CN102236254B - Radiation sensitive composition - Google Patents
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- CN102236254B CN102236254B CN 201010153239 CN201010153239A CN102236254B CN 102236254 B CN102236254 B CN 102236254B CN 201010153239 CN201010153239 CN 201010153239 CN 201010153239 A CN201010153239 A CN 201010153239A CN 102236254 B CN102236254 B CN 102236254B
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Abstract
The invention discloses a radiation sensitive composition. The composition comprises modified film forming resin, high molecular copolymers, an acid forming agent, radiation absorbent dye, and the like. The composite is coated on a proper substrate, and is baked, exposed and developed, such that an image is obtained. The image has good hardness, wear-resistance, good adhesive force, and printing strength. The development allowance can also be increased.
Description
Technical field
The invention relates to a kind of radiation-sensitive composition for lithographic plate.
Background technology
Lithographic characteristic is that the image area (image area) of inking on the lithographic plate and the non-image district of not inking exist together in one plane.Wherein, image area is oleophilic drainage, and non-image district then is hydrophilic oleophobic.Lithographic mode of operation, namely be to utilize oil (oily matter or printing ink) and the immiscible characteristic of water, water for first forme, make non-image district form the moisture film of hydrophilic oleophobic, and then to the forme inking, make image area partly attach printing ink, under the effect of squeegee pressure, the picture and text on the forme are transferred to paper or other stock surface through blanket cylinder.Usually printing ink is to be transferred to the blanket (blanket) that is commonly referred to as intermediate materials, and then printing ink is transferred to the material surface for the treatment of duplicating image, namely such as surfaces such as paper, cloth, plastics or metals.
Precoating formula sensing optical activity lithographic plate (Pre-Sensitized Plate, the PS version) manufacture method, roughly be that electrolysis or grinding are passed through first in the surface of an aluminium sheet, the Grains that needs to form a plurality of printshops, again the radiation-sensitive composition of sensing optical activity or thermonasty is coated on the Grains of this aluminium sheet to form a radiation-sensitive coating, and this radiation-sensitive coating is toasted slaking.Then, by an egative film with predetermined image and literal, the image on this egative film and literal are transferred on the radiation-sensitive coating in the mode of exposing and develop, to make in order to the galley on file with image and text printout.
In recent years, process and the widespread use of digitizing technique of image output information with computing machine, the new image output mode of various correspondences is practical.On lithography if omit the making of egative film, directly with the digital pattern of computing machine via the exposure imaging program, be transferred on the radiation-sensitive coating, to make in order to the galley on file with image and text printout, the plate-making operation is greatly simplified, can significantly be increased printing speed and reduce cost, this kind technology is called Computer To Plate (Computer To Plate, CTP), the galley that and how to obtain being applicable to this technology becomes important problem.
After being coated on the radiation-sensitive composition exposure on the employed surface of aluminum plate of lithography, its exposed portion changes alkali-soluble into, thereby at developing process it is removed.This kind version is called the positive type light sensitive version; Otherwise exposed part can harden (curing), changes the alkali insolubility into, then is called the negative photosensitive version.When above-mentioned two situation, residual image area is absorbency or lipophilicity, but not image area is water absorptivity or water wettability.The eurymeric of light sensitive plate or minus depend on the radiation-sensitive composition that surface of aluminum plate is coated with.
Above-mentioned radiation-sensitive composition mainly is comprised of following different materials: radiation absorption dyestuff (emulsion or sensible heat agent), acid forming agent, phenolics (film forming agent), copolymerization macromolecule, solvent, and other auxiliary agent.
Prior art, for example United States Patent (USP) the 6th, disclose a kind of positive type light sensitive version that is coated with the potpourri of phenolics (novolac) or cresol-formaldehyde resin (cresol-formaldehyde) or polyhydroxystyrene resin (poly (hydroxystyrene)) and infrared ray absorbing dyestuff for 063, No. 544.In addition, United States Patent (USP) the 5th, 372,907,5,372,915,5,340,699,5,491, No. 046, then be coated with the potpourri of novolac type phenolics, cresol type phenolics, infrared ray absorbing dyestuff or pigment and potentiality Bronsted acid (Latent Bronstedacid).When these versions were exposed to infrared radiation, the potentiality Bronsted acid decomposed a kind of different kenel phenolics (for example novolac and cresol) that impel of generation crosslinked material occurs, and makes the mixture cures in the exposure region.Further during the galley of this exposure of heating, filming of this exposure hardened more and it is become be insoluble in the alkaline-based developer, yet still be dissolvable in water in the developer solution without the zone of exposure.United States Patent (USP) the 5th, 919, disclose the radiation-sensitive composition that is formed by resin glue (binder resin), crosslinking chemical, thermal excitation acid forming agent (thermal-activated acid generator) and infrared absorbent No. 601, after this composition is exposed to infrared ray, this acid forming agent divides and explains acid, and then causes the cross-linking reaction that resin glue is carried out by crosslinking chemical by this acid.
The common shortcoming of above-mentioned each technology, be exactly after the galley video picture its image area that manifests often be short of integrality (integrity), can't be for long-time effectively printing, so that sharpness and the printing quality inequality of the printing images that produces.
Yet, constantly be required to improve plate-making efficient and printing quality the printer, under the prerequisite that promotes industrial competitiveness, the sensitivity of the radiation-sensitive coating on the galley is required must be faster, and namely its required energy that exposes time lower or that its exposure is required is shorter.And exposed portion needs the easier liquid that is developed to wash off when developing, the immersion that unexposed portion then needs more anti-developer solution with wash away, that is when developing developer solution temperature, concentration, and to soak the tolerance of the conditions such as time of washing away larger.Simultaneously, also must be able to keep fine resolution, inking, and the abrasion performance of the radiation-sensitive coating of finishing.In addition, the then property of radiation-sensitive coating and aluminium sheet also needs better.
Many patents propose different viewpoints and solve printer's different requirements from method, such as United States Patent (USP) the 7th, 425,402 and 7,455, No. 949 for phenolics or copolymerization macromolecule in the radiation-sensitive coating prescription, phenolic aldehyde monomeric unit in its structure (phenolic monomeric unit) carries out modification, the carbon atom on phenolic group (phenol group) with acid imide (imide) or thioimides (thioimide) functional group bond can improve the chemical resistance (chemical resistance) of radiation-sensitive coating.United States Patent (USP) the 7th, 458, No. 320 for phenolics or copolymerization macromolecule in the radiation-sensitive coating prescription, phenolic aldehyde monomeric unit in its structure carries out modification, with the hydrogen atom of acid imide functional group bond hydroxyl on the hydrogen atom on the phenolic group or phenolic group, can improve chemical resistance and the development latitude of radiation-sensitive coating.United States Patent (USP) the 7th, 563, No. 556 narration phenolic aldehyde monomeric unit carries out modification, and structure is shown in (A), and the prepared radiation-sensitive coating of this structure can obtain cleaner pattern in developing process, and less residue and residual is stayed in the pattern.
Structural formula (A)
Wherein, R is H, D
1Or D
2R
1Alkyl for H or C1～C2; N is 1,2 or 3; R
2Alkyl or alkoxy for H or C1～C6.
As mentioned above, most of patent all narrates how to improve radiation-sensitive coating through the characteristic on forme behind the exposure imaging, and the developing manufacture process tolerance of less narration radiation-sensitive coating, so the present invention mainly attempts seeking the method that other can improve the developing manufacture process tolerance.
United States Patent (USP) the 5th, 770,750,6,166,151 and 6,291, the method for modifying of narrating phenolics No. 077, the phenolics after the modification are applied in coating industry.In this method of modifying, phenolics and lactone structure (lactone structure) reaction is shown in the following reaction equation (B).
Reaction equation (B)
Summary of the invention
The object of the present invention is to provide a kind of radiation-sensitive composition, this composition is coated suitable base material, for example printing is with on the version, after overbaking, exposure and developing, can obtain image, this image has good hardness, abrasion performance, follows property, anti-seal amount, and can increase the tolerant value of developing, and can significantly improve product yield and quality.
In order to reach above-mentioned purpose, the invention provides a kind of radiation-sensitive composition, it contains the film-forming resin of general formula (I) phenolics and general formula (II) lactone structure reaction modifying.This radiation-sensitive composition is applied on the substrate and forms image layer, can effectively improve development latitude, and not affect hardness, abrasion performance and the stickability of radiation-sensitive coating.
General formula (I)
Wherein Q can be the alkyl of H, C1～C2; D can be alkyl, naphthenic base, alkoxy or the phenyl of H, OH, C1～C8, p=1,2 or 3, n 〉=1.
General formula (II)
The integer of x=0～17 wherein, R
3, R
4, R
5Can be respectively alkyl, naphthenic base, alkoxy or the phenyl of H, C1～C20.
Radiation-sensitive composition of the present invention also can comprise radiation absorption dyestuff, copolymerization macromolecule, solvent, surfactant, colorant, wetting agent, acid forming agent or its combination.
The effect that radiation-sensitive composition of the present invention produces is as follows: the present invention has used the composition of the film-forming resin that contains phenolics or poly-hydroxyl (methyl) styrene resin and lactone structure reaction modifying first, the composition that will contain this film-forming resin is coated on the suitable base material, after overbaking, exposure and developing, can obtain image, this image has good hardness, abrasion performance, follows property, anti-seal amount, and can increase the tolerant value of developing, can significantly improve product yield and quality.This is because after the reaction of phenolics and lactone structure, because of the chain length difference of the hydroxyl on its phenolics to main chain, should have in various degree effect at developing manufacture process and alkaline-based developer, and make the development latitude increase.
Embodiment
The invention provides a kind of radiation-sensitive composition, can form image layer at substrate, and said composition can be used as the coating use of eurymeric and negative photosensitive version.Composition of the present invention is the film-forming resin that contains general formula (I) phenolics and general formula (II) lactone structure reaction modifying, and its structure is as follows:
General formula (I)
Wherein Q can be the alkyl of H, C1～C2; D can be alkyl, naphthenic base, alkoxy or the phenyl of H, OH, C1～C8; P=1,2 or 3; And
General formula (II)
The integer of x=0～17 wherein; R
3, R
4, R
5Can be respectively alkyl, naphthenic base, alkoxy or the phenyl of H, C1～C20.
Film-forming resin after use phenolics and the lactone reaction modification, its structure is as follows:
Wherein, Q can be the alkyl of H, C1～C2; D can be alkyl, naphthenic base, alkoxy or the phenyl of H, OH, C1～C8; P=0,1,2 or 3; R is 1～4 integer, and p+r=4; The integer of x=0～17; R
3, R
4, R
5Can be respectively alkyl, naphthenic base, alkoxy or the phenyl of H, C1～C20.
Wherein E can be H, CH
3S is 1～5 integer; T is integer, and s+t=5; The integer of x=0～17; R
3, R
4, R
5Can be respectively alkyl, naphthenic base, alkoxy or the phenyl of H, C1～C20.
This radiation-sensitive composition can be by 30～95 % by weight film-forming resins (film forming agent), this film-forming resin be the acid forming agent of radiation absorption dyestuff, 0.1～15 % by weight of the copolymerization macromolecule that utilizes phenolics and lactone reaction modification, 4～65 % by weight, 0.1～45 % by weight mix form.The composition that the present invention advocates also can comprise solvent and adjuvant.
The present invention also provides a kind of manufacture method of image, the method comprises: (I) coating one imaging layer on substrate, and this imaging layer to be film-forming resin, copolymerization macromolecule, radiation absorption dyestuff, acid forming agent by phenolics and lactone reaction modification consisted of.This imaging layer also can comprise solvent and adjuvant; (II) make this imaging layer suitably dry; (III) make the imaging area of this imaging layer be exposed to the energy that can fully penetrate, for example can be wavelength at the UV/Vis of 320nm～750nm light beam or wavelength at the IR of 750nm～1350nm light beam; And (IV) this imaging area is contacted with developer solution and with exposed part from the removal of this substrate.
Be applicable to phenolics of the present invention, it can be phenol, orthoresol, metacresol, paracresol, beta naphthal, amphyl or above-mentioned two or more potpourri and aldehyde condensation reaction products such as formaldehyde, acetaldehyde, other aliphatic series or aromatic aldehyde.This phenolics should have between being the interior weight average molecular weight of 300～400,000 scope.
Be applicable to lactone of the present invention, it can be propiolactone (propiolactone), butyrolactone (butyrolactone), valerolactone (Valerolactone), caprolactone (caprolactone) and lactone derivatives thereof.
Be applicable to copolymerization macromolecule of the present invention, monomer whose can be (methyl) acrylic monomers, such as methyl methacrylate (MMA), methacrylic acid (MAA), (methyl) lauryl acrylate, the different hard ester of (methyl) acrylic acid, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) EHA, (methyl) lauryl acrylate etc., Styrene and its derivatives, such as α-methyl styrene, 4-Vinyl phenol (4-hydroxystyrene), to hydroxymethyl styrene (4-hydroxymethylstyrene) halogen-containing (methyl) styrene etc., maleic anhydride (Maleic Anhydride), vinyl cyanide (acrylonitrile AN) and nitrogen substituted maleimide amine monomers (N-substituted maleimide monomer, wherein nitrogen substituted maleimide amine monomers can be N-phenylmaleimide (N-phenylmaleimide PMI), p-hydroxybenzene maleimide (4-hydroxyphenylmaleimide), N-2, (N-(2 for 3 3,5-dimethylphenyl maleimides, 3-dimethylphenyl) Maleimide etc., utilize the high molecular polymerization method that above-mentioned monomer is synthetic according to different compositions and ratio, be applied to light sensitive layer.
Be applicable to radiation absorption dyestuff of the present invention, roughly comprise photosensitivity dye well thermal sensitivity dyestuff.The esterification condensation thing that the photosensitivity dyestuff is shown greatly 1,2-naphthoquinones diazonium-4-sulphonic acid chloride or 1,2-naphthoquinones diazonium-5-sulphonic acid chloride and polyol is main.The thermal sensitivity dyestuff then take absorbing wavelength at the dyestuff of 700-900nm as main, such as cyanine dye (Cyanine dye), polymethine dyestuff (polymethine dyes), naphthoquinone dyestuff (naphthoquinone dyes), phthalocyanine dye (phthalocyanine dyes), anthraquinone dye (anthraquinone dyes), or indoaniline premetallized dye (indoaniline metal complex dyes) etc. is main.
Be applicable to acid forming agent of the present invention, can generate Bronsted acid when being a kind of heat that is exposed to infrared spectral regions or luminous energy.The Bronsted acid that generates can produce photodecomposition at the polymkeric substance in the exposure plot of positive type light sensitive material.This kind material namely can produce the compound of Bronsted acid by thermochemistry, for example be exposed in No. the 5th, 466,557, the United States Patent (USP), and it is for reference that this patent intends incorporating this case into.Useful especially compound is halogen compounds such as halogenation triazine (or S-triazine derivant), halogenation 2-pyrone, halogenation oxazole, halogenation oxadiazoles and halogenation thiazole.These compounds generally have trihalomethyl etc. when being subjected to infrared radiation hot, can generate the poly-halomethyl of desirable halogen acid.The most normal acid forming agent of obtaining can be selected from various trichloromethyl triazines, get final product favourable being selected from, but be not limited to three-trichloromethyl triazine, two-trimethylphenyl triazine, ortho-, meta-or p-or the p-anisyl triazine of two-trichloromethyl, two-trichloromethyl (3,5-dimethoxy) phenyl triazine, two-trichloromethyl naphthyl triazine, two-trichloromethyl 5-methoxy-naphthyl triazine, two-trichloromethyl styryl triazine, two-trichloromethyl styryl triazine and two-trichloromethyl (4-methoxyl) styryl triazine etc.
Solvent used herein can be selected from, for example alcohols, ester class, ketone, ethers, amide-type, fragrant same clan and composition thereof.Particularly 1-methoxyl-2-ethanol, 1-methoxy-2-propanol, ethyl glycol acetate, ethyl acetate, acetone, butanone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, dimethylbenzene, just-propyl alcohol, isopropyl alcohol, tetrahydrofuran, butyrolactone, methyl lactate, dimethylformamide and composition thereof.
Adjuvant used in the present invention can be the additives such as surfactant, colorant and wetting agent.The use of colorant mainly for the usefulness of galley easy resolution image after developing, is applicable to colorant of the present invention and can be oil-soluble dyes or base dyestuff.Such as wherein one or their potpourri such as crystal violet (Crystal Violet), malachite green (Malachite green), Victoria blue (Victoria Blue), methyl blue (Methylene Blue), ethyl violet (Ethyl Violet), oil blue (Oil Blue 603/613), rhodamine B (Rhodamine B).
Below by several embodiment the present invention is described in more detail:
＜embodiment 1〉the film-forming resin modification
With the phenolics-Rezicure5200 (highly purified metacresol phenolics, by SpecialCheme company produce) of 40 grams, the phenolics of 12 grams-
(bis-phenol is main phenolics to SD-1508, produced by Hexion company), 10.0 lactones and 200 of restraining oneself restrain dimethylbenzene and insert in the 500ml four neck reaction bulbs, four-necked bottle connects respectively paddle, thermometer, nitrogen and recirculatory pipe, be warming up to 120 ℃ and treat that phenolics is entirely molten, the stannous octoate (T-9 catalyzer) (0.1%) that adds 2 grams, the sulfuric acid (0.1%) that adds again 2 grams, hold the temperature reaction after being warming up to 130 ℃, after question response is finished, dimethylbenzene drained to obtain modification film forming resin (production code member N-1).
＜embodiment 2〉the film-forming resin modification
Roughly the method for modifying with embodiment 1 is identical, and difference is wherein to use 8.0 lactones of restraining oneself, and this modification film forming resin production code member is N-2.
＜embodiment 3〉the film-forming resin modification
Roughly the method for modifying with embodiment 1 is identical, and difference is wherein to use 6.0 lactones of restraining oneself, and this modification film forming resin production code member is N-3.
＜embodiment 4〉the film-forming resin modification
Roughly the method for modifying with embodiment 1 is identical, and difference is wherein to use 7.5 gram butyrolactone, and this modification film forming resin production code member is N-4.
＜embodiment 5〉the film-forming resin modification
Roughly the method for modifying with embodiment 1 is identical, and difference is wherein to use 6.0 gram butyrolactone, and this modification film forming resin production code member is N-5.
＜embodiment 6〉the film-forming resin modification
Roughly the method for modifying with embodiment 1 is identical, and difference is wherein to use 4.5 gram butyrolactone, and this modification film forming resin production code member is N-6.
＜embodiment 7〉the copolymerization Polymer Synthesizing
With 35 gram N-phenylmaleimides (PMI), 30 gram methyl methacrylates (MMA), 35 gram vinyl cyanide (AN), 1 gram initiating agent (azoisobutyronitrile (AIBN)) and 200 gram solvent (dimethyl formamides, DMF) insert in the 500ml four neck reaction bulbs, four-necked bottle connects respectively paddle, thermometer, nitrogen and recirculatory pipe, temperature is controlled at 70 ℃ of reactions 24 hours, after reaction is finished, cooling is also poured reaction solution in the 6kg water into, the copolymerization macromolecule will be separated out in water, and filtration drying can obtain copolymerization macromolecule (sample code name P-1).Other different copolymerization macromolecules that form also can obtain by said method.
＜embodiment 8〉preparation of sensible heat type radiation-sensitive composition and CTP galley
The phenolics of the phenolics-Rezicure5200 of 20 grams, 6 grams-
The radiation absorption dyestuff of the copolymerization macromolecule (sample code name P-1) of SD-1508,9.0 grams, 0.8 gram-cyanine dye IR dye23b[PCAS] (the dyestuff that under the IR wavelength, can react, produced by PCAS company), 0.24 gram two-trichloromethyl (4-methoxyl) styryl triazine, the colorant-Victoria blue of 0.5 gram, the colorant-crystal violet lactone of 0.5 gram, solvent-ethyl acetate of 6ml, and the solvent-ethyl glycol acetate of 104 grams, be stirred to entirely moltenly, namely get the sensible heat type radiation-sensitive composition of present embodiment.
Prepare in addition a slice through the aluminium sheet of hydrophilic treatment, above-mentioned sensible heat type radiation-sensitive composition is coated on this aluminium sheet, coating film thickness is 1.8g/m
2, after 100 ℃, 4 minutes oven dry, again through 50 ℃, 24 hours maturation, namely get a positive-working, thermally sensitive CTP galley.
＜embodiment 9〉preparation of sensible heat type radiation-sensitive composition and CTP galley
Roughly the positive-working, thermally sensitive CTP galley with embodiment 8 is identical, difference be 20 the gram phenolics-Rezicure5200 and 6 the gram phenolics-
SD-1508 replaces with 26 gram modification film-forming resins (N-1).
＜embodiment 10〉preparation of sensible heat type radiation-sensitive composition and CTP galley
Roughly the positive-working, thermally sensitive CTP galley with embodiment 9 is identical, and difference is wherein to use sample number into spectrum to be the modification film-forming resin of N-2.
＜embodiment 11〉preparation of sensible heat type radiation-sensitive composition and CTP galley
Roughly the positive-working, thermally sensitive CTP galley with embodiment 9 is identical, and difference is wherein to use sample number into spectrum to be the modification film-forming resin of N-3.
＜embodiment 12〉preparation of sensible heat type radiation-sensitive composition and CTP galley
Roughly the positive-working, thermally sensitive CTP galley with embodiment 9 is identical, and difference is wherein to use sample number into spectrum to be the modification film-forming resin of N-4.
＜embodiment 13〉preparation of sensible heat type radiation-sensitive composition and CTP galley
Roughly the positive-working, thermally sensitive CTP galley with embodiment 9 is identical, and difference is wherein to use sample number into spectrum to be the modification film-forming resin of N-5.
＜embodiment 14〉preparation of sensible heat type radiation-sensitive composition and CTP galley
Roughly the positive-working, thermally sensitive CTP galley with embodiment 9 is identical, and difference is wherein to use sample number into spectrum to be the modification film-forming resin of N-6.
The positive-working, thermally sensitive CTP galley that above-described embodiment 8 to embodiment 14 makes is carried out the exposure imaging test.The developer solution of testing that develops is Kodak premium (Kodak's product), the temperature of developer solution is that 23 ℃, development time are 30 seconds, iCPlate2[X-rite] galley measuring instrument (being produced by X. Rite Inc.) carries out 50% site imaging test.Its etc. result arrangement such as following table 1.
Table 1
| Numbering/energy value (mJ/cm 2) | 146 | 155 | 165 | 176 | 188 | 203 | 220 |
| Embodiment 8 | 52.5 | 52.0 | 51.3 | 50.4 | 49.5 | 49.1 | 48.0 |
| Embodiment 9 | 52.1 | 51.5 | 49.8 | 50.4 | 49.4 | 48.6 | 47.9 |
| Embodiment 10 | 52.3 | 51.2 | 51.4 | 49.9 | 49.2 | 48.0 | 47.5 |
| Embodiment 11 | 52.1 | 51.5 | 51.1 | 49.5 | 49.4 | 49.8 | 47.9 |
| Embodiment 12 | 52.8 | 51.5 | 49.8 | 49.5 | 49.2 | 49.8 | 47.5 |
| Embodiment 13 | 52.1 | 51.2 | 51.4 | 49.9 | 50.1 | 48.6 | 47.5 |
| Embodiment 14 | 53.0 | 52.5 | 51.1 | 49.5 | 50.1 | 48.0 | 48.5 |
With X-rite 528 colorimetric analysis instruments (being produced by X. Rite Inc.) measure the attenuate difference (being the ratio that reduces before and after the photographic layer) of embodiment 8 to embodiment 14 and drop to edition take alcohol at the bottom of without change color as benchmark, measure the clear point (clean point) of its correspondence such as grade, usually photographic layer contains pigment, blue pigment for example, if residual on the substrate have a photographic layer, alcohol can be with the pigment stripping in the photographic layer, namely whether measures on the substrate the residual photographic layer that has without sensitization by alcohol.In addition, because the contact of finger is to cause the printing surface in contact to come off or the main cause of scratch, so with experiment of hardness product is carried out surperficial scratch test, indicate with the standard pencil hardness, differentiate product surface hardness.Use 3M#610 type adhesive tape, adhesive tape is affixed on the plating, firmly compresses, and does not have air to remain in adhesive tape and plating bonding place, after having pasted, left standstill one minute, the adhesive tape of tearing after a minute is if plating is good working condition, then follow OK, if plating is torn, then follow NG.Use the rub resistance machine, the wet type method of testing rubs 100 times back and forth, and the observation surface has or not wearing and tearing, is divided into three grades, is respectively poor, common and good.Finally to accelerate the abrasion printing condition, test the commercial number to be printed of accepting quality image of this substrate.Its etc. result arrangement such as following table 2.
Table 2
| Numbering | Attenuate difference (%) | Clear point | Hardness (H) | Then | Abrasion performance | Anti-seal amount |
| Embodiment 8 | 0.11 | 146mJ/cm 2 | 4H | NG | Poor | 45000 |
| Embodiment 9 | 0.13 | 146mJ/cm 2 | ≥4H | OK | Good | 120000 |
| Embodiment 10 | 0.12 | 146mJ/cm 2 | ≥4H | OK | Good | 110000 |
| Embodiment 11 | 0.13 | 146mJ/cm 2 | ≥4H | OK | Good | 130000 |
| Embodiment 12 | 0.12 | 146mJ/cm 2 | ≥4H | OK | Good | 110000 |
| Embodiment 13 | 0.12 | 146mJ/cm 2 | ≥4H | OK | Good | 120000 |
| Embodiment 14 | 0.12 | 146mJ/cm 2 | ≥4H | OK | Good | 110000 |
The developer solution of testing that develops is Kodak premium, the temperature of developer solution is that 23 ℃, development time are 45 seconds, iCPlate2[X-rite] measuring instrument carry out 50% site imaging test and drop to edition with the attenuate difference of X-rite 528 colorimetric analysis apparatus measures embodiment 8 to embodiment 14 and take alcohol at the bottom of without change color as reference measurement its etc. corresponding clear point.Its etc. result arrangement such as following table 3.
Table 3
| Numbering/energy value (mJ/cm 2) | Clear point | 130 | 146 | 155 | 165 | 176 | 188 | 203 | Attenuate difference (%) |
| Embodiment 8 | 130 | 46.2 | 45.7 | 45.0 | 44.2 | 43.5 | 42.8 | 42.1 | 0.32 |
| Embodiment 9 | 130 | 49.8 | 48.7 | 48.1 | 47.3 | 46.2 | 45.6 | 45.1 | 0.21 |
| Embodiment 10 | 130 | 50.2 | 49.5 | 48.9 | 48.2 | 47.4 | 46.9 | 45.9 | 0.19 |
| Embodiment 11 | 130 | 50.7 | 50.1 | 49.7 | 48.5 | 48.0 | 47.4 | 47.0 | 0.19 |
| Embodiment 12 | 130 | 49.9 | 49.4 | 48.7 | 47.8 | 47.2 | 46.6 | 46.3 | 0.20 |
| Embodiment 13 | 130 | 50.0 | 49.1 | 48.5 | 48.0 | 47.6 | 47.3 | 46.9 | 0.19 |
| Embodiment 14 | 130 | 49.7 | 48.7 | 48.3 | 47.6 | 47.2 | 46.6 | 46.1 | 0.18 |
The developer solution of testing that develops is Kodak premium, the temperature of developer solution is that 25 ℃, development time are 30 seconds, iCPlate2[X-rite] measuring instrument carry out the test of 50% site imaging and drop to edition with the attenuate difference of X-rite 528 colorimetric analysis apparatus measures embodiment 8 to embodiment 14 and take alcohol at the bottom of without change color as benchmark, measure the clear point of its correspondence such as grade.Its etc. result arrangement such as following table 4.
Table 4
| Numbering/energy value (mJ/cm 2) | Clear point | 130 | 146 | 155 | 165 | 176 | 188 | 203 | Attenuate difference (%) |
| Embodiment 8 | 130 | 46.0 | 45.3 | 45.1 | 44.5 | 43.4 | 42.8 | 42.3 | 0.35 |
| Embodiment 9 | 130 | 49.5 | 48.3 | 48.4 | 47.1 | 46.0 | 45.7 | 45.2 | 0.22 |
| Embodiment 10 | 130 | 49.9 | 49.3 | 48.8 | 48.3 | 47.3 | 46.5 | 45.4 | 0.18 |
| Embodiment 11 | 130 | 50.5 | 50.2 | 49.6 | 48.6 | 48.1 | 47.4 | 47.1 | 0.19 |
| Embodiment 12 | 130 | 50.1 | 49.7 | 48.8 | 47.7 | 47.1 | 46.8 | 46.2 | 0.21 |
| Embodiment 13 | 130 | 50.2 | 49.6 | 48.4 | 48.1 | 47.5 | 47.0 | 46.4 | 0.20 |
| Embodiment 14 | 130 | 49.6 | 48.5 | 48.2 | 47.9 | 47.3 | 46.9 | 46.3 | 0.17 |
Can find that by above-mentioned data the present invention imports that the positive-working, thermally sensitive CTP galley sensitivity of modification film-forming resin is high, alkali resistance is good, after prolonging development time or improving development temperature, 50% site performance difference is very little, as seen can the Effective Raise development latitude.So import the modification film-forming resin and can increase the sensitivity of galley, hardness, then, the characteristics such as abrasion performance and anti-seal amount, can improve product yield and quality by this method.
Claims (4)
1. a radiation-sensitive composition is applied on the substrate and forms image layer, it is characterized in that: said composition is the film-forming resin that contains general formula (I) phenolics and general formula (II) lactone structure reaction modifying, and its structure is as follows:
General formula (I)
Wherein Q is the alkyl of H, C 1～C2; D is alkyl, naphthenic base, alkoxy or the phenyl of H, OH, C1～C8; P=1,2 or 3; And
General formula (II)
The integer of x=0～17 wherein; R
3, R
4, R
5Be respectively alkyl, naphthenic base, alkoxy or the phenyl of H, C1～C20.
2. radiation-sensitive composition as claimed in claim 1, this film-forming resin is the resin after phenolics and the lactone reaction modification, its structure is as follows:
Wherein, Q is the alkyl of H, C1～C2; D is alkyl, naphthenic base, alkoxy or the phenyl of H, OH, C1～C8; P=0,1,2 or 3; R is 1～4 integer, and p+r=4; The integer of x=0～17; R
3, R
4, R
5Be respectively alkyl, naphthenic base, alkoxy or the phenyl of H, C1～C20.
3. radiation-sensitive composition as claimed in claim 1 also comprises radiation absorption dyestuff, copolymerization macromolecule, solvent, surfactant, colorant, wetting agent, acid forming agent or its combination.
4. radiation-sensitive composition as claimed in claim 1, wherein, this substrate is a printing with version.
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| CN 201010153239 CN102236254B (en) | 2010-04-21 | 2010-04-21 | Radiation sensitive composition |
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| CN 201010153239 CN102236254B (en) | 2010-04-21 | 2010-04-21 | Radiation sensitive composition |
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| CN102236254B true CN102236254B (en) | 2013-01-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340699A (en) * | 1993-05-19 | 1994-08-23 | Eastman Kodak Company | Radiation-sensitive composition containing a resole resin and a novolac resin and use thereof in lithographic printing plates |
| US5770750A (en) * | 1997-01-10 | 1998-06-23 | Georgia-Pacific Resins, Inc. | Alkyd and aralkyd derivatives of phenolic polymers |
| US6166151A (en) * | 1999-06-22 | 2000-12-26 | Georgia-Pacific Resins, Inc. | Lactone chain-extended phenolic polyester polyols |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4157497B2 (en) * | 2004-06-11 | 2008-10-01 | 株式会社東芝 | Photosensitive composition and pattern forming method using the same |
| JP2006084592A (en) * | 2004-09-14 | 2006-03-30 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JP4756501B2 (en) * | 2005-11-09 | 2011-08-24 | リンテック株式会社 | Method for producing photodegradable polymer compound |
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2010
- 2010-04-21 CN CN 201010153239 patent/CN102236254B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5340699A (en) * | 1993-05-19 | 1994-08-23 | Eastman Kodak Company | Radiation-sensitive composition containing a resole resin and a novolac resin and use thereof in lithographic printing plates |
| US5770750A (en) * | 1997-01-10 | 1998-06-23 | Georgia-Pacific Resins, Inc. | Alkyd and aralkyd derivatives of phenolic polymers |
| US6166151A (en) * | 1999-06-22 | 2000-12-26 | Georgia-Pacific Resins, Inc. | Lactone chain-extended phenolic polyester polyols |
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| CN102236254A (en) | 2011-11-09 |
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