CN100587597C - Positive PS printing plate light sensitive composition - Google Patents
Positive PS printing plate light sensitive composition Download PDFInfo
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- CN100587597C CN100587597C CN200510107310A CN200510107310A CN100587597C CN 100587597 C CN100587597 C CN 100587597C CN 200510107310 A CN200510107310 A CN 200510107310A CN 200510107310 A CN200510107310 A CN 200510107310A CN 100587597 C CN100587597 C CN 100587597C
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- positive
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- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 239000000975 dye Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical group 0.000 claims description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 31
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 14
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 8
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 claims description 6
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 6
- 239000004922 lacquer Substances 0.000 claims description 6
- -1 methylidene, ethyl Chemical group 0.000 claims description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims description 3
- HLMLWEGDMMDCDW-UHFFFAOYSA-N 2-butylphenol;formaldehyde Chemical group O=C.CCCCC1=CC=CC=C1O HLMLWEGDMMDCDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- 229940114055 beta-resorcylic acid Drugs 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 claims description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- ZCAXVIHEALTJJY-UHFFFAOYSA-N 5-methyl-1-phenylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)C(C)N1C1=CC=CC=C1 ZCAXVIHEALTJJY-UHFFFAOYSA-N 0.000 claims description 2
- LRAOXIUUXITRTC-UHFFFAOYSA-N CCC1C(=O)NC(=O)N1C(C)C2=CC=CC=C2 Chemical compound CCC1C(=O)NC(=O)N1C(C)C2=CC=CC=C2 LRAOXIUUXITRTC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 17
- 239000002585 base Substances 0.000 abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000004576 sand Substances 0.000 abstract description 3
- 206010070834 Sensitisation Diseases 0.000 abstract 3
- 230000008313 sensitization Effects 0.000 abstract 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000018109 developmental process Effects 0.000 description 16
- 235000013824 polyphenols Nutrition 0.000 description 16
- 239000000470 constituent Substances 0.000 description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 11
- 206010034960 Photophobia Diseases 0.000 description 9
- 208000013469 light sensitivity Diseases 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- NAOAMSZZEPAPNP-UHFFFAOYSA-N 3-chlorosulfonyl-2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical compound C1=CC=C2C(=O)C(=[N+]=[N-])C(S(=O)(=O)Cl)C(=O)C2=C1 NAOAMSZZEPAPNP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Materials For Photolithography (AREA)
Abstract
The sensitization composition includes one or more line form phenolic resins, one or more additive resins, one or more modified resins, one or more photosensitive resins, one or more dyes, and one ormore solvents. The sensitization composition is coated on coarsened aluminum printing base plate with structure of sand screen mesh. Positive graph PS printing plate is obtained after the said aluminum printing base plate is dried. Keeping high sensitivity, the sensitization composition possesses features of excellent reducibility of microdot, better developing performance anti alkali, large development latitude in weak base, outstanding performance for eliminating making up printing and durable printing operability so as to reach better balance among capabilities.
Description
Technical field
The present invention relates to a kind ofly, specifically, relate to a kind of about positive PS printing plate light sensitive composition used in the lithography in positivity photosensitive resin constituent.
Background technology
All the time, widely used positive PS printing plate is the photonasty coating fluid that o-quinone triazo-compound and film forming phenolics are formed to be coated through alligatoring have on the aluminum substrate of sand screen mesh structure, drying and obtaining.The o-quinone triazo-compound is to the ultraviolet light sensitivity, and azido decomposes after UV-irradiation, and the o-quinone triazo-compound generates indone, changes indenes acid afterwards into.Like this, when developing with alkaline-based developer, the part of seeing light on the plate is dissolved and remove, and exposes hydrophilic aluminum substrate, shows water wettability, becomes hydrophilic non-graphic part when printing; And unexposed part, intermolecular association takes place in the phenolic hydroxyl group on o-quinone triazo-compound and the film forming phenolics, form six stable circular ring structures, thereby strengthened the alkali resistant dissolubility of coating, can do not dissolved by alkaline-based developer, therefore unexposed part is still stayed on the aluminum substrate on the plate, becomes oil loving picture and text part when printing.
For positive PS printing plate, its performance comprises plate-making performance, developing performance and printing performance.Wherein performance is printed in have light sensitivity, site reducing property and the cancellation layout of influence plate-making performance; Influence the anti-highly basic developing performance of having of developing performance, weak base development tolerance etc.; What influence printing performance has last China ink, a pressrun etc.
The positive PS printing plate of a high-quality performance should have high light sensitivity, big highly basic or weak base development tolerance, site reducing property and high pressrun etc. preferably simultaneously.
Yet because the self-characteristic of phenolics and o-quinone nitrine resin is limit, some performance often is difficult to reach balance preferably.As: the balance of the balance of balance, high sensitivity and the pressrun of ISO and anti-highly basic development, anti-highly basic development and elimination layout seal performance etc.As everyone knows, for the positive PS printing plate constituent of fixed system, improve anti-highly basic development, light sensitivity and elimination layout seal performance will descend; Improve light sensitivity, anti-highly basic development and pressrun will descend.
For a long time, people are devoted to by to phenolic resin modified or add special resin and improve the light sensitivity of positive PS printing plate, but when having improved light sensitivity, have lost otherwise performance more or less.
Summary of the invention
Purpose of the present invention just is to provide a kind of positive PS printing plate light sensitive composition that has reached the balance preferably of each performance.When keeping ISO, has site reducing property brilliance, anti-highly basic development is excellent, weak base development tolerance big, the outstanding and high characteristics of pressrun of cancellation layout seal performance.
Purpose of the present invention can realize by following measure:
The present invention comprises: one or more lacquer resin, one or more interpolation resin, one or more modified phenolic resin, one or more optical light sensitive adhesive, one or more dyestuff, one or more solvent, with following structural formula I and II compound
Structure I hydantoin derivative structure I I benzoic acid derivative
Wherein
In the compound in structural formula I:
R1 represents aromatic group;
R2 represents O or S atom;
R3 represents hydrogen atom or alkyl;
R4 represents O or S atom;
R5 represents alkyl or alkoxy base;
In the compound of structural formula II:
R1, R2, R3, R4, R5 represent hydrogen atom, hydroxyl or carboxylic group;
Neutral line phenolics of the present invention is one or more in phenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol-formaldehyde resin, phenol-tertiary butyl phenol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, the metacresol-orthoresol-formaldehyde resin.
Adding resin among the present invention is the 1,2,3,-thrihydroxy-benzene condensation of acetone resin of low polymerization degree, has following structure:
Compound III
N represents 2-10.
The modified phenolic resin is modification tertiary butyl phenol urea formaldehyde or rosin modified phenolic resin among the present invention; Described optical light sensitive adhesive is the graft resin of 215 sulfonic acid chlorides and 1,2,3,-thrihydroxy-benzene condensation of acetone resin.
Dyestuff is one or more in Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet, the methylene blue among the present invention.
Solvent adopts one or more in ether solvent, esters solvent, ketones solvent, the heterocyclic solvent among the present invention.
Among the present invention in the compound in structural formula I: R1 represents in phenyl, benzyl, phenethyl, the benzyl group one, R2 and R4 represention oxygen atom, and R3 represents hydrogen atom, arbitrary group in R5 represent methylidene, ethyl, methoxyl, the ethoxy.
Compound in structural formula I is in 1-phenyl-5-methyl hydantoin, 1-benzyl-5-methoxyl glycolylurea, 1-benzyl-5-ethoxy glycolylurea or the 1-phenethyl-5-ethylhydantoin any among the present invention;
Among the present invention in the compound of structural formula II: R1 represent hydrogen atom, hydroxyl, carboxyl any, R2, R3 represent hydrogen atom, hydroxyl, carboxyl any, R4 represent hydrogen atom, hydroxyl, carboxyl any.
The compound of structural formula II is 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 5-hydroxybenzoic acid, 3 among the present invention, 4-dihydroxy-benzoic acid, 3,5-dihydroxy-benzoic acid, 2,4-dihydroxy-benzoic acid, 3,4, the 5-trihydroxybenzoic acid, any.
The present invention is owing to adopt such scheme, by studying intensively, invented a kind of positive PS printing plate light sensitive constituent, this photosensitive composition is coated through alligatoring to be had on the aluminum substrate of sand screen mesh structure, obtains positive PS printing plate after drying, when keeping ISO, have that site reducing property brilliance, anti-highly basic development are excellent, weak base development tolerance big, the outstanding and high characteristics of pressrun of cancellation layout seal performance, reached the balance preferably of each performance.
Embodiment
The present invention does with detailed description below in conjunction with embodiment:
Embodiment 1,
Positive PS printing plate light sensitive composition of the present invention comprises: one or more lacquer resin, one or more interpolation resin, one or more modified phenolic resin, one or more optical light sensitive adhesive, one or more dyestuff, one or more solvent, with following structural formula I and II compound
Structure I hydantoin derivative structure I I benzoic acid derivative
Wherein
In the compound in structural formula I:
R1 represents aromatic group;
R2 represents O or S atom;
R3 represents hydrogen atom or alkyl;
R4 represents O or S atom;
R5 represents alkyl or alkoxy base;
In the compound of structural formula II:
R1, R2, R3, R4 represent hydrogen atom, hydroxyl or carboxylic group;
The 1,2,3,-thrihydroxy-benzene condensation of acetone resin that described interpolation resin is a low polymerization degree has following structure:
Compound III
N represents 2-10;
Described modified phenolic resin is modification tertiary butyl phenol urea formaldehyde or rosin modified phenolic resin; Described photosensitive tree
Ester is the graft resin of 2-nitrine-1-naphthoquinones-5-sulfonic acid chloride and 1,2,3,-thrihydroxy-benzene condensation of acetone resin.
The compound of described structural formula II is 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 3,4-dihydroxy-benzoic acid, 3,5-dihydroxy-benzoic acid, 2,4-dihydroxy-benzoic acid, 3,4, the 5-trihydroxybenzoic acid, any.
Used one or more lacquer resin among the present invention can be the linear phenolic resin that phenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol-formaldehyde resin, phenol-tertiary butyl phenol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, metacresol-orthoresol-a kind of phenols such as formaldehyde resin, two kinds of phenols even three kinds of phenols and formaldehyde form by the different proportion polycondensation.The lacquer resin consumption is 40%～80%, preferred 50%～70%.
Employed one or more interpolation resin is the 1,2,3,-thrihydroxy-benzene condensation of acetone resin of low polymerization degree among the present invention, has following structure:
N represents 2-10, the natural number of preferred 3-6.1,2,3,-thrihydroxy-benzene condensation of acetone resin can synthesize with well-known method.Usually, adding the interpolation resin in the positive light sensitive layer thing is in order to improve its anti-wear performance, just to say on this meaning, also can add the interpolation resin that other improve wearing qualities, but effect being less than the present invention.The consumption that adds resin is 1%～10% of a total solid film forming matter, preferred 2%～5%.
The modified phenolic resin of one or more that the present invention is used is modification tertiary butyl phenol urea formaldehyde or rosin modified phenolic resin.Certainly, also can replace resin of the present invention, but effect is not as the present invention with other phenol-formaldehyde resin modifieds.Its consumption is 5%～20% of a total solid film forming matter, preferred 8%～15%.
Employed one or more photosensitive resin is the diazonium naphthoquinone sulphonate compounds in traditional positive PS printing plate light sensitive component among the present invention, its esterification parent can be low molecule polyhydric phenols, also can be macromolecular compounds such as linear phenolic resin.Used resistance solvent obtains the part of hydroxyl esterification of linear phenolic resin as graft with the diazo naphthoquinone sulfonic acid chloride by the importing parent of linear phenolic resin as the resistance soluble macromolecular among the present invention.The synthetic used linear phenolic resin of this family macromolecule resistance solvent can be an above-mentioned film-forming resin phenolics commonly used, and example has phenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol (mole ratio 3: 7-7: 3)-formaldehyde resin, phenol-tertiary butyl phenol (mole ratio 3: 1-1.5: 1)-formaldehyde resin, metacresol-paracresol (mole ratio 9: 1-5: 5)-formaldehyde resin, metacresol-orthoresol-a kind of phenols such as formaldehyde resin, the linear phenolic resin that two kinds of phenols even three kinds of phenols and formaldehyde form by the different proportion polycondensation.Their weight-average molecular weight is generally selected 2000-10000, and preferred 2500-7500 most preferably is 2500-4000; M
w/ M
nBe 1.5-20, preferred 1.5-10 most preferably is 2.0-4.0.The hydroxy esterification rate can be the 10-80% of initial hydroxyl, preferred 20-50%.The synthetic Photoactive compounds of institute use amount in photosensitive composition is 10-40%, is preferably 10-20%, if consumption is too big, it is too strong to hinder molten ability, the difficulty of developing; If consumption very little, hinders molten scarce capacity, alkali resistance is poor, is easy to produce the photodissociation stripping phenomenon, a little less than the pressrun of plate.
The used compound in structural formula I of the present invention, wherein R1 represents aromatic group; R2 represents O or S atom; R3 represents hydrogen atom hydrogen atom or alkyl; R4 represents O or S atom; R5 represents alkyl or alkoxy base; R2 and R4 can be identical, also can be inequality.This compound also can replace with its similar compounds, but does not reach effect of the present invention.The consumption of this compound is 1%～10% of a total solid film forming matter, preferred 2%～6%.
The compound of the used structural formula structure I of the present invention I, wherein R1, R2, R3, R4, R5 represent hydrogen atom.Hydroxyl or carboxylic group; R1, R2, R3, R4, R5 can be identical also can be inequality.This compound also can replace with its similar compounds, but does not reach effect of the present invention.The consumption of this compound is 1%～5% of a total solid film forming matter, preferred 2%～4%.
Used one or more the dyestuff of the present invention can be selected from dyestuffs such as Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet, methylene blue.Consider and to reduce the plate sensitivity that preferred Victoria's ethereal blue, alkaline bright blue, solvent blue etc. are comparatively desirable to ultraviolet absorption.The consumption of dyestuff is 1%～5% of a total solid film forming matter, preferred 2%～4%.
Solvent for use of the present invention can be selected from ethers: ethylene glycol monomethyl ether, ethylene glycol monoemethyl ether, the only ether of propylene glycol, the only methyl ether of propylene glycol etc.; Ester class: ethyl acetate, butyl acetate, glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate, isobutyl acetate etc.; Ketone: MEK, methylisobutylketone, butanone, cyclohexanone etc.; Heterocyclic: dioxane, dioxolanes, hexahydro furyl etc.When using single component solvent, should select the solvent that can both dissolve for use to all components.
Below by example explanation the present invention, but be not limited in this example." part " of below mentioning all refers to parts by weight if no special instructions.Starting material are as follows:
Became the chemical plant in linear phenol-aldehyde resin ST-1071 days
Modification tertiary butyl phenol urea formaldehyde Tianjin Yongming grease manufacturing plant
Rosin modified phenolic resin Nanda Chemical Plant, Shanghai
Compound III second photographic film plant
Photosensitive resin P-3000 PCAS company
Chromotropic dye TB Beijing Normal University
The blue dyestuff BO-603 of oil-soluble Beijing Chemical Plant
Ethylene glycol monomethyl ether Plant of Tianjin Petrochemical Company three factories
Propylene glycol monomethyl ether Plant of Tianjin Petrochemical Company three factories
Concrete data are as follows:
Be made into coating fluid with following component, and filter, on the reel automatic assembly line, be coated with then, make the PS version through the core of 0.1 μ m.Prepared PS version is 95 ℃ of down bakings 10 minutes, treat natural cooling after, get one and measure light sensitivity, site reducing property, alkali resistance, weak base development tolerance, cancellation layout seal performance.Other gets one and makes printing plate, prints on the J410413 type printing machine of Jing Dezhen.The result charges in the table one.
2.76 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
Compound III (n=4) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Embodiment 2
Identical with the preparation method of above-mentioned example, just following the variation takes place in formula constituent:
2.76 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as above-mentioned method, the result charges to table one.
Embodiment 3
With above-mentioned example the preparation method identical, just following the variation takes place in formula constituent:
2.76 parts of linear phenol-aldehyde resin ST-1071
0.6 part of rosin modified phenolic resin
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
Compound III (n=6) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as the method for above-mentioned example, the result charges to table one.
Example 4
Identical with the preparation method of above-mentioned example, just following the variation takes place in formula constituent:
2.76 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of propylene glycol monomethyl ethers
Measure every performance as the method for above-mentioned example, the result charges to table one.
Example 5
Identical with the preparation method of above-mentioned example, just following the variation takes place in formula constituent:
2.76 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
28.8 parts of propylene glycol monomethyl ethers
7.2 parts of dioxane
Characteristics of the present invention can be described as follows by concrete test comparative example correlation data:
The result charges to table one.
Comparative example 1
Identical with the preparation method of example one, just following the variation takes place in formula constituent:
2.76 parts of linear phenol-aldehyde resin ST-1071
0.6 part in tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as the method for example one, the result charges to table one.
Comparative example 2
Identical with the preparation method of example one, just following the variation takes place in formula constituent:
12.76 parts of linear phenol-aldehyde resin ST-107
0.6 part in tertiary butyl phenol phenolics
1.8 parts of phenolics grafting 215 photosensitive resins
Compound I 0.30
Compound I I 0.18
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as the method for example one, the result charges to table one.
Comparative example 3
Identical with the preparation method of example one, just following the variation takes place in formula constituent:
3.06 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I I 0.18
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as the method for example one, the result charges to table one.
Comparative example 4
Identical with the preparation method of example one, just following the variation takes place in formula constituent:
2.94 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound III (n=8) 0.24
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as the method for example one, the result charges to table one.
Comparative example five
Identical with the preparation method of example one, just following the variation takes place in formula constituent:
3.0 parts of linear phenol-aldehyde resin ST-1071
0.6 part in modification tertiary butyl phenol phenolics
1.8 parts of photosensitive resin P-3000
Compound I 0.30
Compound I I 0.18
0.096 part of the blue dyestuff BO-603 of oil-soluble
0.024 part of chromotropic dye TB
34.0 parts of ethylene glycol monomethyl ethers
Measure every performance as the method for example one, the result charges to table one.
Table one
Annotate:
1. the printing down of ultraviolet printer is used in light sensitivity test, develops with magnificent light PD-1 developer solution, dilution in 1: 6,23 ± 2 ℃ of developments 1 minute, and UGLA step-wedge bar three extremely totally is considered as standard;
2. the alkali resistant loss percentage is used magnificent light PD-1 developer solution, dilution in 1: 4, and 25 ℃ are soaked test in 2 minutes;
3. after weak base development tolerance is used magnificent light PD-1 developer solution dilution, 23 ± 2 ℃ of tests down;
4. cancellation layout seal performance is used the layout of 0.1mm layout sheet base, doubles exposure by annotating a condition sensitivity, and normal development is observed and removed layout seal performance then, and it be excellent going clean substantially, during slight residual is, heavier residual be poor.
As can be seen from Table I, the positive PS printing plate light sensitive degree height that photosensitive composition of the present invention is made, site reducing property brilliance, anti-highly basic development are excellent, weak base development tolerance big, cancellation layout seal performance is outstanding, and can obtain long seal journey.
Claims (6)
1, a kind of positive PS printing plate light sensitive composition, it is characterized in that: it comprises: one or more lacquer resin, one or more interpolation resin, one or more modified phenolic resin, one or more optical light sensitive adhesive, one or more dyestuff, one or more solvent, with following structural formula I and II compound
Structure I hydantoin derivative structure I I benzoic acid derivative
Wherein
In the compound in structural formula I:
R1 represents aromatic group;
R2 represents O or S atom;
R3 represents hydrogen atom or alkyl;
R4 represents O or S atom;
R5 represents alkyl or alkoxy base;
In the compound of structural formula II:
R1, R2, R3, R4 represent hydrogen atom, hydroxyl or carboxylic group;
The 1,2,3,-thrihydroxy-benzene condensation of acetone resin that described interpolation resin is a low polymerization degree has following structure:
Compound III
N represents 2-10;
Described modified phenolic resin is modification tertiary butyl phenol urea formaldehyde or rosin modified phenolic resin; Described optical light sensitive adhesive is the graft resin of 2-nitrine-1-naphthoquinones-5-sulfonic acid chloride and 1,2,3,-thrihydroxy-benzene condensation of acetone resin.
The compound of described structural formula II is 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxy-benzoic acid, 3,5-dihydroxy-benzoic acid, 2,4-dihydroxy-benzoic acid, 3,4, the 5-trihydroxybenzoic acid, any;
Remember that by weight percentage the consumption of lacquer resin is 40%～80%; Add resin demand and account for 1%～10% of total solid film forming matter; The phenol-formaldehyde resin modified consumption accounts for 5%～20% of total solid film forming matter; Photosensitive resin consumption use amount in photosensitive composition is 10-40%, and dye dosage accounts for 1%～5% of total solid film forming matter; The compound in structural formula I consumption accounts for 1%～10% of total solid film forming matter; The compound amount of structural formula II accounts for 1%～5% of total solid film forming matter.
2, positive PS printing plate light sensitive composition according to claim 1, it is characterized in that described linear phenolic resin is one or more in phenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol-formaldehyde resin, phenol-tertiary butyl phenol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, the metacresol-orthoresol-formaldehyde resin.
3, positive PS printing plate light sensitive composition according to claim 1 and 2 is characterized in that, described dyestuff is one or more in Victoria's ethereal blue, alkaline bright blue, solvent blue, crystal violet, methyl violet, the methylene blue.
4, positive PS printing plate light sensitive composition according to claim 1 and 2 is characterized in that, described solvent adopts one or more in ether solvent, esters solvent, ketones solvent, the heterocyclic solvent.
5, positive PS printing plate light sensitive composition according to claim 1 and 2, it is characterized in that: in the described compound in structural formula I: R1 represents in phenyl, benzyl, phenethyl, the benzyl group one, R2 and R4 represention oxygen atom, R3 represents hydrogen atom, arbitrary group in R5 represent methylidene, ethyl, methoxyl, the ethoxy.
6, positive PS printing plate light sensitive composition according to claim 1 and 2, it is characterized in that compound in structural formula I is in 1-phenyl-5-methyl hydantoin, 1-benzyl-5-methoxyl glycolylurea, 1-benzyl-5-ethoxy glycolylurea or the 1-phenethyl-5-ethylhydantoin any.
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