CN1037552C - Negative photosensitive printed board and its making method - Google Patents
Negative photosensitive printed board and its making method Download PDFInfo
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- CN1037552C CN1037552C CN91101679A CN91101679A CN1037552C CN 1037552 C CN1037552 C CN 1037552C CN 91101679 A CN91101679 A CN 91101679A CN 91101679 A CN91101679 A CN 91101679A CN 1037552 C CN1037552 C CN 1037552C
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- diazo
- salt
- sensitive layer
- light sensitive
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Abstract
The present invention relates to a negative photosensitive printing plate and a manufacturing method thereof. The printing plate comprises a baseplate and a photosensitive coating, wherein the main ingredient of the photosensitive coating is photosensitive diazo resin formed by the condensation of a substituted diphenylamine diazo salt or a compound salt thereof and aldehyde or substituted aromatic ether. The resin aqueous solution is coated on the baseplate used for printing, so that the required printing plate can be made. A photographic negative with a character images is attached to the plate, a glass plate is pressed on the photographic negative, and the photographic negative is exposed by sunlight or ultraviolet light and is developed with water, so an offset printing plate with clear character images is formed.
Description
The present invention relates to a kind of negative photosensitive printed board and method for making thereof.In prior art, the light sensitive layer of negative photosensitive printed board mainly contains photographic diazoresin, generally uses diphenylamine diazoresin, but the thermotolerance of this light sensitive layer and storability are very poor, do not meet application request.(US.4,248,959 (1981) such as W.Jeffers, US.4,486,529 (1984)) J.E, (US.4 such as Wall, 436,804 (1984), US.4,448,873 (1984)) reported the diphenylamine diazoresin, the particularly light sensitive layer of 3-methoxy diphenylamine diazo resin composition that contains the 3-replacement, its photosensitive property and stability are all better.Japanese Laid-Open Patent Application (close the room person of outstanding talent etc., clear 58-209731,1983) similar content also disclosed.But still need to provide the negative photosensitive printed board that really share, photosensitive property is good, stability is strong, manufacturing is simple, easy to use at present, this also is a purpose of the present invention.
The substituted diphenylamine diazo salt that negative photosensitive printed board light sensitive layer Main Ingredients and Appearance of the present invention is a following general formula (I) or its double salt and aldehyde compound or the water soluble light-sensitive diazo resin that forms with the condensation of substituted aroma ethers are applied to this resin aqueous solution on the base plate of printing usefulness and promptly can be made into light sensitive plate.Attached one photographic negative that character image arranged is pressed a glass plate thereon again on this galley, and through daylight or ultraviolet photoetching, water or the aqueous solution that wherein contains an amount of alcohols, surfactant, stabilizing agent are developed, and then become available negativity galley.
Photographic diazoresin of the present invention is under the lucifuge condition, by the substituted diphenylamine diazo salt of general formula (I) or itself and the inorganic salts for example double salt that forms of zinc chloride and aldehyde or make with aromatic ether condensation in acid medium of replacement:
R in the formula
1Represent hydrogen atom, C
1-4Alkyl or halogen,
R
2Representation carboxy, cyano group, halogen or nitro,
R
3Represent hydrogen atom, C
1-4Alkyl,
R
4, R
5Can be identical, also can be inequality, can be hydrogen atom, halogen separately, C
1-4Alkyl, C
1-4Alkoxy or hydroxyl.
X
-Represent halogen anion, inorganic or organic acid.The viscosity (measuring with one point method) of control condensation product is between 0.120-0.140dl/g.Diazo salt and double salt thereof used in the reaction can use Chinese patent (Cao Weixiao etc., CN87101207,1990) disclosed method or method similarly and other known method to make, and described acid medium comprises: 85% phosphoric acid, 98% sulfuric acid etc.Be reflected at 5-50 ℃ and carry out, need 2-6 hour approximately.Aldehyde in the reactant mainly is fatty aldehydes, and for example formaldehyde, acetaldehyde etc. also can add the phenolic compound of the 15-20% mole of suitable diazo salt or its double salt molal quantity, as phenol, cresols etc. during with aldehyde reaction.Above-mentioned substituted aroma ether comprises: 4,4 '-dimethoxy methyl diphenyl ether, benzyl ether etc.The mol ratio of reactant diazo salt or its double salt and aldehyde or ether can be respectively: 1: (1.1-1.5), 1: (2-2.5).Operation and product treatment etc. are seen example 1-5.
The photographic diazoresin that as above makes promptly can be used for preparing the light sensitive layer liquid of negative photosensitive printed board.Because the main body of light sensitive layer is a photographic diazoresin, therefore, the solution of this resin aqueous solution or its water-miscible organic solvent, for example glycol monoethyl ether etc. promptly can be used as light sensitive layer liquid, needn't add other materials and get final product.But in order to make stable more the contrast after its exposure and the firm anti-seal of galley etc. of increasing of light sensitive layer, the water-soluble dye that also can in its solution, add a small amount of (0.1-1%), for example peacock green, ethyl rhodamine B etc. and stabilizing agent, as sodium dihydrogen phosphate, p-toluenesulfonic acid etc., also can add some polymkeric substance in addition, available polymkeric substance comprises: polyvinyl alcohol (PVA), Pioloform, polyvinyl acetal, polyacrylamide, polyacrylic acid or their potpourri, its amount can be 0.1-5 times of diazo resin weight.
Above-mentioned light sensitive layer liquid is comprised with the base plate that known method is coated on printing usefulness: plastic plate, paper substrate plate, sheet metal, on the base plate as aluminium sheet commonly used etc., after the lucifuge drying, promptly become desired negative photosensitive printed board, coating thickness is generally the 5-10 micron, and coating weight is generally 0.05-0.1mg/cm
2
Attached one has the photographic negative of character image and presses a glass thereon on the above-mentioned galley that makes, and through ultraviolet photoetching 2-5 minute of daylight or 300-400nm, immediately develops then.A developer solution water gets final product, also available alcohols, surfactant, the aqueous solution of stabilizing agent is developed, the solution that is mixed with of water, propyl alcohol, sodium dodecylsulphonate, sodium dihydrogen phosphate for example, their weight ratio can be: 70: 30: 2: 1, this ratio can arbitrarily change as the case may be.Through developing and the water flushing, can obtain the galley of clear character image.Former sensitization galley coating, sensitization part then form firm neither molten light gray (not adding dyestuff) or coloured material in water and organic solvent, still are retained on the base plate and the oleophylic China ink.Unexposed portion is soluble in water when developing, and leaves base plate.
The negative photosensitive printed board that makes with said method is no matter all comparatively simple and convenient aspect preparation and use at present.And its sensitization and thermal stability and wearing quality have all reached excellent level.In order to be illustrated more clearly in the present invention, enumerate following examples, but these there is not any restriction to scope of the present invention.
Example 1
Under the lucifuge condition, the double salt that 0.9 gram chlorination 2-nitrodiphenylamine-4-diazo salt and zinc chloride are formed is dissolved in 25 milliliter 85% the phosphoric acid, under agitation, splash into 0.65 gram 4 in 35-40 ℃, 4 '-the dimethoxy methyl diphenyl ether, drip off the back and continue to stir 24 hours, add 80 ml waters and 0.7 gram 1,3, the 5-tri-methyl p-toluenesulfonate gets yellow solid, washing back lucifuge drying, product weighs 1.7 grams, measures its viscosity (η)=0.125dl/g with one point method.
Example 2
Under the lucifuge condition, the double salt that 3.41 gram chlorination 2-nitrodiphenylamine-4-diazo salts and zinc chloride are formed are dissolved in 6.5 milliliter 98% the sulfuric acid, and the control temperature adds 0.52 and restrains paraformaldehyde below 10 ℃.Stir and after 3 hours reactant is poured in the absolute ethyl alcohol, be settled out yellow diazo resin, wash with ethanol and strive the final vacuum drying, product 3.6 grams are measured its viscosity with one point method and are (1)=0.135dl/g.
Example 3
Under the lucifuge condition, the double salt described in the 3.41 gram examples 2 is dissolved in 85% phosphoric acid, add 0.52 gram paraformaldehyde, after 48 hours, add 0.141 gram phenol in reaction about 40 ℃, continue reaction 2 hours, reactant is dissolved in 50 ml waters, filter.The saline solution of adding 20% in filtrate is settled out brown diazo resin 3.42 grams.〔η〕＝0.130dl/g。
Example 4
Under the lucifuge condition, with 20 gram hydrogen sulfates 4 '-double salt of hydroxy-2-methyl diphenylamine-4-diazonium salt and zinc chloride formation is dissolved in 40 milliliter of 98% sulfuric acid, when temperature is lower than 10 ℃, add 3 gram paraformaldehydes, stir after 5 hours, reactant is poured in the absolute ethyl alcohol, there is yellow mercury oxide to separate out, clean the final vacuum drying with ethanol, get product 21 grams, (η)=0.140dl/g.
Example 5
Under the lucifuge condition, 2.8 gram chlorination 2-nitro hexichol-4-diazo salts are dissolved in 30 milliliter of 85% phosphoric acid, in the time of 40 ℃, add 3 gram paraformaldehydes, keep this temperature to stir 50 hours.Reactant is dissolved in 70 ml waters filters, in filtrate, add saturated aqueous common salt, separate out diazo resin 2 grams, (η)=0.135dl/g.
Example 6
Under the lucifuge condition, with diazo resin 0.15 gram that example 1 makes, polyvinyl alcohol (PVA) butyraldehyde 0.35 gram, O.03, the ethyl rhodamine B restrains and p-toluenesulfonic acid 0.01 gram, is dissolved in 25 milliliters of glycol monoethyl ethers, filters, filtrate is applied on the aluminium sheet of printing usefulness, is negative photosensitive printed board after the drying.Attached thereon one has the photographic negative of character image, press a glass plate on it again, through the ultraviolet photoetching of daylight or 350-400nm 3 minutes, water, propyl alcohol, sodium dodecylsulphonate, sodium dihydrogen phosphate immediately, their weight was respectively 70: 30: 2: the solution development of 1 preparation 2-4 minute, water flushing again gets character image galley fully aware of.
Example 7
As example 6, peacock green of the 3 gram diazo resins that make of examples 2 and each 0.5 gram and sodium dihydrogen phosphate be dissolved in 100 ml waters filter, dry after filtrate is coated in phosphoric acid dip with 2-3%, use again on the water-moistened printing aluminium sheet, oven dry is used after (below 50 ℃) or is stored stand-by, similar to example 6 during use, development can a water.
Example 8
Peacock green and sodium dihydrogen phosphate of the 3 gram diazo resins that make of examples 4 and each 0.5 gram are dissolved in 100 ml waters, filter, filtrate is applied on the aluminium sheet as example 7.Available 40 ℃ hot water develops during use.
Claims (5)
1, a kind of negative photosensitive printed board is characterized in that, described galley is formed by scribbling light sensitive layer on base plate and its, and is described
1. base plate: sheet metal, plastic plate (film) or the paper substrate plate that can select printing usefulness for use;
2. light sensitive layer: comprise double salt that the substituted diphenylamine diazo salt of following general formula (I) or itself and inorganic salts form and aldehyde compound or with the water soluble light-sensitive diazo resin of the fragrant ethers condensation formation that replaces, water miscible polymkeric substance, available polymkeric substance comprises: polyvinyl alcohol (PVA), Pioloform, polyvinyl acetal, polyacrylamide, polyacrylic acid or their potpourri, its amount is 0.1-5 a times of diazo resin weight, water-soluble dye, comprise: peacock green, the ethyl rhodamine B, stabilizing agent, comprise: sodium dihydrogen phosphate, p-toluenesulfonic acid
R in the formula
1Represent hydrogen atom, C
1-4Alkyl or halogen,
R
2Represent nitro,
R
3Represent hydrogen atom, C
1-4Alkyl,
R
4And R
5Can be identical, also can be inequality, each is hydrogen atom, halogen, C naturally
1-4Alkyl, C
1-4Alkoxy or hydroxyl,
X
-Represent halogen anion, inorganic or organic acid.
2, by the described galley of claim 1, it is characterized in that, described base plate is the aluminium sheet or the zine plate of printing usefulness, and described light sensitive layer comprises: weight resin, peacock green, sodium dihydrogen phosphate that double salt that chlorination 2-nitrodiphenylamine-4-diazo salt and zinc chloride form and formaldehyde condensation form.
3, by the described galley of claim 1, it is characterized in that, described base plate is aluminium sheet or zine plate, described light sensitive layer comprises: the double salt and 4,4 that chlorination 2-nitrodiphenylamine-4-diazo salt and zinc chloride form '-diazo resin, polyvinyl butyral, ethyl rhodamine B, the p-toluenesulfonic acid of dimethoxy methyl diphenyl ether condensation formation.
4, by the described galley of claim 1, it is characterized in that, described base plate is an aluminium sheet, and described light sensitive layer comprises: hydrogen sulfate 4 '-hydroxy-n-methyldiphenylamine-4-diazo salt and the double salt of zinc chloride formation and weight resin, peacock green and the sodium dihydrogen phosphate that formaldehyde condensation forms.
5, by claim 1,2,3 or 4 the preparation method who states galley, it is characterized in that described preparation method comprises;
1. prepare photographic diazoresin: under the lucifuge condition, make double salt that the substituted diphenylamine diazo salt of aforementioned formula (I) or itself and inorganic salts form at inorganic acid medium, comprise: 85% phosphoric acid, 98% sulfuric acid, reacted 2-6 hour with aldehyde compound or with substituted diphenylamine ether in 5-50 ℃, generate sensitization diazonium fat, its viscosity is measured with one point method, between 0.120-0.140dl/g; Above-mentioned aldehyde compound comprises: formaldehyde, acetaldehyde; During with aldehyde reaction, add the phenolic compound of the 15-20% mole of suitable diazo salt or its double salt molal quantity, phenol or cresols; Above-mentioned substituted aroma ether comprises: 4,4 '-dimethoxy methyl diphenyl ether, benzyl ether; The mol ratio of reactant diazo salt or its double salt and aldehyde or ether is respectively: 1: (1.1-1.5), 1: (2-2.5).
2. prepare light sensitive layer: with described photographic diazoresin molten with water or water-soluble solubleness organic solvent in, optional spent glycol monomethyl ether, be sensitization liquid, in this solution, add water-soluble dye, stabilizing agent or high polymer, available superpolymer comprises: polyvinyl alcohol (PVA), Pioloform, polyvinyl acetal, polyacrylamide, polyacrylic acid or their potpourri, its addition are 0.1-5 times of weight resin;
3. the coating of photosensitive printed board: above-mentioned sensitization liquid is applied on the base plate of printing usefulness, comprises plastic bottom board, paper substrate plate, sheet metal, lucifuge drying, the light sensitive layer of formation 5-10 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91101679A CN1037552C (en) | 1991-03-21 | 1991-03-21 | Negative photosensitive printed board and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91101679A CN1037552C (en) | 1991-03-21 | 1991-03-21 | Negative photosensitive printed board and its making method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065143A CN1065143A (en) | 1992-10-07 |
| CN1037552C true CN1037552C (en) | 1998-02-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91101679A Expired - Fee Related CN1037552C (en) | 1991-03-21 | 1991-03-21 | Negative photosensitive printed board and its making method |
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| CN (1) | CN1037552C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102096323A (en) * | 2011-01-24 | 2011-06-15 | 北京师范大学 | Positive light-sensitive waterless offset printing plate containing heavy-nitrogen resin and manufacturing method thereof |
| CN102998900A (en) * | 2012-12-01 | 2013-03-27 | 刘华礼 | Manufacturing method of photosensitive plate with ultrathin photosensitive layer |
| CN104530342B (en) * | 2015-01-09 | 2017-08-08 | 京东方科技集团股份有限公司 | Diazo resin, photoetching compositions and its compound method |
| CN107145037B (en) * | 2017-07-07 | 2020-05-12 | 京东方科技集团股份有限公司 | Photoresist composition and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US486529A (en) * | 1892-11-22 | Scoop-board for wagons | ||
| US3300309A (en) * | 1963-09-06 | 1967-01-24 | Polychrome Corp | Moisture-resistant planographic plates and methods of producing same |
| US4248959A (en) * | 1978-12-07 | 1981-02-03 | American Hoechst Corporation | Preparation of diazo printing plates using laser exposure |
| EP0023722A2 (en) * | 1979-08-06 | 1981-02-11 | Howard A. Fromson | Lithographic printing plate and process |
| EP0083835A2 (en) * | 1982-01-12 | 1983-07-20 | Autotype International Limited | Stabilization of diazo-resin sensitisers |
| US4469772A (en) * | 1982-06-03 | 1984-09-04 | American Hoechst Corporation | Water developable dye coating on substrate with two diazo polycondensation products and water soluble polymeric binder |
| EP0415422A2 (en) * | 1989-08-31 | 1991-03-06 | Fuji Photo Film Co., Ltd. | Method for forming images |
-
1991
- 1991-03-21 CN CN91101679A patent/CN1037552C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US486529A (en) * | 1892-11-22 | Scoop-board for wagons | ||
| US3300309A (en) * | 1963-09-06 | 1967-01-24 | Polychrome Corp | Moisture-resistant planographic plates and methods of producing same |
| US4248959A (en) * | 1978-12-07 | 1981-02-03 | American Hoechst Corporation | Preparation of diazo printing plates using laser exposure |
| EP0023722A2 (en) * | 1979-08-06 | 1981-02-11 | Howard A. Fromson | Lithographic printing plate and process |
| EP0083835A2 (en) * | 1982-01-12 | 1983-07-20 | Autotype International Limited | Stabilization of diazo-resin sensitisers |
| US4469772A (en) * | 1982-06-03 | 1984-09-04 | American Hoechst Corporation | Water developable dye coating on substrate with two diazo polycondensation products and water soluble polymeric binder |
| EP0415422A2 (en) * | 1989-08-31 | 1991-03-06 | Fuji Photo Film Co., Ltd. | Method for forming images |
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| Publication number | Publication date |
|---|---|
| CN1065143A (en) | 1992-10-07 |
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