JPH05281714A - Damping waterless photosensitive planographic form plate - Google Patents

Abstract

PURPOSE:To obtain a damping waterless photosensitive planographic form plate with high sensitivity by incorporating a specific photo-polymerizing monomer in a photosensitive resin layer. CONSTITUTION:The form plate has a layered configuration which is formed by laminating the photosensitive resin layer and a silicon rubber layer in this order on a substrate. The photosensitive resin layer incorporates a compound which was reacted at least two mols compounds which incorporated a group which could react with an amino compound with was represented with a formula; R<1>HN-L-NHR<2> and a polymerizing ethylenically unsaturated group, with one mol of the amino compound, a photopolymerization initiator, and a high- molecular weight compound having a film forming capability. In the formula, R<1>, R<2> are represented by hydrogen atoms, 1-20C substd. or unsubstd. aralkyl groups, substd. or unsubstd. phenyl groups, and substd. or unsubstd. aralkyl groups and they may be same or different. Also L indicates a divalent connecting group excluded m-CH2-C6H4-CH2-.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate which does not require fountain solution and is suitable for producing a lithographic printing plate which does not require fountain solution and can be printed without using 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 require no fountain solution for lithographic printing without using fountain solution. Among them, the one in which a photosensitive resin layer and a silicone rubber layer are sequentially coated on a substrate has extremely excellent performance and is described in, for example, Japanese Patent Publication No. 54-26923 and Japanese Patent Publication No. 55-22781. I can list the things that are.

The silicone rubber layer used in these photosensitive lithographic printing plates that do not require fountain solution is usually one obtained by partially cross-linking a polymer having a main skeleton of polysiloxane with a cross-linking 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 terminals 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: polysiloxane having ≡Si-H group and -CH
A method for producing a silicone rubber by addition-reacting a polysiloxane having a ═CH— group (JP-A-61-731)
56, Japanese Patent Application No. 1-301568, etc.).

The condensation type silicone rubber of (1) has a sensitivity which is different from that of a photosensitive printing plate which does not require dampening water, because its curability and the adhesive force 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, it is considered that the addition type silicone rubber (2), which does not have such a defect, is superior. As the photosensitive resin layer, in the case of a positive type lithographic printing plate, a photopolymerizable photosensitive composition which is cured by exposure has been used.
As an image forming method of a photosensitive lithographic printing plate having this layer structure, generally, a photosensitive resin layer is cured by exposure, 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 with the developer, thereby forming a non-image portion formed of the silicone rubber layer.
On the other hand, the image area is formed by penetrating 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 has the drawback of long exposure time and poor workability.

[0005]

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

[0006]

Means for Solving the Problems The present inventor has specified that the photosensitive resin layer of a photosensitive lithographic printing plate which does not require fountain solution is formed by laminating a photosensitive resin layer and a silicone rubber layer on a substrate in this order. It was found that by adding a photopolymerizable monomer, a highly sensitive fountain solution-free 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 method which does not require a fountain solution and which comprises a substrate, a photosensitive resin layer provided on the substrate, and a silicone rubber layer provided on the photosensitive resin layer. In the plate, the photosensitive resin layer contains at least the following components, which is a photosensitive lithographic printing plate not requiring fountain solution. (1) At least 2 mol of a compound having a group capable of reacting with the amino compound and a polymerizable ethylenically unsaturated group is reacted with 1 mol of at least one kind of the amino compound represented by the following general formula (I). Compound (I) R ¹ HN-L-NHR ² [wherein R ¹ and R ² are hydrogen electrons, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted It is an unsubstituted aralkyl group and may be the same or different.

L represents a divalent linking group. However, m-CH ₂
Excludes −C ₆ H ₄ −CH ₂ −. ] (2) A photopolymerization initiator and (3) a polymer compound having film forming ability. Hereinafter, the present invention will be described in detail. 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 may 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.
70 and the one using a urethane resin disclosed in 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 by the additive as long as it is within the range in which the film layer can be formed. In addition, these primer layers, along with the above purpose, dyes, pH indicators, printout agents, photopolymerization initiators, adhesion aids (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 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 of the present invention has the above-mentioned (1), (2)
Including the component of (3). Furthermore, the following component (4) can be contained if necessary. Hereinafter, these components will be described. Component (1): React with amino compound (I) and the amino compound
Compounds containing a polymerizable group and a polymerizable ethylenically unsaturated group
In the general formula (I) of the amino compound, R ¹ , R
² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group. The substituent has 1 carbon atom
To 6 alkyl groups, halogen atoms, hydroxyl groups, and aryl groups. Preferably, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, hydroxymethyl group, hydroxypropyl group, chloromethyl group, bromomethyl group, phenyl group, p- Examples thereof include a hydroxyphenyl group, p-bromophenyl group, p-tolyl group, o-tolyl group and benzyl group. The divalent linking group L preferably has the general formula
It is shown by (L ¹ ) _p − (L ² ) _q −.

In the formula, L ¹ 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 and an aryl group. L ² is -O
^{-E 1 -, -SE 2 -,} -NH-E 3 -, -CO-OE 4 -, -SO 2 -NH-E 5
-, E ¹ , E ² , E ³ , E ⁴ , and E ⁵ are the above-mentioned alkylene, phenylene, and aralkylene. p represents an integer of 1 or more, q represents 0 or an integer of 1 or more.

More preferably, when p is 1 and q is 0,
L¹Is an alkylene having 1 to 6 carbon atoms, p is 1 and q is 1
L is an integer greater than or equal to¹Is an alkyle having 1 to 6 carbon atoms
N, L ²Is -O-E¹ -, -NH-E³-And then E¹, E³Is the carbon number
1 to 6 alkylene. Reacts with the amino compound
Compound containing a polymerizable group and a polymerizable ethylenically unsaturated group
The compound is represented by the following general formula (II), (III) or (IV).
Compounds that can be mentioned.

[0013]

[Chemical 1]

In the formula, R ³ , R ⁴ , R ⁶ and R ⁷ are a hydrogen atom or a methyl group. A is -CO-O-, -CO-NH-, or a substituted or unsubstituted phenylene group. L ³ , L ⁴ , L ⁵ , L ⁶
Is synonymous with L of the aforementioned amino compound. R ⁵ represents COX or SO ₂ X, and X represents a halogen atom. a, b, c,
d, e, f, and g represent 0 or 1.

Specific examples include glycidyl (meth) acrylate, (meth) acrylic acid chloride, and (meth) acrylic acid anhydride. An ethylenically unsaturated group-containing compound (I) to be added to 1 mol of the amine compound (I).
I) is the number of moles capable of reacting with 2 to all active hydrogen of (I). The compound (II) may be used as a mixture.
Specific examples of the compound of component (I) are shown in Table 1, but the compound is not limited thereto. Also, these compounds may be used as a mixture. Table I (I) ^{* 2)} (II) Compound ^{* 1)} L structural formula Number of moles added ^{* 3)} A-(CH ₂ ) ₂ -CH ₂ = CCH ₃ COOG 4 B-(CH ₂ ) ₆ -〃 4 C -CH ₂ (CH ₂ OCH ₂ ) ₄ CH ₂ -〃 4 D -CH ₂ (CH ₂ OCH ₂ ) ₁₂ CH ₂ -〃 4 E -CHCH ₃ -CH _2- (OCH ₂ CHCH ₃ ) _5.6 -〃 4 F -CH _2- (CH ₂ NHCH ₂ ) ₂ -CH ₃ -〃 6 * 1) Reaction product of compound (I) and compound (II) * 2) R ¹ and R ² are both hydrogen atoms * 3) Number of moles of compound (II) added to 1 mole of compound (I) G represents a glycidyl group. Component (2): Photopolymerization initiator As the photopolymerization initiator used in the present invention, US Pat.
Vicinal polyketaldonyl compounds disclosed in 2,367,660, U.S. Patents 2,367,661 and 2,36
Α-carbonyl compounds disclosed in 7,670, acyloin ethers disclosed in U.S. Pat.No. 2,448,828, and α-positions disclosed in U.S. Pat. Aromatic acyloin compounds, U.S. Pat.Nos. 3,046,127 and 2,951,758
Disclosed in U.S. Pat. No. 3,549,367, triaryl imidazole dimer / p-aminophenyl ketone combinations disclosed in U.S. Pat. Thiazole compounds, benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in U.S. Pat. No. 4,239,850 and U.S. Pat. No. 3,75.
Acridine and phenazine compounds disclosed in 1,259, oxadiazole compounds disclosed in U.S. Pat. No. 4,212,970, U.S. Pat.
JP-A-53-133428, U.S. Pat.No. 4,189,323, JP-A-60-105667, JP-A-62-58241, and JP-A-63-15354.
A trihalomethyl-s-triazine compound having a chromophore group disclosed in JP-A No. 59-197401,
Examples thereof include benzophenone group-containing peroxyester compounds disclosed in JP-A-60-76503. 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): a polymer compound capable of forming a film, as the polymer compound capable of forming a film used in the present invention, a methacrylic acid copolymer, an acrylic acid copolymer,
Crotonic acid copolymer, maleic 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, water-soluble urethane, gelatin, water-soluble cellulose derivative 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 / other addition-polymerizable vinyl monomer copolymers as described in JP-A-59-53836. ,
And its alkali metal salts or amine salts; JP-B-59-4
A product obtained by reacting a hydroxyethyl (meth) acrylate / (meth) acrylic acid / alkyl (meth) acrylate copolymer and its alkali metal salt or amine salt with (meth) acrylic acid chloride described in JP-A-5979; 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 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 reacted with maleic anhydride or itaconic anhydride And the alkali metal salt or amine salt thereof; hydroxyalkyl (meth) acrylate / (meth) acrylic acid copolymer reacted with 2,4-tolylene diisocyanate / hydroxyalkyl (meth) acrylate = 1/1 adduct And the alkali metal salt or amine salt thereof;
Part of the (meth) acrylic acid copolymer described in JP-A-9-53836 is reacted with allyl glycidyl ether and its alkali metal salt or amine salt; vinyl (meth) acrylate / (meth) acrylic Acid copolymer and its alkali metal salt or amine salt; (meth) allyl acrylate / sodium styrene sulfonate copolymer;
Vinyl (meth) acrylate / sodium styrenesulfonate 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 90% by weight, preferably 50 to 97% by weight, based on the total photosensitive composition. Component (4): Ethylene other than the monomer represented by the general formula (I)
Renenically unsaturated group-containing monomer or oligomer In the present invention, an ethylenically unsaturated group-containing monomer or oligomer other than the monomer represented by the general formula (I) can be used, if necessary. Examples of such monomers or oligomers include monomers or oligomers having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples thereof include acrylic acid or methacrylic acid ester of alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.), carboxylic acids (eg, acetic acid, propionic acid, benzoic acid). Acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl metaxylylenediamine, amide derivative (For example, acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), a reaction product of an epoxy compound and acrylic acid or methacrylic acid, and the like. That.

More specifically, Japanese Examined Patent Publication No. 48-41708
No. 5, Japanese Patent Publication No. 60-6034, Japanese Patent Laid-Open No. 51-37193.
Urethane acrylates such as those described in JP-A-48-64183 and JP-B-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, U.S. Pat.
The N-methylol acrylamide derivative described in 4540649 can be mentioned. Furthermore, Japan Adhesive Association magazine
Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers, can also 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. The monomer and oligomer of the component (1) and the component (4) may be contained in an amount of 1 to 70% by weight, preferably 3 to 60% by weight, based on the total photosensitive composition. Also, component (1)
The weight ratio of component (4) 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 , such as 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, etc. 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 with respect to 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 silane coupling agent containing a (meth) acryloyl group or an allyl group 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 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.

-(SiR ₂ -O) -wherein R represents an alkyl group, an aryl group, an alkenyl group or a monovalent group in which these are combined, and these are a halogen atom, an amino group, a hydroxy group, an alkoxy group. It may have a functional group such as an aryloxy 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 and having a molecular weight of several thousand to tens of thousands is used. Then, the silicone rubber layer is obtained by crosslinking and curing. 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 organic acid or an amine is added, and the polysiloxane and the silane-based crosslinking agent are heated or condensed and cured at room temperature.

R _n SiX _4-n Here, n is an integer of 1 to 3, R is a substituent similar to R shown above, and X is —OH, —OR ² , —OAc, —O—. N =
CR ² R ^3, represents -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 acetyl group.

Other organopolysiloxane or hydrogen polysiloxane cross-linking agent having a hydroxyl group at the terminal and, if necessary, the above silane cross-linking agent are condensation-cured. In addition, 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 has an advantage that it is relatively insensitive to humidity during curing, can be crosslinked at high speed, and can easily obtain a silicone rubber layer having certain physical properties. The addition-type silicone rubber layer used here is obtained by reacting a polyvalent hydrogenorganopolysiloxane with a polysiloxane compound having two or more -CH = CH- bonds in one molecule, and preferably the following Component: (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 Organohydrogenpolysiloxane 0.1 to 1000 parts by weight (3) A composition comprising 0.0001 to 10 parts by weight of an addition catalyst, which is cured and crosslinked. The alkenyl group of the component (1) may be at either the terminal of the molecular chain or at the middle, and a preferable organic group other than the alkenyl group
It is a substituted or unsubstituted alkyl group or aryl group.
The component (1) may have a small amount of hydroxyl groups. Component (2) reacts with 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 that of 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 total number of methyl groups, from the viewpoint of improving 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. It is preferable that the molecular weight of (1) exceeds 1,000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the like. Examples include hydrogen-containing polydimethylsiloxane, α, ω-dimethylpolymethylhydrogensiloxane, (methylhydrogensiloxane) (dimethylsiloxane) copolymers having methyl groups at both ends, 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 speed 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 composition is rubberized is lengthened,
For the purpose of shortening the curing time on the photosensitive layer, the curing conditions of the composition should be such that the characteristics of the support and photosensitive layer do not change, and that the composition is 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, and 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 repellent layer. When the thickness is small, there are problems such as a decrease in ink repelling property and easy scratching. From this point of view, the thickness is preferably 0.5 μm to 5 μm. In the photosensitive lithographic printing plate requiring no fountain solution described above, it is optional to further coat various silicone rubber layers on the silicone rubber layer, and the adhesive force between the photosensitive resin layer and the silicone rubber layer may be applied. It is optional to provide an adhesive layer between the photosensitive resin layer and the silicone rubber layer for the purpose of increasing the temperature 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 is laminated on the silicone rubber layer. Alternatively, a polymer coating may be applied. These films may be stretched before use. 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 a 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) 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) Further, water is added to the organic solvent-based developer or the organic solvent is added. Solubilized in water using a surfactant, etc.,
Further, an alkaline agent, for example, sodium carbonate, monoethanolamine, diethanolamine, triethanolamine, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, sodium borate, or the like, 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 the development. The development can be carried out by a known method such as rubbing the plate surface with a developing pad containing the above-described developing solution 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 primer layer is exposed, and that area becomes the ink receiving area, 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.

[0035]

The fountain solution-free photosensitive lithographic printing plate 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 A compound obtained by reacting at least 2 mol of a compound having a group capable of reacting with the amino compound and a polymerizable ethylenically unsaturated group with 1 mol of the amino compound represented by the general formula (I).
High sensitivity because it contains (2) a photopolymerization initiator and (3) a polymer compound capable of forming a film.

[0036]

[Synthesis Example] Synthesis of Compound A (Table 1) Glycidyl methacrylate, 114 g (0.8 mol)
Then, 12 g (0.2 mol) of ethylenediamine was added dropwise at room temperature. After the dropwise addition, stirring was continued at 80 ° C. and the disappearance of the raw materials was confirmed using liquid chromatography to obtain compound A.

[0037]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 A 0.3 mm thick JIS A1050 aluminum plate degreased by a conventional method was used as an amine silane coupling agent K.
It was immersed in a 1% aqueous solution of BM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) and then dried at room temperature. The following primer solution was applied onto this aluminum plate so that the dry weight was 4 g / m ^2, and the film was dried and hardened by heating at 140 ° C. for 2 minutes.

Samprene IB 1700D (10 parts by weight of thermoplastic polyurethane containing terminal hydroxyl group, resin, 30% solution of methyl ethyl ketone, manufactured by Sanyo Kasei Co., Ltd.) Takenate D100N (polyfunctional isocyanate compound, 0.5% by weight of ethyl acetate 75% solution, Takeda Pharmaceutical Co., Ltd.) TiO ₂ 0.1 part by weight MCF323 (fluorine nonionic surfactant, methyl isobutyl 0.03 part by weight ketone 30% solution, Dainippon Ink and Chemicals, Inc.) propylene glycol methyl ether acetate 50 parts by weight 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.

Crisbon 3006LV (manufactured by Dainippon Ink and Chemicals, Inc.) 1.5 parts by weight Compound A 1.0 parts by weight CH ₂ = CHCOO- (CH ₂ CH ₂ O) ₁₄ -COCH = CH ₂ 1.0 parts by weight (Shin Nakamura Chemical ( A-600) Ethyl Michler's ketone 0.15 part by weight 2,4-diethylthioxanthone 0.15 part by weight Victoria Pure Blue BOH naphthalene sulfonate 0.01 part by weight MCF323 (fluorine nonionic surfactant, methyl isobutyl 0.03 part by weight ketone) 30% solution, manufactured by Dainippon Ink and Chemicals, Inc. Methyl ethyl ketone 10 parts by weight Propylene glycol methyl ether 20 parts by weight Next, on the above photopolymerizable photosensitive layer, the following composition liquid for silicone rubber layer is dried by weight. It was applied at 2.0 g / m ² and dried at 140 ° C. for 2 minutes to obtain a silicone rubber cured layer.

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 - (manufactured by Esso chemical Co.) chloroplatinic acid 0.2 part by weight of inhibitor 0.3 parts by weight of Isopar G 140 parts by weight of the A 12 μm-thick, single-sided, matt biaxially oriented polypropylene film was laminated on the surface of the silicone rubber layer obtained as described above so that the non-matted surface was in contact with the silicone rubber layer. I got a printing plate. Examples 2 to 6 All the same as Example 1 except that compounds B, C, D, E and F in Table 1 were used in the photosensitive layer instead of the compound A in the photosensitive layer of Example 1. Example 7 The following silicone rubber composition was coated 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 a minute to obtain a silicone rubber layer.

Α, ω-dihydroxypolydimethylsiloxane (polymerization degree: about 700) 9 parts by weight CH ₃ -Si (O-COCH ₃ ) ₃ 0.3 parts by weight Tin catalyst 0.1 parts by weight Isopar G (Esso Chemical Co., Ltd., petroleum 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, and no fountain solution is required. Got 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 7 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, and the fountain solution-free photosensitive lithographic printing plates of Comparative Examples 1 and 2 were obtained. Obtained. 200 lines /
Positive film with halftone dot image and optical density difference of 0.
Grayscale (G / S) of 15 was overlaid and exposed for 30 counts using a Nuark FT261V UDNS ULTRA-PLUS FLIPTOP PLATE MAKER vacuum exposure machine, and then the laminated film was peeled off and 40 of tripropylene glycol
After immersing the plate in a liquid at 0 ° C. for 1 minute, the plate was rubbed with a developing pad in water to remove the silicone rubber layer in the unexposed area, thereby obtaining 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 steps in the gray scale density at which 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.

[0044]

Claims (1)

[Claims] 1. A photosensitive lithographic printing plate not requiring a fountain solution, which comprises 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 that does not require fountain solution, wherein the photosensitive resin layer contains at least the following components. (1) At least 2 mol of a compound having a group capable of reacting with the amino compound and a polymerizable ethylenically unsaturated group is reacted with 1 mol of at least one kind of the amino compound represented by the following general formula (I). Compound (I) R ¹ HN-L-NHR ² [wherein R ¹ and R ² are hydrogen electrons, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted It is an unsubstituted aralkyl group and may be the same or different. L represents a divalent linking group. However _{m-CH 2 -C 6 H 4} -CH 2 - except. ] (2) A photopolymerization initiator and (3) a polymer compound having film forming ability.