CN114133572A - Photosensitive organic silicon resin, preparation method and application - Google Patents
Photosensitive organic silicon resin, preparation method and application Download PDFInfo
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- CN114133572A CN114133572A CN202210008733.4A CN202210008733A CN114133572A CN 114133572 A CN114133572 A CN 114133572A CN 202210008733 A CN202210008733 A CN 202210008733A CN 114133572 A CN114133572 A CN 114133572A
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- siloxane
- photoinitiator
- pdms
- catalyst
- resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 37
- 239000011347 resin Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 33
- 229910052710 silicon Inorganic materials 0.000 title claims description 33
- 239000010703 silicon Substances 0.000 title claims description 33
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 38
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 38
- 229920002050 silicone resin Polymers 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- -1 isocyanatosiloxane Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract 12
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract 12
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims abstract 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- 239000004925 Acrylic resin Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 125000005376 alkyl siloxane group Chemical group 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-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
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- JUVLPJNXBKOSFH-UHFFFAOYSA-N 2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C1=CC(C(=O)C(N(C)C)CC)=CC=C1N1CCOCC1 JUVLPJNXBKOSFH-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- QZUFYZAIYPHVTL-UHFFFAOYSA-L diacetyloxy(butyl)tin Chemical compound CCCC[Sn](OC(C)=O)OC(C)=O QZUFYZAIYPHVTL-UHFFFAOYSA-L 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 17
- 230000003373 anti-fouling effect Effects 0.000 abstract description 9
- 230000003666 anti-fingerprint Effects 0.000 abstract description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract 1
- 238000013517 stratification Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- 229940079593 drug Drugs 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
本发明提供一种感光有机硅树脂、制备方法及应用，属于感光分子材料技术领域。将光引发剂和催化剂I溶解在溶剂I中，加异氰酸酯基硅氧烷，升温搅拌反应，正己烷洗涤后，减压蒸馏得硅氧烷化光引发剂；将羟基封端的PDMS、异氰酸酯基硅氧烷、催化剂I和溶剂II混合，升温搅拌反应，乙腈洗涤后，减压蒸馏得硅氧烷化PDMS；将硅氧烷化光引发剂、硅氧烷化PDMS、烷烃基硅氧烷和溶剂III混合，升温至40℃～60℃，加催化剂II和去离子水的混合物，加六甲基二硅氧烷，静置分层后取下层，减压蒸馏得到感光有机硅树脂。制备方法简单易控制，感光有机硅树脂表面能低、硬度高，用于制备涂层，防污和耐指纹。The invention provides a photosensitive organosilicon resin, a preparation method and an application, and belongs to the technical field of photosensitive molecular materials. Dissolve the photoinitiator and catalyst I in solvent I, add isocyanatosiloxane, heat up and stir to react, after washing with n-hexane, distill under reduced pressure to obtain a siloxane photoinitiator; the hydroxyl-terminated PDMS, isocyanatosiloxane Oxane, catalyst I and solvent II are mixed, heated and stirred for reaction, washed with acetonitrile, and distilled under reduced pressure to obtain siloxane PDMS; Mix III, heat up to 40°C to 60°C, add a mixture of catalyst II and deionized water, add hexamethyldisiloxane, stand for stratification, remove the lower layer, and distill under reduced pressure to obtain a photosensitive silicone resin. The preparation method is simple and easy to control, and the photosensitive organosilicon resin has low surface energy and high hardness, and is used for preparing a coating, which is anti-fouling and anti-fingerprint.
Description
Technical Field
The invention belongs to the technical field of photosensitive molecular materials, and particularly relates to photosensitive organic silicon resin, a preparation method and application thereof.
Background
The ultraviolet curing technology has more and more attention due to the unique advantages of room temperature curing, wide adaptability, low energy consumption, high efficiency, environmental protection and the like, and is widely applied to the fields of coatings, printing ink, adhesives, microelectronics, tooth restoration and the like.
Ultraviolet light cured coatings often have poor antifouling performance, are easily contaminated by aqueous and oily stains, and are difficult to clean. Fluorine-or silicon-containing components are often grafted into the polymer to improve the stain resistance durability of the coating. Although the fluorine-containing component has an excellent antifouling effect, the application of the fluorine-containing component is limited by the high cost, high toxicity and biological accumulation, and an antifouling coating prepared by combining low-surface-energy, non-toxic and low-cost Polydimethylsiloxane (PDMS) and a polymer matrix has the characteristics of high light transmittance, excellent hydrophobic and oleophobic properties and the like, so that the fluorine-containing component is more suitable for practical application. The molecular chains of PDMS have very good flexibility, but the hardness of the resulting coatings after curing is often not very high.
The silicone resin prepared by the acid hydrolysis condensation method has many excellent physical and chemical properties such as high hardness, high and low temperature resistance, oxidation resistance, weather resistance and the like, and the silicone resin has more excellent wear resistance compared with polyurethane resin, epoxy resin and acrylate resin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the photosensitive organic silicon resin, the preparation method and the application, the preparation method is simple and easy to control, the prepared photosensitive organic silicon resin has the characteristics of low surface energy and high hardness, and a coating prepared by compounding the photosensitive organic silicon resin with the multifunctional acrylate resin has high hardness and also has the characteristics of antifouling and fingerprint resistance.
The invention provides a preparation method of photosensitive organic silicon resin, which solves the technical problem of how to prepare photosensitive organic silicon resin capable of being applied to coating technology, and the preparation method is simple and easy to control and comprises the following steps:
(1) preparation of siloxane photoinitiators
The photoinitiator and the catalyst I are dissolved in the solvent I, and then the isocyanate siloxane is added dropwise. Raising the temperature to 40-60 ℃, continuously stirring and reacting for 5-8 hours, washing by using n-hexane, and carrying out reduced pressure distillation to obtain a siloxane photoinitiator;
(2) preparation of siloxane PDMS
Mixing hydroxyl-terminated PDMS, isocyanate siloxane, a catalyst I and a solvent II, heating to 50-70 ℃, stirring for reaction for 5-10 hours, washing with acetonitrile, and carrying out reduced pressure distillation to obtain siloxane PDMS;
(3) preparation of photosensitive organic silicon resin
Mixing a siloxane photoinitiator, siloxane PDMS, alkyl siloxane and a solvent III, heating to 40-60 ℃, dropwise adding a mixture of a catalyst II and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-60 ℃, stirring for 5-10 hours, adding hexamethyldisiloxane, heating to 60-80 ℃, stirring for 1-3 hours, standing for layering, taking down a layer, and carrying out reduced pressure distillation to obtain photosensitive organic silicon resin;
wherein the catalyst I is one or more of dibutyltin dilaurate, stannous octoate and butyltin diacetate; the solvent I is one or more of chloroform, tetrahydrofuran and methyl ethyl ketone; the solvent II is one or more of methyl ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; the catalyst II is one or more of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; the solvent III is one or more of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran;
in one or more embodiments, the siloxane photoinitiator of step (1) has the following structure:
wherein X is a micromolecular photoinitiator with hydroxyl or amino, namely benzoin with hydroxyl or amino and derivatives thereof, benzil, alkyl benzophenones, benzophenones and thioxanthone compounds, and R is1is-CH3or-CH2CH3。
In one or more embodiments, the molar ratio of the photoinitiator to the isocyanate siloxane in the step (1) is 1: 1 to 1.5; the dosage of the catalyst I is 0.1-3% of the total mass of the photoinitiator and the isocyanate siloxane.
In one or more embodiments, the siliconized PDMS of step (2) has the following structure:
wherein R is1is-CH3or-CH2CH3，R3Is composed of
the weight average molecular weight of the hydroxyl-terminated PDMS in the step (2) is 1000-5000 g/mol;
the molar ratio of the hydroxyl-terminated PDMS to the isocyanate siloxane in the step (2) is 1: 1-5; the dosage of the catalyst I is 0.1-3% of the total mass of the hydroxyl-terminated PDMS and the isocyanate siloxane.
In one or more embodiments, the alkanyl siloxane in step (3) has the structure:
R3-Si(OR1)3
wherein R is1is-CH3or-CH2CH3，R3is-CH3、-CH2CH3or-CH2CH2CH3。
In one or more embodiments, the molar amount of the deionized water in the step (3) is 3 to 9 times of the total molar number of the siloxane photoinitiator, the siloxane containing long-chain PDMS and the alkyl siloxane;
the amount of the catalyst II used in the step (3) is 0.1-5% of the mass of the water;
the molar ratio of the siloxane photoinitiator, the siloxane PDMS, the alkyl siloxane and the hexamethyldisiloxane in the step (3) is 1: 0.01-1: 1-5: 0.5-2.
In one or more embodiments, the isocyanate siloxane in steps (1) and (2) is one or more of 3-isocyanatopropyl trimethoxy silane and 3-isocyanatopropyl triethoxy silane.
As a second aspect of the present invention, there is provided a photosensitive silicone resin prepared as described above, having the following structure:
wherein X is a micromolecular photoinitiator with hydroxyl or amino, R1is-CH3or-CH2CH3，R2Is composed of
The third aspect of the invention provides an application of photosensitive organic silicon resin, wherein the photosensitive organic silicon resin, the multifunctional acrylate resin and the photoinitiator are mixed, and then coated on a substrate, and then irradiated by ultraviolet light to be cured to form a film;
wherein the photoinitiator is selected from one or more of 2, 4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide;
the dosage of the photoinitiator is 1 to 5 percent of the total mass of the multifunctional acrylate resin and the silicon-containing resin capable of being photoinitiated and polymerized;
the multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin;
the base material is selected from one or more of a PC plate, a PMMA plate, a wood plate, a steel plate and a glass plate.
In one or more embodiments, the photosensitive silicone resin is used in an amount of 1% to 15% by weight of the multifunctional acrylate resin.
The invention at least comprises the following beneficial effects:
the invention firstly utilizes isocyanate siloxane to react with micromolecular photoinitiator and PDMS respectively to prepare siloxane photoinitiator and siloxane PDMS, and then the siloxane photoinitiator and the siloxane PDMS are hydrolyzed and condensed with alkyl siloxane and hexamethyldisiloxane to synthesize the photosensitive organic silicon resin. Siliconized PDMS is used to provide excellent high contact angle and low sliding angle to obtain excellent antifouling properties; the siloxane photoinitiator can be cracked to generate free radicals under the irradiation of ultraviolet light, and can react with multifunctional acrylate, and the PDMS component with low surface energy in the photosensitive organic silicon resin can be subjected to surface migration in the ultraviolet curing process, so that the concentration of the free radicals on the surface of the coating is improved, and oxygen inhibition can be reduced to a certain extent. After the photosensitive organic silicon resin and the multifunctional acrylate resin are compounded, the coating prepared by ultraviolet curing has excellent wear resistance, and the pencil hardness can reach 4H; the anti-fingerprint and easy-to-wipe performance is good, the durability is good, and the effect is good after the friction cycle test is 5000 times; the curing film has good hydrophobic and oleophobic performances, the water contact angle can reach more than 110 degrees, and the hexadecane contact angle can reach more than 37 degrees; the conversion rate of double bonds is more than 94%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to specific embodiments, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The application of the photo-initiation polymerizable silicon-containing resin in the coating of the invention is tested and evaluated with reference to table 1 for the basic properties of the coating:
TABLE 1 coating Performance test method
The raw materials and sources used in examples 1 to 5 and comparative examples 1 to 3 of the present invention are shown in Table 2:
TABLE 2 raw materials and sources for examples and comparative examples
| Name of raw materials | Source of raw materials |
| Photoinitiator 2959 | Mecline reagent |
| Catalyst I: dibutyl tin dilaurate | Chemical Co Ltd of the national drug group |
| 3-isocyanatopropyltrimethoxysilane | Aladdin Ltd |
| Solvent I: methyl ethyl ketone | Aladdin Ltd |
| Monohydroxy terminated PDMS (M)w＝1000) | Shanghai provinceMichelle chemical technology Ltd |
| N-hexane | Chemical Co Ltd of the national drug group |
| Acetonitrile | Chemical Co Ltd of the national drug group |
| Propyl trimethoxy silane | Mecline reagent |
| And (2) solvent II: isopropanol (I-propanol) | Chemical Co Ltd of the national drug group |
| Catalyst II: hydrochloric acid | Chemical Co Ltd of the national drug group |
| Hexamethyldisiloxane | Chemical Co Ltd of the national drug group |
| Urethane acrylate resin | JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |
| Epoxy acrylate resin | JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |
| Polyester acrylate resin | JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |
| 3-isocyanatopropyltriethoxysilane | Mecline reagent |
| Catalyst I: stannous octoate | Chemical Co Ltd of the national drug group |
| Dihydroxy terminated PDMS (M)w＝1000) | Shanghai Mairuier Chemical Technology Co., Ltd. |
| Ethyl trimethoxysilane | Mecline reagent |
| Catalyst II: oxalic acid | Chemical Co Ltd of the national drug group |
| Monohydroxy terminated PDMS (M)w＝2000) | Shanghai Mairuier Chemical Technology Co., Ltd. |
| Photoinitiator 1173 | Mecline reagent |
| Photoinitiator 184 | Mecline reagent |
| Propyl trimethoxy silane | Chemical Co Ltd of the national drug group |
| And (2) solvent II: acetone (II) | Chemical Co Ltd of the national drug group |
| Photoinitiator HMBP | Mecline reagent |
| Methyltrimethoxysilane | Mecline reagent |
| Photoinitiator ABP | Mecline reagent |
| Ethyl triethoxysilane | Aladdin Ltd |
Example 1
(1) Preparation of the siloxane photoinitiator 2959-IPTES
11.21g (0.05mol)2959 (2-hydroxy-2-methyl-p-hydroxyethyl etherylphenyl-1-propanone) and 0.15g dibutyltin dilaurate were dissolved in 4g methyl ethyl ketone, and 10.27g (0.05mol) IPTS (3-isocyanatopropyltrimethoxysilane) were added dropwise. The temperature was raised to 50 ℃ and the reaction was continued with stirring for 6 hours, after washing with n-hexane, distillation under reduced pressure gave the siloxane photoinitiator 2959-IPTES.
(2) Preparation of siloxane PDMS-1-1000-IPTES
Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer were charged 16.422g (0.08mol) of IPTES, 50g (0.05mol) of monohydroxy-terminated PDMS (M)w1000), 0.061g of dibutyltin dilaurate, and 10g of methyl ethyl ketone were stirred in a 70 ℃ oil bath to react for 6 hours. Then washing with acetonitrile for three times, and distilling under reduced pressure to obtain siloxane PDMS-1-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.30g (0.01mol) of 2959-IPTES, 6.03g (0.005mol) of PDMS-1-1000-IPTES, 6.57g (0.04mol) of propyltrimethoxysilane and 5g of isopropanol were mixed, stirred well and warmed to 50 ℃. A mixture of 0.041g concentrated hydrochloric acid and 2.97g (0.165mol) deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 6 hours. Thereafter, 1.461g (0.009mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 3 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a1,
wherein X is
R1is-CH3，R2Is composed of
，R3is-CH2CH2CH3)。
(4) Curing of photosensitive silicone resins
Mixing 100 parts by mass of urethane acrylate resin, 1 part by mass of photosensitive organic silicon resin (A1) and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, coating a film on a PMMA plate, and then irradiating by ultraviolet light to cure and form the film.
Example 2
(1) Preparation of siloxane photoinitiator 1173-IPTMS
8.21g (0.05mol) of 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone) and 0.14g of stannous octoate were dissolved in 4g of chloroform, and 12.35g (0.05mol) of IPTMS (3-isocyanatopropyltriethoxysilane) were added dropwise. The temperature is raised to 55 ℃, the reaction is continued for 5 hours under stirring, and after washing by n-hexane, reduced pressure distillation is carried out to obtain the siloxane photoinitiator 1173-IPTMS.
(2) Preparation of siloxane PDMS-2-1000-IPTMS
To a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer were added 39.52g (0.16mol) of IPTMS, 50g (0.05mol) of bishydroxy-terminated PDMS (M)w1000), stannous octoate 0.063g and toluene 10g, and the reaction was stirred in an oil bath at 70 ℃ for 8 hours. Then washing with acetonitrile for three times, and distilling under reduced pressure to obtain siloxane PDMS-2-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.12g (0.01mol)1173-IPTMS, 4.48g (0.003mol) PDMS-1-1000-IPTMS, 3.76g (0.025mol) ethyltrimethoxysilane and 5g of toluene were mixed, stirred well and warmed to 45 ℃. A mixture of 0.043g of oxalic acid and 2.05g (0.114mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 55 ℃ for 8 hours. Then, 1.79g (0.011mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 2 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a2,
wherein X is
R1is-CH3and-CH2CH3，R2Is composed of
，R3is-CH2CH3)。
(4) Curing of photosensitive silicone resins
100 parts by mass of polyester acrylate resin, 1.5 parts by mass of photosensitive silicone resin (A2) and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone were mixed, and then a film was coated on a PC board, followed by ultraviolet irradiation and curing to form a film.
Example 3
(1) Preparation of the siloxane photoinitiator 184-IPTMS
10.22g (0.05mol)184 (1-hydroxy-cyclohexyl-phenyl-methanone) and 0.14g dibutyltin dilaurate were dissolved in 7g methyl ethyl ketone, and 14.82g (0.06mol) IPTMS was added dropwise. The temperature is raised to 60 ℃, the reaction is continued for 6 hours under stirring, and after the n-hexane is washed, the siloxane photoinitiator 184-IPTMS is obtained by reduced pressure distillation.
(2) Preparation of siloxane PDMS-2-1000-IPTMS
Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer were charged 24.70g (0.10mol) of IPTMS, 100g (0.05mol) of monohydroxy-terminated PDMS (M)w2000), 0.081g of stannous octoate and 20g of xylene, and the reaction was stirred in an oil bath at 70 ℃ for 10 hours. Then washing with acetonitrile for three times, and distilling under reduced pressure to obtain siloxane PDMS-1-2000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.51g (0.01mol)184-IPTMS, 4.49g (0.002mol) PDMS-1-2000-IPTMS, 4.93g (0.03mol) propyltrimethoxysilane and 6g of acetone were mixed, stirred well and warmed to 45 ℃. A mixture of 0.043g of oxalic acid and 2.05g (0.114mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 55 ℃ for 9 hours. Thereafter, 1.95g (0.012mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 75 ℃ to conduct the reaction for 3 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a3,
wherein X is
R1is-CH3and-CH2CH3，R2Is composed of
，R3is-CH2CH3)。
(4) Curing of photosensitive silicone resins
100 parts by mass of epoxy acrylate resin, 2 parts by mass of photosensitive organic silicon resin (A3) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then coated on a wood board, and then irradiated by ultraviolet light, and cured to form a film.
Example 4
(1) Preparation of siloxane photoinitiator HMBP-IPTES
10.61g (0.05mol) of HMBP (4-hydroxymethyldiphenylketone) and 0.16g of dibutyltin dilaurate were dissolved in 5g of methylethylketone, and 12.32g (0.06mol) of IPTS was added dropwise. The temperature is raised to 60 ℃, the stirring reaction is continued for 7 hours, and after the normal hexane is washed, the reduced pressure distillation is carried out to obtain the siloxane photoinitiator HMBP-IPTES.
(2) Preparation of siloxane PDMS
The procedure of example 1 was used to prepare the siloxylated PDMS-1-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.18g (0.01mol) of HMBP-IPTMS, 3.62g (0.003mol) of PDMS-1-1000-IPTMS, 4.77g (0.035mol) of methyltrimethoxysilane and 4g of acetone were mixed, stirred well and warmed to 45 ℃. A mixture of 0.051g of glacial acetic acid and 2.52g (0.144mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 6 hours. Then, 2.11g (0.013mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 2 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a4,
wherein X is
R1is-CH3，R2Is composed of
，R3is-CH3)。
(4) Curing of photosensitive silicone resins
100 parts by mass of urethane acrylate resin, 1 part by mass of photosensitive silicone resin (A4) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then coated on a wood board, and then irradiated by ultraviolet light to be cured into a film.
Example 5
(1) Preparation of siloxane photoinitiator ABP-IPTES
9.91g (0.05mol) of ABP (4-aminodiphenylketone) and 0.03g of dibutyltin dilaurate were dissolved in 5g of methyl ethyl ketone, and 10.27g (0.05mol) of IPTS was added dropwise. The temperature is raised to 40 ℃, the stirring reaction is continued for 5 hours, and after the normal hexane is washed, the reduced pressure distillation is carried out to obtain the siloxane photoinitiated ABP-IPTES.
(2) Preparation of siloxane PDMS
The procedure of example 2 was used to prepare the siloxylated PDMS-2-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.04g (0.01mol) ABP-IPTES, 4.48g (0.003mol) PDMS-1-1000-IPTMS, 3.85g (0.02mol) ethyltriethoxysilane and 5g isopropanol were mixed, stirred well and warmed to 50 ℃. A mixture of 0.051g concentrated HCl and 1.78g (0.099mol) deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 5 hours. Thereafter, 1.63g (0.01mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 2.5 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a5,
wherein X is
R1is-CH3and-CH3，R2Is composed of
，R3is-CH2CH3)。
(4) Curing of photosensitive silicone resins
100 parts by mass of polyester acrylate resin, 1 part by mass of photosensitive silicone resin (A5) and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone are mixed, and then a film is coated on a steel plate, and then ultraviolet irradiation is performed to cure the mixture to form a film.
Comparative example 1
(1) Curing of urethane acrylate resins
Mixing 100 parts by mass of urethane acrylate resin and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, coating a film on a PMMA plate, irradiating by ultraviolet light, and curing to form a film.
Comparative example 2
(1) Curing of epoxy acrylate resins
Mixing 100 parts by mass of epoxy acrylate resin and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone, coating a film on a PVC plate, and then irradiating by ultraviolet light to cure and form a film.
Comparative example 3
(1) Curing of polyester acrylate resins
100 parts by mass of polyester acrylate resin and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then a film is coated on a PC plate, and then ultraviolet irradiation is carried out to cure the mixture to form a film.
With reference to the test methods and test standards of table 1, the following technical performance tests were performed on the paint films of the above examples 1 to 5 and comparative examples 1 to 3, and the results of the performance tests are as follows: the test results are shown in table 3:
as can be seen from the performance test results of examples 1-5 and comparative examples 1-3 in Table 3, the hardness of the photosensitive organic silicon resin prepared in examples 1-5 of the invention can reach 4H when being used as a photocuring antifouling coating; the initial water drop angle of the coating reaches more than 110 degrees, the initial hexadecane contact angle reaches more than 37 degrees, the coating has good fingerprint and contamination resistance effects, and after 3000 times and 5000 times of friction cycle tests, the coating still has high water and hexadecane contact angles, so that the long-acting antifouling effect can be kept; the comparative examples 1 to 3 have poor wear resistance, no antifouling and fingerprint resistance and low double bond conversion rate under the condition of not adding photosensitive organic silicon resin.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of photosensitive organic silicon resin is characterized by comprising the following steps:
(1) preparation of siloxane photoinitiators
Dissolving a photoinitiator and a catalyst I in a solvent I, then dropwise adding isocyanate siloxane, raising the temperature to 40-60 ℃, continuously stirring for reacting for 5-8 hours, washing with n-hexane, and carrying out reduced pressure distillation to obtain a siloxane photoinitiator;
(2) preparation of siloxane PDMS
Mixing hydroxyl-terminated PDMS, isocyanate siloxane, a catalyst I and a solvent II, heating to 50-70 ℃, stirring for reaction for 5-10 hours, washing with acetonitrile, and carrying out reduced pressure distillation to obtain siloxane PDMS;
(3) preparation of photosensitive organic silicon resin
Mixing the siloxane photoinitiator, the siloxane PDMS, alkyl siloxane and a solvent III, heating to 40-60 ℃, dropwise adding a mixture of a catalyst II and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-60 ℃, stirring for 5-10 hours, adding hexamethyldisiloxane, heating to 60-80 ℃, stirring for 1-3 hours, standing for layering, taking down a layer, and carrying out reduced pressure distillation to obtain photosensitive organic silicon resin;
wherein the catalyst I is at least one of dibutyltin dilaurate, stannous octoate and butyltin diacetate; the solvent I is at least one of chloroform, tetrahydrofuran and methyl ethyl ketone; the solvent II is at least one of methyl ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; the catalyst II is at least one of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; the solvent III is at least one of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran.
2. The process for preparing a photosensitive silicone resin according to claim 1, wherein the siloxane photoinitiator in step (1) has the following structure:
wherein, X is a micromolecular photoinitiator with hydroxyl or amino, namely benzoin with hydroxyl or amino and derivatives thereof, benzil, alkyl benzophenones, benzophenones and thioxanthone compounds; r1is-CH3or-CH2CH3。
3. A process for preparing a photosensitive silicone resin according to claim 1, wherein the molar ratio of the photoinitiator to the isocyanate siloxane in step (1) is 1: 1 to 1.5; the dosage of the catalyst I is 0.1-3% of the total mass of the photoinitiator and the isocyanate siloxane.
4. The method of preparing a photosensitive silicone resin according to claim 1, wherein the siliconized PDMS in step (2) has the following structure:
wherein R is1is-CH3or-CH2CH3，R3Is composed of
n is a natural number of 8-64;
the weight average molecular weight of the hydroxyl-terminated PDMS in the step (2) is 1000-5000 g/mol;
the molar ratio of the hydroxyl-terminated PDMS to the isocyanate siloxane in the step (2) is 1: 1-5; the dosage of the catalyst I is 0.1-3% of the total mass of the hydroxyl-terminated PDMS and the isocyanate siloxane.
5. The process for preparing a photosensitive silicone resin according to claim 1, wherein the alkyl siloxane in step (3) has the following structure:
R3-Si(OR1)3
wherein R is1is-CH3or-CH2CH3，R3is-CH3、-CH2CH3or-CH2CH2CH3。
6. The method according to claim 1, wherein the molar amount of deionized water used in step (3) is 3 to 9 times the total molar amount of the siloxane photoinitiator, the long-chain PDMS-containing siloxane and the alkyl siloxane;
the amount of the catalyst II used in the step (3) is 0.1-5% of the mass of the water;
the molar ratio of the siloxane photoinitiator, the siloxane PDMS, the alkyl siloxane and the hexamethyldisiloxane in the step (3) is 1: 0.01-1: 1-5: 0.5-2.
7. A process for preparing a photosensitive silicone resin according to any one of claims 1 to 6, wherein the isocyanatosiloxane in steps (1) and (2) is at least one of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
8. A photosensitive silicone resin, characterized by being prepared by the preparation method of any one of claims 1 to 7, and having the following structure:
wherein X is a micromolecular photoinitiator with hydroxyl or amino, R1is-CH3or-CH2CH3，R2Is composed of
R3is-CH3、-CH2CH3or-CH2CH2CH3。
9. The application of photosensitive organic silicon resin is characterized in that the photosensitive organic silicon resin, the multifunctional acrylate resin and the photoinitiator according to claim 8 are mixed, and then a film is coated on a substrate, and then ultraviolet irradiation is carried out to cure the film into a film;
wherein the photoinitiator is selected from one or more of 2, 4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide;
the dosage of the photoinitiator is 1 to 5 percent of the total mass of the multifunctional acrylate resin and the silicon-containing resin capable of being photoinitiated and polymerized;
the multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin;
the base material is selected from one or more of a PC plate, a PMMA plate, a wood plate, a steel plate and a glass plate.
10. The use according to claim 9, wherein the photosensitive silicone resin is used in an amount of 1% to 15% by mass of the multifunctional acrylate resin.
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Cited By (5)
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| CN116731063A (en) * | 2022-06-14 | 2023-09-12 | 北京鼎材科技有限公司 | Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent |
| WO2023172029A1 (en) * | 2022-03-07 | 2023-09-14 | 주식회사 엘지화학 | Compound |
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| CN118700659A (en) * | 2024-08-27 | 2024-09-27 | 安徽斯迈特新材料股份有限公司 | A kind of hydrophobic organosilicon leather and its manufacturing process |
| WO2025075041A1 (en) * | 2023-10-02 | 2025-04-10 | ダイキン工業株式会社 | Silane compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023172029A1 (en) * | 2022-03-07 | 2023-09-14 | 주식회사 엘지화학 | Compound |
| EP4491688A4 (en) * | 2022-03-07 | 2025-07-09 | Lg Chemical Ltd | CONNECTION |
| CN116731063A (en) * | 2022-06-14 | 2023-09-12 | 北京鼎材科技有限公司 | Silane coupling agent, application thereof and photosensitive resin composition containing silane coupling agent |
| WO2025075041A1 (en) * | 2023-10-02 | 2025-04-10 | ダイキン工業株式会社 | Silane compound |
| JP2025062586A (en) * | 2023-10-02 | 2025-04-14 | ダイキン工業株式会社 | Silane compound |
| CN117285879A (en) * | 2023-11-24 | 2023-12-26 | 江苏凯伦建材股份有限公司 | Pre-laid waterproof coiled material and preparation method thereof |
| CN117285879B (en) * | 2023-11-24 | 2024-02-27 | 江苏凯伦建材股份有限公司 | Pre-laid waterproof coiled material and preparation method thereof |
| WO2025108002A1 (en) * | 2023-11-24 | 2025-05-30 | 江苏凯伦建材股份有限公司 | Pre-applied waterproofing sheet and preparation method therefor |
| CN118700659A (en) * | 2024-08-27 | 2024-09-27 | 安徽斯迈特新材料股份有限公司 | A kind of hydrophobic organosilicon leather and its manufacturing process |
| CN118700659B (en) * | 2024-08-27 | 2024-12-20 | 安徽斯迈特新材料股份有限公司 | Hydrophobic organosilicon leather and manufacturing process thereof |
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