CN1815364A - Light-sensitive composition for chemical amplitude type negative PS plate and chemical amplitude type negative PS plate thereof - Google Patents
Light-sensitive composition for chemical amplitude type negative PS plate and chemical amplitude type negative PS plate thereof Download PDFInfo
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Abstract
The sensitization composition for PS printing plate includes following portions in wt% : (1) 45-90% film forming resin; (2) 1-20% crosslinking agent;(3) 0.1-10% source for producing acid; (4) 0.1-5% background dyestuff; (5) 1-20% assist crosslinking agent or surface antiwear agent; (6) 5-50% solvent. The weight percent is base on total mass of solid in the composition. The invention also discloses PS printing plate in negative pattern prepared by using the said sensitization composition. Advantages of the PS printing plate in negative pattern are: high sensitivity, good resolution, durable, large tolerance for development, and usable traditional developer for PS printing plate in positive pattern.
Description
Technical field
The invention belongs to the synthetic preparation and the applied technical field of optical information recording material.More particularly, the present invention relates to presensitized plate material in the printing industry (PS version) with photosensitive composition and by the chemical amplitude type negative PS version of described preparation of compositions.
Technical background
Developed successfully and commercial negative PS version countries in the world in the past, its photosensitive composition all belongs to non-chemically amplification type bar none and in advance photosensitive composition is coated with built on the aluminum substrate of special processing, make precoating the master (PS version) of light sensitive layer is arranged, add a cover the printing film in use and carry out the close contact exposure of vacuum with the near ultraviolet light source, then the PS version is carried out development treatment at normal temperatures with the developer solution of stipulating, obtain forme.With regard to negative PS plate photosensitive composition, over half a century was once applied for countless patents in the past, and had a variety of commodity to emerge, but summarized to get up, the light initiation polymerization type is arranged, photolysis cross-linking type, a photo-crosslinking aggretion type (Mi Zehui man of virtue and ability, PS version outline, publishing department of Japan printing association, 1993; Liu Xiaoya, Yu Shangxian, diazonium is the general introduction of negative PS version photosensitive material, Chinese printing, No.1,1994).
Early 1980s, the people such as H.Ito of IBM Corporation proposed the new ideas of chemically amplified photo resist agent, and application puts it in the photoresist field.People attempt to be applied to the manufacture view (Yu Shangxian, the general introduction of photoresist of negative PS version, Chinese printing, No.17,1987) of positive and negative PS version afterwards, but regrettably all do not have commodity to come out up to 20 end of the centurys always.Kodak and Creo Co., Ltd jointly release the thermosensitive CTP plate-making technology in the world after the nineteen ninety-five Drupa printing exhibition.The principle that Kodak's commercial negative heat cross-linking type thermal CTP plate material just is based on the chemically amplified photo resist agent is developed (US 5,340,699, and US 5,491,046, US5,466,557) successfully.
We in 2003 once with regard to negative heat cross-linking type heat-sensitive CTP plate with the image forming composition application patent of invention (the imperial PS version printing material of Beijing Normal University and Guangxi Yulin gold company limited, Chinese patent application number 03143500.9).More than these technology constituted the technical foundation of negative PS version of the present invention.
No matter the commercial negative PS in countries in the world version was photo-polymerization type (comprising the photodimerization reaction), photo-crosslinking type or photolysis cross-linking type in the past, matrix resin in the photosensitive composition is not with the linear phenol resin of the used weak base solubility of traditional diazo naphthoquinone type positive PS printing plate, but with organic solvent or the soluble non-linear phenol resin of aqueous alkali.This brings following shortcoming just in the past negative PS version:
1) requirement that aluminum substrate is handled must be carried out the sealing of hole processing or be coated with special undercoat when harshness, particularly Rz (the Grains degree of depth) value are big, and it is dirty to guarantee not keep on file in the developing process.
2) coating of photographic layer often needs double-deck coating except the precoating undercoat, needs coating surface oxygen barrier protective seam as radical photoinitiator initiated polymerization type photosensitive composition.This not only makes coating process and equipment complicated, and yield rate reduces, and has also increased the production cost of plate.
3) developer solution can not be a developer solution with sodium silicate with traditional positive PS printing plate, often need the organic solvent of a great deal of or special development promoter, this is a very big shortcoming of negative PS version, has not only increased the cost of development consumptive material, and the three-waste pollution of discarded developer solution is also bigger.
4) owing to above-mentioned and other many reason, the production cost of negative PS version is higher.
Summary of the invention
At the existing foregoing problems of PS version in the past, the present inventor is according to the ultimate principle of chemically amplified photo resist agent, proposition with the linear phenol resin of sodium silicate aqueous solution solubility as film-forming resin, with alkoxymethyl melamine with buck dispersibility or solubility and the linear phenol resin of methylolation or methylolation polyphenolic substance as crosslinking chemical and assistant crosslinking agent, thereby reach the purpose that overcomes the aforementioned various shortcomings that negative PS version in the past had and solve following key technical problem:
1) obtain negative PS plate originals with traditional positive PS printing plate with the basic single coating of version of no sealing of hole, no undercoat, the version base of having simplified the PS version is greatly handled and the Processes and apparatus of photosensitive coated layer;
2) be that developer solution develops with traditional positive PS printing plate sodium silicate;
3) with minimum imaging exposure exposure, the preliminary drying technology through before developing realizes the chemical amplification process of heat cross-linking imaging, thereby has improved the sensitivity of PS version effectively.But also can be by the height of baking temperature and stoving time control amplification amplification and sensitivity;
4) imaging performances such as the resolution of made forme, site reductibility, pressrun are improved.Based on this, the present invention is accomplished.
The purpose of this invention is to provide a kind of new chemical amplitude type negative PS version photosensitive composition, it comprises film-forming resin, crosslinking chemical, light and produces acid source, background dye, assistant crosslinking agent or abrasion-resistant surface agent and solvent, uses said composition to prepare to have the sensitivity height, good resolution, good printing-force-resistence, the development tolerance is big and the negative PS version that can use series of advantages such as traditional positive PS printing plate developer solution develops.
Another object of the present invention provides the purposes of above-mentioned photosensitive composition in preparation chemical amplitude type negative PS version.
Therefore, one aspect of the present invention provides a kind of chemical amplitude type negative PS plate photosensitive composition, comprises following component:
A) film-forming resin of 45-90% weight;
B) crosslinking chemical of 1-20% weight;
C) light of 0.1-10% weight produces acid source;
D) background dye of 0.1-5% weight;
E) assistant crosslinking agent of 1-20% weight or abrasion-resistant surface agent; With
F) making the solid content of described composition is the solvent of 5-50% weight;
Wherein said percent by weight is based on the solid gross mass of described composition.
The present invention provides the purposes of above-mentioned photosensitive composition in preparation chemical amplitude type negative PS version on the other hand.
Detailed Description Of The Invention
In photosensitive composition of the present invention, component is a film-forming resin as the main body composition a).This film-forming resin is a kind of crosslinkable resin, contains the phenolic hydroxyl group and the unreacted reactivity point of q.s in the promptly this resin, and resin is originally solvable in the sodium silicate developer solution of 1-5% weight.Based on above-mentioned requirements, the present invention selects for use linear phenol resin as film-forming resin.Linear phenol resin can be weight-average molecular weight M
wBe 2000-12000, the poly(4-hydroxystyrene) of preferred 5000-10000; M
wBetween 2000-8000, the linear phenolic resin of preferred 3000-6000; Or their potpourri.Linear phenolic resin can be selected from metacresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, metacresol-paracresol-phenol-formaldehyde resin, metacresol-orthoresol-formaldehyde resin, metacresol-phenol-formaldehyde resin, metacresol-phenol-paracresol-formaldehyde resin, metacresol-phenol-tertiary butyl phenol-formaldehyde resin, paracresol-phenol-formaldehyde resin, paracresol-orthoresol-formaldehyde resin, orthoresol-formaldehyde resin, orthoresol-phenol-formaldehyde resin, orthoresol-phenol-tertiary butyl phenol-formaldehyde resin, phenol-formaldehyde resin, phenol-tertiary butyl phenol-formaldehyde resin, phenol-halo resinox, resorcinol-formaldehyde resin, resorcinol-paracresol-formaldehyde resin, resorcinol-tertiary butyl phenol-formaldehyde resin, catechol-formaldehyde resin, catechol-paracresol-formaldehyde resin, catechol-tertiary butyl phenol-formaldehyde resin and their potpourri.In above various phenolics, preferably contain those of metacresol, as metacresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, metacresol-paracresol-phenol-formaldehyde resin, metacresol-orthoresol-formaldehyde resin, metacresol-phenol-formaldehyde resin, metacresol-phenol-paracresol-formaldehyde resin, metacresol-phenol-tertiary butyl phenol-formaldehyde resin, and their potpourri.In these linear phenol resin, the match ratio of phenols is to satisfy the M/A value at 6.5-7.5, and preferred 6.8-7.1 is a principle, and wherein M is the gross mass of linear phenol resin, and A is the gross mass of phenolic hydroxyl group in the phenol resin gross mass.In these linear phenol resin, the molar ratio between phenol and the aldehyde is 1: 1-1: select between 0.8.Linear phenol resin accounts for 45-90% weight in the solid gross mass of photosensitive composition of the present invention, preferred 50-80% weight.If consumption is too big, then image is easy to subtract film loss of gloss phenomenon in the developing process; And if consumption is too little, then take place easily to develop not cause keeping on file dirty only.In addition, if the molecular weight of linear phenol resin is too little, then because the not enough same image that easily produces of crosslinking curing subtracts film loss of gloss phenomenon; And if molecular weight is too big, then because self alkali solubility is relatively poor, it is dirty to be easy in the developing process keep on file, and the flaking phenomenon takes place sometimes.
In photosensitive composition of the present invention, components b) be crosslinking chemical.According to the present invention, mainly use alkoxymethyl melamine as crosslinking chemical, for example methylated methylol melamine, ethoxymethyl melamine, the third oxygen methyl melamine or fourth oxygen methyl melamine.In above-mentioned alkoxymethyl melamine, can there be various r-o-methylation ratios.For example can use three alkoxymethyl melamines, four alkoxymethyl melamines, five alkoxymethyl melamines, six alkoxymethyl melamines.For the crosslinking rate of raising photosensitive composition and the sensitivity of photosensitive composition, preferably select the high methylated methylol melamine of r-o-methylation ratio for use, for example near the methylated melamine resin of hexakis-methoxy.Use fourth oxygen methyl melamine or the alkoxymethyl melamine bigger than butyl, in cross-linking process, dealcoholysis speed is too slow, thereby crosslinking rate descends the sensitivity step-down of photosensitive composition.In addition, the stability decreases of the PS version photographic layer that melamine resin coated that the r-o-methylation ratio is too low is easy to take place dark reaction in plate preservation process, and cross-linking reaction speed descends in chemical amplification heat cross-linking process.
Above-mentioned crosslinking chemical accounts for 1-20% weight in the solid gross mass of photosensitive composition, preferred 5-15% weight.If the consumption of crosslinking chemical is lower than 1) % weight, crosslinking curing deficiency then, sensitivity obviously reduces; If the consumption of crosslinking chemical is higher than 20% weight, the problem of development difficulty and precoating master resistance to abrasion difference then appears easily.When particularly using the low melamine resin of r-o-methylation ratio, above-mentioned shortcoming is even more serious.
In photosensitive composition of the present invention, as amount of component b) light to produce acid source can be the high product acidic materials of near ultraviolet band decomposition efficiency, trichloromethyl compound in triazine class for example, as 1-to methoxy styryl-3, the two trichloromethyl triazines of 5-, 1-is to methoxy-naphthyl-3, the two trichloromethyl triazines of 5-, 1-Chinese cassia tree fork methine-3, the two trichloromethyl triazines of 5-, 1-furans vinyl-3, the two trichloromethyl triazines of 5-, 1-styryl-3, the two trichloromethyl triazines of 5-, 1-anisyl-3, the two trichloromethyl triazines of 5-, 1-(2, the two methoxy styryls of 4-)-3, the two trichloromethyl triazines of 5-, 1-(2-methyl-4-methoxy styryl)-3, the two trichloromethyl triazines of 5-, dichloroacetophenone, right-the phenoxy group dichloroacetophenone, the tribromo-benzene ethyl ketone, trisbromomethyl phenyl sulfone, the p-toluenesulfonic esters of N-hydroxyl carbimide, 2 of N-hydroxyl carbimide, 1, the 4-diazonium naphthoquinone sulphonate, San Lv Jia Ji oxazole compounds, as 2-trichloromethyl-5-coumarone Yi Xi Ji oxazole, and the compatibility negative ion is a chlorion, the carbonic acid negative ion, the p-toluenesulfonic acid negative ion, replace the p-toluenesulfonic acid negative ion, the perchloric acid negative ion, the fluoboric acid negative ion, the diazenium compound of fluorophosphoric acid negative ion.Consider the matching of above-mentioned product acid source maximum absorption wavelength and near ultraviolet light source, preferentially select for use absorbing wavelength the strong 1-that absorbs to be arranged between 320-420nm to methoxy-naphthyl-3, the two trichloromethyl triazines of 5-, 1-is to methoxy styryl-3, the two trichloromethyl triazines of 5-, 1-Chinese cassia tree fork methine-3, the two trichloromethyl triazines of 5-, 1-furans vinyl-3, the two trichloromethyl triazines of 5-, 2-trichloromethyl-5-coumarone Yi Xi Ji oxazole and compatibility ion are that p-toluenesulfonic acid or the diazenium compound that replaces p-toluenesulfonic acid are that light produces acid source.They account for 0.1-10% weight in the solid gross mass of photosensitive composition, preferred 0.5-5% weight.If consumption is greater than 10% weight, then the intensity of sensitization rete and deep layer photosensitive property descend, and it is residual dirty easily to keep on file in the developing process.If consumption is less than 0.1% weight, then sensitivity obviously descends.
In photosensitive composition of the present invention, can be used as component d) coloring background dye be selected from the used coloring background dye of traditional PS version one or more, for example solvent blue, Victoria's ethereal blue, alkaline bright blue, methylene blue, phthalocyanine blue, indigo, careless phenol indigo plant, malachite green, phthalocyanine green, crystal violet, bromothymol blue, methyl violet, fluorescein, dimethyl yellow, methyl orange, eosin etc.In order to increase the color contrast of exposure front and back, often be easy to the dyestuff of variable color after the acid of employing product, for example the solvent blue of easy generation colour killing, Victoria's ethereal blue, alkaline bright blue etc. after the product acid.As desire to make sensitization partly to darken then can to use triphenylmethane be the latent colour solid of royal purple dyestuff, as desire to make exposed portion to become other darker colors by blueness or blue-green, can use methyl orange, fluorescein, dimethyl yellow and triphenylmethane is the compound latent colour solid of royal purple dyestuff.
In photosensitive composition of the present invention, coloring background dye generally accounts for 0.1-5% weight in the solid gross mass of photosensitive composition, preferred 0.5-2% weight.If consumption is lower than 0.1% weight, then made forme pattern colour density is too low; If consumption is higher than 5% weight, then will influence the sensitivity of photosensitive composition, particularly deep layer exposure performance and developing performance.
In photosensitive composition of the present invention, as component e) assistant crosslinking agent or the abrasion-resistant surface agent for the sensitivity that improves photosensitive composition and improve and be coated with abrasion-resistant surface or the resistance to marring of making the PS master and play an important role.Can select the methylolation polyphenolic substance for use as assistant crosslinking agent, for example the methylolation compound of bisphenol-A, dimer or trimerical methylol compound are as two methylol bisphenol-As, inferior ethylene four phenol of tetra methylol etc.Can also use many methylolations derivant of the above-mentioned linear phenol resin of mentioning as film-forming resin, i.e. methylolation phenol resin, particularly those contain the linear phenol resin of methylolation of phenol or metacresol unit.Their consumption is a principle with the consumption that is no more than main crosslinking chemical.The sensitivity of the too big not only PS version of consumption descends, and the bin stability of plate also is adversely affected.
For anti-dry grinding property in the surface of improving the PS version or resistance to marring, can add some than bigger ternary that methacrylic acid, Jia Jibingxisuanβ-Qiang Yizhi, methyl methacrylate and/or vinyl cyanide synthesized or the quadripolymer of main body film-forming resin molecular weight, its weight-average molecular weight between 20000-60000, preferred 36000-45000.Owing to contain hydroxyl and carboxyl in their molecule, under strong acid catalysis, can react or the etherificate cross-linking reaction with crosslinking chemical generation esterification and crosslinking, and improved the resistance to abrasion and the resistance to marring of PS version, but their consumption can not be too many, generally is limited in below 30% of main body film-forming resin.If consumption is too many, the coating performance variation of sensitization liquid then, the oleophylic China ink of image rete significantly descends, and developing performance also can be had a strong impact on.Also can use by phthalate anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride and azanol synthetic N-hydroxyl carbimide compounds and many N-hydroxyl carbimide compounds.Because their fusing point is higher, have the temperature tolerance imide structure again, be mixed in generally can both improve in the photosensitive composition and be coated with the resistance to abrasion of making the PS version, and since the N-hydroxyl easily and crosslinking chemical generation etherificate cross-linking reaction, image section intensity after crosslinked is bigger, and forme has good pressrun.The addition of these materials is limited to its solvent nature, generally uses below 10% of main film-forming resin weight.If consumption is too big, then, influences coating performance, and, can have influence on the ink affinity of forme because its polarity is stronger owing to solubilizing poorly in sensitization liquid.Using above-mentioned assistant crosslinking agent or abrasion-resistant surface agent in photosensitive composition dexterously can make this photosensitive composition have more practicality in actual coated version, plate-making process.
Above-mentioned assistant crosslinking agent or abrasion-resistant surface agent account for 1-20% weight in the solid gross mass of photosensitive composition of the present invention, preferred 3-10% weight.
Solvent in the photosensitive composition of the present invention can be selected traditional PS version solvent for use for use, for example ethylene glycol monoalkyl ether (as ethylene glycol monoethyl ether, glycol monoethyl ether etc.), propylene-glycol monoalky lether (as dihydroxypropane single-ether, propylene glycol monomethyl ether etc.), ethylene glycol monoalkyl ether acetate (as ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate etc.), ethyl lactate, gamma-butyrolacton, butyl acetate, cyclohexanone, MEK, dioxane, they can use separately, also can multiple compound use.Because the present invention adds some special interpolation auxiliary agents, selects for use double solvents often to have better dissolving and levelling effect.Also add small amount of N-ethyl pyrrolidone under some situation, or dimethyl formamide, to improve the dissolubility of imide analog compounds.The consumption of solvent is decided according to desired viscosity of preparation sensitization liquid and solid content, and maximum consumption is 95% of a sensitization liquid general assembly (TW), and minimum amount is 50% of a sensitization liquid general assembly (TW).For preparation low viscosity sensitization liquid, solvent load is between 95-85%, and medium-viscosity sensitization liquid is between 80-70%, and high viscosity sensitization liquid is between 70-50%.It is 5-50% weight that the consumption of preferred solvent should make the solid content of gained photosensitive composition, preferred 10-40% weight, and the viscosity under the room temperature is the 30-40 centipoise.
Photosensitive composition of the present invention can be used to prepare chemical amplitude type negative PS version.Concrete preparation process for example is performed as follows: photosensitive composition of the present invention is coated on edition base according to a conventional method, carries out imaging and exposure then, about 1 minute of 120-140 ℃ of following prebake conditions, develop according to a conventional method then.
Below by with Comparative Examples the present invention being described in more detail in conjunction with the embodiments, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Poly(4-hydroxystyrene) (M
w=8000, M
w/ M
n=1.2, Japanese Cao Da company) 8g
Hexamethoxymethyl melamine (Weihai, the Shandong economic technology that contains the hydroxymethyl phenol resin
The sky, development area becomes chemical industry company limited, BTC-101) 1.5g
1-is to methoxy-naphthyl-3, the two trichloromethyl triazine 0.1g of 5-
Victoria's ethereal blue 0.1g
Methylolation orthoresol linear phenolic resin (M
w=2200, M
w/ M
n=2, Shandong
Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-31) 0.3g
Ethylene glycol monoethyl ether 90g
Compound method
At first will between 20-40 ℃, be dissolved in ethylene glycol monoethyl ether as the triaizine compounds that light produces acid source, after other component under agitation added and fully stirring 4-6 hour, filter with coarse filter paper, again with the dissolving of explication de texte filter paper, filter, prepare sensitization liquid SL-1.
Embodiment 2
Poly(4-hydroxystyrene) (M
w=12000, M
w/ M
n=2.3, Japanese Cao Da company) 4g
Metacresol-paracresol-mixed phenol phenolics (M
w=3000, M
w/ M
n=2.8, the mountain
East Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-25L) 3.5g
Hexamethoxymethyl melamine (Weihai, the Shandong economic technology that contains the hydroxymethyl phenol resin
The sky, development area becomes chemical industry company limited, BTC-101) 1.25g
1-is to methoxy styryl-3, the two trichloromethyl triazine 0.125g of 5-
Alkaline bright blue 0.1g
Dimethyl yellow 0.025g
(per molecule contains the bisphenol-A of 2 methylols to the methylol bisphenol-A, Weihai, Shandong warp
Ji technological development zone sky becomes chemical industry company limited, HBP-A1) 1g
Glycol monoethyl ether 90g
Make sensitization liquid SL-2 with the compound method identical with embodiment 1.
Embodiment 3
Metacresol-formaldehyde resin (M
w=4800, M
w/ M
n=5.0, softening point 105-110 ℃,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-26M) 8.0g
Hexamethoxymethyl melamine (Weihai, the Shandong economic technology that contains the hydroxymethyl phenol resin
The sky, development area becomes chemical industry company limited, BTC-101) 1.5g
1-is to methoxy-naphthyl-3, the two trichloromethyl triazine 0.1g of 5-
1-furans vinyl-3, two trichloromethyl triazine (Chemical Pilot Plant, Beijing Normal Univ.) 0.05g of 5-
Crystal violet 0.05g
Alkaline bright blue 0.1g
Ethylene glycol monoethyl ether 80g
Gamma-butyrolacton 10g
Make sensitization liquid SL-3 with the compound method identical with embodiment 1.
Embodiment 4
Metacresol-paracresol-mixed phenol phenolics (M
w=3000, M
w/ M
n=2.8, Shandong
Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-25L) 8g
Hexamethoxymethyl melamine 1.0g
1-Chinese cassia tree fork methine-3, the two trichloromethyl triazine 0.1g of 5-
1-is to methoxy styryl-3, the two three oxygen methyl triazine 0.05g of 5-
Alkaline bright blue 0.1g
Methylolation orthoresol linear phenolic resin (M
w=2200, M
w/ M
n=2, Shandong
Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-31) 0.75g
Ethylene glycol monoethyl ether 80g
Dioxane 10g
Make sensitization liquid SL-4 with the compound method identical with embodiment 1.
Embodiment 5
Metacresol-formaldehyde resin (M
w=6500, M
w/ M
n=7.0, Weihai, Shandong economic technology is opened
Send out district day one-tenth chemical industry company limited, BTB-26H) 8.0g
(Weihai, Shandong economic technology is opened to contain the hexamethoxymethyl melamine of hydroxymethyl phenol resin
Send out district day one-tenth chemical industry company limited, BTC-101) 1.25g
1-Chinese cassia tree fork methine-3, two trichloromethyl triazine (Chemical Pilot Plant, Beijing Normal Univ.) 0.15g of 5-
The gorgeous 0.1g of alkalescence
Two-N-dihydroxy benaophenonel four acyl diimines (Beijing Normal University photosensitive high molecular research department) 0.5g
Glycol monoethyl ether 80g
N-ethyl pyrrolidone 5g
Gamma-butyrolacton 5g
Make sensitization liquid SL-5 with the compound method identical with embodiment 1.
Embodiment 6
Metacresol-paracresol mixes phenol phenolics (M
w=3000, M
w/ M
n=2.8, Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-25L) 6.4g
Metacresol-formaldehyde resin (M
w=4800, M
w/ M
n=5.0, softening point 105-110 ℃,
Weihai, Shandong economic and technological development zone sky becomes chemical industry company limited, BTB-26M) 2g
Hexamethoxymethyl melamine 1.25g
2-trichloromethyl-5-coumarone Yi Xi Ji oxazole 0.2g
Victoria's ethereal blue 0.1g
Crystal violet 0.05g
Ethylene glycol monoethyl ether 90g
Make sensitization liquid SL-6 with the compound method identical with embodiment 1.
Embodiment 7
Phenol phenolics (M mixes in phenol-paracresol-tertiary butyl phenol system
w=4200, M
w/ M
n=4.3,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-22) 4.0g
Phenol phenolics (M mixes in phenol-paracresol-metacresol system
w=3800, M
w/ M
n=4.0,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-66) 4.0g
(Weihai, Shandong economic technology is opened to contain the hexamethoxymethyl melamine of hydroxymethyl phenol resin
Send out district day one-tenth chemical industry company limited, BTC-101) 1.0g
Methylolation phenol-paracresol linear phenolic resin (M
w=4000, M
w/ M
n=3.8,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., HM-24) 0.5g
The compatibility ion be the p-toluenesulfonic acid root to diazonium diphenylamine formaldehyde resin
Diazo salt (company in the Japanese village) 0.4g
Methyl violet 0.05g
Solvent blue 0.05g
Glycol monoethyl ether 50g
Propylene glycol monomethyl ether 30g
MEK 5g
Dioxane 5g
Make sensitization liquid SL-7 with the compound method identical with embodiment 1.
Embodiment 8
Metacresol-formaldehyde resin (110 ℃ of softening points, Benxi light industry research institute) 4.5g
Metacresol-paracresol mixes phenol phenolics (105 ℃ of softening points, Benxi light industry research institute) 4.0g
Contain hexamethoxymethyl melamine (Weihai, Shandong economic technology exploitation of hydroxymethyl phenol resin
Qu Tian becomes chemical industry company limited, BTC-101) 1.25g
Right-phenoxy group dichloroacetophenone 0.15g
Phthalocyanine blue 0.05g
Methylene blue 0.05g
Dihydroxypropane single-ether 80g
Butyl acetate 5g
Cyclohexanone 5g
Make sensitization liquid SL-8 with the compound method identical with embodiment 1.
Embodiment 9
(128 ℃ of softening points, sky, economic and technological development zone, Weihai, Shandong becomes orthoresol-formaldehyde resin
Chemical industry company limited, BTB-28) 4.0g
Metacresol-paracresol mixes phenol phenolics (M
w=3000, M
w/ M
n=2.8, Weihai, Shandong
The sky, economic and technological development zone becomes chemical industry company limited, BTB-25L) 4.0g
Contain hexamethoxymethyl melamine (Weihai, Shandong economic technology exploitation of hydroxymethyl phenol resin
Qu Tian becomes chemical industry company limited, BTC-101) 1.0g
Dimethyl tetramethyl oxygen phenyl diazonium fluoride borate 0.4g
Phthalocyanine blue 0.1g
Methacrylic acid-Jia Jibingxisuanβ-Qiang Yizhi-methyl methacrylate copolymer
(M
w＝40000，M
w/M
n＝2.7) 0.5g
Ethylene glycol monoethyl ether acetate 80g
Gamma-butyrolacton 5g
Cyclohexanone 5g
Make sensitization liquid SL-9 with the compound method identical with embodiment 1.
Embodiment 10
Metacresol-formaldehyde resin (M
w=4800, M
w/ M
n=5.0, softening point 105-110 ℃,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-26M) 8.0g
(Weihai, Shandong economic technology is opened to contain the hexamethoxymethyl melamine of hydroxymethyl phenol resin
Send out district day one-tenth chemical industry company limited, BTC-101) 1.0g
The two N-hydroxyl acid imide 0.25g of equal benzene tetramethyl acyl
Methylolation orthoresol linear phenolic resin (M
w=2200, M
w/ M
n=2, Shandong
Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-31) 0.5g
1-is to methoxy-naphthyl-3, the two trichloromethyl triazine 0.125g of 5-
Victoria's ethereal blue 0.1g
Dimethyl yellow 0.025g
Ethylene glycol monoethyl ether 80g
N-ethyl pyrrolidone 5g
MEK 5g
Make sensitization liquid SL-10 with the compound method identical with embodiment 1.
Reference example 1
Metacresol-formaldehyde resin (M
W=4800, M
W/ M
n=5.0, Weihai, Shandong economic technology
The sky, development area becomes chemical industry company limited, BTB-26M) 8.3g
Methylolation orthoresol linear phenolic resin (M
w=2200, M
w/ M
n=2, Shandong
Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-31) 0.5g
Methylolation phenol-paracresol linear phenolic resin (M
w=4000, M
w/ M
n=3.8,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., HM-24) 1.0g
1-is to methoxy-naphthyl-3, the two trichloromethyl triazine 0.1g of 5-
Victoria's ethereal blue 0.1g
Ethylene glycol monoethyl ether 90g
Make sensitization liquid SL-ginseng 1 with the compound method identical with embodiment 1.
Reference example 2
Metacresol-formaldehyde resin (M
w=3000, M
w/ M
n=2.8, softening point 98-102 ℃,
Shandong Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd., BTB-26L) 8.3g
(Weihai, Shandong economic technology is opened to contain five methylated methylol melamines of hydroxymethyl phenol resin
Send out district day one-tenth chemical industry company limited, BTC-102) 1.5g
1-is to methoxy styryl-3, two trichloromethyl triazine (the Beijing Normal University's chemical engineering experiments of 5-
Factory) 0.1g
Alkaline bright blue 0.1g
Ethylene glycol monoethyl ether 90g
Make sensitization liquid SL-ginseng 2 with the compound method identical with embodiment 1.
The invention effect
Disposal methods with traditional diazo naphthoquinone type positive PS printing plate aluminum substrate obtains thick 0.27mm, and Grains Ra is 0.5-0.7mm, and Rh (Rz) is 3-4 μ m, and the oxide film amount is 2.8-3.2g/m
2Version base (the imperial PS version printing material of Guangxi Yulin gold company limited), handle without sealing of hole or primary coat, directly the sensitization liquid with embodiment 1-10 and reference example 1 and 2 is coated with respectively with centrifugal rubbing method, obtains corresponding PS version, adjust centrifugal coating machine rotating speed, making coating weight is 1.8-2.1g/m
2, 110 ℃ of baking temperatures, 3 minutes drying times.The rete solvent is less than 3% of rete weight.Gained PS pressing sequence number is respectively PS-1, PS-2 ... PS-10 and PS-ginseng 1, PS-ginseng 2.The performance of above-mentioned plate and plate-making effect are listed in the table 1.
The performance of table 1 embodiment of the invention and Comparative Examples and plate-making effect
| The pressing sequence number | Plate is apparent | Anti-dry grinding number of times (before the exposure) | Sensitivity ① (mJ/cm 2) | Differentiate wire spoke (%) | Dot reproduction (%) | Development effect ② |
| PS-1 | ◎ | 6 | 50 | 7 | 2-99 | ○ |
| PS-2 | ◎ | 5 | 50 | 7 | 1-99 | ◎ |
| PS-3 | ◎ | 4 | 70 | 7 | 2-99 | ◎ |
| PS-4 | ◎ | 5 | 60 | 7 | 2-98 | ○ |
| PS-5 | ○ | 5 | 60 | 7 | 2-99 | ○ |
| PS-6 | ◎ | 5 | 70 | 7 | 1-98 | ○ |
| PS-7 | ◎ | 4 | 70 | 8 | 1-99 | ◎ |
| PS-8 | ○ | 6 | 80 | 8 | 2-98 | ○ |
| PS-9 | ◎ | 7 | 90 | 10 | 2-98 | △ |
| PS-10 | ○ | 5 | 70 | 7 | 1-99 | ○ |
| PS-ginseng 1 | ◎ | 5 | ＞300 | 12 | 5-95 | × |
| PS-ginseng 2 | ◎ | 1 | 100 | 8 | 2-98 | △ |
1. before developed in the exposure back, baking was 1 minute in 130 ℃ of baking ovens, thoroughly solidified 5 sections exposure.
2. refer to developing powder, have or not subtract film, the look phenomenon of keeping on file.
◎, zero, △ and * to represent described effect respectively be excellent, good, general and poor.
Claims (9)
1. chemical amplitude type negative PS plate photosensitive composition comprises following component:
A) 45-90% weight, the film-forming resin of preferred 50-80% weight;
B) 1-20% weight, the crosslinking chemical of preferred 5-15% weight;
C) 0.1-10% weight, the light of preferred 0.5-5% weight produces acid source;
D) 0.1-5% weight, the background dye of preferred 0.5-2% weight;
E) 1-20% weight, the assistant crosslinking agent or the abrasion-resistant surface agent of preferred 3-10% weight; With
F) making the solid content of described composition is 5-50% weight, the solvent of preferred 10-40% weight; Wherein said percent by weight is based on the solid gross mass of described composition.
2. according to the photosensitive composition of claim 1, wherein said film-forming resin is to be selected from following linear phenol resin: weight-average molecular weight M
wBe 2000-12000, the poly(4-hydroxystyrene) of preferred 5000-10000; Weight-average molecular weight M
wBe 2000-8000, the linear phenolic resin of preferred 3000-6000; And their potpourri.
3. according to the photosensitive composition of claim 2, wherein said linear phenolic resin is selected from metacresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, metacresol-paracresol-phenol-formaldehyde resin, metacresol-orthoresol-formaldehyde resin, metacresol-phenol-formaldehyde resin, metacresol-phenol-paracresol-formaldehyde resin, metacresol-phenol-tertiary butyl phenol-formaldehyde resin, paracresol-phenol-formaldehyde resin, paracresol-orthoresol-formaldehyde resin, orthoresol-formaldehyde resin, orthoresol-phenol-formaldehyde resin, orthoresol-phenol-tertiary butyl phenol-formaldehyde resin, phenol-formaldehyde resin, phenol-tertiary butyl phenol-formaldehyde resin, phenol-halo resinox, resorcinol-formaldehyde resin, resorcinol-paracresol-formaldehyde resin, resorcinol-tertiary butyl phenol-formaldehyde resin, catechol-formaldehyde resin, catechol-paracresol-formaldehyde resin, catechol-tertiary butyl phenol-formaldehyde resin and their potpourri, be preferably selected from metacresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, metacresol-paracresol-phenol-formaldehyde resin, metacresol-orthoresol-formaldehyde resin, metacresol-phenol-formaldehyde resin, metacresol-phenol-paracresol-formaldehyde resin, metacresol-phenol-tertiary butyl phenol-formaldehyde resin, and their potpourri.
4. according to the photosensitive composition of claim 1, wherein crosslinking chemical is selected from alkoxymethyl melamine, for example methylated methylol melamine, ethoxymethyl melamine, the third oxygen methyl melamine or fourth oxygen methyl melamine, the potpourri of the alkoxymethyl melamine of preferred different r-o-methylation ratios, as the potpourri of three alkoxymethyl melamines, four alkoxymethyl melamines, five alkoxymethyl melamines, six alkoxymethyl melamines, the methylated melamine resin of hexakis-methoxy most preferably.
5. according to the photosensitive composition of claim 1, wherein light produces acid source and is selected from the trichloromethyl compound in triazine class, as 1-to methoxy styryl-3, the two trichloromethyl triazines of 5-, 1-is to methoxy-naphthyl-3, the two trichloromethyl triazines of 5-, 1-Chinese cassia tree fork methine-3, the two trichloromethyl triazines of 5-, 1-furans vinyl-3, the two trichloromethyl triazines of 5-, 1-styryl-3, the two trichloromethyl triazines of 5-, 1-anisyl-3, the two trichloromethyl triazines of 5-, 1-(2, the two methoxy styryls of 4-)-3, the two trichloromethyl triazines of 5-, 1-(2-methyl-4-methoxy styryl)-3, the two trichloromethyl triazines of 5-, dichloroacetophenone, right-the phenoxy group dichloroacetophenone, the tribromo-benzene ethyl ketone, trisbromomethyl phenyl sulfone, the p-toluenesulfonic esters of N-hydroxyl carbimide, 2 of N-hydroxyl carbimide, 1,4-diazonium naphthoquinone sulphonate, San Lv Jia Ji oxazole compounds, as 2-trichloromethyl-5-coumarone Yi Xi Ji oxazole, and the compatibility negative ion is a chlorion, the carbonic acid negative ion, the p-toluenesulfonic acid negative ion, replace the p-toluenesulfonic acid negative ion, the perchloric acid negative ion, the fluoboric acid negative ion, the diazenium compound of fluorophosphoric acid negative ion.
6. according to the photosensitive composition of claim 1, wherein coloring background dye is to be selected from solvent blue, Victoria's ethereal blue, alkaline bright blue, methylene blue, phthalocyanine blue, indigo, careless phenol indigo plant, malachite green, phthalocyanine green, crystal violet, bromothymol blue, methyl violet, fluorescein, dimethyl yellow, methyl orange, the eosin one or more.
7. according to the photosensitive composition of claim 1, wherein assistant crosslinking agent or abrasion-resistant surface agent are selected from the linear phenol resin of methylolation, the methylolation polyphenolic substance, N-hydroxyl carbimide and many N-hydroxyl carbimide compounds, the multiple copolymer of methacrylic acid, methyl methacrylate, Jia Jibingxisuanβ-Qiang Yizhi and/or acrylonitrile.
8. according to the photosensitive composition of claim 1, wherein solvent is selected from ethylene glycol monoalkyl ether (as ethylene glycol monoethyl ether, glycol monoethyl ether etc.), propylene-glycol monoalky lether (as dihydroxypropane single-ether, propylene glycol monomethyl ether etc.), ethylene glycol monoalkyl ether acetate (as ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate etc.), ethyl lactate, gamma-butyrolacton, butyl acetate, cyclohexanone, MEK, dioxane.
9. according to the photosensitive composition of claim 1 purposes in preparation chemical amplitude type negative PS version.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510007283 CN1815364A (en) | 2005-02-06 | 2005-02-06 | Light-sensitive composition for chemical amplitude type negative PS plate and chemical amplitude type negative PS plate thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510007283 CN1815364A (en) | 2005-02-06 | 2005-02-06 | Light-sensitive composition for chemical amplitude type negative PS plate and chemical amplitude type negative PS plate thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1815364A true CN1815364A (en) | 2006-08-09 |
Family
ID=36907613
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510007283 Pending CN1815364A (en) | 2005-02-06 | 2005-02-06 | Light-sensitive composition for chemical amplitude type negative PS plate and chemical amplitude type negative PS plate thereof |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281369B (en) * | 2007-04-02 | 2012-01-11 | 三星电子株式会社 | Photoresist composition and method for forming photoresist pattern using the same |
| CN104529861A (en) * | 2015-01-13 | 2015-04-22 | 威海经济技术开发区天成化工有限公司 | Method for synthesizing imide group modified low-molecular-weight line-type phenolic resin and sensitization imaging composition containing imide group modified low-molecular-weight line-type phenolic resin |
| CN116574425A (en) * | 2023-06-08 | 2023-08-11 | 诺奇兄弟新材料(吴江)有限公司 | Finished product water-based paint and preparation method thereof |
-
2005
- 2005-02-06 CN CN 200510007283 patent/CN1815364A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281369B (en) * | 2007-04-02 | 2012-01-11 | 三星电子株式会社 | Photoresist composition and method for forming photoresist pattern using the same |
| CN104529861A (en) * | 2015-01-13 | 2015-04-22 | 威海经济技术开发区天成化工有限公司 | Method for synthesizing imide group modified low-molecular-weight line-type phenolic resin and sensitization imaging composition containing imide group modified low-molecular-weight line-type phenolic resin |
| CN116574425A (en) * | 2023-06-08 | 2023-08-11 | 诺奇兄弟新材料(吴江)有限公司 | Finished product water-based paint and preparation method thereof |
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