CN102393606B - Heat-sensitive positive image CTP (Computer To Plate) photosensitive resist liquid and preparation method thereof - Google Patents
Heat-sensitive positive image CTP (Computer To Plate) photosensitive resist liquid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heat-sensitive positive image CTP (Computer To Plate) photosensitive resist liquid. The solid content of the photosensitive resist liquid is 10-40 percent; the adopted solvent is one or more of ethyl methyl ketone, ethylene glyeolmonobutyl ether, ethylene glycol monoemethyl ether, butyl acetate, dioxane or tetrahydrofuran; and a solid raw material comprises the following components in percentage by weight: 1-20 percent of photo-thermal acid-producing agent, 50-80 percent of film forming resin, 10-40 percent of dissolution inhibiting and promoting agent, 1-10 percent of infrared dye and 0.1-5 percent of coloring background dye. The heat-sensitive CTP photosensitive resist liquid has the characteristics of high alkali resistance, high developing tolerance level, high sensitivity, high mesh point reducibility, high plate making resistance, no need of ageing and high storage stability of the resist liquid and a printing plate material.
Description
Technical field
What the present invention relates to is a kind of heat-sensitive positive-working CTP photosensitive liquid and preparation method thereof.
Background technology:
CTP (Computer To Plate is called for short CTP) is meant through computing machine picture and text is directly outputed to the technological process on the printing plate, mainly is meant the direct mask-making technology process of off line.The CTP technology is that the digital page is directly changed into forme, has saved layout, the printing down of laser photo-typesetting sensitive film or electric separation machine colour separation film, the technology of process and relevant device before tradition such as the PS version flushing seal.Not only simplified production technology, reduced printing cost, and avoided the site loss in the image information transfer process, all right large-scale application modulating net has improved processing quality and production efficiency.
At present, CTP technical development speed is very fast in the world, and various CTP system all competitively comes on stage, and is wherein with the fastest developing speed with thermosensitive CTP, CTP total installed capacity amount be the heat-sensitive plate-making machine more than 60%.Release the temperature-sensitive version from Kodak in 1996 and Ke Liao to market, the temperature-sensitive technology just becomes one of main flow direction of CTP technical development and popularization.
The thermosensitive CTP photoresists are to be coated on thermosensitive CTP forme plate surface, in order to form the micrographics rapidoprint of image latent image, the required output image of recovery.Maturation along with domestic thermosensitive CTP technology likewise, as the CTP photoresists of consumptive material, also more and more receives people's attention.The thermosensitive CTP photoresists are coated on the CTP plate, can directly accept by computer-controlled laser scanning light beam, can go up the machine printing through suitable processing.The light sensitive layer technology of all these plates is all grasped in the world and is printed giant on hand now, and technology barriers are stern, can't obtain at all.At present, homemade photoresists not only can not satisfy the demands on amount, and qualitatively especially can't with the comparing favourably of import.
Summary of the invention
The object of the invention aims to provide that a kind of to have alkali resistance strong; The development tolerance is big; Sensitivity is high; The site is Well-recovered; The anti-seal performance of making a plate is good and need not wear out; The thermosensitive CTP photosensitive liquid of the characteristics that the storage stability of glue and plate is good.
Another object of the present invention aims to provide the preparation method of above-mentioned thermosensitive CTP photosensitive liquid, has simply, and is easy to the characteristics of industrializing implementation.
Technical scheme of the present invention is:
The solid content of photosensitive liquid of the present invention is 10-40%; Said solvent is one or more in MEK, ethylene glycol monomethyl ether, ethylene glycol monoemethyl ether, butyl acetate, dioxane or the tetrahydrofuran;
Wherein, the content of each composition is in the solid material: following each composition all by weight percentage,
Photo-thermal acid agent: 1-20%
Film-forming resin: 50-80%
Chaotropic agent: 10-40% is dissolved in resistance
IR dyes: 1-10%
Coloring background dye: 0.1-5%;
Described acid agent is: 4, and 6-two (trichloromethyl)-1,3,5-triazines analog derivative has structure shown in the formula III:
(III)
R is alkyl, phenyl, styryl, naphthyl, piperonyl, substituted phenyl, substituted styryl or substituted naphthyl, and the C number of R is for being no more than 15;
Described IR dyes is: benzindole is the perhaps infrared absorbing dye of λ max=810-830nm in imaging system of cyanine dyes, step cyanine dye;
Said background illuminating colour is a crystal violet, malachite green, Victoria's ethereal blue, solvent blue, methylene blue, one or several in the eosin;
Said film-forming resin is a linear phenol-aldehyde resin, comprises that weight-average molecular weight is 3000-10000 and M
w/ M
nBe phenol-metacresol-formaldehyde resin, the phenol-paracresol-formaldehyde resin, 3 of 2.0-10, one or more in 5-dimethyl benzene resinox, phenol-orthoresol-formaldehyde resin, the resorcinol-formaldehyde resin;
It is the macromolecule ester acetal polymer that chaotropic agent is dissolved in said resistance, and its general molecular formula has shown in the formula (I):
R
2Be derived from structure shown in the formula (II):
Rosin acrylic acid
Formula II
R
1Be following group, R
1For:
At this moment, m=1, R
0For-CH
2-or do not have group; R
1For :-CH
2-, at this moment, m≤4, R
0For :-CH
2-.
Acid agent of the present invention is 4,6-two (trichloromethyl)-1,3,5-triazines analog derivative; Belong to the triazines acid agent,, help pyrolysis and produce acid because the pyrolysis of triazine is themopositive reaction; So make it have the luminous sensitivity height, decomposes is fast, the characteristics of favorable solubility in organic solvent.
What IR dyes of the present invention was selected for use is that benzindole is the perhaps infrared absorbing dye of λ max=780-830nm in imaging system of cyanine dyes, step cyanine dye.Because emission laser is succeeded in developing the Ga-As of 780～830nm semiconductor laser, the infrared absorbing dye demand of λ max=780-830nm also increases accordingly in the imaging system; Dyestuff with this function mainly contains cyanine type dye, phthalocyanines dye, premetallized dye, oxyketone dye, azo dyes, free radical dyestuff, fragrant methane type dye etc.Wherein cyanine type dye has high molar extinction coefficient, high-fluorescence quantum yield and big advantages such as Stokes displacement, but it is poor slightly to the stability of light and heat.The dyestuff that preferably has structure shown in the formula IV; Through on the polymethine chain of cyanine dyes, introducing the bridge chain; Can increase its light stability and thermal stability, use such IR dyes, make the heat conversion in this formula system higher than other similar infrared absorbing agents; Make the plate that adopts this glue to be coated with version can access the better pictures latent image under the same conditions; Thereby make picture quality that further raising arranged, the discrimination between exposure area and the territory, non-exposed area increases, and also makes the back baking tolerance of plate be improved.
The concrete preparation method that chaotropic agent is dissolved in resistance of the present invention can be referring to patent publication No.: the file description of CN101130596A prepares.What the present invention selected for use is by rosin acrylic acid and the synthetic ester acetal superpolymer of divinyl ether; It is one type of straight chain polymer polymkeric substance; This base polymer is soluble in organic solvent commonly used; Have higher softening point, Heat stability is good, experiment shows that they heats the easy carboxyl that decomposes, discharges under acid catalysis.Dissolve chaotropic agent with this ester acetal compound that gets up to obtain as resistance to carboxy protective, the chemical amplification type anti-corrosion agent photosensitive composition of acquisition has outstanding imaging performance such as high sensitivity, high resolution and high development tolerance.Simultaneously because rosin acrylic acid has outstanding filming performance, its thick and polynary alicyclic structure make it to be used for photoresist and should have good anti-plasma etching ability.
On the basis of above technical scheme, optimized technical scheme of the present invention is:
The solid content of described photosensitive liquid is 10-25%
Wherein, the weight content of each composition is in the solid material:
Photo-thermal acid agent: 5-10%
Film-forming resin: 65-80%
Chaotropic agent: 10-20% is dissolved in resistance
IR dyes: 2-5%
Coloring background dye: 0.2-2%.
The above-mentioned photosensitive liquid preparation method of the present invention is: above-mentioned raw materials IR dyes, acid agent, film-forming resin and coloring background dye are dissolved in solvent fully; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; To hinder again and dissolve chaotropic agent dissolving fully in solvent; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
In the technical scheme of the present invention, the selection of each composition and consumption are through the insistent experiment of inventor, and trial repeatedly is able to just that proportioning obtains.The consumption of chaotropic agent is dissolved in resistance wherein, and the inventor because the molten chaotropic agent of the resistance that the present invention selects for use heats and can decompose rapidly, discharges carboxyl through discovering under acid catalysis, is dissolved by the insoluble alkali that becomes of alkali.Its consumption is 10%～40% of a photosensitive composition raw material general assembly (TW), helps just using of product, if consumption is lower than 10%, does not then reach resistance before the scanning and dissolves purpose, and the short dissolubility in scanning back can be also very poor, and the development tolerance significantly diminishes; If consumption is greater than 40%, rete sensitivity step-down, in case under-exposed, it is dirty to be easy to the residual end.Because the action principle of acid agent be it under the effect of suitably illumination or heat, can produce Bronsted acid or lewis acid, the resistance that the strong acid of generation can the catalysis exposure area is dissolved chaotropic agent and is decomposed, and it is solvable to make the exposure area become alkali, thus formation positive image; When particularly the consumption of the molten chaotropic agent of resistance is 10-20%, can make photosensitive liquid of the present invention have outstanding imaging performance such as stronger high sensitivity, high resolution and high development tolerance.
Though compound in triazine class is widely used in the photosensitive composition; But the maximum absorption wavelength of the triazine derivative that uses in the market is longer; This can not operate it in bright chamber; Because decomposition temperature is lower, acid agent decomposes in storage process easily simultaneously, and CTP plate quality is descended.Among the present invention, dissolve short use of dissolving compound in order to cooperate resistance, the special preferred acid generators of inventor is: 4; 6-two (trichloromethyl)-1,3,5-triazines analog derivative; Its maximal ultraviolet visible absorbance is generally at 330～392nm;＜400nm, heat decomposition temperature have good thermal stability generally at 200～300 ℃; And its consumption is limited to 1%～20% of photosensitive composition solid material general assembly (TW), and greater than 20%, then intensity in the sensitization rete and depth perception optical property descend, and it is residual dirty to be prone in the developing process keep on file as if consumption; If consumption less than 1%, then produces subacidity, the sensitivity of sheet material is obviously descended.In addition, preferred content is that 5-10% can make that plate sensitivity performance of the present invention is better.
When said IR dyes received laser radiation, dye molecule absorbed luminous energy, changes into heat energy, makes the acid agent decomposes, generated strong acid.IR dyes used among the present invention is: benzindole is the perhaps infrared absorbing dye of λ max=810-830nm in imaging system of cyanine dyes, step cyanine dye; The present invention is controlled at 1%～10% of photosensitive composition solid material general assembly (TW) with its consumption, can avoid because of consumption less than 1% o'clock, the exposed portion heating temp is low, is not enough to decompose acid agent, thereby reduces the sensitivity of sheet material significantly; Consumption was greater than 10% o'clock, because the dissolubility of infrared absorbing dye in common solvent is relatively poor, the photosensitive composition preparation is met difficulty, and the plate storage stability that coats is descended, and had increased considerably the condition of cost appearance of plate; Therefore, the present invention's special preferred content in application process is 2-5%.
The inventor also is selected in the background illuminating colour and is crystal violet, malachite green, Victoria's ethereal blue; Solvent blue, methylene blue, one or several in the eosin; And the control consumption accounts for 0.1～5% of photosensitive composition solid material general assembly (TW), and is same, also is because the inventor finds at experimentation; Adopt above raw material, less than 0.1%, then made forme pattern colour density is too low as if consumption; If consumption is higher than 5%, then will influence the sensitivity of photosensitive composition, particularly deep layer exposure performance and developing performance.Preferred content of the present invention is 0.2-2%.
The film-forming resin that the present invention selected for use is a linear phenol-aldehyde resin, comprises that weight-average molecular weight is 3000-10000 and M
w/ M
nBe phenol-metacresol-formaldehyde resin, the phenol-paracresol-formaldehyde resin, 3 of 2.0-10, one or more in 5-dimethyl benzene resinox, phenol-orthoresol-formaldehyde resin, the resorcinol-formaldehyde resin.If the molecular weight of linear phenolic resin is too little, resistance is dissolved a little less than the ability, is prone to subtract the film loss of gloss in the developing process; If molecular weight is too big, then because self alkali solubility is relatively poor, developing powder is slow, is easy to keep on file, and the flaking phenomenon takes place sometimes.Therefore, among the present invention the film-forming resin preferable weight-average molecular weight at 5000～8000 linear phenolic resin.Its consumption accounts for 50%～80% of photosensitive composition weight, and ability is not enough if consumption greater than 80%, is easy to take place the resistance dissolubility, and the problem that alkali resistance descends is easy to lose photolyzed film, even loses image in the middle of the developing process; The use amount of film-forming resin is less than 50%, and promptly the relative consumption of resistance solvent is too big, the difficulty that is easy to produce to develop, and the serious problem of keeping on file also can reduce the resolution and the dot reproduction property of image.The present invention more preferred content is 65-80%.
Solvent among the present invention is used for dissolving photonasty material and film-forming resin; But the inventor also it should be noted that the solvent of being selected for use and can not react with photoactive substance and film-forming resin; And volatilization easily in the photographic layer dry run, choose and the consumption of solvent directly influence the photosensitive liquid quality.Therefore, the inventor fully combines polarity phase approximately principle, solvation principle, solubility parameters phase approximately principle, has chosen solvent: one or more in MEK, ethylene glycol monomethyl ether, ethylene glycol monoemethyl ether, butyl acetate, dioxane or the tetrahydrofuran.And control its consumption and make that the solid content of said photosensitive composition is 10%～40%, because the inventor finds as if content less than 10% through experimental study; Then the viscosity of sensitization liquid is on the low side; Adhesion descends, and can not well stick on edition base, and the plate storage stability dies down; If content is higher than 40%, then sensitization viscosity also is higher, makes that the plate light sensitive layer is blocked up, and light sensitivity reduces, and plate keeps on file to track down and recover stolen goods easily.The more preferred solid content of the present invention is 10-25%.
The effective cooperation of the present invention through each component makes it not only have photo sensitivity height, strong adhesion, dissolving difference degree is big, the ink separating effect is outstanding advantage, and good printing-force-resistence, the development tolerance is big, the alkali resistant membrane left rate is high, solvent resistance is strong.Compare with domestic like product at aspects such as exposure sensitivity, processing tolerance, image quality and all have a clear superiority in.
Description of drawings
Fig. 1 is the infrared spectrogram of the resistance solvent polymkeric substance of embodiments of the invention 1.
Embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1:
Rosin acrylic acid and the reaction of ethylene glycol bisthioglycolate vinyl ether
The rosin acrylic acid and 11.4g (0.1mol) the ethylene glycol bisthioglycolate vinyl ether that in having the 500ml four-hole boiling flask of mechanical raking, thermometer, condenser pipe, add 37.4g (0.1mol); Add 50ml xylene; Heated and stirred makes its dissolving, is warming up to 120-130 ℃, and stirring reaction finished in 4 hours.
The infrared spectrogram of this resistance solvent polymkeric substance: see also Fig. 1:
In the infrared spectrum at 3400cm
-1And 1690cm
-1Near carboxyl absorbs and disappears, and ethylene double bond is at 1635cm
-1Place's absorption peak disappears basically, and expression reacts completely.
The preparation of thermosensitive CTP photosensitive liquid:
At first IR dyes (Beijing chemical reagent factory production), the 1.25g structure of 0.5g structure like (V) is dissolved in the 50g MEK like acid agent, 0.08g crystal violet, the 14.5g phenolics (production of Hebei Cheng Feng resin processing plant) of (VI); After treating thoroughly dissolving; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; The resistance that again embodiment 1 is obtained is dissolved chaotropic agent 2.5g and is dissolved in the 25g ethyl acetate; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture after treating thoroughly to dissolve carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
IR dyes (V) acid agent (VI)
Embodiment 2:
Rosin acrylic acid and 1, the reaction of 4-butylene glycol divinyl ether
In having the 500ml four-hole boiling flask of mechanical raking, thermometer, condenser pipe, add 37.4g (0.1mol) rosin acrylic acid and 14.2g (0.1mol) butylene glycol divinyl ether; Add 50ml xylene; Heated and stirred makes its dissolving, is warming up to 120～130 ℃, and stirring reaction finished in 4 hours.
In the infrared spectrum at 3400cm
-1And 1690cm
-1Near carboxyl absorbs and disappears, and ethylene double bond is at 1635cm
-1Place's absorption peak disappears basically, and expression reacts completely.
The preparation of thermosensitive CTP photosensitive liquid:
At first IR dyes (Beijing chemical reagent factory production), 1.4g structure acid agent (wherein R be ethyl), 0.3g methylene blue, the 16.5g phenolics (Hebei Cheng Feng resin processing plant production) as (III) shown in of 0.6g structure like (V) is dissolved in the 50g MEK; After treating thoroughly dissolving; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; The resistance that again embodiment 2 is obtained is dissolved chaotropic agent 3.3g and is dissolved in the 25g ethyl acetate; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture after treating thoroughly to dissolve carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
Embodiment 3:
Rosin acrylic acid and 1, the reaction of 4-divinyl oxide ylmethyl cyclohexane
In having the 500ml four-hole boiling flask of mechanical raking, thermometer, condenser pipe, add 37.4g (0.1mol) rosin acrylic acid and 19.6g (0.1mol) 1; 4-divinyl oxide ylmethyl cyclohexane; Add the 50ml cyclohexanone; Heated and stirred makes its dissolving, is warming up to 120～130 ℃, and stirring reaction finished in 4 hours.
In the infrared spectrum at 3400cm
-1And 1690cm
-1Near carboxyl absorbs and disappears, and ethylene double bond is at 1635cm
-1Place's absorption peak disappears basically, and expression reacts completely.
The preparation of thermosensitive CTP photosensitive liquid:
At first IR dyes (Beijing chemical reagent factory production), 1.2g structure acid agent (wherein R be phenyl), 0.3g malachite green, the 13.38g phenolics (Hebei Cheng Feng resin processing plant production) as (III) shown in of 0.8g structure like (V) is dissolved in the 50g dioxane; After treating thoroughly dissolving; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; The resistance that again embodiment 3 is obtained is dissolved chaotropic agent 1.85g and is dissolved in the 25g dioxane; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture after treating thoroughly to dissolve carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
Embodiment 4:
The preparation of thermosensitive CTP photosensitive liquid:
At first IR dyes (Beijing chemical reagent factory production), 1.5g structure acid agent (wherein R be methyl), 0.4g Victoria ethereal blue, the 15.6g phenolics (Hebei Cheng Feng resin processing plant production) as (III) shown in of 0.6g structure like (V) is dissolved in the 50g ethylene glycol monoemethyl ether; After treating thoroughly dissolving; Filter core with 8 μ m, 2 μ m, 0.5 μ m0 aperture carries out three-stage filtration; Again chaotropic agent 2.1g being dissolved in the resistance that obtains among the embodiment 1 is dissolved in the 25g tetrahydrofuran; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture after treating thoroughly to dissolve carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
Embodiment 5:
The preparation of thermosensitive CTP photosensitive liquid:
At first IR dyes (Beijing chemical reagent factory production), 1.8g structure acid agent (wherein R be naphthyl), 0.5g Victoria ethereal blue, the 17.8g phenolics (Hebei Cheng Feng resin processing plant production) as (III) shown in of 0.65g structure like (V) is dissolved in the 50g ethylene glycol monoemethyl ether; After treating thoroughly dissolving; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; Again chaotropic agent 3.6g being dissolved in the resistance that obtains among the embodiment 2 is dissolved in the 25g tetrahydrofuran; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture after treating thoroughly to dissolve carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
Embodiment 6:
The preparation of thermosensitive CTP photosensitive liquid:
At first IR dyes (Beijing chemical reagent factory production), 1.58g structure acid agent (wherein R be styryl), 0.3g crystal violet, the 17.2g phenolics (Hebei Cheng Feng resin processing plant production) as (III) shown in of 0.75g structure like (V) is dissolved in the 50g ethylene glycol monoemethyl ether; After treating thoroughly dissolving; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; Again chaotropic agent 4.1g being dissolved in the resistance that obtains among the embodiment 3 is dissolved in the 25g dioxane; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture after treating thoroughly to dissolve carries out three-stage filtration, both mixed heat-sensitive positive-working CTP photosensitive liquids that get.
Embodiment 1～6 preparation photosensitive liquid is coated on the CTP plate, and its correlated performance is as shown in the table:
| Sensitization CTP | Solid content | Light sensitivity | The site reduction | Pressrun | The dissolvent residual rate | Resolution |
| Embodiment 1 | 20.1％ | 130mj/cm 2 | 1～99％ | >=10 ten thousand seals | 2.8％ | 250dpi |
| Embodiment 2 | 22.8％ | 120mj/cm 2 | 1～99％ | >=10 ten thousand seals | 3.2％ | 250dpi |
| Embodiment 3 | 18.9％ | 130mj/cm 2 | 1～99％ | >=10 ten thousand seals | 3.0％ | 200dpi |
| Embodiment 4 | 21.2％ | 120mj/cm 2 | 1～99％ | >=10 ten thousand seals | 2.6％ | 200dpi |
| Embodiment 5 | 24.5％ | 120mj/cm 2 | 1～99％ | >=10 ten thousand seals | 3.5％ | 250dpi |
| Embodiment 6 | 24.2％ | 110mj/cm 2 | 1～99％ | >=10 ten thousand seals | 3.3％ | 250dpi |
The reel coating, on the version base of suitable sealing of hole, coating thickness 1.8 ± 0.2g/m
2, the plate-making of 830nm thermosensitive laser platemaking machine is adopted supporting developer solution of my company or suitable commercially available developer solution, 20～25 ℃ of development temperatures, development time 25～30S.
Use the plate of photosensitive liquid coating of the present invention, light sensitivity is 100-130mj/cm
2, fine rule is the 8-10 micron, and the site is reduced to 1%～99%, and not roasting version pressrun reaches 100,000 seals; And not needing slaking in the dry run, after the glue coating, plate can directly be used for producing; Omitted the step of slaking, the dissolvent residual rate is less than 3.5%, more domestic like product; Its alkali resistance is strengthened greatly, and difficult dirty, and ageing resistance is good.
Alkali resistance is one of important indicator of weighing the photoresists quality; The photosensitive liquid alkali resistant membrane left rate of the present invention's preparation is improved than common photoresists product alkali resistant membrane left rate of the same type; The alkali resistant time has obtained prolongation, and surpassing general development time does not have tangible glue-line to peel off phenomenon in 30 seconds to two minutes.Make the plate that uses photoresists coating of the present invention during whole development, the image areas photosensitive layer can quite intactly be preserved, and development operation is safer, and tolerance is bigger.
The plate of present stage generally all has maturing process; Concrete slaking divides high-temperature maturing and ripening at low temperature again, and the plate of high-temperature maturing is slaking 2～3 days under the high temperature more than 50 ℃ generally speaking, waits slaking to accomplish; Plate is relatively stable, but in several days after the slaking, advises ambient stable.The plate of ripening at low temperature is not have maturing process, but will accomplish the stable of colloid at normal temperatures.The plate medicine film of domestic part producer is soft partially, and overcure phase not, plate has irregular thin scuffing in producer's inspection version, transportation or when using.General maturation period of the plate of domestic manufacturer is about 1 month.If may be more longer in winter.And use the plate of the photosensitive liquid coating that the present invention prepared can omit the step of slaking, and directly can be used for producing printing, practiced thrift the time, improved work efficiency, avoid the appearance of the possible problem that plate causes because of the need slaking.
Photoresists product of the present invention can satisfy the ctp request of high-quality thermal CTP plate material, and it is strong to have alkali resistance; The development tolerance is big; Sensitivity is high; The site is Well-recovered; The anti-seal performance of making a plate is good and need not wear out; Advantages such as the storage stability of glue and plate is good.
Claims (4)
1. heat-sensitive positive-working CTP photosensitive liquid, the solid content of described photosensitive liquid is 10-40%; The solvent that is adopted is one or more in MEK, ethylene glycol monomethyl ether, ethylene glycol monoemethyl ether, butyl acetate, dioxane or the tetrahydrofuran;
Wherein, the weight content of each composition of solid material is:
Photo-thermal acid agent: 1-20%
Film-forming resin: 50-80%
Chaotropic agent: 10-40% is dissolved in resistance
IR dyes: 1-10%
Coloring background dye: 0.1-5%
Described acid agent is: 4, and 6-two (trichloromethyl)-1,3,5-triazines analog derivative has structure shown in the formula III:
The formula III
R is alkyl, phenyl, styryl, naphthyl, piperonyl, substituted phenyl, substituted styryl or substituted naphthyl, and the carbon number of R is for being no more than 15;
Described IR dyes is: benzindole is the perhaps infrared absorbing dye of λ max=780-830nm in imaging system of cyanine dyes, step cyanine dye;
Said background illuminating colour is a crystal violet, malachite green, Victoria's ethereal blue, solvent blue, methylene blue, one or several in the eosin;
Said film-forming resin is a linear phenol-aldehyde resin, comprises that weight-average molecular weight is 3000-10000 and M
w/ M
nBe phenol-metacresol-formaldehyde resin, the phenol-paracresol-formaldehyde resin, 3 of 2.0-10, one or more in 5-dimethyl benzene resinox, phenol-orthoresol-formaldehyde resin, the resorcinol-formaldehyde resin;
It is the macromolecule ester acetal polymer that chaotropic agent is dissolved in said resistance, and its general molecular formula has shown in the formula I:
R
2Be derived from structure shown in the formula II:
R
1Be following group, R
1For:
At this moment, m=1, R
0For-CH
2-or do not have group; R
1For :-CH
2-, at this moment, m≤4, R
0For :-CH
2-.
2. a kind of heat-sensitive positive-working CTP photosensitive liquid according to claim 1, the solid content of described photosensitive liquid is 10-25%.
Wherein, the weight content of each composition is in the solid material:
Photo-thermal acid agent: 5-10%
Film-forming resin: 65-80%
Chaotropic agent: 10-20% is dissolved in resistance
IR dyes: 2-5%
Coloring background dye: 0.2-2%.
3. a kind of heat-sensitive positive-working CTP photosensitive liquid according to claim 1 and 2 is characterized in that: said in imaging system structure shown in the infrared absorbing dye tool formula IV of λ max=780-830nm:
The formula IV.
4. the preparation method of claim 1 or 2 or 3 described heat-sensitive positive-working CTP photosensitive liquids; It is characterized in that: raw material IR dyes, photo-thermal acid agent, film-forming resin and coloring background dye are dissolved in solvent fully; Filter core with 8 μ m, 2 μ m, 0.5 μ m aperture carries out three-stage filtration; To hinder and dissolve chaotropic agent dissolving fully in solvent, and carry out three-stage filtration with the filter core in 8 μ m, 2 μ m, 0.5 μ m aperture, both are mixed must heat-sensitive positive-working CTP photosensitive liquids.
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|---|---|---|---|---|
| JP3992550B2 (en) * | 2002-07-04 | 2007-10-17 | 國宏 市村 | Active energy ray resin composition, active energy ray resin film, and pattern forming method using the film |
| KR101385946B1 (en) * | 2007-04-02 | 2014-04-16 | 주식회사 동진쎄미켐 | Photoresist composition and method of forming photoresist pattern using the same |
| CN101762976B (en) * | 2009-10-30 | 2012-01-11 | 泰兴市东方实业公司 | Active etherate of pyrogallol acetonide resin as heat-sensitive CTP thermo-sensitive imaging liquid of dissolution inhibitor |
| CN101930175B (en) * | 2009-10-30 | 2012-05-23 | 泰兴市东方实业公司 | Photosensitive imaging liquid containing alpha-diazonium-1,3-diketone structure and used for photosensitive macromolecule flat printing plate |
| CN102109764B (en) * | 2010-12-31 | 2012-11-21 | 浙江康尔达新材料股份有限公司 | Positive-type thermosensitive computer to plate (CPT) plate |
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