometallic compound having an organic functional group and a group which undergoes polycondensation following hydrolysis.
A photosensitive lithographic printing plate characterized in that a photosensitive resin composition layer is provided on an aluminum surface which has been treated by being applied to an aluminum surface.