CN100510959C - Photosensitive composition and lithograph plate made of same - Google Patents
Photosensitive composition and lithograph plate made of same Download PDFInfo
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- CN100510959C CN100510959C CNB2004100103803A CN200410010380A CN100510959C CN 100510959 C CN100510959 C CN 100510959C CN B2004100103803 A CNB2004100103803 A CN B2004100103803A CN 200410010380 A CN200410010380 A CN 200410010380A CN 100510959 C CN100510959 C CN 100510959C
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- 239000000203 mixture Substances 0.000 title claims description 78
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 33
- 238000007639 printing Methods 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 36
- 238000004132 cross linking Methods 0.000 claims description 34
- -1 salt compounds Chemical class 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- 229920001568 phenolic resin Polymers 0.000 claims description 21
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 230000035755 proliferation Effects 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 238000007031 hydroxymethylation reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 claims description 7
- XGJZQNMUVTZITK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexamethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CON(OC)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 XGJZQNMUVTZITK-UHFFFAOYSA-N 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 6
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 claims description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- LIIOKUFYMPKYKL-UHFFFAOYSA-N 1-diazoindene Chemical compound C1=CC=C2C(=[N+]=[N-])C=CC2=C1 LIIOKUFYMPKYKL-UHFFFAOYSA-N 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 150000004714 phosphonium salts Chemical class 0.000 claims description 5
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000009395 breeding Methods 0.000 abstract 1
- 230000001488 breeding effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VZQBDGHUOBRFAA-UHFFFAOYSA-N 2-(2,6-dihydroxyphenyl)benzaldehyde Chemical compound C1(O)=C(C(O)=CC=C1)C1=CC=CC=C1C=O VZQBDGHUOBRFAA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 229910004713 HPF6 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- SDPFNAZQUMPARM-UHFFFAOYSA-N formaldehyde;2-(hydroxymethyl)phenol Chemical compound O=C.OCC1=CC=CC=C1O SDPFNAZQUMPARM-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
Abstract
This invention discloses a light sensitive compound and the lithoprint plate using the compound. The light sensitive compound comprises the following as weight percent: 30 t0 60 percent of resin, 5 to 20 percent of infrared absorbing compound, 30 to 60 percent of potential protonic acid, 0 to 10 percent o f acid breeding agent. The lithoprint plate comprises base with a base coating layer of hydrophilicity polymer attached with the above light sensitive layer on. The sample in this invention can get print plate 1 images more than one hundred thousand times through the multiple printing plate experience. If the plate is baked under a temperature of 220 degrees for ten minutes, the printing time can be three hundred times. The printing plate 2 can achieve one hundred times, If the plate is baked under a temperature of 220 degrees for ten minutes, the printing time can achieve five hundred times.
Description
Technical Field
The invention relates to a photosensitive substance and a printing plate, in particular to a photosensitive composition and a lithographic plate manufactured by using the photosensitive composition.
Background
Conventional photosensitive lithographic printing plates include a photosensitive layer on a hydrophilic substrate, for example, in negative working photosensitive lithographic printing plates, a photosensitive layer that is ink-receptive to visible light (e.g., ultraviolet light, laser light, etc.) is formed on a hydrophilic substrate, and the non-visible coating can be removed to expose the surface of the hydrophilic substrate. In lithography, this difference in properties is exploited to achieve ink-water balance.
Ctp (Computer-to-plate) is becoming more and more mature with the development of Computer technology and laser technology. The CTP technology utilizes a computer to modulate and control laser beams, scans the surface of a printing plate, and obtains the plate material which can be printed on a machine through development. Because many work of the CTP technology can be carried out on a computer, the working procedures of developing, fixing, manual makeup and the like of a film are removed in the processing process, the quality and the efficiency of printing work are improved, the working period is shortened, the cost is reduced, and the CTP technology becomes the trend of the printing industry. Among all CTP technologies, the thermosensitive CTP technology (infrared laser) has the characteristics of high printing durability, high resolution, and capability of being operated in a bright room, and has become the mainstream of the CTP technology.
As a known thermosensitive CTP plate material technology, tests show that the thermosensitive CTP plate material has the defects of poor stability, low plate making speed and the like to different degrees. Some photosensitive components are difficult to prepare or use solvents that are not environmentally friendly, some require two exposures (one laser and one full UV exposure), some require more material (e.g., two phenolic resins used simultaneously), and so on.
As techniques for imparting hydrophilicity to the surface of a substrate, there are generally known: techniques for providing a hydrophilic layer comprising a water-soluble polymer on the surface of the plate substrate, and others. However, when the hydrophilicity is increased by the above-mentioned technique, problems such as a decrease in press resistance occur. Therefore, it is extremely difficult to satisfy all of the properties of high press resistance, high sensitivity, high development suitability, and hydrophilicity at the same time.
Disclosure of Invention
The present invention aims to provide an infrared laser-sensitive composition satisfying high press durability, high sensitivity, high development suitability and hydrophilic property, and a lithographic plate using the same.
The object of the invention can be achieved by the following measures:
the composite material comprises thermal crosslinking resin, potential protonic acid, an infrared absorption compound and an acid proliferation agent, wherein the resin accounts for 30-60% of the total solid content of the composite material, the infrared absorption compound accounts for 5-20% of the total solid content of the composite material, the potential protonic acid accounts for 3060% of the total solid content of the composite material, and the acid proliferation agent accounts for 0-10% of the total solid content of the composite material; according to the invention, the resin accounts for 35-45% of the total solid content of the composition, the infrared absorption compound accounts for 10-15% of the total solid content of the composition, the latent protonic acid accounts for 35-45% of the total solid content of the composition, and the thermal crosslinking resin is a hydroxymethylation product of m-cresol formaldehyde resin and has the following structure:
n is a natural number of 1 to 12.
The infrared absorbing compounds of the present invention are preferably used in an amount of 1-5% based on the total solids of the composition.
The thermal crosslinking resin is a hydroxymethylation product of mixed phenolic resin, and has the following structure:
wherein R represents a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group, an aryl group, a halogen atom or the like, which is preferably a hydrocarbon group or a hydrocarbyloxy group of 1 to 6 carbons or an aryl group, and m, n represents a natural number between 1 and 12.
The thermal crosslinking resin is prepared by taking m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde as raw materials, acetone or ethanol as a solvent and an alkaline compound as a catalyst, reacting in a reflux state, and distilling under reduced pressure. The alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2CO3One or more of (a). The latent protic acid is a polyhalogen compound. The latent protonic acid is one or more of onium salt compounds, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts and diazonium salts.
The latent protonic acid has the following structure;
wherein R represents a hydrogen atom, a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group or the like; x represents halogen ion, p-toluenesulfonate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, tetrafluoroborate and the like; n represents a natural number of 1 to 12.
The infrared absorption compound is one or more of the following compounds: carbon black, phthalocyanine, merocyanine, diazoindene, and the like.
The infrared absorbing compound has the following structure:
the acid proliferator has the following structure:
a lithographic printing plate produced using the photosensitive composition according to claim 1, which comprises a substrate, on which is an undercoat layer comprising a hydrophilic polymer, and on which is attached a photosensitive coating layer of the photosensitive composition.
In the present invention, the hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more compounds of the group. The hydrophilic group-containing substance in the hydrophilic polymer-containing primer layer is one or more of PVA, polyvinylpyrrolidone and acrylic acid type copolymer hexamethoxymelamine resin HMMM.
The invention adopts the components, and the sample is obtained by the experiment of a plurality of printing plates: the plate 1 was exposed to light using a Lotem400V (manufactured by Creo corporation), imaged and developed using a TNDM860 processor (manufactured by leksi group second film) at a preheating temperature of 120 ℃ for 1 minute, and then the plate was wiped with TG (manufactured by leksi group second film) using a TND developer. The image printing process can reach 10 ten thousand times, if the plate is baked for 10 minutes at 220 ℃, the printing process can reach 30 ten thousand times. The plate 2 was exposed to light using a Lotem400V (manufactured by Creo corporation), imaged and developed using a TNDM860 processor (manufactured by dick) at a preheating temperature of 110 ℃ for 1 minute, and then the plate surface was wiped with TG (manufactured by dick) using a TND developer. The image printing process can reach 10 ten thousand times, if the plate is baked for 10 minutes at 220 ℃, the printing process can reach 50 ten thousand times.
Detailed Description
The invention is described in detail below with reference to the figures and examples:
example 1
The composition comprises thermal crosslinking resin, potential protonic acid, infrared absorption compound and acid proliferation agent, wherein the resin accounts for 30% of the total solid content of the composition in percentage by weight, the infrared absorption compound accounts for 5% of the total solid content of the composition, the potential protonic acid accounts for 60% of the total solid content of the composition, and the acid proliferation agent accounts for 5% of the total solid content of the composition.
The thermal crosslinking resin is a hydroxymethylation product of m-cresol formaldehyde resin and has the following structure:
n is a natural number of 1 to 12.
The thermal crosslinking resin is prepared by reacting m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde serving as raw materials under a reflux state by using acetone or ethanol as a solvent and an alkaline compound as a catalyst, and distilling under reduced pressure.
The alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2CO3One or more of (a).
The latent protic acid is a polyhalogen compound.
The infrared absorption compound is one or more of the following compounds: carbon black, phthalocyanine, merocyanine, diazoindene.
The acid proliferator has the following structure:
the lithographic printing plate manufactured by the photosensitive composition of the present invention comprises a substrate, an undercoat layer containing a hydrophilic polymer on the substrate, and a photosensitive coating layer of the photosensitive composition attached to the undercoat layer.
The hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more compounds of the group.
Example 2
The composition comprises 60 weight percent of resin, 10 weight percent of infrared absorption compound, 30 weight percent of potential protonic acid and 0 weight percent of acid proliferation agent.
The thermal crosslinking resin is a hydroxymethylation product of mixed phenolic resin, and has the following structure:
wherein R represents a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group, an aryl group, a halogen atom or the like, which is preferably a hydrocarbon group or a hydrocarbyloxy group of 1 to 6 carbons or an aryl group, and m, n represents a natural number between 1 and 12.
The thermal crosslinking resin is obtained by reacting m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde serving as raw materials under a reflux state by taking acetone or ethanol as a solvent and an alkaline compound as a catalyst and distilling under reduced pressure.
The alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2CO3One or more of (a).
The latent protonic acid is one or more of onium salt compounds, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts and diazonium salts.
The infrared absorbing compound has the following structure:
the acid proliferator has the following structure:
a lithographic plate made of the photosensitive composition comprises a substrate, an undercoat layer comprising a hydrophilic polymer on the substrate, and a photosensitive layer of the photosensitive composition attached to the undercoat layer.
The hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more compounds of the group.
The lithographic printing plate according to claim 13, wherein: the hydrophilic group-containing substance in the hydrophilic polymer-containing primer layer is one or more of PVA, polyvinylpyrrolidone and acrylic acid type copolymer hexamethoxymelamine resin HMMM.
Example 3
The composition comprises thermal crosslinking resin, potential protonic acid, infrared absorption compound and acid proliferation agent, wherein the resin accounts for 35% of the total solid content of the composition in percentage by weight, the infrared absorption compound accounts for 10% of the total solid content of the composition, the potential protonic acid accounts for 45% of the total solid content of the composition, and the acid proliferation agent accounts for 10% of the total solid content of the composition.
The photosensitive composition according to claim 1 or 2 in the invention, characterized in that: the thermal crosslinking resin is a hydroxymethylation product of m-cresol formaldehyde resin and has the following structure:
n is a natural number of 1 to 12.
The thermal crosslinking resin is prepared by reacting m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde serving as raw materials under a reflux state by using acetone or ethanol as a solvent and an alkaline compound as a catalyst, and distilling under reduced pressure.
The alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2One or more of CO.
The latent protonic acid is one or more of onium salt compounds, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts and diazonium salts.
The infrared absorption compound is one or more of the following compounds: carbon black, phthalocyanine, merocyanine, diazoindene, and the like.
The acid proliferator has the following structure:
a lithographic plate made of the photosensitive composition comprises a substrate, an undercoat layer comprising a hydrophilic polymer on the substrate, and a photosensitive layer of the photosensitive composition attached to the undercoat layer.
The hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more compounds of the group.
The hydrophilic group-containing substance in the hydrophilic polymer-containing primer layer is one or more of PVA, polyvinylpyrrolidone and acrylic acid type copolymer hexamethoxymelamine resin HMMM.
Example 4
The composition comprises a thermal crosslinking resin, a latent protonic acid, an infrared absorbing compound and an acid proliferation agent, wherein the resin accounts for 45% of the total solid content of the composition, the infrared absorbing compound accounts for 15% of the total solid content of the composition, the latent protonic acid accounts for 35% of the total solid content of the composition, and the acid proliferation agent accounts for 5% of the total solid content of the composition.
The thermal crosslinking resin is a hydroxymethylation product of m-cresol formaldehyde resin and has the following structure:
n is a natural number of 1 to 12.
The thermal crosslinking resin is obtained by reacting m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde serving as raw materials under a reflux state by taking acetone or ethanol as a solvent and an alkaline compound as a catalyst and distilling under reduced pressure.
The alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2CO3One or more of (a).
The latent protonic acid has the following structure;
wherein R represents a hydrogen atom, a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group or the like; x represents halogen ion, p-toluenesulfonate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, tetrafluoroborate and the like; n represents a natural number of 1 to 12.
The infrared absorbing compound has the following structure:
the acid proliferator has the following structure:
a lithographic plate made of the photosensitive composition comprises a substrate, an undercoat layer comprising a hydrophilic polymer on the substrate, and a photosensitive layer of the photosensitive composition attached to the undercoat layer.
The hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more compounds of the group.
The hydrophilic group-containing substance in the hydrophilic polymer-containing primer layer is one or more of PVA, polyvinylpyrrolidone and acrylic acid type copolymer hexamethoxymelamine resin HMMM.
Example 5
The photosensitive composition of the present invention comprises a thermally crosslinkable resin, a latent protonic acid, an infrared absorbing compound and an acid amplifier in amounts ranging from 30 to 60% by weight of the total solids of the composition, 5 to 20% by weight of the infrared absorbing compound, 30 to 60% by weight of the latent protonic acid and 0 to 10% by weight of the acid amplifier, excluding the values given in the preceding examples. Furthermore, as a preferred ratio range, the resin is used in an amount of 35-45% by weight of the total composition solids, the infrared absorbing compound is used in an amount of 10-15% by weight of the total composition solids, the latent protonic acid is used in an amount of 35-45% by weight of the total composition solids, and the infrared absorbing compound is used in an amount of 1-5% by weight of the total composition solids. Any of these may be used.
The thermal crosslinking resin is a methylolation product of m-cresol formaldehyde resin and has the following structure:
n is a natural number of 1 to 12.
The thermal crosslinking resin can also adopt a methylolation product of a mixed phenolic resin, which has the following structure:
wherein R represents a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group, an aryl group, a halogen atom or the like, which is preferably a hydrocarbon group or a hydrocarbyloxy group of 1 to 6 carbons or an aryl group, and m, n represents a natural number between 1 and 12.
The thermal crosslinking resin is obtained by reacting m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde serving as raw materials under a reflux state by taking acetone or ethanol as a solvent and an alkaline compound as a catalyst and distilling under reduced pressure.
The alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2CO3One or more of (a).
The latent protic acid is a polyhalogen compound. Or the latent protonic acid is one or more of onium salt compounds, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts and diazonium salts.
The latent protonic acid has the following structure;
wherein R represents a hydrogen atom, a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group or the like; x represents halogen ion, p-toluenesulfonate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate and tetrafluoroborate; n represents a natural number of 1 to 12.
The infrared absorption compound is one or more of the following compounds: carbon black, phthalocyanine, merocyanine, diazoindene.
Alternatively, the infrared absorbing compound has the following structure:
the acid proliferator has the following structure:
the lithographic printing plate manufactured by the photosensitive composition comprises a substrate, an undercoat layer containing a hydrophilic polymer is arranged on the substrate, and the photosensitive coating layer of the photosensitive composition is adhered on the undercoat layer. The hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more compounds of the group. The hydrophilic group-containing substance in the hydrophilic polymer-containing primer layer is one or more of PVA, polyvinylpyrrolidone and acrylic acid type copolymer hexamethoxymelamine resin HMMM.
Example 6
The invention provides an infrared laser sensing composition which can meet the requirements of high pressrun, high sensitivity, high development adaptability and hydrophilic performance, and a thermosensitive computer direct plate making plate material is manufactured by using the composition. The formulations and compositions are as set forth in the preceding examples.
The thermally crosslinkable resin used in the present invention is a phenolic resin containing a methylol group. Phenolic resins are well known for a wide variety of uses and are obtained by reacting a phenolic compound with an aldehyde. The reaction product of excessive phenol and aldehyde is linear phenolic resin under acidic condition; under alkaline conditions, phenolic materials react with excess aldehyde to give thermosetting phenol-formaldehyde resins, also known as methylol phenol-formaldehyde resins. The thermally crosslinkable resin used in the present invention is obtained by methylolation of a phenol novolac resin, and has both properties of the phenol novolac resin and the methylol phenol novolac resin. The phenol-formaldehyde novolac resins capable of being methylolated include phenol-formaldehyde resins, m-cresol-formaldehyde resins, m-and p-mixed cresol-formaldehyde resins, resorcinol-benzaldehyde resins, and poly-p-hydroxystyrene resins. Useful resin structures can be represented by the general formula:
resin 1
Resin 2
The resin 1, n is a natural number between 1 and 12, preferably 4 to 8. Resin 2, wherein R represents alkyl, alkoxy, aryl, halogen atom, etc. with 1-12 carbon atoms, preferably alkyl, alkoxy or aryl with 1-6 carbon atoms, m, n represents natural number between 1-12, preferably 4-8. In view of crosslinking activity and storage stability of the photosensitive composition, the methylolation ratio of the resin should be 10 to 90%, preferably 40 to 50%. The weight average molecular weight of the resin is 1000-8000, preferably 3000-5000.
The cross-linked resin with the structure of resin 1 can be produced by using BTB-24 (produced by Weihai Tian chemical plant) as a raw material, and the cross-linked resin with the structure of resin 2 can be produced by using R-32 (second film factory of Lekei group). The amount of resin is 30-60%, preferably 35-45% of the total solid content of the composition.
The infrared absorbing compound used in the heat-sensitive composition of the present invention may be a dye or a pigment. The compounds are of wide range and include cyanine, merocyanine, indolizine, phthalocyanine, pyran, indole, etc. These compounds are capable of absorbing infrared laser light and generating thermal energy. The infrared absorber used in the present invention is carbon black and NK-4680 (Japanese pigment) dye. NK-4680 has the following structure:
the infrared absorbing compound is present in an amount of 5-20%, preferably 10-15%, based on the total solids of the composition.
As used herein, a latent protonic acid is a precursor which forms a protonic acid by thermal decomposition, which is capable of generating HCL, HPF6And the like, which is a catalyst for crosslinking and curing the thermally crosslinked resin. Can be used for the present inventionThere are many potential protonic acids, including ionic and nonionic ones, such as various onium salt compounds, haloalkyl-substituted triazine compounds, and specific sulfonic acid ester compounds. The present invention uses a diazo salt high molecular resin as latent protonic acid, so that the infrared light sensitive composition and the photosensitive lithographic plate using the composition have high sensitivity and high printing durability. The specific structural general formula is as follows:
wherein R represents a hydrogen atom, a hydrocarbon group of 1 to 12 carbons, a hydrocarbyloxy group or the like; x represents halogen ion, p-toluenesulfonate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, tetrafluoroborate and the like; n represents a natural number of 1 to 12, preferably 2 to 5, and N-5000 (Lekei group II film factory) is a representative substance. The amount of latent protonic acid is 30-60%, preferably 35-45% of the total composition solids.
The acid proliferator used in the present invention acts on H+In the presence of the acid amplifier compound, the acid amplifier compound can generate additional acid, so that the sensitivity of the printing plate is improved. The present invention uses:
the amount of the acid proliferation agent is 0-10%, preferably 1-5% of the total solid content of the composition.
In addition to the above materials, the thermosensitive composition of the present invention should also include colorants, stabilizers, auxiliary sensitizers, exposure indicators, surfactants, and the like.
The support of the lithographic plate can be an aluminum plate or other metal plate, and can also be a polyester film base, a paper base coated with polymers and the like. The best support is an anodized, oxidized aluminum plate coated with a coating containing-COOH, -NH2，—OH, and the like. The following compounds are preferably used to form the hydrophilic layer: vinyl type resins and derivatives thereof, such as PVA (polyvinyl alcohol), modified PVA, polyvinyl pyrrolidone and polyvinyl imidazoline; acrylic acid type copolymers, such as polyacrylic acid, polyacrylamide, and the like.
Specifically, the following operation 1 is performed:
synthesis of thermally crosslinkable resin 1:
78g of BTB-24 phenolic resin (produced by Wailan chemical plant), 300ml of ethanol, 60ml of 37% formaldehyde solution and 1g of sodium hydroxide are added into a 500ml three-neck flask provided with a stirrer, a condenser and a thermometer, the mixture is reacted for 6 hours at 80-90 ℃, the solvent is distilled off by vacuum pumping, and the product is poured out when the product is hot, so that 80g of the product is obtained.
Making a base plate
An aluminum plate (alloy 1050) having a thickness of 0.3mm was washed and degreased with trichloroethylene, then sanded with a nylon brush and a 400 mesh (mesh) pumice-water suspension, and washed with water. The plate was immersed in 25% aqueous sodium hydroxide solution at 45 ℃ for 9 seconds. Then, the plate was coated with the following coating liquid, dried and coated at 80 ℃ for 15 seconds to obtain a plate base, and the coating coverage was 15g/m after drying2
Coating liquid 1:
hexamethoxymelamine resin HMMM (hexamethylolmethlylmethylmelamine) 0.3g
Methanol 100g
1g of water
The photosensitive solution was adjusted so that the photosensitive solution 1 was applied to the substrate in an amount of 1.3g/m2The drying temperature was 110 ℃ for 3 minutes, thereby obtaining a planographic printing plate 1.
Photosensitive solution 1:
thermal crosslinking resin 10.5 g
N-5000 (produced by Lekai group II film) 0.5g
NK-468 (Japanese pigment) 0.1g
BO-603 (Beijing chemical plant) 0.01g
A-1 0.01g
Cyclohexanone 5g
Ethylene glycol monoethyl ether 5g
The plate was exposed to light using a Lotem400V (manufactured by Creo corporation), imaged and developed using a TNDM860 processor (manufactured by leksi group second film) at a preheating temperature of 120 ℃ for 1 minute, and then the plate was wiped with TG (manufactured by leksi group second film) using a TND developer. The image printing process can reach 10 ten thousand times, if the plate is baked for 10 minutes at 220 ℃, the printing process can reach 30 ten thousand times.
Photosensitive liquid 2
In the photosensitive solution 1, A-1 was replaced with A-2 in equal amounts, and the above operation was repeated to obtain the same results.
Alternatively, the specific embodiment is as follows, operation 2
Synthesis of thermally crosslinked resin 2:
r-32 (Lekeka group second film factory) was charged into a 500ml three-neck beaker equipped with a stirrer, a cooling tube and a thermometer, and the operation of operation 1 was repeated to obtain thermally crosslinked resin 2. The aluminum plate base and the coating liquid are the same as the operation 1:
photosensitive liquid 3
The thermal crosslinking resin 1 was replaced with the thermal crosslinking resin 2, and the others were not changed.
The photosensitive liquid 2 was applied to the substrate so that the coating amount was 1.3g/m2The drying temperature was 120 ℃ for 3 minutes, thereby obtaining a planographic printing plate 2.
The plate 2 was exposed to light using a Lotem400V (manufactured by Creo corporation), imaged and developed using a TNDM860 processor (manufactured by dick) at a preheating temperature of 110 ℃ for 1 minute, and then the plate surface was wiped with TG (manufactured by dick) using a TND developer. The image printing process can reach 10 ten thousand times, if the plate is baked for 10 minutes at 220 ℃, the printing process can reach 50 ten thousand times.
Claims (13)
1. A photosensitive composition characterized by: the composition comprises thermal crosslinking resin, potential protonic acid, an infrared absorption compound and an acid proliferation agent, wherein the dosage of the resin accounts for 30-60% of the total solid content of the composition, the dosage of the infrared absorption compound accounts for 5-20% of the total solid content of the composition, the dosage of the potential protonic acid accounts for 30-60% of the total solid content of the composition, and the dosage of the acid proliferation agent accounts for 0-10% of the total solid content of the composition;
the thermal crosslinking resin is a hydroxymethylation product of m-cresol formaldehyde resin and has the following structure:
n is a natural number of 1-12; or,
the thermal crosslinking resin is a hydroxymethylation product of mixed phenolic resin, and has the following structure:
wherein R represents alkyl, alkoxy, aryl and halogen atoms with 1-12 carbons, m and n represent natural numbers between 1-12;
the latent protonic acid is one or more of polyhalogen compounds or onium salt compounds.
2. The photosensitive composition of claim 1, wherein: the protonic acid is one or a combination of more of iodonium salt, sulfonium salt, phosphonium salt and selenonium salt.
3. The photosensitive composition of claim 1, wherein: the latent protonic acid has the following structure;
wherein R represents a hydrogen atom, a hydrocarbon group of 1 to 12 carbons or a hydrocarbyloxy group; x represents halogen ion, p-toluenesulfonate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate and tetrafluoroborate; n represents a natural number of 1 to 12.
4. The photosensitive composition of claim 1, wherein: the resin accounts for 35-45% of the total solid content of the composition, the infrared absorbing compound accounts for 10-15% of the total solid content of the composition, and the latent protonic acid accounts for 35-45% of the total solid content of the composition.
5. The photosensitive composition of claim 1, wherein: in the structural formula of the hydroxymethylation product of the mixed phenolic resin, R represents alkyl or alkoxy or aryl with 1-6 carbons.
6. The photosensitive composition of claim 1 or 2 or 3 or 4, wherein: the thermal crosslinking resin is obtained by reacting m-cresol or mixed phenol-formaldehyde resin and formaldehyde or paraformaldehyde serving as raw materials under a reflux state by taking acetone or ethanol as a solvent and an alkaline compound as a catalyst and distilling under reduced pressure.
7. The photosensitive composition of claim 1 or 2 or 3 or 4, wherein: the alkaline compound used as catalyst in the thermal crosslinking resin reaction is NaOH, KOH, Na2CO3One or more of (a).
8. The photosensitive composition of claim 1 or 2 or 3 or 4, wherein: the infrared absorption compound is one or more of the following compounds: carbon black, phthalocyanine, merocyanine, diazoindene.
9. The photosensitive composition of claim 1 or 2 or 3 or 4, wherein: the above-mentioned
The infrared absorbing compound has the following structure:
10. the photosensitive composition of claim 1 or 2 or 3 or 4, wherein: the above-mentioned
The acid proliferator has the following structure:
11. a lithographic printing plate made using the photosensitive composition of claim 1, wherein: it comprises a substrate, on which is an undercoat layer containing a hydrophilic polymer, to which is attached a photosensitive coating layer of the photosensitive composition.
12. The lithographic printing plate according to claim 11, wherein: the hydrophilic polymer-containing primer layer contains-COOH, -CH2OH or-NH2One or more of the above groups of compounds.
13. The lithographic printing plate according to claim 11, wherein: the hydrophilic group-containing substance in the hydrophilic polymer-containing primer layer is one or more of PVA, polyvinylpyrrolidone, acrylic acid type copolymer and hexamethoxymelamine resin HMMM.
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| CN101770167B (en) * | 2008-12-30 | 2012-05-16 | 乐凯集团第二胶片厂 | Positive type infrared light sensitive composition and positive heat-sensitive lithographic plate |
| CN103587273B (en) * | 2013-11-04 | 2018-11-27 | 北京中科纳新印刷技术有限公司 | A kind of photosensitive grain-free printing plate and the preparation method and application thereof |
| CN107045260B (en) * | 2017-04-12 | 2020-06-26 | 安徽强邦印刷材料有限公司 | Photosensitive layer of heat-sensitive positive image CTP plate |
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