JPH08184959A - Damping waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE: To provide a damping waterless planographic printing plate excellent in sensitivity, reproducibility of dots, printing durability and scratching resistance, and can be developed with a water-base developer by incorporating at least one kind of specified photopolymerizable monomer into a photopolymerizable photosensitive layer. CONSTITUTION: This printing plate is produced by successively depositing a photopolymerizable photosensitive layer and a silicone rubber layer in this order on a substrate. The photopolymerizable photosensitive layer contains at least one kind of photopolymerizable monomer expressed by the formula. In the formula, R1 , R2 are independently substd. or unsubstd. alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aralkyl groups, aralkoxy groups, or halogen groups, (h) is an integer 0 to 4, (i) is an integer 0 to 4, and h+i<=4. L1 , L2 are independently substd. or unsubstd. alkylene groups, pheylene groups, or aralkylene groups, (j) is 0 or 1, (k) is 0 or 1, and R3 , R4 , R5 , R6 are hydrogen atoms, alkyl groups or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a photopolymerizable photosensitive layer and a silicone rubber layer on a substrate in this order, and is excellent in sensitivity, halftone dot reproducibility, printing durability, and scratch resistance. The present invention relates to a photosensitive lithographic printing plate that does not require fountain solution and can be developed with an aqueous solution of an organic solvent as a component (hereinafter referred to as an aqueous developer) (hereinafter referred to as a waterless lithographic printing plate).

[0002]

2. Description of the Related Art Various waterless lithographic printing plates have been proposed for performing lithographic printing without using fountain solution. Among them, the one in which the photosensitive layer and the ink repellent layer are applied in this order on the substrate has extremely excellent performance. Those using silicone rubber as the ink repellent layer are disclosed, for example, in Japanese Examined Patent Publication Nos. 54-26923 and 55-22.
No. 781, Japanese Patent Publication No. 56-23150 and Japanese Patent Laid-Open No. 2-150.
JP-A No. 58-215411 and JP-A No. 2-10, which use a fluororesin, are disclosed in Japanese Patent No. 236550.
Although described in Japanese Patent No. 3047, it is preferable to use silicone rubber from the viewpoint of ink repulsion.

As the photosensitive layer, in the case of a positive type lithographic printing plate, a photopolymerizable photosensitive composition which is cured by exposure has been used. In the image forming method of the photosensitive lithographic printing plate having this layer structure, the non-image portion is hardened by exposure to light and the photo-adhesion at the interface with the silicone rubber layer above it is performed to firmly bond both layers. Then, the silicone rubber layer is formed by suppressing the permeation by the developing solution and / or the accompanying elution of the photosensitive layer composition. On the other hand, in the image area, the developing solution is permeated through the silicone rubber layer, and a part or all of the uncured photosensitive layer composition is dissolved by the developing solution, and then the silicone rubber layer above is removed by physical force. Is generally formed.

As a method for developing a waterless planographic printing plate on which an image is formed in this way, Japanese Patent Publication No. 56-23150 is available.
JP-A-57-13448 and JP-A-59-1460.
54 and JP-A-63-52145 are disclosed. However, these developing methods are expensive because the main component of the processing liquid is an organic solvent, and require special consideration in handling due to the risk of ignition. In order to solve this problem, JP-A-1-159644 discloses a developing solution containing water as a main component. In order to use such an aqueous developer, it is necessary to add a compound having hydrophilicity as a photopolymerizable monomer in the photosensitive layer,
Monomers having polyethylene oxide chains or polypropylene oxide chains are described in JP-A-4-174437, JP-A-4-338954, JP-A-5-94007, JP-A-5-224415, JP-A-6-118629 and the like. However, good images can be obtained by using these monomers.

However, in the waterless lithographic printing plate developed with an aqueous developer, a waterless lithographic printing plate satisfying all of sensitivity, halftone dot reproducibility, printing durability and scratch resistance has been obtained so far. Has not been done.

[0006]

Therefore, the object of the present invention is to provide excellent sensitivity, halftone dot reproducibility, printing durability, and scratch resistance,
It is an object of the present invention to provide a waterless planographic printing plate that can be developed with an aqueous developer.

[0007]

Means for Solving the Problems The present inventors have laminated a photopolymerizable photosensitive layer and a silicone rubber layer on a substrate in this order, and the photopolymerizable photosensitive layer is represented by the following formula (I). The above-mentioned object of the present invention has been achieved by a waterless lithographic printing plate characterized by containing at least one photopolymerizable monomer.

[0008]

[Chemical 4]

In formula (I), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkoxy group, halogen group, h Is an integer of 0 to 4, i is 0 to 4
Is an integer, and h + i ≦ 4. L ₁ and L ₂ each independently represent a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, j is 0 or 1, and k is 0 or 1.

R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group or the formula (II) and may be the same or different, but at least two of them are of the formula (II). .

[0011]

Embedded image

In the formula (II), R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents -CO- or a phenylene group. R ₈ and R ₉ each represent a hydrogen atom or a methyl group, and 1 R ₈ and n R ₉ may be the same or different, and are an integer of 1 = 0 to 15 and n = 0 to 0. It is an integer of 15. However, all l of R ₃ , R ₄ , R ₅ and R ₆ are
And n cannot be 0 at the same time.

In the formula (II), Y is represented by the following formula (III),
Represents (IV) or (V), and m is 0 or 1.

[0014]

[Chemical 6]

[0015]

In the present invention, the photopolymerizable photosensitive layer contains the compound of formula (I) so that the photosensitive layer forming a non-image area after image exposure is formed of the compound of formula (I). Due to the flexibility of the cross-linked polymer, a cured photosensitive layer having flexibility capable of withstanding scratches and high number of copies printing is formed, scratch resistance and printing durability are improved, and hydrophilicity of the compound of formula (I) Thus, the object of the present invention was achieved by enabling good image formation even with an aqueous developer.

The present invention will be described in detail below. The substrate in the waterless lithographic printing plate of the present invention must have flexibility so that it can be set in an ordinary printing machine and at the same time withstand a load applied during printing. Therefore, as a typical substrate, coated paper, a metal plate such as aluminum, a plastic film such as polyethylene terephthalate, rubber or a combination thereof (for example, a composite plate in which the upper and lower sides of paper are sandwiched by aluminum) is used. Of these, aluminum and aluminum-containing alloys (for example, alloys of aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel) are more preferable.

In such a substrate, when it is necessary to remove the rolling oil on the surface of the aluminum plate, degreasing treatment can be performed by showering or dipping the acid aqueous solution. The acid used at this time may be any acid known as a metal cleaning acid, but is preferably sulfuric acid or phosphoric acid. After the acid treatment, it is preferable to wash with water for an appropriate time. After degreasing, a coating such as a photosensitive layer may be provided directly, but surface treatment such as graining, anodic oxidation, treatment with an aqueous solution of silicate such as sodium silicate or potassium silicate (also referred to as "silicate treatment") You may go. Of these, silicate treatment is preferable. Further, the support may be surface-treated with a silane coupling agent for the purpose of improving the adhesion to the coating film.

The photopolymerizable photosensitive layer in the waterless lithographic printing plate of the present invention contains at least one photopolymerizable monomer represented by the following formula (I), and usually has a photopolymerization initiator and a film forming ability. It includes a polymer compound. Further, it comprises a composition which may optionally contain a monomer or oligomer having a polymerizable ethylenically unsaturated group other than the monomer represented by the formula (I).

[0019]

[Chemical 7]

In the formula (I), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkoxy group or halogen group. The alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, and aralkoxy group preferably have 1 to 12 carbon atoms, and examples thereof include a methyl group, a methoxy group, and a benzyl group, and examples of the halogen group include a chlorine atom. Can be mentioned. Examples of the substituent of the alkyl group, the alkoxy group, the aryl group, the aryloxy group, the aralkyl group, and the aralkoxy group include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a hydroxyl group, a halogen group, and the like. The preferred carbon number of the group, aralkyl group and alkoxy group is 1
And 6 and a chlorine atom is a specific example of the halogen atom. h is an integer of 0 to 4, i is an integer of 0 to 4, and h + i ≦ 4.

L ₁ and L ₂ are each independently substituted or
It represents an unsubstituted alkylene group, a phenylene group or an aralkylene group, and the preferred carbon number is 1 to 12, and examples thereof include a methylene group, an ethylene group, a propylene group and a xylylene group. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a hydroxyl group, a halogen group and the like, and an alkyl group, an aryl group, an aralkyl group and an alkoxy group preferably have 1 to 6 carbon atoms, and a halogen atom. A chlorine atom is mentioned as a specific example of the atom. j
Is 0 or 1 and k is 0 or 1.

R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10) or the formula (II).
And may be the same or different, but at least two are preferably groups of formula (II) and all are groups of formula (II).

[0023]

Embedded image

In the formula (II), R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group or an ethyl group). X represents -CO- or a phenylene group, and preferably -CO-. R ₈ and R ₉ each represent a hydrogen atom or a methyl group, and 1 R ₈ and n
R _9's may be the same or different, and l = 0 to 1
It is an integer of 5 and n is an integer of 0 to 15. However, R ₃ ,
All l and n of R ₄ , R ₅ and R ₆ do not become 0 at the same time, and the total number of ethylene oxide groups or propylene oxide groups contained in the molecule of the formula (I) is preferably 60 or less. And more preferably 30
It is below, and most preferably 2 to 25.

In the formula (II), Y is represented by the following formula (III),
Represents (IV) or (V), and m is 0 or 1.

[0026]

[Chemical 9]

The photopolymerizable monomer of the formula (I) may be used alone or in combination of two or more, and the content thereof in the total photopolymerizable photosensitive layer composition is 1 to 80% by weight. And preferably 5 to 60% by weight, more preferably 10 to 4
0% by weight. Specific examples of the photopolymerizable monomer represented by the formula (I) are shown below, but the photopolymerizable monomer is not limited thereto.

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

The photopolymerization initiator used in the photopolymerizable photosensitive layer of the present invention may be a compound capable of generating radicals by light, regardless of whether it is a sensitized system or a non-sensitized system. The following can be given as typical examples, but the present invention is not limited to these. (A) Benzophenone derivative, for example, benzophenone, dimethylaminobenzophenone, diethylaminobenzophenone, xanthone, anthrone, thioxanthone, acridone, 2-chloroacridone, 2-chloro-
N-n-butylacridone, 2,4-diethylthioxanthone, fluorenone, etc. (b) Benzoin derivative, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, etc. (c) Quinones, for example, p-benzoquinone, β-naphthoquinone , Β-methylanthraquinone, etc. (d) Sulfur compounds, for example, dibenzyl disulfide, di-n-butyl disulfide, etc. (e) Azo or diazo compounds, for example, 2-azobisisobutyronitrile, 1-azo- Bis-1-cyclohexanecarbonitrile, p-diazobenzylethylaniline, Congo red, etc. (f) Halogen compounds such as carbon tetrabromide, silver bromide,
α-Chloromethylnaphthalene, trihalomethyl-s-triazine compounds, trihalomethyloxadiazole compounds, etc. (g) Peroxides such as benzoyl peroxide.

These may be used alone or in combination. The amount of these photopolymerization initiators added is 0.1 to 25% by weight, preferably 3 to 20% by weight, based on the total photopolymerizable photosensitive layer composition. In the photopolymerizable photosensitive layer of the present invention, a polymer compound having the above film-forming ability is used for the purpose of forming a film. As such a polymer compound, the following polymers and copolymers may be used. it can.

(1) Vinyl polymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral,
Polyvinyl methyl ether, polyvinyl chloride, polyethylene, etc., and copolymers thereof. (2) (Meth) acrylic acid ester polymers and alkyl (meth) acrylamide polymers such as ethyl poly (meth) acrylate, butyl poly (meth) acrylate, poly t-butyl acrylamide, poly diacetone acrylamide, etc., and copolymers thereof. , And copolymers with (meth) acrylic acid.

(3) Unvulcanized rubber such as natural rubber, polybutadiene, polyisobutylene, polyneoprene, and copolymers thereof. (4) Polyether, such as polyethylene oxide, polypropylene oxide, etc. (5) Polyamide, copolymer of the following monomers,
For example, caprolactam, laurolactam, hexamethylenediamine, 4,4′-bis-aminocyclohexylmethane, 2,4,4-trimethylhexamethylenediamine, isophoronediamine, diglycols, isophthalic acid, adipic acid, sebacic acid and the like.

(6) Polyester, for example, a condensate of terephthalic acid, adipic acid and the like with ethylene glycol, 1,4-butanediol and the like. (7) Polyurethane such as hexamethylene diisocyanate, toluene diisocyanate, naphthalene-I,
Polyurethane of 5-diisocyanate, isophorone diisocyanate and the like with ethylene glycol, 1,4-butanediol, polyester diol and polyether. Further, isophoronediamine, hexamethylenediamine, or the like may be used as the chain extender.

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. It is not limited.
Further, these polymer compounds may be used alone or in combination. The polymer compound may be contained in an amount of 10 to 90% by weight, preferably 25 to 75% by weight, based on the total photopolymerizable photosensitive layer composition.

In the photopolymerizable photosensitive layer of the waterless lithographic printing plate of the present invention, further optionally: a monomer having a polymerizable ethylenically unsaturated group other than the monomer represented by the general formula (I). , Or an oligomer. Examples of such monomers and oligomers include (A) alcohols (eg, glycerin, hexanediol, trimethylolpropane, pentaerythritol, sorbitol, triethylene glycol, (poly) ethylene glycol, (poly) propylene glycol, and the like). Furthermore, glycerin, hexanediol,
Acrylic acid or methacrylic acid ester of ethylene oxide such as trimethylolpropane, pentaerythritol, and sorbitol, propyne oxide, or a mixed adduct thereof, (B) amines (eg, ethylamine, ethylenediamine, hexamethylenediamine,
Reaction products of diethylenetriamine, xylylenediamine, ethanolamine, aniline, etc. with glycidyl acrylate, glycidyl methacrylate or allyl glucidyl, (C) carboxylic acids (eg acrylic acid, methacrylic acid, succinic acid, maleic acid, (Phthalic acid and the like) and glycidyl acrylate, glycidyl methacrylate or allyl glycidyl, a (D) amide derivative (eg, methylenebisacrylamide, xylylenediacrylamide, etc.), and the like.

More specifically, Japanese Patent Publication No. 48-41708
No., JP-B-50-6034, JP-A-51-37193.
Urethane acrylates as described in JP-A-48-64183 and JP-B-49-4319
No. 1, polyester acrylates and epoxy resins described in JP-B-52-30490 and (meth)
Polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid, US Patent No. 45
The N-methylol acrylamide derivative described in No. 40649 can be mentioned. Furthermore, the Japan Adhesives Association Vol. 20, No. 7, 300 to 308 pages (1
Those described as photo-curable monomers and oligomers in (984) etc. can also be used. However, it is not limited to these, in the polyfunctional monomer, the unsaturated group is acrylic, methacrylic, allyl,
Vinyl groups and the like may be mixed and present. In addition, these may be used alone or in combination.

The amount of these photopolymerizable monomers added is 0 to 50% by weight, preferably 0 to 40% by weight, more preferably 3 to 30% by weight, based on the total photopolymerizable photosensitive layer composition. In the photopolymerizable photosensitive layer, it is preferable to add a thermal polymerization inhibitor in order to improve stability over time, and examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol and di-t-. Butyl-p-cresol, pyrogallol, t-butylcatechol, 4,
4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-)
Butylphenol), 2-mercaptobenzimidazo-
Are useful. In some cases, a dye or pigment may be added for the purpose of coloring the photopolymerizable photosensitive layer, and a pH indicator or a leuco dye may be added as a printing agent. 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 photopolymerizable photosensitive layer. You may add the silicone compound of. A silicone-based surfactant or a fluorine-based surfactant may be added to improve coatability. Further, a diazo resin may be added to improve the adhesion between the photopolymerizable photosensitive layer and the primer layer described later. In addition, a plasticizer (for example, polyethylene glycol, polypropylene glycol, tricresyl phosphate, etc.) and a stabilizer (for example, phosphoric acid) for imparting flexibility to the coating film may be added.

The addition amount of these additives is usually 10% by weight or less based on the total photopolymerizable photosensitive layer composition. In some cases, a hydrophobic silica powder treated with a (meth) acryloyl group- or allyl group-containing silane coupling agent may be added in an amount of 10% by weight or less based on the total photopolymerizable photosensitive layer composition. The above-mentioned photopolymerizable photosensitive layer composition used in the present invention is, for example, water, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, ethanol, methyl ethyl ketone. , N, N-dimethylacetamide, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate or the like alone or dissolved in a mixed solvent thereof and coated on the substrate. Its coating weight may range by weight in a 0.1 to 20 g / m ² after drying is is suitable, and preferably from 0.5 to 10 g / m ^2.

The silicone rubber layer in the present invention is an ink repellent layer, and a film formed by curing the following composition A or B can be used. [Composition A (condensation type)] (a) Diorganopolysiloxane (having a number average molecular weight of 3,000 to 200,000) 100 parts by weight (b) Condensation type crosslinking agent 3 to 70 parts by weight (c) Catalyst 0 0.01 to 40 parts by weight The diorganopolysiloxane of the component (a) is a polymer having a repeating unit represented by the following formula (a),
₁₀ and R ₁₁ are alkyl groups having 1 to 10 carbon atoms, vinyl groups and aryl groups, and may have other substituents. Generally, it is preferable that 60% or more of R ₁₀ and R ₁₁ are methyl groups, halogenated vinyl groups, halogenated phenyl groups, or the like.

[0043]

Embedded image

It is preferable to use a diorganopolysiloxane having a hydroxyl group at both ends. The component (a) has a number average molecular weight of 3,000 to 200,
000, and more preferably 5,000 to 100,
000. The component (b) may be of any condensation type, but is preferably one represented by the following general formula (b).

[0045]

[Chemical 15]

In the general formula (b), R ₁₂ has 1 to 10 carbon atoms.
10 represents an alkyl group, a vinyl group or an aryl group,
Z is a hydrogen atom, a halogen atom (Cl, Br, I, etc.),
—OH, —OCOR ₁₃ , —OR ₁₃ (wherein R ₁₃ is the above R
Synonymous with ₁₂ ), or a group represented by the following formula (wherein R ₁₄ , R
₁₅ , R ₁₆ and R ₁₇ represent an alkyl group having 1 to 10 carbon atoms)
, A represents 0, 1 or 2, b represents 2, 3 or 4, and a + b is 4.

[0047]

Embedded image

Component (c) is tin, zinc, lead, calcium,
Examples thereof include metal carboxylates such as manganese, for example, known catalysts such as dibutyl laurate, lead octylate, lead naphthenate, and chloroplatinic acid. [Composition B (addition type)] (d) Diorganopolysiloxane having an addition-reactive functional group (number average molecular weight is 3,000 to 200,000) 100 parts by weight (e) Organohydrogenpolysiloxane 0.1 -10 parts by weight (f) Addition catalyst 0.00001 to 1 part by weight The diorganopolysiloxane having an addition-reactive functional group of the component (d) is an alkenyl group directly bonded to a silicon atom in one molecule (more Organopolysiloxane having at least two (preferably vinyl groups) (number-average molecular weight of 3,000 to 200,000) is disclosed in Japanese Patent Application No. 4-238.
What was described in the specification of No. 497 can be used. The alkenyl group may be at both terminals or in the middle of the molecule, and the organic group other than the alkenyl group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group. Further, it is optional that the component (d) has a small amount of hydroxyl groups. The component (d) has a number average molecular weight of 3,000.
˜200,000, more preferably 5,000
100 to 100,000.

As the component (e), polydimethylsiloxane having hydrogen groups at both ends, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, cyclic polymethylsiloxane, both Examples thereof include polymethylsiloxane having a terminal trimethylsilyl group and a (dimethylsiloxane) (methylsiloxane) copolymer having a trimethylsilyl group at both terminals disclosed in JP-A-4-68353.

The component (f) 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. In the silicone rubber layer of the waterless lithographic printing plate of the present invention, a vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane for the purpose of controlling the curing rate of these compositions,
It is also possible to add a crosslinking inhibitor such as alcohol containing carbon-carbon triple bond, acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol monomethyl ether.

In the silicone rubber layer, if necessary, fine particles of an inorganic substance such as silica, calcium carbonate, titanium oxide, an adhesion aid such as a silane coupling agent, a titanate coupling agent or an aluminum coupling agent. Further, a photopolymerization initiator, an aromatic-substituted polydimethylsiloxane as disclosed in JP-A No. 1-179047, and silicone oil may be added.

In the present invention, it is preferable to use the addition type silicone rubber in view of the curability of the silicone rubber.
The ink repellent layer comprising the silicone rubber layer of the present invention has problems that the ink repellent property decreases when the coating amount is small and scratches easily occur, and the developability deteriorates when the coating amount is large. , The coating amount is 0.5 to 5 g /
m ² is preferable, and 1 to 3 g / m ² is more preferable.

In the present invention, a primer layer may be provided between the substrate and the photosensitive layer. As the primer layer used in the present invention, various types can be used for the purpose of improving the adhesion between the substrate and the photopolymerizable photosensitive 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 layer, are disclosed in JP-A-62-50760. Of epoxy resin that has been heat-cured
The one disclosed in JP-A-3-133151 in which gelatin is hardened, the one using the urethane resin and the silane coupling agent disclosed in JP-A-3-200965, and JP-A-3-273248. And the like using the urethane resin disclosed in. In addition, those obtained by hardening gelatin or casein are also effective. Further, for the purpose of softening the primer layer, polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber having a glass transition temperature of room temperature or less, in the primer layer,
Acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile / butadiene rubber, polyisoprene, acrylate rubber, polyethylene, chlorinated polyethylene,
A polymer such as 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. In addition, these primer layers have a dye, a pH indicator, a printout agent, a photopolymerization initiator, and
Additives such as an adhesion aid (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling agent or an aluminum coupling agent), a pigment (for example, TiO ₂ ) or a silica powder can be contained. Further, after coating, it can be cured by exposure. Generally, the coating amount of the primer layer is 0.1 to 20 by dry weight.
The range of g / m ² is suitable, and preferably 1 to 10 g / m ²
Is.

In the waterless lithographic printing plate of the present invention, various ink repellent layers may be further coated on the ink repellent layer composed of the silicone rubber layer. Further, in order to increase the adhesive force between the photopolymerizable photosensitive layer and the ink repellent layer, or to prevent poisoning of the catalyst in the ink repellent layer composition, the photopolymerizable photosensitive layer and the ink repellent layer are An intermediate layer may be provided between them.

Furthermore, in order to protect the surface of the ink repellent layer,
A transparent film such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate or cellophane may be laminated on the ink repellent layer, or a polymer coating may be applied. These films may be used after being stretched. Further, this film may be matted to improve the vacuum adhesion in the baking frame at the time of image exposure, and a coating is applied to the contact surface of the film with the ink repellent layer to improve the peeling property of the film. May be.

The waterless lithographic printing plate of the present invention comprises a developer capable of dissolving or swelling a part or all of the photosensitive layer in the image area (unexposed area) after being exposed through a transparent original image, or an ink repellent layer. Develop with a swellable developer. In this case, the photosensitive layer and the ink repellent layer in the image area may be removed or only the ink repellent layer in the image area may be removed, which can be controlled by the strength of the developing solution.

As the developing solution used in the present invention, those known as a developing solution for a waterless planographic printing plate can be used, but an aqueous developing solution is particularly preferable. Known examples of this water-based developer include water (tap water, pure water, distilled water, etc.) or an aqueous solution of an organic solvent containing water as a main component, such as the following polar organic solvent added to water or surface active Examples thereof include those solubilized in water using an agent and the like, and an alkaline agent (for example, sodium carbonate, diethanolamine, sodium hydroxide, etc.) may be added, but considering safety and flammability, Particularly, a developer containing only water is desirable.

The polar organic solvent includes: alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, etc. ・ Ketones (acetone, methyl ethyl ketone, etc.) ・ Esters (ethyl acetate, methyl lactate, butyl lactate,
Propylene glycol monomethyl ether acetate,
Diethylene glycol acetate, diethyl phthalate, etc.)-Others (triethyl phosphate, tricresyl phosphate, etc.) can be mentioned.

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 performed by a known method such as rubbing the plate surface while immersing the plate in the developer as described above with a developing vat, or pouring the developer onto the plate surface and then rubbing with a developing brush in water. it can. Development can be carried out at any liquid temperature, but is preferably 10 ° C to 60 ° C. As a result, the ink repellent layer in the image area is removed, and that area becomes the ink receiving area.

In the printing plate thus obtained, the exposed image portion can be dyed with a dyeing solution so as to be detected so as to confirm the image forming property. When the developer does not contain a dye for dyeing the exposed image area, it is treated with a dyeing solution after development. By soaking the dyeing solution in a soft pad and rubbing the image area lightly, only the exposed image area of the photosensitive layer is dyed, whereby it can be confirmed that the development is sufficiently performed up to the highlight area. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes can be used alone or in a mixture of two or more of water, alcohols, ketones and ethers. What is dissolved or dispersed is used. In order to improve the dyeability, carboxylic acids, amines, surfactants,
It is also effective to add a dyeing aid, an antifoaming agent and the like.

The printing plate dyed with the dyeing solution is preferably washed with water and then dried, whereby the dye adhering to the non-image area and the back surface of the plate can be removed and the stickiness of the plate surface can be suppressed. The handling of the plate can be improved. Further, when the printing plates thus treated are stacked and stored, it is preferable to insert and sandwich a slip sheet for protecting the printing plates.

It is preferable that the above-mentioned development and dyeing treatments, or subsequent washing and drying treatments are carried out by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-220061. less than,
The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0063]

【Example】

Synthesis Example (1) Synthesis of Compound A 6.25 g (0.02 mol) of MXDA EO-4 (manufactured by Mitsubishi Gas Chemical Co., Inc.) obtained by adding 4 mol of ethylene oxide to 1 mol of metaxylenediamine, 16 g of triethylamine ( 0.16 mol), dichloromethane 100
To ml and nitrobenzene (0.5 g), 8.4 g (0.08 mol) of methacrylic acid chloride was added dropwise at 15 ° C or lower.

After completion of dropping, the mixture was stirred for 2 hours, and then water 100 was added.
ml was added, and the mixture was extracted with dichloromethane. After the solvent was distilled off, 11.3 g of compound A-1 was obtained. Similarly, ethylene oxide 6, 10, 1 was added to 1 mol of meta-xylene diamine.
MXDA EO-6 and MXD obtained by adding 5 mol
Compound A by reacting A EO-10 and MXDA EO-15 (manufactured by Mitsubishi Gas Chemical Co., Inc.) (0.02 mol) with methacrylic acid chloride (0.08 mol).
-2, A-3 and A-4 were synthesized. Synthesis Example (2) Synthesis of Compound B 2- (2- (2-chloroethoxy) ethoxy) ethanol 16.9 g (0.1 mol), N-methylpyrrolidone 5
0 g (0.5 mol), dichloromethane 100 ml, nitrobenzene (0.5 g), methacrylic acid chloride 1
0.5 g (0.1 mol) was added dropwise at 15 ° C or lower.

After completion of dropping, the mixture was stirred for 8 hours, and then water 200 was added.
ml was added, the mixture was extracted with dichloromethane, washed with water, dried and the solvent was distilled off to obtain 22 g of an oily compound. 3.4 g (0.025 mol) of meta-xylenediamine, 10 g of sodium hydrogen carbonate, and ethanol 1 were added to the obtained compound.
00 ml was added and the mixture was refluxed for 8 hours. Add 300 ml of water,
It was extracted with dichloromethane.

After the solvent was distilled off, 16.5 g of compound B-3 was obtained. Instead of 2- (2- (2-chloroethoxy) ethoxy) ethanol, 2- (2-chloroethoxy) ethanol and 2-chloroethanol (each 0.02 mol) were used to carry out the same reaction to give compound B. -2, B-1 were synthesized. Synthesis Example (3) Synthesis of Compound C 6.25 g (0.02 mol) of MXDA EO-4 (manufactured by Mitsubishi Gas Chemical Co., Inc.) obtained by adding 4 mol of ethylene oxide to 1 mol of metaxylenediamine and activated alumina ( Neutral, activity I, 1 g of Wako Pure Chemical Industries, Ltd. was stirred in 100 ml of dimethoxyethane, and 11.4 g (0.08 mol) of glycidyl methacrylate and hydroquinone monomethyl ether (0.07 g) were stirred therein. ) Added 5
Heated to reflux for hours.

After completion of heating, 300 ml of water was added and the mixture was extracted with dichloromethane. After washing with water and drying, the solvent was distilled off to obtain 17 g of Compound C-1. Similarly, MXDA EO-6 and MXDA EO obtained by adding 6, 10 and 15 mol of ethylene oxide to 1 mol of metaxylenediamine
-10, MXDA EO-15 (Mitsubishi Gas Chemical Co., Inc.)
Compound (C-) by reacting glycidyl methacrylate (0.08 mol) with (manufactured) (0.02 mol).
2, C-3 and C-4 were synthesized. Synthesis Example (4) Synthesis of Compound D 17 g (0.1 mol) of BLEMMER PE-90 (diethylene glycol monomethacrylate, manufactured by NOF CORPORATION)
And activated alumina (neutral, activity I, Wako Pure Chemical Industries, Ltd.)
1 g) was stirred in 100 ml of dimethoxyethane, and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Inc.) was added thereto.
9.0 g (0.025 mol) was added and the mixture was heated under reflux for 5 hours.

After completion of heating, 300 ml of water was added and the mixture was extracted with ethyl acetate. After washing with water and drying, the solvent was distilled off to give compound D-
125 g were obtained. Similarly, Bremmer PE-20
0 (polyethylene glycol monomethacrylate, manufactured by NOF CORPORATION) to 28 g (0.1 mol), TETRAD
Compound D-2 was synthesized by reacting 9.0 g (0.025 mol) of -X (manufactured by Mitsubishi Gas Chemical Co., Inc.).

[0069]

[Chemical 17]

Examples 1 to 9 and Comparative Examples 1 to 4 [Primer layer] 0.3 mm thick JI degreased by a conventional method.
An aluminum plate of SA 1050 material was immersed in a 1% aqueous solution of KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an aminosilane coupling agent, and then dried at room temperature. The following primer layer was applied on the aluminum plate so that the dry weight was 4 g / m ^2, and the coating was dried by heating at 140 ° C. for 2 minutes. Polyurethane resin Sunprene IB1700D (Sanyo Kasei Co., Ltd.) 10 parts by weight p-diazo diphenyl amine and hexafluorophosphate salt 0.1 part by weight TiO ₂ 0.1 part by weight Surfactant of polycondensation products of paraformaldehyde Activator MCF323 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.03 parts by weight-Propylene glycol methyl ether acetate 50 parts by weight-Methyl lactate 20 parts by weight-Pure water 1 part by weight Then, a vacuum exposure machine (FT261V manufactured by Nuark) UDNS ULTRA-
PLUS FLIPTOP PLATE MAKER) was used for 20 count exposure. [Photosensitive layer] On an aluminum plate coated with the above primer layer,
A photopolymerizable photosensitive solution having the following composition was applied so as to have a dry weight of 4 g / m ^2, and dried at 100 ° C. for 1 minute. Polyurethane resin 1.5 parts by weight [isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / tetraethylene glycol) / isophorone diamine] 1.5 parts by weight of a photopolymerizable polyfunctional monomer described in Table 1 below. Part-Ethyl Michler's ketone 0.35 part by weight 2-Chlorthioxanthone 0.10 part by weight-Victoria Pure Blue BOH naphthalene sulfonate 0.01 part by weight-MCF323 (manufactured by Dainippon Ink and Chemicals, Inc.) 0 0.03 parts by weight Methyl ethyl ketone 10 parts by weight Propylene glycol methyl ether 25 parts by weight [Ink repellent layer] The following silicone rubber composition liquid was applied on the above photopolymerizable photosensitive layer so that the dry weight was 2 g / m ² . It was dried at 140 ° C. for 2 minutes.・ Α, ω-divinylpolydimethylsiloxane (polymerization degree: about 700) 9 parts by weight ・ (CH ₃ ) ₃ -Si-O- (SiH (CH ₃ ) -O) ₈ -Si (CH ₃ ) ₃ 0.5 part by weight Parts-polydimethylsiloxane (polymerization degree of about 8,000) 0.5 parts by weight-olefin-chloroplatinic acid 0.2 parts by weight-tetracyclo (methylvinyl) siloxane 0.3 parts by weight-ISOPAR G (Esso Chemical Co., Ltd.) 140 parts by weight A single-sided matt 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 unmatted surface is in contact with the silicone rubber layer. A waterless planographic printing plate of the present invention was obtained.

One of these printing plates was prepared and 20
A positive film having a halftone image of 0 lines / inch and a gray scale (G / S) having an optical density difference of 0.15 are overlaid,
Vacuum exposure machine (FT251V UDNS ULTRA-PLUS FLI manufactured by Nuark)
It was exposed for 50 counts using a (PT0P PLATE MAKER). Then, the laminate film was peeled off, and the following development processing was immediately performed. [Development Treatment] While immersing the printing plate in water at 35 ° C., it was rubbed with a development pad to remove the silicone rubber layer in the unexposed area. Subsequently, it was dyed with a dyeing solution having the following composition, and the sensitivity (G / S clear sensitivity) and halftone dot reproducibility (reproducible halftone dot area, unit:%) were evaluated. (Staining solution) -Crystal violet 0.1 part by weight-Diethylene glycol monoethyl ether 15 parts by weight-Pure water 85 parts by weight Then, before printing, a scratch test of a non-image area was performed in advance using a sapphire needle having a diameter of 0.5 mm ( HEIDON-14 scratch tester, load 100 g to 500 g) was used, and using these plates, in a Heidelberg GTO printing machine without a dampening water supply device, Aqualess G black ink (TOYO KING ULTRA TUK manufactured by Toyo Ink). ), 100,000 sheets are printed, scratches on the non-image area begin to appear on the printed matter (damage resistance), and the silicone rubber layer on the non-image area is destroyed.
The number of printed sheets (printing durability) until the printed matter became dirty was evaluated.

[0072]

[Table 1]

From Table 1, the waterless planographic printing plate of the present invention is
It showed good sensitivity, halftone dot reproducibility, printing durability and scratch resistance. The polyfunctional monomers T, U, V and W used as comparative examples in Table 1 are represented by the following formulas.

[0074]

Embedded image

In addition, Examples 1 to 9 exposed in the same manner as above
Printing plate TWL860K (Toray Industries, Inc.)
Developed) using a developing solution PP-1 (manufactured by Toray Co., Ltd.) and a dyeing solution PA-1 (manufactured by Toray Co., Ltd.). It showed reproducibility, printing durability, and scratch resistance.

[0076]

According to the waterless lithographic printing plate of the present invention, the photo-cured photosensitive layer after imagewise exposure can be made to have flexibility, and it has excellent printing durability and scratch resistance, and is an aqueous developer. A waterless lithographic printing plate excellent in sensitivity and halftone dot reproducibility when developed in 1. can be obtained.

Claims (1)

[Claims] 1. A photopolymerizable photosensitive layer and a silicone rubber layer are laminated in this order on a substrate, and the photopolymerizable photosensitive layer contains at least one photopolymerizable monomer represented by the following formula (I). A photosensitive lithographic printing plate that does not require dampening water. Embedded image In formula (I), R ₁ and R ₂ are each independently substituted or
It represents an unsubstituted alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, or a halogen group, h is an integer of 0 to 4, i is an integer of 0 to 4, and h + i ≦ 4. L ₁ and L ₂ each independently represent a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, j is 0 or 1, and k is 0 or 1. R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group or the following formula (II) and may be the same or different, but at least two of them are the formula (II). Embedded image In formula (II), R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a —CO— or a phenylene group. R ₈ and R ₉ each represent a hydrogen atom or a methyl group,
l R ₈ and n R ₉ may be the same or different and are an integer of 1 = 0 to 15 and an integer of n = 0 to 15.
However, all l and n of R ₃ , R ₄ , R ₅ and R ₆ are
It cannot be 0 at the same time. Further, in the formula (II), Y is
It represents the following formula (III), (IV) or (V), and m is 0 or 1. Embedded image