CN116897194A - Coating liquid for spraying, method for producing same, and method for producing base material with antiglare layer - Google Patents
Coating liquid for spraying, method for producing same, and method for producing base material with antiglare layer Download PDFInfo
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- CN116897194A CN116897194A CN202280012732.5A CN202280012732A CN116897194A CN 116897194 A CN116897194 A CN 116897194A CN 202280012732 A CN202280012732 A CN 202280012732A CN 116897194 A CN116897194 A CN 116897194A
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- Prior art keywords
- coating liquid
- producing
- silica precursor
- antiglare layer
- spray
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- 239000011248 coating agent Substances 0.000 title claims abstract description 136
- 238000000576 coating method Methods 0.000 title claims abstract description 136
- 239000007788 liquid Substances 0.000 title claims abstract description 130
- 238000005507 spraying Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000002243 precursor Substances 0.000 claims abstract description 67
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 26
- 239000010419 fine particle Substances 0.000 claims description 20
- -1 alkoxy silane Chemical compound 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 239000011859 microparticle Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 230000032683 aging Effects 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000004313 glare Effects 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241001675646 Panaceae Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UGXMKSYKRKUMGY-UHFFFAOYSA-N 1,3,5,2,4,6-triazatrisilinane Chemical compound N1[SiH2]N[SiH2]N[SiH2]1 UGXMKSYKRKUMGY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920004934 Dacron® Polymers 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- TWSOFXCPBRATKD-UHFFFAOYSA-N [diphenyl-(triphenylsilylamino)silyl]benzene Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)N[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 TWSOFXCPBRATKD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003426 chemical strengthening reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention relates to a coating liquid for spray coating which, when an antiglare layer is formed by a spray coating method, can suppress the occurrence of a flare of an antiglare surface having a concave-convex structure, wherein the coating liquid for spray coating contains a silica precursor and a solvent, and wherein the average value of the molecular size of the silica precursor based on the intensity of scattered light measured by a dynamic light scattering method is 5.6nm or more.
Description
Technical Field
The present invention relates to a coating liquid for spray coating, a method for producing the same, and a method for producing a base material with an antiglare layer using the coating liquid for spray coating.
Background
Conventionally, in display screens of mobile phones, tablet terminals, televisions, digital billboards, and the like, there are cases where reflection images are reflected by external light such as indoor illumination (fluorescent lamps, and the like) and sunlight and fall on a display surface, resulting in a decrease in visual visibility. As a treatment for suppressing such reflection due to external light, treatments such as an antiglare treatment and an antireflection treatment are known.
Patent document 1 discloses a transparent product comprising a transparent substrate and an antiglare layer provided on at least one side surface of the transparent substrate. In patent document 1, an antiglare layer is formed by applying a coating material containing a matrix precursor by a spray method. As the matrix precursor, a precursor selected from SiO 2 、Al 2 O 3 、ZrO 2 、TiO 2 At least one of them.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2018-106014
Disclosure of Invention
Problems to be solved by the invention
However, when an antiglare layer is formed by applying a coating material containing a matrix precursor by a spray coating method as in patent document 1, flickering called a flash point may occur on the antiglare surface. Therefore, there is a problem that the visibility of the display is not sufficiently improved.
The purpose of the present invention is to provide a coating liquid for spraying, which can suppress the glare of an antiglare surface of a concave-convex structure when an antiglare layer is formed by a spraying method, a method for producing the coating liquid for spraying, and a method for producing a substrate with an antiglare layer using the coating liquid for spraying.
Means for solving the problems
The coating liquid for spray coating of the present invention is characterized by comprising a silica precursor and a solvent, wherein the average value of the molecular size of the silica precursor measured by a dynamic light scattering method based on the intensity of scattered light is 5.6nm or more.
In the present invention, the average value of the molecular size of the silica precursor based on the scattered light intensity measured by the dynamic light scattering method is preferably 30nm or less.
The method for producing a coating liquid for spray coating according to the present invention is a method for producing a coating liquid for spray coating comprising: preparing a mixed solution of a raw material containing the silica precursor and a solvent; and curing the mixture.
In the present invention, the silica precursor is preferably a monomer or oligomer of an alkoxysilane as a raw material.
In the present invention, the alkoxysilane is preferably tetramethoxysilane or tetraethoxysilane.
In the present invention, the mixed solution preferably further contains oxide fine particles, and the content of the oxide fine particles is less than 0.05 mass%.
In the present invention, it is preferable that the silica precursor is a matrix-forming component in forming the antiglare layer by a spray method, and the oxide fine particles are different from the matrix-forming component.
In the present invention, the content of the component having a boiling point higher than 100 ℃ and lower than 120 ℃ in the mixed solution is preferably 0 mass% or more and 15 mass% or less.
In the present invention, the content of the component having a boiling point of 120 ℃ or higher in the mixed solution is preferably 5 mass% or less.
The method for producing a substrate with an antiglare layer according to the present invention is characterized by comprising: a step of preparing a coating liquid for spray coating according to the method for producing a coating liquid for spray coating of the present invention; and forming an anti-glare layer by applying the coating liquid for spraying on a substrate.
In the present invention, the coating liquid for spraying is preferably applied using a two-fluid spray gun.
Effects of the invention
According to the present invention, it is possible to provide a coating liquid for spray coating that can suppress the glare spot on the antiglare surface of the uneven structure when the antiglare layer is formed by a spray coating method, a method for producing the coating liquid for spray coating, and a method for producing a substrate with an antiglare layer using the coating liquid for spray coating.
Drawings
FIG. 1 is a schematic diagram showing the relationship between the curing time and the molecular size of a silica precursor at curing temperatures of 20℃and 45 ℃.
FIG. 2 is a schematic diagram showing the relationship between the amount of alcohol used in curing, curing time and the molecular size of the silica precursor for various coating liquids.
Fig. 3 (a) and 3 (b) are schematic cross-sectional views for explaining a method of manufacturing a substrate with an antiglare layer according to an embodiment of the present invention.
Detailed Description
The preferred embodiments are described below. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments.
[ coating liquid for spray coating ]
The coating liquid for spray coating of the present invention is a coating liquid for forming a coating film by a spray coating method. The coating liquid for spray coating (hereinafter simply referred to as "coating liquid") is not particularly limited, and is used for forming an antiglare layer by, for example, a spray coating method. The antiglare layer is a layer provided to provide a so-called antiglare effect such as suppressing reflection of external light.
The coating liquid of the present invention contains a silica precursor and a solvent. The average value of the molecular size of the silica precursor contained in the coating liquid, measured by a dynamic light scattering method, based on the scattered light intensity is 5.6nm or more.
The scattered light intensity measurement according to the dynamic light scattering method may be performed using, for example, the model "Zetasizer Nano S" manufactured by malvern panaceae (Malvern Panalytical ltd.). The measurement may be performed, for example, at a fixed position where the average scattering intensity is 500kcps, with a 3 second execution time and 30 execution times, and the average is performed 45 times after the measurement, and the particle size distribution is calculated by a non-negative least square method to obtain the average value of the scattered light intensity standard. As for other parameters, measurement and analysis can be performed under the conditions of a measurement temperature of 20.0 ℃, a particle size classification number of 70, a particle size distribution lower limit of 0.4, a display upper limit of 10000, a lower limit threshold of 0.05, an upper limit threshold of 0.01, a resolution of standard, a display range lower limit of 0.6, and a display upper limit of 300. In the measurement, a coating liquid immediately before the spraying is preferably used.
According to the coating liquid of the present invention, when the antiglare layer is formed by the spray coating method, the glare spot on the antiglare surface of the uneven structure can be suppressed. Therefore, when such an antiglare layer is used for a display panel or the like, visual recognition can be further improved.
Conventionally, when an antiglare layer is formed by applying a coating material containing a matrix precursor by a spray method, there is a possibility that a antiglare surface may flash called a flare point. Therefore, there is a problem that the visibility of the display is not sufficiently improved.
In contrast, the inventors of the present invention focused on the molecular size of the silica precursor contained in the coating liquid, and found that: by setting the average value of the molecular size based on the scattered light intensity measured by the dynamic light scattering method to 5.6nm or more, the flash point on the antiglare surface of the uneven structure can be suppressed.
In the present invention, the average value of the molecular size of the silica precursor contained in the coating liquid based on the scattered light intensity measured by the dynamic light scattering method is 5.6nm or more, preferably 7.0nm or more, and more preferably 8.0nm or more. When the molecular size of the silica precursor is not less than the above lower limit, the flash point on the antiglare surface of the uneven structure can be further suppressed.
In the present invention, the average value of the molecular size of the silica precursor contained in the coating liquid based on the scattered light intensity measured by the dynamic light scattering method is preferably 30nm or less, more preferably 20nm or less, and still more preferably 18nm or less. When the molecular size of the silica precursor is equal to or smaller than the upper limit, the haze can be further suppressed from increasing and the haze can be further reduced when the antiglare layer is formed by the spray method. Therefore, when the antiglare layer is used for a display panel or the like, visual recognition can be further improved.
The silica precursor contained in the coating liquid of the present invention can be used as a matrix-forming component in forming an antiglare layer by, for example, a spray coating method.
Details of each component contained in the coating liquid of the present invention are described below.
(silica precursor)
Examples of the silica precursor include a silane compound having a hydrolyzable group bonded to a silicon atom, a hydrolytic condensate of a silazane compound, and the like. Since cracking of the antiglare layer can be suppressed more reliably even when a thicker antiglare layer is formed, the silica precursor preferably contains at least a hydrolytic condensate of a silane compound.
The raw materials of the silica precursor include a silane compound and a silazane compound.
The silane compound has a hydrolyzable group bonded to a silicon atom.
Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminooxy group, an amide group, an isocyanate group, and a halogen atom. From the viewpoint of balance between stability of the silane compound and ease of hydrolysis, an alkoxy group, an isocyanate group or a halogen atom, particularly a chlorine atom is preferable. The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group.
Examples of the silane compound include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetraisopropoxysilane, alkoxysilanes having an alkyl group such as methyltrimethoxysilane and ethyltriethoxysilane, alkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, alkoxysilanes having an acryloxy group such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane and 3-glycidoxypropyl triethoxysilane, and alkoxysilanes having an acryloxy group such as 3-acryloxypropyl trimethoxysilane. Among these silane compounds, either one or both of alkoxysilane and a hydrolytic condensate of alkoxysilane are preferably used, and a hydrolytic condensate of alkoxysilane is more preferably used.
The hydrolysis condensate of an alkoxysilane may be a silicate oligomer obtained by prepolymerizing the above-mentioned alkoxysilane. In this case, the antiglare effect of the antiglare layer formed by the spray coating method can be further improved.
The silazane compound is a compound having a silazane bond (-SiN-) in its structure. The silazane compound may be a low-molecular compound or a high-molecular compound (polymer having a predetermined repeating unit). Examples of the low-molecular-weight silazane compound include hexamethyldisilazane, hexaphenyl disilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, 1,3, 5-hexamethylcyclotrisilazane, and the like.
The content of the silica precursor is SiO based on the total amount of the coating liquid 2 The content is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less in terms of the content. When the content of the silica precursor is within the above range, the antiglare effect of the antiglare layer formed by the spray coating method can be further improved.
(solvent)
The solvent is not particularly limited, and may be appropriately selected depending on the kind of the silica precursor. As the solvent, for example, water, alcohols, and the like described below can be used.
Water:
the water used as the solvent may be used alone, but is preferably a mixed liquid of water and a solvent other than water. Among them, a mixed liquid of water and alcohols is more preferable.
The content of water in the production of the coating liquid for spray application is preferably 2.7 mass% or more, more preferably 4.0 mass% or more, still more preferably 10.1 mass% or less, and still more preferably 8.0 mass% or less, relative to the total amount of the coating liquid (state before hydrolysis condensation of the raw material of the silica precursor). When the water content in the coating liquid is not less than the lower limit, hydrolysis can be performed more reliably, and a substrate can be formed more reliably; on the other hand, when the water content in the coating liquid is equal to or less than the upper limit value, the glare spot on the antiglare surface of the uneven structure can be further suppressed.
Alcohols:
examples of the alcohols include methanol, ethanol, 2-propanol, 1-butanol, and 2-butanol. These alcohols may be used alone or in combination of 1 or more. Among them, 2-propanol is preferably contained as the solvent.
The content of the alcohol is preferably 30 mass% or more, more preferably 40 mass% or more, and preferably 90 mass% or less, more preferably 80 mass% or less, with respect to the total amount of the coating liquid (state before hydrolytic condensation of the raw material of the silica precursor). In this case, the unevenness of the antiglare treatment can be formed more efficiently.
Other solvents:
the coating liquid of the present invention may further contain other solvents as long as the effects of the present invention are not impaired.
Examples of the other solvents include, but are not particularly limited to, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, and the like.
Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of the ethers include tetrahydrofuran and 1, 4-dioxane.
Examples of cellosolve include methyl cellosolve and ethyl cellosolve.
Examples of the esters include methyl acetate and ethyl acetate.
Examples of the glycol ethers include ethylene glycol monoalkyl ethers.
Examples of the nitrogen-containing compound include N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and the like.
Examples of the sulfur-containing compound include dimethylsulfoxide.
These other solvents may be used alone or in combination of 1 or more.
The content of the other solvent is, for example, 40 mass% or less relative to the total amount of the coating liquid (the state before the hydrolysis and condensation of the raw material of the silica precursor).
(catalyst)
The coating liquid of the present invention may further contain an acid catalyst as a catalyst. As the acid catalyst, for example, a raw material of a silica precursor or a catalyst that promotes hydrolysis and condensation reaction of the silica precursor can be used.
More specifically, as the acid catalyst, for example, an inorganic acid (nitric acid, sulfuric acid, hydrochloric acid), an organic acid (formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid) can be used.
The pH of the coating liquid is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 7 or less, more preferably 6 or less, still more preferably 5 or less. When the pH of the coating liquid is equal to or higher than the lower limit value, damage to coating equipment such as a nozzle can be further reduced; on the other hand, when the pH of the coating liquid is equal to or lower than the upper limit value, an antiglare layer having a higher hardness and a higher density can be formed.
The coating liquid of the present invention may contain a base catalyst as a catalyst. The coating liquid of the present invention may contain additives other than those described above, insofar as the effects of the present invention are not impaired.
(solid component)
The content of the solid component (heating residue) of the coating liquid of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 2.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 4% by mass or less. When the content of the solid component (heating residue) is not less than the above lower limit value, the unevenness of the antiglare layer can be formed more efficiently; when the content of the solid component (heating residue) is less than the above-described upper limit value, the flash point of the antiglare surface of the uneven structure can be further suppressed.
[ method for producing coating liquid for spray coating ]
An example of the method for producing the coating liquid of the present invention will be described below.
First, a raw material of a silica precursor, a solvent, and an acid catalyst or a base catalyst as needed are mixed to obtain a mixed solution.
In the present invention, the mixed solution preferably contains substantially no oxide fine particles of a raw material different from the silica precursor. In this case, the coating liquid can be more easily mixed, and the occurrence of a flare point due to the aggregation of the oxide fine particles can be further suppressed. In addition, when the antiglare layer is formed on the substrate by the spray coating method, the adhesion and hardness of the substrate and the antiglare layer can be further improved, and the occurrence of appearance defects due to the oxide fine particle aggregates can be further prevented. The oxide fine particles are preferably a component different from the matrix-forming component.
The oxide fine particles are fine particles having an average particle diameter of 300nm or less as measured by observation with a transmission electron microscope. The average particle diameter of the oxide fine particles is preferably 4nm or more, more preferably 6nm or more, preferably 200nm or less, more preferably 100nm or less.
The substantially free oxide fine particles mean that the content of the oxide fine particles is less than 0.05 mass% relative to the total amount of the coating liquid (state before hydrolysis and condensation of the raw material of the silica precursor).
When the oxide fine particles are contained, the content of the oxide fine particles is preferably 0.5 mass% or less, more preferably 0.1 mass% or less, relative to the total amount of the coating liquid (state before hydrolysis condensation of the raw material of the silica precursor).
The oxide fine particles are not particularly limited, and silica, titania, zirconia, antimony oxide, alumina, indium oxide, a mixture thereof, and the like can be used, for example.
In the present invention, the content of the component having a boiling point of higher than 100 ℃ and lower than 120 ℃ is preferably 0 mass% or more, more preferably 3 mass% or more, still more preferably 5 mass% or more, preferably 15 mass% or less, still more preferably 10 mass% or less, still more preferably 8 mass% or less, relative to the total amount of the coating liquid (state before hydrolysis condensation of the raw material of the silica precursor). When the content of the component having a boiling point of more than 100 ℃ and less than 120 ℃ is not less than the above lower limit value, the increase in haze can be further suppressed when the antiglare layer is formed by the spray coating method; when the content of the component having a boiling point of more than 100 ℃ and less than 120 ℃ is equal to or less than the upper limit value, the glare point on the antiglare surface of the uneven structure can be further suppressed.
Examples of the component having a boiling point higher than 100℃and lower than 120℃include isobutanol and 1-butanol.
In the present invention, the content of the solvent component having a boiling point of 120 ℃ or higher is preferably 5 mass% or less, more preferably 4 mass% or less, and still more preferably 2 mass% or less, relative to the total amount of the coating liquid (state before hydrolysis condensation of the raw material of the silica precursor). When the content of the solvent component having a boiling point of 120 ℃ or higher is equal to or lower than the upper limit value, the irregularities of the antiglare layer can be formed more efficiently even without containing oxide fine particles. In addition, the solvent contained in the coating liquid may be completely free of components having a boiling point of 120 ℃ or higher.
Examples of the component having a boiling point of 120℃or higher include diacetone alcohol, 3-methoxybutyl acetate, 1-methyl-2-pyrrolidone, methyl cellosolve, ethyl cellosolve, and the like.
Then, the obtained mixed solution was stirred and left to stand, whereby the mixed solution was cured. This allows hydrolysis and condensation reactions to proceed, thereby obtaining a coating liquid. In this case, the standing time is the aging time, and the standing temperature is the aging temperature. In addition, stirring may be continued instead of standing. In this case, the stirring time is the above-mentioned aging time, and the stirring temperature is the above-mentioned aging temperature. The concentration of the matrix-forming component may be, for example, 2 to 20% by mass as a solid component (heating residue).
In the method for producing a coating liquid of the present invention, the coating liquid is prepared so that the average value of the molecular size of the silica precursor based on the scattered light intensity measured by the dynamic light scattering method is 5.6nm or more. Therefore, when the antiglare layer is formed by a spraying method using the obtained coating liquid, a flare point of the antiglare surface can be suppressed.
In the present invention, the molecular size of the silica precursor measured by the dynamic light scattering method can be adjusted according to the degree of aging of the mixed solution in the above-described production method. Specifically, the longer the curing time, the larger the molecular size of the silica precursor. Therefore, in the curing process, it is preferable to cure the mixed solution while keeping monitoring of the molecular size of the silica precursor.
The curing time may be, for example, 1 to 480 hours, preferably 2 to 6 hours. The curing temperature is preferably 15℃or higher, more preferably 18℃or higher. When the aging temperature is above the above lower limit, the molecular size of the silica precursor can be increased in a shorter time. The upper limit of the curing temperature is not particularly limited, and may be set to, for example, 60 ℃. FIG. 1 shows the relationship between curing time and molecular size of the silica precursor at curing temperatures of 20℃and 45 ℃. As can be seen from the figure: the higher the curing temperature, the more the molecular size of the silica precursor can be increased in a shorter curing time.
The obtained coating liquid may be diluted 1.2 to 10 times by adding a solvent such as alcohol as needed. Specifically, when the above-mentioned mixed solution is prepared, the mixture may be mixed in an amount of about 1/30 to 1/3 of the amount of the final alcohol, and the remainder may be added after aging. In this case, the molecular size of the silica precursor can be increased in a shorter time. FIG. 2 shows the relationship between the amount of alcohol used in curing, curing time and the molecular size of the silica precursor for various coating liquids. In the preparation of the coating liquid, tetraethoxysilane (TEOS), water (H 2 O), the mixing quality of the alcohol is shown in fig. 2. As can be seen from fig. 2, by reducing the amount of alcohol at the time of curing, the molecular size of the silica precursor can be increased in a shorter time.
[ method for producing substrate with antiglare layer ]
A method for manufacturing a substrate with an antiglare layer according to an embodiment of the present invention will be described below with reference to fig. 3 (a) and (b).
In an example of a method for producing a substrate with an antiglare layer, first, a substrate 2 shown in fig. 3 (a) is prepared.
Examples of the material of the substrate 2 include transparent materials such as glass, ceramics, glass ceramics, and resins. Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass. In this case, the base material 2 may be subjected to a strengthening treatment such as air cooling strengthening or chemical strengthening. Examples of the ceramics include sapphire. Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, and polymethyl methacrylate.
The shape of the substrate 2 is not particularly limited, and examples thereof include a plate shape, a film shape, and the like. The substrate 2 may have a curved shape matching the shape of the display screen.
The base material 2 may have a functional layer on the surface of the substrate body. Examples of the functional layer include an undercoat layer, an adhesion improving layer, a protective layer, and a coloring layer.
On the other hand, the coating liquid was prepared according to the above-described method for producing a coating liquid.
Next, the prepared coating liquid is coated on the substrate 2 and dried. Thus, the antiglare layer 1 shown in fig. 3 (b) can be formed, and the substrate 10 with an antiglare layer can be obtained.
When the coating liquid is applied, the coating liquid is preferably sprayed on the substrate 2 by a spraying method. Examples of the nozzle used in the spraying method include a two-fluid nozzle and a single-fluid nozzle, but a two-fluid spray gun using a two-fluid nozzle is preferable. In this case, even if the oxide fine particles are not contained, the irregularities of the antiglare layer can be formed more efficiently. In addition, when the antiglare layer is formed on the base material by the spray coating method, the adhesion between the base material and the antiglare layer can be further improved.
The droplet size of the coating liquid discharged from the nozzle is usually 0.1 μm to 100. Mu.m, preferably 1 μm to 50. Mu.m. When the droplet size is equal to or larger than the lower limit value, irregularities that sufficiently exhibit an antiglare effect can be formed in a shorter time. When the droplet size is equal to or smaller than the upper limit value, moderate irregularities that sufficiently exhibit an antiglare effect can be easily formed. The droplet size of the coating liquid may be appropriately adjusted according to the type of nozzle, the flow rate of the air, the amount of the liquid, and the like. For example, in a two-fluid nozzle, the higher the airflow rate, the smaller the droplets, and the larger the amount of liquid, the larger the droplets. The droplet size refers to a median particle size at a volume basis measured by a laser diffraction particle size distribution analyzer. The air flow rate may be, for example, 50L/min to 300L/min.
The ejection distance may be, for example, 20mm to 300 mm. The ejection distance is a distance from the nozzle to the surface of the substrate 2 to be film-formed.
The coating amount of the coating liquid may be, for example, 1mL/m 2 Above, 300mL/m 2 The following is given.
The coating temperature of the coating liquid may be, for example, 10 ℃ to 80 ℃.
The surface temperature of the substrate 2 at the time of applying the coating liquid is preferably, for example, 15 to 75 ℃. The humidity at the time of applying the coating liquid is preferably, for example, 20% to 80%, and more preferably 50% or more.
The drying temperature of the coating liquid may be, for example, 100 ℃ or more and 600 ℃ or less. The drying time may be, for example, 10 minutes to 600 minutes.
In addition, after the antiglare layer 1 is formed, an antireflection layer or an antifouling layer may be provided on the antiglare layer 1.
In the method for producing the base material with an antiglare layer 10 of the present embodiment, since a coating liquid for spray application is used in which the average value of the molecular size of the silica precursor based on the scattered light intensity measured by the dynamic light scattering method is 5.6nm or more, the flare point of the antiglare surface can be suppressed. Further, since the flare point of the antiglare surface can be suppressed, when used in a display panel or the like, visual recognition can be improved.
Therefore, the substrate with an anti-glare layer obtained by the manufacturing method of the present invention can be applied to display screens of mobile phones, tablet terminals, televisions, digital billboards, and the like.
The present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples, and may be carried out with appropriate modifications within the scope of not changing the gist thereof.
Example 1
Tetraethoxysilane (TEOS, tokyo chemical Co., ltd. Product model "T0100"), water, alcohol (a mixture of ethanol, methanol and isopropanol, co., ltd. Product model "Neoethanol IPM", dacron chemical Co., ltd.), nitric acid were mixed and cured in a ratio (mass ratio) of TEOS to water to alcohol=1.0:0.6:7.8 to obtain a coating liquid having a molecular size of 5.6nm as an average value of scattered light intensity standard measured by a dynamic light scattering method. Nitric acid was mixed to adjust ph=4. When the above raw materials are mixed, substantially no oxide fine particles are contained.
The amount of heated residue in the obtained coating liquid was 3.0 mass% in example 1.
Then, the obtained coating liquid was sprayed on a reinforced glass substrate (T2X-1 manufactured by japan electric nitrate co., ltd.) as a base material to form an antiglare layer, thereby obtaining a base material with an antiglare layer. The coating amount at the time of spraying was 20mL/m 2 . Further, a two-fluid gun was used, the spray travel speed (nozzle travel speed) was 45 m/min, and the spray distance was 60mm. In addition, the flow rate of the air stream was 120L/min.
Example 2
In example 2, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1, except that the average molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to 7.1 nm.
Example 3
In example 3, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1, except that the average value of the molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to 7.2 nm.
Example 4
In example 4, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1, except that the average molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to 8.0 nm.
Example 5
In example 5, a coating liquid having an average molecular size of 7.1nm as a reference of scattered light intensity measured by a dynamic light scattering method was obtained by mixing and aging in a ratio (mass ratio) of TEOS to water to alcohol=1.0:0.9:7.0. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1.
Example 6
In example 6, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 5, except that the average value of the molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to 8.9 nm.
Example 7
In example 7, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 5, except that the average value of the molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to 11.0 nm.
Example 8
In example 8, TEOS as a silicate monomer was replaced with an oligomer using Tetramethoxysilane (TMOS) as a silicate oligomer (average tetramer, "methyl silicate 51" manufactured by Colcoat corporation). Further, a coating liquid having an average molecular size of 18.1nm as a reference of scattered light intensity measured by a dynamic light scattering method was obtained by mixing and aging at a ratio (mass ratio) of TMOS to water to alcohols=1.0:1.1:13.7. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1.
Example 9
In example 9, a coating liquid having an average molecular size of 8.4nm as a reference of scattered light intensity measured by a dynamic light scattering method was obtained by mixing and aging in a ratio (mass ratio) of TEOS to water to alcohol=1.0:1.2:5.9. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1.
Example 10
In example 10, a coating liquid having an average molecular size of 8.9nm as a reference of scattered light intensity measured by a dynamic light scattering method was obtained by mixing and aging in a ratio (mass ratio) of TEOS to water to alcohol=1.0:0.26:8.5. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1.
Example 11
In example 11, a coating liquid having an average molecular size of 8.4nm as a reference of scattered light intensity measured by a dynamic light scattering method was obtained by mixing and aging in a ratio (mass ratio) of TEOS to water to alcohol=1.0:0.6:5.2. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1.
Comparative example 1
In comparative example 1, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1, except that the curing time in the preparation of the coating liquid was shorter than in example 1, and the average value of the molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to 3.1 nm.
Example 12
In example 12, a mixture of ethanol, methanol and isopropanol was replaced with isopropanol (model "TOKUSOH IPA" manufactured by Nippon Co., ltd.) as an alcohol. Further, the mixture was cured at a ratio (mass ratio) of TEOS to water to alcohol=1.0:0.79:7.7 to obtain a coating liquid having an average value of 6.3nm of the molecular size on the basis of the scattered light intensity measured by the dynamic light scattering method. In addition, nitric acid was mixed to adjust to ph=3.5. In addition, the coating amount was set to 50mL/m in the case of spraying 2 The jet movement speed (nozzle movement speed) was 20 m/min, the jet distance was 100mm, and the airflow rate was 141L/min. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 1.
Example 13
In example 13, TEOS as the silicate monomer was replaced with an oligomer (average decamer, "ethyl silicate 48" manufactured by Colcoat corporation) using TEOS as the silicate oligomer. In addition, the mixture was cured in a ratio (mass ratio) of TEOS oligomer to water to alcohol=1.0:0.9:12.7 to obtain a dispersion measured by a dynamic light scattering methodThe average value of the molecular size of the light intensity standard was 7.0 nm. In addition, nitric acid was mixed to adjust to ph=4.0. In addition, the coating amount was set to 61mL/m in the case of spraying 2 The jet movement speed (nozzle movement speed) was 17 m/min, the jet distance was 58mm, and the airflow rate was 79L/min. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 12.
Example 14
In example 14, 1-butanol (manufactured by Nacalai Tesque Co., ltd.) was further added as another alcohol, and the mixture was mixed and aged in a ratio (mass ratio) of TEOS oligomer to water to alcohol to 1-butanol=1.0:0.9:12.7:0.9 to obtain a coating liquid having an average value of 7.1nm in terms of the molecular size of the scattered light intensity measured by the dynamic light scattering method. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 13.
Example 15
In example 15, a coating liquid having an average value of the molecular size of 6.9nm as measured by a dynamic light scattering method on the basis of the scattered light intensity was obtained by mixing and aging the mixture in a ratio (mass ratio) of TEOS oligomer to water to alcohol to 1-butanol=1.0:0.9:12.7:0.9. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 14.
Example 16
In example 16, a coating liquid having an average molecular size of 7.1nm as measured by a dynamic light scattering method on the basis of the scattered light intensity was obtained by mixing and aging the mixture in a ratio (mass ratio) of TEOS oligomer to water to alcohol to 1-butanol=1.0:0.9:12.7:1.2. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 14.
Example 17
In example 17, a coating liquid having an average value of the molecular size of 6.9nm as measured by a dynamic light scattering method on the basis of the scattered light intensity was obtained by mixing and aging the mixture in a ratio (mass ratio) of TEOS oligomer to water to alcohol to 1-butanol=1.0:0.9:12.7:1.5. Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 14.
Example 18
In example 18, a coating liquid having an average value of the molecular size of 6.9nm as measured by a dynamic light scattering method on the basis of the scattered light intensity was obtained by mixing and curing TEOS oligomer, water, alcohol, 1-butanol=1.0:0.9:12.7:2.0 (mass ratio). Otherwise, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 14.
Comparative example 2
In comparative example 2, a coating liquid and a base material with an antiglare layer were obtained in the same manner as in example 12, except that the amount of alcohol during curing of the coating liquid was adjusted to be higher than in example 12, and the average value of the molecular size of the scattered light intensity standard measured by the dynamic light scattering method was adjusted to be 3.0 nm.
Reference example 1
Ethyl silicate 48 (manufactured by Colcoat corporation) which is an ethyl silicate oligomer having an average of ten polymers was diluted with IPA, and the average molecular size of the scattered light intensity standard measured by the dynamic light scattering method was measured in a state where the hydrolysis condensation reaction was not caused, and the value was 2.9nm.
[ evaluation ]
(evaluation by dynamic light Scattering method)
Scattered light intensities of the coating liquids obtained in examples 1 to 18, comparative examples 1 and 2 and reference example 1 were measured by a dynamic light scattering method. As the measuring device, the model "Zetasizer Nano S" manufactured by malvern panaceae was used. The molecular size of the silica precursor was determined from the average value of the scattered light intensity references measured by the dynamic light scattering method. The measurement is to take the average value of 45 times of measurement under the conditions of 3 seconds of execution time and 30 times of execution time at a fixed position with the average scattering intensity of 500kcps, calculate the particle size distribution by a non-negative least square method, and obtain the average value of the scattering light intensity standard. As other parameters, measurement and analysis were performed under the conditions of a measurement temperature of 20.0 ℃, a particle size classification level of 70, a particle size distribution lower limit of 0.4, a display upper limit of 10000, a lower limit threshold of 0.05, an upper limit threshold of 0.01, a resolution of standard, a display range lower limit of 0.6, and a display upper limit of 300.
(evaluation of anti-glare Property)
The base materials with an antiglare layer obtained in examples 1 to 18 and comparative examples 1 and 2 were measured for glossiness as a glossiness index, haze as a haze index, and a sparkle point as a sparkle index. The gloss is based on JIS Z8741: 1997, gloss at 60℃of incident angle of the base material with an antiglare layer was measured using microglos (60 ℃) (manufactured by BYK Co.). Haze is based on JIS K7136: 2000, NDH-5000 (manufactured by Nippon electric Co., ltd.). The flash was measured in a flash measurement mode using SMS-1000 (manufactured by Display-message technology & system).
(hardness)
According to JIS K5600-5-4: 1999, the pencil hardness was measured, and the hardness of the base materials with an antiglare layer obtained in examples 1 to 18 and comparative examples 1 and 2 was obtained.
The results are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
In the cases of examples 1 to 11 and comparative example 1, which have a gloss of 123% to 144%, it can be confirmed from tables 1 and 2 that: examples 1 to 11 using the silica precursor having an average value of the molecular size of the silica precursor based on the scattered light intensity of 5.6nm or more, which was measured by the dynamic light scattering method, were able to suppress the flare point as compared with comparative example 1 using the silica precursor having an average value of the molecular size of the silica precursor based on the scattered light intensity of 3.1nm, which was measured by the dynamic light scattering method. In the cases of examples 12 to 18 and comparative example 2, which had a gloss of 25% to 72%, it can be confirmed from tables 1 and 2 that: examples 12 to 18 using the silica precursor having an average value of the molecular size of the silica precursor based on the scattered light intensity of 6.3nm or more, which was measured by the dynamic light scattering method, were able to suppress the flare point, compared with comparative example 2 using the silica precursor having an average value of the molecular size of the silica precursor based on the scattered light intensity of 3.0nm, which was measured by the dynamic light scattering method.
Symbol description
1: anti-glare layer, 2: a base material, 10: base material with anti-glare layer
Claims (11)
1. A coating liquid for spray coating comprising a silica precursor and a solvent, characterized in that,
the average value of the molecular size of the silica precursor based on the intensity of scattered light measured by a dynamic light scattering method is 5.6nm or more.
2. The coating liquid for spray coating according to claim 1, wherein,
the average value of the molecular size of the silica precursor based on the intensity of scattered light measured by a dynamic light scattering method is 30nm or less.
3. A method for producing the coating liquid for spray coating according to claim 1 or 2, comprising:
a step of preparing a mixed solution of a raw material containing the silica precursor and a solvent; and
and curing the prepared mixed solution.
4. The method for producing a coating liquid for spray coating according to claim 3, wherein,
the raw material of the silicon dioxide precursor is monomer or oligomer of alkoxy silane.
5. The method for producing a coating liquid for spray coating according to claim 4, wherein,
the alkoxy silane is tetramethoxy silane or tetraethoxy silane.
6. The method for producing a coating liquid for spray coating according to any one of claim 3 to 5, wherein,
the mixed solution further contains oxide fine particles, and the content of the oxide fine particles is less than 0.05 mass%.
7. The method for producing a coating liquid for spray coating according to claim 6, wherein,
the silica precursor is a matrix-forming component in forming an anti-glare layer by a spray method,
the oxide microparticles are a different component than the matrix forming component.
8. The method for producing a coating liquid for spray coating according to any one of claim 3 to 7, wherein,
the content of the component having a boiling point higher than 100 ℃ and lower than 120 ℃ in the mixed solution is 0 mass% or more and 15 mass% or less.
9. The method for producing a coating liquid for spray coating according to any one of claim 3 to 8, wherein,
the content of the component having a boiling point of 120 ℃ or higher in the mixed solution is 5 mass% or less.
10. A method for producing a base material with an antiglare layer, comprising:
a step of preparing a coating liquid for spray coating by the method for producing a coating liquid for spray coating according to any one of claims 3 to 9; and
and forming an anti-glare layer by applying the coating liquid for spraying on a substrate.
11. The method for producing a substrate with an antiglare layer according to claim 10,
the coating liquid for spraying was applied using a two-fluid spray gun.
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| JP2021-046082 | 2021-03-19 | ||
| JP2021182578A JP2022145461A (en) | 2021-03-19 | 2021-11-09 | Coating liquid for spray coat and its manufacturing method, as well as manufacturing method of base material with antiglare layer |
| JP2021-182578 | 2021-11-09 | ||
| PCT/JP2022/005795 WO2022196218A1 (en) | 2021-03-19 | 2022-02-15 | Coating fluid for spray coating, production method therefor, and method for producing substrate coated with antiglare layer |
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