JPH021856A - Photosensitive planographic plate - Google Patents

Abstract

PURPOSE:To improve coatability in the production stage of a photosensitive layer, safelight characteristic and visibility of exposed picture image in the production stage of a printing plate by incorporating a fluorine-contg. surface active agent and a surface active agent contg. no fluorine into a photosensitive layer. CONSTITUTION:A photosensitive layer of the title planographic plate is constituted of a compsn. contg.(A) an o-quinone diazide compd., (B) an alkali-soluble resin, (C) a fluorine-contg. surface active agent and (D) a surface active agent contg. no fluorine. A nonionic fluorine-contg. surface active agent may be useable as the component(C), and polyoxyethylene sorbitan fatty acid ester, etc. may be useable as the component(D). An esterified compd. of o-naphthoquinone diazide sulfonic acid with a desired polycondensation resin, etc., may be useable as the component(A), and a novolak resin, etc., may be useable as the component(B).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate, and in particular to an O
- It relates to a positive-working photosensitive lithographic printing plate containing a quinonediazide compound as a photosensitive substance.

[Background of the Invention] A photosensitive lithographic printing plate is obtained by dissolving a photosensitive composition containing a photosensitive substance in an appropriate solvent, coating it on a support, and drying it. The formation of an uneven photosensitive layer with unevenness, pinholes, streaks (vertical streaks), etc. not only impairs the value of the product in terms of appearance, but also affects various aspects of the photosensitive lithographic printing plate, such as sensitivity and printing durability. causes instability in the properties of To solve this problem, for example, Japanese Patent Application Laid-Open Nos. 57-178242 and 62-36657 disclose methods for coating by adding a relatively low concentration of fluorine-based surfactant to a specific coating solvent. It is stated that unevenness was improved by doing so. However, although the above technique is effective for certain unevenness, it is not sufficiently effective in improving the streaks, especially vertical streaks. Furthermore, the safelight properties and exposure visible image properties, which have become problems in recent years, were also insufficient. In other words, "safelight property" here refers to the fact that when a photosensitive lithographic printing plate is made under white fluorescent light, light fog may occur and the photosensitive layer in the image area may be eroded during the next development process. However, the resistance of white fluorescent lamps to light fogging is called "safelight property," and photosensitive materials with improved safelight properties are used. A photosensitive lithographic printing plate having layers was desired.

In addition, "exposure visible image quality" refers to the change in position between film originals, such as when performing so-called "multi-sided printing" in which multiple film originals are printed one after another on a photosensitive planographic printing plate in different positions. To facilitate matching, it is necessary to be able to distinguish between exposed and unexposed areas, and this visual identification of exposed areas and unexposed areas by exposure is called ``exposure visibility''.

In other words, there has been a desire for a photosensitive lithographic printing plate that has improved coating properties, particularly the occurrence of vertical streaks, and has excellent various properties.

[Object of the Invention] The object of the present invention is to provide a photosensitive lithographic printing plate that has improved coating properties, particularly the occurrence of vertical streaks, and is also excellent in safe fly 1 resistance and visible exposure property, and a photosensitive material suitable for the printing plate. An object of the present invention is to provide a composition.

[Structure of the Invention] The above object of the present invention is to provide a photosensitive composition comprising a photosensitive composition containing at least an 0-quinonediazide compound, an alkali-soluble resin, a fluorine surfactant, and a fluorine atom-free surfactant on a support. It was produced rapidly by a photosensitive lithographic printing plate with layers.

[Specific Structure of the Invention] The fluorine-based surfactant used in the present invention has hydrogen atoms bonded to the carbon atoms of the hydrophobic group of the surfactant,
It is partially or completely substituted with fluorine atoms, and any of the following anionic, cationic, nonionic, amphoteric, and polymeric types can be used, but nonionic fluorine surfactants are I like it.

<1) Anionic fluorochemical surface active agent 1000M, -0803M-803 as the hydrophilic group 2
M, -0P(OH)21e-containing -6 molecules, for example, RfCOOM, RfS02NCR'hC)(,C0
0M.

RH3NR'C,H,O20,M, RfS ○,
4゜RfCH20CmH2mSO-M, M○,
5-CHCOOC)(, RfOCH, C00CH, RfRfBNCmH2naoP(OH)-, etc.

<In the formula, Rf is a fluorocarbon group (having 2 carbon atoms) in which some or all of the hydrogen atoms of an alkyl group are replaced with fluorine atoms.
~20), B represents C○, SC2, R' represents a hydrogen atom or a lower alkyl group, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal, (2) Cation type fluorine-based Surfactant R' A hydrophilic group containing -N-HX, -)N•XO, etc., for example, R' (wherein RI+ represents a hydrogen atom or a lower alkyl group, and where HX represents an acid.R
r, B and R' have the same meanings as Rr, B and R', respectively, in the anionic fluorosurfactant.

(3) Amphoteric fluorosurfactant For example, Rf B N H (C2H()N (R')2 C+
n) I 2mc OOO■ ■ 0 RfBNHC+lIH2mN (R"hCe etc. are mentioned.

(In the formula, Rf, B and R' have the same meaning as Rr, B and R' in the anionic surfactant, respectively.) (4) -01-i- Sulmonote containing 3l-1, -〇-, etc., e.g. Eva, Rr 01-1. Rr SH.

Rt -A (C2H40fR etc. are halfway through.

(In the formula, A is +CH2→yschNR++CR2ko-
, +CH2 Cypress C0NR2-8○3-, -Co2-, J
5 and -3O2N (R3)CH2Co2-, n represents an integer of 0 to 20, m represents an integer of 0 to 5, and R+, R2 and R3 are a hydrogen atom and the number of carbon atoms, respectively. 1-6 alkyl group or +CH2CH2
0sX represents R4, and R1R2 and R3 may each be the same or different. × represents an integer of 1 to 20, and R4 represents an alkyl group having 1 to 6 carbon atoms.)
(5) Polymer-type fluorine-based surfactant, for example, COOC containing the structural unit -+CH2-CH←
Examples include H2Pf polymer compounds.

Preferred specific examples of the nonionic fluorosurfactant are illustrated below.

[Exemplary Compounds] (1) CF3 (CF2)?・(CH2CH20)1.
H(2) CF, (CF2), 5O2N(C,R5)(
CH, CH20), H(3) CF, (CF2), 5
o2N(C2H7)CH3COO(CH,CH20),
, H(4) CF, (CF2), ・(CF,), ・C0
N(CH,) (CH,CH20),. H(5)CF,
(CF2), S○2N (C, R5) C, H, (QC, H
,)50H(6) Cn H17S+, CH2C COO+CHfi F, -10 star J (However, 2 is O~2, m is O~3, a is 1 or 2, b and C are each integers from 1 to 5o ) In the present invention, the following can be used as the above-mentioned fluorosurfactant.

(1) Anionic fluorosurfactant: Fluorade F
C-93, Fluorade FC-95, Fluorade FC
-98, Fluorade FC-129 (manufactured by 3M)
; F-TOP EF-102, F-TOP EF-103,
F-TOP EF-123△, F-TOP EF-1231
3 (manufactured by Shin-Akihi Kasei Co., Ltd.).

(2) Cationic fluorosurfactant: Fluorade F
C, -135 (manufactured by 3M): F-TOP EF-132
(Manufactured by Shinjuyo Kasei Co., Ltd.).

(4) Nonionic fluorosurfactant: Fluorade F
C-1700. Fluorade FC-430, Fluorade FC-431 (manufactured by 3M): F-TOP EF-
121, F-TOP EF-122A, F-TOP EF-
122B, F-Top EF-122C, F-Tub E
F-301, F-TOP E F-303 (manufactured by Shinjuyo Kasei Co., Ltd.): Megafuck F-171, Megafuck F
-173 (manufactured by Dainippon Ink); Asahi Guard AG
-710 (manufactured by Asahi Glass ■).

As the above-mentioned fluorine-based surfactant, especially Fluorade F
C-430 and Fluorade FC-431 are preferably used.

The proportion of the fluorosurfactant used in the present invention in the photosensitive layer is preferably 0.01 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight.

Various known surfactants that do not contain fluorine atoms can be used together with the above-mentioned fluorine-containing surfactants in the present invention, and preferred examples include the following.

(1) Polyoxyethylene alkyl ether (2) Polyoxyethylene alkyl phenyl ether (3) Polyoxyethylene polyoxybrobylene block polymer (4) Polyoxyethylene ester fatty acid ester and ether of the fatty acid (5) Polyoxyethylene polyoxypropylene block polymer Oxyethylene sorbitol fatty acid ester and ether of the fatty acid (6) Polyoxyethylene glycerin fatty acid ester (7) Polyethylene glycol fatty acid ester (8) Polyoxyethylene fatty acid amine (10) Fatty acid monoglyceride (10) Sorbitan fatty acid ester (11) Pentaerythritol fat Iv3m ester (1
2) Propylene glycol fatty acid ester (13) Polyglycerin fatty acid ester (14) Fatty acid alkanolamide (15) Amine oxide (16) Polyoxyethylene castor oil, among which (4) (5) (6)
(7) (9) (10) (11) (
12L(13)(14)(16) are more preferable,
(4)(5)(6)(9)(10)(16) are more preferred.

Specific examples of the polyoxyethylene alkyl ether represented by the general formula RO(CH20H20)TIH include the following.

Adekatol SO-80 Electrified Adekatol 3 Q-105 Electrified Adekatol SO-120 Electrified Adekatol 3 Q-135 Electrified Adekatol 3 Q-145 Electrified Adekatol SO-160 Electrified Adekatol L○-3 Electrified Adekatol LO-5 Electrified adekanol LO-7 electrified adekanol LO-9 electrified adekanol LO-12 electrified adekanol LO O-15 electrified adekanol l Q-20 electrified emulgen 106 R=IC12 positive emulgen 1
20 R=C+2 Positive Emulgen 147
R=C+2 Seisei Emulgen 210
R = C + S Masasa Emalgen 220 Emalgen 306P Emalgen 404 Emargen 408 Emargen 420 Emargen 420 Bridge 30 Bridge 30 Bridge 30 Bridge 35 Emalmin 40 R = C + AF, C + S Emulmin 50R = C + SF, C + 6 Emalmin 60 R = C + AF / C16 Emalmin 70 R = C + AF, C+s Emulmin 110 R=C+aF, C+s Emulmin 140 R=C+5 R=C+a R=C+a R=nioleyl=nioleyl=nioleyl=nioleyl=(,+2 R=C+2 Positive Positive Positive Positive Positive Positive Positive Positive Positive Positive Masaharu Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei R=C+sF, C+s Emulmin 240 R=C+aF, C+s Emulmin L -380 R=C+2 Noni Ball Soft 3S-55 R= CI2, C+3. Cl4) Two Ball Soft 33 -7O R-CI2, (, +3. (, +4) 2-ball soft 33-9O R=C+2.C+3.C Cloudy Pole Soft S S -+20 R=C+2.013.C+Dou-no-2 Ball Soft 5W- 55 R=C++, C+3.01s Noni Ball Soft SW -8S R=C++, C+3.0+s Noni Ball Soft SW -95 8"C++, C+3.0+s Conion LT Series Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Sanyo Kasei R = C + 2 > 60% Various HLB Shin Nippon Rika Conion ST Series R = (, +a 60~70% Various HLB New ° Shin Hon Nihon Rika Non UA Series R = C + aF 35 ~ 45% C+sF<5% Ricanon UB series R=C+8F 40-45% C+sF<1% Ricanon UAN series R=C+aF 55-60% (, +6F4-7% Ricanon UE series R=C+aF 30-35% C2oF10-15% C+sF 10~15% Ricanon UN series R=C+aF 80~90% C+sF6~8% Various HLB New Japan Chemical various HLB New Japan Chemical various HLB New Japan Chemical various HLB New Japan Chemical various HLB New Japan Chemical NUNON A series R=2 -Octyldodecanol Various HLB Shin Nippon Rika Neugen E
T-60 R = Nioleyl Daiichi Kogyo Seiyaku Neugen E
T-1a.

R = Nioleyl Daiichi Kogyo Seiyaku Neugen ET
-83 R = Nilauryl Daiichi Kogyo Seiyaku Neugen E
T-102 R = Nilauril Daiichi Kogyo Seiyaku Nogun ET
-95 R=C12 and others Secondary alcohol-based Dai-Kogyo Seiyaku Neugen ET-135 R=C+2 and others Secondary alcohol-based Dai-Kogyo Seiyaku Neugen ET-97 R=Nidopanol C12, C13 Dai-ichi Kogyo Seiyaku Neugen ET-147 R=Nidopanol Igen ET-878 R-Dopanol C12.

Neugen ET-157A R-dopanol C14.

ps Neugen ET-187A R = Nidopano Le 14.

ps C13'C15 Dai-ichi Kogyo Seiyaku Dai-ichi Kogyo Seiyaku Dai-ichi Kogyo Seiyaku Dai-ichi Kogyo Seiyaku Bionin Q-1105 R=C+2>90% Pionin O-1520 R-Oleyl Begnol L-1O R=(, +2 Pegnol C
18 R=(, +s Pegnol○-16 R=Nioleyl Emalex 60 Takemoto Yushi Takemoto Yushi Toho Chemical Toho Chemical Toho Chemical R=C+s Nippon Emulsion Emalex 500 R=Nioleyl Nippon Emulsion Emalex 100 R=C+s Nippon Emulsion Emalex 700 R=CI2 Nippon Emulsion Nikol BL-type R=CI2 Nippon Surfactant Niracol BC-type R=C+s Nippon Buch 7cutonitsukol BO-type R=Nioleyl Japan Size-77cutonitsunitsunonion PR R=C+s Nippon Oil & Fats Nirasan Nonion S R=C+a NOF Nirasan Nonion K R=C,+2 NOF Chive Sambar Soft NK-60G NOF Chive Sambar Soft NK-100G NOF Actinol R-10
0 R=C+2 Matsumoto Yushi Pharmaceutical Valu 22
00 R=C+295%, n=5~30 Marubishi Yuka Valu 2500 R-C+o 85%, n=5~30 Marubishi Yuka Beletex 2400 R=C+2 Miyoshi Yuka Beletex 2800 R=(, +s, (, +a Myoshi Oil Beletex 2900 R-oleyl Myoshi Oil Eggal O Highly Conch Morin Chemical Cobel Salt WY
Morin Chemical Emalox LX-Series R = C + 2 > 90% Furumura Yukagaku Emalox ST-Series R = C + s'> 60% Yoshimura Yukagaku Emalox CA-Series R = C + o > 85% Liponox 0WO R = Nioleylponox W - 105 R=Cs Liponox DCG R-Cs~C++ Liponox ECI R-C++~Cps Liponox ICD R=(, +2~CH Liponox ICII R=C+2~CI4 Liponox ICJ R=C12'C14 Novonox ICW R= C+2-CI4 Liponox KCE R=CI2-C15 Liponox KCI Yoshimura Yukagaku Lion Yushi Lion Yushi Lion Yushi Lion Yushi Lion Yushi Lion Yushi Lion Yushi Lion Yushi R-C+2ゝC15 Liponox KCJ R=CI2~Cps Liponox KCN R=CI2~Cps Liponox OCS Lion Oil Lion Oil Lion Oil Polyoxyethylene alkylphenyl ethers include the following as specific examples.

Emulgen 810 R=Ca Seisei Emulgen 905 R-Cs Seisei Emulgen 9
09 R=Cs Seisei Emulgen 910
R-C9 Seisei Emulgen 913 R=09 Seisei Emulgen 920 R=09 Seisei Emulgen 9
35 R=C9 Positive Emulgen 950 R=Cs Positive Emulgen 985 R=09 Positive Octaball 50 R=Ca Mie Kasei Octaball 60 Octaball 100 Octaball 200 Octaball 300 Octaball 400 ] Two Ball 40 Noni Ball 60 Noni Ball 85 Noni Ball 100 Noni Ball 160 Noni Ball 200 Noni Ball 400 Neugen E A -80 Neugen E A -12O R=Cs Neugen E A -112 R=Ca Neugen E A -+42 R=Ca Neugen E △-83 R=Ca R=Ca R=Ca R=Cs -Ca R=Cs R=(,9 R=CriR=CriR=Cs -Cs R=Cs -Cs Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Mie Kasei Dai-Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical R=C12 Dai-ichi Kogyo Seiyaku Neugen E A -143 R=C+2 Daiichi Kogyo Seiyaku Emulgit 9 n-30~100 Daiichi Kogyo Seiyaku Emulgit 16 n=30~100 Daiichi Kogyo Seiyaku Pionin [1-308 R=Ca, HLB=12.6 Heavy fat bionin [) -410 R=Cs, HLB=13.3 Quality Heavy Oil Nonal 108 R=Ca Toho Chemical Nonal 209 R=Cs Toho Chemical Nonal 53
0 R=Cs, dialkyl Toho Chemical Sunmol 6
6 R=Cs NICCA Chemical Emmalex NP
-Type R-Cs B-Emulsion Emulsion OP-Type R=Ca Nippon Emulsion Nikkor NP-Type R=Cs B-Model-Factant Nikkor OP-Type R=Ca Japan Surfactant Sencanol SX R= C9, n = 8-10 Nippon Senka Nitsusan Nonion N5 R=Cs B Honyaku Nitsusan Nonion H8 R=Ca Nippon Oil and Fat Benerol N-100H,C.

R=Ca Matsumoto Yushi Pharmaceutical Valu 36
00 R = Ca, n = 4-14 Marubishi Yuka Valu 3700 R = Cs, n = 4-14 Marubishi Yuka Pelletex 1200 n = 3-50 Myoshi Yuka Schnell SB Highly Conc Morin Kagaku Emalox NX-
Series R=Cs Liponox NCA Liponox NCD Liponox NCE Liponox NCF Liponox NCG Liponox NCH Liponox N (1 Liponox NCJ Liponox NCK Liponox NCM Liponox NCN Liponox NGO Liponox NCT Liponox NCY Liponox NC6E -Cs Liponox NC2Y R=C9 R=Cs R=Cs R=C9 R=Cs R=Cs R=Cs R=Cs R=Cs R=Cs R=Cs R=Cs R=Cs R=Cs R= Cs Yoshimura Oil Chemical Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil Lion Oil General formula HO (CH2CH20)II (C,HsO)n
Specific examples of polyoxyethylene polyoxybrobylene block polymers represented by (CH2CH2O)nH include the following.

Pluronic Shi-31 Pluronic Shi-44 Pluronic Shi-61 Pluronic L-62 Pluronic Shi-64 Pluronic Shi-12 Pluronic L-101 Pluronic L-121 Pluronic L-122 Pluronic P-84 Pluronic P-85 Pluronic P-103 Pluronic F -68 Pluronic F-88 Pluronic l" -108 Emulgen P P -230 Emulgen P P -250 Emulgen P P -290 New Ball PE-61 New Ball PE-62 New Ball PE-64 New Ball PE-68 New Ball PE-78 Evan 450 PPG molecular weight 1200 Evan 485 PPG molecular weight 1200 Evan 720 PPG molecular weight 2000 Evan 740 PPG molecular weight 2000 Evan U-103 PPG molecular weight> 2000 Evan U-104 PPG molecular weight> 2000 Seisei Seisei Seisei Seiko Note Kasei Ko Note Kasei Ko Note Kasei Ko Note Kasei Kogyo Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Dai-ichi Kogyo Pharmaceutical Bionine 0-121 Heavy oil and fat block D
Naru 5T-1 Toho Kagaku Rijinmol P-230 Nicca Kagaku Nitsuzanbronon Nihon Yushi Actinol P-2085 Matsumoto Yushi Pharmaceutical Ebonol
Marubishi Yuka 1 Nookon 956Y
Specific examples of lion fat polyoxyethylene sorbitan fatty acid ester and 1, for example, expressed in the formula -% (%) are as follows.

Tween 21 Lauric acid Seisei Tween 21 Lauric acid Seisei Tween 40
Myristic acid Seisei Tween 60 Stearic acid Seisei Tween 61 Stearic acid Seisei Tween 65 Stearic acid Seisei Tween 80 Tween 81 Tween 85 Ionet T-20 Lauric acid, n=20 Ionet T-60 Stearic acid, n=20 Ionet T -80 Oleic acid, n=20 Sorgen T W -20 Sorgen Lauric acid T W -60 Sorgen Stearate T W -80 Bionin oleate [) -941 Lauric acid >90%.

HLB=16.7 Pionin D-9457 Oleic acid>70%.

Oleic acid Oleic acid oleic acid oleic acid oleic acid oleic acid oleic acid oleic acid Turupon T-40 Turupon valmitate T-60 Nikkol stearate T L-10 Lauric acid, n=20 Toho Chemical Toho Chemical Toho Chemical Nippon Surfactan Toniracol TP-10 Palmitin, Rho 20 Nippon Surfactan 1 to Niracol T S-10 Stearic acid, n=20 Japan Surfactant Niracol TS-106 Stearic acid, n=20 Japan Surfactant Niracol TS-30 Tristearic acid, n=20 Japan Surfactant Niracol T O-10 Oleic acid, n=20 Nippon Surfactant Niracol T O-106 Oleic acid, n=6 Nippon Surfactant Niracol T O-30 Trioleic acid, n=20 Japan Surfactant Nirasan Nonion L T-221 Lauric acid Nippon Oil & Fats Nirasan Nonion S T-221 Stearic acid Japan Nirasannonion OT-221 Oleic acid NOF Silpan T
-20 Lauric acid Matsumoto Yushi Pharmaceutical Silpan T-
60 Stearic acid Matsumoto Yushi Pharmaceutical Silpan T-
80 Oleic acid Matsumoto Yushi Pharmaceutical Riquemar Q
-320 Oleic acid Riken Vitamin Oil Suchemal 3
-320 Stearic acid Riken Vitamin Oil Suchemal P
-320 Valmitic acid Riken Vitamin Oil Suchemal L
-320 Lauric acid Riken vitamin oil polyoxyethylene glycerin fatty acid esters, for example, are as follows:

Adekanol NK-4 Electrified Adekanol NK-7 Electrified Adekanol NK-10 Electrified Adekanol NK-15 Electrified Adekanol NK-20 Asahi Denka Emarex GWS-100 Stearic acid Nippon Emulsion Nitsukor T
MGS-10 Stearic acid, n=10 Japan Leaf Actant Poem S -105 Boheme Stearate S -120 Rikemal Stearate S-105 Rikemal Stearate S -120 Boheme Stearate 0-105 Boheme Oleate O-120 Boheme Oleate O-105 Richemal Oleic Acid 0-120 Oleic Acid Riken Vitamin Oil Riken Vitamin Oil Riken Vitamin Oil Riken Vitamin Oil Riken Vitamin Oil Riken Vitamin Oil Riken Vitamin Oil Riken Vitamin Oil General Formula RCOO(CH2CH20), A(A:H or -0CR ) Specific examples of polyethylene glycol fatty acid esters include the following.

Azocanistol OE G-102 Oleic acid Asahi Denka Azocanistol OE G-104 Oleic acid Asahi Denka Azocanistol OE G-106 Oleic acid Asahi Denka Azocanistol OE G-204 Dioleic acid Electrified Azocanistol 5EG-102 Stearic acid Asahi Denka Azocanistol S EG-104 Stearic acid
Asahi Denka Azocanistol S E G -106 Stearic Acid Asahi Denka Emanone 11
12 Lauric acid Seisei Emanone 3115
Stearic Acid Kao Emanone 3199 Emanone Stearate 3299R Emanone Stearate 4110 Ionet Oleate M 3-400 Ionet Stearate M 3-1000 Ionet Stearate M O-200 Ionet Oleate M Q -400 Ionet Oleate MO-600 Ionet Oleate D L -200 Dilauric acid ionet [) l-400 Dilauric acid ionet D S -300 Distearic acid ionet D S -400 Seisei Seisei Seiko Note Kasei Ko Note Kasei Ko Note Kasei Ko Note Kasei Ko Note Kasei Ko Note Kasei Kochu Kasei Kochu Kasei Distearic Acid Mie Kasei Ionet D
0-200 Dioleic acid Mie Kasei Io7 1-
OQ-400 Dioleic acid Mie Kasei Ionet 1~
D O-600 Dioleic acid Mie Kasei Ionet D
O-1000 Dioleic acid Mie Kasei Neugen E
S-160 Oleic acid Daiichi Kogyo Seiyaku Neugen [)
3-604 Distialic acid Daiichi Kogyo Seiyaku Bionin D
-2507 Oleic acid>70%, HLB=10. ．． 1 Begnol 1
4-O Begnol 24-O Emmalex 800 Stearic acid Oleic acid Dioleic acid heavy oil 11:i Toho Chemical Toho Chemical Japan Emulsion Emmalex OE Oleic acid Nippon Emulsion Emmalex P E l- Lauric acid Japan Emulsion Niracol M
YS-type stearic acid Nippon Surfactant Nitsukol M
Y S -40 Stearic acid, n=40 Nippon Surfactant Nitcol MYL-type Nirasan nonion laurate L Nirasan nonion laurate S Nirasan nonion stearate C Nirasan nonion oleate T Beef tallow fatty acid Burianshi-400 Nippon Surfactant Japan Nippon Oil & Fats Nippon Oil & Fats Nippon Oil & Fats Lauric Acid Balu 1200 Lauric acid, n=4-25 Balu 1400 Oleic acid, n-4-25 Beretex E451 Fat II! (C12-C2o) Emaroc series lauric acid>60% Emaroc S-series stearic acid>60% Emaroc O-series oleic acid>60% Esophyt O/15 Esophyt oleate O/20 Esophat oleate 60/15 Stearic acid Esofat 60/ 25 Matsumoto Yushi Pharmaceutical Marubishi Yuka Marubishi Yuka Miyoshi Yushi Yoshimura Oil Chemical Yoshimura Oil Chemical Yoshimura Yukagaku Lion Akzo Lion Akzo Lion Akzo Stearate Lion Akzo Esophat 242/ 25 0 Lion Zinate Akzooxyethylene fatty acid Specific examples of amines include the following.

Electrostopper EA Lauril, N = Total 2 Masashi Amit 105
Lauril Masaaki Amit 308
Stearyl Seisei Amit 320 Stearyl Seisei Ionet A T -+o.

Stearyl Ionette A-300 Stearyl Amingin C-1802 0=2 Aminejin Sanyo Kasei Sanyo Kasei Dai-ichi Kogyo Seiyaku Bionin [1-3110 Lauryl > 80% Base Oil Pegnol HA -120 Cetyl Toho Chemical Nitsukor TAMN
S-type Stearyl Nippon Leefactor Nitsukol T
AMNO-type oleyl Nippon Leefactor Sencanol CW Alkyl C=18. EO≧30 Nippon Dyeing Nissan Naimeen L Lauryl NOF Nissan Naimeen P Coconut amine NOF Nissan Naimeen S Stearyl NOF Nissan Naimeen T Beef tallow amine NOF Zontes AL
-10 Lauryl Matsumoto Yushi Pharmaceutical Valu 420
0 lauryl, n=2-15 Marubishi Yuka Valu 4
500 Stearyl, n=2-30 Marubishi Yuka Pelletex 4400 Lauryl, n-3-10 Myoshi Oil Pelletex 4800 Stearyl, n=5-15 Myoshi Oil Calazin CW Highly Conch Morin Chemical Emaro Ivy OA-
Series Stearyl〉65% Yoshimura Oil Chemical Esomin C
/12.15.20.25 Palm Amin Lion Akzoesomin S/
12.15.20.25 Soybean amine Lion Akzoesomine T/
12.15.25 Tallow Amine Lion Akzo Armostat 310 Fatty Amine, n-2 Lion Akzo Armostat 410 Fatty Amine, n=2 Lion Akzo Esomide H
T/15.60 Hydrogenated beef tallow amide, n>2 Lion Akzoesomide O
/15 Oleylamide, n>2 Lion Akzo CH200C
R fatty acid monoglyceride, for example C1 (20HCH10
Specific examples of what is represented by H include the following:

Atbal 84 Seishi Atbal 1
24 Seisho Atbal 122
Seisei Atbal P-408 Seisei Atbal T-95 Seisei Atmos 150 Seisei Atmos 300 Positive Pressure TG-C Stearic Acid Sanyo Kasei Sunsoft No. 30 Stearin M, C+a>90% Taiyo Kagaku Sannft No. 0-30 Olein Acid Taiyo Kagaku Sunsoft N
0.230 Stearic acid Sunsoft N 0.530 Erucic acid Sunsoft No, 118 Stearic acid Sunsoft N 0.1030 Behenic acid Sunsoft N 0.1330 Stearic acid Sunsoft N00208 Stearic acid Sunsoft N0.866 Stearic acid. Oleic acid Sunsoft N O, 8000 Stearic acid, 1. V, <2 Sunsoft No, 8030 Stearic acid/oleic acid.

1, V, <'=, 30 Sunsoft NO, 8070 Solar chemistry Solar chemistry Solar chemistry Solar chemistry Solar chemistry Solar chemistry Solar chemistry Solar chemistry Oleic acid, I, V, <-70 Solar chemistry Sunsoft NO, 8080 Oleic acid, 1. V, <'=80 Taiyo Kagaku Sunsoft No, 700 P-2 Caprylic acid Taiyo Kagaku Nilacol M
GO Oleic Acid Japan Refactorant Nikkor M
GS-type stearic acid Nippon Leaf Actan 1 to Nitsukor MGS-F type stearic acid Nippon Leaf Actan Nitsukor M
GS-type SE Stearic acid, self-emulsifying type Nippon Refactor Tonirasan Monogly M Stearic acid monolite Stearic acid>70% Boem 0-100 Oleic acid Nippon Oil & Fat Miyoshi Oil Riken Vitamin Oil Boem s-io.

Stearic acid Riken Vitamin Oil Boheme S -
200 Stearic acid Riken Vitamin Oil Suchemal Q
-100 Olein M 3g! RIKEN VITAMIN OIL RIKEMAL S-100 Stearic acid RIKEN VITAMIN OIL RIKEMAL S
-200 Stearic acid Riken Vitamin Oil Suchemal O
L-100 Oleic acid Riken vitamin oil Suchemal R
-200 Wasylic acid Riken vitamin oil sorbitan fatty acid ester Specific examples of those represented by are as follows.

Span 20 Lauric acid Seishin Span 4
0 Myristic acid Seishin Span 60
Stearic acid Positive pressure span 65 Tristearic acid Positive pressure span 80 Oleic acid Positive pressure span 8
5 Trioleic acid Positive pressure Araselle 20 Lauric acid Positive pressure Araselle 40 Myristic acid Positive pressure Araselle 60
Stearic acid Positive pressure Araselle 80 Oleic acid Positive pressure Araselle 83 Sesquioleic acid Positive pressure Ionet 5-20 Lauric acid Mie Kasei Ionet S-60C Stearic acid Mie Kasei Ionet 5
-80 Oleic acid Mie Kasei Ionet 5
-85 Trioleic acid Mie Kasei Sorgen 30 Sesquioleic acid Daiichi Kogyo Seiyaku Sorgen 40 Oleic acid Daiichi Kogyo Seiyaku Sorgen 50 Stearic acid Daiichi Kogyo Seiyaku Sorgen 9
0 Lauric acid Daiichi Kogyo Seiyaku Sunsoft N
o, 678 Stearic acid, HLB = 6.7 Taiyo Kagaku Sunsoft No. 618 Stearic acid, HLB = 5.2 Taiyo Kagaku Sunsoft No. 60T Sesquistearic acid.

HLD=4.4 Taiyo Kagaku Sunsoft No. 63G Distearin 1. HLB = 3.6 Taiyo Kagaku Sunsoft No. 657 Tristearic acid, HLB = 2.1 Taiyo Kagaku Sunsoft No. 0.87N Oleic acid, HLB = 6.7 Taiyo Kagaku Sunsoft No. 813 Oleic acid, 1-ILB = 5.3 Sunsoft N0
．． 80T Sesquioleic acid, HLB = Sunsoft No., 85T Dioleic acid, ILB = 2.0 Turpon 3-20 Turupon laurate 5-40 Turupon palmitate 3-60 Turupon stearate 5-80 Nylachol oleate 5L-10 Laurin Nylacol Acid 5P-10 Nylacol Palmitate S S -10 Nylacol Stearate S S -15 Nylacol Sesquistearate Nippon Surfactant Nippon Surfactant Nippon Surfactant Taiyo Kagaku Taiyo Kagaku Taiyo Kagaku Toho Chemical Toho Chemical Toho Chemical Toho Chemical Nippon Surfactant Nilacol S S -30 Nylacol tristearate S O-10 Nylacol oleate S O-15 Nylacol sesquioleate 3 Q -30 Nylasan trioleate LP Nylasan laurate PP Nyrasan nonion palmitate SP Nylasan stearate Nonionic OP Silpan oleate 5-20 Silpan laurate 5-60 Stearic acid Nippon Surfactant Nippon Surfactant Nippon Surfactant Nippon Surfactant Nippon Oil & Oil Oil Nippon Oil & Fat Nippon Oil & Fat Matsumoto Yushi Pharmaceutical Matsumoto Yushi Pharmaceutical Silpan 5-80 Oleic acid M-200 Fatty acid (Ca -C24) Riquemal 3-300 Rikemal stearate S -250 Rikemal stearate p -300 Rikemal palmitate P -250 Rikemal palmitate O-300 Rikemal oleate O-250 Rikemal oleate L -300 Rikemal laurate L -250 Laurin Acid Matsumoto Yushi Pharmaceutical Myoji Yushi Riken Vitamin Yu Riken Vitamin Yu Riken Vitamin Yu Riken Vitamin Yu Riken Vitamin Yu Riken Vitamin Yu Riken Vitamin Oil Pentaerythritol Fatty Acid Ester For example CI (20
Specific examples of COR 11OH2C-C-CH,01 (H20H) include the following.

Sunoil PE 2-ethylhexylic acid Taiyo Kagaku-Fukudai RC
Specific examples of glycol fatty acid esters represented by OOCH2-CH-OH include the following.

Homotex PS-90 Stearic Acid Positive Pressure Sunsoft No.
, 25-S Stearic acid Taiyo Kagaku Sunsoft N
O,25-〇Oleic acid Taiyo Kagaku Sunsoft N
0125-C Stearic acid Taiyo Kagaku Sunsoft N
o, 25-A Araxic acid Taiyo Kagaku Emmalex PGS Stearic acid Nippon Emulsion Emmalex PGdlO Dioleic acid Nippon Emulsion Nikkor P
MS Stearic Acid Nippon Leaf Factor Trichemal P
S-100 Stearic acid Riken Vitamin Oil Suchemal P
O-100 Oleic acid Riken vitamin oil Suchemal p
p−+o.

Palmitic acid Riken vitamin oil polyglycerol fatty acid ester (RCOO) QA A: Polyglycerin residues 1 to 4 Specific examples include Sunoil DGO diglycerol oleate ester.

Taiyo Chemistry Fatty acid alkanolamides e.g. Specifically, the following can be mentioned.

Efcosol COA Coconut Fatty Acid Jetanolamide Adecafine Chemical Aminol C-02 Coconut Fatty Acid Jetanolamide Amitool 5-02 Stearic Acid Jetanolamide Prophane Series Lycanone W C-020 Coconut Fatty Acid Jetanolamide Masho Masho Mie Kasei Shinnihon Rika Dianol 300 Jetanolamide Daiichi Kogyo Seiyaku Bionin Lauric acid Jetanolamide (1:2 form) Uchimizu Oil Tohol N-120 Lauric acid monoethanolamide Toho Chemical Tohol N-230 Lauric acid Jetanol Amide Toho Chemical Tohole N
-230X Lauric acid jetanolamide extra form Toho Kagaku Senka Salt MP R=C+2~C+a Nippon Senka Nissan Stahome F, FK type NOF Mabon NM Lauric acid jetanolamide (1:1 form) Matsumoto Yushi Pharmaceutical Mabon LK Lauric acid Jetanolamide (1:2 form) Matsumoto Yushi Pharmaceutical Amicol S
M Stearic acid monoethanolamide Miyoshi oil and fat Amicol CM Lauric acid monoethanolamide Miyoshi oil and fat Amicol CDE Lauric acid 1 diethanolamide (1:1 form) 2 diethanolamide (1:2 form) Miyoshi oil emalox GLO C, 2>50 %, Jetanolamide Furumura Yukagaku Esomite HT/15. HT/60 Aromox DWC R=Coconut fatty acid, R'=CH3 Lion Akzo Aromox C/12.7/12.18/12R'=
Examples include CH2CH20H.

R′ RN-SIO specifically includes a polyoxyalkylene sorbitol fatty acid ester compound, or the ether compound of the fatty acid includes a polyoxyethylene sorbitol fatty acid ester compound or an ether compound of the fatty acid, and a polyoxypropylene sorbitol fatty acid ester compound. Alternatively, examples thereof include ether compounds of the fatty acids, polyoxyethylene/polyoxypropylene sorbitol fatty acid ester compounds, and ether compounds of the fatty acids.

Specific examples include polyoxyethylene sorbitol hexastearate, polyoxyethylene sorbitol tetrastearate, polyoxyethylene sorbitoltetraoleate, polyoxyethylene sorbitol [hexaoleate, polyoxyethylene sorbitol monooleate] ,
Polyoxyethylene sorbit monolaurate, polyoxyethylene sorbit 1 to tetralaurate, polyoxyethylene sorbit hexalaurate, polyoxypropylene sorbit hexastearate, polyoxypropylene sorbit tetraoleate, polyoxypropylene sorbit hexaoleate, polyoxyethylene sorbitol Oxypropylene sorbitol monolaurate, polyoxyethylene
polyoxypropylene sorbitol hexastearate,
Polyoxyethylene/polyoxypropylene sorbitate tetrastearate, polyoxyethylene/polyoxypropylene sorbitol monooleate, polyoxyethylene/polyoxypropylene sorbittetraoleate, polyoxyethylene sorbitol hexastearyl ether, polyoxyethylene sorbitol tetrastearyl Examples include ether, polyoxyethylene sorbit monooleyl ether, polyoxyethylene sorbit monooleyl ether, polyoxyethylene sorbit monooleyl ether, and the like.

As the polyoxyethylene castor oil, ethylene oxide adducts of castor oil and hydrogenated castor oil are used, and as the polyoxyethylene castor oil, Nyrakol C0-3, Nyrakol C0-10, Nikko-) LtCo-20TX1 Nikkol-C are used. ○-40TX, Nikkor Co-50TX, Nilakol C0-60TX; Nilakol HCO-5, Nilakol HCO as polyoxyethylene hydrogenated castor oil
-7,5, Niracol HCO-10, Nikol H'
Examples include G O-20, Niracol 1-I CO-30, Niracol HCO-40, Niracol HCO-30, Niracol HCO-60, Niracol HCC)-80, and Niracol HCO-100 (all manufactured by Nikko Chemicals).

Further, the fluorine-free surfactant used in the present invention includes polyalkylene glycols, and examples of such polyalkylene glycols include polyethylene glycol, polypropylene glycol, etc., each having a molecular weight of 100 to 100. The number is preferably 10,000, more preferably 500 to 6,000.

The proportion of the fluorine-free surfactant used in the present invention in the photosensitive layer is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight.

Examples of the O-quinonediazide compound used in the present invention include O-naphthoquinonediazide sulfonic acid and ester compounds with polycondensation resins of phenols and aldehydes or quinones.

Examples of the phenols include phenol, 0-
Cresol, m-cresol, p-cresol, 3,5
- Monohydric phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, m-cresol/formaldehyde resin, 1-1p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/acetone resin, and the like.

The condensation rate of O-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol in the O-naphthoquinonediazide compound (reaction rate with respect to one OH group) is 15 to 80%.
is preferable, and more preferably 20 to 45%.

Further, as the O-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, known 1,2-quinonediazides such as 1°2-benzoquinonediazide sulfonic acid ester, 1,2-naphthoquinonediazide sulfonic acid ester, 1,2-benzoquinonediazide sulfonic acid amide, and 1,2-naphthoquinonediazide sulfonic acid amide. Compounds, specifically by J. Kosar (J.

Kosar) [Light Sensitive System] (
”L 1oht-3intensive 3yste
John Wiley & Sons, pp. 339-352 (1965)
& 3ons) New York) and W.
Nis De Forest (W, S, De For
est) by [) 1st Heregisto” (”Photo
1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1°, described in McGraw-Hill Co., Ltd., Volume 50 (1975), 2.1'
, 2'-di(benzoquinonediazide-4-sulfonyl)-dihydroxybiphenyl, 1°2-benzoquinonediazide-4-(N-ethyl-N-β-naphthyl)-sulfonamide, 1.2naphthoquinonediazide-5-sulfone Acid cyclohexyl ester, 1-(1,2-naf[
-quinonediazide-5-sulfonyl)-3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfonic acid-4''-hydroxydiphenyl-4''-azo-
β-naphthol ester, N,N-di(1,2-naphthoquinonediazide-5-sulfonyl)-aniline, 2'
-(1,2-nara-1-quinonediazide-5-sulfonyloxy)-1-hydroxy-anthraquinone, 1.2-
Naphthoquinonediazide-5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1. °2-naphthoquinonediazide 2 moles of 5-sulfonic acid chloride and 4,4'-
Condensate of 1 mole of diaminobenzophenone, 2 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4
．． Condensate of 1 mole of 4'-dihydroxy-1,1'-diphenylsulfone, 1,2-naphthoquinonediazide-5-
Examples include condensates of 1 mole of sulfonic acid chloride and 1 mole of purbrogalin, and 1,2-quinonediazide compounds such as 1,2-naphthoquinonediazide-5-(N-dihydroabiethyl)-sulfonamide. Also, Special Publication No. 37-1953, No. 37-3627, No. 37-13
No. 109, No. 40-26126, No. 40-3801, No. 45-5604, No. 45-27345, No. 51
-13013, JP-A No. 48-96575, JP-A No. 48-
63802 and 48-63802 can also be mentioned.

As the 0-quinonediazide compound of the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination.

The proportion of the 0-quinonediazide compound used in the present invention in the photosensitive layer is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight.

As the alkali-soluble resin in the present invention, various resins known in the art can be used, but novolak resins and vinyl polymers having a structural unit having a phenolic hydroxyl group in the molecular structure are particularly preferred.

Novolac resins preferably used in the present invention include:
Examples include resins obtained by condensing phenols and formaldehyde in the presence of an acid catalyst. Examples of the phenols include phenol, 0-cresol, m-cresol, p-cresol, 3,5-xylenol, 2. 4-
Xylenol, 2.5-xylenol, carvacrol, thymol, catechol, resorcinol, hydroquinone,
Examples include pyrogallol and phloroglucin.

The above-mentioned phenolic compounds can be used alone or in combination with formaldehyde to obtain a resin. Among these, a preferred novolac resin is a resin obtained by copolycondensing formaldehyde with at least one selected from phenol, m-cresol (or 0-cresol), and p-cresol. For example, phenol/formaldehyde resin, m-cresol/formaldehyde resin, O-cresol/formaldehyde resin, phenol/p-cresol/formaldehyde copolymer resin, m-cresol/p-cresol/formaldehyde copolycondensate resin, 0- Examples include cresol/p-cresol/formaldehyde copolycondensate resin, phenol/l-cresol/p-cresol/formaldehyde copolycondensate resin, and phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin. Furthermore, among the above novolac resins, phenol/m
-Cresol/p-cresolteformaldehyde resin is preferred.

In the present invention, the above novolac resins may be used alone or in combination of two or more.

The molecular weight (polystyrene standard) of the above novolak resin is:
Overflow average molecular world MW is 2.0X103 to 2.0X104
So, the number average molecule ffiMn is 7.0×102 to 5.0X
The value is preferably within the range of 103, more preferably MW is 3.0 x 103 to 6.0 x 103, Mn
is a value within the range of 7.7X102 to 1.2X103. The measurement of the molecular weight of the novolak resin in the present invention is as follows:
This is performed using the GPC described above.

The amount of novolac resin in the photosensitive layer of the present invention is 0,
01 to 50% by weight is preferable, more preferably 1 to 14% by weight.
It is a heavy percentage.

Furthermore, the vinyl polymer having a structural unit having a phenolic hydroxyl group in its molecular structure, which is preferably used in the present invention as an alkali-soluble resin, is a polymer formed by polymerization by cleavage of a carbon-carbon double bond. Therefore, a polymer containing at least one structural unit of the following items [I] to [VI] is preferred.

General formula [T] +CR+ R2-CR3→- 0-CO-B-OH General formula [■] 1+CR+ R2-CR3→- CONR4→A 揄B -01-を-clothing cost [I[1] % formula % General formula [IV] +CRIR2 CR3→- B-OH General formula [V OH C, , R7, C+ σn OO) (wherein, R1 and R2 are each a hydrogen atom, an alkyl group, or a carboxyl group , preferably a hydrogen atom.R3 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group.R+ represents a hydrogen atom, an alkyl group, or an aryl group. represents a group, earth or aralkyl group, preferably a hydrogen atom.A represents an alkynone group which may have a substituent connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, ml, m number from tO to 10, and B does not represent a phenylene group that may have a substituent or a naphthylene group that may have a substituent. At least one structural unit represented by
A copolymer containing two or more is preferred.

The vinyl polymer has a copolymer type structure,
In such a copolymer, the above-mentioned clothing cost [I] to [V
Examples of monomer units that can be used in combination with at least one of the structural units represented by each of I] include ethylene, propylene, isobutylene, butadiene,
Ethylenically unsaturated olefins such as isoprene, such as styrene, α-methylstyrene, p-methylstyrene,
Styrenes such as p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, itaconic acid,
Unsaturated aliphatic dicarboxylic acids such as maleic acid and maleic anhydride, such as methyl acrylate, ethyl acrylate,
α-methylene aliphatic monocarboxes such as 1ln-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylate, etc. acid esters,
For example, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-
Anilides such as nitroacrylanilide and m-methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, etc. vinyl ethers, vinyl chloride, vinylidene chloride, nylidene cyanide, such as 1-
Methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethyl
~xycarbonylethylene ethylene derivatives, such as vinyl monomers such as N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylvirolone, and N-vinylpyrrolidone.

These vinyl monomers exist in polymer compounds with a structure in which unsaturated two-handed bonds are cleaved.

Among the above monomers, those used in combination with at least one of the structural units represented by [1] to [VI'l include (meth)acrylic acids, esters of aliphatic monocarboxylic acids, Nitriles are preferred because they exhibit superior overall performance. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate and the like.

These monomers may be bonded in the vinyl polymer either in a block or random manner.

In the vinyl polymer, -clothing cost [I] to [VI
] The content of the structural units shown in each is 5 to 70
It is preferably mol %, particularly preferably 10 to 40 mol %.

Further, the proportion of the vinyl polymer in the photosensitive layer is 50 to 95% by weight, preferably 60 to 90% by weight.
Weight%.

The above-mentioned polymers may be used alone in the above-mentioned combination, or two or more kinds thereof may be used in combination in the photosensitive composition.

Typical examples of vinyl polymers used in the present invention are listed below. In addition, in the compounds exemplified below, MW
is the weight average molecular weight, Mn is the number average molecular weight, s, and 1.
o, m and n each represent mol% of the structural unit.

Margin below Exemplary compound CH.

Cl-i.

CH.

CH.

Margin below (j) (k) CH.

CH.

CH.

In addition to A5, an exposure visible image imparting agent and a dye may be added to the photosensitive lithographic printing plate of the present invention, if necessary.

As the exposure visible image imparting agent, a substance that generates an acid upon exposure to light is generally used, and as the dye, a compound that forms a salt with this acid is generally used.

As the compound that generates an acid upon exposure to light, a trihaloalkyl compound or a diazonium salt compound represented by the following formula [I] or [lI] is preferably used.

General formula "Ding" Mu (wherein, Xa represents a 1-lyhaloalkyl group having 1 to 3 carbon atoms, W represents C, NXS, Se or one each atom, and Z represents ○, N, S , Se, or P, and Y has a chromophore group and represents a group consisting of a group of nonmetallic atoms necessary to cyclize W and Z.) - Clothes [II] Ar - N2 , [■] or [
V].

-Fukudai [lff1 (wherein, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, B' is a hydrogen atom or a methyl group A' is a substituted or unsubstituted aryl group or a heterocyclic group, and n is Oll
Or 2. )-Fukudai [II[] Specific examples of compounds include oxadiazole compounds having a benzofuran ring such as Xa,
2-trichloromethyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
Examples include 3,4-oxadiazole compounds.

In addition, as examples of compounds for -fukudai [rV] and [V], 4-(2
, 4-dimethoxy-4-styryl)-6-dolichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6-11-me1-xystyryl-8-triazine compound, 2.4-bis -(trichloromethyl)-6
-p-dimethylaminostyryl-5-t-lyazine compound and the like.

On the other hand, the diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and a counter ion of an inorganic compound is recommended as the counter ion part. Specific examples include aromatic diazonium salts in which the anion moiety of the diazonium salt is at least one of phosphorus fluoride ion, arsenic fluoride ion, antimony fluoride ion, antimony chloride ion, tin chloride ion, bismuth chloride ion, and zinc chloride ion. Paradiazophenylamine salt is preferred.

On the other hand, as the dye, any compound that forms a salt with a generally known acid can be used, such as triphenylmethane dyes, cyanine dyes, diazo dyes, styryl dyes, and the like.

Specifically, Victoria Pure Blue BOH, Ethyl Violet, Crystal Violet, Brilliant Green, Paysic Tsukushin, Eosin, Phenolphthalein, Xylenol Blue Congo Red, Malachite Green, Oil Blue #603, Oil Pink #3
12, cresol red, auramine, 4-1)-diethylaminophenylimino naphthoquinone, leucomalachite green, leuco crystal violet, and the like.

The photosensitive lithographic printing plate of the present invention may further contain a plasticizer, a sulfuric acid, an acid anhydride, and the like, if necessary.

Furthermore, the photosensitive lithographic printing plate of the present invention may contain, for example, p-tert in order to improve the oil sensitivity of the photosensitive lithographic printing plate.
-butyl phenylene, norformaldehyde resin, p-
It is also possible to contain n-octylphenol formaldehyde resin or a resin partially esterified with an 0-quinonediazide compound. The photosensitive lithographic printing plate of the present invention can be formed by dissolving each of these components in the following solvents and coating and drying the solution on the surface of a suitable support to provide a photosensitive layer.

Solvents that can be used to dissolve each of the above components include:
Examples include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in combination of two or more.

Coating methods that can be applied to the production of the photosensitive lithographic printing plate of the present invention include conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating. It is possible. At this time, the coating amount varies depending on the application, but is preferably 0.5 to 5.0 l/v2 in terms of solid content.

Supports used in the photosensitive lithographic printing plate of the present invention include metal plates made of aluminum, zinc, steel, copper, etc.; metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc.; Examples include paper, plastic film and glass plates, paper coated with resin, paper covered with metal foil such as aluminum, and plastic film treated to make it hydrophilic. Among these, aluminum plates are preferred. As the support for the photosensitive lithographic printing plate of the present invention, it is more preferable to use an aluminum plate that has been subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.

Known methods can be applied to these treatments.

Generally, a photosensitive lithographic printing plate is exposed to light using a printing device and then developed with a developer. As a result, only the unexposed portion remains on the surface of the support, creating a positive-positive relief image.

As the developer used for developing the photosensitive lithographic printing plate of the present invention, an aqueous alkaline developer is suitable. Examples of the aqueous alkaline phenomenon liquid include aqueous solutions of alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, trisodium phosphate, and trisodium phosphate. can be mentioned.

Examples of the photosensitive lithographic printing plate of the present invention will be described in detail below, but the present invention is not limited to these Examples.

(Example) Example 1 After degreasing an aluminum plate with a thickness of 0.24 mm,
It was electrolytically polished in an aqueous hydrochloric acid solution and desmutted in an aqueous caustic soda solution. Next, after anodic oxidation treatment in an aqueous sulfuric acid solution, a hot water sealing treatment was performed to obtain an aluminum plate for a lithographic printing plate.

Next, the following photosensitive liquid was applied to this aluminum plate under the following coating conditions and dried to obtain a photosensitive lithographic printing plate sample.

Photosensitive liquid - Condensate of trihydroxybenzophenone and naphthoquinone <1.2)-diazide 5-sulfonyl chloride Type 2 assembly - Mixed cresol (phenol dim-cresol: p-cresol = 2 = 5:3) formalin novolac resin (fffffi average molecule fjtMW = 10.000)
81 parts by weight of 2-trichloromethyl-β(2'benzofuryl)vinyl 1.3.4-oxadiazole 006 parts by weight of a condensate of p-octylphenol and naphthoquinone (1,2)-diazide-5-sulfonyl chloride ( Condensation rate of hydroxyl groups: 50 mol%) 0.1 weight part, Victoria Pure Blue BOH (manufactured by Odogaya Chemical Co., Ltd.) 0.08 weight part, fluorine surfactant shown in Table 1 (F-1) 0.02 weight Part・Fluorine atom-free surfactants shown in Table 2 (Compound-1) 0.21fit part・Methyl cellosolve/Ethyl cellosolve (2/8)
53 parts by weight Coating conditions - Coater: Roll coater (bat method) - Coating speed: 40 m/nzn - Drying time = 3 minutes - Drying temperature = 85°C - Drying air volume: 15 ml 1 1 A (1) The unevenness and streaks on the coated surface after application of 1000111 were visually determined.

The performance of the thus obtained photosensitive lithographic printing plate was evaluated using the following film original under the following exposure conditions, plate making conditions, and printing conditions.

Film manuscript Nistep Tablet No. 2 (Eastman Kodak (
Exposure conditions: Development conditions: Printing conditions: Table 1 Next, after partially covering the photosensitive lithographic printing plate with black paper, it was exposed to white fluorescent light FF1 (2 lines of 40W). The film was left standing at a position of 2 m for a certain period of time with the photosensitive layer side up, and then developed under the above-mentioned development conditions. The time at which the difference between the area covered with black paper and the exposed area could be clearly observed was determined. Using the above evaluation method, the coating properties and exposure visible image properties were determined, and the clear sensitivity, solid sensitivity, and safelight time were determined from the printing plate after development, and the results are shown in Table 4.

Below margins Below margins Examples 2 to 19, Comparative Examples 1 and 2 Same as Example 1 except that the fluorine-based surfactant and the surfactants not containing fluorine atoms were changed as shown in Table 3. Table 4 shows the results of Examples 2 to 19 and Comparative Examples 1 and 2 in the same manner. Moreover, all the printed matter were of good quality.

Margin table below - 4 Book 1 Spreadability (unevenness) ◎: Uniform and even O: Slight tangerine skin Δ: Slightly noticeable tangerine skin ×: Umbrella 2 with noticeable tangerine skin Spreadability (vertical streaks: streaks in the direction of application) ◎ : Uniform and uneven O: Slight streaks Δ: Slightly noticeable streaks ×: Stains are noticeable*3 Exposure visible image quality (visual judgment at 2m under yellow light (20W 1 line)) ◎: Registration mark on film original I can see it clearly.

○: Dragonfly mark and pattern are clearly visible.

Δ: I don't really understand dragonflies, but I can understand the pictures.

×-The dragonfly mark and pattern are not visible.

As is clear from Table 4, the photosensitive lithographic printing plate of the present invention containing both a fluorine-containing surfactant and a fluorine-free surfactant can be applied to a photosensitive lithographic printing plate that does not contain either of them. It is excellent in all properties, exposure and visible image properties, and safelight properties.

[Effects of the Invention] As described above in detail, the present invention provides a photosensitive lithographic printing plate excellent in all of coating properties, safelight properties, and exposure visible image properties, and a photosensitive composition suitable for the printing plate. Ta.

Patent applicant Konica Corporation (1 other person) Representative Patent attorney Miyao Ichinose, -1'j゛1

Claims (1)

[Claims] A photosensitive lithographic printing plate having, on a support, a photosensitive layer comprising a photosensitive composition containing at least an o-quinonediazide compound, an alkali-soluble resin, a fluorine-containing surfactant, and a fluorine atom-free surfactant.