JPH10161304A - Laser direct image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laser direct image forming material having excellent sensitivity by incorporating a polymer compd. having azide groups and having a structure derived from specified polymerizable monomers. SOLUTION: The laser direct image forming material has a photosensitive layer containing at least a photo-thermal exchanging material on a substrate, and the photosensitive layer contains a polymer compd. having azide groups and having a structure derived from polymerizable monomers expressed by the formula. In the formula, R<1> is a hydrogen atom or 1 to 15C alkyl group, R<2> is 1 to 15C alkylene chain, and to this alkylene chain, substituents selected from the following groups may be bonded. The substituents are 1 to 15C alkyl groups, bromine atoms, chlorine atoms, iodine atoms, hydroxyl groups, 1 to 10C alkoxy groups, 1 to 10C alkoxy carbonyl groups, 1 to 10C acyl groups, 1 to 10C acyloxy groups, phenyl groups and naphthyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a lithographic printing plate, a color image for printing proofing (Bruf), a gravure, or a copper etching resist for a wiring board, a color filter, etc., directly from digital image data using a semiconductor laser. The present invention relates to a laser direct image forming material.

[0002]

2. Description of the Related Art In recent years,
With the progress of digital image processing technology using a semiconductor laser and a computer, a semiconductor laser is directly scanned on a photosensitive lithographic printing plate from digital image data formed on a computer without using a silver halide film for a printing plate. After performing exposure and insolubilizing or solubilizing the exposed portion, an image is formed by developing with an aqueous solution (wet developing process), or the exposed portion is deteriorated, sublimated, melted and removed (dry developing process). Laser direct plate making technology, which forms an image with a laser, has attracted attention. In particular, there is no need to consider the balance between water and printing ink, the printing operation is easy, there is little wasted paper at the beginning of printing, and the printing time is short. It is expected to be a new printing system because it can produce printed matter.

[0003] Various attempts have been made for laser-direct fountain-free photosensitive lithographic printing plates used in fountain-free digital printing systems. For example,
(A) A photosensitive layer and a silicone rubber layer are coated in this order on a support, and the silicone rubber layer is removed by melting, volatilizing or burning by heat generated by ablation of an exposed portion of the photosensitive layer (Japanese Patent Application Laid-Open No. -164773, 6-18
6750, 6-199064, 7-30900
1), (b) a method in which the silicone rubber layer is degraded by heat generated by ablation of the exposed portion of the photosensitive layer to reduce the adhesiveness to the photosensitive layer, and is rubbed later (JP-A-6-5)
5723, 6-55869, and 6-92050),
(C) A method of forming an ink-adhesive toner image on a support provided with a silicone rubber layer by an electrophotographic method (JP-A-51-66008) is known. Among these methods, the method (a) is considered to be more preferable because the image forming process is the simplest and the one having excellent image quality is easily obtained.

However, a photosensitive lithographic printing plate requiring no laser dampening solution utilizing the above-mentioned application (a) has a low sensitivity and requires a high-power laser light source. Is required. As an attempt to improve the sensitivity of the printing plate, a method of adding a self-oxidizing resin such as a nitrocellulose resin to a photosensitive layer has been known (Japanese Patent Application Laid-Open No. Sho 50-1).
58405). However, with ordinary nitrocellulose resins, the improvement in sensitivity is not so large, and using nitrocellulose containing a large amount of nitro groups in order to further enhance photosensitivity poses a safety problem. The present invention seeks to provide a laser direct imaging material having excellent sensitivity.

[0005]

According to the present invention, in a laser direct image forming material having a photosensitive layer containing at least a photothermal conversion substance on a substrate, the polymerizable compound represented by the formula (4) is contained in the photosensitive layer. By including a polymer compound having an azide group having a structure derived from a monomer, a highly sensitive laser direct image forming material can be obtained.

[0006]

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[Wherein, R ¹ is a hydrogen atom or a C ¹ -C 1
5 represents an alkyl group. R ² represents an alkylene chain having 1 to 15 carbon atoms, and has 1 to 10 carbon atoms on the alkylene chain.
An alkyl group, a bromine atom, a chlorine atom, an iodine atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms,
A substituent selected from an acyloxy group having 1 to 10 carbon atoms, a phenyl group and a naphthyl group may be bonded. ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the substrate used in the present invention, any substrate can be used as long as it has flexibility that can be set in an ordinary image forming apparatus and can withstand a load applied during image formation. For example, paper such as coated paper, a metal plate such as an aluminum plate, or a plastic film such as polyethylene terephthalate is used. Among these, polyethylene terephthalate, an aluminum plate, or a composite material of an aluminum foil and another material is preferable. The thickness of the substrate is usually 10 μm to 1 mm, preferably 20 μm to 0.5 mm.

The photosensitive layer formed on the substrate efficiently absorbs the laser beam and converts it into heat, causing ablation of the photosensitive layer to change the solubility of the exposed photosensitive layer portion or to change the solubility of the exposed photosensitive layer portion. Contains a light-to-heat conversion material. In the photosensitive printing plate requiring no dampening solution according to one embodiment of the present invention, the silicone rubber layer is provided on the photosensitive layer. In this case, the silicone rubber layer is also ablated in response to ablation that causes the photosensitive layer to disappear. Induces melting, volatilization,
A light-to-heat conversion substance that causes the silicone rubber layer to disappear by combustion, pressure, or the like is used. As the photothermal conversion substance, any substance can be used as long as it has a function of efficiently converting light energy into heat energy. Usually, organic and inorganic pigments, organic dyes, metals, etc.
What absorbs near-infrared rays of up to 1200 nm, preferably 680 to 1200 nm is used.

For example, carbon black (MA-7, MA-100, MA-220, #
5, # 10, Color Black F, a product of Degussa
Graphite; metals such as titanium and chromium; metal oxides such as titanium oxide, tin oxide, zinc oxide, vanadium oxide and tungsten oxide; metal carbides such as titanium carbide; metal borides ;
Inorganic black pigments, azo black pigments, and lionol green 2 described in JP-A-4-322219
Organic pigments such as black and green such as YS and green pigment 7 are used. In addition, "Special Function Dyes" (edited by Ikemori and Sumiya, 19
1986, published by CMC Inc.), "Chemicals of Functional Dyes" (edited by Higaki, published by CMC Inc. 1981), "Dye Handbook" (edited by Okawa, Hirashima, Matsuoka, Kitao, published by Kodansha), ( Japan Photographic Dye Laboratories Inc. 19
Catalog published in 1995 and Exciton In
c. And dyes having absorption in the near-infrared region described in Laser Dye Catalog published in 1989. Further, Japanese Patent Application Laid-Open Nos. 3-97590, 97591, 63185, 26593, 97589,
2074, 2075, 2076, etc., organic dyes having absorption in the near infrared region, IR manufactured by Nippon Kayaku Co., Ltd.
Dyes having absorption in the near infrared region such as 820B are also used. Some of such dyes having absorption in the near infrared are exemplified in Table 1 below.

[0011]

[Table 1]

[0012]

[Table 2]

[0013]

[Table 3]

[0014]

[Table 4]

[0015]

[Table 5]

[0016]

[Table 6]

[0017]

[Table 7]

[0018]

[Table 8]

[0019]

[Table 9]

[0020]

Table 10 S-34 polymethine dye; IR-820B (manufactured by Nippon Kayaku Co., Ltd.) S-35 nigrosine dye; Color Index Solvent Black 5 S-36 nigrosine dye; Color Index Solvent Black 7 S-37 nigrosine dye; Color Index Acid Black 2 S-38 carbon black; MA-100 (manufactured by Mitsubishi Chemical Corporation) S-39 titanium monoxide; titanium black 13M (manufactured by Mitsubishi Materials Corporation) S-40 titanium monoxide; titanium black 13B (manufactured by Mitsubishi Materials Corporation)

[0021]

[Table 11]

[0022]

[Table 12]

[0023]

[Table 13]

These near-infrared absorbers are used alone or as a mixture of two or more, and are usually used by dissolving or dispersing them in a coating solution for a photosensitive layer. The proportion of the near-infrared absorbing agent in the photosensitive layer is usually from 0.5 to 90% by weight. Preferably, the near-infrared absorbing agent is 1.0 to 80% by weight of the photosensitive layer, especially 2.0 to 7%.
Used to account for 0% by weight. If the proportion of the near-infrared absorber in the photosensitive layer is too small, the laser beam cannot be sufficiently absorbed, and as a result, it is difficult to cause sufficient ablation. In the invention, the photosensitive layer contains a polymer compound having an azide group having a structure derived from the polymerizable monomer represented by the formula (5). When this polymer compound is present, the photosensitive layer

[0025]

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The sensitivity is significantly improved. The reason is that azide groups are decomposed by the heat generated by the near-infrared absorber that has absorbed the laser light to generate a gas such as nitrogen gas, which is formed on the photosensitive layer and, if necessary, on the photosensitive layer. This is probably due to promoting the disappearance of the silicone layer. In the formula (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and R ² represents a 1 to 1 carbon atom.
Represents 15 alkylene chains. Examples of the substituent of the alkylene chain include an alkyl group having 1 to 10 carbon atoms, a bromine atom, a chlorine atom, an iodine atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and 1 carbon atom. And acyl groups having 1 to 10 carbon atoms, acyloxy groups having 1 to 10 carbon atoms, phenyl groups, and naphthyl groups. Preferred examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a phenyl group and a naphthyl group.

Usually, R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group, and R ² is a methylene group, an ethylene group, a methylethylene group, an n-propylene group or a 2-methyl group. -N-propylene group, n-butylene group, a linear alkylene group having 1 to 5 carbon atoms such as 1,1-dimethylethylene group or an alkyl group having 1 to 5 carbon atoms, a phenyl group, a naphthyl group and the like. It is a substituted alkylene group. Preferably, R ¹ is a hydrogen atom or a methyl group, and R ² is an ethylene or n-propylene group.

The compound of the formula (5) can be used as a homopolymer or a copolymer between the compounds of the formula (5), or a copolymer with another polymerizable compound copolymerizable therewith. Can also be used. As the polymerizable compound to be copolymerized with the compound of the formula (5), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate (Meth) acrylic acid ester, styrene, α-methylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl pivalate, vinyl versatate and the like. Also, hydroxy-α-methylstyrene, hydroxystyrene, hydroxyphenyl (meth) acrylamide, N-hydroxyphenyl (α-methyl) vinylsulfonamide, hydroxyphenyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) ) A compound having a hydroxyl group or a carboxyl group such as acrylate, (meth) acrylic acid, and itaconic acid is also used.

The proportion of these copolymer components in the polymer compound having an azide group is usually from 0 to 80 mol%.
Preferably, the proportion of the copolymer component is 0 to 70 mol%,
In particular, it is 0 to 60 mol%. The weight average molecular weight (Mw) of the polymer compound having an azide group is usually 10 ³ to 10.
⁶ Preferably, 1.5 × 10 ^{3 to} 5 × 10 ⁵ , particularly 1.5 × 10 ^{3 to} 3 × 10 ⁵ is used.

The polymer compound having an azide group can be produced by a known method. For example, a halogenated alkyl vinyl ether is reacted with sodium azide to give an azido alkyl vinyl ether, which is used as it is or together with another polymerizable compound (Y) in the presence of a polymerization initiator by light or heat to undergo radical polymerization, Cationic or anionic polymerization can be performed.

[0031]

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Alternatively, radical polymerization, anion polymerization or cationic polymerization of the halogenated alkyl vinyl ether as it is or together with the other copolymer component (Y) is carried out by light or heat, and sodium azide is added to the obtained polymer. May be reacted.

[0033]

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Some of the thus obtained polymer compounds having an azide group are shown in Table 2 below.

[0035]

[Table 14]

[0036]

[Table 15]

The polymer compound having an azide group is usually
It accounts for 5 to 90% by weight of the photosensitive layer. Preferably, it accounts for 10 to 80% by weight, especially 15 to 75% by weight of the photosensitive layer. The photosensitive layer is basically composed of the above-mentioned near infrared ray absorbent and a polymer compound having an azide group, but in addition to this, applicability, compatibility with the near infrared ray absorbent,
For the purpose of increasing the film strength and the effect of ablation, other organic polymer substances can be contained. Examples of such organic polymer substances include unsaturated acids such as (meth) acrylic acid and itaconic acid, alkyl (meth) acrylate, phenyl (meth) acrylate, and (meth) acrylate.
Copolymers with benzyl acrylate, styrene, α-methylstyrene and the like; alkyl methacrylate and alkyl acrylate polymers represented by polymethyl methacrylate;
Copolymer of alkyl (meth) acrylate with acrylonitrile, vinyl chloride, vinylidene chloride, styrene, etc .; copolymer of acrylonitrile with vinyl chloride or vinylidene chloride; modified cellulose having carboxyl group in side chain; polyethylene oxide; Polyvinylpyrrolidone; novolak resin obtained by condensation reaction of phenol, o-, m-, p-cresol, and / or xylesol with aldehyde, acetone, etc .; polyether of epichlorohydrin and bisphenol A; soluble nylon; Vinylidene chloride; chlorinated polyolefin; copolymer of vinyl chloride and vinyl acetate, vinyl acetate, vinyl pivalate,
Polymers such as vinyl versatate and their copolymers, copolymers of acrylonitrile and styrene; copolymers of acrylonitrile, butadiene and styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyurethane; polyethylene terephthalate isophthalate Acetylcellulose; acetylpropoxycellulose; acetylbutoxycellulose; nitrocellulose; celluloid; polyvinyl butyral; These organic polymer substances are used so as to occupy 0 to 80% by weight of the photosensitive layer. It is preferably used so as to account for 2 to 70% by weight, particularly 5 to 60% by weight.

The photosensitive layer may contain a coloring material other than a near-infrared absorbing agent, if necessary, for the purpose of coloring the photosensitive layer to form a multicolor image. Dyes and pigments are used as coloring materials. For use in color proofing, dyes and pigments having a color tone that matches yellow, magenta, cyan, and black are required. In addition, metal powders, white pigments, fluorescent pigments, and the like can also be used.

Specific examples of dyes and pigments include Victoria Pure Blue (42595) and Auramine O (4100).
0), Kachiron Brilliant Flavin (Basic 1)
3), Rhodamine 6 GCP (45160), Rhodamine B (45170), Safranin OK 70: 100 (50
240), Erioglaucine X (42080), Fast Black HB (26150), No. 120 / Lionol Yellow (21090), Lionol Yellow G
RO (21090), Shimla First Yellow 8G
F (21105), Benzidine Yellow 4T-564D
(21095), Shimla Fast Red 4015
(12355), Lionol Red 7B4401 (15
850), Fast Gen Blue TGR-L (7416
0), Lionol Blue SM (26150), Mitsubishi Carbon Black MA-100, Mitsubishi Carbon Black # 4
0 and the like (the numbers in parentheses above indicate the color index (CI)). These coloring materials are generally used so as to account for 5 to 60% by weight of the photosensitive layer. The thickness of the photosensitive layer is usually from 0.3 to 5 μm.
It is preferably from 0.3 to 3 μm, particularly preferably from 0.5 to 2 μm.

The laser direct image forming material according to the present invention can directly obtain a colored image sheet or a printing plate used for a print proofing group by ablating the photosensitive layer with a laser beam. Also,
By improving the solubility of the photosensitive layer in the exposed portion by ablation with a laser beam, it can be used for wet image formation with an aqueous alkaline solution. That is, the exposed portion of the photosensitive layer can be removed with an aqueous alkali solution to form a positive photosensitive layer image.

Further, the laser direct image forming material according to the present invention can be provided as a printing plate requiring no dampening solution by further providing an ink-repellent silicone rubber layer on the photosensitive layer. In addition, a printing plate for wet printing may be provided by providing a hydrophilic layer on the photosensitive layer for preventing adhesion of printing ink. The silicone rubber layer can be appropriately selected from those described in JP-A-7-164773 and the like. Preferably, a silicone rubber composition is cured by a condensation reaction described below, and a silicone rubber layer is cured by an addition reaction. Either of two types of addition-crosslinking type for curing the composition is used. The condensation-crosslinking type silicone rubber composition contains, as essential components, a linear organopolysiloxane having hydroxyl groups at both ends and a reactive silane compound which forms a silicone rubber layer by crosslinking with the same. As the linear organopolysiloxane having hydroxyl groups at both ends, those represented by the following formula (8) are used.

[0042]

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(Wherein two R ³ each independently represent a hydrogen atom, a methyl group, a phenyl group, or a vinyl group;
The following integers are shown. Among the compounds of the formula (8), those in which R ¹ is a methyl group are preferably used. The weight average molecular weight (Mw) of the organopolysiloxane is 5 × 10 ³ to 1 × 10 ⁶ ,
Preferably it is 1 × 10 ⁴ to 1 × 10 ⁶ . When Mw is extremely low, the film strength of the silicone rubber layer is reduced, and the printing resistance is reduced. Conversely, when Mw is extremely high, the effect of removing the silicone rubber layer by ablation is reduced, and sensitivity and image reproducibility are likely to be reduced.

The reactive silane compound which undergoes a cross-linking reaction with the linear organopolysiloxane reacts with a hydroxyl group of the linear organopolysiloxane to form a condensation such as a deacetic acid type, a deoxime type, a dealcohol type, a deamino acid type or a dehydration type. Having two or more functional groups capable of causing cross-linking
000 or less reactive silane compound. Examples of such a functional group include the following.

[0045]

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(In the formula, R ⁴ represents an alkyl group having 1 to 5 carbon atoms. When two R ⁴ are present in the same atomic group, they may be the same or different.) Group is an acyloxy group (—OCO
R ⁴ ) having a functional group number of 3 or more, or a functional group having an alkoxy group (—OR ³ ) having a functional group number of 3 or more forms a silicone rubber layer in a short time after drying treatment after coating. preferable. Particularly preferred are those in which the functional group is an acetoxy group and the number of functional groups is 3 or more, or those in which the functional group is an alkoxy group and the number of functional groups is 6 or more. As the reactive silane compound, for example, the following general formulas (9) to (12)
The compound represented by is used. In the formula, Q represents a functional group which reacts with a hydroxyl group of the above-mentioned linear organopolysiloxane having hydroxyl groups at both ends, and Q is present at least two in one molecule.

[0047]

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(Wherein X is an alkyl group having 1 to 5 carbon atoms;
Phenyl group, vinyl _{group, H 2 N- (CH 2)} h -, CH
₂ ＣC (CH ₃ ) CO—, CH ₂ ＣＨCHCO—,

[0049]

Embedded image R ⁴ represents an alkyl group having 1 to 5 carbon atoms as described above, and R ⁵ represents an allyl group or — (CH ₂ ) _q —SiR ⁴
_3-p Q indicates _P, R ⁶ is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a phenyl group, R ^4, R ^5, when each of R ⁶ there are a plurality in the same molecule, Each of the plurality may be the same or different, h, j and q each represent an integer of 1 to 5, p and r each represent an integer of 1 to 3, s represents an integer of 2 to 4 And t and u each represent an integer of 0 to 5. Table 3 lists some of the reactive silane compounds.

[0050]

[Table 16]

[0051]

[Table 17]

[0052]

[Table 18]

[0053]

[Table 19]

The condensation-crosslinking type silicone rubber composition comprises an organic carboxylic acid, a titanate, and a stannic acid in order to increase the reaction efficiency of the condensation crosslinking reaction between the above-mentioned organopolysiloxane having hydroxyl groups at both ends and a reactive silane compound. An appropriate condensation catalyst such as an ester, an aluminate ester or a platinum-based catalyst is added to carry out a condensation reaction to cure. The ratio of the organopolysiloxane having hydroxyl groups at both ends to the condensation crosslinking silicone rubber composition, the reactive silane compound and the condensation catalyst is such that the organopolysiloxane having hydroxyl groups at both ends is 80 to 98% by weight, preferably 85 to 98% by weight.
98% by weight, the reactive silane compound is 2 to 20% by weight,
It is preferably 2 to 15% by weight, and the condensation catalyst is 0.05 to 5% by weight, preferably 0.1 to 3% by weight.

If the proportions of the reactive silane compound and the condensation catalyst are too high, the ink repellency decreases, and it becomes difficult to remove the silicone rubber layer during ablation, and the sensitivity and image reproducibility decrease. Conversely, if the proportion of these components is too low, the film strength of the silicone rubber layer will decrease, and the printing durability will decrease. The most preferable proportions of the reactive silane compound and the condensation catalyst in the composition are 2 to 7% by weight and 0.1 to 1% by weight, respectively.

In order to increase the ink repellency of the silicone rubber layer, a condensation-crosslinking type silicone rubber composition is used.
Polysiloxanes other than the polyorganosiloxane having a hydroxyl group at both ends can be contained. The amount preferably accounts for 2 to 15% by weight, especially 3 to 12% by weight of the silicone rubber layer. As such a polysiloxane, for example, a polydimethylsiloxane having a weight average molecular weight of 1 × 10 ⁴ to 1 × 10 ⁶ , which is trimethylsilylated at both terminals, is used.

The composition for forming the addition-crosslinking type silicone rubber has at least two aliphatic unsaturated groups in one molecule.
And an organopolysiloxane having at least two Si—H bonds in one molecule, which forms a silicone rubber layer by crosslinking with the organopolysiloxane, as essential components. The organopolysiloxane having at least two aliphatic unsaturated groups in one molecule may have any of a chain structure, a cyclic structure and a branched structure, but is preferably a chain structure. Examples of the aliphatic unsaturated group include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group, cycloheptenyl group and cyclooctenyl group; ethynyl group ,
Alkynyl groups such as a propynyl group, a butynyl group, a pentynyl group and a hexynyl group are exemplified. Among these, an alkenyl group having an unsaturated bond at a terminal is preferable from the viewpoint of reactivity, and a vinyl group is particularly preferable. The remaining substituents other than the aliphatic unsaturated groups are preferably methyl groups in order to obtain good printing ink repellency.

At least two aliphatic unsaturated groups are present in one molecule.
Weight average molecular weight Mw of the organopolysiloxane
Is usually 5 × 10 ^{2 to} 5 × 10 ⁵ , preferably 1 × 10 ³
３3 × 10 ⁵ . When Mw is too small, the strength of the silicone rubber layer is reduced, the silicone rubber layer is easily damaged at the time of printing, and the printing ink repellency of the portion is reduced,
Ink easily adheres, causing printing stains. On the other hand, if the Mw is too high, the removal of the silicone rubber layer by ablation becomes poor, and the sensitivity and the image reproducibility are likely to be reduced.

An organopolysiloxane having at least two Si—H bonds in one molecule has a chain-like structure.
It may be cyclic or branched, but is preferably chain. S
The i-H bond may be at the terminal or at the middle of the siloxane skeleton, and the ratio of hydrogen atoms to the total number of substituents is usually 1 to 60%, preferably 2 to 5%.
0%. The remaining substituents other than hydrogen atoms are preferably methyl groups in order to obtain good printing ink repellency.
The weight average molecular weight Mw of an organopolysiloxane having at least two Si—H bonds in one molecule is usually 3 × 10
^{It is 2 to} 3 × 10 ⁵ , preferably 5 × 10 ² to 2 × 10 ⁵ . If the Mw is extremely high, the sensitivity and the image reproducibility tend to decrease.

In order to carry out an addition reaction between the above-mentioned organopolysiloxane having at least two aliphatic unsaturated groups in one molecule and the organopolysiloxane having at least two Si—H bonds in one molecule, An addition reaction catalyst is used. The addition reaction catalyst can be arbitrarily selected from known catalysts, but a platinum-based catalyst is preferable, and one or a mixture of two or more selected from platinum group metals and platinum group compounds is used. As the platinum group metal, a simple substance of platinum (for example, platinum black), a simple substance of palladium (for example, palladium black), a simple substance of rhodium, or the like is used. The platinum group compounds include chloroplatinic acid, platinum-
Olefin complexes, platinum-alcohol complexes, platinum-ketone complexes, complexes of platinum and vinylsiloxane, tetrakis (triphenylphosphine) platinum, tetrakis (triphenylphosphine) palladium, and the like are used. Among these, those obtained by dissolving chloroplatinic acid or a platinum-olefin complex in an alcohol solvent, a ketone solvent, an ether solvent, a hydrocarbon solvent or the like are particularly preferable.

The proportion of each component in the composition forming the silicone rubber layer is such that the organopolysiloxane having at least two aliphatic unsaturated groups in one molecule is 80 to 98% by weight based on the total solid content. And preferably 85 to 98% by weight, and 2 to 20% by weight, preferably 2 to 15% by weight of an organopolysiloxane having at least two Si—H bonds in one molecule. 0.0
It is 0001 to 10% by weight, preferably 0.0001 to 5% by weight.

If the compounding ratio of the organopolysiloxane having at least two Si—H bonds in one molecule is too low, the film strength of the silicone rubber layer is reduced, and the repulsion and printing resistance of the printing ink are reduced. If the compounding ratio is too high, the sensitivity and the image reproducibility decrease. In addition, in the composition for forming the addition-crosslinking type silicone rubber layer, in addition to the above components, for the purpose of further increasing the film strength of the silicone rubber layer,
An amino-based organosilicon compound having a hydrolyzable group represented by the following formula (13) can be added.

[0063]

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(Wherein, Z represents a hydrolyzable group, R ⁷ represents a divalent hydrocarbon group, R ⁸ represents a monovalent hydrocarbon group which may be substituted, and two R ⁹ each independently hydrogen atom, a monovalent optionally substituted hydrocarbon group or -R ⁷ -SiR ⁸ _3-p Z groups represented by _p, p is an integer of 1-3. Examples of the hydrolyzable group represented by Z include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group;
An alkenyloxy group such as a propenyloxy group; an aryloxy group such as a phenoxy group; an acyloxy group such as an acetyloxy group. Among these, a methoxy group, an ethoxy group, and an acetyloxy group are preferred in terms of stability, curability, and the like. Examples of the divalent hydrocarbon group for R ⁷ include:

[0065]

Embedded image

Is preferred. Examples of the monovalent hydrocarbon group which may be substituted among the substituents represented by R ⁸ and R ⁹ include, for example, alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cyclopropyl group, cyclobutyl Group,
Cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group such as cyclooctyl group; vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, etc. alkenyl group; cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, Cycloalkenyl groups such as cyclooctenyl group; substituted alkyl groups such as glycidoxypropyl group, acryloxypropyl group, methacryloxypropyl group and aminoethyl group. From the viewpoint of curability, R ⁸ and R ⁹ are preferably a vinyl group, an allyl group, a glycidyl group, a methacryl group, or a γ-glycidoxypropyl group.

Examples of the amino organosilicon compound represented by the formula (13) include 3- [N-allyl-N- (2
-Aminoethyl)] aminopropyltrimethoxysilane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N-allyl-N-methacryl) aminopropyltrimethoxysilane, N-glycidyl-N , N-bis [3- (methyldimethoxysilyl)
Propyl] amine, N-glycidyl-N, N-bis [3
-(Trimethoxysilyl) propyl] amine, aminopropyltrimethoxysilane, aminopropyltriacetyloxysilane, 3- [N-allyl-N- (2-aminoethyl)] aminopropyltriacetyloxysilane,
3- (N-allyl-N-glycidyl) aminopropyltriacetyloxysilane, 3- (N-allyl-N-methacryl) aminopropyltriacetyloxysilane and the like. These may be used as a mixture of two or more.

The amino-based organosilicon compound is generally used in an amount of 0 to 1 based on the total solid content of the composition forming the silicone rubber layer.
It is used in an amount of 0% by weight, preferably 0 to 5% by weight. Further, a curing retarder can be added to the composition for forming the addition-crosslinking type silicone rubber layer in order to prevent rapid curing of the silicone rubber layer composition when applying the silicone rubber layer. The curing retarder can be arbitrarily selected from commonly known acetylenic alcohols, maleic esters, silylated acetylenic alcohols, silylated maleic acids, triallyl isocyanurate, vinyl siloxane, and the like.

The addition amount of the curing retarder varies depending on the desired curing speed, but is usually 0.0001 to 1.0 part by weight based on the total solids of the composition forming the silicone rubber layer. The above-mentioned condensation-crosslinking type and addition-crosslinking type silicone rubber layers may contain an inorganic filler such as silica, titanium oxide or aluminum oxide for the purpose of improving the strength, and silica is particularly preferably used. From the viewpoint of dispersibility or dispersion stability, it is preferable to use a filler having an average particle diameter of 500 μm or less.

These silicone rubber layers have excellent printing ink repellency and printing resistance, and are easily removed by ablation, and have a function of providing high sensitivity and high image reproducibility. The scratch strength of the silicone rubber layer is 10 to 10
0 g (scratch strength is 0.2 m
m sapphire needle 10 cm while applying weight on the sample
/ G (represents the weight (g) required to cause scratching when moved at a speed of / min). When the scratch strength is in the above range, the printing suitability such as printing ink repellency, printing resistance, sensitivity, and image reproducibility is improved. The thickness of the silicone rubber layer is usually 0.1 to 10 μm. It is preferably from 0.2 to 5 μm, particularly preferably from 0.3 to 2 μm.

The laser direct image forming material according to the present invention can be provided as a printing plate for wet printing by providing a hydrophilic layer on the photosensitive layer instead of the silicone rubber layer. The surface of the hydrophilic layer is covered with a thin film of water (wet state) by fountain solution supplied during printing, and prevents the adhesion of lipophilic ink particles when it comes into contact with the printing ink in an emulsion state. It has a function of forming a non-image portion on printed matter. In the hydrophilic layer, to maintain hydrophilicity,
If necessary, a hydrophilic binder polymer cured with a crosslinking agent or the like is contained in an amount of 5 to 100 parts by weight based on the total solid content of the hydrophilic layer. The preferred proportion of the hydrophilic binder polymer in the hydrophilic layer is 20 to 95% by weight, particularly 40 to 9%.
0% by weight.

As the hydrophilic binder polymer, a carboxyl group, an amino group, a phosphoric acid group, a sulfonic acid group, or a salt, a hydroxyl group, an amide group, a polyoxy group, or a carboxyl group, an amino group, a phosphoric acid group, or a side chain thereof may be used. A networked polymer having a plurality of hydrophilic functional groups such as an ethylene group, or a polymer in which a hetero atom such as oxygen, nitrogen, sulfur, or phosphorus is interposed in a carbon-carbon bond or a carboxyl group in a side chain thereof, A polymer having a plurality of hydrophilic functional groups such as an amino group, a phosphoric acid group, a sulfonic acid group, a salt thereof, a hydroxyl group, an amide group, and a polyoxyethylene group is used. For example, poly (meth) acrylate type, polyoxyalkylene type, polyurethane type, epoxy ring-opening addition polymerization type, poly (meth) acrylic acid type, poly (meth) acrylamide type, polyester type, polyamide type, polyamine type, polyvinyl type Polymers such as polysaccharides and cellulose derivatives are used. Among them, any one of a hydroxyl group, a carboxyl group or an alkali metal salt thereof, an amino group or a hydrogen halide salt thereof, a sulfonic acid group or an amine thereof, an alkali metal, an alkaline earth metal salt, or an amide group on the side chain, or these Are repeatedly used, and those having a polyoxyethylene group in a part of the main chain segment in addition to the hydrophilic functional group of these side chains are preferable because of high hydrophilicity. Further, those having a urethane bond or a urea bond in the main chain or side chain of the hydrophilic binder polymer are more preferable because not only the hydrophilicity but also the printing durability of the non-image area are improved.

The hydrophilic binder polymer can be obtained by various known methods. For example, a hydrophilic binder polymer can be obtained by polymerizing a polymerizable compound having a hydrophilic functional group or by copolymerizing it with another polymerizable monomer. Examples of the polymerizable compound having a hydrophilic functional group include (meth) acrylic acid or its alkali, amine salt, itaconic acid or its alkali, amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N- Monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, 3-vinylpropionic acid or its alkali, amine salt, vinylsulfonic acid or its alkali, amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono Hydroxyl groups such as (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, allylamine or hydrohalide thereof, Hexyl group, a sulfonic acid group, a phosphoric acid or a salt thereof, an amide group, an amino group, a compound having a hydrophilic group such as an ether group is used.

In order to crosslink the hydrophilic layer, for example, a hydroxyl group, a carboxyl group, an amino group,
A binder polymer obtained by introducing a polymerizable unsaturated group such as a vinyl group, an allyl group, a (meth) acryl group, or a cinnamoyl group into a hydrophilic polymer using a functional group such as an epoxy group is used as a binder polymer. What is necessary is just to dissolve it in a suitable solvent together with the monomer capable of copolymerizing with the unsaturated group and the polymerization initiator, apply it to the photosensitive layer, and carry out three-dimensional crosslinking after drying or also as drying. Further, a hydrophilic binder polymer containing an active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group is added to an active hydrogen-free solvent together with an isocyanate compound or a blocked polyisocyanate compound, and applied on the photosensitive layer, and dried or dried. Reaction may also be performed to effect three-dimensional crosslinking.

When a monomer having a glycidyl group such as glycidyl (meth) acrylate is used in combination with the copolymer component of the hydrophilic binder polymer, α, such as 1,2-ethanedicarboxylic acid or adipic acid, is used as a crosslinking agent. ω-alkane or alkenedicarboxylic acid, 1,
Polycarboxylic acids such as 2,3-propanetricarboxylic acid and trimellitic acid, 1,2-ethanediamine, diethylenediamine, diethylenetriamine, α, ω-bis- (3
Polyamino compounds such as -aminopropyl) -polyethylene glycol ether; oligoalkylene or polyalkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and tetraethylene glycol; and polyhydroxy compounds such as trimethylolpropane, glycerin, pentaerythritol and sorbitol. And three-dimensional cross-linking by utilizing a ring-opening reaction therewith.

The hydrophilic binder polymer having a carboxyl group or an amino group may be used as a crosslinking agent such as ethylene or propylene glycol diglycidyl ether, polyethylene or polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
Three-dimensional crosslinking can be performed using an epoxy ring-opening reaction using a polyepoxy compound such as 1,6-hexanediol diglycidyl ether and trimethylolpropane triglycidyl ether.

Polysaccharides such as cellulose derivatives, polyvinyl alcohol or partially saponified products thereof, glycidol homo- or copolymers, or hydrophilic binder polymers based on these are used for the above-mentioned functional groups capable of undergoing a crosslinking reaction by utilizing the hydroxyl groups contained therein. Groups can be introduced to provide a three-dimensional crosslinked structure in the manner described above. As another method for forming a three-dimensional crosslinked structure, when the synthesized hydrophilic polyurethane precursor has an isocyanate group terminal, glycerol mono (meth) acrylate,
Has active hydrogen such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, (meth) acrylic acid, cinnamic acid, and cinnamic alcohol When the compound has a hydroxyl group or an amino group terminal, there is a method of reacting the compound with (meth) acrylic acid, glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, or the like.

Further, after applying a polybasic acid and a polyol or a polybasic acid and a polyamine, a three-dimensional cross-linking is carried out by heating, or a water-soluble colloid-forming compound such as casein, glue or gelatin is three-dimensionally cross-linked by heating. A hydrophilic binder polymer having a structure may be formed. Furthermore, hydroxyl- and amino-group-containing hydrophilic groups such as homo- or copolymers synthesized from hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate and vinyl alcohol, and allylamine, polysaccharides such as partially saponified polyvinyl alcohol and cellulose derivatives, and glycidol homo or copolymers. There is also a method of forming a three-dimensionally crosslinked hydrophilic binder polymer by reacting a hydrophilic polymer with a polybasic acid anhydride having two or more acid anhydride groups in one molecule.

Examples of polybasic acid anhydrides include ethylene glycol bis anhydro trimellitate, glycerol tris anhydro trimellitate, 1,3,3
a, 4,5,9b hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2
-C] furan-1,3-dione, 3,3 ', 4,4'-
Diphenylsulfonetetracarboxylic dianhydride, 1,
2,3,4-butanetetracarboxylic dianhydride can be used.

An active hydrogen-containing compound such as a polyurethane or a polyamine or a polyol having an isocyanate group at the end and other components described below are dissolved or dispersed in a solvent and coated on a support to remove the solvent. Can be cured at a temperature at which they do not break down to form a three-dimensional crosslink. In this case, the hydrophilicity is either the segment of the polyurethane or the active hydrogen containing compound or both,
It may be provided by introducing a hydrophilic functional group into the side chain. The segment and the functional group that express hydrophilicity may be appropriately selected from the above description.

As the polyisocyanate compound, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, lysine diisocyanate, Triphenylmethane triisocyanate, bicycloheptane triisocyanate and the like are used.

In handling before and after the coating step, it is sometimes preferable to block (mask) the isocyanate group by a known method in order to prevent the isocyanate group from changing. For example, Keiji Iwata, "Plastic Materials Course Polyurethane Resin", Nikkan Kogyo Shimbun (1974), pp. 51-52, Keiji Iwata, "Polyurethane Resin Handbook", Nikkan Kogyo Shimbun (198)
7), pages 98, 419, 423, 499, etc., it may be blocked with sodium acid sulfite, aromatic secondary amine, tertiary alcohol, amide, phenol, lactam, heterocyclic compound, ketoxime or the like. It is preferable that the isocyanate regeneration temperature is low and hydrophilic such as sodium acid sulfite.

An addition-polymerizable unsaturated group may be introduced into any of the above-mentioned unblocked or blocked polyisocyanates and used for strengthening crosslinking. The degree of the degree of crosslinking such as the average molecular weight between crosslinks varies depending on the type of the segment used, the type and amount of the functional group, and the like, but may be determined according to the required printing durability. Usually, the average molecular weight between crosslinks is 500-5.
It is set in the range of 10,000. If it is shorter than 500, it tends to be brittle, and if it is longer than 50,000, it may be unfavorable because it swells with fountain solution and printing durability is impaired. 800 to 30,000, or even 1000 to 1 on balance of printing durability and hydrophilicity
About ten thousand is practical. In the hydrophilic binder polymer, various monofunctional or polyfunctional monomers as described below may be used in combination.

Shinzo Yamashita and Tosuke Kaneko, "Crosslinking Agent Handbook" Taiseisha Publishing (1981), Kiyomi Kato, "Ultraviolet Curing System", published by Integrated Technology Center (1989), Kiyomi Kato, "UV / EB Curing Handbook ( N, N'-methylenebisacrylamide described in Polymer Publishing Association (1985), edited by Kiyoshi Akamatsu, "Practical Technology of New Photosensitive Resins", CMC, pp. 102-14, (1987). , (Meth) acryloylmorpholine, vinylpyridine, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoneopentyl (meth ) Acrylate, N- vinyl -
2-pyrrolidone, diacetone acrylamide, N-methylol (meth) acrylamide, p-styrenesulfonic acid and its salt,

Methoxytriethylene glycol (meth)
Acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (PEG has a number average molecular weight of 40
0), methoxypolyethylene glycol (meth) acrylate, (PEG number average molecular weight 1000), butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonyl Phenoxyethyl (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, polyethylene glycol di (meth) acrylate (PEG has a number average molecular weight of 40
0), polyethylene glycol di (meth) acrylate (number average molecular weight of PEG 600), polyethylene glycol di (meth) acrylate (number average molecular weight of PEG 1)
000), polypropylene glycol di (meth) acrylate (number average molecular weight of PEG 400),

2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2
-Bis [4- (methacryloxypolyethoxy) phenyl] propane or its acrylate, β- (meth)
Acryloyloxyethyl hydrogendiene phthalate,
β- (meth) acryloyloxyethyl hydrogen succinate, polyethylene or polypropylene glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1, 6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate,

Tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, isobornia (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate , Cyclohexyl (meth) acrylate, tetrafurfuryl (meth) acrylate, benzyl (meth) acrylate, mono (2-acryloyloxyethyl) acid phosphate or its methacrylic body, glycerin mono- or di (meth) acrylate,
Tris (2-acryloxyethyl), isocyanurate or its methacrylic body, N-phenylmaleimide, N
-(Meth) acryloxysuccinimide, N-vinylcarbazole, divinylethyleneurea, divinylpropyleneurea and the like.

The hydrophilic layer used in the present invention has a particle diameter of 10 to 4 for the purpose of improving the water retention of the dampening solution.
0 nm colloidal silica, colloidal alumina having a particle size of 10 to 100 nm, acetic acid, formic acid, citric acid, tartaric acid, malic acid, a carboxylic acid such as itaconic acid or a salt thereof, relative to the total solid content of the hydrophilic layer, is 0 to 90% by weight, preferably 0 to 80% by weight can be contained.

Further, an appropriate surfactant is added to the hydrophilic layer in an amount of 0.01 to 0.01% based on the total solid content of the hydrophilic layer coating solution for the purpose of improving the coating property on the photosensitive layer. A blending ratio of 10% by weight can be contained. In the hydrophilic layer used in the present invention, in order to facilitate the removal of the hydrophilic layer during ablation of the photosensitive layer, the photothermal conversion dye or pigment used in the photosensitive layer is added to the total solid content of the hydrophilic layer. 5 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight.

The hydrophilic layer used in the present invention has a thickness of
It is 0.1 to 100 μm, preferably 0.2 to 50 μm, and more preferably 0.5 to 20 μm. The composition for forming the above-mentioned photosensitive layer or silicone rubber layer or hydrophilic layer was dissolved in an appropriate solvent, respectively, and coated on a support or a photosensitive layer by various coating devices such as a wire bar, a spinner, and a roll coater. Thereafter, drying is performed to form a photosensitive layer, a silicone rubber layer, or a hydrophilic layer, respectively. Examples of the coating solvent for the photosensitive layer include ketones such as methyl ethyl ketone and cyclohexanone; esters such as butyl acetate, amyl acetate and ethyl propionate; and hydrocarbons such as toluene, xylene, monochlorobenzene, carbon tetrachloride, trichloroethylene, and trichloroethane. And halogenated hydrocarbons, ethers such as methyl cellosolve, ethyl cellosolve, and tetrahydrofuran, as well as common ones such as propylene glycol monomethyl ether acetate, bentquinone, and dimethylformamide. As the coating solvent for the silicone rubber layer, n-hexane, cyclohexane, petroleum ether, aliphatic hydrocarbon solvent Exxon Chemical Co., Ltd .: Isopar E, H, G, and these solvents and the above-mentioned photosensitive layer coating solvent A mixed solvent or the like can be used. As a coating solvent for the hydrophilic layer, water, methanol, ethanol or the like is usually used. In addition, on the silicone rubber layer,
Further, in order to protect this, a release plastic sheet such as a polypropylene sheet, a polyethylene sheet, or a polyethylene terephthalate, or a release paper may be laminated.

The laser direct image-forming material according to the present invention is usually subjected to ablation of the exposed portion by scanning and exposing a semiconductor laser beam oscillating near infrared light of 680 to 1100 nm with a beam spot condensed to a diameter of 5 to 30 μm. It is used as a resist image, color material image, or printing plate without post-processing, but is necessary on the surface of the image forming material for the purpose of removing fine particles of the photosensitive layer or silicone rubber layer or hydrophilic layer generated by ablation. Post-treatment for applying physical stimuli such as brushes, pads, ultrasonic waves, and sprays may be performed while supplying an aqueous solution or an organic solvent accordingly.

As another method for removing fine particles generated by ablation, a cover sheet having a surface having a high adhesiveness to the fine particles is placed on an exposed image forming material, and the photosensitive surface of the image forming material is removed. After ranmeating so that the adhesive cover sheet surfaces fit together, a method of peeling or laminating such a cover sheet through which laser light passes before exposure in the same manner as above, and peeling after exposure on the image forming material There is also a method for removing fine particles. As such a cover sheet, a sheet provided with an adhesive layer of silicone rubber, ionomer, vinyl acetate, or the like on polyethylene terephthalate, polypropylene, polycarbonate, paper, or the like is used.

As a method for preparing a printing plate with the laser direct image forming material according to the present invention, in addition to the methods described above, the above method was applied to an aluminum sheet or the like whose surface was made hydrophilic by roughening and anodizing. Images can be superposed, heated and transferred to an aluminum sheet or the like for use. . As still another alternative, the image forming material according to the present invention is overlaid on the aluminum sheet or the like, and a laser beam is irradiated from the back surface of the image forming material,
It is also possible to adopt a method in which the photosensitive layer in the exposed portion is transferred onto an aluminum sheet by ablation.

[0094]

The present invention will be described more specifically with reference to the following examples. Synthesis of polymer compound (P-1) having an azide group; 2-chloroethyl vinyl ether was added to dichloromethane in the form of 1.
An internal light irradiation type photoreactor equipped with a 1 kW high-pressure mercury lamp, and 300 ml of a solution in which 5 × 10 ⁻² mol / l and triphenylsulfonium tetrafluoroborate are dissolved at 3.5 × 10 ⁻⁵ mol / l. And reacted at room temperature for 4 hours while blowing nitrogen gas into the solution. Then, 10 times the amount of n-hexane was added thereto, and the resulting poly (2
-Chloroethyl vinyl ether) was collected by precipitation. Recovered poly (2-chloroethyl vinyl ether)
Was vacuum dried at 60 ° C.

Poly (2-chloroethyl vinyl ether)
2 g and 2 g of sodium azide were added to 30 g of dimethyl sulfoxide, and reacted at 80 ° C. for 30 hours with stirring. The reaction solution was returned to room temperature, 100 g of water was gradually added thereto with stirring, and the precipitated polymer compound having an azide group (P-1 in Table 2) was recovered and dried in vacuo at 40 ° C.
Similarly, polymer compounds having an azide group of P-9 and P-11 in Table 2 were synthesized.

Examples 1 to 10 and Comparative Examples 1 to 3 Preparation of Laser Direct Image Forming Materials; Near-Infrared Absorbers for Forming Photosensitive Layers, Polymer Compounds Having Azide Groups and Organic Polymer Substances as shown in Table 4 Was added to a solvent (N-methylpyrrolidone, cyclohexanone and ethanol were mixed at a weight ratio of 6: 3: 1) to prepare a coating solution for forming a photosensitive layer. In Table 4, the values in parentheses indicate the weight percentage of solid content. This is dried on a substrate to a dry thickness of 1.5 μm.
To form an image forming material. The following were used as the substrate, near-infrared absorber and organic polymer substance.

Substrate; Substrate (A): a composite sheet obtained by laminating a 30 μm-thick polyethylene sheet as a heat-softening layer on a 100 μm-thick polyethylene terephthalate sheet. Substrate (B): an aluminum sheet having a 150 μm-thick aluminum sheet whose surface has been made hydrophilic by performing a roughening treatment and an anodizing treatment.

[0098]

Embedded image

Absorbent (B): Nigrosine (N-90, product of Oriental Dye) Organic polymer; Polymer (A): Phenoxy resin (PKH-J, product of Union Carbide) Polymer (B) : Vinyl acetate-vinyl versatate copolymer (Corponyl 1635, manufactured by Nippon Synthetic Chemical Co., Ltd.) Polymeric substance (C): phenol-formamide condensed novolak resin (phenol: O-cresol and meta-cresol in a molar ratio of 20:30) : Condensate of formaldehyde and a mixture obtained by mixing at a ratio of 50: 4500)

Image formation and evaluation; Table 4 shows the results of image formation and evaluation of the sensitivity by the following four methods. Image formation (A): The image forming material was fixed on a rotating drum having a circumference of 20 cm such that the photosensitive layer was on the outside. While rotating this, a laser beam (830 nm, 830 nm from a semiconductor laser (manufactured by Hitachi, Ltd., HL8325G)) was applied thereto.
(30 mW) was condensed to a beam diameter of 15 μm, irradiated, scanned and exposed to remove the exposed portion of the photosensitive layer by ablation to form an image. Image formation (B): superimposing an image receiving sheet on a photosensitive layer of an image forming material on which an image has been formed by image formation (A);
Using a roller at 100 ° C. and a pressure of ² kg / cm ² ,
The image was transferred onto the image receiving sheet by pressing at a speed of 0 cm / min. Image formation (C): An image receiving sheet was superimposed on a photosensitive layer of an image forming material, and attached to a rotating drum having a circumference of 20 cm with the substrate of the image forming material facing outside.
While rotating this, a laser beam (830n) from a semiconductor laser (HL8325L, manufactured by Hitachi, Ltd.)
m, 30 mW) was condensed to a beam diameter of 15 μm and irradiated, and the exposed portion of the photosensitive layer was transferred to the image receiving sheet by ablation to form an image on the image receiving sheet. Image formation (D): The image forming material was mounted on a rotating drum having a circumference of 20 cm such that the photosensitive layer was on the outside. While rotating this, a laser beam (830 nm, from a semiconductor laser (HL8325L, manufactured by Hitachi, Ltd.))
(30 mW) was condensed to a beam diameter of 15 μm and irradiated, and the light was exposed to such an extent that a portion of the exposed portion of the photosensitive layer was ablated. Then, the exposed image forming material was washed with an alkali developing solution for positive photosensitive lithographic plate (DP-4 manufactured by Konica Co., Ltd.).
(One-fold diluted) at 25 ° C. for 1 minute, and then rubbed with a sponge five times to form a positive image on the substrate.

In the above image formations (B) and (C), the following image-receiving sheets were used. Image receiving sheet (A): Foamed polyethylene terephthalate sheet having a thickness of 100 μm Image receiving sheet (B): Tokishi Art (Mitsubishi Paper Manufacturing Co., Ltd.) Sensitivity evaluation: Exposure is performed by changing the number of revolutions of the rotating drum (= scanning speed). The maximum scanning speed (cm / s) at which image formation is possible (image formation on the substrate in image formation (A) and (D), image formation on the image receiving sheet in image formation (B) and (C)) is measured. did.

[0102]

[Table 20]

* 1 A composition for forming a silicone rubber layer having the following composition was applied on the photosensitive layer to provide a silicone rubber layer having a thickness of 1 μm, thereby preparing a printing plate requiring no dampening solution.

[0104]

Embedded image

* 2 A 10% by weight aqueous solution of polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was applied on the photosensitive layer to provide a hydrophilic layer having a thickness of 1 μm. * 3 No image was formed.

[0106]

According to the present invention, a laser direct image forming material having an improved ablation effect of the photosensitive layer and excellent sensitivity can be provided.

Claims (5)

[Claims] 1. A laser direct image forming material having a photosensitive layer containing at least a photothermal conversion substance on a substrate, wherein an azide group having a structure derived from a polymerizable monomer represented by the formula (1) in the photosensitive layer. A laser direct image-forming material comprising a polymer compound having the following formula: Embedded image [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. R ² represents an alkylene chain having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, a bromine atom, a chlorine atom, an iodine atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 10 alkoxycarbonyl groups, 1 to 10 carbon acyl groups, 1 to 1 carbon atoms
Ten substituents selected from an acyloxy group, a phenyl group and a naphthyl group may be bonded. ] 2. In the formula (1), R¹Is a hydrogen atom or
A methyl group, ^TwoIs an ethylene or n-propylene group
2. The laser die according to claim 1, wherein
Image forming material. 3. A laser direct dampening water-free photosensitive printing plate having a photosensitive layer containing at least a photothermal conversion substance on a substrate and having a silicone rubber layer on the photosensitive layer, wherein the formula (2) is contained in the photosensitive layer. A laser direct dampening solution-free photosensitive printing plate comprising a polymer compound having an azide group having a structure derived from a polymerizable monomer represented by the formula: Embedded image [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. R ² represents an alkylene chain having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, a bromine atom, a chlorine atom, an iodine atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 10 alkoxycarbonyl groups, 1 to 10 carbon acyl groups, 1 to 1 carbon atoms
Ten substituents selected from an acyloxy group, a phenyl group and a naphthyl group may be bonded. ] 4. In a laser direct photosensitive printing plate having a photosensitive layer containing at least a photothermal conversion substance on a substrate and a hydrophilic layer thereon, the polymerization represented by the formula (3) is contained in the photosensitive layer. A laser direct photosensitive printing plate comprising a polymer compound having an azide group having a structure derived from a hydrophilic monomer. Embedded image [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. R ² represents an alkylene chain having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, a bromine atom, a chlorine atom, an iodine atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, 1 to 10 alkoxycarbonyl groups, 1 to 10 carbon acyl groups, 1 to 1 carbon atoms
Ten substituents selected from an acyloxy group, a phenyl group and a naphthyl group may be bonded. ] 5. In the formula (2) or (3), R ¹ is a hydrogen atom or a methyl group, and R ² is ethylene or n-
5. The photosensitive printing plate according to claim 3, wherein the photosensitive printing plate is a propylene group.