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 PDFInfo
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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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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
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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| CN113896663A (en) * | 2021-10-29 | 2022-01-07 | 北京印刷学院 | Heat-sensitive acid generator and preparation method and application thereof |
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| US2766118A (en) * | 1952-10-01 | 1956-10-09 | Azoplate Corp | Light-sensitive material for the photomechanical reproduction and process for the production of images |
| 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 |
| CN102101948A (en) * | 2009-12-21 | 2011-06-22 | 威海经济技术开发区天成化工有限公司 | Ammonia-releasing, nitrogen-releasing, acid-producing foaming dissolution inhibitor/promoter for thermosensitive computer to plate (CTP) plate, and preparation method and use thereof |
| CN102314084A (en) * | 2010-07-09 | 2012-01-11 | 乐凯集团第二胶片厂 | Light sensitization composition using p-toluenesulfonylhydrazide hydrazone compound and application of light sensitization composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7049044B2 (en) * | 2002-12-19 | 2006-05-23 | The University Of North Carolina At Charlotte | Nanocomposite negative resists for next generation lithographies |
| KR101612285B1 (en) * | 2007-02-28 | 2016-04-14 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Novel polymers and photoresist compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2766118A (en) * | 1952-10-01 | 1956-10-09 | Azoplate Corp | Light-sensitive material for the photomechanical reproduction and process for the production of images |
| 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 |
| CN102101948A (en) * | 2009-12-21 | 2011-06-22 | 威海经济技术开发区天成化工有限公司 | Ammonia-releasing, nitrogen-releasing, acid-producing foaming dissolution inhibitor/promoter for thermosensitive computer to plate (CTP) plate, and preparation method and use thereof |
| CN102314084A (en) * | 2010-07-09 | 2012-01-11 | 乐凯集团第二胶片厂 | Light sensitization composition using p-toluenesulfonylhydrazide hydrazone compound and application of light sensitization composition |
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