CA1046332A

CA1046332A - Light sensitivbe copying layer containing a halide of o-naphthoquinone diazide-4-sulfonic acid

Info

Publication number: CA1046332A
Application number: CA202,661A
Authority: CA
Inventors: Paul Stahlhofen; Rainer Beutel
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1973-06-20
Filing date: 1974-06-17
Publication date: 1979-01-16
Also published as: GB1463717A; AU7015774A; SE391404B; DK327274A; NO742238L; DK144345C; DK144345B; FR2234584B1; NL7407678A; ZA743882B; NL177353C; FR2234584A1; DE2331377C2; ATA508274A; DE2331377A1; JPS5036209A; ES427391A1; AR199440A1; FI58221B; US3969118A

Abstract

Abstract of the Disclosure This invention relates to an improvement in a light-sensitive copy-ing layer containing an ester or an amide of an o-naphthoquinone diazide sulfonic acid or carboxylic acid together with an organic dyestuff and which changes its color shade upon exposure to light, the improvement comprising that it contains, calculated on its total content of o-napthoquinone diazide compounds, 10 to 75 per cent by weight of a halide of o-napthoquinone diazide-4-sulfonic acid and, as the dyestuff, an organic compound capable of salt formation in a quantity of 1 to 50 per cent by weight, calculated on the same basis.

Description

LIGHT-SENSITIVE COPYING LAYER
- This invention relates to a light-sensitive copying layer which contains an o-naphthoquinone diazide compound as the photosensitive substance and a dye, and yields a visible image corresponding to the original after ~xposure to light.
It is known to use naphthoquinone-(1,2)-diazide compounds as photosensitive substances for the production of presensitized printing plates. Such sensitized layers are described in German Patents Nos.
854,890 and 938,233, for example. They have the disadvantage that the yellow naphthoquinone-(1 ,2)~diazide layers bleach upon exposure to llght to glve a faded, yellow llght-decompositlon product whereby the layer portlons not decomposed by the light (image areas) and the llght-decomposltlon products (non-image areas) can be differentiated only wlth dlfflculty. In practlce, this very often leads to defectlve coples, partlcularly upon exposure ln so-called step-and-repeat copy-lng machlnes where a dlaposltlve ls projected several tlmes slde-by-side on the prlntlng plate. Slnce the contrast between the image and the non-lmage areas on the prlntlng plate ls poor after exposure, par-tlcularly ln the presence of yellow light, as is necessary in copylng rooms for processlng photosensltlve prlntlng plates, lt is very diffl-cult to perform exact and space-savlng reglsterlng work.
It ls known to overcome thls dra~Tback ln that a colored organlc indicator dye ls added in homogeneous distribution to the llght-sensltlve layer, which dye changes its color in the pH range between

2.5 and 6.5. Furthermore, lt ls known that o-qulnone diazldes or naphthoquinone diazides wlth a leuco dye, after exposure, yield a colored lmage ln the exposed areas (compare U. S. Patent No.

3,669,658). But it is disadvantageous that the lmage contrast achleved 104~33Z
is not yet sufficient in many cases un~er conditions in practice. It is also disadvantageous that the image contrast again disappears upon subsequent de-velopment.
According to the present invention there is provid~d a light-sensitive copying layer containing an ester or an amide of an o-naphthoquinone diazide sulfonic acid or carboxylic acid, 10 to 75 per cent by weight of a halide of o-naphthoquinone diazide-4-sulfonic acid, calculated on the total content of o-naphthoquinone diazide compounds, and 1 to 50 per cent by weight of an organic dyestuff capable of salt formation, calculated on the same basis, which copying layer changes its color shade upon exposure to light.
Thus the present invention provides a light-sensitive copying la~er of the above-described kind, e.g. for the production of printing plates, conductor images, screen printing stencils, and photoresists, which layer, after exposure to light under an original, exhibits a reproduction of the original which is richer in contrast than that obtained with conventional copying materials of the sa~e kind and, after development with alkaline solu-tions, remains rich in contrast. This is achieved by starting from a known copying layer which contains an ester or an amide of an o-naphthoquinone diazite sulfonic acid or carboxylic acid together with an organic dyestuff and changes its shade upon exposure to light. The copying layer upon which -the invention is based contains, calculated on the total content thereof of o-naphthoquinone diazide compounds, 10 to 75 per cent by weight of a halide of o-naphthoquinone diazide-4-sulfonic acid and, as the dyestuff, an organic compound capsble of salt formation in a quantity of 1 to 50 per cent by weight.
It is ver~ probable that the halide of the o-naphthoquinone diazide-4-sulfonic acid present in the light-sensitive copying layer accord-ing to the invention is photolytically cleaved upon exposure to light and re-acts in a subsequent reaction with the organic dyestuff present, with change of shade, so that, after exposure to actinic light, a marked contrast between the exposed and unexposed areas is obtained. The colored areas not struck by ~ - 2 -,B

..
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-10~ 3Z

light ~image areas~, are resistant to the corresponding developer so that, after developing, also a colored reproduction of the original which is rich in contrast is obtained.

- 2a --10~;332 K-2230 The diazo group of the halides of the o-naphthoquinone~iazide-4-sulfonic- acid used in accordance with the invention may be in the 1- -or 2-position. Due to their better photosensitivity and easier manufac-ture, the halides of the naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid are preferred, however. Surprisingly, only the compounds with the sulfonic acid hallde group in 4-position yield the good image con-trast after exposure which is achieved in accordance with the invention.
Suitable dyestuffs are, for example, particularly basic dyestuffs from the group of the triphenyl methanes or from the group of the azines, 10 e.g. phenazines, oxazines or dyestuffs from the group of the anthra-qulnones, e.g. Crystal Violet (42 555), Methyl Violet 2 B (42 535), Malachlte Green (42 000), fuchsine (42 510), Crystal Violet carblnol , B base (42 555: 1), parafuchsine (42 500), Sudan Blue G (61 520), Acilan Brllllant Blue 5 B (42 740), Acilan Violet S 4 BN (42 640), Astradiamond Green GX (42 040), Rhodamine B (45 170), Samaron Blue GSL (62 500), Vlctorla Blue B (44 045), Allzarine Direct Blue (62 055), Victoria Pure Blue BOD (42 595), Brilliant Green (42 040), Nil Blue BX (51 185), Neutral Red (50 040) and Rhoduline Pure Blue 3 G (51 004). The num-bers in brackets mean the C. I. constitution number used ln the five-20 volume work "Colour Index", 3rd Edition (1971, London) for identifying the dyestuffs.
Most distlnct is the desired image-wise color contrast of the exposed layer when the dyestuff contained therein is red, blue or green.
Such dyestuffs therefore are preferably used.
As the photosensitive substance, the copying layers, in addi-tlon to the hallde of the o-naphthoqulnone-diazide-4-sulfonic acid, - contain one or more of the above o-naphthoquinone diazide compounds.
Their production is described in German Patents Nos. 854,890; 865,109;
~T~

104~33Z
879,203; 894,959; 938,233; 1,109,521; 1,114,705; 1,118,606;
1,120,273; and 1,124,817, for example.
The copylng layers of the invention may contain, in known manner, resins, plastlcizers, and other conventional additives and auxlliaries usual for light-sensitive layers. The resin content may be considerable and may amount to several hundred per cent of the total content by weight of the o-naphthoquinone diazide compounds, for example .
As copylng layer supports, there may be used those conven-tlonal for the reproduction methods concerned, e.g. plates or folls irom metal, such as alumlnum or zinc, with correspondingly pretreated surfaces; furthermore multi-metal plates, e.g. chromium/copper, chromlum/copper/alumlnum, chromlum/copper/zlnc; furthermore paper, plastlc fllms, fabrics suitable for screen printing, or metallized plates of insulating material.
Wlth the same content of organic dyestuff capable of salt for-matlon ln the copylng layer, the image contrast is the more distinct the greater the quantlty of the halide of o-naphthoquinone diazide-4-sulfonlc acid wlth respect to the total content of o-naphthoquinone dlazlde compound of the copylng layer. Copylng layers with a very large quantlty of hallde of o-naphthoqulnone diazide-4-sulfonic acid have a low storability, particularly when stored in an atmosphere of hlgh humldlty. Therefore, the portion of halide of o-naphthoquinone dlazlde-4-sulfonic acid, ln accordance with the invention, is limited to a maxlmum of 75 per cent by weight, calculated on the total content by welght of o-naphthoquinone diazide compounds. An increase in the quantlty of hallde of o-naphthoqulnone diazide-4-sulfonic acid, furthermore, entails the disadvantages that less prints result and that ~O~ 33Z K-2230 the gradation of the copying layer becomes softer which, in most ca se s, i s undesirable . - Further, the copying layer is more readily sub- -~ect to damage upon excessively long action of the conventional alka-line devclopor solutions or upon the application of excessively alka-llne developer solutions. It is therefore most advantageous to main-tain the content of the halide of o-naphthoquinone-diazide-4-sulfonic acid, calculated on the total content of o-naphthoquinone diazide compounds, in the range from 10 to 50 per cent by weight.
The image contrast after exposure to light and particularly also after development, as is to be expected, is more distinct the greater the content of dyestuff, to be used in accordance with the invention, ln the copying layer. In the case of dyestuff contents below 1 per cent by welght, caiculated on the content in the copying layer of all o-naphthoqulnone dlazlde compounds, the image contrasts after develop-ment, however, are very poor: ln accordance wlth the inventlon, the content of dyestuff thus should be at least 1 per cent by welght of the o-naphthoqulnone dlazlde compounds. A distlnct image conkast after exposure, as well as prior to and after development of the copylng layers, ls obtained when they have a content of dyestuff of at least 5. 0 per cent by welght, calculated as above. Slnce a considerable dyestuff content of the copylng layer ylelds no advantages but, lnter alla, the dlsadvantage that the copylng layer requlres longer exposure tlmes than wlth a lower content of dyestuff, the maxlmum content of the dyestuff, ln accordance wlth the invention, should be 50 per cent by welght, calculated as above. It is more advantageous, however, to have not more than 30 per cent by welght of the dyestuff in the copylng layer, calculated as above.

By use of the copying layer of the invention, it is possible for the first time to obtain, in the positive-working copying layers known for many years, a distinct color change in the exposed areas by expo-sure even when the copying layer has a full inherent color due to the dyestuff contained therein. Thus there is obtained an image rich in contrast which, also in the case of yellow illumination, distinctly con-trasts with the unexposed areas.
After the removal of the exposed parts with an alkaline devel-oper, there also can be seen a stencil rich in contrast corresponding to the original. Film edges and register marks also copied and which must be removed or corrected after development thus become more dis-tinctly visible. There is thus no need to dye copied film edges to make them more easily visible.
In the following examples, 1 part by volume is 1 ml when 1 part by welght ls 1 g.
ExamPle 1 1.5 parts by welght of the esterlflcatlon product obtalned by condensing 1 mole of 2 ,4-dlhydroxybenzophenone and 2 moles of the chlorlde of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acld, 0.75 part by weight of the chloride of naphthoqulnone-(1,2)-diazide-(2)-4-sulfonic acid, 0,35 part by welght of Crystal Vlolet, 6.5 parts by welght of novolak (softenlng point 112 to 118 C;
content of phenolic OH groups 14 per cent by weight), 0.45 part by welght of polyvinyl butyral, and O . 75 part by welght of plasticizer, e . g . phosphoric acid trl-(,13-chloroethyl)-ester, .

are dissolved in a solvent mixture of 80 parts by volume of ethylene glycol monomethyl ether, and 15 parts by volume of butyl acetate.
An aluminum foil roughened by brushing is coated with this so lutlon .
The thus obtained photosensitive printing plate has an intense-ly blue colored copying layer. After exposure thereof to light under a diapositive, the unexposed areas of the layer remain intensely blue colored, whereas the exposed areas of the layer appear only slightly colQred to almost colorless. The image of the original thus can be seen with a good contrast so that it also can be distinctly recognized ln aLI details under yellow light.
If, ln the production of the printing plate, the quantity of the chloride of naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid in the coatlng solutlon is eliminated or substituted by a correspondingly lncreased portion of the above esterification product, only a poor contrast appears, after exposure of the printlng plate, between the exposed and unexposed layer areas so that the image, particularly under yellow light, can be recognized in all details only with diffi-culty.
For the production of a printing form, the exposed printing plate is developed in known manner with an aqueous alkaline solution, the exposed layer areas being thereby removed. The remaining unex-posed layer areas remain visible with a good contrast with respect to the uncolored background.
The procedure in the following examples 2 to 10 is similar to - that in the above Example 1 and, after exposure of the obtained photo-sensitive printing plates, substantially equivalent results are obtained .. . . .
' . . ' ::.

104~332 K-2 2 3 0 with respect to image contrast prior to and also after development. In the following examples, therefore, in most cases only the composi-tions of the coating solutions and the type of the copying layer supports used are lndlcated; occasionally there are added further brief remarks.
Exam~le 2 Coatlng solution:
0.65 part by weight of the esterification product obtained by condenslng 1 mole of 2,3,4-trihydroxy-benzophenone and 2 moles of the chloride of naphthoquinone-(1,2)-diazide-(2)-5-sillfonlc acld, 0.73 part by welght of the esterlfication product obtained by condenslng 1 mole of 2,2'-dlhydroxy-dlnaphthyl-(1,1~)-methane and 2 moles of the chlorlde of naphthoqulnone-(1,2)-dlazlde-(2)-5-sulfonlc acld, 0.78 part by welght of the chlorlde of naphthoqulnone-(1,2)-dlazlde-(2)-4-sulfonlc ocld, 0.32 part by welght of Crystal Violet base, 6.25 parts by welght of novolak (as ln Example 1), 0.52 part by welght of epoxide resln, 0. 75 part by welght of plastlclzer (as ln Example 1), and 90 parts by volume of a solvent mixture as ln Example 1.
` Copylng layer support: as in Example 1.
`;~ ` ExamPle 3 Ooatlng solutlon:
;; 0.94 part by welght of the p-cumylphenol ester of naphtho-qulnone-(1,2)-dlazlde-(2)-4-sulfonlo acld, 0.81 part-by welght of the esterlflcatlon product obtained by :. , ~ . .
condenslng 1 mole of 2,2'-dlhydroxy-dlnaphthyl-(1,1')-':

methane and 2 moles of the chloride of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid, 0.60 part by weight of the chloride of naphthoquinone-(1,2)-dlazlde-(2)-4-sulfonic acid, 0.32 part by weight of Crystal Violet, 6.01 parts by weight of novolak (as in Example 1), 0.65 part by weight of a copolymer of (225 parts by weight) .. :
ethyl methacrylate and (40 parts by weight) methacrylic :
acld, 0.75 part by weight of plasticizer (as in Example 1), and ~ ..
90 parts by volume of a solvent mixture as in Example 1.
Copying layer support: Chromium layer of a trimetal plate of an alumi-num supportlng foil with a chrome-plated copper layer.
Exam~le 4 Goating solution:
I.S parts by welght of the esterification product obtained by condenslng 1 mole.of 2,4-dihydroxybenzophenone and 2 moles of the chloride of naphthoquinone-(1,2)-diazide-~ : (2)-5-sulfonic acid, ?".,~ 0 ` 0.75 part by weight of the fluoride of naphthoquinone-(1,2)- . .
r,~ "~ diazide-(2)-4-sulfonic acid, 0, 35 part by wei~ht of VictQria Blue B, .. ~ . , . : -5.2 parts by weight of novolak (as in Example 1), 1.O part by weight of vlnyl chloride copolymer (Lutofan~) 200 L3, "., ~ . - -and: ~
90 ~ ~parts by volume of a solvent mixture as in Example 1.
: ~ Copying layer 8upport: Brushed aluminum foil. ~ .
.-:- - Exam~le 5 .,. ~ . . ~ ' ., . , . _ g_ '' .

104~33Z K-2 2 3 0 Coating solution:
1.5 parts by weight of the esterification product obtained by condenslng 1 mole of 2,3,4-trihydroxy-benzophenone and 2 moles of the chloride of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid, 0.8 part by weight of the chloride of naphthoquinone-(1,2)-dlazide-(2)-4-sulfonic acid, 0.35 part by weight of Astradiamond Green GX, 6.5 parts by welght of novolak as in Example 1, but about I0 half of the phenolic OH groups of whlch are etherified ln known manner wlth the sodlum salt of monochloroacetlc acld, 0.8 part by weight of the copolymer from styrene and malelc acid anhydride (Lytron~) 820), 0"75 part by welght of plastlclzer (as in Example 1), and 90 parts by vo.lume of a solvent mL~cture of 80 parts by volume of ethy.lene g.lycol monomethyl ether and 10 parts by volume of butyl acetate.
Copylng layer support: polyester film, provided with a hydrophilic :~
precoat.
: ~ - .
~0l ExamPle 6 .

~; ~ Coatlng solutlon: .

; ~ I . 5 parts by weight of the esterlfication product obtained by ..

: ` ~ condensing 1 mole of 2,3,4-trihydroxy-benzophenone ., .
. ',, ~ `~ ~ .
and 2 moles of the chloride of naphthoquinone-(1,2)- -dlazide-(2)-5-sulfonlc acid, 0 . 8 part by weight of the fluorlde of naphthoquinone- (1, 2~ - :
~, . .
dlazlde-(2)-4-sulfonic acid, ~- 0.35 part :by weight of Sudan Blue G, . .:

~ : ' ' ':
- 10- ,, 104f633Z K-2 2 3 0 6.5 parts by weight of novolak (as in Example 1), 0.8 part by weight of carbamic acid ester/aldehyde con-densate (Uresin~) B), 0.75 part by weight of plastlcizer (as in Example 1), and 90 parts by volume of a solvent mLxture as in Example 5.
Copylng layer support: Brushed aluminum foil.
ExamPle 7 Coating solution:
2 parts by weight of the esterlfication product obtained by condensing 1 mole of 2, 4-dihydroxy-benzophenone wlth 2 moles of the chloride of naphthoquinone-(1,2)-diazide-O-5-sulfonic acid, 0.6 part byweight of the chloride of naphtho~uinone-(1,2)-dlazlde- (2)-4-sulfonlc acid, ~ .
û.25 part by welght of Samaron Blue GSL, parts by welght of novolak (as ln Example 1), . :
- 0.5 part by welght of cellulose acetate butyrate (with 17 per cent by welght of butyryl, 29.5 per cent by weight of ace.tyl, and 1. 5 per cent by welght of hydroxyl groups), and ;
2 0 130 parts by volume of a solvent mixture of tetrahydrofuran, :
` ~ ethylene g.lycol monomethylether, and butyl acetate in a .
`i . ` . ` ratlo by volume of 5: 4: 1.
. ~ ~ . . .. .
Copylng layer support: a) cellulose acetate film, surface saponified b)~ brushed aluminum foil ` ~.
opylng layer thickness: 2 g per m2 (dry welght).
Exàm~e 8 ~ ~.
Coatlng solutldn:

, . - . :

: .

104~33Z
part by weight of the p-cumylphenol ester of naphtho-quinone-(l,2)-diazide-(2)-4-sulfonic acid, part by weight of the chloride of naphthoquinone-(1,2)-dlazide-(2)-4-sulfonic acid, 0.4 part by weight of Brilliant Green, 3 parts by weight of novolak (softening range 110 to 118C), 0.2 part by weight of acrylate resin (Synthacryl~) SC 200), and 120 parts by volume of a solvent mixture as in Example 7.
Copylng layer support: paper printing foil.
When the copylng layer support is a brushed aluminum foil it ls sufflcient to use in the above composltion 0 . 6 part by weight of the chloride of naphthoquinone-(1,2)-dlazlde-(2)-4-sulfonlc acid to achleve a good lmage contrast aiter exposure to llght.
Example 9 Goatlng solution:

4 parts by welght of the esterificatlon product obtained by oondenslng 1 mole of 2, 3, 4-trlhydroxy-benzophenone wlth 2 moles of the chloride of naphthoquinone-(1,2)-dlazlde-(2)-5-sulfonlc acld, .
`20 2 parts by weight of the chloride of naphthoqulnone-(1,2)-" dlazide-(2)-4-sulfonlc acid, `~ 1 part by welght of Rhodulln Pure Blue 3 G, 16 parts by welght of novolak resln (meltlng range 108 to 118C), 1.6 parts by weight of a copolymer of acrylic acld and ethyl acrylate (in a ratlo by welght of 1: 9), and 140 parts by volume of a solvent mixture as ln Example 7. --Copylng làyer support: zlnc piate, polished.
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.. . . - . ; . - - : , Development is followed by heating for 15 minutes at 240 C
which, after cooling down, is followed by etching for 6 minutes with 6 per cent by weight nltric acid. A relief printing form is thereby ob-talned .
ExamPle 10 Coating solution:
part by weight of the butyl amide of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid, 0.6 part by weight of the chlorlde of naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid, 0.3 part by weight of Crystal Violet base,

5.5 parts by weight of novolak ~AInovol(~ PN 430), 0.4 part by weight of polyvinyl butyral, and 100 parts by volume of a solvent mixture of 80 parts by volume of ethylene glycol monomethyl ether and 20 parts by volume of butyl acetate .
Copylng layer support: Brushed aluminum foil.
Exam~le 11 Thls example describes the production of a transfer copying ;
material whlch is useful in the productlon of electric conductor plates.
The copylng layer support used is a 0.036 mm thlck polyester film pre-treated by a brlef lmmerslon ln 10 per oent by welght aqueous trichloro-~; acetic aold solution containing 1 per cent by weight of polyvinyl alcohol, and by subsequent drying at 100C. The light-sensitive . .
copying layer is produced from the coating solution lndicated below by : ~; application to the support and drylng, and is then covered with a 0.025 ~ mm thick polyethylene top film.
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In use, the top film is stripped and the copying layer is trans-ferred to a copper layer on a plate of insulating material. The conduc- ,c tor lmage is produced in known manner by exposure to light, develop-ment, and etching. Immediately upon exposure to light, the conductor lmage ls vlsible with an lntense contrast on the copper foil provided wlth the copying layer so that possible defects can be recognized ea sily .
Coatlng solutlon:
10 parts by welght of the p-cumylphenol ester of naphtho-quinone- (1, 2)-dlazlde~(2)-4-sulfonlc acld, 10 parts by welght of the chlorlde of naphthoqulnone-(1,2)-dlazlde-(2)-4-sulfonlc acld, 0.6 part by weight of Crystal Violet, 30.8 parts by weight of novolak (as ln Example 1), 5.1 parts by weight of polyethylene acrylate, of low viscosity, 5.1 parts by welght of polyethyl acrylate, of hlgh viscosity, 12,8 part9 by welght of polyvinyl methyl ether (Lutanol~) M 40), ; ~ ~ 25 . 6 parts by weight of polyvinyl ethyl ether, of low vlscosity LutonalG~) A 2S), and ~ ~-100 parts by volume of methyl ethyl ketone.
Exam~le 12 - This example descrlbeo a copying layer solution which can be used as a posltlve photoresist composition for various purposes, par-:
:
tloularly for the productlon of etch reslsts, e.g., for etching shaped .~ . ~ I ~ ` . . .
rtlales and signboards and in the production of conductor images, ~ ;
partlcularly also in microeloctronics. The solution has a long storage llfe. The type of coatlng and the layer thickness may be adapted " ~ wlthln wide limlts to the respective requirements. After exposure to .

., ~ ..
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104~33Z K-2230 light, the exposed areas are light green and contrast considerably with the unexposed areas which remain intensely blue colored. The exposed , areas can be removed easily with an alkaline developer (pH about 12.8).
Wlthout the content of chloride of naphthoquinone-(l ,2)-diazide-(2)-4-sulfonlc acid, the difference in appearance after exposure to light, of the copying layer between its exposed and unexposed areas .
ls very small. ~ -Composltion of the copying layer solution:
1.5 parts by weight of the esterification product obtained by condensing 1 mole of 2,3,4-trioxybenzophenone with 2 moles of the chloride of naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid, 0.4 part by weight of the chloride of naphthoquinone-(1,2)-dlazlde-(2)-4-sulfonlc acid, 0.1 part by welght of Crystal Violet, 10 parts by welght of novolak (Alnovol~) PN 430), 2 parts by welght of epoxy resin (Eplkote 1001), and 86 parts by welght of solvent, composed of trichloroethylene, lsopropanol, and butyl acetate ln a ratlo by welght of 6: 3: 1. - -`~ 20 ~xamole 13 `~ ` Coating solutlon:
2.17 parts by welght of the p-cumylphenol ester of naphtho-qulnone- (l, 2) -dlazlde- (2 ) -4 -sulfonic acid, ` - 1. 02 parts by welght of the esterification product obtained by ` oondenslng 1 mole of 2,2'-dihydroxy-dinaphthyl-(1,1')-methane and 2 moles of the chloride of naphthoquinone-(1,2)-dlazide-(2)-S-sulfonlc acid, : .

~ 1 5 ~ ,.

. ~, . ,, -. . -- ~

~046332 0.37 part by weight of the chloride of naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid, 0.12 part by weight of Crystal Violet base, 9.90 parts by weight of a cresol-formaldehyde novolak (softening range: 112 to 118 C), 43 parts by volume of tetrahydrofuran, 35 parts by volume of ethylene glycol monomethyl ether, and 9 parts by volume of butyl acetate.
Copying layer support: electrolytically roughened and anodized alumlnum foll.
Exam~le 14 Coatlng solutlon:
0.70 part by weight of the esterlficatlon product obtalned by condenslng 1 mole of 2,4-dlhydroxybenzophenone and 2 moles of the chlorlde of naphthoqulnone-(l ,2)-diazide-(2)-5-sulfonic acid, 0,95 part by weight of the esterlficatlon product obtalned by condensing 1 mole of 2, 2 ' -dlhydroxy-dlnaphthyl- (1,1 ') -methane and 2 moles of the chlorlde of naphthoqulnone-`20 (1,2)-dlazlde-(2~)-S-sulfonic acid, 0.45 part by weight of the chloride of naphthoqulnone-(1,2)-~, ~; diazide-~2)-4-sulfonlc acid, 0.15 part by weight of Crystal Vlolet base, 5.10 parts by weight of novolak (as ln Example 1), 0.15 part by welght of polyvinyl butyral, :
?'" ~ ` 0,58 part by welght of plastlcizer (as in Example 1), ;; 40 parts by volume of ethylene glycol monomethyl ether, 50 parts byvolume of tetrahydrofuran, and 8 parts by volume of butyl acetate.

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Copying layer support: mechanically roughened aluminum foil.
Examples 15 to 19 In these five examples, mechanically roughened aluminum foils are provlded wlth a copying layer by applying coating solutions con-taining the constituents of the following list dissolved in 92 parts by volume of solvent, composed of 48 parts by volume of tetrahydrofuran, 36 parts by volume of ethylene glycol monomethyl ether, and 8 parts by volume of butyl acetate.
Example Parts by welght15 16 17 18 19 Dlazo A 0.70 0.57 0.750.75 0.57 Dlazo B 0.84 0.78 0.880.88 0.70 Dlazo C 0.18 0.45 0.180.18 0.45 Crystal Vlolet0.15 0.018 0.0180.09 0.15 Novolak 5.2 5.2 5.2 5.2 5.2 Polyvlnyl butyral 0.18 0.180.18 0.18 O.I8 Epoxy resln 0.25 0.30 0.300.30 0.25 Plastlclzer 0.58 0.58 0.580.58 0.58 ; ; ` `20 Dlazo A ls the esterlflcatlon product obtalned by condenslng 1 ~ mole of 2,4-dlhydroxybenzophenone and 1 mole of the chlorlde of .; , ..
naphthoquinone-(1,2)-dlazlde- (2)-5-sulfonlc acld .

Diazo B ls the esterlficatlon product obtained by condensing 1 , . ~
mole of 2,2'-dihydroxydlnaphthyl-(1,1')-methane and 2 moles of the chlorlde of naphthoqulnone-(1,2)-dlazlde-(2)-5-sulfonlc acld.

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Diazo C is the chloride of naphthoquinone-(1,2)-diazide-(2)-4-sulfonic acid. Novolak and epoxy resin are the same as those used ln Example 1.
It will be obvious to those skilled in the art that many modifi-cations may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications .

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A light-sensitive copying layer containing an ester or an amide of an o-naphthoquinone diazide sulfonic acid or carboxylic acid, 10 to 75 per cent by weight of a halide of o-naphthoquinone diazide-4-sulfonic acid, calculated on the total content of o-naphthoquinone diazide compounds, and 1 to 50 per cent by weight of an organic dyestuff capable of salt forma-tion, calculated on the same basis, which copying layer changes its color shade upon exposure to light.

2. A light-sensitive copying layer according to claim 1 containing 10 to 50 per cent by weight of the halide of o-naphthoquinone diazide-4-sulfonic acid, and 5 to 30 per cent by weight of the dyestuff, calculated as in claim 1.

3. A light-sensitive copying layer according to claim 1 in which the dyestuff is a red, blue or green dyestuff.