JPS60256140A - Photosensitive composition and 2-component diazo type material comprising the same - Google Patents

Abstract

1. A light-sensitive mixture, composed of a diazonium salt, a coupler, a resin binder, a stabilizer, conventional additives and a liquid phase, which comprises a combination of a) at least one p-aminobenzenediazonium hexafluophosphate, b) at least one 4,4-dihydroxy-diphenyl sulfide, if appropriate as a mixture with a further coupler, c) an acid stabilizer in a concentration from zero to 20 per cent by weight, relative to the diazonium salt employed, d) at least one plastic which contains acid groups, has an acid number of at least 100 and is derived from the maleic acid or phthalic acid type, as the resin binder, and e) lower alcohols, glycol ethers, ketones water or mixtures of these solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition comprising a cyazonium salt, a coupler, a fat binder, an acid stabilizer, a conventional additive and a liquid phase, and a two-component siatib material prepared using this composition. KIJ41'″f'ru.

(8) PRIOR ART It is known to use siazonium salts co-pressively with coupling components in formulations to obtain two-component siacitib materials. The cyazonium salt used is one fermented from 1% p-phenylenecyamine.

4-Sialkylamino-6-chloropenzenezazonium compounds for use in siacitib materials are known from the literature. They are commonly precipitated as salts of sulfuric acid or etetrafluoroboric acid or as double salts with zinc chloride, cadmium chloride or tin tetrachloride, and are commercially available in the form of these salts for coatings. Used for the manufacture of prescriptions.

Zinc chloride double salts and tetrafluoroborates of 4-dimethylamino- and 4-diethylamino-6-chloropenzenezazonium compounds are conventionally known [FIAT RgponT 813. 7
96-1048], on the basis of their comparative coupling limitations, it is advantageous to present resorcinol and phloroglucinol as coupling components in an alkaline buffered water bath solution. Used in the production of one-component zoazotizo materials. mono- and poly-
Due to the very good UV absorption aK of the dyes obtained from them with hydroxybenzene derivatives, these diazo compounds are suitable for temporary or
% suitable for the production of one-component siatib materials to obtain lginals).

4-methyl-cyclohexylamino-6-florbenzenediazonium salt (Oranta Tokuken No. 243429),
4-Methyl-cyclohexylamino-2,5-dichlorobenzenediazonium salt (West German Patent Application Publication No. 12)
90809) and 4-methyl-cyclohexylamino-5-chloro-2-trifluoromethylbenzene siazonium salts (West German Machichin No. 2226532), 4-dimethylamino- and 4-diethylamino-6 - Faster (coupling) than florbenzenezadenium compounds.

The former diazo compounds are therefore particularly suitable for the production of one-component diazo compounds which can be prepared with an aqueous solution containing resorcinol and phloroglucinol buffered with a neutral to weak acid. If a transparent layer support is used, such one-component shear-type materials may be
! , is very suitable as a temporary original for obtaining copies on KUV sensitive injection materials. These diazo compounds are advantageously
Zinc chloride or as a salt of sulfuric acid or tetrafluoroboric acid,
It is used industrially as a double salt with cadmium chloride or tin tetrachloride and as such.

4-aminobenzenesoazonium compound having 710 dene atoms in 3 to the cyazonium group and one halogen atom in the first position to the cyazonium group and 10rn atoms in 6 (additional to i), ether, 4-Aminobenzene cyazonium compounds with thioether or trifluoromethyl groups have higher photosensitivity and coupling activity (11) and are more thermally resistant than compounds without one of the above-mentioned substituents. In addition, the 4-amino-6-halonebenzenezoazonium compounds and mono- and/or poly-hydroxybenzene derivatives are more stable in terms of 3- and/or 6-position substituted moieties or ether or thioether groups. 4- does not have
Absorbs KUV# more effectively than azo dyes from amine benzenezazonicum compounds. In the field of commercially available alkaline injections or neutral-to-slightly acidic buffered water bath solutions containing resorcinol and phloroglucinol, deep dark dyes with high absorption in the visible and ultraviolet spectral regions are used. can get.

Based on their relatively high coupling activity, public fD
The 4-amino-6-nolodenbenzenezazonium compound's hydrogen sulfate salt, tetrafluorochloride salt and double salt with zinc chloride, cadmium chloride and tin tetrachloride can be combined with a coupling component of low activity. can only be used to obtain a two-component siatative material, where the acid stabilizer is relatively fuzzy (1
2) can be used to prevent premature coupling of undeveloped cyacitaino material even when present in a two-component cyacitaib layer. However, the presence of a relatively multineedle stabilizer often leads to inconsistencies in the coating composition, and the layer support of such sheathable materials under steam storage and under normal conditions. Precipitate on top (
blooming; blooming).

Blooming in sheath type materials is often undesirable in practice as it poses considerable drawbacks to the application. West German Percentage Publication No. 1772072 describes a two-component sheet material. this is,
It contains the zinc chloride double salt of 4-tmethylamino- or 4-zoetelaminochlorobenzenezazonium chloride in combination with 4-morpholino-2,5-sialkylphenol and a significant amount of negligible acid stabilizer. This sheathable material is prepared in an alkaline buffer and can be very easily used as a material for obtaining temporary originals when transparent paper is used as layer support. Despite high stabilizer concentrations, the shelf life of undeveloped material, especially under hot steam storage conditions, is very limited and FiA K is not completely satisfactory. Additionally, the shear type material has a tendency to bloom during storage and development events.

Transback Film C) -2 (Transpa
queFllm G-2; Th1okol/Dy
Nachem Corporation)
Diazo film materials have recently become known, which are
As a photosensitive compound, it has a structure based on benzenediazonium hekitefluorophosphate. After image-wise exposure, this film yields a tan copy with good UV contrast and reasonable visual contrast. However, the shelf life of this film under hot steam conditions at 40 DEG C. and 80 DEG relative humidity in the present steel condition is unsatisfactory. In addition, the undesirable damage of the coating [wrinkle structure based on the formation of blisters (Crinkle structure) due to the formation of blister
structure)) occurs during processing under steam and highly hostile field conditions. Diazo copies obtained under such development conditions are no longer suitable for use.

The purpose of the present invention is to provide a coating for coating by the user.
Cyazonium salt, coupler, south binder, cyacitaino auxiliary agent, fe7. obtaining a liquid photoresist in the form of a mixture of acidic acid and, if appropriate, an acid stabilizer;
Here, the individual constituents of the liquid photoresist or semi-finished product, consisting of the liquid phase, the binder, the cassillary, the cyacitaino auxiliary and, if appropriate, the acid stabilizer, are the photosensitive diasols at the point of use for coating. The compound and the compound may exist separately. Another object of the present invention is to have a relatively low stable AIJm degree, still have a good shelf life even under the more forgiving conditions of steam storage, and that the s7 azo type layer can be used under extreme conditions. The objective was to obtain a photosensitive two-component cyasitib material which also shows blooming in the storage and ff1l of the present invention and therefore does not show the formation of precipitates on the film layer. This material should also not form undesirable small blisters during events under very wet and warm conditions. Furthermore, using this material! A temporary original should have high UV contrast and good visual contrast.

This task consists of: (a) p-Aminebenzenediazonium hexanefluorophosphate as a mixture with at least one fbJ and, if appropriate, a coupler, of cyhydroxy-zophenyl salunide (also at least one fcl); Used siazonium, 0-20% of salt
Acid stabilizers (fd) at a concentration of (fd) If fat binders have acid groups and have an acid value of at least 100, R4 plastics from the maleic or phthalic acid type (both 1 and 16 ) (θ) Lower alcohol as a liquid phase, RI:I
- a photosensitive composition of the above type consisting of a ether, a ketone and water alone or in combination, and a two-component photosensitive composition prepared using this composition and having a photosensitive layer consisting of components a) to (d); achieved. 1. Used p-aminobenzene siazonium hexafluorophosphate, especially 1. General formula; or cycloalkyl having up to 8 carbon atoms, R2 being non-reverting or substituted alkyl having 1 to 18 carbon atoms;
Alkenyl having at most -4 carbon atoms, from 6 carbon atoms
cycloalkyl having 12 or unsubstituted or substituted aralkyl having 7 to 12 carbon atoms, or R1 and R2 together with the nitrogen atom bonded to them are 1F, tIt, or or a substituted 5- to 8-membered heterocyclic group, X is chlorine or bromine, and Y is hydrogen, chlorine, bromine, torineluomethyl, ether or thioether group. Teyo ^.

The dihydroxycyphenyl sulfide used is
General formula: [In the formula, R3 and R4 are the same or different, hydrogen, alkyl having 1 to 4 carbon atoms, oHmi
It may be a compound with a small number of positions ortho to c (both 1 ml is occupied by hydrogen), and when 4 is appropriate, the compound has the formula: (19) [wherein R5 and R6 are the same or different] is hydrogen, carboxyl, carboxami P or a non-tii substituted carboxyalkyl- or carboxyaryl-amide substituted with a hydroxyl or air-amino group, and R) and R8 are the same or different; Hydrogen, 1 to 4 carbon atoms
Alkyl (2J) R, alkenyl or hytaloxyalkyl or R is unsubstituted or substituted aryl having 6 to 12 carbon atoms;
9, RIO and R11 are the same or different, hydrogen,
unsubstituted or substituted alkyl having 1 to +1' carbon atoms, cycloalkyl having 6 to 12 carbon atoms, or aryl or aralgyl having 6 to 12 carbon atoms, or RIO and R11 are bonded to these; unsubstituted or substituted 5jlj~
is an 8-membered heterocyclic group, R12 is hydrogen, and R1
3 is an unsubstituted or a carbon atom substituted with an alkyl group, so it is a cycloalkyl group with the lowest 8 atoms, an aralkyl group with a base atom number of 10, or an unsubstituted or 11-substituted aryl, or Rlfa and R13 are Together with the nitrogen atoms bonded to these, non-111-substituted or Wt-substituted 5-membered
\8 is a negative heterocyclic group, 2 is hydrogen, chlorine or JA
The mixture is mixed with at least one coupler.

Possible heterocyclic groups are pyrrolidino, piperidino, piperazino, morpholino, thiomorpholino, hexamethyleneimino or heptamethyleneimino groups.

4-Tmethylamino- as a siazonium salt in the composition
6-Chlorpenzenezoadenicum fluorophosunate is present, with 2,2'-dimethyl-4,4'-zohydroxy-5,5'-cy(1)-butyl- as a coupler. Preferably diphenyl sulfide and 2,4-dihydroxybenzoic acid are present.

In a further advantageous composition, the cyazonium salt used is 4-dimethylamino-6-chloropenzene siazonium salt hexafluorophosphate teary, and the coupler used is 2.
2'-dimethyl-4゜4'-dihydroxy-5,5'-
C(1,)-zotyluzophenylternide, 2.
4-dihydroxybenzoic acid and 2,3-dihydroxynaphthalene-6-sulfone ffN-(4'-chlorophenyl)-amide or the cyazonium salt used is 4
-Methyl-cyclohexylamino-6-chlorobenzene siazonium hexafluorophosphate, and the Cassirer used is 2,2'-dimethyl-4,4'-zohydroxy=5,5'-cy(t)-butyl. -diphenyl sulfide and 1-hydroxy-3-N-(4'-chlorophenyl)-amidesulfonyl-8-N-(n-but?
)-amidosulfonyl-naphthalene, or the diazonium salt used is 4-diethylamino-2,5-zochlorobenzenezazonium fluorophosphate and the coupler used is 2,2'-dimethyl-4,4 The cyazonium salt used is 4-methyl-cyclohexylamino-3-10-2, or 4-methyl-cyclohexylamino-3-10-dihydroxybenzoic acid. - To! 7 fluoromethylbenzene zoazonicum hexafluorophosphate, and the coupler used is 2゜kudimethyl-4,4'-
They are zohydroxy-5,5'-di(1)-butyl-diphenyl sulfide and 3,5-dihydroxybenzoic acid.

Examples of p-aminobenzene cyazonium hexafluorophosphates of the above general formula present in the compositions according to the invention are listed in the following table A: N2PF.

j-CH3-CH2Cl B 2- CH3-CH3B r H 6-CH3-CH2Cl C1 4-CH, -CH3C1-CF3 5 -C'H3-CH3Br -CF3ts-CH3-
CH3C1cH, ()s-7-CH3-CH3CI C
1+0- 8-02H5-02H, CI H (25) Continuation of Table A 9 -C, B5-C2H, CI C1 1[1-C, B5-C2H5C1-CF311 -C2
H5-C2H5CI C45-12-C! 2H, -C2
H5CI CH30 Yato-13-C+H5-C2H5C
I CH30-14-C2H) -C3H7CI B 15 -C! , H, -C4H9CI Hl(5-C,H
, -C4H9CI C117-CI (2-CH-CH,
-CH2-CF(=CH,CI C118-CH3-C
3[(7(!L B 19-CH3-C4H, CI H 2O-CH3-C16H33C1-CF+321 -c
H3-CHεOH2@CI B22 -CHlI-C
B2CH2@Sr -CF525 -CH3■ CI
B 24-CH3(E) CI C1 25-CH3<E> C1-CF3 (24) Continuation of Table A 7% RIR, X Y 26-CH3(ff) Br -CF331-CH3-
cH2@CI B 32-cH3-CH2@CI C1 34-CB2-CH(I(2(t) CI B35 -
CH3(CH2)s-11J+(CH3)3C1-C
I C166- ■ ω CI H Table A continued - 44 A CI CF3 Table A continued 49 CH3Cl H ■ 50CH3CI C1 (27) RI R2X Y p-aminobenzene siazonium used in the composition according to the invention Hexafluorophosphate is prepared from the corresponding known p-amine benzenezazonium hydrodenesulfate or zinc chloride chain by reaction with commercially available hexatefluoroacetate (85%) or from these alkali metals. It can be obtained from salt in a water bath solution. According to the present invention? Fluophosphate is only slightly soluble in water and therefore precipitates almost constantly from the bath solution, even in houseworms. The yellow precipitate of diIh is filtered off, washed with water and dried at 20-60° C. in a circulating air drying cabinet. The p-aminobenzene cyazonium hekitefluorophosphate & ester according to the invention prepared by this method,
Obtained in high purity and in this quality, the composition according to the invention can be used directly for the production of photosensitive compositions or for coating purposes to obtain two-coat zoazotyzo materials. Examples of Cassirer that can be used are shown in Arrow's 8-coat, 0-table, D-coat, E-table and F-coat;

6 CH3 (CH3)2CH 0 table Z IH-COOE(H 2H-C! 0NH2H 3H-CONH2C1 4H-CONH2Br 5 H-CONHCH2CH, OHH 6H-CONH@H 9-COOHHH lo-CONH2HH 11-CONHCH2CH20HHH (61) D table IHH 2-C4[(9-C4H.

@ 4 @ -CH2CH20H b °C)) CH3-CH3 6GCl -C4H9 (62) Table E No. 16 R9RIOR11 Table F When using Kagura in Table B, it absorbs very weakly in the visible spectrum range (absorbs from 360 to 45 A yellow dye is obtained which strongly absorbs in the ultraviolet wavelength range of nm.Based on this absorption percentage note, the azo components of table B are highly suitable for the production of two-component siatative materials for obtaining temporary originals. It is.

In order to increase the absorption of these dyes in the visible spectral range, compounds of tables CXD, E and F, which couple to give red or evening azo dyes, can be mixed with the azo component of table B. can. Cassirer B and CS D
, E or F, the color becomes Km red during development.
A material is obtained which gives a brown dye and has excellent absorption in the external and oral regions. Such temporary originals are extremely suitable for the production of photoreceptors and as exposure masks in the original manufacturing of printed wiring boards and integrated circuits in microelectronics. Owing to the advantageous transparency with visible chain acids and at the same time the high absorption aK in the outer spectral range, such exposure masks are particularly suitable. This is because it makes it possible to precisely place the original and markings on the photosensitive layer of the substrate, e.g. holes in printed wiring boards, and easily to Because you can.

However, the produced temporary Zoadetype originals can also be used in the printing sector, especially where UV absorption is particularly advantageous and simultaneous visible transparency is advantageous.
[Example: ◆zu] Can be used for non-stick mounting in A11ll and gravure printing. Mask is a very advantageous VC, Seibetsu 1. Historically, diazo exposure masks are easier and cheaper to manufacture than silver exposure masks.

Cassirer which can be used in combination according to the invention is disclosed in the literature. These include dihydroxybenzene [Kosar's Light-Sensitive System (L
light-sensitive 5yszecos,
'(65) Willly & 5ons, New York)
(1965, pp. 220-248)] and 111! in the naphthalene ring system! il or derivatives of mono- and shea-hydroxynaphthalenes with two sulfonamide groups (EP-A) No. 4574, Part 1498
2 and the specification of European Patent (EP-B) ml 7699).

The acid stabilizers used in combination according to the invention are already known in the cyacitaino process. However, this is preferably from 5 to 15 m% O~20 m% based on the cyazonium salt used.
It exists in the density of heavy wrinkles. Compared to conventional acidic additives, this concentration is low, but it nevertheless has an excellent stabilizing effect and, in some cases, may even be more stable than known formulations. The preferred compound used is 15-sulfosalicylic acid.

The town fat binder used in combination according to the present invention is a plastic having acid groups and having a tR1 curve of at least 100 (66). These are West Germany special! ! I-
No. 2,652,942 is also known, and copolymers such as monoethyl, monoisozolobyl or It is a monobutyl ester.

In the liquid phase for producing the photosensitive composition according to the invention, cyazonium hexafluorophosphate, cassiller, stabilizers and other auxiliary agents customary for the cyasytaino process can be used.
A m-drug or a mixture of m-drugs is used. Examples of suitable m-agents are lower alcohols such as methanol, ethanol, inzolopanol, n-sitanols, and/or glycol ethers such as methyl glycol, ethyl glycol, solovir glycol, methyl triglycol,
Butyl triglycol and methoxybutanol and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone and the like and mixtures of these solvents with water.

Known compounds can be used as conventional additives or auxiliary agents! may be included in the photosensitive composition according to the invention, for example, zinc chloride for increasing contrast, thiourea, thiourea visiting conductors and small key dyes for improving contrast and copying background, developing Glycerin, monoacetylglycerin/, cyacetylglycerin and triacetylglycerin as accelerators and urea and alkylated ureas and Newtonian additives to improve blocking resistance and to prevent air ownership during dew in a vacuum frame. Finely dispersed silica or alumina can be added to avoid formation of silica or alumina.

The photosensitive composition according to the invention is presented to the user in the form of a liquid photoresist, either as individual components or as a semi-finished product consisting of a liquid phase, a resin binder, a coupler, a cyacytate auxiliary, a stabilizer and a photosensitive zoazo compound. Words and phrases.

Furthermore, the photosensitive composition according to the invention can be processed in the form of a photosensitive layer consisting of components a '' d of item 1 of the Fff Freezing Range applied as a two-component cyazotiso material on a support layer. In this case, it is advantageous to apply one photosensitive layer to at least one layer support surface.

Suitable support layers for the two-component zoazotizo materials according to the invention are all customary opaque and transparent materials such as coated or uncoated paper, inorganic and gold bases such as glass, aluminium, silicon, steel, iron. In addition, cellulose esters include plastic films of cellulose 2''/2 acetate and triacetyl cellulose, polyesters such as the preferred polyethylene terephthalate, vinyl polymers such as polyvinyl acetate or polystyrene and alkene polymers such as polyethylene or polyzolopyrene.

Particularly when using plastic films, glazed materials or slat substrates, a film-forming resin binder may also be added to the photosensitive composition, thus producing a (69) modified mixture (sheath tie blacker). is advantageously applied to the surface of the substrate. Suitable film-forming resin binders are: cellulose ethers such as ethyl cellulose, cellulose esters such as cellulose acetate, cellulose acetozologionate, acetol! I!
IPR cellulose and cellulose hyphenate, vinyl polymers such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, vinyl acetate copolymers, poly(methyl methacrylate), copolymers of alkyl acrylates and acrylic acid or polyphenylene oxide and etching glycols. /isophthalic acid/terephthalic acid terpolymer. Advantageously, a coated polyethylene terephthalate film is used as a support) The two-component diazotyzo material prepared using the photosensitive composition according to the invention can be It has excellent storage stability despite the very low concentration of stabilizer in the layer. Furthermore, no precipitates are formed on the layer surface even under steam and temporary storage (4U) and dust column conditions.

Additionally, film-based blisters (
No peeling-off of the layer in the form of b11stθr nibbling structure 1k) is observed.

Otherwise, this layer blister will cause complete disappearance and destruction of the layered layer of clear information on this diazocopy.

The two-component soazotizo material according to the present invention is a conventionally known diazo film material based on 4-amino-6-no)lodenbenzenediazonium tetrafluoroborate, hydrogen ate, and zinc chloride double salt, and a known photosensitive material. Transopaque film G-2 (Tr
ansopaque Fllm G-2)
Ktljj white and half U different.

The two-component zoazotite material according to the invention is treated in the conventional manner by contact flashing under a transparent original using a UV-rich light source, such as a mercury high-pressure lamp or a fireworks lamp.

Next, heat the copy using a conventional method using ammonia gas, or by applying an alkaline water bath at room temperature or elevated temperature.

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Stored mma with the following composition: Acetone 1360g Methanol 6459 N-Butanol 50.9 Methyl glycol 5[1,9] 18 coating samples of 50.9% were collected from Gantrez AN119; Part 1
In each of the 9 coating samples (A), 75% of 5-sulfosalicylic acid &U (46) 4-zobutylamino-6-chlorobenzenezazonicum hekitefluorophosphate (molecules - 327,5) 6[J[]. lν, and 490 drops of 5-sulfosalicylic acid Z5η and 4-tumenalamino-6-chlorobenzenezoagnium tetrafluoroborate (Molecular Lid 269) were added into each of the remaining 9 coating samples (B) as comparative samples. Kading.

The diazo coating sample H&AI, A produced in this way
2,...A9 and B1. B2...B
, is called. Then the following coupling compound 1.83
X1υ-3 moles as Al/B□, A2/B+・
...Put into the diazo-coated sample of the A9/Be pair and fold I@ with mechanical stirring: A1/B1: 2 + 2'-tumethyl-4,4'-
Dihydroxy-5,5'-c(t)-glythyl-diphenyl sulfide (molecule 11t358) (44) 60Tn9 A2//B2: 2,4-dihydroxybenzoic acid hydroxyethylamide (molecule 197), 560%' A3/ 83: 2,4-dihydroxybenzoic acid amide (molecule size 152) 280~A4/84' 4-bromo-6,5-dihydroxybenzoic acid amide (molecule size jt276) 500 minoAl)/85: 2,4 -dihydroxybenzoic acid (
Molecule 11155) 280IIv Aa/Ba: 5.5-Sohibiroxybenzoic V (molecule tt153) 2801'IF Afu/B7: 1-Hydroxy-3-N-(4'-
Chlorphenyl)-amido-sulfonyl-8-N-(n-butyl)-amido-sulfonylnaphthalene (molecule J1479) 870 drops As/B8: 2-hydroxy-6=N-(4'-
methylenyl)-ys dosulfonyl-6-naphthoic dN-(4'~methylphenyl)-amide (molecule [446) 820 A9/B9: 2,3-dihydroxynaphthalene-
6-Sulfonic acid N-(4'-chlor7enyl)-amide (molecule 11350) 640 ■.

The corresponding bath liquid of each sample was mixed with IQc with a gap width of 0.16
+++ Width draw coater aw-coater
) 125 μm with conventional layer accelerator no.
The liquid diazo coating layer is dried for 1 minute at 90"C in a circulating air dryer 4. The diazo film samples thus obtained are graded A1, A1, depending on the diazo coating sample. AIl...A9 and 81.B
It is called 2...89. No. 1 of each sample is 8~
9j//171".

For stability comparisons, half of a partial section of each film sample was covered under jJV opaque original material and r5
Zoade film copying device available on site (Kalle 0zaf1-che 066)
) is completely and optically rolled in a photoreceptor, and developed using moist ammonia gas; this removal results in a well-formed film section with a minimum density of film background, and complete gradation. The maximum density of is obtained in the unexposed film section.

In the opaque exposed film sections, film samples A1 and B develop a yellow tone, film samples A2-A6 and B, -B6 develop a red tone, and film samples A7-A and B develop a red tone. .

~B9 develops into a dark purple tone. The full length of each film section is colorless.

The other sections of each film were stored for 24 hours at 55° C. and 65% relative humidity and developed as described above. The film background density thus obtained is measured and compared with the film background density of a corresponding diazo film sample that was not stored. This optical density measurement is performed using a Macbeth-Quantalog Densitometer (47).
meter) TD 205 and Kodak Filter Ratten.
er Wra also ben) A 106 (Dvls)
is for the visible spectral range, and the 5chott filter U G 4
(Duv) is used for the extravasation vector range.

result'? : Summarized in Table 1.

(48) Table 1 Film Not stored ψ Stored Film back sample l2vis r2UV r2vis pUv
Ground person 1 υ, 03 tJ, 08 0.04
0.10 Almost colorless Bl O,040,100,08
0,42 light yellow A 2 0.030.060.040.
09 Colorless B2 0.03 0.08 0.42 0.7
1 Reddish brown A 3 0.03 [1,080,040
,09 Colorless 83 [J, 030.10 U, 310.6
1 bright red A 4 0. C50,080,040,09 Colorless B4 0.030.070.721.00 Reddish brown A5
0.04 [J, 060.040.08 Colorless B5 0
．． 040.080.14'0.46 yellowish brown A 6 C1
,030,090,040,08 points colorless 6 0.03
0.06 U, 380.63 Red A7 [J, 040.
14 [J, 040.161tlfi color B 7 D,
tJ40,161,240.50 #Vote color A8 0.0
4 [J, 35 0.06 [J, 41 No color 88 0
．． 040.381,440.92 H#Colorful A 9 0
．． 040.080.100.14 Light pink B9 Ll, 0
4 [1, [J8 U, 96 Ll, 45 e ligatures] In this film samples A1 to A9, no significant change in the film background was observed even when stored under dusty conditions; It can be said that 11 couplings did not occur in between. However, film test NBx
~89, even with the same storage material, there was a significant change in the film background, indicating that premature coupling occurred during storage. Fee A on film
Some of the film samples B1-B9 become completely unusable under the same storage conditions, while 1-A can still be completely removed in the storage stage.

The results clearly demonstrate that the general formula benzene siazonium hexafluorophosphate, in combination with the coupling component, is superior to the known compatible benzene/seinzoazonium tetrafluorophosphate. It is shown in Instead of 4-dimethyl7mino-6-chloropenzenecyazonium tetrafluoroposite (Bl ” Bo ), the corresponding 4-zometelamino-6-chlorobenzenezazonicum hydrodensulfate or 4-dimethylamino- 6-chlorpendensoazonium chloride Zn012
Depressurization using bale salt gives similar results.

These diazo coating solutions A1 to A9 are stable for 24 hours at room temperature when protecting them from the source, and the dye formation in the target solution (both are stable for 24 hours), and dye formation in the target solution (too much manual processing). Under these conditions, it became unusable based on K.

Example 2 An acidic bath solution with a composition of 100% was divided into 9 12 coating samples of 50% each.

Acetone 680g Methanol 170# n-sitanol 22I! Methyl glycol 22 & acetosoropion cellulose 9 [J, 9, f I
J-(methyl vinyl ether/maleic anhydride) 7
．． 51 5-Sulfosalicylic acid 1.7y 2,z-dimethyl-4,4'-zo and droxy-5,5'-cy1t) -gtyluzophenyl sulfide 16.1.9 Of this 12 coating sample (C) Sensitize with 1.83 x 10-'' moles of the cyazonium salt of YF in each case: cl: 4-tumethylimino-6-chloropenzenezazonium hexafluorophosphate (328 molecules) 6[JU9D1; 4-dimethyl Amino-6-chlorpenzenezazonium tetrafluoroborate (molecule jd269) 490YaC2:4-
Diethylamino-2,b-zochlorpenzene siazonium hexafluorophosphate (690 minutes) 710-C8:4-7 ether ε-no 2,5- (51) Dichlorobenzene diazonium chloride (ZnCl2 double salt) ( 349) 640η c3: 4-Methylcyclohexylamino/-3-chlorobenzene siazonium hexafluorophosphate (369) 730111&D3: 4-methylcyclohexylamino-6-chlorobenzenequazonium chloride (ZnCl2 complex) salt) (separator 413), 760 m9 C4: 4-methylcyclohexylamino-2-trifluoromethyl-5-chlorobenzenequazonicum hexafluorophosphate (molecular type 464) 850 daD,: 4-methylcyclohexylamino- 2-Trifluoromethyl-5-chlorobenzene siazonium chloride (ZnC1a'fJI salt) (min (52
) 524 ) 960 da C δ: 4-methylamino-2-(4'-methylphenyl)-mercapto 5-chlorobenzene siazonium hexafluorophosunate (1418 molecules) 770 da C 5: 4-zomethylamino-2 - (4'-Methylphenyl)-mercapto 5-chlorobenzenediazonium hydrodansulfate (molecule 73711) 680&C6: to 4-dimethylamino-2-(4'-chlorophenoxy)-5-chlorobenzenediazonium (xafluorophosphere) (molecule 1 454) 860 DaD6: 4-dimethylamino-2-(4'-chlorophenoxy)-5-chlorobenzene siazonium chloride (ZnCl2 double salt) (spectroscopy 1it413) 76
The diazo coating samples prepared with 09 siazonium hexafluorophosphate are referred to as CELC6, and those prepared with cyazonium hydrobin sulfate and ZnCl2M salt are referred to as D1-D6. Diazo film samples are prepared from valley zoazo coated samples as described in Example 1.

The layer weight of the diazo film sample is 8-9! //m2.

For comparative testing of the stability of film samples, the method of Example 1 is followed. In the film sections that are not fully exposed, considering the films gRcx-C6 and D1-D6, a yellow to magenta-yellow tone results.

Table 2 shows the results of a comparison between samples stored under harsh conditions and corresponding new comparison samples that were not stored.

Table 2 The film background of film samples C1-C6 changed very bloody or did not change at all on the storage iron. In other words, it can be said that virtually no manual coupling (55) occurs. Film sample D
In some cases of I''D6, the film background did not change significantly under the same storage conditions.

That is, extensive manual coupling during storage has been recorded. On the contrary, film samples C-C6 were still completely intact after storage carried out under harsh conditions, and film samples D1-D6 were still completely intact after storage carried out under harsh conditions; Current 1'I! can be done.

Similar results were obtained by replacing 2,2'-dimethyl-4,4'-dihydroxy-5,5'-cy(1)-butyl-diphenyl sulfide with the same amount of other listed diphenyl tylphide cups. When using ring compounds, Mr. KM＼
You can get Tsumugi N.

In this test system as well, the measured results in Table 2 are similar to those of benzenediazonium hexafluorophosphate compared to the corresponding known benzenediazonium tetrafluoroborate, hydrodansulfate and benzenediazonium chloride (ZnCl4 double salt) Ic. Eight's obvious excellence 1!4'fi! : Show (56).

Example 6 A 125 Arn thick polyethylene terephthalate film with an adhesion promoting layer is sensitized on a primed surface with a coating material of the following composition:

Acetone 67.5 # Methanol 17.5i n-getanol 4. [J & Methyl Glycol 4.09 Cellulose Acetoglobionate 7. tJ, 9bo! I
-(Methyl vinyl ether/Anhydrous 7247 version) Skin 75,? 5-sulfoterityl rIR[J, 15112.2'-
Dimethyl-4,4'-dihydroxy-5,5'-cy(
1) -Dithyl-diphenyl-length runide 1. Ll, 9
2.4-Dihydroxybenzoic acid [J, 1, ? 4-
Dimethylamino-3-chlorobenzenediazonium hexafluorophosphiny) 1.709 Coating and drying are carried out as described for N1. The layer weight t is 7,69/=2.

Part section' of the produced film sample (g)?
Ammonia gas
[066]]. From this K, an original bozotegucoby with an orange-red line on a colorless transparent film background is obtained. This high contrast in the extra-base spectral range) (DU04%, max: 2.8, D[J[
)4. min: 0.08), this copy was deposited as a temporary original film for the da of other copies on UV-sensitive material (preferred). D
Uv1o6゜max: 0-6, DUy 106 1
m1n' 0-04) Based on K, such a temporary original film is also very suitable as a mask in the photolithography of integrated circuits in printed wiring boards and microelectronics. Based on its favorable OJ visual transparency and simultaneous low UV absorption, such temporary original film is excellent in the field of multi-purpose silver film mask applications.

A second part section of the undeveloped film sample (E) is exposed as described in Example 1, developed, and the degree of roundness in the film background is measured.

6 other parts of the unrealistic film examination (k)
Store at 0° C. and 80% relative humidity for 24 hours, then process as described above and measure the original 4-density in the film background. 4-dimethylamino-6
- Instead of chlorpenzene siazonium hexafluorophosphate, commercially available 4-dimethylamino-6-
Florbenzenediazonilam tetrafluoroborate (=
1.4y) was used to obtain a film sample (F), which has a rather low stability under the storage conditions mentioned above.

(59) Placement of rMw, 5-sulfosalicylic acid using 4-dimethylamino-6-florbenzenezaadenium tetrafluoroporate in a diazo lacquer coating composition:
0.20 g of tartaric acid as acid stabilizer and additionally 0.20 g of tartaric acid as acid stabilizer.
Increasing the pressure above 30 g can dramatically reduce premature coupling. The drawbacks of the film sample (G) thus produced are that during the storage of the raw film material and under hot water vapor conditions (40% for the raw film material)
0”C/80% relative humidity, current 1#! about 70”O/8
During the current period under 0% relative humidity, an obvious visible precipitate (blooming) is formed on the layer surface.

The results of this test system are summarized in Section 6.

(60) Table 6 Cassirer 2-hydroxy-6-N-(4'-methyl-
phenyl)-amidosulfonyl-6-naphthoic [N
-(4'-methylphenyl)amide 0.01 # or coupler 2,6-dihydroxynaphthalene-6-sulfonic acid N-(4'-chlorophenyl)-amide O, [J
Adding 1g' to the coating composition yields a 1'1'' film material with similarly good copy and storage results.

- In the current iron sickle using electric light and moist ammonia gas according to the force, both film materials yield a copy of the original of the brown rock on a colorless transparent background.

1+! , 14 Sensitize on both sides of a 125 μm thick polyethylene terephthalate film provided with an adhesion promoting layer on both sides with a coating material of the following composition: Acetone 67.59 Methanol '17.51i n-Butanol 4.0 g Methyl glycol 4.0.9 Cellulose acetozolopionate 7. OF poly-(methyl vinyl ether/maleic anhydride) tJ, 7511 5-sulfosalicylic acid tJ, [J75#2.7-dimethyl-4,4'-dihydroxy-5,5'-c(t)-butyl-diphenylthyl Phido [J, 66.91-hydroxy-3-N-
(4'-Chlorphenyl)-amidosulfonyl-8-N-(n)-gutylamidosulfonyl-naphthalene [J, 10, p4-methylcyclohexylamino-3-chlorobenzene-zoadenium hexafluorophosunate) [1, 73g Coating and drying is carried out as described in Example 1. The tm redness of each film measurement is 7.51//In2.

in this way! li! Part sections of the ffi film samples are quaternized under the d-film original, and then the M-copies are developed using humid ammonia gas using commercially available continuous equipment. In this way, the original bozotizocoby with brown lines and a colorless transparent background is obtained.

Owing to the favorable visual transparency of the brown axis, such films are particularly suitable as quaternary masks in photolithography for integration in printed circuit boards and microenctronics.

The above-mentioned pre-processing film material (film material H) (7) storage solution was prepared by using the corresponding ZnCl2 of equivalent molar fraction instead of 4-methylcyclohexylamino-6-chloropenzenezazonium hexitefluorophosphate. The storage of film materials CI) using m-salts (65) is significantly better than the stable injection.

Table 4 Example 5 One side of a glass plate is synthesized with a coating material having the following composition: Acetone 67.5 g Methanol 17.5 I n-butanol 4.0 g Methyl glycol 4.0 g Cellulose acetopropionate 7. Dgiv-<methyl vinyl ether/maleic anhydride) 0.7511 5-sulfosalicylic acid [1,15,! i'2.2'-
Dimethyl-4,4'-dihyde (64) Roxy5.5'-no(t)-butylusoneenyl sulfide [J, 66 g2.4-ritoxybenzenyl amide LJ, 2094-diethylamino-2, 5-
Cyclolbenzene-zoazonium hekibufluorophosphate 1.42II Coating and drying are carried out as described in Example 1.

The layer weight is 86g/m''.
Using a W pulsed xenon lamp, expose under the silver film original until the yellow film layer not covered by the original is completely whitened. It is then heated with ammonia gas in a closed oven at room temperature. This yields an original bozochibucoby with a red line on a colorless transparent back-brown r, a copy of which is highly suitable as an original material for the production of printed circuit boards and circuit boards by photolithography. .

The storage stability of this diazo film glass plate (K) is very good. When 4-noethylamino-2,5-dichlorobenzenediazonium hexafluorophosphate is replaced by the corresponding ZnCl24) J salt with an equimolar cap,
Storage of such material (L) 4 stable injection at 55℃, 65%
Significantly poorer relative humidity over 24 hours.

Table 5 4-diethylamino-2,5-zochlorobenzene siazonium hexaneluophosphate instead of 4-diethylamino-2,5-zochlorobenzene siazonium
Similarly good results are obtained using -methylcyclohexylamino-6-chloro-2-trifluoromethylbenzene siazonium hexafluorophosphate.

Example 6 One side of a polyethylene terephthalate film with a thickness of 75 μm coated on both sides with cellulose acetopropionate containing silica and alumina as finely ground pigments was sensitized with a bath solution of the following composition, and the applied bath solution was dried. Make: Impropanol 80III! Acetone 12IIIl n-butanol 4□l Formic acid (85%) 4ml Water 8d Ho! J-(Methyl vinyl ether/maleic acid) monoisozoro and ester (Gantretsu ■gs-635) 1500 da-5-sulfosalicylic acid 1259 2,z-methyl-4,4'-dihydroxy-5,b'-cy(2)-pte Luzophenyl sulfide 188U'& 6.5-dihydroxybenzoic acid 18[JIll & 4-bromo-6,5-dihydroxybenzoic acid N -(2'-dimethylamino(67) phenyl)-amide 60111 & 4-dimethylamino-6 - fluorbenzenediazonium hexafluorophosphate 1000 ~ This cyacitaib material produced by this method (under the pencil drawing of the colorless transparent material after coloring according to the path light and subsequent exposure with moist ammonia gas) A punch copy of the original with brown lines on the background is obtained.

Under certain hostile dyeing conditions, the storage stability of undeveloped I station materials is as follows:
It is more elegant and better than when using the corresponding 4-dimethylamino-6-florbenzenezazonium tetrafluoroborate (film sample N) with the same molar cap. Similarly good results are obtained when a transparent paper coated on both sides with cellulose acetobutyrate is used as the support layer for the photosensitive cylindrical layer.

(68) No. 6 Table Example 7 Each No. 100 6:+-ting sample with the following composition was taken out from both solutions: Acetone 675y Methanol 175I n-Butanol 40 g Methyl glycol 40 g Cellulose acetopropionate 7tJ &ylt”J
-(Methyl vinyl ether/maleic anhydride) 7.
b g 2.2'-tumethyl-4,4'-nohydroxy-5,5
'-C(1,)Ptyrusophenyl sulfite 10
g 2.4-dihydroxybenzoic acid 1 g Into this 6-coat/g sample (0), introduce the following: a) 4-dimethylamino-6-chlorobenzenezazonium hexafluorophosphate 1700 g (Sample 03
) and a) +5-sulfosalicylic acid 150 ■ (sample 01) a) → 5-sulfosalicylic acid 67.5 ■ (sample 02) The following were introduced into the remaining 6 coating samples (P) and b) 4-dimethylamino-6-chloropenzenezazonium tetrafluoroborate 1400 ■ (sample p6) and b) +5-sulfosalicylic acid 1501 V (sample P1) and b) → 5-sulfosalicylic acid 67.5 ■ (Sample P2) In this way! Each of the coating samples left in A (c) Prepare the diazo film samples from each in the same manner as in Example 1! l! !
The corresponding coating samples RK were numbered 01-03 and P1-P6, respectively.

The layer arrangement of each diazo film sample is 8-9I/rJL2
It is.

The method of Example 1 was followed for a comparative study of the storage stability of the undeveloped Zoazofil samples 01-05 and P1-P6.

Transobac film G-2 (Transovac film G-2) is based on benzenesiazonium to tefluorophosphate.
paque F'i1m G-2; Th1oKol
/Dynachem Corp,) product name"'Q
Publicly known (')! /' 7 f films were also included as a comparison in this storage stability test.

In the film sections that were not completely rewrote, diazo film grades 01-06 and P1-P3 were
M produces a reddish color aMl, and transobac film o-2 produces a pale brown hue due to practical considerations.

The results of storing film samples of Film Samples 01-06 and P1-P6 and (72) Transopac Film G-2 under severe conditions are shown in Table 7 in comparison with the corresponding new comparative samples.

In Table 7, it can be seen that the film background in film samples 01-06 changed only slightly, ie, very little premature coupling occurred during storage.

However, in film samples P1-P3, the film back brown varies significantly under the same storage conditions, i.e., especially in the DUV spectral region (DUV
) Significant underhand cassilling occurs during savings.

Trans-opaque film G-2r'! Film sample P
The trans-onoyak film samples P1-P6 and the trans-onoyak film G-2, which exhibit unfavorable behavior of class 1 or higher with those of 1-P6, exhibit insufficient stability under warm and humid storage conditions;
Film samples according to the invention are clearly more stable under these storage conditions.

Example 8 Effect fj during acupuncture on the thigh using very moist ammonia gas! 0: For comparison purposes, film samples 01-06 from Example 7 were tested in comparison with the known Tojinsuopak Film (2).

We planned a test example with full color tones. Tani sample 95～
The reaction was carried out using a given volume of aqueous ammonia (28%) at a temperature of 10 J°C. The residence time of each film sample in the phenomenon testing apparatus was 10 to 60 sheets.

Table 8 summarizes the results after the first dormitory.

Table 8 These results show that the films gN01-03i, the very extreme current 11J! There is also a problem with condition D (one condition is possible, and ratio V
The sample shows that under the same current iron condition, a clear OJ degeneration occurs in the film layer and a complete disappearance of layer adhesion occurs in the inverted curve.

Based on the very wide current wear conditions, the diazo film samples according to the present invention (75) are clearly superior to the wear material ' Even in the case of current equipment of the type that can be used on the market, it can be realized without layer loss and loss of attachment.

The former student, Naoki Tadashi, mentioned in the example of death, used the Macbeth Densitometer.
) TD205 is used to obtain the OT night spectrum Dv□8, K is the Kodak filter
(Wratten) I U 6'l is used, and in order to obtain the outer ray spectral range (DUv), a Scott filter (5chott flitter) u o is used.
4k is used.

(76)

Claims (1)

[Scope of Claims] 1. A photosensitive composition comprising a siazonium salt, a coupler, a resin binder, a stabilizer, a conventional koikado and a liquid phase, which comprises: ta) p-aminobenzene siazonium hexazonium; Fluofosunate at least 1a1 (b) At least 1 fc in zohytaloxyzophenylter 7i, if appropriate as a mixture with other couplers) 0 to 2o weight relative to the diazonium salt used! 1 to 1% acid stabilizer + (1) as a fat binder, plastics with acid groups and less (both 100 acid + 1thY) derived from maleic or phthalic type and f8) A photosensitive composition characterized in that it consists of a lower alcohol, a glycol ether, a ketone, and water alone or in combination as a liquid phase. 2. The p-aminebenzenediazonium hekitefluorophosphate present is represented by the formula: [wherein R1 is alkyl having 1 to 6 carbon atoms, alkenyl having 1 to 4 carbon atoms, or alkenyl having up to 8 carbon atoms]
and R2 is a cycloalkyl group having 1 carbon atom.
unsubstituted or substituted alkyl having ~18;
Alkenyl having strictly 4 carbon atoms, 6 to 6 carbon atoms
Cycloalkyl or urinary Ig having 12 atoms 7 to 1
2 is an unsubstituted or substituted aralkyl, but rK R1 and R2 together with the family atoms attached to them are unsubstituted or substituted aralkyl ~8j4.
is a heterocyclic group, X is chlorine or bromine, and Y is water, bromine, trifluoromethyl, ether or thioether group], %fF according to claim 1 Composition of. 6. The existing Zohyroxyzonenyl sulfide has the formula: [In the formula, R3 and R4 are the same or different, and hydrogen,
It is an alkyl having 1 to 4 because of the R atom, and is a compound with a small number of ortho i to the OH group (both 1 is occupied by hydrogen), and when appropriate, the formula: [in the formula R5 and R6 are the same or different and are hydrogen, carboxyl, carboxamide or non-tIIL-substituted carboxyalkyl- or carboxyaryl-amino group substituted with loxyl or amino group, and R7 and R
8 are the same or different and are hydrogen, sulfalkyl, alkenyl or hibiroxyalkyl having 1 to 4 carbon atoms, or non-*M or rimmed aryl having 6 to 12 carbon atoms\R9, RIO and R11 are the same or different, hydrogen, (6) unsubstituted or substituted alkyl having 1 to 6 carbon atoms, cycloalkyl having 6 to 12 carbon atoms, or 6 to 12 carbon atoms; or RIO and R11 are trapped together with the nitrogen atoms bonded to them, and are unsubstituted or substituted 5^~
is an 8-membered heterocyclic group, R12 is hydrogen, and R1
3 is unsubstituted or substituted with an alkyl group, cycloalkyl having up to 8 carbon atoms, aralkyl having up to 10 carbon atoms, or unsubstituted or tj/L-substituted aryl, or R12 and R13 are, together with the nitrogen atom attached to them, an unsubstituted or substituted 5-membered Xka-membered heterocyclic group, and Z is hydrogen, chlorine or bromine. 1. The composition according to item 1, wherein the cyazonium salt present is 4-dimethylamino-6.
-Florbenzene-diasonium hexafluorophosphate and the present Ka(4) The composition according to claim 1, which is sulfide and 2,4-zohydroxybenzoic acid. 5. The cyazonium salt present is 4-dimethylamino-
6-Florobenzene-cyazonium hexafluorophosphate, and the couplers present are 2,2'-dimethyl-4,4'-zoyl and roxy5,5'-cy(mo)-
Glythyl-diphenyl sulfide, 2,4-dihydroxybenzoic acid and 2,6-dihydroxy-naphthalene-6
-sulfonic acid N-(4'-chlorophenyl)-amide, the composition according to item 1, wherein the % retention range is desired. 66 The diazonium salt present is 4-methylcyclohexylamino-6-chlorobenzene siazonium hexitefluorophosphate, and the cassilla present is 2,
7-dimethyl-4,4'-dihydroxy-5,5'-cy(1)-tethyrusophenyl sulfide and 1-hydroxy-3-N-(4'-chlorophenyl)-7midosulfonyl-6-N-( 2. A composition according to claim 1, which is n-butyl)-amidosulfonylnaphthalene. Z The cyanium salt present is 4-zoethyl 7mi/
-2,5-zochlorobenzene-zoazonium hexafluorophosphate, and the coupler present is 2,2'
-dimethyl-4゜4'-dihydroxy-5,5'-c(1)-zotylcyphenyl sulfide and 2,4-
2. The composition of claim 1, which is 1-hydroxybenzoic acid. 8. The diazonium salt present is 4-methylcyclohegysylamino-6-chloro-2-to-IJ fluoromethylbenzene siazonium hekitefluorophosphate;
The ka-12- present is 2,2'-dimethyl-4,4'
-dihydroxy-5,5'-c(t)-butyl-diphenyl sulfide and 3,5-dihydroxybenzoic acid. 9 Binders present are cellulose acyl esters and maleic till! A composition according to claim 1, which is a mixture of a copolymer of a derivative and an alkene compound. 10, layer support and fa) p-aminobenzene cyazonium hexitefluorophosphate at least 1a [(b) zohyrloki/-syn, as a mixture with other couplers in appropriate combinations 0 to 20% by weight of the cyazonium salt used as an acid stabilizer t (1) If as a fat binder, having an acid group and containing at least 100 acids A two-component zoazoquizo material, characterized in that it consists of a photosensitive layer consisting of at least one layer of plastic cast from mannic acid or 7-talic acid type. 12. A diazotype material according to claim M10, comprising a coated polyethylene terephthalate film'&tf as layer support. 13. A diazotype material according to claim M10, comprising: 14. A lipstick material as claimed in claim 10, having a glass space as a material. The sheet material according to any one of the items.