JPS6240463A - Photosensitive printing plate - Google Patents

Abstract

PURPOSE:To obtain the titled plate having an excellent adhesion under a vacuum and a less tendency for generating an electrostatic charge on the surface of a photosensitive layer and having a less tendency for generating a rough dotted image and a stain of a printed matter by incorporating a mat material contg. a solid particle of an org. compd. having a fluorine atom soluble to a developer to the titled plate. CONSTITUTION:The org. compd. contd. in the mat material has the fluorine atom in a molecule, and is a compd. soluble to at least one of the developers capable of developing the titled plate by fixing the mat material on the surface of said plate. The preferable mat material comprises a polymer cong. the fluorine atom and a group capable of solubilizing the org. comps. to an alkaline solution and a polymer having a monomer unit contg. the fluorine atom and a monomer unit contg. the group capable of solubilizing the org. compd. to the alkaline solution. The former monomer comprises a monomer unit derived from for example, an alkylvinylether and an olefin contg. the fluorine atom respectively. The latter monomer comprises a monomer having an ethylenic bond and a carboxylic group.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to photosensitive printing plates, and in particular, when performing the vacuum V bonding method in which a film base plate is brought into close contact with a photosensitive printing plate during exposure during plate making, the surface of the photosensitive printing base plate is roughened in order to quickly achieve this adhesion. Concerning surface-formed photosensitive printing plates.

[Conventional technology]

Printing plates, such as lithographic printing plates, have been made from photosensitive printing plates. For example, to create a lithographic printing plate, a film base plate of an original is applied to the photosensitive layer of a photosensitive printing plate that has a photosensitive layer on a support such as a surface-treated aluminum coat, and exposed to light. A hardened area and a non-hardened area are formed by applying exposure corresponding to the brightness and darkness of the image of the original, and an image area and a non-image area are formed by dissolving and removing the non-hardened area with a developer. be. Since the image area becomes lipophilic and the non-image area becomes hydrophilic, the hydrophilic printing ink adheres only to the image area and is transferred to the printing area such as paper. By the way, when applying the above-mentioned film base plate, if the film base plate is exposed without being brought into close contact with the photosensitive layer, the image formed on the photosensitive layer will be blurred, so the task is to ensure and quickly achieve this close contact. Important in terms of efficiency. Conventionally, a vacuum adhesion method has been used to bring the film original plate into close contact with the photosensitive layer. In this method, a film original plate and a photosensitive lithographic printing plate are sandwiched between a glass plate and a rubber sheet with the photosensitive layer in contact with the film original plate, and these are supported in a vacuum printing frame. This is to create a vacuum between the sheets and bring the film original plate and photosensitive printing original plate into close contact. By the way, the surface of a photosensitive printing plate is smooth.
According to the vacuum adhesion method mentioned above, the air between the film original plate and the photosensitive layer is removed from the periphery, and the adhesion between the two is gradually achieved from the periphery, making it difficult to remove air from the center of both. , it takes an extremely long time to remove this and bring the film base plate into close contact with the entire surface of the photosensitive printing base plate. Since this reduces work efficiency, several attempts have been made to improve it. One of them is a method of scattering solid powder such as talc on the surface of the photosensitive layer (referred to as balubbling) immediately before the process of exposing and baking a film original plate in close contact with the photosensitive layer. 23 (1970) Benjo, Iino, and Printed Information 33 (11), 90 (1973) Hyakude, etc. According to this method, flrJ, which simply sprinkles solid powder,! Roughening the photosensitive layer using the 1' method (
It is possible to form a gap between the film original plate and the photosensitive layer by forming a cloak), and use this as a passage to remove the air in the center.The vacuum adhesion of the film original plate can be improved.However, its disadvantages On the other hand, since the solid powder is merely attached to the photosensitive layer, it may fall off during handling and not only may not provide the expected vacuum adhesion, but also contaminate the surrounding area. On the other hand, when solid powder is scattered, it scatters and contaminates the air in the plate-making work room and surrounding equipment, causing various problems in the plate-making process, causing occupational hygiene problems, and even This caused various problems during work, such as requiring a lot of time to clean the equipment.''In order to improve these two problems, a coating solution containing a photosensitive composition A method was proposed to obtain a photosensitive printing plate with excellent vacuum adhesion by dispersing a suitable fine powder substance. For example, JP-A-55-124147, JP-A-56-1
As described in No. 56831 and No. 57-115548, photosensitive printing plates containing fine powder particles of plastics such as polystyrene, polyethylene, and thermosetting 7 ethanol resin have been proposed. However, since these plastic fine powder particles are insoluble in the developer, the following problems often occur. That is, when a large number of such photosensitive printing plates are developed with a tired developer, the fine powder particles remain in the non-image areas, the photosensitive layer is not removed, and the non-image areas are printed. It was found that it caused stains. Mata, JP-A-51-111102 and JP-A-52-293
As described in each publication of No. 02, a method is known in which a mantle layer that is removed during development is provided as the uppermost layer of a photosensitive printing plate. However, the above photosensitive printing plate has the following deficiencies. That is, in general, when a photosensitive printing plate is packaged, the surface of the photosensitive layer is covered with paper, plastic sheet, synthetic paper, etc. to protect the photosensitive layer. It is a type of plastic layer, and when the interleaving paper is peeled off, the surface is easily charged, and when it is touched by hand, it generates discharge and is difficult to handle.Also, when the interleaving paper is peeled off, zero electricity is generated, causing dust and dirt in the vicinity. It has the disadvantage that it tends to attract particles, which often has an adverse effect on the image on the printing plate created through the exposure and development process. Furthermore, as described in JP-A No. 56-9739, silica, aluminum oxide, silicon dioxide, etc. are used as fine powder particles for matting the surface of the photosensitive layer. However, probably because these fine powder particles are heavy, they tend to settle in a coating solution containing a photosensitive composition, resulting in poor dispersion stability. S from such a coating liquid! ! The photosensitive printing plates left behind are
When a printing plate is obtained by exposure and development, and printed by a printing press, the area of the halftone dots on the printed matter becomes uneven, and the halftone dots themselves tend to become rough. This is considered to be due to the generation of large particles in the coating liquid.

OBJECT OF THE INVENTION The object of the present invention is to provide a photosensitive printing plate which has excellent vacuum adhesion to a film original plate, prevents charging of the photosensitive/FJ surface, and does not cause roughening or staining of halftone dots on printed matter. Our goal is to provide the following.

[Structure of the invention]

As a result of extensive research, the present inventors have discovered that, in photosensitive printing plates having solid powder fixed to the surface of the photosensitive layer, the solid powder contains a matting agent containing an organic compound containing fluorine that is soluble in a developer. It has been found that the above object can be achieved by a photosensitive printing plate characterized by containing. The present invention will be explained in detail below. The above-mentioned organic compound contained in the capping agent according to the present invention has a fluorine atom in its molecule and is compatible with at least one developer capable of developing a photosensitive printing plate having the matting agent fixed to the surface. It is a compound that is soluble. Preferred examples of such organic compounds include polymers having a heptadium atom and an alkali solubilizing group. Polymers with 7 atoms and alkali solubilizing groups include:
Polymers having one moama unit having 7/atomic atoms and an alkali solubilizing group, and polymers having one moama unit having 7 atoms and one moama unit having an alkali solubilizing group are included. Examples of the monomer unit having a fluorine atom include alkyl vinyl ethers, alkyl isopropenyl ethers, alkyl carbonyls, oxyethylenes, styrenes, alkylstyrenes, acrylic esters, acrylamides, and Mention may be made of moama units derived from olefins. Preferred examples of the MoA 7 units derived from alkyl vinyl ethers having a fluorine atom and alkyl isopropenyl ethers having a V fluorine atom include the following A.
Preferred examples of the Moama unit derived from alkylcarbonyloxyethylenes having 7 chord atoms include the following Group B. Preferred examples of Moama units derived from styrenes having a fluorine atom include the following group C, and preferred examples of Moama units derived from alkylstyrenes having a fluorine atom include the following group: , Preferred examples of Moama units derived from acrylic acid esters having a fluorine atom include the following Group E, and preferred examples of Moama units derived from acrylamides having a fluorine atom include the following Group F: Preferred olefins having fluorine atoms include those having 2 to 3 carbon atoms. Rs R7 Group B -C-C- R・0COR' Rs R+. R14R+a Group E -C-C- R,5COOR,□ Ft+s R2O Here, R1, R2, R5, R6, R7, R11%R1
2, R13, R1-R15, R1-R1'l and R2゜ are each a hydrogen atom or a fluorine atom, R3 and R16 are each a hydrogen atom, a fluorine atom or a methyl group (this methyl group is substituted with a heptadium atom, etc.) ), R4
and R17 may each be substituted with an alkyl group (this alkyl group is 7) or the like. ), R3, R5 and R1° each represent a hydrogen atom or a chlorine atom, R2 and R22 each represent a hydrogen atom, an alkyl group or an aryl group, and Rp and R1 each represent an alkyl substituted with at least one fluorine atom. group, m represents an integer of O to 5, ++ represents an integer of 1 to 5, and when n is an integer of 2 to 5, each R? may be the same or different. Also, R2, R3 and R
At least one of 4 and at least one of R14, RIS, R16 and R17 is a group having a fluorine atom or a 7.7 element, and when m is 0, at least one of R, R, and R4° is a seven elemental atom. Next, the Moama unit of Group A will be described in more detail. The alkyl group represented by R may be linear or branched, and preferably has 1 to 15 carbon atoms. Also, ^-3
This alkyl group may have a substituent (including substituent atoms, the same applies hereinafter) other than the 7 atoms, and examples of the substituent include an alkyloxy group (preferably ^-4 is a group having 1 to 10 carbon atoms). ), alkyloxycarbonyl groups (preferably 2 to 11), and the like. Preferred as R6 is -(CI42)l)(CF2)QX(
2. 8 ra, 1) C an integer from 1 to 10, and q from 0 to 2.
The integer of is expressed as CF3 (χ represents a hydrogen atom, a fluorine atom, or -CF).
8-6■ 0(CF2)mcOOcnH2n l ^-8 υ-1. :ntozn+-CI+2. -CI+-0CH2(CF2),)l-(:)12C)l-■oc)I2CF. =CH2-CH-0CII2C3F. -C)12-CH- 0CII2(CF2)2CF(CF,h--CF2-C
F- ■ C2115 oc, Il. Next, the Moama unit of Group B will be explained in more detail.C-
3. The alkyl group substituted with a fluorine atom represented by R' may be linear or branched, preferably has 1 to 10 carbon atoms, and has a substituent other than a fluorine atom (for example, a phenyl group). You can. B'-C1t2-C)I-0COCF. B-2-CIl2-CIl-C-6 Straight 0COC2F5 0COC,F,. A specific example of one Moama unit of Group 0 is given below. " -CFH-CF - Next, the Moama unit of Group D will be explained. The alkyl group substituted with a fluorine atom represented by R2 may be linear or branched, and preferably has 1 to 3 carbon atoms. and may have a substituent other than a fluorine atom (for example, a hydroxyl group). Specific examples of the Moama unit of Group D are listed below. The group represented by R17 of Group E is about R4 of Group A. The same thing can be said as stated above. A specific example of one monomer unit of group E is given below. -CF2-CF- C00C2115 E-2-CF2-CF - 曾C00CII 3 C00C=Hs One monomer unit of group F Specific examples include the following: F-3-CF2-CF- C0NHC2H. Examples of moama units of olefins having a fluorine atom include the following: G-1-CF2-CF2- G-2-CF2-CFII- G-3-CF2-CFCQ- G-4-CF2-CI (2- G-5-CF2-CHC!u- G-6-CFH-C112- CF. G-7- CF2-CF- G-8-CF2-CH- CF. G-9-CFII-CF- CF. G-10-CH2-CH-

[CF, -C-CF. G-11-CH2-CH-2F5-C112-CH-CF. G-13-CI+2-CFCQ- Day CF. G-15CF, CF3 CF-C- C(C2F5h Fi CF, CF(CF,)2 CF-C- CF(CF,)2 G-17CF. Other moama units having 77 elementary atoms are as follows. Z-CF2-CF - The alkali solubilizing group in the present invention is a group that can be introduced into a polymer to make the polymer easily soluble in alkali, and is preferably a carboxyl group. Examples of moama units having an alkali solubilizing group include those having an ethylene bond and a carboxyl group, and specific examples include the following: 1-1 -CH2-CH- COOH CH3 1-2-CH2 -C- 0OH COOHC00I( 1-4-CIl -CIl - I C0OI(C00C41(I 0OH -C1(, -C- CH2C00)I Examples of mono-7 units having a fluorine atom and an alkali solubilizing group include the following: , ■-1 -CF2-CF- 0OII 0(CF2)2C112CHCQCOOH"
CF2 CF- 0 (CF2), CFC, QCOOH Fluorine atom and alkali solubilizing group 1. Examples of such polymers include polymers having at least one monomer unit having a fluorine atom and an alkali solubilizing group, and polymers having at least one monomer unit having a fluorine atom and at least one monomer unit having an alkali solubilizing group. Examples include polymers having one monomer unit, and the polymers may further have another moamer unit. Examples of the other moamers include monomers having at least one ethylenic double bond. For example, ethylene,
Olefins such as propylene, 1-butene, isobutyne, vinyl chloride, vinylidene chloride, 2-methylbutene;
1.1. Diolefins such as 4,4-tetramethylbutanoene; Olefin alcohol esters such as vinyl acetate, allyl acetate; Methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, methyl 7
Olefin carboxylic esters such as acrylate, butyl acrylate, and ethyl acrylate; Olefin ethers such as methyl vinyl ether and ethyl vinyl ether; Acrylonitrile; Vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone; Divinylbenzene, allyl acrylate, and allyl methacrylate ,1
゜3-butylene diacrylate, 1,3-butylene dimethacrylate, diethylene glycol noacrylate,
diethylene glycol dimethacrylate, vinyl acrylate, vinyl methacrylate, ), diethylene glycol noacrylate, triethylene glycol dimethacrylate, ethylene diacrylate, ethylene dimethacrylate, 1゜6-hexanoacrylate, 1.6-
Examples include those having two or more ethylenically unsaturated double bonds such as hexanoacrylate. Among the above polymers, those in which one moama unit having a fluorine atom (including one moama unit having a fluorine atom and an alkali solubilizing group) account for 10% by weight or more are preferable, and those in which the moama unit has a fluorine atom and an alkali solubilizing group account for 10% by weight or more are preferred, and those in which the moama unit having a fluorine atom (including one moama unit having a fluorine atom and an alkali solubilizing group) account for 30% by weight or more are preferable. More preferred. Further, it is preferable that one Mo7 unit having an alkali solubilizing group (including the monomer position having a fluorine atom and an alkali solubilizing group) accounts for 20 to 90 mol%, and 20 to
More preferably, it accounts for 70 mol%. Further, it is preferable that the amount of the other moama unit is 70 mol % or less. Specific examples of the above polymers are listed below. (The ratio of one unit of Moama is expressed in mol%) The following margin □-P-1-)CF2-CF-)-0(CF2)4-Cool('-"-+CF2 CFhs 4CI
I, -CF2hs0OH P-7-+CF 2 CFhs A Ctl
. -CHFh5C00)I →CF2-CFho -+C1l2-CF rule. OON (0)Q(CF2)mcOOH Q:0.1 m: An integer of o-10, however, when Ω=0, m≠00H P-19(CIIr-CIIhofcL C)l)i
. 0CH2CF, C0OH QC,F, C0OH (Ctlr-CHho(CHr-IJfh00CHzC
J t C00HP-22(C)l-CHh
o) CH-CHh. oC,F,ffC0OH ■ 0COCF , C0OHUl, ;LjL
;2t's 0COCL
COOC211, C0OH All of the above polymers can be easily synthesized by conventionally known methods such as solution polymerization, bulk polymerization, suspension polymerization, etc. For example, in solution polymerization, generally a suitable solvent (e.g. A mixture of two or three monomers at appropriate concentrations in ethanol, methanol, etc. (usually 4% to the solvent)
A mixture of two or three monomers at a concentration of 0 wt % or less, 67 + or 10 to 25 wt %) in the presence of a polymerization initiator (e.g. benzoyl peroxide, azobisisobutyronitrile, etc.) at an appropriate temperature (e.g. 40-120℃,
The copolymerization reaction is carried out by heating to preferably 50 to 100°C. Thereafter, the reaction mixture is poured into a medium such as water to allow the precipitate to settle, and then the unreacted mixture is separated and removed by drying. Furthermore, in the synthesis of the above polymer, it is not always essential to polymerize in advance using a monomer having an alkali-solubilizing group; after obtaining a polymer that does not have such a group, alkali Solubilizing groups may also be generated. For example, the specific examples P-1 to P-4 are
According to No. 303, a polymer can be obtained using alkoxycarbonylfluoroalkylfluorovinyl ether as a monomer, and then a carboxyl group can be generated by hydrolysis. In addition, P-5 to p-8, P-11, etc. can be obtained by hydrolyzing a perfluoroallyl fluorosal heptaate polymer as described in Japanese Patent Publication No. 58-5908, or by Journat of the A+eri
can Che+n1cal 5ociety+Vo1
．． 100, 1948 (1978), polyolefins may be fluorinated in the presence of oxygen to obtain -COF groups followed by -COO11 groups. P-12 is as described in JP-A-53-141188,
It can be obtained by reducing a polymer having a sulfamoyl group with HNO2, and P-13 can be obtained by oxidizing the chlorosulfonyl group in the polymer as described in JP-A-54-83982. P-13 is JP-A-54-321
As described in No. 89, it can be obtained by adding an olefin carboxylic acid to a chlorosulfonyl group in a polymer. Furthermore, P-15 can be obtained by graft polymerizing an olefin carboxylic acid to a fluorinated polyolefin. In the present invention, [matting agent containing a fluorine-containing organic compound that is soluble in a developer] means that the entire particle of the matting agent may be composed of the above-mentioned organic compound, or a part of the particle may be composed of the above-mentioned organic compound. It means that it may be composed of a compound. In the latter case, it is preferable that the particle surface is coated with the above polymer, and examples of the core material coated with the above polymer include silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, Known matting agents include inorganic compounds such as carbonic acid, glass, and talc, and organic compounds such as polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate, ethyl cellulose, starch, and benzoguanamine-formaldehyde condensate. In addition, substances other than those mentioned above can be freely used as long as they do not adversely affect the photographic properties. Various methods can be used to produce matting agent particles using the above polymer according to the present invention. For example, to produce particles whose surfaces are coated with the polymer, the particles of the core material are immersed in a solution of the polymer that does not dissolve the material, and then dried; Alternatively, the above-mentioned polymer can be made to exist on the surface of the nuclear material by a method of grafting Moa7- having a fluorine atom and Moamer having an alkali solubilizing group onto the surface of the nuclear material by plasma polymerization. In addition, when a nuclear material is not used, for example, an organic solvent solution of the above polymer is injected into an aqueous surfactant solution (which may contain a hydrophilic colloid such as gelatin) under stirring, and the resulting emulsion is prepared. After removing the solvent under reduced pressure from
Polymer particles may be separated by centrifugation. Furthermore, it may be made into fine particles by pulverization means. Alternatively, particles can be obtained immediately from the emulsion obtained by the polymerization reaction by centrifugation. In addition, layer structure mats such as particles made of the organic compound according to the present invention whose surface is coated with another polymer or cloak agent particles other than the matte agent of the present invention whose surface is coated with a fluorine-containing organic compound Agent particles can also be used as the capping agent of the present invention. The photosensitive printing plate of the present invention may use the matting agent of the present invention alone, or may contain other matting agents such as silicon dioxide, zinc oxide, aluminum oxide, titanium oxide, polymers other than the organic compound according to the present invention ( For example, polystyrene, polyethylene, polymethyl methacrylate), gum arabic,
Gelatin, cellulose derivatives, starches, etc., natural polymeric compounds such as alginic acid, acrylic acid (or its salts), methacrylic l! Monomers having carboxylic acids (or salts thereof) such as Il (or salts thereof), such as ethylene sulfonic acid (or salts thereof),
Monomers containing styrene sulfonic acid (or its salts), monomers containing aromatic hydroxyl groups such as hydroxystyrene, N-(hydroxyphenyl) methacrylamide, etc., such as acrylamide, methacrylamide It may be used in combination with a matting agent consisting of particles of a synthetic polymer compound such as a homopolymer of a moamer having an amide such as or a copolymer containing at least 1' of these moamers. However, since these known mantle agents other than the matting agent of the present invention have the above-mentioned problems, it is desirable to use the matting agent of the present invention alone. In the present invention, "the solid powder fixed to the surface of the photosensitive layer side contains the matting agent according to the present invention" means that at least one part of the particles in the particle group that is the solid powder is the matting agent according to the present invention. It refers to a matting agent, and the above-mentioned solid powder is a solid powder known as a matting agent that is not spread on the surface of the photosensitive layer and fixed! In addition to embodiment a, it also includes embodiments such as a discontinuous layer obtained by applying a dissolution or dispersion of a polymer compound to the surface of the photosensitive layer by spraying or the like and then drying the discontinuous layer. . The shape of the surface of the photosensitive layer side of the photosensitive printing plate of the present invention is such that when the solid powder particles are fixed, the height of the solid powder particles above the surface is 2 to 40μ, particularly 5 to 20μIf.
The solid powder particle size (maximum diameter projected onto the surface of the photosensitive printing plate) is preferably in the range of 2 to 100 f.
μ[n, particularly preferably 3 to 50 μm. In addition, its density is 1 to 300 pieces/ω1112, especially 10 to 150 pieces/ω1112.
The range of 111111'' is preferable, and the surface roughness is Ra
(center line surface roughness) 0.05 to 20 μm, especially 0
A range of 1 to 10 μm is preferable. The photosensitive printing plate according to the present invention basically has a photosensitive layer on a support, and includes photosensitive lithographic printing plates, photosensitive letterpress printing plates, and photosensitive intaglio printing plates. , and also includes those in which an oil layer is further provided on the photosensitive layer. In the production of the photosensitive printing plate of the present invention, the matting agent used in the present invention is added to the surface of the photosensitive printing plate on the photosensitive layer side. In order to fix it, a method of applying a coating liquid containing a matting agent onto the photosensitive printing plate with a gravure roll, as described in JP-A-51-111.102, is described in JP-A-51-111. 1
As described in Japanese Patent Publication No. 2974, a method of thermally fusing a printing agent to a photosensitive layer, as described in Japanese Patent Application Laid-open No. 57-34558, a method of melting or melting a resin on the surface of a photosensitive printing plate. A method such as spraying a dispersed aqueous solution can be used. The photosensitive printing plate used in the present invention has a photosensitive layer, which will be described later, on a support, and the support used is a previously unknown plate-shaped support. These are appropriately selected depending on the purpose of use, method of use, method of use, etc. of the photosensitive printing plate. Examples of materials for the support include paper, plastic (including paper laminated with plastic), gold yA (
(including paper or plastic with metal vapor-deposited and laminated). Examples of the plastics include polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polyvinyl acetal, polycarbonate, nitrocellulose, diacetylcellulose, triacetylcellulose, and the like. Further, examples of the metal include aluminum (including alloys), zinc, copper, iron, and the like. Among these, aluminum is preferable in the case of flat plate printing, and aluminum, zinc, iron or polyethylene terephthalate is preferable in the case of letterpress printing. The surface of the support may be treated in advance depending on the surface type, and if the surface type is a lithographic type, it is subjected to a hydrophilic treatment. This hydrophilic treatment method can be appropriately selected depending on the material of the support surface. When a metal such as aluminum is used as the support surface, roughening treatment, anodizing treatment, immersion in a fluorozirconate aqueous solution, immersion in a silicate aqueous solution, immersion in a phosphate aqueous solution are used. A method of doing so is preferred. These various hydrophilic treatment methods may be combined; for example, a method in which surface roughening treatment and immersion in a sodium silicate aqueous solution are sequentially performed (U.S. Pat. No. 2,714,
066), a method in which immersion in an anodized silicate aqueous solution is performed sequentially (U.S. Pat. No. 318
146), etc.). - When the material of the surface of the force support is plastic, a method known as so-called silver salt photography can be used. Examples include electrical discharge treatment, chemical treatment, laser treatment, and a method of providing undercoating waste. As the photosensitive composition constituting the photosensitive layer provided on the support described above, conventionally known ones can be used. This photosensitive composition contains a photosensitive substance as an essential component, and this photosensitive substance includes those that cause a difference in the solubility of the photosensitive layer in a developer upon exposure, and those that cause intermolecular adhesion before and after exposure. It is possible to use a material that causes a difference in strength, or a material that causes a difference in affinity for water and oil between photosensitive layers upon exposure. Typical examples will be explained below. First, conventionally known. Examples include quinonediatide-type photosensitive substances such as quinone diate compounds. The 0-quinonenoanodo compound is at least one. -quinodicyanodo group, preferably 〇-penzoquiny/diacid group or. - Compounds having a 7-toquinone noazide group, such as compounds with various known structures, such as J-Koser-IF
rLigl+t 5ensitiv e S yst
eJ (John W 1ley & Sons, I
ne, y 1965) pages 399-353. Especially with various hydroxyl compounds. -su7toquinonenoazidosul7t
Esters with phosphoric acid are preferred. Preferred hydroxyl compounds include condensation of phenols and compounds with a carbonyl group f! (fats, especially 134 fats obtained by condensation in the presence of an acidic catalyst, examples of the above-mentioned phenols include 7-ethyl, resorcinol, cresol, pyrogallol, etc., and examples of the carbonyl group-containing compounds include:
Examples include aldehydes such as formaldehyde and benzaldehyde, and ketones such as acetone. Especially 72/
Preferred are -l formaldehyde resin, cresol Φ formaldehyde resin, pyrrolol Φ acetone resin, and resorcinol benzaldehyde resin. Representative specific examples of O-quinonediazide compounds include penzoquinone-(1,2)-diazidosulfonyl chloride or quinone-(1,2)-noacytosulfonyl chloride and Esters with formaldehyde resins or cresol-formaldehyde resins, sulfonic acid esters of 7-toquinone-(1,2)-noacytosulfonyl chloride and pyrogallol-acetone resins as described in U.S. Pat. No. 3,635,709 , Machi 1 [Condensation product of 7-toquinone-(1,2)-diazide-(2)-5-sulfonyl chloride described in Publication No. 56-1044 and resorcinol benzaldehyde resin, JP-A-55-76346 Su7toki/n-(1,2)-noando(2)-5 described in
Ester compounds of sulfol chloride and resorcinol/pyro copolycondensate with roll/acetone, and other useful 0
- As the quinian dianodo compound, JP-A-50-117
To the polyester having a hydroxyl group at the end described in Publication No. 503. -Esterification reaction of 7-toquinonediazide sulfonyl chloride, JP-A-5
A homopolymer of p-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in Japanese Patent No. 0-113305+: A homopolymer of p-hydroxystyrene and a copolymer thereof with other copolymerizable monomers: Examples include things such as these. The content of the -quinanoanodone compound is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition. Such a quinonediazide type photosensitive substance can be used in combination with an alkali-soluble resin as a binder, if necessary. As the alkali-soluble resin, those obtained by combining phenols and ketones or aldehydes under an acidic catalyst are preferred. Examples of the 72/-ls include 7-7-yl, cresol, p-substituted 7-7-yl, and the like. Examples of the above-mentioned flute acids include acetaldehyde, formaldehyde, etc., with formaldehyde being preferred. Acetone is preferred as the ketone. Preferred alkali-soluble resins include, for example, 7-7-
Formaldehyde resin, cresol/formaldehyde resin, phenol/cresol/formaldehyde copolycondensate (resin) described in JP-A-55-57841; pfM-converted phenol phenol or copolycondensate of cresol and formaldehyde υI fat,
Resorcinol/benzaldehyde resin, pyrogallol/penzaldehyde U (condensation product of polyvalent heptenols such as fats and penzaldehyne Y, pyrobrol/resorcinol ◆Copolycondensate of polyhydric phenol such as acetone resin and a7tone, xylem The content of these alkali-soluble resins is preferably 30 to 90% by weight, particularly preferably 50 to 85% by weight, based on the total solid content of the photosensitive composition. As the photosensitive substance, diazo resins typified by condensates of aromatic diazonium salts and formaldehyde are used. Particularly preferred are salts of condensates of p-diazonophenylamine and formaldehyde or acetaldehyde, such as hexa Noazo!! fatty inorganic salts which are reaction products of fluorophosphates, tetrafluoroborates, perchlorates or periodates with the above condensates, and U.S. Pat.
For diazo, which is a reaction product of the above condensate and sulfonic acids, as described in No. 300゜309;
Examples include organic salts. Additionally, diazo resins are used with preferred binders. Various polymeric compounds can be used as such a binder, but monomers having an aromatic hydroxyl group such as those described in JP-A No. 54-98613, such as N-(4 Copolymerization of -hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, 0-1- or p-hydroxystyrene, 0-1r0-1 or p-hydroxyphenyl methacrylate, etc. with other monomers Union,
Polymers containing hydroxyethyl methacrylate units or hydroxylethyl methacrylate units as a main repeating unit as described in U.S. Pat. No. 4,123,276, natural resins such as shellac and ronone, polyvinyl alcohol, and 3.751,2
Polyamide resins described in US Pat. No. 57, linear polyurethane uJ resins described in US Pat. Includes celluloses such as epoxy resins, cellulose acetate, and cellulose acetate 7-talate. Furthermore, other photosensitive materials include those whose main component is a photosensitive polymer such as polyester neck, polyamides, and polycarbonates containing -CH=CH-C- as a photosensitive group in the polymer main chain or side chain. is also suitable. For example, phenylenenoethyl acrylate and hydrogenated bis7E7 as described in JP-A No. 55-40415
- photosensitive polyesters obtained by condensation with ole A and triethylene glycol, such as cinnamylidene malonic acid (2-probelidene), as described in U.S. Pat. Examples include photosensitive polyesters derived from malonic acid compounds and difunctional glycols. Still other photosensitive substances include aromatic at compounds in which an azide group is bonded directly or via a carbonyl group or a sulfonyl group to an aromatic ring. Polyazidostyrene, polyvinyl-p-
andbenzoate, polyvinyl-ρ-azidobenzal, the reaction product of 7-do-7-lylsul-7T-nylchlor +7-do and unsaturated hydrocarbon polymer described in Jibun Sho 5-9613, and No. 21067,
No. 44-229, No. 44-22954, No. 45-2
Examples include polymers having sulfonyl and and carbonyl azide, as described in fIf& in each publication of No. 4915. Furthermore, as another photosensitive substance, a photopolymerizable composition comprising an addition polymerizable unsaturated compound is used. The developer used in the photosensitive printing plate of the present invention may vary depending on the type of photosensitive composition used in the photosensitive printing plate, but is preferably an alkaline solution containing at least one alkaline agent. . Examples of alkali agents include sodium silicate, potassium silicate, lithium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, Inorganic alkaline agents such as potassium diphosphate, tertiary ammonium phosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, etc., mono-, no-, or triethanolamine; 11
- Organic amine compounds such as butylamine, more, no, or triisopropafuramine, ethyleneimine, ethylenediimine, and the like. First, when the photosensitive composition provided on the hydrophilic surface of the support contains a negative type noazo compound (hereinafter referred to as negative type 7
It is written as the 7128th edition. ), the developer is preferably an alkaline aqueous solution containing an organic solvent, and the organic solvent should have a solubility in water of 0% by weight or less at 20°C in order to improve the developability of the negative type Noazo PS plate and the ink. α is preferable because it improves ink receptivity and water retention. Some examples of organic solvents with solubility in water at 20°C of 10% by weight or less include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benyl acetate, ethyl acetate, ethylene glycol mobutyl acetate. , carboxylic acid esters such as ethyl malonate, butyl lactate, butyl levulinate, ketones such as ethyl butyl ketone, methyl imbutyl ketone, cyclohexane, ethylene glycol moabutyl ether, ethylene glycol monobutyl Phenyl ether, ethylene glycol mono-bennol ether, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-phenyl ether, propylene glycol mo-phenyl ether, benol alcohol, ethoxyethanol,
Methyl 7enylcarbyl, n-7yl alcohol,
Methyl amyl alcohol, 4-phenyl-1-buta7-
alcohols such as alcohol, β-7enethyl alcohol, and 3-phenyl-1-propanol, alkyl-substituted aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene, etc. There is. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol moaphenyl ether and benzyl alcohol are particularly effective. In addition, the content of these organic solvents in the developer is as follows:
Preferably 1 to 20% by weight, especially 2 to 10% by weight
More favorable results are obtained when Further, the preferable content of the alkaline agent contained in the developer for the Ne-type noazo PS plate is 0.05 to 4% by weight, preferably 0.5 to 2% by weight. Furthermore, it is preferable to include an anionic surfactant, a water-soluble sulfite, a solubilizer, etc. in the developing solution of the negative-working diazo PS plate in order to improve the developability. Higher alcohol sulfate esters, aliphatic alcohol phosphate ester salts, alkylaryl sulfonates, alkylamides X/L, phonates, sulfonate salts of dibasic fatty acid esters, and flu Examples include kylnaphthalene sulfonate and formaldehyde condensate of alkylnaphthalene sulfonate. Among these, sodium butylnaphthalene sulfonate and sodium butylnaphthalene sulfonate are particularly preferred because of their strong separation and solubility from formaldehyde. The content of these 7-ion surfactants in the developer component is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight. Water-soluble sulfites have the effect of preventing the photosensitive composition from sticking or remaining on hydrophilic surfaces due to side reactions and improving developability. Specific examples include alkali or alkaline earth metal salts of sulfites. Preferred examples include sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The preferred content of sulfite in the development i composition is 0.
．． 05 to 4% by weight, more preferably 0.1 to 1% by weight
It is. Since the solubilizer assists in dissolving the aforementioned organic solvent having a solubility of 10% or less in water at 20°C, it is preferably an organic solvent that is more easily soluble in water, such as low-molecular alcohols, ketones, It is better to include lactams. Specifically, for example, methanol, ethanol, propatool, butyl, acetone, methyl ethyl ketone, ethylene glycol more ethyl ether, ethylene glycol more ethyl ether, methoxybutanol, ethoxybutanol 1.4-methoxy-4-methylbutanol. Le, N
-Methylpyrrolidone and the like are preferred. The amount of solubilizer used is preferably 30% by weight or less in the developer. In addition, a photosensitive printing plate (hereinafter referred to as Bot type 7
7128 version) is preferably an alkaline aqueous solution, and the alkaline agent is preferably potassium silicate, lithium silicate, sodium silicate, sodium hydroxide, potassium hydroxide, hydroxide. Examples include lithium, tribasic sodium phosphate, dibasic sodium phosphate, tribasic potassium phosphate, dibasic potassium phosphate, sodium carbonate, potassium carbonate, and the like. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, or sodium silicate is most preferable because it has good development gradation, and the composition of the alkali silicate is (S 1o2) / CM )=0.5-1.5<Kokoni CS 1o2) CM ) t! Tsure F hSiO2
and the molarity of total alkali metals. ) and containing 0.8 to 8% by weight of SiO2 is preferably used. Of this alkali silicate composition,
In particular, the molar ratio (Si○2]/(M) = 0.5 to 0.75
and a developer containing 0.8 to 4% by weight of SiO2 is:
It is preferably used because it is easy to neutralize the developing waste solution due to its low concentration.On the other hand, a developing solution with a molar ratio exceeding 0.75 and up to 0.3 and containing 1 to 8% by weight of SiO2 has a low buffering power. It is suitably used because it has a high processing capacity. In addition, in the developer of the Bot type diazo PS plate,
By containing at least one of an anionic surfactant and an amphoteric surfactant as described in Japanese Patent Application Laid-Open No. 55-95964,
As described in Japanese Patent Publication No. 56-142528, the inclusion of a polymer electrolyte can improve the wettability to the photosensitive composition and further improve the gradation, and is therefore preferably used. The amount of such surfactant added is not particularly limited, but is preferably 0.003 to 3% by weight, particularly 0.0003 to 3% by weight.
A concentration of 0.06 to 1% by weight is preferred. Furthermore, it is preferable that the alkali metal of the alkali silicate contains 20 mol% or more of potassium based on the total alkali metals, since the generation of insoluble matters in the developing solution is small.
The potassium content is 0 mol% or more, and the most preferred is 00 mol% potassium. In addition, examples of organic solvents used in the developer include EVA,
Alcohols such as methanol, ethanol, benzyl alcohol; for example, 2-methoxyethanol, 2-nitoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate 2-furkoxy alcohol, 2-7 lyloxy alcohol, and their acetate esters; alkyl esters of oxycarboxylic acids such as methyl lactate, ethyl lactate, propyl lactate; acetic acid such as ethyl acetate, butyl acetate, etc. Esters; for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and γ-butyrolactone; for example, amides such as trimethylformamide, N-methylpyrrolidone, butyrolactam, and caprolactam; and the like. These are used alone or in combination of two or more,
Furthermore, additives such as surfactants may be added. Regardless of whether the photosensitive composition is a negative type or a positive type, the developer used may contain an antifoaming agent. Suitable antifoaming agents include organosilane compounds. Various conventionally known methods can be used to develop the photosensitive printing plate that has been imagewise exposed with the developer described above. Specifically, a method of immersing an image-exposed photosensitive printing plate in a developer, a method of squirting a developer from a number of nozzles onto the photosensitive layer of the photosensitive printing plate, and a method of using a sponge moistened with a developer. Examples include a method of wiping the photosensitive layer of the photosensitive printing plate with water, a method of applying a developer to the surface of the photosensitive layer of the photosensitive printing plate with a roller, and the like. Further, after applying the developer to the photosensitive layer of the photosensitive printing plate in this manner, the surface of the photosensitive layer may be lightly rubbed with a brush or the like. The developing conditions can be appropriately selected depending on the developing method. - For example, in the development method by immersion, a method of immersing the material in a developer at about 10 to 35° C. for about 10 to 80 seconds is selected. EXAMPLES Examples of the present invention are shown below, but the present invention is not limited thereto. Example 1 An aluminum plate was immersed in a 20% aqueous solution of sodium phosphate to degrease it, roughened by electrolytic etching, anodized in a sulfuric acid solution, and then immersed in a silicate solution. A sealing process was performed. A photosensitive solution having the following composition was applied onto this aluminum plate (1003 x 800 mm) using a spin coater and dried at 85°C for 3 minutes to obtain a photosensitive lithographic printing plate. The coating amount after drying was 2.7 g/l112. (Photosensitive liquid composition) Esterified product of 7-(1,2)-diazide-5-sulfonic acid chloride and m-cresol formaldehyde resin (condensation rate 25 mol%)
3.5g Cresol Formaldehyde 04 fat 8.0g Toquinone-(1,2)-diazide-4-sulfonic acid chloride 0
．． Esterified product of 15g p-octylphenol formaldehyde resin and 7toquinone-(1,2)-cyanodo-5-sulfonic acid chloride (condensation rate 50 mol%)
0.12g oil blue 960
3 (Product name, manufactured by Orient Chemical Industry Co., Ltd., dye)
0.2g ethylene glycol monoethyl ether 00g Illustrated compound P on the surface of the photosensitive layer of this photosensitive lithographic printing plate
A 20% by weight aqueous solution of -1 was sprayed and dried at 60°C for 5 seconds. The amount of P-11 sprayed was approximately 0.1 g 7 m2. A positive manuscript was adhered to the photosensitive layer side of the positive type 28 plate obtained in this manner by a vacuum adhesion method, and a metal halide lamp (manufactured by Iwasaki Electric Co., Ltd., Idolfin 200
After exposing the plate to light for 80 seconds from a distance of 11 using 0) as a light source, it was immersed in a 4% by weight aqueous sodium metasilicate solution and developed for 45 seconds at 25°C to obtain a lithographic printing plate. When this printing plate was then printed on an offset printing machine, many printed matter with clear images and no rough halftone dots were obtained. Example 2 A Bonn mold 98 plate was obtained in the same manner as in Example 1 except that Exemplified Compound P-2 was used instead of Exemplified Compound P-1 in Example 1. This positive type 28 plate was developed and printed in the same manner as in Example 1, and the same results as in Example 1 were obtained. Example 3 P-6 (average particle size 13 μl), which was ground with a ball mill and classified with a classifier (Nogzag classifier manufactured by Albime), was applied to the surface of the photosensitive printing plate having the photosensitive layer obtained in Example 1. Batter the solid powder with a spray gun and heat to 150°C.
It was exposed to an air bath for 5 seconds to make it stick. The amount of the solid powder spread was about 0.05 g/l112. The thus obtained Bot type 28 plate was developed and printed in the same manner as in Example 1, and the same results as in Example 1 were obtained. Example 4 A positive 28 plate was obtained in the same manner as in Example 3 except that P-21 was used instead of P-6 in Example 3, and then developed and printed. As a result, the same plate as in Example 3 was obtained. Got the results. Example 5 An aluminum plate was immersed in a 20% sodium phosphate aqueous solution to degrease it, subjected to electrolytic etching to roughen the surface, anodized in a sulfuric acid solution, and then immersed in a sodium silicate solution to seal the surface. processed. A photosensitive plate having the following composition was coated on this aluminum plate (1003 x 800 + I1 m) using a rotary coating machine, and 85
It was dried at ℃ for 3 minutes to obtain a photosensitive planographic printing plate. The amount of cloth after drying was 2.0 g/1112. (Photosensitive liquid composition) Copolymer A 5.0g Diazo resin B O, 5g Jurimer A C-10L (Product name, manufactured by Nippon Pure Chemical Industries, Ltd., acrylic acid polymer) 0.1g Victoria Pico, Abreu BOH (Product name, Manufactured by Hodogaya Chemical Co., Ltd., dye) 0. Ig ethylene glycol mo/methyl ether 100TIIQ However, in the above copolymer A, monomers with a molar ratio of p-hydroxyphenylmethacrylamide/acrylonide 1 nor/ethyl acrylate/methacrylic acid = 10/30/60/6 are added to methyl cellosolve. The mixture was dissolved and heated at 65° C. for 10 hours in a sealed tube purged with nitrogen. After the reaction was completed, the reaction solution was poured into water with stirring, and the resulting white precipitate was filtered and dried. Noazoki l11rB is 5% by weight at room temperature.
A diazo resin (D-012 manufactured by E, H. C Co., Ltd.) aqueous solution and a 10% by weight ammonium hexafluorophosphate aqueous solution were mixed, the resulting precipitate was filtered by absorption, and dried under reduced pressure at 30 to 40 °C. Hexafluorophosphate obtained by The weight average molecular weight of the above copolymer was 80,000, and when the molecular weight distribution of the above diazo resin was measured by delvermination chromatography (GPC), 93 mol% of the total was sj 1 or less. . The surface of the photosensitive lithographic printing plate obtained in this way was parablated with a solid powder of classified P-11 (average particle size 16 μm) using a spray gun, and then heated to an air temperature of 150°C for 5 minutes.
It was exposed for a second to make it stick. The amount of the solid powder sprinkled above is approximately 0.
．． It was 12g/l112. The photosensitive layer of the PS plate thus obtained was then exposed to light for 42 seconds from a distance of 1111 mm using a 2Kw metal halide lamp as a light source, and a developer with the following composition was applied. Development was performed at 25° C. for 45 seconds to obtain a lithographic printing plate. (Developer composition) Ethylene glycol phenyl ether 160g Noethanolamine 70g Bionin A-
44B (trade name, Takemoto Yushi Co., Ltd., anionic surfactant) 50g water
780g was then printed using an offset printing machine, and a clear printed matter with no rough halftone dots was obtained. Example 6 A negative type PS plate was obtained in the same manner as in Example 5 except that P-14 (average particle size 10 μl) was used instead of P-11 in Example 5, and then developed and printed. Results ,
Similar results to Example 5 were obtained. Comparative Example 1 Silica sol (average particle size 10
0.24 g of P-μm) was added to the surface of the photosensitive layer.
A photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that No. 11 was not sprayed. The photosensitive printing plate thus obtained was exposed and developed in the same manner as in Example 1 to obtain a lithographic printing plate. When this printing plate was then printed using an offset printing machine, the area of the halftone dots was uneven and the shape of the halftone dots was rough. This is probably because the dispersion stability of the photosensitive liquid was poor and large particles were generated. Comparative Example 2 Polystyrene (
A photosensitive printing plate was obtained in the same manner as in Comparative Example 1, except that an average particle diameter of 1θμ was used, and exposure and development were performed to obtain a lithographic printing plate. When this lithographic printing plate was carefully observed with a 25x magnifying glass, polystyrene particles remained in the non-image areas among the halftone dots. Also, using developer 1 to 9 used in Example 1, Example 1
Comparative Example 2
In the sample, particles that appear to be polystyrene remained in a part of the non-image area, and the developing ink (SPO-1, Konishiroku Photography Co., Ltd.)
Co., Ltd.), the ink adhered to that area. Comparative Example 3 A photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that copolymer C having the following composition was used in place of Exemplified Compound P-1 in Example 1, and exposed and developed to perform lithographic printing. Got the edition. Copolymer C C)+3 Comparative Example 4 Exemplary compound P-11 in Example 5 (average particle size 16μ
A Ne-type PS plate was obtained in the same manner as in Example 5, except that a copolymer having the following composition was used instead of (transport). A lithographic printing plate was obtained by exposure and development. Table 1 shows the plate-making performance and triboelectric charging properties of the photosensitive printing plates prepared in each of the Examples and Comparative Examples. The measurement method is as follows. Plate-making performance: The halftone dot shape was exposed and developed using a Brunner chart, and measured with an area gauge (halftone dot measuring device manufactured by Konishiroku Photo Industry Co., Ltd.). Regarding developability, Examples 1, 2, 3 and 4 and Comparative Examples 1, 2 and v3 were developed with the developer of Example 1, and 2. O+e
``At the time of development, a developing ink (S P O-1, manufactured by Konishiroku Photo Industry Co., Ltd.) was placed and the non-image area was observed with the naked eye. After developing with the same developer and developing with 10.0 so2, apply developing ink (S P O-1) and visually inspect the non-image area.
L guessed it. Frictional charging properties After pressing the gold paper against the plate and keeping it in close contact, the gold paper is rubbed against the plate. Then, pinch the edge of the gold paper and slowly lift it up to completely separate the interleaving paper and the plate. Measure the bottom edge of the lifted paper, the side that was facing the plate. Measurement conditions: Temperature: 22℃, Humidity: 51% Version size:
500 x 800 mm Insert paper: The one described in Example 1 of JP-A-57-99647, Charge meter: Static volt meter
"Station M" (manufactured by SL+1shid.Co, tLtd) Table 1 As is clear from Table 1, the photosensitive printing plate of the present invention has a lower halftone dot shape, that is, a printed matter, compared to one using a known matting agent. It has excellent halftone dot roughness and staining properties as well as antistatic properties, and also has good developability. Effects of the Invention The photosensitive printing plate of the present invention has excellent vacuum adhesion, improves charging on the surface of the photosensitive layer, and does not cause rough halftone dots or stains on printed matter.

Claims (1)

[Claims] A photosensitive printing plate having a solid powder fixed to the surface of the photosensitive layer, characterized in that the solid powder contains a matting agent containing a fluorine-containing organic compound that is soluble in a developer. Edition.