JPS5931944A - Silver halide photosensitive material for plate making and its reduction process - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material large in reduction degree, and small in fluctuation of reduction performance, by forming an upper nonphotosensitive layer on the upper part of a photosensitive silver halide emulsion layer, and using a combination of a polymer hardening agent and a low mol. wt. hardening agent having activated vinyl groups, and rendering the necessary melting time of the nonphotosensitive layer longer than that of the photosensitive layer. CONSTITUTION:A combination of a polymer hardening agent and a low mol. wt. hardening agent having activated vinyl groups is used for a photosensitive material for plate making, and at least one of upper nonphotosensitive layers is hardened so as to have a melting time longer than that of the photosensitive silver halide emulsion layer. It is desired for the nonphotosensitive layer to be given a melting time longer by >=100sec than the photosensitive layer by setting an amt. of hardening agent to be used. To synthesize a typical vinyl sulfonic group used for synthesis of said polymer hardening agent, 2-(3-chloroethylsulfonyl)-propionyloxy-ethyl acrylate is usable. A typical example of said low mol. wt. hardening agent having activated vinyl groups is CH2=CHSO2CH2 CH2CH2SO2CH=CH2, etc.

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a halogenated daughter: r, 4: Shinkanbori material for plate making and a reduction processing method using the same. In addition, if you use a unique combination of hardeners 11
．． 1, the IJ, mackerel force-treated animals were significantly improved, and ■ One, horse true ability, (1 ψj simulation progress l/1:, i mass dural fish, and preservation of hardness i' :++! Plate making 1 with improved degree dependence 111. This relates to a power reduction processing method.It is used in the fields of printing industry, etc. to convert a b'\-C grayscale image into a halftone image, and to photograph a line image. It is a kangetsu that is used in moderation.
-C (: 1, a picture suitable for special printing (iQ Q moon) (in order to satisfy the strange tone IJ present and military LC expression, -C for the plate making impression) Area force office J, T
1+1i L is used to partially or completely modify the image, such as reducing the halftone ifu printing or increasing or decreasing the width of the line drawing by 1.・There are many cases where it is very thin.For this reason, for plate making 1

[&In the shrine, there are 4 fires that increase the sense of internal strength °'(
= It is very important whether or not it is done (there are seven important points: In this method, a method is used in which the gold or silver forming the single point or line image is brought into contact with a reducing force a.Many types of reducing forces are known, for example: , The Theory by Mies
Of the Photographic Process (Mees)
, i,'be 'l'beo ry o (t
hePbotograpbic Process
) No. 731-7J ri l'4 (/9! 47, M
Published by Acmillan 1)) contains permanganate,
Reducing fluids using θ-forming components such as cerium salt, blush salt, chromate, and persulfate have been described. Since the image is oxidized and dissolved, when the halftone dot area is reduced by the lifting process which processes the halftone dot 1IllI image with ++, :it force, the halftone dot area is reduced by Darkening of points (1
(M of lotus IJ snoring, 5ν is generated. 1 is 71...V power station J111 makes If jl: Possible mouth 1 shu + 1 i
The rLA of 1110^ fine spots is 11.
, one-C is limited/, (ru. 11 irises 2
, delivered, 1 point 1 pile 11'! 1. 1, correct, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1.
, it is possible to use a small amount of clothing (Table A). In this specification [4], the blackening of the halftone dots is achieved by the power reduction process to the minimum value required in the printing process.
, has decreased (1.'f, N1 and 4-point curve 11! It is expressed in the term 4. This reduction force 11" is wide (J, the reduction treatment is high /, c
It goes without saying that the technique of rejuvenating a person is as follows:
Example body 1! [Open/close! , 2-A and 4/F publication 1t
A reduction method containing a mercapto compound is known when feeling the force of force, but a special reduction liquid and/or a reduction liquid and ζ゛When it became 4, it became a messenger.
Raise your power, ζ-ring, ξ-wa and praise it, a.
Widening "Kyo no Tsuki 1", t, 1 has a sense of power"・l! Is it possible to change Jl;su1 life to i+7;,'4-?This method requires the necessary membrane strength] ``Is 147 f',C. The wish to repackage Hanyu (4)
・The most self-effective method among J is the silver h(
The goal is to increase the amount of 1(l(ra, i'1iJj
Small J2 U (26 戊力所川 1) is to oxidize the silver image with a reducing liquid and s t?iI'l・1',
-) Copper unit surface 11 forming a silver painting 4 on the throw [The more floors there are, the more λ, the more Kutsuki 1, and the force 1ψ, January 1! Ii
This is because the field can be corrected by n4 (1f1) [J wide/C]. Therefore, 14 units of 1) r, +rn rate used for encapsidation for plate making are applied 1j1 per ti,
Although Hatumenotsuki IJ will be wider, the well-known 1III
< frl, i:L extremely high master and helmet i1. /,'(
Because it is a thing, 'i7'? 'li&lJ
LiI eye 2J costume 1 for plate making to remove tits
1) Arrived from the elementary school? l jl"+! From the point of view, it's good to be seen by others. It's about the second thing ('), l...k force + l+ is widely used, 14, low, 1" (2 silver dissolution rit The circle is for the emulsion layer -J1 (different techniques are required between the target direction and the horizontal direction. That is, heat (defeat t6 resolution r river! The larger the value, the better. (In order to show the idea in practice, the present inventors investigated 410 different values: A hardening technology (coating technology (i-layer ++IIq)) that independently controls the degree of hardening of the halogen emulsion and
Required 12, by increasing the size of the upper layer of the non-linear game C meter, 1] Shikinozuki 13 becomes wider, and the reduction processing n: ・4
I found that the raw material was improved by sweating (lees 1!l)
'l'llll/l! l-/g06 Otoriyumi). Among the coating layer-by-layer coating techniques mentioned above, non-Δ'C'
It is also effective to add a non-diffusive high/f-element curing agent to the two-part layer, while using a non-diffusive low-molecular curing agent in this layer or other layers. However, the expansion agent used in combination (1 molecule htj4 II, tI + f of the agent
If the composition of i'J force reduction/IM can be imitated by 3a'j, dl, (the change in force + l+ and force reduction time becomes large A: L, < 1.c phenomenon occurs J- On the other hand, the composition of 16 abrasive materials, 1f of hardening of 1φ (] is often combined with: 4' gives a slight shaky sound to the shintokuo, so it is always photographed, l; (electric shock material is... 1] After hardening 1 (response is completed, 1 temple to the moon r゛ [raw is stocked with the soil that makes a woman's voice,
Only then will it be shipped. The progress of the hardening reaction in the culm is 1lJ1), and the old ``111'' is used, so the pulling cost is low.
That's outrageous. Also, the above Q month IN conversion reaction Q month 11 line is the surrounding /::A 7! II> ll:(!rx+, l: 7
Ju! , I#') ()) Shadow 1'j',! :”f
::Ke+= < I+:t, To, hair during the Futtsuku period 1', j hair 1j11! , IJ,? -・I'4 becomes easier to close. However, V'4. , 11 minutes J-hardening firmness! skinned skin j
Heart speed +434 Lt Since it is generally slow, the above-mentioned June 1 season 1
”, 111ill 11114 (M using
IJym 1.1% book j (secondary strike)
The gap becomes 2, and the speed of the curing reaction is 11, which is 1 for stock. ^L'! +ii jJ↓'t';
t,;',i? 7+', r, +
was there. 1 child C-A<The purpose of the invention is firstly to make the person's energy more popular.
And 1 power liquid 1 [[1 power 1 life 17 points 1 + i, 11 is a little t, c to provide an impression of suppression] ”). The [] target of the present invention (-J, firstly 61p conversion 1.C1, line 115 is 1.ij (and the surrounding 11° 11 effect! 1
Depending on the 5th degree (17Fi, which has a small number of leaves, is suitable for use with the sensitive material for the plate and the 4" width). The present invention's [1] 11.1ζ
The object of the present invention is to provide a power processing method that can handle almost the same ambiguous power even if the power lfk is used. The object of the invention is to provide at least 1i of ij to the support.
1 (:, halogenated emulsion H-I and at least 7 interlayers in two parts of the emulsion layer)
In the plate-making sensitizer made with 'l', it is non-existent! + each) '6
The melting time j+'C of at least 7 layers in kL- is 1
'C, the product J-curing agent was added so that the melting time of the silver halide 4IL agent layer was longer than the melting time of the silver halide 4IL layer.
A small molecule containing 4 (1-1 chemical reaction 1-4)
ノ, 11υ for plate making which has been converted to i] and this 111 for plate making! The moon is 6"!j)'(,=・J seeing(9(processj!ys L, after that, it is achieved by the power processing power method of processing the power processing j7. Interlayer in the present invention)'C; l Car upper layer F, 1.11
i'! 4) "C1") - Copper halide emulsion II' - -> A layer consisting of a water droplet colloid, which is also provided over the entire surface of the two parts. Such a non-Lllll(,l
'SiL part 19 old man/layer only is fine, depending on the situation!
Even if there is more than 1 layer L'q; Lt, it is not possible. In this invention, td rir ljj%) 11 silver halide ヱ [, agent j 111 is sensitized) °0 畦 silver halide t+'7f
- is a layer formed by dispersing in extrahydrophilic colloid, such extra-photosensitive halogenated ζ may be only 14 milk A11 layer 1 year old/layer, depending on the case, -21i4i or more "Z setting (Jl:
')' L is also acceptable. According to the present invention, the melting time of at least 7 layers in the upper part + r of the interlayer) is longer than the melting time of the silver halide emulsion layer IJ, the layer ir+'? This means that the MIE J two-part layer is more rigid than the emulsion layer J by 't4i < t+LQ +.' As a method for evaluating the degree of 11 to 1 of the 1-curved layer to 1iil', this graph; '(9 in the world.
! 'J It) l, I went to both cities (J It was the same car that caused 4 flea, Q, 5 using needle-shaped star flass,
Shima 1-) Net tensile strength is well known, but for the purpose of the present invention '1i14 valence, hardening 11.
I kept it at a constant temperature, then jumped inside.
l! The time in yL when (melts #:r), that is, 1ijl (+ne
c: Mi'), the 1jili value j- is ll
, it is also effective. The formula for melting time is 7" 0
θ, 2NNa (1 month for C) θ, 2NNa (month 1 It is M and t to be carried out in the Ifi liquid (however, it is not necessarily limited to this).The plate making month 1 feeling t/1 of the present invention is Item J' hardening agent and active vinyl, low molecular weight that increases ζ to 11 (1 pill!
1 At least 7 layers are i; i<)Y; circular halogenation 94.!
It is hardened to have a greater melt % It,'i than emulsion IP4. Sieving (' l1j Qing agent is I\i
Since it is a t molecule, it has a diffusion layer, so when 7115 is added to at least 7 layers of the 1-soil layer (interlayer), only that layer is selectively changed to 1, +jj. The 110 layer is cured with a low-molecular curing agent that has 4 activated tetrahinyl 11. The agent may be added to either the interlayer) 'a I'4' upper layer or the Emulsion 1n. In this case, the low-molecular-weight curing agent that makes up the viscous 1'l vinyl J4 diffuses into the upper layer of non-linear 94 to which the above-mentioned product 'f-1+Ji-forming agent is added. It will harden, so it will harden very strongly. 1￥11 molecules - curing agent /l'+ iJ: It is difficult to uniquely define the ILI fit of the low molecular weight 11 lycolating agent possessed by vinyl groups, and the 6i:l+M time of each layer is Measure Bl ((J' , +7-1- rl (preferably by the measurement method described in 1! O 2 particularly 1- larger than the melting time of silver halide), J, Use of sea urchin curing agent 11.1 It is preferable to set the molecular curing agent Ll!t';r used in the present invention.
1973-a 6r (, 1/5.s., British special M
r condolence/, 3.22, ri7/issue, Matatonkuni Q'! j A
'l-condolence 3. Otsu7/,)56n, Kino's i'Q+ +
! 'l, and l+, 84.1. Iurncss J,
Pot+racJier ”', I'bei'I+eo
ry o(tbe l'l+oLoB!rapbi
cJ! rocesS"l/lh ed, ('I', 1
1. James cd, ), 8'121mm m1lla
n, New York, Tough 7, Ill
) and 47°, CLA, (-:au+pL)el I,
L, I! , mountain + ntil ton, 1. s. Pontlccllo, “Polymeric Am
1nep n d Δnm+on i um Sa
It s” (E, J, (Joell+alse
d,) J’ergamon J”ress, New Y
ork/q7ri, ppJ,! /~J3.2,
r: (Has a functional thread that reacts with Zeraboon in any number position; it is a polymer. In particular, a polymeric curing agent with a molecule of 1.'l/10,000) This convex molecule 11! is preferably a primary compound having the general formulas (1), (II) and (Ill), and is particularly preferably a compound having the general formula (1). +A-)X <-CH2-C→,
(l)■ノS (,l 2- represents an ethylenically unsaturated monomer that can be combined with the monomer unit shown to the right. , In the formula, 1 is a hydrogen atom or / represents a lower alkylno having 6 carbon atoms, -. Q is lL+ -eU2-, -CO-N- [however, 1 also represents 1 to J, the same as above] or 70 from O carbon 11.
ij (- is either to ゛1 Leeren that a.
a divalent group having from 3 to 75 carbon atoms containing at least one bond, or 1 or l -(J-, -N-, -C(, )−. −8() −, 8()2−,
8 (J3. 1 also I I also II I also 1
l too]5(J2N, NC(JN
-, NC1J2 [1, l+1 represent the same as mentioned above] is any of the divalent groups containing at least one of the bonds /from/, which connects two anthrax atoms. It 2
represents a vinyl group or its 1 uil & form 'B Nosai, -CH=C)(2, -CH2CH2X. Represents a releasable group. In the formula, x and y represent mole percentage, and X is O or
y takes a value of / to 100. Ethylene tetraunsaturated monomer A represented by 8 in formula (1) (,441t'J, ethylene, propylene, l-butene, isobutyne, styrene, chloromethylstyrene, human dimethylstyrene, vinylbenzene Sodium sulfonate, sodium vinylbenzyl sulfonate, N, N, N-
Trimethyl-N-vinylbenzylammonium chloride, N,N-di'methyl-N-benzy-N-vinylbenzylammonium chloride, α-methylstyrene,
Vinyltoluene, gouvinylpyridine, λ-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, /-vinyl-comethylimidazole, monoethylene unsaturated 441 ester of fatty 1&lrf (e.g. vinyl acetate, allyl acetate), ethylene+41E unsaturated monocarboxylic or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate)
, maleic anhydride, esters of ethylenically tetraunsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hegycyl acrylate, hydroxyethyl acrylate, cy)'noethyl acrylate, N
, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate I/-), hydroxyethyl acrylate, chloroethyl methacrylate-1, methoxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, N
, N, N-triethyl-N-methacryloyl
J ~ ammonium I)-toluenesulfonate, N,
N-diethyl-N-methyl-N-methacryloyl mekinethyl ammonium % p-) luenesulfonate, dimethyl itaconate, maleic acid monobenzyl ester), ethylene monocarboxylic acid Amides of acidic acids (for example, acrylamide N. N-(N-acryloylpropyl)ammonium p-toluenesulfonate, sodium non-acrylamide-J-methylpropanesulfonate, acryloylmorpholine, methacryl'
1'Mido NlN-dimethyl-N'-acry[t-ylpropanediamineprobionate betaine, N,N-dimethyl-N'-methacryloylpronone diamine acedate betaine). Moreover, in 1 of the present invention, the combination is cross-linked]1. When used as a latex, in addition to the ethylenically unsaturated heptamers mentioned above, a heptamer having at least one or two copolymerizable ethylenically unsaturated groups (for example, hashivinylbenzene) is used as A. , methylene his'/''/ IJ lumide, ethylene glycol diacrylate-1, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, nembenthyl glycol dimethacrylate, etc.). Examples of R1 in 1) include E-i methyl, ethyl, zubur thread, and 0-hexyl group. QI: includes the following groups: 113 -C02-, -C(JN[ -J-, -C(JN-. J] includes the following groups: -('112Csu2(U112-
. ---(Z1120■ 2(zu(J 2c ト+2(+11 2-((:11□+5(fJJ2C1
1□011□-(-C'l+,,→,o(,'02('
ll2C112--(:lI 2 N11(:(>C1
l 2--(,:1I2NlllLnD(colll 2 (
-” II 2(-el12→3NlIC(J('ll
2CI+. -(Sho(Σ11゜→ 5 NIIC(ノC1
1゜('II 2-''ε(Il 2→,,t,NII
C(ノ(rl+2('+12 --CIl(J
CI2- -CI(,,CH□0C112CI.(,,'11□=
-C(JCI-42CH2- -(: l:l 2 L: (-) CH2C1-I
2-- S U ("H2C112- -Ct12SUC)12(,',tJ2--8(]2(
'll2(N12- -8(]2 (C 2 CIJ 2 δ02 C
tl 2 (-“!(2-8(J2C), 12(,'
ll 28() 2 (", II 2 (,'
It (S 112. (11 -S (J 3 Ctl 2 ('II 2 ("II
2-- 8 (13Cl-12C 2CHze H
2--S (No3 C112C) 12C (J 2 CIJ
+CH2--8(J2NHC1+2('(J2C[]2
CIIl-8(J2N11Ct-12CJ-12c(J
2C112CH2--N IJ C (J N HC1J
2 C[4z --C)12 N1ICLINl-1c
ll 2 (,:LJ 2--Nl(CCJ2C112
C112- -4: rlzNHC(]2 (,: l(2CH2 The 1 mo2 in the formula (1) contains the following groups. -Ctj=CLI2, -CI-12CI(2C,7
,-CLI 2 (,'ll 2 Ll r.-C)J2(shi112(month1.-C112C",1(2
02, cc, N3゜-(shi112clI2(J2CIF
3. -C1(z(:'L12(J2CCIIc7!
. /6/, No. 07, is a repeating unit that can be written in the following formula (b). -(A-) +C)-42(Es1 (J)
It is a monomer capable of producing ethylene or a seven-mer l (old compound). In the formula, x and y represent the molar fraction, Q takes the value of percent. 1t is a hydrogen atom or/and an alkyl group connecting 6 carbon atoms; 1mo' is =C1-4=C[-12 or -C142CH2X. Represents a thread that can be removed in the form of X depending on a group that can be substituted or a base thread. (linking group selected from isobutylene, etc.), 6 to 7.
Arylene having two carbon atoms (for example, a linkage p, s selected from phenylene, tolylene, naphthalene, etc.)
, or -C(J Z-5 or =C(J Z
N23-1 [Here 1 and 3 are / to 411? Alkylene with carbon atom f in il, or arylene with i from 6 to 72 carbon atoms, /) is 1 "rigid radical j"
- or NIJ). ] This is the good news of connection. Examples of A in formula (IIl) include the same as A in formula (1). As an example of l( in formula (11), C is 11 in formula (1), and the same example is used. 4.8 Formula (11)(, I is also an example of '), and It 2 in formula (1) Other preferred molecular curing agents include the same examples as in the British Kasu Revised/. Retract single 431
I am 7. 1 is also ■ In the formula, AtJ, the monomer shown to the right [(1st position and copolymerization 0
J is a hydrogen atom or an alkyl group having 3 carbon atoms; J is a divalent monomer having 20 carbon atoms; Conjunction, ζ (preferably in town=CON IJ
- or -c (J-bond'), number of carbon atoms containing at least 7 /~/,! (1) divalent group): X to active ester: X, y are molar fractions , X takes a value from 0 to 7J', y takes a value from j to 100, and ■11 is O or /. Examples of A in formula (III) include the same examples as A in formula (1). Formula (III) 0) It) contains the same thing as the example of 1 mo 1 of formula (1), and is written as "-". L in formula (■1) includes the following /[ group. -C(J N 14 C142-, -CU N I-I
CI-J2CLl2-. -CUNt4C112Ct(,C[(2-. -e(]NHCtl2(]-1zc[(2C
1, I 2C112-. -C(]Cl 12 CH2(JC(]CH2C1l
2-. -(゛() N1(C112(shi (JNI-IC+,
, +2−. -C(ノNIJCI[zC(JN)], CIJ 2
C(JNI-12CIJ 2-.-('() CL12-.-(:()N11(,'It 2 NHC(Jt'
ll 2 (GUH25CI-] 2 (,”H
2-. -('(JNIICII 2 (>CO(112L'l
l 2-lc. yS (Ill) 0) To X!・;t, <l: C
ノ+J-U/: c J, jζ or including * J anti). 02 10(ツ2(-”1I2cN -straight) 2
Ct, -12C(, + 2 C,2It s-(', (
J 2 ("It 2 CUNIII 2 -C0
2C:I42 (,,'(JC'li 3-C(ノ2
N=ClIC:I-13-C(ノ2 N=C(CI-1
3) 2-(,,:tJ2c112(,'H2H+・
-(゛(ノ2 (-'I+2t'l)
12 ('N3 -(,:()2CII2CII2(-')N -c
'113c' chisel ("113 on the tree) is used for light, 1', and 1 '7' 1. )
(with υ('', /[I,. /''1'-/ +C1l□(Σ11+81 UON) IC(CI'13)2C:11□5tJ3N
a1 - , 2 + (, :N 2c
ll-) x■ to (JNIIC(C)13) 2 (l[2S(]3
Na[J-3÷('112('I(→8!')INll(: (('113) 2 C1l
25IJ3NaP-4t ÷CH2C1t+x C0NHC(C:L43) 2(1-128(J3Na
+(-82(-11+ y
x/y =3//C(ノ(JC
HCH(JC(JCII.δ()2(for=Cf122(-n(2c++→,
x, /y=3//CUNHCII NF
IC'0C1120)+ □8021=cl(. +Cl12(I)+y
x/y=:J//('UNLIC)l
2 Ctl 2 C1l 2 N11('()C1f
2 CH2S U 2 (11J'll 21J-s
+('112cll→8■ 8s3 N a 1] - 7 4CI+2("th+8"('11C(C,C3)2c', IJ2.1(J3
Na)' g ((,,
'112(,,',tl+yC(J(JM +C',1I2CI-(-)y
x/y=3//C(, r
Nr-4COCH2(-2SLJ2CH=CI(2-
(CIl 2 ell-) yX/Yfu3//(゛(c)C1]2C11□()C(JCll □8()2C1
12C112(7-f CH2('H-) y
χ7y=37
i(,'0NIIcUel12(,'ll 2 SO2
(,142(')I 2tノ（JNI(CI(2C(
JCH2(”IJ 2 So 2 (112ell 2
C7 However, N1 is a hydrogen atom, a sodium source f'', and a potassium atom, and x + y are the molar fractions of each unit, and in addition to the above, jC<
xth 01. C Ishi Tazo, Y Toma/or 100 II
Take L). Typical vinyl sulfone groups or their precursors used in the present invention are as follows: Synthesis example / , 2 (J-chloroethylsulfonyl)-
Synthesis of propioylmexy)-ethyl acrylate Into the reaction vessel were added θOmg of tetrahydrofuran, t/-, t, lrf/, 3 of hydroxyl acrylate.
-(Add l-chloroethylsulfonyl phyto 722 and cool with ice water 1) While stirring,
From 0C to F, pyridine 3/. , 2f? /R dissolved in 100 mn of tetrahydrofuran is /. It was completed in 75 hours. After that, stirring was continued for 2 hours at room temperature, and the reaction sample was
2. Pour into ice water of JL and add 300ml of chloroform.
1 and extracted twice. - (After drying several layers of 1N with 41!1f sodium chloride, 2-(3-(chloroethylsulfonyl)-zolobioyloxy)-ethyl acrylate 7?woi', again. (Yield ratio) Synthesis example 2N-((j-(riUroethylsulfonyl)propioyl)amizmedel)-acrylamide, in a 2t reaction vessel, add distilled water/g00ml+, diluted sodium oxide , 2211?, Sodium carbonate, 7.7
Q? Add chlorine sulfonyl chloride 2 to 02, stir to dissolve in ice water, cool and add about 50 (2 parts) of chloroene sulfonyl chloride to 02 parts, J 1+.'11 parts to 1 part
・1, ta. After stirring the iq & q% I'lf acid/oP for about 75 minutes at 0C for 7 hours and filtering the precipitated crystals, the crystals were evaporated into ) I'1 was allowed to settle, and the liquids 2 and 9 and the top of the washing liquid were combined and placed in a 1C3t reaction vessel. In this, methylene bisacrylamide, 2 g t2, distilled water θml,
The solution dissolved in ethanol/ηO+nF was stirred for 30 minutes at about 100 ml while cooling with water, and the whole was left in the refrigerator for 1000 days to complete the reaction. The precipitated crystals were filtered. The sample was washed with 100 ml of cooled distilled water, and a monomer (seed crystal C1,2/R?) was obtained from the 20001 jθ chetanol water M solution.The yield was 4t5.
'%Met. (Analysis results, measured values, IJ: j,
/7, C: J7.90, N: F. 4tl,C
l:/2,jl) Synthesis Example 3 (Preparation of 3-(chloroethylsulfonyl)-probioyl)-aminomethylstyrene 1 Into a reaction vessel, 100 mQ of tetrahydrofuran,
Vinylbenzylamine, 2.0,/f, IJ ethylamine/1. ．． 7V, hydroquinone 0. /"?It was placed,
Cool with ice water and dissolve β-chloroethylnulfonylprobionic acid dichloride 36IVfa7.200
mg of tetrahydrofuran was added dropwise over 30 minutes. Thereafter, the reaction sample was left at room temperature overnight, and the reaction sample was dissolved in concentrated hydrochloric acid/jr. ! f to ice water/. ! Solu diluted with 1? The resulting precipitate was collected by filtration. This precipitate was mixed with ethanol, 200 mO, and water. 200 m
Reconsolidate from the mixed solvent of 9, Coro, g? The N-vinylbenzyl-β-gloloethylsulfonylprobiamide is used. (Yield j7%, min 4Ji result actual measurement value, l]
:j. 71. t, C: J3. Gua, N; 13, α:
10. Tata, S: / 0, Gua) Synthesis example Hiro / - (
(,2-(F-vinylben(nsulfonyl)-ethyl)
Synthesis of -sulfonyl)-3-chloroethylsulfonyl-j-furononol/,3-bischloroethylsulfonyl-copropanol/r7'? (
Synthesis method Japan 4'! Request a patent! /-/329.2 Risen 1
! <t), add methanol/1% distilled water/l, ψ
g ″ (1 to 1) While heating, add vinyl benyan sulfin l phthalate 329 to methanol / l / /
0 0 ml. , distilled water 100m9 to r valley 111'l
The liquid was added dropwise over an hour. then v6 °
While maintaining the temperature at C, continue to stir the mixture for 5 seconds, filter the resulting sediment, and remove the SSV. 2-(/-vinylbenzenesulfonyl)-edylsulfonyl-3-chloroethylnulfonyl [1 panol]. (Et-Jt
Section 9', analysis result actual measurement 1a, ) 4: 41! ,
a7, (:3ri,ffF,S:,2/.μ3) Further, an example of synthesis of a sieving +11 historicizing agent suitable for the present invention is given below. Synthesis example! Synthesis of BoJ'-(-2-(3-(vinylsulfonyl)-propimeyloxy)-ethyl acrylate-acrylamide-methylpronoξsulfonic acid sodium) (P-/) N,N-dimethyl Formamide Omo, 2
-(3-(chloroethylsulfonyl)-propimeyloxy)-ethyl acrylate/ri. ! ? , acrylamide-methylpronosulfonic acid, 23. jt? After degassing with nitrogen gas,
-(,2,,2'-azobis(7,&-dimethylvaleronitrile)o, aoy was added to the mixture and heated (tl, stirring was continued for 2 hours. Then, 2..2'- Azobis(,2,Hiro-dimethylvaleronitrile)0,.2F
After adding and continuing to heat and stir for 1 hour,! Cool to 0C and add carbonated soda 1.2? , triethylamine q, and ri2 were added and stirred for 7 hours. After stirring for 1 hour at ¥ temperature, the reaction sample was placed in a cellulose tube and dialyzed for several days, and the white polymer of 3j9 was lyophilized. (Yield: t%), the vinyl sulfone content of this polymer is 0.
, J' / :X 3 10 h1', / ? Met. Synthesis Example t Poly-(N-((3-(vinylsulfonyl)
Synthesis of sodium propioyl)aminomethyl)acrylamide]-co-acrylamide-no-methylpropanesulfonate (P-, 2), Synthesis example - No. , 13? , anrylamide no methylpropanesulfonic acid sodadata, /6ri1. t71)%
Add 0ml of ethanol aqueous solution and add O while stirring.
Heat to oC, add λ, co'-azobis(,2,ψ-dimethylvaleronitrile) (commercially available from Wako Junjijuu Kogyo ■ as v-g), and further add 3
After 0 minutes, get the same thing 0, / f jJIJ,
Heating and stirring were continued for 7 hours. After that, IJ with ice water
Cool to about /o'C -C1 triethylamine! . Add j2 to 10 mff of ethanol, stir for 1 hour, pour the reaction sample into 1 liter of acetone with stirring, collect the precipitate by filtration, 2. I humiliated P-co from Group 2. The yield is gs%, and the yield is tW [η3=0. ．． 2J7, vinyl sulfone a
Fa14 o, cy, 3″A/o current/
It was 2. Synthesis Example 'y Synthesis of poly-((J-(chloroethylsulfonyl)-propioyl)-aminomethylstyrene-co-acrylamide-methylpropane sulfonate (,t'-/&) In a reaction vessel, < 3-(vinylsulfonyl)-propioyl)-aminomethylstyrene/j, 2, acrylamide-λ-methylpropanesulfonic acid sodium, 2J, l, f', N, N-dimethylbormamide 7tm9 was added, and nitrogen gas was added. Deaeration (, zo
0c+-heat to 1.22.2'-Azobis(,2,ψ
-dimethylvaleronilyl) o, 7s? Processing, heating, and stirring were continued for 3 hours. Then N, N-
Dimethyl formaldehyde 2. Add tn+Il, add triethylamine 6,/2 dropwise at room temperature, continue stirring for 7 hours, filter and pour the filtrate into acetone 100rnI, collect the formed precipitate by filtration, dry, 3t, 2V light yellow polymer is the first prize. (yield tag %), the vinylnurphone content h1 of this polymer is o, g'o'y, io''
The actual number was /9. Synthesis Example Poly-(/-((,2-(guvinylbenzenesulfonyl)-ethyl)-sulfonyl)-3-chloroethylsulfonyl-,2-buA nor-co-acrylic acid) (1'-77) IN to the synthesis reaction vessel of
N-dimethylformamide 300 +1111, -1 (
/-vinylbenzenesulfonyl)-, ethylsulfonyl-3-chloroethylsulfonyl-λ-propertoolμ0
, / f, acrylic acid / 3゜0? After heating with nitrogen gas and heating to 70'C to 1.2+, 2'-
Azobis (,2, Hiro-dimethylnogleronitrile) 0.
! 39 and continued heating and stirring for i, s hours. after that! 9. Pour 0.33P of 2'-azobis(2,II-dimethylvaleronitrile) into the IJ and continue to heat and stir for 7 hours. Cool to room 11A for 11'J. From, sodium methyla i・,!ξthimethanol solution #
The reaction sample was placed in a cellulose tube, dialyzed for 2 LJ, and lyophilized to give 309 pale yellow poly-7-. . (Yield: $56%) This polymer contains vinyl sulfone.
1 is 1. It was μx10/1. Incidentally, the molecules 1d of the polymer curing agents synthesized in Synthesis Examples j-f were all less than 1 d. The low molecular weight curing agent having an active tetravinyl group used in the present invention includes an acryloyl curing agent and a vinyl sulfone curing agent. It is preferably a compound having a molecular weight of 1000 or less. jli to this invention! Examples of acryloyl curing agents that are widely used include compounds having at least two acryloyl groups in the molecule, and compounds in which one carbonyl group is linked to two vinyl groups (for example, the following Exemplary compounds A-<z) are also included. Next, I will give a representative example. A-/ (,'H2=CI(-CONl(-CH2CH2-NH
C(JCIJ=(II□A−λ−J A−gCtl 2=CI−1−C,0−CIJ=CH2
. 7.20, British special A' + Tata Hiro 1g Otsu No. 7, West German clock clock No. 7.2,113, special public Shoti tr -/ or r
It can be synthesized according to the method described in ';-+i, 4/, 7-/3/≠/, etc. As the molecular curing agent for modifying the active vinyl yarn used in the present invention, a vinyl sulfone-based low molecular weight curing agent is particularly preferred. Many vinyl sulfone-based low-molecular curing agents are known in the field of abrasive materials, and any of them can be used in the present invention. For example, American clock 3. t/
,ri0. No. 71, No. 3, gll, 2, Kou No. 16, No. 3,1//, No. 117, No. 3, 3,1411゜g7
．． No. 2, 3. g! θ, No. 637, 31g Otsu 1, . 2
! No. 7, same a, ovg, ays bow, same"+/341
, No. 71, No. 73, No. 770, No. 71, /37
, 0g, 2+i'4, hardness, /J7, 4tqO,
41. /11.2.19'7, 4/, /71,9
Vinylsulfonylalkyl compounds with carbon atoms bonded with heteroatoms, 1
``Midoya Young is a vinyl sulfone compound bonded to an ester group, )! A heterocyclic ring such as J azine ring
In addition to vinyl sulfone compounds such as
(For example, the following exemplified compounds V-JJ') can also be used. On the other hand, the following are typical examples of the low molecular weight curing agent having active vinyl 2& used in the present invention. Compound example'l/-/ CHz=CL4S(JzCL12C[(C1(2sS2
C1,i = C112(Jll ■-2 (JI-1(Jl-1 -3 C1(2=CI-J・802C[I□C)J・(Go11
□CHC[(2SLJ2C'[l=C1121 (Jt1014 -g (JllI (J-1 -5
■-6 (CI-12=CIJ-8tJ2CHI2CUNII
U2ell□-7 (ci-1□=CIJS(J2C1l□('UNI-f
C112→2■-g ((:ll□-=(Itso 2(1-1□e(JNl
((-112→2(:112V-ta)' r:0C112S
(J2(,'1l-C'll□(J V-/,! ■-73 C11□-('11802ell.S(F2CH=(
'II □■-/ gu('It -CIl, S(J 2('ll □ell
2S(ノ2('Ij=C11. -- -1s Cal -('II・1)(J2(koll2('I(2
('N25t)2(-'1l=(田.-V-/6-77 C2H,('("II □5()241-(ko11□
),. -ig CH(', H8(J2CH□C11("tl 2SO2
c'1l=cII□- SO('1I=('+12 V-,!/ (C1422CIJS(J2C112) 4('>
shi shi
〉1 1
1〉
〉? 4

(J-cho
II〉
hmm >>> . １ 工、L ′-） １ 工 連 h
○Narukamachi ~)1 1 1
1〉〉C-3 g C1l = CH8 (J Ull-C11222-3511 1. Addition method of polymer curing rill is water or a) 1. Curing Wll 'a? Add interview ID≦ to the group whose degree of Izization you want to control. The low-molecular curing agent 1 containing active vinyl groups is a non-photosensitive layer containing a surface molecule and a curing agent. Butomata Toko emulsion 1fd liJ≦
The added C may be diffused into the entire layer. The diffusion-resistant polymer curing agent is
Add the curing agent according to the ftt of the reaction yarn. In this way, at least seven layers of the upper layer (interlayer) are deposited in selected amounts (by curing -C11 !112 force fluid &Id 11-l! II
It becomes possible to provide anisotropic i-generation to the speed stage that converts and dissolves ξ. That is, at least 7 layers of "non-photosensitive" 2 parts j1.1 have a silver image formed thereon.
+Since it is hardened more strongly than the silver germide emulsion layer, j,
It force liquid is ++ of silver 11i11 statue! ! The silver l11. lI song 11111 Direction C resulting in reduction of image area Nu-11. The silver image will be attacked more from the -C horizontal direction). i no f means 'I!' of 1 elephant in Kiuremei! , '2 Reduction of image area for low IQ 11] Increasing Znawa l- and reduction force +l+ becomes "J" ability.If the upper layer of photographic printing material C is hardened more strongly than the lower layer, When high-temperature processing is performed with a degraded processing solution, a net-like pattern called reticulation may occur [R, J,
CoxNIRiL, Tojo et al. Yen + otographic Ge1atin (/
P72). Academlc Press, P 4'ri~6/]
In the present invention, such reticulation can be prevented by containing polymer latex in the gold, non-photosensitive 1'1-, and Jz portion layers. In the present invention, the polymer ditex used for the non-photosensitive upper t', +s M is, for example, US Pat.
7.2. /AJ issue, times 3, 3 KoJ, λza issue 4, same 3゜hiro//, ri 77 issue, same, ? ,,? //, 5'/, No. 2, No. 3,! , 2! ,/,, No. 20, Research Disclosure (Research Disclosure)
e) Ht: Acrylic acid ester, Nisdel methacrylate, as described in A/Resili<i>s'o July 2010); . Things that are good for cows are methyl acrylate, edyl acrylate, pugol acrylate,
Alkyl acrylates such as methyl methacrylate and ethyl methacrylate, homopolymers of alkyl methacrylates, or copolymers of these alkyl acrylates and alkyl methacrylates with other vinyl polymers, such as acrylic acid, N-methylolacrylamide, etc. Examples include. The average particle diameter of the polymer latex used in the present invention is preferably in the range of 0.001 to 0.001/μ, particularly 0.0.2 to 0.0000. /μ. By using such a polymer latex, the occurrence of reticulation can be extremely effectively prevented. Furthermore, among the above polymer latexes, the glass transition point ('r
Latexes with high g) are preferred for further improved surface 1 adhesion performance. It is preferable that In' has a Tg of at least room temperature. For example, hydrates of homovinyl polymers such as methyl methacrylate, ethyl methacrylate, and styrene, or copolymers of these vinyl polymers with other vinyl polymers, such as acrylic acid, N-methylolacrylamide, etc., are particularly suitable. preferable. The amount of polymer ditex to be added is j to λooc4 per weight of hydrophilic colloid in the layer to be added.
Person o is preferable. Specific examples of the polymer latex used in the present invention (1) are shown below, but are not limited to these. OR knee CH3, -C2H51-C4H9R L-4t CHa 0CHa 0H (x/y=ri3/7) OCHa 0H (x/y=ri3/7) -1 (X/I-9,7/7) CH3L , -7 0 (x/y=5'3/7) -4 Hs ■ (x/y 3/7) CH3 (x/y/z-3/3/g) Li. Ha 0 CHs OHN)F(J-i20H(xl
y/y=! PJ/J74t) L-//CH3 Synthesis example Polymer latex (methyl methacrylate) 10o equipped with gas inlet pipe, reflux condenser, and stirring device
In a three-necked flask, add 2 tOOml of distilled water.
710 in a solution of sodium lauryl sulfate of 2.
．． Of methyl methacrylate was emulsified and dispersed, and ferrous chloride and tmLl? added. Keep the indoor bath at tooc:,
0.0ml to 2oml distilled water. After dissolving ≠/2 potassium persulfate and further dissolving 0.7AV sodium bisulfite,
Oml of 1N ammonia water λ was added, and this was added as f: a polymerization initiator. After 1 hour, the same polymerization initiator was further added and post-polymerization was carried out for 2 hours. After cooling, filter through thin filter paper to determine the concentration/! , weight ratio, particle size 0.0
≠μ, pT-IA, /3 protein color MebuI methacrylic acid meburu, I jellymer latex can be synthesized using the present method. As the hydrophilic colloid used in the photosensitive upper layer and the photosensitive halogenated emulsion layer (d-gelatin is preferred), gelatin is subjected to so-called alkali treatment (lime treatment) in which it is immersed in an alkaline bath before gelatin extraction during its manufacturing process. Gelatin, acid treated gelatin soaked in an acid bath, also 1.1BullSoc Scl Photo Jap
As described in anJA/J, page 30 (/4J), any of 7) fermented gelatin, derivative gelatin, and modified i<t gelatin may be used. Furthermore, in addition to the above-mentioned gelatins, high-viscosity gelatin, high-jelly-strength gelatin, dual-soak gelatin, etc. may be used as the gelatin used in the non-photosensitive upper layer to control the diffusion of the reducing solution. can be done. Hydrophilic colloids other than gelatin can be used in conjunction with or in isolation from the gelatin. For example, graft polymers of gelatin and other polymers, albumin, casein-like proteins; sugar derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose derivatives, sodium alginate, and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to the above-mentioned hydrophilic colloidal binder (eg gelatin) and polymer latex, the non-photosensitive upper layer of the present invention contains surfactants, antistatic agents, matting agents, slip agents, colloidal silica, gelatin plasticizers, etc. It can be made to contain oxidizing agents, etc. As a matting agent, polymethyl methacrylate, silicon dioxide, etc. Particles with a culm of /~10μ, ~j p are preferred. Matting agent 1171 may be added to a layer below the non-photosensitive upper layer, or may be added to a coating solution containing a polymeric hardener. The dry thickness of the non-photosensitive upper layer of the present invention is 0°3~j for the entire layer.
It is preferable to apply the coating so that the thickness is 0.3 to 3 μ. The photosensitive material for plate making in the present invention (/i, as mentioned above, is a photosensitive material used in printing halftone images and line images by photolithography in the printing industry, and its types and Although the performance is not particularly limited, the most common photosensitive material is a high-contrast photosensitive material such as a so-called lithium film. The silver is not particularly limited, and silver chlorobromide, chloriobromide parent, iodine, silver oxide, silver bromide, etc. can be used, but in particular, silver chloride can be used in an amount of at least to molt (preferably 7j molt or more). Silver chlorobromide or silver chloroiodobromide containing 0-j mole of silver iodide is preferred.There are no restrictions on the morphology, crystal habit, size distribution, etc. of the silver iodide grains, but the grain size θ
, 7μ or less is preferable. Silver halide emulsions include gold compounds such as chlorauric acid salts, gold trichloride, etc., metal bases such as rhodium and iridium, sulfur compounds that react with silver salts to form silver sulfate, stannous salts, and amines. It is possible to increase the sensitivity without making the particles coarser by using reducing substances such as the following. Further, a salt of a metal group such as rhodium or iridium, or a blush 14y A+'r iron compound may be present during the physical ripening of silver halogenide grains or during nucleation. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used for the purpose of supersensitization. It is used if Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are listed in Research Disclosure (Re5).
7. Volume A
/7J4tJ (Published in February /77r) Page 23 ■-5
It is described in the section. V-hydroxy-t is used as an antifoggant in photographic emulsions.
-Methyl-/,! , 3th, 7-chitraazaindene,
3-Methylbenzothiazole, /-phenyl-! - Many heterocyclic compounds including mercaptotetrazole, mercury-containing compounds, mercapto compounds, etc., as well as JP-A-4'P-r
ioλhiro, 30-4304. Same jtO-/F Hirokota,
Compounds well known in the art can be used, such as those described in US Patent No. 3°RZO, T3R. The photosensitive silver halide emulsion layer of the present invention contains coating aids,
Surfactants can be added for the purpose of improving photographic properties. Surfactants 7 [7] Natural surfactants such as Zabonin, nonionic surfactants such as alkylene oxide "ide" series, cricidol series, etc., carboxylic acids, sulfonic acids (for example, US special W [3, Hiroshi/!, 6 ≠ surfactant described in No. 3),
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid ester groups, and phosphoric ester groups, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric esters of amino alcohols are preferably used. The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 or more carbon atoms, such as ethylene oxide, propylene-/, 2-oxide, butylene-7,
A polyalkylene oxide consisting of at least 10 units, such as λ-oxide, preferably ethylene oxide, and water, a 11Fr1IJj group alcohol, an aromatic alcohol,
It includes condensates with compounds having at least one active hydrogen atom, such as fatty acids, organic amines, and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, as polyalkylene oxide compounds, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, realkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) esters, polyalkylene glycol esters, polyalkylene glycol fatty acids, etc. Polyalkylene glycol amine version 1 Polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, etc. can be used. Specific examples of polyalkylene oxide compounds preferably used in the present invention are as follows. Polyalkylene oxide compound example 1, HO(CH2CH2O)CH2-C1z)tz! l0(CH2CH20)lsH&
C3H17CH:CHC8H160(CH2CH20
) 11) H5, Ctt) tz3cOO(CJtzCI-
(zO)so)t6, CI IH23cONH(C
H2CH20hsI(&C14H29N(CH2)
(CH2CH20)24H9, H(CH2CH20)a
(CH2H20)b(CH2CH20)(, H3 a + b + d : jθ b: a + c = 10:?
, ri No. 77, 3.4'//, ri/, No. 2, same j, /
lI2. ! fl, I, same 3,3λ! , λgt No. 3
．． ! r'17, 6.3'0 Kano, 'FF Kouakihiro J--J-
J'J' 11. It can be included for the purpose of improving the dimensional stability of monthly yield, improving the physical properties of the film, etc. In the photosensitive silver halide emulsion I of the present invention, the colloidal binder of the colloidal binder is //, 2) or more in 2 or more copies. Misfire [Going to Jll at 11, A': In addition, it may be V~1 or more. (Ql, 4ba feeling) In II'1, where the halogenated emulsion layer consists of two layers, 2 layers; 1) 1-silver halide/ It is more preferable that the amount of the aqueous colloid binder is 1/l or less, and that the photosensitive emulsion layer of the soil layer contains a hydrophilic colloid binder more effectively than the lower emulsion layer. In addition, it is preferable that the coating output of silver halide is 1, calculated as silver plate/per square meter, θ~6.07, especially i,s-≠6oy. This is particularly noticeable when the amount is small.For curing of the photosensitive silver halide emulsion layer, it is preferable to use the above-mentioned low-molecular hardener, but in some cases, the above-mentioned polymer hardener and low-molecular hardener may be used. As the support for the photosensitive material for plate making of the present invention, polyester films such as polyethylene terephthalate film and cellulose ester films such as cellulose triacetate film are preferably used.The present invention In order to obtain an image, the light may be provided using the usual methods: natural light (sunlight), Dungesten lamps, fluorescent lamps, mercury lamps, xenon, arc lamps, carbon arc lamps, xenon lamps. Any of the various known light sources such as a flash lamp or a cathode ray tube flying spot can be used. More like a furnace, 9 lights, such as a canon flashlight or a cathode ray T.
Exposures of 10 to 10 seconds can be used, or exposures longer than 7 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Regarding the development procedure 1 and processing method of the photosensitive material for plate making of the present invention,
T:? The present invention is not limited to 1-1, and any of those generally used for processing photosensitive materials for plate making can be used. k Shima Tl1l Banken Isamu: Kehi】Mountain/g 0c to jOoC
Between Beba Luka, IR 0cx low? R,rr''
-4fi p, J-, soo °c'1 temperature above 〃〃〃゛゛゛゛゛゛゛. are dihydroyarnbenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminephenols (such as IldiN-methyl-p-aminephenol), l-phenyl-3 - pyrazolines, ascorbic acid, and as described in U.S. Pat. No. OA 7,172/;
Z, 3. Element 1ζ1 compounds in which a II-tetrahydroquinoline ring and an intrene ring are condensed can be used alone or in combination. The developing solution generally contains other known preservatives, alkaline agents, buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color conditioning agents, development accelerators, surfactants, erasers, etc. It may also contain foaming agents, water softeners, hardeners, viscosity-imparting agents, and the like. The so-called squirrel developer is particularly preferably used in the present invention, and it basically contains ortho- or para-dihydroxybenzene, an alkaline agent, a small amount of free sulfite, and sulfite ions. It consists of Zuffer et al. The ortho- or )ξ-radihydroxybenzene used as the developing agent can be appropriately selected from those well known in the field of photography. Specific examples include hydroquinone, croconohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone,
Tip 3-Dichlorohydroquinone 1.2. Examples include j-dimethylhydroquinone. Among these, hydroquinone is particularly practical. These g+, (<p main'!F': k, l: alone,
It is also used in combination. (The amount of image agent added is)
J (1 image solution/l portrait l~100, good bite r; l:
Do J~ioy. A sulfite ion buffer is used to keep the sulfite concentration in the developer almost constant.
%+, acetone submerged < iKe sodium hydrogen acid Junka 1/
Sunoki Ketone-Bisulfite alkali addition'l? , 4
, carbonyl-bis(,2-hydroxyethyl)amine methanesulfonate (1".;
and acid-amine condensation products. Use of sulfite ion buffer is developer solution/per unit/3 to/302
It is. To the developer used in the present invention, an alkali sulfite salt such as sodium sulfite is added to concentrate free sulfite ions.
The fee can be I. Addition of sulfite rv salt n:
]Usual liquid per liquid! It is generally less than 1, particularly preferably less than 37, but of course it may be more than jl. It is preferable to contain a bromide such as (bromide) as a development regulator.It is preferable that the alkali chloride is added in an amount of 0.0/~/θ7, preferably 0./~j2 per developer. An alkaline agent is added to bring the pH of the solution to 7 or higher (7.7~). For suitable developing solutions, sodium carbonate or potassium carbonate is used as the alkaline agent, and There are various amounts of addition.As the fixer, those with commonly used compositions can be used.As the fixer, thiosulfate or thiocyanate I5 or I5, which is known to be effective as a fixer, can be used. An organic sulfur compound can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, a conventional method can be applied. It may be done depending on the method of production, or it may be carried out using a developing machine.There are no particular restrictions on the method of assembly and conveyance (for example, roller 141 Ishinomaki, belt conveyance). Instead, it is possible to use a transport type automatic developing machine used in the industry.
l' J T O+2 j + 77ri No. 3゜07
11.0.21. 3. i, z, z, ort issue,
43, /417. ! ! / issue, same! ,/! &,/No.73,
Same 3. ．． 22g, jjt A issue, same! , ! 73, de/wo issue etc. can be referred to. Regarding the silver halide emulsion layer, other layers, support, processing method, etc. of the photosensitive material for plate making of the present invention, please refer to Research.
Disclosure magazine/7A@, 2λ~, 2g pages (79
You can refer to the description in July 1971 (February 1971). There are no particular limitations on the reducing fluid used in the present invention, and for example, those described in "The Fist Theory of the Photographic Process" by Mies mentioned above can be effectively used. That is, reduction of strength of permanganates, persulfates, ferric salts, cupric salts, ceric salts, red blood salts, dichromate groups, etc./7
V1 minute alone or in combination, and if necessary, an inorganic acid such as sulfuric acid, an alcohol, etc. A reducing solution containing a 7't silver chloride solvent such as a rhodan salt, thiourea or a derivative thereof, and, if necessary, a weight acid such as sulfuric acid is used. 16, and furthermore, it is possible to contain a compound having a mercapto group as disclosed in Japanese Patent Application Laid-open No. 11-16, 2003, No. 11-1 in Japanese Unexamined Patent Application, First Publication No. 16-16, 2003. There are no particular restrictions on the composition of the power fluid and the processing conditions (temperature, time, etc.), and those skilled in the art can appropriately determine them. Regarding the power reducing fluid and the power reducing method r1, please refer to the descriptions in the following patents. JP-A-J/-/4'073j, J, 2-#Ill/2
, same j3-/4'ri O/, same j4t-//ri, 2J7゜same j Hiro-/l ri, 237, same! Ma-u, 24jJ-1 giant 1j! -, 224'4', same jj-/7/λ3, same 1.
! r-7riIl, 41.4I1 J-J-4/3≠g The present invention will be described in more detail below with reference to Examples, but the technical scope of the present invention will be explained in more detail with reference to the following Examples. There are no limitations, but various types of fruit may be in a li state (sheep is in a state of 01?). Example 1 A multilayer structure was formed in which each layer of the following formulation was sequentially laminated from the support side on a polyethylene terephthalate film base containing undercoat M. Samples coated using the simultaneous coating method/~/3
I made one piece of gold. Layer-/ )・Silver Rodanide emulsion layer,! -0moJl, % silver chloride, /ri, jmonoto silver bromide, θ, jmo/I/% (i) silver iodide)
Then, a silver chloride emulsion was prepared by sensitizing it by gold sensitization in the usual manner (the gelatin contained in this emulsion was) compared to the silver chloride emulsion. Atatsu1'c)
. This emulsion contains 3-carboxymethyl-6-C-2-<3
-ethinoto-thiazolinidenephethylidene]0-danine (spectral sensitizer), ≠-hydroxy/, 3. ja, 7-
Citradeindene (polyoxoethylene nonylphenyl ether containing stabilizer Otori Ethi L/7J°*', 'do1MkjO, Patent No. 111J 41!-J' 3
After adding 1 liter of polymer ditex described in the manufacturer's prescription 3 of issue 1, add low-molecular curing firmness as shown in Table 1 to make the coating silver amount i, 01/m2. Apply 7 coats like this. 1), 2) Dry the first non-photosensitive upper layer and apply a wall cloth to a thickness of /μ. Layer-, f-th, 1! i commercial light note upper layer (#soil layer) dry'M
Apply oil so that the film thickness is OIt. Next K each sample industry, 2joC1bo%R1-(,7s%I
Store it at a humidity of L11, store it over time, measure the swelling expressed by the following formula in water at 2j0C, and find the l-1 number (after application) at which the degree of swelling is constant. Ta. Furthermore, I#:jYun Akihiroj-, f33/Specification Example 1
Measure the feeding properties over time using the same method as above, and calculate the relative sensitivity and the number of days (after application) for which the sensitivity (IJ) decreases.
child. Obtained 1 result 2? j<, 1゛ shown in Table 2. In the process, the above-mentioned method was used to remove the interlayer) with the upper layer and the photosensitive layer
・Measure the melting time of the emulsion layer for the first time.
J-8 Sample number in Table 2, / indicates a low molecular curing agent other than the present invention (
Glyoxal alone exhibits fairly fast curing performance, but when a polymeric curing agent is used, the curing rate is extremely slow.
Although the curing speed was faster when stored in C7J%It H, it was much slower than in the others. Furthermore, the disadvantage of rH is,
2ta 0C60chi Ji, big difference compared to 14 preserved item @
(In other words, it is highly dependent on humidity during storage). On the other hand, as is clear from the comparison of sample numbers 3 and 6, or j and 6, the sample of this study, 6t, has a slow curing process and its dependence on storage humidity is very small. ,
It can be seen that 100% of the ingredients have been added. father, activated t-tohinyl low molecular curing agent between layers) 'I, j'
I: The sample (common name 7) in which the additive was distributed and applied to the soil layer and the emulsion layer also showed similar excellent performance compared to Ao Lano 1. -U
There is. ej', -2 As is clear from Table 2, samples using combinations of curing agents other than those of the present invention, 1r, which has hard skin, has a strong humidity dependence, and re-Alfj properties are also extremely humidity dependent. However, when the curing agent combination of the present invention is used, it is found that the storage humidity dependence of the custom-made sample A is significantly improved. Next, apply the full halftone image to the above sample using the following method.
Shi1ko. Commercially available gray contact screen (ljO line/
A step wedge with a step height of O1/2 is passed through the sample, and white tungsten light is applied for 70 seconds).
7: <It glowed. 3. Using the developer described in F and q, apply this wiping F to
High temperature rapid development was carried out for λO seconds at g0c, followed by sterilization, washing with water, and drying according to the conventional method. Developer solution Sodium carbonate (/water salt //7 Potassium bromide 32 Hydroquinone
Co37/-phenyl-3-pyrazolidone
0. 7 Sodium sulfite 677
Potassium hydroxide //7 Add water
/l Irritated X point strips are pumped down h1-signature cerium-based reduction a()o ・(゛) soaked in l ~ rinsed with water for 1 time. Along the reduced force (1) fff acid white 1. Nicerium, 2j2
4 Sulfuric acid
307 Addition of water - (, / d Also, the same <14I, Lycoconutate strisobus, the following ethylene-aminetetroacetic acid amount,), iron-based reducing solution (
, 20° CI K ru 6ft, Water i'it)
l, 7 (-0 reducing liquid (11) ethylenediamineutoraacetic acid 2 zaj7 iron boo
L. Liu Person 1 Thiourea 6j7 Citric acid
toym acid (p
l-1o, 03-f' le:M) Add water to 11
/l The halftone dot area of the halftone dots t and rits obtained in this way is f and there are 7 halftone dots a1
The change in concentration of the stiffness was measured using a microdensitometer, and after the halftone dots on the halftone dot surface were reduced in force, the density of the 11 halftone dots was determined by placing each silk dot at j, 1 (: The area was determined, and the difference between the two was determined to obtain the reduced force I+]Tsukuda.Furthermore, as is clear from the third table 1, the sample (number -1μ, number -1μ, 6.7), the reduction force I13 is wide in all cases.In particular, the samples of the present invention (No. Hiroshi, Otsu, 7,
In g), there is no difference in performance between 1 and 1 (1-, that is, there is no dependence on the type of reducing fluid) between the reducing fluids ① and II, and the performance is extremely excellent in all 7 points. Moreover, the deceleration time is of reasonable magnitude. sword)
This ability can be said to be one of the outstanding features of the present invention. In addition, sample numbers l to g were subjected to the same development process as above,
The extent of reticulation after treatment was observed for each sample using a bell, but no reticulation occurred in any of the samples. Example 2 In the same manner as in Example 1, polymer latex and polymer curing agent were added to sample /3 as shown in Table ψ.
I changed everything and created 7c. For each distinction, the swelling degree and feeling [all Examples 1 and 1iiJ
The Il:I number (after application) at which the performance becomes constant was determined by setting d111 as shown in Table 6. The results are shown in Table 6. /3), it is clear that the dependence on storage humidity is small.Furthermore, even if the amount of curing agent added increases,
Similar to i1j1, the sample was reduced in strength using the reducing fluid (I) of Example 1, which showed extremely poor curing performance. Addition of the polymeric curing agent shown in Table 7/JDi' (c increases the melting time of the non-photosensitive upper layer, and as the curing increases, the paper strength increases by 1J). It's a shame, all the samples according to the present invention show good reduction performance.It is clear that the reduction time can also be increased by adjusting the amount of addition. .

Claims (2)

[Claims] (1) At least 7 layers of silver halide agent layer and part of the emulsion layer have at least 7 layers on the support.
Melting of at least 7 layers of the second layer) +1; sense of time) + (:, t/l
Thicker than the melting period 11!1 of silver halide milk '711III/i 1. cru J, sea urchin, commercial molecule hardening cutting activity fl
A low fraction containing a vinyl group -j-f+! , fi conversion 1111
and'+? (The feature is that it is 11ψ for Jl use and 4-
Halogenation for plate making 61! ! ']zuill, 1%)
'j; E, 4, +1. (2) A silver halide emulsion 1r/i with at least 100% of silver halide on the support and a small amount of 100% of the emulsion layer on a part of the emulsion layer.
11
・U conversion 6: IJ ink ) 'CC material Jr'r -C, non-linear > uI production] At least 51 layers of fil in the second part 114! l grouping time balding time C halogenated daughter emulsion 1 color melting Iy' (so that it is larger than time:
Halogenated plane for Taisaka 7fi point %j, 11 + iron) "C phase material" which was cured using a combination of A-1 molecule 1 + l Jj chemical formula vinyl sulfone group - r- hard 1 h 11 exposure·
1. Performing power reduction processing on the book image obtained by the current IW processing.
゛,〒〒〒Halogenization for plate making & lJ '+ firmness, feel) 16 materials * l sincerity treatment +'1. ++One method.