US2593839A - Diazotype photoprinting material - Google Patents
Diazotype photoprinting material Download PDFInfo
- Publication number
- US2593839A US2593839A US61727A US6172748A US2593839A US 2593839 A US2593839 A US 2593839A US 61727 A US61727 A US 61727A US 6172748 A US6172748 A US 6172748A US 2593839 A US2593839 A US 2593839A
- Authority
- US
- United States
- Prior art keywords
- diazotype
- light sensitive
- resorcinol
- component
- crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims description 20
- 239000007859 condensation product Substances 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- -1 DIAZO Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 15
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 150000008049 diazo compounds Chemical class 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000006149 azo coupling reaction Methods 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 3
- 230000002028 premature Effects 0.000 description 3
- JYXJUIJEYIELLT-UHFFFAOYSA-N 2-(2,6-dihydroxyphenyl)acetaldehyde Chemical compound OC1=CC=CC(O)=C1CC=O JYXJUIJEYIELLT-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GQOYDWTWEHXGDV-UHFFFAOYSA-N acetaldehyde;benzene-1,3-diol Chemical compound CC=O.OC1=CC=CC(O)=C1 GQOYDWTWEHXGDV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- SYXUBXTYGFJFEH-UHFFFAOYSA-N oat triterpenoid saponin Chemical compound CNC1=CC=CC=C1C(=O)OC1C(C=O)(C)CC2C3(C(O3)CC3C4(CCC5C(C)(CO)C(OC6C(C(O)C(OC7C(C(O)C(O)C(CO)O7)O)CO6)OC6C(C(O)C(O)C(CO)O6)O)CCC53C)C)C4(C)CC(O)C2(C)C1 SYXUBXTYGFJFEH-UHFFFAOYSA-N 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000033458 reproduction Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YFCXTPKUVYRXFI-UHFFFAOYSA-M 4-(diethylamino)benzenediazonium;chloride Chemical compound [Cl-].CCN(CC)C1=CC=C([N+]#N)C=C1 YFCXTPKUVYRXFI-UHFFFAOYSA-M 0.000 description 1
- VVYWUQOTMZEJRJ-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N)C=C1 VVYWUQOTMZEJRJ-UHFFFAOYSA-N 0.000 description 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical class OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- LRSYZHFYNDZXMU-UHFFFAOYSA-N 9h-carbazol-3-amine Chemical compound C1=CC=C2C3=CC(N)=CC=C3NC2=C1 LRSYZHFYNDZXMU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YQYUUNRAPYPAPC-UHFFFAOYSA-N n,n-diethyl-2-methylaniline Chemical compound CCN(CC)C1=CC=CC=C1C YQYUUNRAPYPAPC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003000 phloroglucinols Chemical class 0.000 description 1
- 239000011092 plastic-coated paper Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
- G03C1/58—Coupling substances therefor
Definitions
- This invention relates to diazotype photoprinting material and process for the manufacture thereof. More particularly, this invention relates to diazotype photoprinting material having a two-component diazotype light sensitive layer and a method for making the same.
- Two-component diazotype light sensitive layers contain a light sensitive diazo compound, suitably stabilized against premature coupling prior to development of the material, together with an azo coupling component.
- the diazo compound Upon exposure of such a layer to light of locally varied intensity in accordance with an original pattern or design to be reproduced, the diazo compound is partly or completely destroyed in the light exposed portions, so that upon subjecting the layer .to developing treatment as by exposure to alkaline vapors, e. g. ammonia, or treatment with an alkaline solution, the residual diazo compound couples with the azo component to form an azo dye image of the original pattern.
- alkaline vapors e. g. ammonia
- the development is conveniently carried out in the dry process by exposing the layer to ammonia or a volatile amine, or by the wet or semi-wet process in which an alkaline developer solution is applied to the layer after exposure thereof.
- the sensitizing components are generally applied or deposited successively or in combination on a support such as paper, plastic materials, metals, glass or the like.
- a support such as paper, plastic materials, metals, glass or the like.
- the sensitizing composition can be used in aqueous solution, while for plastics it has been suggested to use a solution containing an organic solvent which has a solvent or swelling action upon the plastic support.
- sensitizing components in diazotype layers which yield dark shades adapted to reproduce the opaque parts of the original, While at the same timehaving a sufficiently moderate gradation to reproduce a wide range of densities as are generally found in photographs.
- Diazotype images produced with two-component layers containing resorcinol as a coupler are subject to disadvantages.
- the image is subject to migration or ofisetting, causing blurring or spreading of the lines and. margins of the image.
- the colorations produced are not fast to washing and hence often yield a blurred image when the development is carried out by the wet or semi-wet process.
- the brown colorations ordinarily obtained with resorcinol have a definite reddish tint which is not desirable, especially in photographic reproductions.
- a m-polyhydric phenol resorcin-ol, phloroglucinol
- the azo coupling components employed in accordance with this invention can be conveniently prepared, by the procedure of Niederl et al. in J. A. C. S. 62 (1940), p 2512-2513, by mixing 1 mol of resorcinol or phloroglucinol with 0.9-1 mol of a hydrocarbon aldehyde, wherein the hydrocarbon contains 1-6 carbon atoms, in aqueous or aqueous alcoholic sulfuric acid of 5-10% concentration, and allowing the reaction mixture to stand without external heating until the crystalline condensation product separates.
- water can be used, while for aldehydes containing 4 or more carbon atoms, equal parts by weight of ethyl alcohol and water are employed as a reaction medium to retain the aldehyde solution;
- concentration of the aldehyde and m-polyhydric phenol in the reaction mixture is generally 2-7%, the reaction being carried out by dissolving the m-polyhydric phenol in a portion of aqueous or aqueous alcoholic sulfuric acid, dissolving the aldehyde in the remainder of the reaction medium, and gradually adding the aldehyde solution to the m-polyhydric phenol solution.
- the crystalline condensation product which separates from the The products thus obtained 3 4 from resorcinol, as given by Niederl et al., is as compounds against premature coupling and defollows; composition comprise organic acids such as for- OH R (])H mic, citric, tartaric, mellitic, and sulfosalicylic acids; anti-oxidants such as thiourea, and stabi- 5 lizing salts such as zinc chloride or other halides forming complex addition products with the diazo salts, e. g. boron trifluoride.
- Colloidal wetting 2 agents such as saponine are likewise advantal H geously included.
- Example 1 OH H 4 grams of tetrameric crystalline condensa- R being the hydrocarbon radical of the aldetion product of equimolecular amounts of acetalhyde. However, it is believed th structure may dehyde and resorcinol were dissolved in 100 cc. be of the open-chain type as follows: of ethyl alcohol, and the resulting solution coated i R R-onoH- -CH 5H--' t11- HO- OH HO- -o11 HO- OH HO- -on R having the same significance as above. Coron paper, After drying, the paper was coated responding derivatives of phloroglucinol have an with a solution of the following composition: additional hydroxyl group in the benzene rings in m-position to the other hydroxyl groups.
- diazotype photoprinting material containing the crystalline tetra-meric condensation products described above may be applied simultaneously or successively with a light sensitive diazo compound, suitably stabilized a against premature coupling to a base or 3 gl-diethyilamrnobcnzene dlaZOI'lllllTl chloride port.
- the products are applied in solvents adaptn 2 douo e Sal ed for impregnation of the carrier.
- al- 40 diluted with water to avolume of 100 cc.
- Asharp purplish-brown image was obor other polyvinyl resins, are employed as cartained of excellent fastness to light, of deeper riers, a solvent mixture is preferably employed shade, and better fastness to washing than an imfor applying the coupling components, said mixage produced with a sensitizing composition simiture having a swelling or slight solvent action on lar to that described herein but containing rethe plastic carrier employed.
- solusorcinol instead of the acetaldehyde resorcinol tions containing 'y-valerolactone in aqueous alcocondensation product.
- holic medium (containing for example, methanol, Exam Z6 2 ethanol, isopropanol and butanol) can be adva'np tageously used for impregnating cellulose acetate.
- a sensitizing solution was prepared having the Since the coupling components of this invenfollowin composition: tion are water-insoluble or of low solubility in water, an alcoholic solution thereof can be first applied to an absorbent base such as paper, and the light sensitive diazo component, together with stabilizers, anti-oxidants and the like, subse- 6 quently applied in aqueous solution to the same base after evaporating the alcoholic solution.
- a mixed solvent is employed, adapted to dissolve both the coupling component and the light sensitive diazo compound, such a solution can be used to sensitize a base in a single operation.
- the light sensitive diazo compounds are preferably diazotized diamines of the benzene series,
- the resulting solution was heated to about 50 C. particularly those having at least one substituent and coated at this temperature on cellulose ace- 50 parts water 20 parts isopropyl alcohol 1 part zinc chloride 2 parts thiourea 10 parts 'y-valerolactone 5 parts sulfosalicylic acid 5 parts formic acid 5 parts butanol 4 parts p-diethylamino-2-methyl benzene diazonium chloride ZI1C12 double salt; and 6 parts of the resorcinol acetaldehyde tetrai'neric condensation product of Example 1.
- Development can be eifected either with ammonia or with an aqueous alkalin solution such as aqueous ammonia, sodium carbonate, tri-sodium phosphate, or tri-ethanolamine.
- aqueous alkalin solution such as aqueous ammonia, sodium carbonate, tri-sodium phosphate, or tri-ethanolamine.
- the resulting image was likewise of dark purplish-brown color, of excellent sharpness showing no migration or ofisetting and of excellent fastness to light.
- resorcinol acetaldehyde condensation product of the foregoing examples there can be employed the corresponding crystalline tetrameric equirnolecular condensation product of acetaldehyde with pholorglucinol, or of propionaldehyde, butyraldehyde, isobutyraldehyde, hexaldehyde, or benzaldehyde with either resorcinol or pholorogiucinol, whereby images having similarly advantageous properties are obtained.
- diazo compounds of p-ethylamino m-toluidene, p amino N diethyl m-toluidene, p-amino-N- methylaniline, p-amino Z-methoxy-N-cyclohexylaniline, p-amino N 2' hydroxyethylaniline, p-amino N ethyl-N-Z-hydroxyethylaniline, 3 aminocarbazole, 1,2-, 2,1-, or 1,4-aminonaphthol, 1,2-aminonaphthol-e-sulfonic acid, or 2,1-aminonaphthol-3,6-disulfo acid.
- These diazo compounds can be employed in the form of their diazonium chloride zinc chloride double salts or the corresponding boron trifluoride complex addition products.
- alcohols such as methanol, ethanol, isopropanol and butanol can be employed as media for impregnating absorbent bases with the aldehyde polyhydric phenol condensation products of this invention, particularly when applied separately from the light sensitive diazo component, and mixed solvents containing water, alcohols and a softening agent for plastics such as 'y-valerolactone, can be used as a medium for applying the light sensitive diazo component as well as coupling components of this invention in a single operation to a plastic support.
- Diazotype photoprinting material comprising in a light sensitive layer, a light sensitive diazo component, and as a coupling component, a crystalline tetrameric condensation product of a m-polyhydric phenol with an equimolecular amount of an aldehyde having the formula RCHO, wherein R is a hydrocarbon radical having 1-6 carbon atoms.
- Diazotype photoprinting material comprising a plastic base impregnated with a light sensitive diazo component and with a coupling component which is a crystalline tetrameric condensation product of a m--polyhydric phenol with an equimolecular amount of an aldehyde having the formula RCHO, wherein R is a hydrocarbon radical having l6 carbon atoms.
- Diazotype photoprinting material comprising in a light sensitive layer, a light sensitive diazotized p-diamine of the benzene series, and as a coupling component, a crystalline tetrameric c0ndensation product or" resorcinol with an equimolecular amount of acetaldehyde.
- Diazotype photoprinting material comprising a paper case impregnated with the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, and with the zinc chloride double salt of p-diethylaminobenzene diazonium chloride.
- Diazotype photoprinting material comprising a plastic layer impregnated with the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, and With the zinc chloride double salt of p diethylamino 2 methyl benzene diaz'onium chloride.
- a process for the manufacture of light sensitive diazotype materials which comprises impregnating an absorbent base with an alcoholic solution of the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, drying the base, and impregnating the latter with an aqueous solution containing the zinc chloride double salt of pdiethylaminobenzene diazonium chloride.
- a process for the manufacture of light sensitive diazotype materials which comprises impregnating a plastic base with an aqueous alcoholic solution containing -valerolactone, of the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, and containing the zinc chloride double salt of p-diethylamino-Z-methyl benzene diazonium chloride.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
Patented Apr. 22, 1952 DIAZOTYPE PHOTOPRINTING MATERIAL Saul R. Buc, Northampton County, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application November 23, 1948, Serial No. 61,727
7 Claims.
This invention relates to diazotype photoprinting material and process for the manufacture thereof. More particularly, this invention relates to diazotype photoprinting material having a two-component diazotype light sensitive layer and a method for making the same.
Two-component diazotype light sensitive layers contain a light sensitive diazo compound, suitably stabilized against premature coupling prior to development of the material, together with an azo coupling component. Upon exposure of such a layer to light of locally varied intensity in accordance with an original pattern or design to be reproduced, the diazo compound is partly or completely destroyed in the light exposed portions, so that upon subjecting the layer .to developing treatment as by exposure to alkaline vapors, e. g. ammonia, or treatment with an alkaline solution, the residual diazo compound couples with the azo component to form an azo dye image of the original pattern. The development is conveniently carried out in the dry process by exposing the layer to ammonia or a volatile amine, or by the wet or semi-wet process in which an alkaline developer solution is applied to the layer after exposure thereof.
To manufacture two-component diazotype layers, the sensitizing components are generally applied or deposited successively or in combination on a support such as paper, plastic materials, metals, glass or the like. For absorbent materials like paper, the sensitizing composition can be used in aqueous solution, while for plastics it has been suggested to use a solution containing an organic solvent which has a solvent or swelling action upon the plastic support.
Many of the sensitizing materials heretofore employed in two-component layers were defective in that the image lacked fastness to water and aqueous solutions because of the solubility in water of the resulting azo dye. Moreover, when incorporated in a plastic carrier, the azo dye produced on development was subject to migration or offsetting in the layer. Both of these conditions cause blurring of the image, rendering such compositions unsuitable for prints in which sharpness of the image is required.
At the same time it is desirable to use sensitizing components in diazotype layers which yield dark shades adapted to reproduce the opaque parts of the original, While at the same timehaving a sufficiently moderate gradation to reproduce a wide range of densities as are generally found in photographs.
Diazotype images produced with two-component layers containing resorcinol as a coupler are subject to disadvantages. When such images are formed on a plastic base, the image is subject to migration or ofisetting, causing blurring or spreading of the lines and. margins of the image. The colorations produced are not fast to washing and hence often yield a blurred image when the development is carried out by the wet or semi-wet process. The brown colorations ordinarily obtained with resorcinol have a definite reddish tint which is not desirable, especially in photographic reproductions.
It is an object of this invention to provide novel two-component diazotype layers which yield dark purplish-brown images having a wide range of gradation suitable for the reproduction of photographic originals, which are not subject to ofisetting or migration when produced on plastic carriers, and having good fastness to water and aqueous solutions.
I have discovered that diazotype layers containing, as the azo coupling component, a crystalline tetrameric condensation product of a m-polyhydric phenol (resorcin-ol, phloroglucinol) with an equimolecular amount of an aldehyde having the formula RCHO, wherein R is a hydrocarbon radical of l-6 carbon atoms, yield prints having dark purplish brown images of good fastness to light which do not offset or migrate in a plastic carrier and which have excellent fastness to water and aqueous solutions.
The azo coupling components employed in accordance with this invention can be conveniently prepared, by the procedure of Niederl et al. in J. A. C. S. 62 (1940), p 2512-2513, by mixing 1 mol of resorcinol or phloroglucinol with 0.9-1 mol of a hydrocarbon aldehyde, wherein the hydrocarbon contains 1-6 carbon atoms, in aqueous or aqueous alcoholic sulfuric acid of 5-10% concentration, and allowing the reaction mixture to stand without external heating until the crystalline condensation product separates. For lower aldehydes, water can be used, while for aldehydes containing 4 or more carbon atoms, equal parts by weight of ethyl alcohol and water are employed as a reaction medium to retain the aldehyde solution; The concentration of the aldehyde and m-polyhydric phenol in the reaction mixture is generally 2-7%, the reaction being carried out by dissolving the m-polyhydric phenol in a portion of aqueous or aqueous alcoholic sulfuric acid, dissolving the aldehyde in the remainder of the reaction medium, and gradually adding the aldehyde solution to the m-polyhydric phenol solution. The crystalline condensation product which separates from the The products thus obtained 3 4 from resorcinol, as given by Niederl et al., is as compounds against premature coupling and defollows; composition comprise organic acids such as for- OH R (])H mic, citric, tartaric, mellitic, and sulfosalicylic acids; anti-oxidants such as thiourea, and stabi- 5 lizing salts such as zinc chloride or other halides forming complex addition products with the diazo salts, e. g. boron trifluoride. Colloidal wetting 2: agents such as saponine are likewise advantal H geously included.
My invention will be more fully understood 011 from the following examples wherein the parts are by weight unless otherwise indicated.
1 (5 Example 1 OH H 4 grams of tetrameric crystalline condensa- R being the hydrocarbon radical of the aldetion product of equimolecular amounts of acetalhyde. However, it is believed th structure may dehyde and resorcinol were dissolved in 100 cc. be of the open-chain type as follows: of ethyl alcohol, and the resulting solution coated i R R-onoH- -CH 5H--' t11- HO- OH HO- -o11 HO- OH HO- -on R having the same significance as above. Coron paper, After drying, the paper was coated responding derivatives of phloroglucinol have an with a solution of the following composition: additional hydroxyl group in the benzene rings in m-position to the other hydroxyl groups.
In preparing diazotype photoprinting material containing the crystalline tetra-meric condensation products described above, the latter may be applied simultaneously or successively with a light sensitive diazo compound, suitably stabilized a against premature coupling to a base or 3 gl-diethyilamrnobcnzene dlaZOI'lllllTl chloride port. The products are applied in solvents adaptn 2 douo e Sal ed for impregnation of the carrier. Thus, al- 40 diluted with water to avolume of 100 cc.
1 cc. isopropanol 5 cc. ethylene glycol 5 g. citric acid 5 g. zinc chloride 5 g. thiourea 0.1 g. saponine cohols (ethanol, methanol, isopropanol) are suit- After drying, the resulting sensitized material able as solvents for applying the coupling comwas exposed under an original pattern to be reponents to paper and other absorbent carriers. produced, such as an opaque line drawing on a When plastic materials such as a cellulose ester translucent background or a photographic diaor ether, e. g. cellulose acetate of ether cellulose, 7 positive, and thereafter developed by exposure to or a resinous polymer, such as polyvinyl alcohol ammonia. Asharp purplish-brown image was obor other polyvinyl resins, are employed as cartained of excellent fastness to light, of deeper riers, a solvent mixture is preferably employed shade, and better fastness to washing than an imfor applying the coupling components, said mixage produced with a sensitizing composition simiture having a swelling or slight solvent action on lar to that described herein but containing rethe plastic carrier employed. For example, solusorcinol instead of the acetaldehyde resorcinol tions containing 'y-valerolactone in aqueous alcocondensation product. holic medium (containing for example, methanol, Exam Z6 2 ethanol, isopropanol and butanol) can be adva'np tageously used for impregnating cellulose acetate. A sensitizing solution was prepared having the Since the coupling components of this invenfollowin composition: tion are water-insoluble or of low solubility in water, an alcoholic solution thereof can be first applied to an absorbent base such as paper, and the light sensitive diazo component, together with stabilizers, anti-oxidants and the like, subse- 6 quently applied in aqueous solution to the same base after evaporating the alcoholic solution. When a mixed solvent is employed, adapted to dissolve both the coupling component and the light sensitive diazo compound, such a solution can be used to sensitize a base in a single operation.
The light sensitive diazo compounds are preferably diazotized diamines of the benzene series, The resulting solution was heated to about 50 C. particularly those having at least one substituent and coated at this temperature on cellulose ace- 50 parts water 20 parts isopropyl alcohol 1 part zinc chloride 2 parts thiourea 10 parts 'y-valerolactone 5 parts sulfosalicylic acid 5 parts formic acid 5 parts butanol 4 parts p-diethylamino-2-methyl benzene diazonium chloride ZI1C12 double salt; and 6 parts of the resorcinol acetaldehyde tetrai'neric condensation product of Example 1.
on one of the amino groups. Diazotized o-aminotate foil and on plastic coated paper. The modnaphthols are also adapted for use at light senerately elevated temperature was employed to sitive diazo compounds in the two-component maintain all of the components of the sensitizing layers of the invention. mixture in solution. After drying, copies were Additional ingredients for stabilizing the diazo made by the procedure described in Example 1.
Development can be eifected either with ammonia or with an aqueous alkalin solution such as aqueous ammonia, sodium carbonate, tri-sodium phosphate, or tri-ethanolamine.
The resulting image was likewise of dark purplish-brown color, of excellent sharpness showing no migration or ofisetting and of excellent fastness to light. A print obtained with diazotype material prepared in the same manner as described in this example but using resorcinol instead of the acetaldehyde resorcinol condensation product, showed substantial migration and ofisetting and had a much lighter color.
Instead of the resorcinol acetaldehyde condensation product of the foregoing examples, there can be employed the corresponding crystalline tetrameric equirnolecular condensation product of acetaldehyde with pholorglucinol, or of propionaldehyde, butyraldehyde, isobutyraldehyde, hexaldehyde, or benzaldehyde with either resorcinol or pholorogiucinol, whereby images having similarly advantageous properties are obtained.
Instead of the light sensitive diazo compounds disclosed in the examples, there can be used the diazo compounds of p-ethylamino m-toluidene, p amino N diethyl m-toluidene, p-amino-N- methylaniline, p-amino Z-methoxy-N-cyclohexylaniline, p-amino N 2' hydroxyethylaniline, p-amino N ethyl-N-Z-hydroxyethylaniline, 3 aminocarbazole, 1,2-, 2,1-, or 1,4-aminonaphthol, 1,2-aminonaphthol-e-sulfonic acid, or 2,1-aminonaphthol-3,6-disulfo acid. These diazo compounds can be employed in the form of their diazonium chloride zinc chloride double salts or the corresponding boron trifluoride complex addition products.
As disclosed in the examples, alcohols such as methanol, ethanol, isopropanol and butanol can be employed as media for impregnating absorbent bases with the aldehyde polyhydric phenol condensation products of this invention, particularly when applied separately from the light sensitive diazo component, and mixed solvents containing water, alcohols and a softening agent for plastics such as 'y-valerolactone, can be used as a medium for applying the light sensitive diazo component as well as coupling components of this invention in a single operation to a plastic support.
Variations and modifications which will be ob- Vious to those skilled in the art can be made in this invention without departing from the scope thereof.
I claim:
1. Diazotype photoprinting material, comprising in a light sensitive layer, a light sensitive diazo component, and as a coupling component, a crystalline tetrameric condensation product of a m-polyhydric phenol with an equimolecular amount of an aldehyde having the formula RCHO, wherein R is a hydrocarbon radical having 1-6 carbon atoms.
2. Diazotype photoprinting material, comprising a plastic base impregnated with a light sensitive diazo component and with a coupling component which is a crystalline tetrameric condensation product of a m--polyhydric phenol with an equimolecular amount of an aldehyde having the formula RCHO, wherein R is a hydrocarbon radical having l6 carbon atoms.
3. Diazotype photoprinting material, comprising in a light sensitive layer, a light sensitive diazotized p-diamine of the benzene series, and as a coupling component, a crystalline tetrameric c0ndensation product or" resorcinol with an equimolecular amount of acetaldehyde.
4. Diazotype photoprinting material, comprising a paper case impregnated with the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, and with the zinc chloride double salt of p-diethylaminobenzene diazonium chloride.
5. Diazotype photoprinting material, comprising a plastic layer impregnated with the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, and With the zinc chloride double salt of p diethylamino 2 methyl benzene diaz'onium chloride.
6. A process for the manufacture of light sensitive diazotype materials, which comprises impregnating an absorbent base with an alcoholic solution of the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, drying the base, and impregnating the latter with an aqueous solution containing the zinc chloride double salt of pdiethylaminobenzene diazonium chloride.
'7. A process for the manufacture of light sensitive diazotype materials, which comprises impregnating a plastic base with an aqueous alcoholic solution containing -valerolactone, of the crystalline tetrameric condensation product of resorcinol with an equimolecular amount of acetaldehyde, and containing the zinc chloride double salt of p-diethylamino-Z-methyl benzene diazonium chloride.
SAUL R. BUC.
REFERENCES CITED FOREIGN PATENTS Country Date Great Britain Aug. 26, 1938 Number
Claims (1)
1. DIAZOTYPE PHOTOPRINTING MATERIAL, COMPRISING IN A LIGHT SENSITIVE LAYER, A LIGHT SENSITIVE DIAZO COMPONENT, AND AS A COUPLING COMPONENT, A CRYSTALLINE TETRAMERIC CONDENSATION PRODUCT OF A M-POLYHYDRIC PHENOL WITH AN EQUIMOLECULAR AMOUNT OF AN ALDEHYDE HAVING THE FORMULA RCHO, WHEREIN R IS A HYDROCARBON RADICAL HAVING 1-6 CARBON ATOMS.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US61727A US2593839A (en) | 1948-11-23 | 1948-11-23 | Diazotype photoprinting material |
GB27861/49A GB660534A (en) | 1948-11-23 | 1949-10-31 | Diazotype photoprinting material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US61727A US2593839A (en) | 1948-11-23 | 1948-11-23 | Diazotype photoprinting material |
Publications (1)
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US2593839A true US2593839A (en) | 1952-04-22 |
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ID=22037725
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Application Number | Title | Priority Date | Filing Date |
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US61727A Expired - Lifetime US2593839A (en) | 1948-11-23 | 1948-11-23 | Diazotype photoprinting material |
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US (1) | US2593839A (en) |
GB (1) | GB660534A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3499763A (en) * | 1967-05-01 | 1970-03-10 | Ibm | Bis phenols as high opacity diazotype couplers |
US3716364A (en) * | 1970-09-02 | 1973-02-13 | Addressograph Multigraph | Diazotype materials |
US3867147A (en) * | 1969-05-20 | 1975-02-18 | Hoechst Co American | Light-sensitive diazo compounds and reproduction material employing the same |
US8002200B2 (en) | 1997-01-24 | 2011-08-23 | 3M Innovative Properties Company | Apparatus for spraying liquids, and disposable containers and liners suitable for use therewith |
US8944351B2 (en) | 2011-05-06 | 2015-02-03 | Saint-Gobain Abrasives, Inc. | Paint cup assembly with an outlet valve |
US9162240B2 (en) | 2004-12-16 | 2015-10-20 | Saint-Gobain Abrasives, Inc./Saint-Gobain Abrasie | Liquid container system for a spray gun |
US9586220B2 (en) | 2011-06-30 | 2017-03-07 | Saint-Gobain Abrasives, Inc. | Paint cup assembly |
US10035156B2 (en) | 2006-06-20 | 2018-07-31 | Saint-Gobain Abrasives, Inc. | Liquid supply assembly |
US10882064B2 (en) | 2011-12-30 | 2021-01-05 | Saint-Gobain Abrasives, Inc./Saint-Gobain Abrasifs | Convertible paint cup assembly with air inlet valve |
US11040360B2 (en) | 2006-06-20 | 2021-06-22 | Saint-Gobain Abrasives, Inc. | Liquid supply assembly |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB491095A (en) * | 1936-03-25 | 1938-08-26 | Kalle & Co Ag | Improvements in or relating to the production of diazo prints |
-
1948
- 1948-11-23 US US61727A patent/US2593839A/en not_active Expired - Lifetime
-
1949
- 1949-10-31 GB GB27861/49A patent/GB660534A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB491095A (en) * | 1936-03-25 | 1938-08-26 | Kalle & Co Ag | Improvements in or relating to the production of diazo prints |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3499763A (en) * | 1967-05-01 | 1970-03-10 | Ibm | Bis phenols as high opacity diazotype couplers |
US3867147A (en) * | 1969-05-20 | 1975-02-18 | Hoechst Co American | Light-sensitive diazo compounds and reproduction material employing the same |
US3716364A (en) * | 1970-09-02 | 1973-02-13 | Addressograph Multigraph | Diazotype materials |
US8002200B2 (en) | 1997-01-24 | 2011-08-23 | 3M Innovative Properties Company | Apparatus for spraying liquids, and disposable containers and liners suitable for use therewith |
US9162240B2 (en) | 2004-12-16 | 2015-10-20 | Saint-Gobain Abrasives, Inc./Saint-Gobain Abrasie | Liquid container system for a spray gun |
US10035156B2 (en) | 2006-06-20 | 2018-07-31 | Saint-Gobain Abrasives, Inc. | Liquid supply assembly |
US11040360B2 (en) | 2006-06-20 | 2021-06-22 | Saint-Gobain Abrasives, Inc. | Liquid supply assembly |
US11548018B1 (en) | 2006-06-20 | 2023-01-10 | Saint-Gobain Abrasives, Inc. | Liquid supply assembly |
US11679399B2 (en) | 2006-06-20 | 2023-06-20 | Saint-Gobain Abrasives, Inc. | Liquid supply assembly |
US8998018B2 (en) | 2011-05-06 | 2015-04-07 | Saint-Gobain Abrasives, Inc. | Paint cup assembly with an extended ring |
US8944351B2 (en) | 2011-05-06 | 2015-02-03 | Saint-Gobain Abrasives, Inc. | Paint cup assembly with an outlet valve |
US9335198B2 (en) | 2011-05-06 | 2016-05-10 | Saint-Gobain Abrasives, Inc. | Method of using a paint cup assembly |
US9586220B2 (en) | 2011-06-30 | 2017-03-07 | Saint-Gobain Abrasives, Inc. | Paint cup assembly |
US10882064B2 (en) | 2011-12-30 | 2021-01-05 | Saint-Gobain Abrasives, Inc./Saint-Gobain Abrasifs | Convertible paint cup assembly with air inlet valve |
Also Published As
Publication number | Publication date |
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GB660534A (en) | 1951-11-07 |
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