JPH0667411A - Waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To improve photosensitivity by incorporating a specified component into a photosensitive resin layer. CONSTITUTION:A photosensitive resin layer and a silicone rubber layer are formed in this order on a substrate. The photosensitive resin layer contains a compd. obtd. by the reaction of one mol of polyamine expressed by formula and two mols of compd. containing polymerizable ethylenic unsatd. groups and groups which can react with this polyamine. In formula, n is an interger >1. Further, the resin contains a photopolymn. initiator and a polymer compd. which can form a film, for example, a polymer compd. having photopolymerizable or photocrosslinkable olefinic unsatd. double bonds in side chains. The obtd. printing plate having this photosensitive resin layer is exposed to light through a transparent master picture, and then developed with a developer which partly or wholly dissolves or swells the photosensitive resin layer in the area to be developed (the area not exposed), or with a developer which can swell the silicone rubber layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fountain solution-free photosensitive lithographic printing plate suitable for producing a fountain solution-free lithographic printing plate that can be printed without using a fountain solution.

[0002]

2. Description of the Related Art There have been proposed various types of photosensitive lithographic printing plates which do not require fountain solution and which do not require fountain solution for performing lithographic printing without using fountain solution. Among them, the one in which the photosensitive resin layer and the silicone rubber layer are sequentially coated on the substrate has extremely excellent performance,
For example, Japanese Patent Publication No. 54-26923 and Japanese Patent Publication No. 55-227.
Those described in Japanese Patent No. 81 can be mentioned.

The silicone rubber layer used in these photosensitive lithographic printing plates that do not require a fountain solution is usually a high molecular polymer having polysiloxane as a main skeleton partially crosslinked with a crosslinking agent. . As the method for curing the silicone rubber layer, the following two methods are usually used. (1) Condensation type: a method in which an organopolysiloxane having hydroxyl groups at both ends is crosslinked with a silane or siloxane having a hydrolyzable functional group directly bonded to a silicon atom to obtain a silicone rubber. (2) Addition type: ≡Si-H group-containing polysiloxane-
A method for producing a silicone rubber by subjecting a polysiloxane having a CH = CH- group to an addition reaction (JP-A-61-
No. 73156, Japanese Patent Application No. 1-301568, etc.).

The condensation-type silicone rubber of (1) has a sensitivity that is different from that of a photosensitive printing plate which does not require dampening water, because its curability and adhesive strength to the photosensitive layer change depending on the amount of water in the atmosphere during curing. It has the drawback that it tends to fluctuate and stable manufacture is difficult. In this respect, the addition type silicone rubber (2), which does not have such a defect, is considered to be superior.

In the case of a positive type lithographic printing plate, a photopolymerizable photosensitive composition which is cured by exposure has been used as the photosensitive resin layer. As an image forming method of a photosensitive lithographic printing plate having this layer structure, generally, a photosensitive resin layer is cured by exposure to light, and in some cases, photoadhesion is performed at an interface with the uppermost silicone rubber layer, The layers are firmly bonded to each other to prevent permeation by the developing solution and the elution of the photosensitive resin layer due to the permeation by the developer, thereby forming a non-image portion formed of the silicone rubber layer. On the other hand, the image area is formed by permeating the developing solution through the silicone rubber layer to dissolve a part or all of the uncured photosensitive resin layer, and then removing the silicone rubber layer on it by physical force. To be done. Although the image is formed in this way, compared to a normal lithographic printing plate that is printed using fountain solution, the sensitivity of the photosensitive lithographic printing plate that does not require fountain solution is low. It had the drawback of being long and poor in workability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly sensitive fountain solution-free photosensitive lithographic printing plate.

[0007]

Means for Solving the Problems The present inventor has specified a specific photosensitive resin layer of a photosensitive lithographic printing plate which does not require fountain solution, which is formed by laminating a photosensitive resin layer and a silicone rubber layer on a substrate in this order. By containing a photopolymerizable compound, it was found that a highly sensitive dampening water unnecessary photosensitive lithographic printing plate can be obtained,
The present invention has been completed based on this finding.

That is, the present invention provides a photosensitive lithographic printing plate that does not require a fountain solution and has a substrate, a photosensitive resin layer provided on the substrate, and a silicone rubber layer provided on the photosensitive resin layer. A photosensitive lithographic printing plate not requiring fountain solution, wherein the photosensitive resin layer contains at least the following components. (1) A compound obtained by reacting at least 2 moles of at least one kind of polyamine represented by the following general formula (I) with a compound having a group capable of reacting with the polyamine and a polymerizable ethylenically unsaturated group.

[0009]

[Chemical 2]

(2) A photopolymerization initiator and (3) a polymer compound capable of forming a film.

The present invention will be described in detail below. The fountain solution-free lithographic printing plate of the present invention must be flexible enough to be set in an ordinary printing machine and capable of withstanding the load applied during printing. Therefore, as a typical substrate, a coated paper, a metal plate such as aluminum, a plastic film such as polyethylene terephthalate, rubber, or a composite thereof can be given. The surface of these substrates can be further coated with a primer layer or the like for the purpose of preventing halation and other purposes.

As the primer layer, various types are used for the purpose of improving the adhesion between the substrate and the photosensitive resin layer, preventing halation, dyeing an image and improving printing characteristics. For example,
Various photosensitive polymers as disclosed in JP-A-60-22903, which are exposed and cured before laminating a photosensitive resin layer, disclosed in JP-A-62-50760. A heat-cured epoxy resin, a gelatin-hardened film disclosed in JP-A-63-133151, and Japanese Patent Application No. 1-2822.
Examples thereof include those using a urethane resin disclosed in Japanese Patent Application No. 70 and Japanese Patent Application No. 2-21072.
In addition, a casein-hardened casein is also effective. Further, for the purpose of softening the primer layer, polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxylic acid-modified, which has a glass transition temperature of room temperature or lower, are contained in the primer layer. Acrylonitrile /
Butadiene rubber, polyisoprene, acrylate rubber,
Polymers such as polyethylene, chlorinated polyethylene and chlorinated polypropylene may be added. The addition ratio is arbitrary, and the primer layer may be formed only with the additive as long as it is within the range in which the film layer can be formed. Further, in these primer layers, along with the above-mentioned purpose, a dye, a pH indicator, a printout agent, a photopolymerization initiator, an adhesion aid (for example,
Polymerizable monomer, diazo resin, silane coupling agent,
Additives such as titanate coupling agents and aluminum coupling agents), white pigments and silica powder can also be included. Generally, the coating amount of the primer layer is preferably in the range of 0.1 to 20 g / m ² as dry weight, and preferably 1
10 to 10 g / m ² .

The photosensitive resin layer used in the present invention is as follows:
It may contain the components (1), (2) and (3), and may further contain the component (4). (1) A compound obtained by reacting at least 2 mol of a compound having a group capable of reacting with the polyamine and a polymerizable ethylenically unsaturated group with at least 1 mol of the polyamine represented by the general formula (I). (2) A photopolymerization initiator and (3) a polymer compound capable of forming a film.

Component (1): Reaction product of polyamine (I) with a compound capable of reacting with the polyamine and a polymerizable ethylenically unsaturated group-containing compound n of the polyamine (I) used in the present invention
Is an integer of 1 or more, but from the viewpoint of synthesis, 1 to 5
It is 0, more preferably 1 to 20.

Examples of the compound having a group capable of reacting with the polyamine and a polymerizable ethylenically unsaturated group include compounds represented by the following general formulas (II), (III) and (IV).

[0016]

[Chemical 3]

In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms or methyl groups. A is -CO-O-, -CO-NH-,
It is a substituted or unsubstituted phenylene group. R ⁵ is CO X, SO ₂ X
And X represents a halogen atom. a, b, c, d, e, f
Indicates 0 or 1. L ¹ , L ² , L ³ and L ⁴ represent a divalent linking group. _{^{Preferably, - (L 5) p -}} (L 6) q - represented by.

In the formula, L ⁵ is a substituted or unsubstituted cyclic or acyclic alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted phenylene, a substituted or unsubstituted alkylene, and the substituent is Examples thereof include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an aryl group and the like. L ⁶ is −
^{(O- (E 1)) -} , - (S- (E 2)) -, - (NH- (E 3))
−, − (CO− (E ⁴ )) −, − (SO ₂ NH − (E ⁵ )) −,
E ¹ , E ² , E ³ , E ⁴ , E ⁵ are the above alkylene,
They are phenylene and aralkylene.

P is an integer of 1 or more, and q is 0 or an integer of 1 or more. More preferably, when p is 1 and q is 0, L
¹ is alkylene having 1 to 6 carbon atoms, p is 1 and q is an integer of 1 or more, L ¹ is alkylene having 1 to 6 carbon atoms,
L ² is-(O- (E ¹ ))-,-(NH- (E ³ ))-and is E ¹ , E ³
Is an alkylene having 1 to 6 carbon atoms.

Specific examples include glycidyl (meth) acrylate, (meth) acrylic acid chloride and (meth) acrylic anhydride. From 1 mol of the polyamine, the compound containing a group reactive with the polyamine and a polymerizable ethylenically unsaturated group is added from 2 mol,
It is the number of moles capable of reacting with all the active hydrogen of (I). Preferably 2 moles to (4 + 3n) moles, more preferably 4 moles.
It is from mol to (4 + 2n) mol. A compound containing a group that reacts with the polyamine and a polymerizable ethylenic unsaturation may be mixed and used. Further, if necessary, an ethylenically unsaturated group-containing monomer or oligomer other than the compound represented by (1) and the compound represented by (4) described later may be added. Specific examples of the compound of component (1) are shown in Table 1, but the present invention is not limited thereto. or,
You may mix and use the compound of a component (1).

[0021]

[Table 1]

Component (2): Photopolymerization initiator As the photopolymerization initiator used in the present invention, US Pat.
Bisinal polyketaldonyl compounds disclosed in 2,367,660, U.S. Patents 2,367,661 and 2,36
Α-carbonyl compounds disclosed in US Pat. No. 7,670, acyloin ethers disclosed in US Pat. No. 2,448,828, α-positions disclosed in US Pat. No. 2,722,512 replaced by hydrocarbons Aromatic acyloin compounds, U.S. Pat. Nos. 3,046,127 and 2,951,75
Polynuclear quinone compounds disclosed in U.S. Pat. No. 3,549,367, triarylimidazole dimer / p-aminophenyl ketone combinations disclosed in U.S. Pat. No. 3,870,524. Benzothiazole compounds, benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in U.S. Pat. No. 4,239,850, and U.S. Pat.
Acridine and phenazine compounds disclosed in 751,259, Oxadiazole compounds disclosed in U.S. Patent No. 4,212,970, U.S. Patent No. 3,954,47
5, JP-A-53-133428, US Pat. No. 4,189,
No. 323, JP-A-60-105667, JP-A-62-5
8241, JP-A-63-153542, and trihalomethyl-s-triazine compounds having a chromophore group, JP-A-59-197401 and JP-A-6.
Examples thereof include benzophenone group-containing peroxyester compounds disclosed in 0-76503. These may be used alone or in combination.

The amount of these photopolymerization initiators added is 0.1 to 20% by weight, more preferably 1 to 20% by weight, based on the total photosensitive composition.
It is 10% by weight.

Component (3): polymer compound having film-forming ability The polymer compound having film-forming ability used in the present invention includes a methacrylic acid copolymer, an acrylic acid copolymer, a crotonic acid copolymer, and maleic acid. Acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative,
Polyvinylpyrrolidone, polyethylene oxide, alcohol-soluble nylon, polyester, unsaturated polyester, polyurethane, polystyrene, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl formal, polyvinyl chloride, polyvinyl alcohol, partially acetalized polyvinyl alcohol, water-soluble nylon,
Examples thereof include water-soluble urethane, gelatin, water-soluble cellulose derivatives and the like.

Further, as the polymer compound capable of forming a film, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in its side chain can be used. Examples of such a polymer compound include allyl (meth) acrylate / (meth) acrylic acid / another addition-polymerizable vinyl monomer copolymer as described in JP-A-59-53836. ,
And its alkali metal salts or amine salts, JP-B-59-4
A hydroxyethyl (meth) acrylate / (meth) acrylic acid / alkyl (meth) acrylate copolymer and an alkali metal salt or amine salt thereof, which are reacted with (meth) acrylic acid chloride, One obtained by half-esterifying a maleic anhydride copolymer with pentaerythritol triacrylate as described in JP-A-59-71048, and its alkali metal salt or amine salt; styrene / maleic anhydride copolymer Monohydroxyalkyl (meth) acrylate, polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate added to the polymer by half-esterification and its alkali metal salts or amine salts; (meth) acrylic acid co- Polymers and crotonic acid copolymers Part of carboxylic acid reacted with glycidyl (meth) acrylate and its alkali metal salts or amine salts; hydroxyalkyl (meth) acrylate copolymer, polyvinyl formal, polyvinyl butyral with maleic anhydride or itaconic anhydride And an alkali metal salt or amine salt thereof; a hydroxyalkyl (meth) acrylate / (meth) acrylic acid copolymer with 2,4-tolylene diisocyanate / bidroxyalkyl (meth) acrylate = 1/1 adduct Reaction products and their alkali metal salts and amine salts;
No. 9-53836, a part of (meth) acrylic acid copolymer reacted with allyl glycidyl ether and its alkali metal salt or amine salt; (meth) vinyl acrylate / (meth) acrylic Acid copolymer and its alkali metal salt or amine salt; (meth) allyl acrylate / sodium styrene sulfonate copolymer;
(Meth) vinyl acrylate / sodium styrene sulfonate copolymer, (meth) allyl acrylate / acrylamide / 1,1-dimethyl sodium sulfonate copolymer, vinyl (meth) acrylate / acrylamide / 1,1-dimethyl Examples thereof include sodium ethylene sulfonate copolymer, 2-allyloxyethyl methacrylate / methacrylic acid copolymer, 2-allyloxyethyl methacrylate / 2-methacryloxyethyl hydrogen succinate copolymer and the like. These may be used alone or in combination.

The polymer compound may be contained in an amount of 30 to 99% by weight, preferably 50 to 97% by weight, based on the total photosensitive composition.

Component (4): ethylenic other than component (1)
Unsaturated group-containing monomer or oligomer As the ethylenically unsaturated group-containing monomer or oligomer other than the component (1) optionally used in the present invention,
Examples include monomers or oligomers having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples thereof include acrylic acid or methacrylic acid esters of (A) alcohols (for example, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.), and (B) amines (for example, Methylamine, ethylamine, butylamine, benzylamine, ethylenediamine, hexylenediamine, diethylenetriamine, hexamethylenediamine, xylylenediamine, dimethylamine, diethylamine, ethanolamine, diethanolamine, aniline) and glycidyl acrylate, allylglycidyl or glycidyl methacrylate A reaction product with (C) a carboxylic acid (for example, acetic acid, propionic acid, benzoic acid, acrylic acid,
Reaction products of methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl metaxylylenediamine, (D) amide derivatives (eg, Acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), (E) a reaction product of an epoxy compound with acrylic acid or methacrylic acid, and the like.

More specifically, Japanese Examined Patent Publication No. 48-41708
No. 5, JP-B-50-6034, JP-A-51-37193
Urethane acrylates as described in JP-A Nos. 48-64183 and 49-4319.
1, polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B No. 52-30490, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and US Pat. No. 4,540,649. The N-methylol acrylamide derivative described in the book can be mentioned. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association Magazine Vol. 20, No. 7 (1984), pages 300 to 308 can be used.

In the polyfunctional monomer, the unsaturated group may be a mixture of acryl, methacryl, and allyl groups.

These may be used alone or in combination.

Monomers and oligomers of the components (1) and (4) are 1 to 70% by weight based on the total photosensitive composition,
Preferably, it may be contained in an amount of 3 to 60% by weight. Further, the component (1): component (4) (weight ratio) is 100: 0 to 20:
80, preferably 80:20 to 40:60.

It is preferable to add a thermal polymerization inhibitor in addition to the above other components , for example, hydroquinone, p-methoxyphenol,
Di-t-butyl-p-cresol, pyrogallol, t-
Butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 '
-Methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful. In some cases, a dye or pigment for the purpose of coloring the photosensitive resin layer or a pH indicator or leuco dye as a printout agent. Can also be added. Depending on the purpose, a small amount of polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, silane coupling agent, silicone diacrylate, silicone dimethacrylate, etc. may be further contained in the photosensitive resin layer. Silicone compounds may be added. A silicone-based surfactant or a fluorine-based surfactant may be added to improve coating suitability. Further, a diazo resin may be added to improve the adhesion between the photosensitive resin layer and the primer layer. The addition amount of these additives is usually 1 based on the total photosensitive composition.
It is 0% by weight or less. In some cases, in order to enhance the adhesiveness with the silicone rubber layer, a silica powder or a hydrophobic silica powder whose surface is treated with a (meth) acryloyl group- or allyl group-containing silane coupling agent is used for all photosensitive compositions. It may be added in an amount of 50% by weight or less.

The photosensitive composition as described above includes, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, methanol, ethanol, methyl ethyl ketone,
A suitable solvent such as water alone or dissolved in a mixed solvent thereof is applied onto a substrate, and its coating amount is preferably in the range of about 0.1 to 20 g / m ^{2 by} weight after drying, is 0.
It is in the range of 5 to 10 g / m ² .

<Silicone Rubber Layer> The silicone rubber layer preferably used in the present invention is a linear or partially cross-linked polydiorganosiloxane and has the following repeating units. —Si (R) ₂ —O— Here, R represents an alkyl group, an aryl group, an alkenyl group or a monovalent group in which these are combined, and they are a halogen atom, an amino group, a hydroxy group, an alkoxy group, an aryloxy group. It may have a functional group such as a group, a (meth) acryloxy group, and a thiol group. In the silicone rubber, if necessary, fine powder of an inorganic substance such as silica, calcium carbonate, titanium oxide, the above-mentioned silane coupling agent, an adhesion aid such as a titanate coupling agent or an aluminum coupling agent, or a light. A polymerization initiator may be added.

As a raw material for a polymer (silicone rubber) having the above polysiloxane as a main skeleton, a polysiloxane having a functional group at the terminal with a molecular weight of several thousand to several hundred thousand is used. A silicone rubber layer is obtained by crosslinking and curing by a method. That is, specifically, a silane-based cross-linking agent represented by the following general formula is mixed into the above polysiloxane having hydroxyl groups at both ends or only at one end, and if necessary, an organometallic compound, for example, an organotin compound. A catalyst such as an inorganic acid or an amine is added to heat the polysiloxane and the silane-based cross-linking agent, or the polysiloxane is condensed and cured at room temperature.

R _n SiX _4-n where n is an integer from 1 to 3, R is a substituent similar to R shown above, and X is -0H, -OR ² , -OAc, -O.
Represents ^{-N = CR 2 R 3, -Cl} , -Br, substituents such as -I. Here, R ² and R ³ have the same meaning as R described above, and R ² and R ³ may be the same or different. Ac represents an athicel group.

In addition, an organopolysiloxane having a hydroxyl group at the terminal and a hydrogenpolysiloxane crosslinking agent and, if necessary, the above-mentioned silane crosslinking agent are condensation-cured.

Besides, an addition type silicone rubber layer which is crosslinked by an addition reaction of ≡SiH group and —CH═CH— group is also useful. The addition-type silicone rubber layer is relatively insensitive to humidity during curing, and has the advantage that it can be crosslinked at high speed and that a silicone rubber layer having certain physical properties can be easily obtained. The addition type silicone rubber layer used here is obtained by reacting a polyvalent hydrogen organopolysiloxane with a polysiloxane compound having two or more —CH═CH— bonds in one molecule, and preferably the following: Ingredients: (1) Organopolysiloxane having at least two alkenyl groups (more desirably vinyl groups) directly bonded to silicon atoms in one molecule 100 parts by weight (2) Having at least two ≡SiH bonds in one molecule It is a composition obtained by curing and crosslinking a composition comprising 0.1 to 10000 parts by weight of orthohydrogenpolysiloxane (3) 0.0001 to 10 parts by weight of addition catalyst. The alkenyl group of the component (1) may be at either the terminal of the molecular chain or at the middle thereof, and a preferable organic group other than the alkenyl group is
A substituted or unsubstituted alkyl group or aryl group.
The component (1) may have a small amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer, but also plays a role of imparting adhesiveness to the photosensitive layer.
The hydrogen group of the component (2) may be at the terminal or in the middle of the molecular chain, and the organic group other than hydrogen is selected from the same as the component (1). It is preferable that the organic groups of the component (1) and the component (2) are, in general, 60% or more of the number of methyl groups, from the viewpoint of improving the ink resilience. The molecular structure of component (1) and component (2) may be linear, cyclic or branched, and it is preferable that at least one of them has a molecular weight of more than 1,000 from the viewpoint of rubber physical properties. (1)
Preferably has a molecular weight of more than 1,000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane, (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the like. Examples thereof include hydrogen-containing polydimethylsiloxane, α, ω-dimethylpolymethylhydrogensiloxane, (methylhydrogensiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals, cyclic, and polymethylhydrogensiloxane.

The addition catalyst of the component (3) is arbitrarily selected from known ones, but a platinum-based compound is particularly preferable, and platinum simple substance, platinum chloride, chloroplatinic acid, olefin coordinated platinum and the like are exemplified. . For the purpose of controlling the curing rate of these compositions, vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohol, acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol monomethyl ether. It is also possible to add a crosslinking inhibitor such as.

These compositions are characterized in that an addition reaction occurs at the time when the three components are mixed and curing begins, but the curing rate rapidly increases as the reaction temperature increases. Therefore, the pot life until the rubber of the composition is lengthened,
In addition, for the purpose of shortening the curing time on the photosensitive layer, the composition should be cured under the temperature conditions in which the characteristics of the support and the photosensitive layer do not change, and kept at a high temperature until completely cured. However, it is preferable in terms of stability of the adhesive force with the photosensitive layer.

In addition to these compositions, a known adhesion-imparting agent such as alkenyltrialkoxysilane may be added, or a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group-containing composition of the condensation type silicone rubber layer may be added. Adding silane (or siloxane) is also optional,
Further, it is optional to add a known filler such as silica for the purpose of improving the rubber strength.

The silicone rubber layer in the present invention serves as a printing ink repulsion layer. If the thickness is small, there are problems such as a decrease in ink repulsion and easy scratches. Therefore, the thickness is preferably 0.5 μm to 5 μm.

In the photosensitive lithographic printing plate not requiring fountain solution described above, it is optional to further coat various silicone rubber layers on the silicone rubber layer, and between the photosensitive resin layer and the silicone rubber layer. It is optional to provide an adhesive layer between the photosensitive resin layer and the silicone rubber layer for the purpose of increasing the adhesive strength of the silicone rubber composition or preventing poisoning of the catalyst in the silicone rubber composition.

Further, in order to protect the surface of the silicone rubber layer, a transparent film such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate or cellophane may be laminated on the silicone rubber layer. Alternatively, a polymer coating may be applied. You may stretch and use these films. Further, the film may be matted to improve the vacuum adhesion in the baking frame during image exposure.

The photosensitive lithographic printing plate requiring no fountain solution according to the present invention is exposed through a transparent original image, and then a developing solution capable of dissolving or swelling part or all of the photosensitive resin layer in the image area (unexposed area), or It is developed with a developer capable of swelling the silicone rubber layer. In this case, the photosensitive resin layer in the image area and the silicone rubber layer on it may be removed, or only the silicone rubber layer in the image area may be removed, which can be controlled by the strength of the developer. it can.

As the developing solution used in the present invention, those known as a developing solution for a photosensitive lithographic printing plate not requiring dampening water can be used. For example, aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene) , Xylene, etc.), or a halogenated hydrocarbon (trichlene, etc.) to which the following polar solvent is added, or the polar solvent itself is preferable.

Alcohols (methanol, ethanol, propanol, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, 2-ethoxyethanol, carbitol monoethyl ether, carbitol monomethyl ether, triethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene glycol, polypropylene glycol, triethylene glycol, tetraethylene glycol) ・ Ketones (acetone, methyl ethyl ketone) ・ Esters (ethyl acetate , Methyl lactate, ethyl lactate,
Butyl lactate, propylene glycol monomethyl ether acetate, carbitol acetate, dimethyl phthalate, diethyl phthalate) Others (triethyl phosphate, tricresyl phosphate) In addition, water is added to the organic solvent-based developer or the organic solvent is used. Solubilized in water using a surfactant, etc.,
Further, an alkaline agent such as sodium carbonate, monoethanolamine, diethanolamine, triethanolamine, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, sodium borate, or the like is added, or in some cases, Simply tap water or alkaline water can be used as the developer.

Further, dyes such as crystal violet, Victoria pure blue, and Astrazone red can be added to the developing solution to dye the image area simultaneously with development.

The development can be carried out by a known method such as rubbing the plate surface with a developing pad containing a developing solution as described above, or pouring the developing solution onto the plate surface and then rubbing it with a developing brush in water. . As a result, the silicone rubber layer and the photosensitive layer in the image area are removed and the surface of the substrate or the primer layer is exposed, and that area becomes the ink receiving section, or only the silicone rubber layer in the image area is removed and the photosensitive layer is exposed. That portion becomes the ink receiving portion.

[0051]

The photosensitive lithographic printing plate not requiring fountain solution of the present invention has a layer structure in which a photosensitive resin layer and a silicone rubber layer are laminated in this order on a substrate, and the photosensitive resin layer is
(1) A reaction product of the polyamine of the general formula (I) with a group capable of reacting with the polyamine and a compound containing a polymerizable ethylenically unsaturated group, (2) a photopolymerization initiator, and (3) a high film-forming ability. High sensitivity because it contains a molecular compound.

[0052]

[Synthesis Example] Synthesis of Compound A (Table 1) 43.3 g (0.305 mol) of glycidyl methacrylate
20g of gascamine 328 (manufactured by Mitsubishi Gas Chemical Co., Inc.)
Was added dropwise at room temperature. After dropping, stir at 80 ° C. for 5 hours,
The reaction was completed.

[0053]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 A 0.3 mm thick JIS A 1050 degreased by a conventional method
The aluminum plate was immersed in a 1% aqueous solution of KBM603 (Shin-Etsu Chemical Co., Ltd.), which is an amine silane coupling agent, and then dried at room temperature. The following primer solution was applied onto the aluminum plate so that the dry weight was 4 g / m ^2, and the film was heated at 140 ° C. for 2 minutes to dry and harden the film. o Samprene IB1700D (Terminal hydroxyl group-containing thermoplastic polyurethane resin, 10 parts by weight Methyl ethyl ketone 30% solution, Sanyo Kasei Co., Ltd.) o Takenate D11ON (Polyfunctional isocyanate compound, ethyl acetate 0.5% by weight 75% solution, Takeda Pharmaceutical Co., Ltd.) OTiO ₂ 0.1 parts by weight oMCF 323 (fluorine nonionic surfactant, methyl isobuty 0.03 parts by weight ruketone 30% solution, Dainippon Ink and Chemicals, Inc.) o propylene glycol methyl ether acetate 50 parts by weight Part o Methyl lactate 20 parts by weight A photopolymerizable photosensitive solution having the following composition was applied on an aluminum plate coated with the above primer layer so that the dry weight was 5 g / m ^2, and dried at 100 ° C. for 1 minute. It was

[0055] o Crisvon 3006LV 1.5 parts by weight (manufactured by Dainippon Ink and Chemicals (Ltd.)) o Compound A 1.0 parts by weight _{oCH 2 = CHCOO - (CH 2} CH 2 O) 14 -COCH = CH 2 1. 0 parts by weight (Shin-Nakamura Chemical Co., Ltd. A-600) o Ethyl Michler's ketone 0.15 parts by weight o2,4-Diethylthioxanthone 0.15 parts by weight o Victoria Pure Blue BOH naphthalene sulfonate 0.01 parts by weight Parts oMCF323 (fluorine nonionic surfactant, methyl iso 0.03 parts by weight butyl ketone 30% solution, Dainippon Ink and Chemicals, Inc.) o methyl ethyl ketone 10 parts by weight o propylene glycol methyl ether 20 parts by weight Next, the above photopolymerization The following composition liquid for the silicone rubber layer was applied onto the photosensitive layer so that the dry weight was 2.0 g / m ^2, and dried at 140 ° C. for 2 minutes to give the silicone rubber. A cured layer was obtained.

Α, ω-divinylpolydimethylsiloxane (polymerization degree: about 700) 9 parts by weight (CH ₃ ) ₃ —Si—O— (Si (CH ₃ ) ₂ —O) ₃₀ — (SiH (CH ₃ ) —O _{) 10 -Si (CH 3) 3} 1.2 parts by weight polydimethylsiloxane (polymerization degree about 8,000) 0.5 parts by weight olefin - chloroplatinic acid 0.2 part by weight of inhibitor 0.3 parts by weight of Isopar G (Esso chemical Co., Ltd.) 140 parts by weight A single-sided matted biaxially oriented polypropylene film having a thickness of 12 μm is laminated on the surface of the silicone rubber layer obtained as described above so that the non-matted surface is in contact with the silicone rubber layer. Then, a dampening water-free photosensitive lithographic printing plate was obtained.

Examples 2 to 5 The same as Example 1 except that compounds B, C, D and E of Table 1 were used in the photosensitive layer instead of the compound A in the photosensitive layer of Example 1. is there.

Example 6 The following silicone rubber composition liquid was applied on the photosensitive layer of Example 1 so that the dry weight was 2.0 g / m ² , and the temperature was 120 ° C.
It was dried for 2 minutes to obtain a silicone rubber layer. α, ω-dihydroxypolydimethylsiloxane (polymerization degree: about 700) 9 parts by weight CH ₃ —Si (O—CO—CH ₃ ) ₃ − − 0.3 parts by weight Tin catalyst 0.1 parts by weight Isopar G (Esso Chemical ( Ltd., petroleum-based solvent) 140 parts by weight The surface of the silicone rubber layer obtained as described above is laminated with a single-sided matt biaxially oriented polypropylene film having a thickness of 12 μm in the same manner as in Example 1 without the need for dampening water. A photosensitive lithographic printing plate was obtained.

Comparative Examples 1 and 2 Instead of the compound A in the photosensitive layer of Example 1, an adduct of 1 mol of metaxylylenediamine and 4 mol of glycidyl methacrylate was used. The silicone rubber layer of Example 1 and the silicone rubber layer of Example 6 were coated on the photosensitive layer. On the surface of the silicone rubber layer thus obtained, the same single-sided matt biaxially oriented polypropylene film as in Example 1 was laminated to obtain the photosensitive lithographic printing plates of Comparative Examples 1 and 2 which did not require fountain solution.

This printing plate was provided with a halftone dot positive film of 200 lines / inch and a gray scale (G) having an optical density difference of 0.15.
/ S), Nuark FT261V UDNS ULTRA-PLUS
FLIPTOP PLATE MAKER Vacuum exposure machine was used for 30 counts of exposure, then the laminate film was peeled off, the plate was immersed in a solution of tripropylene glycol at 40 ° C for 1 minute, and then rubbed with a developing pad in water to expose the unexposed area. The silicone rubber layer of was removed to obtain a lithographic printing plate not requiring dampening water. The gray scale sensitivity at that time was evaluated. The gray scale sensitivity means the number of gray scale steps where the silicone rubber layer was not removed after development, and the larger this value, the higher the sensitivity. The evaluation results are shown in Table 2. It can be seen from Table 2 that by using the monomer of the present invention, a highly sensitive fountain solution-free photosensitive lithographic printing plate can be obtained.

[0061]

[Table 2]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 18, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

[0016]

[Chemical 3]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the formula, L ⁵ is a substituted or unsubstituted cyclic or acyclic alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted phenylene, a substituted or unsubstituted alkylene, and the substituent is Examples thereof include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an aryl group and the like. L ⁶ is −
^{(O- (E 1)) -} , - (S- (E 2)) -, - (Nl
^{l- (E 3)) -,} - (CO-O (E 4)) -, - (S
O ₂ Nll- (E ⁵ ))-with E ¹ , E ² , E ³ ,
E ⁴ and E ⁵ are the above-mentioned alkylene, phenylene and aralkylene.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Added

[Correction content]

[0061]

[Table 2]

Claims (1)

[Claims] 1. A photosensitive lithographic printing plate that does not require a fountain solution and has a substrate, a photosensitive resin layer provided on the substrate, and a silicone rubber layer provided on the photosensitive resin layer. A photosensitive lithographic printing plate not requiring fountain solution, wherein the resin layer contains at least the following components. (1) A compound obtained by reacting at least 2 mol of at least one polyamine represented by the following general formula (I) with a compound having a group capable of reacting with the polyamine and a polymerizable ethylenically unsaturated group: Chemical 1] (2) A photopolymerization initiator and (3) a polymer compound capable of forming a film.