CN103885287B - Photosensitive composition with sulfonyl hydrazone-modified phenolic resin as acid-producing agent and application thereof - Google Patents

Photosensitive composition with sulfonyl hydrazone-modified phenolic resin as acid-producing agent and application thereof Download PDF

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CN103885287B
CN103885287B CN201210563900.8A CN201210563900A CN103885287B CN 103885287 B CN103885287 B CN 103885287B CN 201210563900 A CN201210563900 A CN 201210563900A CN 103885287 B CN103885287 B CN 103885287B
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phenol
phenolic resin
photosensitive composition
modified
sulphonyl hydrazone
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CN103885287A (en
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栗更新
张刚
冯磊
牛红雨
王群英
薛辛琴
张伏潭
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Lucky Huaguang Graphics Co Ltd
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Lucky Huaguang Graphics Co Ltd
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Abstract

The invention discloses a photosensitive composition with sulfonyl hydrazone-modified phenolic resin as an acid-producing agent, which comprises sulfonyl hydrazone-modified linear phenolic resin, alkali-soluble resin, an infrared absorption dye, and a background dye. The acid-producing agent of sulfonyl hydrazone-modified linear phenolic resin is A-R1=N-NH-SO2-R2. The sulfonyl hydrazone-modified phenolic resin is a key component of the composition of the invention. In an application of positive-printing thermosensitive CTP printing plate materials, sulfonyl hydrazone-modified phenolic resin in a scanning area is subjected to chemical reaction under a heating condition, is decomposed to release alkali-soluble groups, such as a phenolic hydroxyl group or a sulfo group, and is further decomposed to generate nitrogen, so as to have foaming and dissolution promotion effects; a non-scanning area has dissolution inhibition effect; therefore, a great dissolution difference between the scanning area and the non-scanning area is formed.

Description

The photosensitive composition as acid agent and its application using sulphonyl hydrazone phenol-formaldehyde resin modified
Technical field
The present invention relates to a kind of technical field of photosensitive composition.Specifically the present invention relates to a kind of modified using sulphonyl hydrazone Application of the phenolic resin as the photosensitive composition of acid agent and its in positive-printing heat-sensitive CTP plate material.
Background technology
Be applied to after offset printing from the PS versions sixties in 20th century, offset plate making technique continue to use always photo-sensation egative film, layout, Technique before the print that printing down, PS versions are developed and printed.But the shortcoming of this plate-making mode also gradually comes out, this kind of plate-making mode flow process Long, site loss is big, printing quality is less high, and particularly environmental pollution is larger, in order to change this situation, 80 years 20th century Generation, the U.S., Japanese some companies start to develop CTP (Computer to plate, abbreviation CTP) skill Art, current CTP technologies are developed rapidly, and in the popularization and application stage.CTP technologies are divided into photosensitive CTP plate-making technologies and heat Quick CTP plate-making technologies, wherein positive heat-sensitive CTP plate-making technology are current most ripe, most stable, the best plate-making technologies of effect. This technology mainly utilizes photothermal conversion principle, i.e., when iraser (830nm) carries out image scanning on plate to expose, sweep Retouch part infrared absorbing dye absorbing light and be converted into heat energy, cause scanned regional temperature to be increased to more than threshold temperature, cause Acid is produced in light thermal acid generator thermal decomposition in plate, and under the action of an acid, the heat susceptible coating for seeing light region is decomposed reaction, with alkali Dissolubility, is dissolved during development treatment, exposes the blank parts that hydrophilic version base becomes hydrophilic;Have no the heat susceptible coating in light region Do not decompose reaction, not with alkali solubility, the space of a whole page is still remained in after development treatment becomes the areas of oleophylic.Wherein version The acid agent used in material is the key component that coating occurs hydrophilic change, and this material can be produced by the thermally-induced product acid source of light Raw proton or free radical, produced acid makes resin decompose under conditions of room temperature or heating, so that illumination coating is sent out Life chemical reaction soluble in water.
Light thermal acid generator main species have diazols compound, salt, organic polyhalogen compound, sulphonic acid ester and triazines Compound etc., these acid agents in use, due to different to light source energy absorption, made by one section of storage having of plate Occur sensitivity after time and decline fast, stability is bad, and phenomenon of keeping on file after some developments, some solvent resistances are poor, also resistance to Print rate is not high, so so far the using effect of this acid agent is not good.For these problems, each company is to temperature-sensitive acid agent Use and substantial amounts of research work has been done in selection, specifically, temperature-sensitive digitized has been invented by the 1980s, Kodak Direct plate-making technology (US5340699, US5491046, US5466557), this plate phenolic resin is used as film-forming resin Hydroxymethyl resins make cross-linking agent, with iodine salt or compound in triazine class as light thermal acid generator.Before this technology is using development Preheating procedure, relatively costly, operation is also long.Journal of the Organic Chemistry, 43 (15) (1978) reports Triphenyl sulfosalt derivant is led.JP7-28237 has reported alkyl sulfide salt derivative, and for example (2- is oxo for cyclohexyl methyl Cyclohexyl) sulfosalt trifluoromethyl sulfonic acid.Journal of th Polymer Science, 56 (1975) have reported hexichol Base iodine salt and succinimide derivatives.Plate obtained in these acid agents, phenomenon of keeping on file after some developments, what is had is anti-molten Agent is poor.Double trichloromethyl-the 1- of 3,5- used by (Unexamined Patent -11-119428,11-24248) are to first in Mitsubishi Chemical Ind's patent The routine acid agent such as diphenyl iodnium used by oxygen styryl triazines chemical combination and Kodak, it is solid in image forming composition Body gross mass accounts for 1-10% weight, but only can only obtain the negative image of preheating with the acid agent that these thermal CTP plate materials are general Hot glue connection type heat-sensitive CTP plate, is difficult to obtain the thermal CTP plate material of positive image or negative image without preheating.CN1380180A discloses one kind The direct method for platemaking of coating type negative thermo-sensitive computer, wherein in heat sensing layer thermal acid generator be with used by Kodak, It is the diphenyl iodnium with hexafluoro-phosphate radical as anion, what is obtained is negative engraving.
The present invention relates to class sulphonyl hydrazone Modified Phenolic Resin compound, its solvent resistance is good, and is preparing Dissolubility is good in liquid, good stability, and other photoactive components have and mix well effect, release under photothermy sour efficiency high and Hurry up.
The content of the invention
The present invention is to provide and a kind of uses sulphonyl hydrazone phenol-formaldehyde resin modified as the photosensitive composition of acid agent and its in sun Application in figure thermal CTP plate material.Sulphonyl hydrazone phenol-formaldehyde resin modified is the key component of the present invention, is scanned when iraser is scanned The infrared absorbing dye in region absorbs infrared light and luminous energy is changed into into heat energy, and the temperature for making scanned region film layer rises to 170 More than DEG C, chemical reaction can occur in this temperature range acid agent of the present invention, decomposition can discharge alkali solubility group-phenol Hydroxyl or sulfonic group, while the nitrogen of generation can further be decomposed, produce foaming dissolution effect, make scanning area and Non-scanning mode Region has larger dissolving contrast.
The technical scheme is that:
The present invention's uses sulphonyl hydrazone phenol-formaldehyde resin modified as the photosensitive composition of acid agent, including the sour resistance solvent of product, Alkali soluble resin, infrared absorbing dye and background dye, described product acid resistance solvent is sulphonyl hydrazone Modified Phenolic Resin.
The general structure of the sour resistance solvent of described product is:
A-(R1=N-NH-SO2-R2)
Wherein A is the phenolic resin parent being grafted, and phenolic resin includes P-F phenolic resin, metacresol-to first Phenol phenolic resin, phenol-metacresol-paracresol phenolic resin, phenol-tert-butyl phenol phenolic resin, phenol-paracresol phenolic aldehyde tree At least one in fat, orthoresol-paracresol phenolic resin, phenol-formaldehyde resin modified.R1Alkyl and company for 1-10 carbon atom Meet substituted or unsubstituted C6-C30 aryl, R2For substituted or unsubstituted C6-C20 aryl, preferably unsubstituted or substituted C6- C14 aryl, is preferably selected from phenyl, p-methylphenyl, to tert-butyl-phenyl, rubigan, naphthyl, isopropyl naphthyl or t-butyl naphthalin Base.
Described sulphonyl hydrazone Modified Phenolic Resin of the present invention is by sulphonyl hydrazone compounds and phenolic resin Grafting synthesis, graft ratio is 20%~30%, between weight average molecular weight range 4000~20000, number-average molecular weight Between 800~2000, between 120 DEG C -170 DEG C of vitrification point, graft ratio is 20%~30% to scope, and graft ratio is little In 20%, acid producing ability is weaker after photosensitive layer exposure, and photosensitive composition development is more difficult;Graft ratio is more than 30%, and photosensitive layer exposes Acid release is relatively strong after light, and photosensitive layer subtracts film.Sulphonyl hydrazone Modified Phenolic Resin of the present invention is by sulfonyl hydrazines chemical combination Thing is closed with phenolic resin grafting
Into, graft ratio is 20%~30%, and between weight average molecular weight range 4000~20000, number is equal
Molecular weight ranges between 800~2000, between 120 DEG C -170 DEG C of vitrification point.The sulfonyl hydrazines chemical combination Thing includes:Benzene sulfonyl hydrazide, unifor, 1,3- disulfonyl hydrazide, 4,4 '-oxidation, two benzene sulfonyl hydrazides, to tert-butyl benzene sulphonyl Hydrazine, 2- naphthalene sulfonyl hydrazines;It is preferred that unifor, most preferably 4,4 '-oxidation, two benzene sulfonyl hydrazides, unifor;Phenolic aldehyde tree Fat includes P-F phenolic resin, metacresol-paracresol phenolic resin, phenol-metacresol-paracresol phenolic resin, benzene In phenol-tert-butyl phenol phenolic resin, phenol-paracresol phenolic resin, orthoresol-paracresol phenolic resin, phenol-formaldehyde resin modified At least one.
Sulphonyl hydrazone phenol-formaldehyde resin modified accounts for the 1~9% of photosensitive composition gross weight as the consumption of acid agent, and preferably 2 ~6%.
Alkali soluble resin is phenolic resin or poly(4-hydroxystyrene) resin.The consumption of alkali soluble resin accounts for photosensitive group The 82~97% of compound gross weight, preferably 85~95%.
The phenolic resin is metacresol-paracresol phenolic resin, phenol-paracresol phenolic resin, orthoresol-paracresol At least one in phenolic resin, phenolic resin.The present invention from alkaline developer soluble resin include phenolic resin or Poly(4-hydroxystyrene) is used as film-forming resin.Available phenolic resin have metacresol phenolic resin (Mw 4000~8000, Mw/Mn 4~8), (mol ratio of metacresol and paracresol is 8: 2~6: 4, Mw 4000 to metacresol-paracresol phenolic resin Between~10000, Mw/Mn be 4~12), phenol-paracresol phenolic resin (mol ratio of phenol and paracresol be 5: 5~3: 7, Mw between 4000~6000, Mw/Mn 4~6), phenol-orthoresol-paracresol phenolic resin (phenol, orthoresol and to first The mol ratio of phenol be 2: 1: 7, Mw between 6000~9000, Mw/Mn 6~9), phenol-metacresol-paracresol phenolic resin (mol ratio of phenol, metacresol and paracresol be 1: 6: 4, Mw between 7000~10000, Mw/Mn 7~10) and modified phenol Urea formaldehyde (Mw between 12000~13500, Mw/Mn 8~11) etc..Poly(4-hydroxystyrene) is from Mw 5000~30000 Between, products of the Mw/Mn 1.1~1.3.Film-forming resin accounts for the 82~97% of photosensitive composition gross weight, and preferably 85~95%. Film-forming resin consumption can have an impact to press resistance rate, the general tree for choosing molecular weight in 8000-14000 on film-forming resin is chosen Fat.
Photosensitive composition also includes photothermal conversion material infrared absorbing dye, i.e., have absorption peak in 790~830nm Infrared absorbing dye, IR dyes are flower cyanines system infrared absorbing dye.It is general to select colored cyanines system INFRARED ABSORPTION commercially available both at home and abroad Dyestuff, the such as LC-01 of Honywell companies, NK-2014, NK-2268, HCD-21 of Lin Yuan companies, the PS-101 of Japanese chemical medicine, NIRD of the S0094 of PS-102, FEW CHEMICALS companies and Liaoning Huahai indigo plant sail etc., the present invention is mainly red from LC-01 Outer dyestuff.The absorption peak wavelength of these infrared absorbing dyes typically in 800~830nm, is determined generally in alcohol solvent Absorption peak is 815~820nm, and the absorption peak in thermosensitive CTP coating fluid is typically in 815nm or so.Its consumption accounts for photosensitive The 1~5% of composition total weight, preferably 2.5~3.5%.Because IR dyes are a kind of alkali insoluble materials, itself has resistance Molten effect, certain difficulty can be caused when IR dyes consumption is too high to development.Generate heat when consumption is too low too low, be scanned part Temperature is not enough to the decomposition of sulphonyl hydrazone phenol-formaldehyde resin modified, under the scanning energy of regulation, is particularly decomposing at aluminum substrate Not thoroughly, easily development is kept on file.
Background dye is solvent blue, alkaline bright blue, Victoria pure blue, phthalocyanine blue, malachite green oxalate, blackish green, phthalocyanine green, knot Any one in crystalviolet, crystal violet, ethyl violet, dimethyl yellow, fluorescein.The consumption of background dye accounts for photosensitive composition gross weight 1~5%, preferably the 2~3.5% of amount.
Photosensitive composition is configured to positive heat-sensitive CTP coating fluid solid content for 7~20%.
Photosensitive composition is configured to thermosensitive CTP coating fluid and selects, evaporation rate good to said components dissolubility moderate and boiling O'clock in 70~150 DEG C of dicyandiamide solution, wherein the boiling point of bulk solvent is preferably at 100~140 DEG C.Available solvent is just like second The only ether of glycol, ethylene glycol monoemethyl ether, the only methyl ether of Propylene Glycol, the only ether of Propylene Glycol, Ketohexamethylene, butanone, ethylene glycol monomethyl ether vinegar At least one in acid esters, propylene-glycol ethyl ether acetate, gamma-butyrolacton, dioxane etc..Solvent load regarded and applied needed for coating machine Depending on the viscosity of cloth liquid, between 10~15%, viscosity is in 3~5mm for the solid content of general photosensitive composition solution2·s-1It Between.Coating fluid viscosity is less than 3mm needed for some high-speed production lines2·s-1, so situation of the solid content less than 10% also has.
Several components should dissolve in the following order during configuration thermosensitive CTP coating fluid, usually first dissolve infrared compared with indissoluble Dyestuff, adds film-forming resin and sulphonyl hydrazone Modified Phenolic Resin after IR dyes are completely dissolved, and is eventually adding background Dyestuff.
Developing agent for the present invention is mainly made up of alkaline aqueous solution.
Alkaline-based developer is a kind of alkaline solution, is mainly made up of developing agent, protective agent, wetting agent etc..Developing agent is used for The photosensitive layer that dissolving positive picture CTP plate has exposed, commonly uses strong alkaline substance, can select:Sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate, sodium silicate, potassium silicate, disodium hydrogen phosphate, or tertiary sodium phosphate, the concentration of strong alkaline substance is preferably 0.5-30% (wt).Protective agent, wetting agent are anionic surfactant, nonionic surfactant in developer solution.
The present invention outstanding feature be:Sulphonyl hydrazone phenol-formaldehyde resin modified discharges alkali soluble as acid agent in exposure region decomposition Property group-phenolic hydroxyl group or sulfonic group, while the nitrogen for producing, can produce the dissolution that foams acts on so that exposure region and non-exposed Area produces larger differential dissolution rate, improves development and the imaging performance of plate.Simultaneously sulphonyl hydrazone Modified Phenolic Resin has Certain anti-alcohol, the raising to positive thermosensitive CTP version pressrun has certain help.
Specific embodiment
Embodiment 1
The preparation of sensitive lithographic plate
(1) preparation of aluminum substrate:
Thickness is the aluminium sheet of 0.28mm, at a temperature of 55 DEG C, carries out at defat in the sodium hydrate aqueous solution of 7wt% Reason 40 seconds, the formation electrolysis of Grains at a temperature of 25 DEG C, is handed in concentration is for the aqueous hydrochloric acid solution of 10wt% with sine wave Stream electricity carries out electrolysis process, 50HZ alternating currents, electric current 50A/dm2, electrolysis time 60 seconds, control Ra=0.3-0.6um, preferably exist 0.4~0.6 μm .Rz(H)It is worth for 2~3 μm,.Then at a temperature of 60 DEG C, in the sodium hydrate aqueous solution of 50wt% concentration Slag treatment 10 seconds, then electric current density is 5A/d m at a temperature of 25 DEG C2, concentration for 20wt% sulfuric acid solution in process 40 Second, control oxide-film=2.5-3.5g/m2.Finally, NaH is adopted at 60 DEG C2PO4- NaF solution carries out sealing pores 30 seconds, you can Obtain being applied to the aluminum substrate of sensitive lithographic plate.
(2) photosensitive composition is configured to the thermosensitive CTP coating fluid that solid content is 10%, is coated in above-mentioned by stick coating method On aluminum plate foundation prepared by method, in 130 DEG C of dryings 2 minutes, then the version is placed in an oven, in 50 DEG C of ripenings 24 hours To a temperature-sensitive sensitive lithographic plate, the film thickness of photosensitive layer is 1.5g/m2
(3) optimum exposure laser quantity measuring method:
On SCREEN8600E laminators, with test strip is carried, screening 175lpi is imaged, exports resolution 2400dpi, According to exposure below condition (being shown in Table) and development conditions (being shown in Table two), the scanning system of different laser energy is carried out on example edition Version, as the exposed laser amount for then determining using the following method, its sensitivity.
The 50% plain net value surveyed under different exposure energies with the density reflectometer IC-Plate2 of X-rite, until finding out ladder Show value of the 50% plain net region in the range of 49.5%-50.4% in chi bar, the value is both the sensitivity of plate.
Record the sensitivity of plate.
Table one
Platemaking machine SCREEN8600E
Drum speed (rpm) 800
Exposure intensity initial value 40%
Exposure intensity stepped intervals 2%
Exposure bar number 20
Remarks Test strip is carried as machine
Table two
Developer solution model TPD-III developer solutions
Developing machine Prosperous prosperous developing machine
Development temperature 24℃
Developing powder 30 seconds (100cm/min);
The control of developer solution electrical conductivity exists 89-91ms/cm
The dynamic of developer solution is supplemented 120ml/m2
(4) development latitude detection:
In SCREEN8600E platemaking machine, it is exposed according to 1.1 times of sensitivity value obtained above of light exposure, uses Carry test strip and plate-making is scanned on sample, in different developing times, under the conditions of (selecting 20s, 30s, 40s here), Development processed is carried out to example edition, plate can be made to reach use requirement, and (blank space is not kept on file, density OD value < 0.29;Apply Layer does not subtract on the spot film, density loss≤4%;Site reductase 12-99%) the peak of developing time and the difference of minimum be The development latitude of the plate.
Photosensitive composition such as table three:
Table three
BTB-225 resins (Weihai day is into Chemical Co., Ltd.) 0.90g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=2: 8) 0.04g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 90gBTB-225 resins are added into 4% sodium hydrate methanol solution, at 60 DEG C or so 2 are reacted Hour, 45g o-chlorobenzaldehyde Tosylhydrazones are subsequently adding, 60 DEG C or so are reacted 5 hours, and reactant is cooled to after room temperature, In adding 0.1% hydrochloric acid solution, there is solid to separate out, sucking filtration, deionized water drip washing, filter cake is obtained in 40 DEG C or so dryings Product.Its structural formula is as follows, and wherein A is graft resin parent BTB-225.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) to develop 30 seconds at 24 DEG C, sensitivity, development latitude result are as shown in table 14.
Embodiment 2
Example edition preparation method is with embodiment 1
Photosensitive composition such as table four:
Table four
BTB-225 resins (Weihai day is into Chemical Co., Ltd.) 0.92g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=2: 8) 0.02g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 90g PD 140A (from hexion specialty chemicals) resin is added into 4% Sodium hydrate methanol solution, reacts 2 hours at 60 DEG C or so, is subsequently adding 45g o-chlorobenzaldehyde Tosylhydrazones, 60 DEG C of left sides Right reaction 5 hours, reactant is cooled to after room temperature, in adding 0.1% hydrochloric acid solution, has solid to separate out, and sucking filtration uses deionization Water wash, filter cake obtains product in 40 DEG C or so dryings.Its structural formula is as follows, and wherein A is graft resin parent PD 140A.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Embodiment 3
Example edition preparation method is with embodiment l
Photosensitive composition such as table five:
Table five
BTB-25H resins (Weihai day is into Chemical Co., Ltd.) 0.90g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=2.5: 7.5) 0.04g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 84gBTB-225 resins are added into 4% sodium hydrate methanol solution, at 60 DEG C or so 2 are reacted Hour, 47g o-chloroacetophenone Tosylhydrazones are subsequently adding, 60 DEG C or so are reacted 5 hours, and reactant is cooled to after room temperature, In adding 0.1% hydrochloric acid solution, there is solid to separate out, sucking filtration, deionized water drip washing, filter cake is obtained in 40 DEG C or so dryings Product.Its structural formula is as follows, and wherein A is graft resin parent BTB-225.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 25 DEG C, sensitivity, development latitude are as shown in table 14.
Embodiment 4
Example edition preparation method is with embodiment 1
Photosensitive composition such as table six:
Table six
BTB-25H resins (Weihai day is into Chemical Co., Ltd.) 0.92g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=2.5: 7.5) 0.02g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 84gBTB-225 resins are added into 4% sodium hydrate methanol solution, at 60 DEG C or so 2 are reacted Hour, 47g o-chloroacetophenone Tosylhydrazones are subsequently adding, 60 DEG C or so are reacted 5 hours, and reactant is cooled to after room temperature, In adding 0.1% hydrochloric acid solution, there is solid to separate out, sucking filtration, deionized water drip washing, filter cake is obtained in 40 DEG C or so dryings Product.Its structural formula is as follows, and wherein A is graft resin parent BTB-225.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Embodiment 5
Example edition preparation method is with embodiment 1
Photosensitive composition such as table seven:
Table seven
BX-20 resins (the auspicious thing in Benxi reaches Chemical Co., Ltd.) 0.90g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=2.7: 7.3) 0.04g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 82g PD 140A (from hexion specialty chemicals) resin is added into 4% Sodium hydrate methanol solution, reacts 2 hours at 60 DEG C or so, is subsequently adding the chloro- Veratraldehydes of 53g 2- to first Benzene sulfonyl hydrazone, 60 DEG C or so are reacted 5 hours, and reactant is cooled to after room temperature, in adding 0.1% hydrochloric acid solution, have solid to analyse Go out, sucking filtration, deionized water drip washing, filter cake obtains product in 40 DEG C or so dryings.Its structural formula is as follows, and wherein A is grafting tree Fat parent PD 140A.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Embodiment 6
Example edition preparation method is with embodiment 1
Photosensitive composition such as table eight:
Table eight
BX-20 resins (the auspicious thing in Benxi reaches Chemical Co., Ltd.) 0.92g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=2.7: 7.3) 0.02g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 82g PD 140A resins are added into 4% sodium hydrate methanol solution, at 60 DEG C or so 2 are reacted Hour, the chloro- Veratraldehyde Tosylhydrazones of 53g 2- are subsequently adding, 60 DEG C or so are reacted 5 hours, reactant After being cooled to room temperature, in adding 0.1% hydrochloric acid solution, there is solid to separate out, sucking filtration, deionized water drip washing, filter cake is at 40 DEG C Left and right is dried, and obtains product.Its structural formula is as follows, and wherein A is graft resin parent PD 140A.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Embodiment 7
Example edition preparation method is with embodiment 1
Photosensitive composition such as table nine:
Table nine
BTB-29 resins (Weihai day is into Chemical Co., Ltd.) 0.90g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=3: 7) 0.04g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 79gBTB-29 resins are added into 4% sodium hydrate methanol solution, it is little in 60 DEG C or so reactions 2 When, 55g 4- chloro benzophenone Tosylhydrazones are subsequently adding, 60 DEG C or so are reacted 5 hours, and reactant is cooled to room temperature Afterwards, in adding 0.1% hydrochloric acid solution, solid separates out, sucking filtration, deionized water drip washing, filter cake is obtained in 40 DEG C or so dryings To product.Its structural formula is as follows, and wherein A is graft resin parent BTB-29.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Embodiment eight
Example edition preparation method is with embodiment 1
Photosensitive composition such as table ten:
Table ten
BTB-29 resins (Weihai day is into Chemical Co., Ltd.) 0.92g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=3: 7) 0.02g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 79gBTB-29 resins are added into 4% sodium hydrate methanol solution, it is little in 60 DEG C or so reactions 2 When, 55g 4- chloro benzophenone Tosylhydrazones are subsequently adding, 60 DEG C or so are reacted 5 hours, and reactant is cooled to room temperature Afterwards, in adding 0.1% hydrochloric acid solution, solid separates out, sucking filtration, deionized water drip washing, filter cake is obtained in 40 DEG C or so dryings To product.Its structural formula is as follows, and wherein A is graft resin parent BTB-29.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Comparative example 1
Example edition preparation method is with embodiment 1
Photosensitive composition such as table 11:
Table 11
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 68g PD 140A resins are added into 4% sodium hydrate methanol solution, at 60 DEG C or so 2 are reacted Hour, the tri isopropyl benzenesulfonyl hydrazone of 62g o-chlorobenzaldehydes 2,4,6- is subsequently adding, 60 DEG C or so are reacted 5 hours, reactant cooling To after room temperature, in adding 0.1% hydrochloric acid solution, there is solid to separate out, sucking filtration, deionized water drip washing, filter cake is at 40 DEG C or so It is dried, obtains product.Its structural formula is as follows, and wherein A is graft resin parent PD 140A.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Comparative example 2
Example edition preparation method is with embodiment 1
Photosensitive composition such as table 12:
Table 12
BTB-29 resins (Weihai day is into Chemical Co., Ltd.) 0.87g
Infrared absorbing dye LC-01 (Honywell companies) 0.03g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=3: 7) 0.07g
Crystal violet 0.03g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method is identical with example 7 with structure in table.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
Comparative example 3
Preparation method is with embodiment 1
Photosensitive composition such as table 13:
Table 13
BX-20 resins (the auspicious thing in Benxi reaches Chemical Co., Ltd.) 0.95g
Infrared absorbing dye LC-01 (Honywell companies) 0.02g
Sulphonyl hydrazone Modified Phenolic Resin (n: m=4: 6) 0.01g
Crystal violet 0.02g
Sulphonyl hydrazone Modified Phenolic Resin synthetic method in table:In 500ml band temperature control heating, mechanical agitation, condense back In the four-hole boiling flask of stream device, 56gBTB-225 resins are added into 4% sodium hydrate methanol solution, at 60 DEG C or so 2 are reacted Hour, 34g o-chlorobenzaldehyde benzene sulfonyl hydrazones are subsequently adding, 60 DEG C or so are reacted 5 hours, and reactant is cooled to after room temperature, are added In 0.1% hydrochloric acid solution, there is solid to separate out, sucking filtration, deionized water drip washing, filter cake obtains product in 40 DEG C or so dryings. Its structural formula is as follows, and wherein A is graft resin parent BTB-225.
Above-mentioned photosensitive sensitive lithographic plate is arranged in platemaking machine and is exposed.With alkaline-based developer TPD-III (Lekai Hua Guangyin The manufacture of brush Science and Technology Ltd.) develop 30 seconds at 24 DEG C, sensitivity, development latitude are as shown in table 14.
The relevant performance of the induced thermal imaging of 14 formulation examples of table 1~8 plate-making

Claims (11)

1. a kind of sour resistance solvent of photosensitive composition for using sulphonyl hydrazone phenol-formaldehyde resin modified as acid agent, including product, alkali are solvable Resin, infrared absorbing dye and background dye, it is characterised in that:Described product acid resistance solvent is sulphonyl hydrazone modified linear phenolic aldehyde tree Fat;The general structure of the sour resistance solvent of described product is:
Wherein A is the phenolic resin parent being grafted, and phenolic resin includes P-F phenolic resin, metacresol-paracresol Phenolic resin, phenol-metacresol-paracresol phenolic resin, phenol-tert-butyl phenol phenolic resin, phenol-paracresol phenolic aldehyde tree At least one in fat, orthoresol-paracresol phenolic resin, phenol-formaldehyde resin modified;R1Alkyl and company for 1-10 carbon atom Meet substituted or unsubstituted C6-C30 aryl, R2For substituted or unsubstituted C6-C20 aryl.
2. use sulphonyl hydrazone phenol-formaldehyde resin modified as the photosensitive composition of acid agent according to claim 1, its feature exists In:The R2Selected from unsubstituted or substituted C6-C14 aryl.
3. use sulphonyl hydrazone phenol-formaldehyde resin modified as the photosensitive composition of acid agent according to claim 1, its feature exists In:The R2Selected from phenyl, p-methylphenyl, to tert-butyl-phenyl, rubigan, naphthyl, isopropyl naphthyl or tert-butyl group naphthyl.
4. sulphonyl hydrazone phenol-formaldehyde resin modified is used as the photosensitive composition of acid agent according to claim 1 or 2 or 3, It is characterized in that:The consumption of the sulphonyl hydrazone phenol-formaldehyde resin modified accounts for the 1-9% of photosensitive composition gross weight.
5. the photosensitive composition for using sulphonyl hydrazone phenol-formaldehyde resin modified as acid agent according to claim 1, its feature It is:The alkali soluble resin is phenolic resin or poly(4-hydroxystyrene) resin.
6. the photosensitive composition for using sulphonyl hydrazone phenol-formaldehyde resin modified as acid agent according to claim 5, its feature It is:The phenolic resin is metacresol-paracresol phenolic resin, phenol-paracresol phenolic resin, orthoresol-paracresol phenol At least one in urea formaldehyde, phenol-formaldehyde resin modified.
7. sulphonyl hydrazone phenol-formaldehyde resin modified is used according to claim 1 or 5 as the photosensitive composition of acid agent, and it is special Levy and be:The consumption of the alkali soluble resin accounts for the 84 ~ 97% of photosensitive composition gross weight.
8. the photosensitive composition for using sulphonyl hydrazone phenol-formaldehyde resin modified as acid agent according to claim 1, its feature It is:The infrared absorbing dye is flower cyanines system infrared absorbing dye.
9. sulphonyl hydrazone phenol-formaldehyde resin modified is used as the photosensitive composition of acid agent according to claim 1 or 8, it is special Levy and be:The consumption of the infrared absorbing dye accounts for the 1 ~ 5% of photosensitive composition gross weight.
10. the photosensitive composition for using sulphonyl hydrazone phenol-formaldehyde resin modified as acid agent according to claim 1, its feature It is:The background dye be solvent blue, alkaline bright blue, Victoria pure blue, phthalocyanine blue, malachite green oxalate, blackish green, phthalocyanine green, Any one in crystal violet, crystal violet, ethyl violet, dimethyl yellow, fluorescein;The consumption of the background dye accounts for photosensitive composition The 1 ~ 5% of thing gross weight.
11. use as claimed in claim 1 sulphonyl hydrazone phenol-formaldehyde resin modified as the photosensitive composition of acid agent in positive image heat Application in quick CTP plates.
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JPH11268437A (en) * 1998-03-19 1999-10-05 Toray Ind Inc Direct drawing type waterless lithographic printing plate
EP1490732A1 (en) * 2002-03-15 2004-12-29 Creo Inc. Sensitivity enhancement of radiation-sensitive elements
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