CN114671988A - Multifunctional group-containing substituted benzyl phenolic aldehyde polymer and preparation method and application thereof - Google Patents
Multifunctional group-containing substituted benzyl phenolic aldehyde polymer and preparation method and application thereof Download PDFInfo
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- CN114671988A CN114671988A CN202011548885.0A CN202011548885A CN114671988A CN 114671988 A CN114671988 A CN 114671988A CN 202011548885 A CN202011548885 A CN 202011548885A CN 114671988 A CN114671988 A CN 114671988A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- -1 benzyl phenolic aldehyde Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 66
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 51
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 9
- 150000002431 hydrogen Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 14
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims 1
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 7
- 230000036211 photosensitivity Effects 0.000 abstract description 7
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 24
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 14
- 150000002931 p-cresols Chemical class 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 12
- 150000002672 m-cresols Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- ZYPDJSJJXZWZJJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-piperidin-4-yloxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCNCC1 ZYPDJSJJXZWZJJ-UHFFFAOYSA-N 0.000 description 1
- YLSVTHSRAUMJIG-UHFFFAOYSA-N 6-diazo-5,8-dioxonaphthalene-1-sulfonic acid Chemical compound O=C1C(=[N+]=[N-])CC(=O)C2=C1C=CC=C2S(=O)(=O)O YLSVTHSRAUMJIG-UHFFFAOYSA-N 0.000 description 1
- QDXTUXGPJHGOOD-UHFFFAOYSA-N C=O.C(C1=CC=CC=C1)C1=C(C=CC=C1)O Chemical class C=O.C(C1=CC=CC=C1)C1=C(C=CC=C1)O QDXTUXGPJHGOOD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a polyfunctional group-containing substituted benzyl phenolic aldehyde polymer, and a preparation method and application thereof. The phenolic polymer has a structure represented by formula (1):
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a multifunctional group-containing substituted benzyl phenolic aldehyde polymer and a preparation method and application thereof.
Background
The phenolic resin belongs to thermoplastic resin, and can be widely applied to the fields of IC, LSI, Liquid Crystal Display (LCD), printed circuit board manufacturing and the like as an important component of a typical ultraviolet photoresist composition due to the easily available raw materials, low price, good molding manufacturability, regular structure and excellent mechanical property and heat resistance. In recent years, semiconductor devices have been highly integrated, patterns have been further thinned, and various heat treatments have been performed in the production process of semiconductors and the like, and these heat treatments have not been applied to some cases where heat resistance is required, and how to improve the heat resistance of phenol resins has become an important trend in the industry.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a multifunctional group substituted benzyl phenolic aldehyde polymer and a preparation method and application thereof, through special design of a molecular structure and introduction of a benzene ring, the heat resistance of the polymer is obviously improved, good photosensitivity is kept, and the photoresist composition containing the benzyl structural unit-containing phenolic aldehyde polymer has excellent developability and thermal stability.
One of the objects of the present invention is to provide a polyfunctional group-containing substituted benzyl phenol-formaldehyde polymer having a structure represented by the following formula (1):
wherein,R1、R2、R3、R4、R5、R6each independently represents any one of hydrogen, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, or an arylcarbonyl group; preferably, R1、R2、R3、R4、R5、R6Each independently is any one of hydrogen, halogen atom, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkenyl, C6-C25 aryl, C6-C25 aralkyl, C1-C15 alkoxycarbonyl or C6-C25 arylcarbonyl; more preferably, R2、R3Not hydrogen at the same time.
Ar1、Ar2、Ar3、Ar4Is an aryl group; ar (Ar)1Is (m)1+n1+2) or less valent aryl, Ar2Is (m)2+n2+3) or lower aryl, Ar3Is (m)3+n3+2) or less valent aryl, Ar4Is an aryl group having a valence of (y + z +1) or less.
m1、m2、m3Respectively represent with Ar1、Ar2、Ar3Number of bonded hydroxyl groups, m1、m2、m3Is an integer of 1 to 3;
n1、n2、n3respectively represent with Ar1、Ar2、Ar3Bonded R1、R5、R4Number of (2), n1、n2、n3Is an integer of 1 to 3; n is1+m1+2 is the number of Ar1 bonds and below, n2+m2+3 is the number of Ar2 bonds and below, n3+m3+2 is the number of Ar3 bonds and below.
z and y are each independently of Ar4Bonded R2、R3The number of the groups, z and y are integers of 1-3;
a. b and c are positive integers larger than zero.
In the polymer of the present application, R1、R2、R3、R4、R5、R6Without limitation, independently any one or more of hydrogen, halogen, alkyl, alkoxy (including methoxy, ethoxy, propoxy, butoxy), alkenyl (including ethenyl, propenyl, butenyl), aryl (including phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl), aralkyl (including benzyl, phenethyl, phenylpropyl), alkoxycarbonyl (including methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl), arylcarbonyl (including phenylcarbonyl, tolylcarbonyl, ethylphenyloxycarbonyl), and the like; wherein R is1Or R4Which may be identical or different, R1Or R4May be, for example, in the 2,3,4, 5, 6 position of the phenyl ring, etc., more preferably, R1、R4、R5Is methyl.
The second purpose of the invention is to provide a preparation method of the multifunctional group-containing substituted benzyl phenolic aldehyde polymer, which comprises the following steps:
a) reacting a compound shown in a formula (2) with a compound shown in a formula (3) to obtain a compound shown in a formula (4);
b) mixing a compound shown in a formula (4), a compound shown in a formula (5) and a compound shown in a formula (6), and reacting with a compound shown in a formula (7) or an aqueous solution thereof under the action of an acid catalyst;
c) adding an organic solvent into the mixture obtained in the step b), heating, and then carrying out atmospheric distillation and reduced pressure distillation to obtain the phenolic aldehyde polymer;
wherein, in the formulas (2), (3), (4), (5), (6) and (7), R1、R2、R3、R4、R5、R6Each independently is any one of hydrogen, halogen atom, alkyl group, alkoxy group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group or arylcarbonyl group; preferably, R1、R2、R3、R4、R5、R6Independently of each other, hydrogen, halogen, C1EAny one of C15 alkyl, C1-C15 alkoxy, C1-C15 alkenyl, C6-C25 aryl, C6-C25 aralkyl, C1-C15 alkoxycarbonyl or C6-C25 arylcarbonyl.
Ar1、Ar2、Ar3、Ar4Is aryl;
m1、m2、m3respectively represent with Ar1、Ar2、Ar3Number of bonded hydroxyl groups, m1、m2、m3Is an integer of 1 to 3;
n1、n2、n3respectively represent with Ar1、Ar2、Ar3Bonded R1、R5、R4Number of (2), n1、n2、n3Is an integer of 1 to 3;
z and y are each independently of Ar4Bonded R2、R3The number z and y are integers of 1-3.
In the polymer of the present application, R1、R2、R3、R4、R5、R6Without limitation, independently any one or more of hydrogen, halogen, alkyl, alkoxy (including methoxy, ethoxy, propoxy, butoxy), alkenyl (including ethenyl, propenyl, butenyl), aryl (including phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl), aralkyl (including benzyl, phenethyl, phenylpropyl), alkoxycarbonyl (including methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl), arylcarbonyl (including phenylcarbonyl, tolylcarbonyl, ethylphenyloxycarbonyl), and the like; wherein R is1Or R4Which may be identical or different, R1Or R4May be, for example, in the 2,3,4, 5, 6 position of the phenyl ring, etc., more preferably, R1、R4、R5Is methyl.
Wherein the compound represented by the formula (5) and the compound represented by the formula (6) may be the same or different.
The preparation process according to the invention is preferably carried out under a nitrogen atmosphere.
In the step a), the molar ratio of the compound shown in the formula (2) to the compound shown in the formula (3) is (0.5-1.2): 1, preferably (0.6-1): 1.
in the step a), the reaction temperature is 120-180 ℃, for example, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ and the like.
In the step a), the reaction time is 1-24 hours; preferably 6-12 h.
In the step b), the ratio of the total molar amount of the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6) to the molar amount of the compound represented by the formula (7) is (1-4): 1, preferably (1.2-3): 1.
in the step b), the molar ratio of the compound of formula (4), the compound of formula (5) and the compound of formula (6) is not particularly limited, and may preferably be (1 to 4): (1-4): (1-4), more preferably (1-2): (1-2): (1-2).
In the step b), the acidic catalyst is one or more of oxalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, p-toluenesulfonic acid, petroleum sulfonic acid, citric acid and the like; preferably, it is oxalic acid.
The acid catalyst is 0.05-5% of the total mass of the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6), and preferably 0.05-0.5%.
In the step b), the compound of formula (7) may be any one of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, valeraldehyde, caproaldehyde, benzaldehyde, phenylacetaldehyde and the like, or a mixture of two or more of them; preferably, it is formaldehyde.
In the step b), the reaction temperature is 80-120 ℃; for example, 90 ℃, 100 ℃, 110 ℃, etc.
In the step b), the reaction time is 1-12 h; preferably, the time is 3-6 h.
In the step c), the organic solvent is an organic solvent which is difficult to dissolve in water, and is selected from one or more of N, N-Dimethylacetamide (DMAC), Dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), methanesulfonic acid (MSA), m-cresol, p-cresol, N-Dimethylpropyleneurea (DMPU), Diphenylsulfone (DPSO), propylene glycol monomethyl ether acetate, toluene, xylene and the like.
The amount of the organic solvent is 0.2 to 10 times, preferably 0.3 to 5 times of the total mass of the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6).
In the step c), heating to 80-120 ℃.
In the step c), the temperature of the atmospheric distillation is 100-160 ℃.
In the step c), the temperature of the reduced pressure distillation is 200-250 ℃; specifically, the temperature may be 210 ℃, 220 ℃, 230 ℃, 240 ℃ or the like.
In the step c), the pressure of the reduced pressure distillation is-0.07 MPa to-0.1 MPa; specifically, it may be-0.08 MPa, -0.09MPa, -0.1MPa or the like.
In one embodiment, the steps of the preparation method may specifically be as follows:
1) under a nitrogen atmosphere, reacting a compound shown as a formula (2) with a compound shown as a formula (3) to prepare a compound shown as a formula (4), wherein the reaction conditions are as follows: heating to 120-180 ℃, and reacting for 1-24 hours;
2) mixing the compound shown in the formula (4), the compound shown in the formula (5) and the compound shown in the formula (6) obtained in the step 1) according to a ratio, adding an acid catalyst and the compound shown in the formula (7) or an aqueous solution thereof, and heating to react, wherein the reaction conditions are as follows: reacting for 1-12 h at 80-120 ℃.
3) Adding an organic solvent which is insoluble in water into a reaction container, stirring, heating to 80-120 ℃, setting the oil bath temperature at 80-100 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) distilling at 100-160 ℃ under normal pressure to remove water and organic solvent, heating to 200-250 ℃, and distilling under reduced pressure at-0.07 MPa to-0.1 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
The invention also aims to provide a multifunctional group-containing substituted benzyl phenolic aldehyde polymer obtained by the preparation method.
The fourth purpose of the invention is to provide the application of the multifunctional group-containing substituted benzyl phenolic aldehyde polymer or the multifunctional group-containing substituted benzyl phenolic aldehyde polymer obtained by the preparation method in serving as a component of a positive photoresist composition.
The phenolic polymer positive photoresist composition can be used in the fields of IC, LSI, Liquid Crystal Display (LCD), printed circuit board manufacturing and the like, and endows the positive photoresist composition with better thermal stability and good photosensitivity.
The invention has the beneficial effects that: the benzyl phenolic aldehyde polymer containing the multifunctional group substitution is alkali soluble resin, and through special design of a molecular structure and introduction of a benzyl structure, particularly the benzyl structure with a side chain structure, the heat resistance and the stability of the resin are remarkably improved, and good photosensitivity is kept. The photoresist composition containing the phenolic aldehyde polymer has excellent thermal stability, and can fully meet the stability requirement of multiple high-temperature baking processes of the photoresist in the processing process.
Detailed Description
The present invention is further described with reference to specific examples in order to better understand the invention and to better demonstrate the beneficial effects of the present invention. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the teachings herein.
The starting materials used in the embodiments of the present invention are commercially available.
Example 1
1) Under a nitrogen atmosphere, mixing 94g of phenol and 276g of dodecyl benzyl alcohol according to a molar ratio of 1: 1 to obtain substituted phenol, wherein the reaction conditions are as follows: heating to 130 ℃, and reacting for 5 hours;
2) 350g of the substituted phenol obtained in the step 1), 108g of m-cresol and 108g of p-cresol are mixed, 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) are added as catalysts, and the mixture is heated to react, wherein the reaction conditions are as follows: reacting for 3 hours at 90 ℃;
3) adding 200g of toluene into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 120 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating the mixture from 100 ℃ to 160 ℃, distilling the mixture under normal pressure to remove water and toluene, heating the mixture to 210 ℃, and distilling the mixture under reduced pressure of-0.08 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 2
1) Under a nitrogen atmosphere, mixing 108g of m-cresol and 276g of dodecyl benzyl alcohol according to a molar ratio of 1: 1 to obtain substituted m-cresol, wherein the reaction conditions are as follows: heating to 130 ℃, and reacting for 5 hours;
2) 370g of the substituted m-cresol obtained in the step 1), 108g of m-cresol and 108g of p-cresol are mixed, 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) are added as catalysts, and the mixture is heated to react under the following conditions: reacting for 4 hours at 90 ℃;
3) adding 200g of toluene into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 120 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating the mixture from 100 ℃ to 160 ℃, distilling the mixture under normal pressure to remove water and toluene, heating the mixture to 220 ℃, and distilling the mixture under reduced pressure of-0.08 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 3
1) Under a nitrogen atmosphere, mixing 108g of p-cresol and 276g of dodecyl benzyl alcohol according to a molar ratio of 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 140 ℃ and reacting for 4 hours;
2) 370g of the substituted p-cresol obtained in the step 1), 108g of m-cresol and 108g of p-cresol are mixed, and 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) are added as catalysts, and the mixture is heated to react under the following conditions: reacting for 3 hours at 95 ℃;
3) adding 200g of dimethylbenzene into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 120 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling under normal pressure to remove water and xylene, heating to 220 ℃, and distilling under reduced pressure of-0.09 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 4
1) Under a nitrogen atmosphere, a mixture of 108g of p-cresol and 276g of dodecylbenzyl alcohol was stirred in the following ratio 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 120 ℃, and reacting for 3 hours; prepared from 108g of m-cresol and 276g of dodecylbenzyl alcohol according to a molar ratio of 1: 1 to obtain substituted m-cresol, wherein the reaction conditions are as follows: heating to 120 ℃, and reacting for 3 hours;
2) mixing 135g of the substituted p-cresol obtained in the step 1), 135g of the substituted m-cresol obtained in the step 1), 108g of the m-cresol and 108g of the p-cresol, adding 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35 percent) as catalysts, and heating for reaction under the following reaction conditions: reacting for 3 hours at 95 ℃;
3) adding 200g of m-cresol into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 120 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling under normal pressure to remove water and m-cresol, heating to 220 ℃, and distilling under reduced pressure under the pressure of-0.08 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 5
1) Under nitrogen atmosphere, mixing 108g of p-cresol with 276g of 2, 4-dihexylbenzyl alcohol according to a molar ratio of 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 170 ℃ and reacting for 3 hours;
2) 370g of the substituted p-cresol obtained in the step 1), 108g of m-cresol and 108g of p-cresol are mixed, and 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) are added as catalysts, and the mixture is heated to react under the following conditions: reacting for 3 hours at 90 ℃;
3) adding 200g of p-cresol into a reaction vessel, stirring, heating to 90 ℃, setting the oil bath temperature at 100 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling under normal pressure to remove moisture and p-cresol, heating to 230 ℃, and distilling under reduced pressure of-0.07 Pa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 6
1) Under nitrogen atmosphere, mixing 108g of m-cresol with 276g of 2, 4-dihexylbenzyl alcohol according to a molar ratio of 1: 1 to obtain substituted m-cresol, wherein the reaction conditions are as follows: heating to 140 ℃ and reacting for 4 hours;
2) 370g of the substituted m-cresol obtained in the step 1), 108g of m-cresol and 108g of p-cresol are mixed, 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) are added as catalysts, and the mixture is heated to react under the following conditions: the reaction was carried out at 90 ℃ for 3 h.
3) Adding 200g of propylene glycol monomethyl ether acetate into a reaction vessel, stirring, heating to 120 ℃, setting the oil bath temperature at 120 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating the mixture from 100 ℃ to 160 ℃, distilling the mixture under normal pressure to remove water and propylene glycol monomethyl ether acetate, heating the mixture to 210 ℃, and distilling the mixture under reduced pressure at the pressure of-0.09 Pa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 7
1) Under nitrogen atmosphere, mixing 108g of p-cresol with 276g of 2, 4-dihexylbenzyl alcohol according to a molar ratio of 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 130 ℃, and reacting for 3 hours;
2) 370g of the substituted p-cresol obtained in the step 1), 94g of phenol and 108g of p-cresol are mixed, and 1.7g of oxalic acid dihydrate and 180g of aqueous formaldehyde solution (the formaldehyde content is 35%) as catalysts are added, and the mixture is heated to react under the following conditions: reacting for 3 hours at 90 ℃;
3) adding 200g of propylene glycol monomethyl ether acetate into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 110 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling under normal pressure to remove water and propylene glycol monomethyl ether acetate, heating to 210 ℃, and distilling under reduced pressure under the pressure of-0.07 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 8
1) Under nitrogen atmosphere, 108g of p-cresol and 276g of 2, 4-dihexylbenzyl alcohol are mixed according to the molar ratio of 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 150 ℃, and reacting for 3 hours; prepared from 108g of m-cresol and 276g of 2, 4-dihexylbenzyl alcohol according to a molar ratio of 1: 1 to obtain substituted m-cresol, wherein the reaction conditions are as follows: heating to 150 ℃, and reacting for 3 hours;
2) mixing 92.5g of the substituted p-cresol obtained in the step 1), 92.5g of the substituted m-cresol obtained in the step 1), 108g of m-cresol and 108g of p-cresol, adding 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) as catalysts, and heating for reaction under the reaction conditions that: reacting for 4 hours at 90 ℃;
3) adding 200g of toluene into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 110 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling under normal pressure to remove water and toluene, heating to 205 ℃, and distilling under reduced pressure of-0.09 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 9
1) Under nitrogen atmosphere, mixing 108g of p-cresol and 360g of 2, 4, 6-trihexylphenylmethanol according to a molar ratio of 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 130 ℃ and reacting for 2 hours; prepared from 108g of m-cresol and 276g of 2, 4-dihexylbenzyl alcohol according to a molar ratio of 1: 1 to obtain substituted m-cresol, wherein the reaction conditions are as follows: heating to 130 ℃, and reacting for 2 hours;
2) mixing 115g of the substituted p-cresol obtained in the step 1), 108g of the substituted m-cresol obtained in the step 1), 92.5g of the m-cresol and 108g of the p-cresol, adding 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35 percent) as catalysts, and heating for reaction under the following reaction conditions: reacting for 2 hours at 95 ℃;
3) adding 200g of dimethylbenzene into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 110 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling at normal pressure to remove water and xylene, heating to 230 ℃, and distilling under reduced pressure of-0.07 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Example 10
1) Under nitrogen atmosphere, mixing 108g of p-cresol and 360g of 2, 4, 6-trihexylphenylmethanol according to a molar ratio of 1: 1 to obtain the substituted p-cresol, wherein the reaction conditions are as follows: heating to 130 ℃, and reacting for 2 hours;
2) mixing 115g of the substituted p-cresol obtained in the step 1), 170g of o-phenylphenol and 108g of m-cresol, adding 1.7g of oxalic acid dihydrate and 180g of formaldehyde aqueous solution (the formaldehyde content is 35%) as catalysts, and heating to perform reaction under the following reaction conditions: reacting for 2 hours at 95 ℃;
3) adding 200g of dimethylbenzene into a reaction vessel, stirring, heating to 110 ℃, setting the oil bath temperature at 110 ℃, stirring for half an hour, standing for layering, and removing a water layer;
4) heating from 100 ℃ to 160 ℃, distilling at normal pressure to remove water and xylene, heating to 230 ℃, and distilling under reduced pressure of-0.07 MPa to remove residual monomer phenol; pouring out the molten resin in the reaction vessel to obtain the multi-functional group substituted benzyl phenolic polymer.
Comparative example 1
1)108g of p-cresol and 108g of m-cresol, adding 1.7g of oxalic acid dihydrate serving as a catalyst, heating, slowly adding 105.4g of 35% formaldehyde aqueous solution, and reacting for 3 hours at 100 ℃;
2) adding methyl isobutyl ketone organic solvent into a reaction vessel, stirring, heating to 100 ℃, adding pure water into the reaction vessel, setting the oil bath temperature at 90 ℃, stirring for half an hour, standing for layering, and removing a water layer;
3) heating to 160 deg.C from 100 deg.C, distilling under normal pressure to remove water and organic solvent, heating to 210 deg.C, and distilling under-0.1 Mpa to remove residual monomer phenol; the molten resin was poured out to obtain a cresol-formaldehyde resin.
Comparative example 2
1)108g of p-cresol and 108g of m-cresol, 2.16g of o-phenylphenol, 1.7g of oxalic acid dihydrate as a catalyst are added, heated, 105.4g of 35 percent formaldehyde aqueous solution is slowly added, and the mixture reacts for 3 hours at the temperature of 100 ℃;
2) raising the temperature, increasing the nitrogen flow rate to 1ml/s, and removing the moisture in the reaction system under normal pressure; and (3) after the temperature of the reaction system rises to 160 ℃, starting a vacuum pump, stripping the incompletely reacted phenol monomers in the system under reduced pressure with the vacuum degree of-0.1 MPa, continuously heating to 200 ℃, keeping for 2 hours, stopping vacuumizing after the phenol monomers in the system are completely stripped, and discharging to obtain the finished product of the phenolic resin.
The examples 1 to 10 and comparative examples 1 to 2 were subjected to performance tests:
alkali dissolution rate test: dissolving the phenolic aldehyde polymer containing the benzyl structure unit obtained in the example and the resin obtained in the comparative example in propylene glycol monomethyl ether acetate respectively to prepare a PGMEA solution of the resin with the solid content of 25 percent; secondly, coating the propylene glycol methyl ether acetate solution of the resin on a diameter silicon wafer, and then putting the silicon wafer on a rotary coating machine for spin coating to form a film, wherein the rotating speed is 3000r/min, and the film thickness is controlled to be 2-3 mu m; thirdly, placing the silicon wafer coated with the film-forming resin on a glue drier at 100 ℃ for baking for 90s to remove the solvent, and then testing the accurate film thickness; soaking the silicon chip coated with the phenolic resin film in a developing solution (2.38 mass percent of tetramethylammonium hydroxide solution) for dissolving, and recording the dissolving time.
And (3) testing the photosensitivity: the phenolic polymer obtained in the example and 25 parts by mass of the resin obtained in the comparative example are respectively added into 70 parts by mass of PGMEA, mixed and dissolved to obtain a solution, then 5 parts by mass of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate photosensitizer is added, mixed and dissolved to obtain a positive photoresist composition, and the energy for completely dissolving the photoresist film layer is measured for 1min at 23 ℃ and 0.4-0.6% NaOH according to the change of exposure energy, and the photosensitive data is obtained by carrying out development under spraying or dipping.
And (3) testing the glass transition temperature: using differential scanning calorimetry, N2The flow is 50mL/min, the heating rate is 20 ℃/min, the first heating is 40-100 ℃, the second heating temperature scanning range is 40-200 ℃, the glass transition temperature (Tg) of the polymer is measured, and a second heating curve is used for testing the Tg.
The test results are shown in table 1 below:
table 1 results of performance tests of examples 1 to 6 and comparative example 1
| Experiment number | Photosensitivity (Eth (mj/cm)2)) | Rate of alkaline dissolution (Angstrom/sec) | Glass transition temperature (. degree. C.) |
| Example 1 | 9 | 740 | 133 |
| Example 2 | 10 | 783 | 137 |
| Example 3 | 9 | 774 | 136 |
| Example 4 | 10 | 723 | 139 |
| Example 5 | 11 | 535 | 148 |
| Example 6 | 9 | 802 | 143 |
| Example 7 | 8 | 803 | 121 |
| Example 8 | 11 | 656 | 138 |
| Example 9 | 9 | 781 | 127 |
| Example 10 | 9 | 701 | 130 |
| Comparative example 1 | 8 | 878 | 105 |
| Comparative example 2 | 9 | 869 | 115 |
As can be seen from the results of the above-mentioned tests, the phenolic polymers containing benzyl structures synthesized in examples 1 to 10 have better heat resistance and higher alkali dissolution rate than the resins of the comparative examples, maintain good photosensitivity, and have better application value in the fields of IC, LSI, liquid crystal display, printed circuit board manufacture, etc.
The protection content of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (10)
1. A polyfunctional group-containing substituted benzyl phenol aldehyde polymer has a structure represented by the following formula (1):
wherein R is1、R2、R3、R4、R5、R6Each independently is any one of hydrogen, halogen atom, alkyl group, alkoxy group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group or arylcarbonyl group; preferably, R1、R2、R3、R4、R5、R6Independently represent hydrogen, halogen atom, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkenyl, C6EAny one of C25 aryl, C6-C25 aralkyl, C1-C15 alkoxycarbonyl or C6-C25 arylcarbonyl;
Ar1、Ar2、Ar3、Ar4is aryl;
m1、m2、m3respectively represent with Ar1、Ar2、Ar3Number of bonded hydroxyl groups, m1、m2、m3Is an integer of 1 to 3;
n1、n2、n3respectively represent with Ar1、Ar2、Ar3Bonded R1、R5、R4Number of (2), n1、n2、n3Is an integer of 1 to 3;
z and y are each independently of Ar4Bonded R2、R3The number z and y are integers of 1-3;
a. b and c are positive integers larger than zero.
2. A method of preparing the phenolic polymer of claim 1, comprising the steps of:
a) reacting a compound shown in a formula (2) with a compound shown in a formula (3) to obtain a compound shown in a formula (4);
b) mixing a compound shown in a formula (4), a compound shown in a formula (5) and a compound shown in a formula (6), and reacting with a compound shown in a formula (7) or an aqueous solution thereof under the action of an acid catalyst;
c) adding an organic solvent into the mixture obtained in the step b), heating, and then carrying out atmospheric distillation and reduced pressure distillation to obtain the phenolic aldehyde polymer;
wherein R is1、R2、R3、R4、R5、R6Each independently hydrogen, halogen, alkyl, alkoxy, alkenyl, aryl, aralkyl, alkoxycarbonyl, or arylAny one of an alkylcarbonyl group;
Ar1、Ar2、Ar3、Ar4is an aryl group;
m1、m2、m3respectively represent with Ar1、Ar2、Ar3Number of bonded hydroxyl groups, m1、m2、m3Is an integer of 1 to 3;
n1、n2、n3respectively represent with Ar1、Ar2、Ar3Bonded R1、R5、R4Number of (2), n1、n2、n3Is an integer of 1 to 3;
z and y are each independently of Ar4Bonded R2、R3The number z and y are integers of 1-3.
3. The method for producing a phenol-based polymer according to claim 2, characterized in that:
in the step a), the molar ratio of the compound shown in the formula (2) to the compound shown in the formula (3) is (0.5-1.2): 1, preferably (0.6-1): 1; and/or the presence of a gas in the gas,
the reaction temperature is 120-180 ℃; and/or the presence of a gas in the gas,
the reaction time is 1-24 h.
4. The method for producing a phenolic polymer according to claim 2, characterized in that:
in the step b), the ratio of the total molar amount of the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6) to the molar amount of the compound represented by the formula (7) is (1-4): 1, preferably (1.2-3): 1.
5. the method for producing a phenol-based polymer according to claim 2, characterized in that:
in the step b), the acidic catalyst is one or more of oxalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, p-toluenesulfonic acid, petroleum sulfonic acid and citric acid; and/or the presence of a gas in the gas,
the acid catalyst is 0.05-5% of the total mass of the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6), and preferably 0.05-0.5%.
6. The method for producing a phenolic polymer according to claim 2, characterized in that:
in the step b), the reaction temperature is 80-120 ℃; and/or the presence of a gas in the gas,
the reaction time is 1-12 h.
7. The method for producing a phenol-based polymer according to claim 2, characterized in that:
in the step c), the organic solvent is one or more of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, methanesulfonic acid, toluene, xylene, m-cresol, p-cresol, N-dimethylpropyleneurea, diphenylsulfone and propylene glycol monomethyl ether acetate; and/or the presence of a gas in the gas,
the amount of the organic solvent is 0.2 to 10 times, preferably 0.3 to 5 times of the total mass of the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6).
8. The method for producing a phenol-based polymer according to claim 2, characterized in that:
in the step c), heating to 80-120 ℃; and/or the presence of a gas in the gas,
the temperature of the atmospheric distillation is 100-160 ℃; and/or the presence of a gas in the gas,
the temperature of the reduced pressure distillation is 200-250 ℃, and the pressure of the reduced pressure distillation is-0.07 MPa-0.1 MPa.
9. The multifunctional group-containing substituted benzyl phenol aldehyde polymer obtained by the preparation method according to any one of claims 2 to 8.
10. Use of the phenolic polymer according to claim 1 or the phenolic polymer obtained by the process according to any one of claims 2 to 8 as a component of a positive photoresist composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| JP2001002745A (en) * | 1999-04-22 | 2001-01-09 | Arakawa Chem Ind Co Ltd | Production of methoxy group-bearing silane-modified phenol resin |
| JP2001329034A (en) * | 2000-05-22 | 2001-11-27 | Sumitomo Bakelite Co Ltd | Production method for phenol resin |
| JP2007121873A (en) * | 2005-10-31 | 2007-05-17 | Fujifilm Corp | Photosensitive resin composition and method for producing semiconductor device using the same |
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| CN102827347A (en) * | 2011-06-15 | 2012-12-19 | 中国石油化工集团公司 | Method for synthesizing ultra-pure o-cresol formaldehyde epoxy resin at low temperature |
| CN111154053A (en) * | 2020-01-06 | 2020-05-15 | 苏州瑞红电子化学品有限公司 | High-heat-resistance carboxyl phenolic resin and synthetic method thereof |
| CN111303362A (en) * | 2018-12-12 | 2020-06-19 | 上海飞凯光电材料股份有限公司 | Phenolic resin, preparation method thereof and photoresist |
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| JP2001002745A (en) * | 1999-04-22 | 2001-01-09 | Arakawa Chem Ind Co Ltd | Production of methoxy group-bearing silane-modified phenol resin |
| JP2001329034A (en) * | 2000-05-22 | 2001-11-27 | Sumitomo Bakelite Co Ltd | Production method for phenol resin |
| JP2007121873A (en) * | 2005-10-31 | 2007-05-17 | Fujifilm Corp | Photosensitive resin composition and method for producing semiconductor device using the same |
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