CN117304631A - Zero phase difference protective film and manufacturing method and application thereof - Google Patents
Zero phase difference protective film and manufacturing method and application thereof Download PDFInfo
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- CN117304631A CN117304631A CN202311288328.3A CN202311288328A CN117304631A CN 117304631 A CN117304631 A CN 117304631A CN 202311288328 A CN202311288328 A CN 202311288328A CN 117304631 A CN117304631 A CN 117304631A
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- protective film
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- 230000001681 protective effect Effects 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 36
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- -1 1, 3-dioxane acrylic ester Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 6
- 230000004224 protection Effects 0.000 claims description 6
- LTGPEBRDBMFYBR-UHFFFAOYSA-N ethyl 4-[(n-ethylanilino)methylideneamino]benzoate Chemical group C1=CC(C(=O)OCC)=CC=C1N=CN(CC)C1=CC=CC=C1 LTGPEBRDBMFYBR-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- LSESCEUNBVHCTC-UHFFFAOYSA-N 6-methylheptane-1-thiol Chemical compound CC(C)CCCCCS LSESCEUNBVHCTC-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 3
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 2
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 claims description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 85
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 20
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000006750 UV protection Effects 0.000 abstract description 5
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012788 optical film Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- XPTBMOFQWMDOIY-UHFFFAOYSA-N 1,3-dioxane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCOC1 XPTBMOFQWMDOIY-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/13362—Illuminating devices providing polarized light, e.g. by converting a polarisation component into another one
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a zero phase difference protective film and a manufacturing method and application thereof, belonging to the technical field of optical films, and comprising the following components in parts by weight: 15-20 parts of modified polymethacrylic resin, 1-5 parts of ultraviolet absorber, 0.5-1 part of dispersing agent and 70-80 parts of dimethyl ether, wherein the modified polymethacrylic resin is prepared by polymerizing methyl methacrylate, siloxane and 1, 3-dioxane cycloacrylate monomers serving as raw materials in the presence of an initiator and a chain transfer agent. The novel modified polymethyl methacrylate material is adopted as a main raw material, and the proper ultraviolet absorber is added to obtain the protective film with low double refractive index, in-plane phase difference and vertical phase difference which are close to zero, so that the protective film has excellent ultraviolet resistance and strong water resistance.
Description
Technical Field
The invention relates to a zero phase difference protective film, a manufacturing method and application thereof, in particular to a zero phase difference protective film prepared from polymethyl methacrylate (PMMA) material and suitable for a polaroid and a preparation method thereof, and also relates to a polaroid and/or a polarizing plate containing the protective film, belonging to the technical field of optical films.
Background
The polaroid is an important component of a liquid crystal panel and an OLED panel, a polarizing layer is used as a core in the polaroid, and the polarizing layer is mainly prepared by stretching and orienting polyvinyl alcohol (PVA) added with iodine molecules. However, in the stretched polyvinyl alcohol film, iodine molecules on a molecular chain are easily arranged in disorder under the irradiation of moisture and ultraviolet light, and the polarization effect is affected, so that it is necessary to attach protective films having high water blocking, high transmittance, and low birefringence (low phase difference) to both sides of the polyvinyl alcohol film. In addition, the panel absorbs more ultraviolet light, and breaks chemical bonds of long-chain liquid crystal molecules to finally influence the display effect, so the protective film facing the incident light must have a certain ultraviolet light prevention characteristic.
Currently, PVA protective films on the market mainly include three types of triacetyl cellulose film (TAC), cycloolefin polyester film (COP), and polyethylene terephthalate (PET). Cellulose Triacetate (TAC) films have relatively poor water resistance, cycloolefin polyester (COP) films have poor ultraviolet resistance, and polyethylene terephthalate (PET) films have large double refractive indexes, so that the process is difficult to control, and the situation of uneven hue (Mura) is easy to occur.
In the prior art, the invention patent with publication number of CN107231978A discloses a methacrylic resin composition, which takes methacrylic resin as a main material, is formed by adding a proper amount of ultraviolet absorbent and a compound formed by a block copolymer or a graft copolymer with weight average molecular weight of about 30 ten thousand through melt mixing, has excellent weather resistance, light resistance and high heat resistance, and can be suitable for preparing a polaroid protective film. And, the invention patent with publication number CN114920871a discloses an optical-grade polymethyl methacrylate resin and use thereof, which is prepared by polymerizing, extruding and devolatilizing methyl methacrylate, long-chain alkyl acrylate and long-chain alkyl acid/ester salt as raw materials, and can be used for improving optical materials such as display light guide plate and optical lens in light transmittance, environmental stability and yellowing resistance, and reducing crystal points in the processing process.
Therefore, polymethyl methacrylate resin materials have application prospects for optical lens protection films, but proper additives are needed to be added into the polymethyl methacrylate resin materials to endow the materials with specific use performances such as heat resistance and yellowing resistance and the like, but no report is made on how to prepare a zero phase difference protection film with high transmittance, strong water resistance, low birefringence and excellent ultraviolet resistance.
Disclosure of Invention
The invention aims to provide a zero phase difference protective film, which adopts a novel modified polymethyl methacrylate material as a main raw material, and is low in birefringence obtained by adding a proper ultraviolet absorber, and has excellent ultraviolet resistance and strong water resistance, wherein the in-plane phase difference and the vertical phase difference are close to zero. Therefore, the invention also provides a preparation method of the zero phase difference protective film and application of the zero phase difference protective film in preparing a polaroid or an image display component.
The invention is realized by the following technical scheme: a zero phase difference protective film comprises the following components in parts by weight: 15 to 20 parts of modified polymethacrylic resin, 1 to 5 parts of ultraviolet absorber, 0.5 to 1 part of dispersing agent and 70 to 80 parts of dimethyl ether,
the modified polymethacrylic resin is prepared by taking methyl methacrylate, siloxane and 1, 3-dioxane acrylic ester monomers as raw materials and polymerizing the raw materials in the presence of an initiator and a chain transfer agent,
the structural formula of the modified polymethacrylic resin is shown in the following formula (1):
（1）
in the formula (1), x is 300-1000; y is 20-200; z is 10 to 160; n is an integer of 1 to 4; m is an integer of 0 to 4; r is R 2 And R is 3 Are respectively selected from alkyl with 1-6C atoms or cycloalkyl with 5-12C atoms; r is R 4 Is H or methyl.
60-95 parts of methyl methacrylate, 0.1-20 parts of siloxane and 0.1-10 parts of 1, 3-dioxane acrylic ester monomer in the modified polymethacrylic resin.
The addition amount of the initiator is 0.03-3% of the raw material consumption, and the initiator is one or more selected from dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxyacetate, 1-bis- (tert-butyl peroxy) -3,3, 5-trimethylcyclohexane and tert-butyl peroxy-3, 5, 5-trimethylhexanoate.
The addition amount of the chain transfer agent is 0.05-0.5% of the raw material dosage, and the chain transfer agent is one or more selected from n-butyl mercaptan, tert-butyl mercaptan, n-octyl mercaptan, isooctyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan.
The ultraviolet absorbent is selected from N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine, 2 '-methylenebis (4-tert-octyl-6-benzotriazole phenol), or 2- (2' -hydroxy-3 '5' -dipentylphenyl) benzotriazole.
The dispersing agent is selected from one of organosilicon leveling agents, such as polydimethylsiloxane or polymethylalkylsiloxane.
In the invention, the dispersing agent has the function of promoting the paint to form a smooth and even coating film in the drying and film forming process; the surface tension of the coating liquid can be effectively reduced, and the leveling property and uniformity of the coating liquid can be improved; can improve the permeability of coating liquid, reduce the possibility of generating spots and marks during brushing, increase the coverage and make the film forming uniform and natural.
The preparation method of the zero phase difference protective film comprises the steps of stirring and uniformly mixing modified polymethacrylic resin, an ultraviolet absorber, a dispersing agent and dimethyl ether according to the component proportion to prepare a coating liquid, and then coating, drying and biaxially stretching to obtain the zero phase difference protective film.
A polarizer comprises the zero phase difference protective film.
An image display assembly comprises the polarizer.
Compared with the prior art, the invention has the following advantages:
(1) The modified polymethyl methacrylate is prepared by polymerizing methyl methacrylate, siloxane and 1, 3-dioxane acrylic ester monomers, has the characteristics of strong water resistance, higher transmittance and low birefringence, and therefore, the protective film prepared by the modified polymethyl methacrylate basically has no phenomenon of uneven color and can be used as an excellent optical material.
(2) The invention provides a novel-structure modified polymethyl methacrylate, which can reduce the surface energy of a polymer through the introduction of silicon atoms, so that the polymer has release property, the release property of the polymer in the processing process is improved, the use of release agent in the processing process is avoided, and the processing quality of a product is improved; in addition, through the introduction of monomer hybridization, the larger steric hindrance can be used for reducing the regularity of a molecular chain, reducing the crystallinity and finally improving the toughness of a polymer, so that the problems of high brittleness, scratch resistance and the like of a resin product in the prior art are overcome, in addition, the yellowing problem of the resin product can be further improved through the introduction of the monomer, and the optical performance is improved.
(3) The invention can prepare the protective film with lower double refractive index, in-plane phase difference and vertical direction phase difference which are close to zero by utilizing the modified polymethyl methacrylate, the transmittance is more than 90 percent, the water resistance is strong, and the water vapor transmittance is lower than that of the protective film。
(4) The invention adopts the modified polymethyl methacrylate as the main raw material, has excellent anti-ultraviolet characteristic after adding proper ultraviolet absorbent, and can achieve the blocking rate of more than 90 percent for ultraviolet light with the wave band of 300nm to 380nm when the thickness is 20 to 100 mu m.
(5) The invention takes modified polymethyl methacrylate as a main raw material, and the coating liquid can be prepared by stirring and mixing after adding a proper amount of ultraviolet absorbent, dispersing agent and dimethyl ether, and the protective film can be obtained after coating, drying and biaxial stretching by combining the technical process, and the mechanical property of the film can be greatly improved, and the bending times can be up to 200 times.
Detailed Description
The objects, technical solutions and advantageous effects of the present invention will be described in further detail below.
It is noted that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed, and unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention relates to a PVA protective film made of polymethyl methacrylate (PMMA), in particular to a PVA protective film which is obtained by taking modified polymethyl methacrylate resin as a main material and adding proper ultraviolet absorber, dispersant and dimethyl ether. The PVA protective film comprises the following components in parts by weight: 15-20 parts of modified polymethacrylic resin, 1-5 parts of ultraviolet absorber, 0.5-1 part of dispersing agent and 70-80 parts of dimethyl ether.
(one) modified polymethacrylic resin
The modified polymethacrylic resin is prepared by taking methyl methacrylate, siloxane and 1, 3-dioxane cycloacrylate monomers as raw materials and polymerizing in the presence of an initiator and a chain transfer agent, wherein the structural formula of the modified polymethacrylic resin is shown as the following formula (1):
（1）
in the formula (1), x is 300-1000; y is 20-200; z is 10 to 160; n is an integer of 1 to 4; m is 0 to 4Is an integer of (2); r is R 2 And R is 3 Are respectively selected from alkyl with 1-6C atoms or cycloalkyl with 5-12C atoms; r is R 4 Is H or methyl.
The modified polymethacrylic resin is prepared by polymerizing the following components in parts by mass:
the amount of methyl methacrylate is 60 to 95 parts, preferably 70 to 90 parts, and more preferably 75 to 85 parts.
The amount of the siloxane is 0.1 to 20 parts, preferably 1 to 18 parts, and more preferably 2 to 15 parts by mass. Where m is an integer from 0 to 4, vinyltrimethoxysilane when m=0, allyltrimethoxysilane when m=1, and so on. When the amount of the siloxane is selected in the above range, the surface energy of the modified polymethacrylic resin polymer can be reduced due to the introduction of silicon atoms, so that the polymer has mold release property, the mold release property in the processing process is improved, the use of a mold release agent in the processing process can be avoided, and the processing quality of a product is improved.
The 1, 3-dioxane acrylate monomer is 0.1 to 10 parts, preferably 0.5 to 8 parts, and more preferably 1 to 5 parts. Because of the introduction of hybridization, the larger steric hindrance can reduce the regularity of molecular chains, reduce crystallinity, and finally improve the toughness of the modified polymethacrylic acid resin, thereby overcoming the problems of large brittleness, no scratch resistance and the like of PMMA products in the prior art.
Further, the preparation method of the modified polymethacrylic resin provided by the invention comprises the following steps:
and (3) batching: the methyl methacrylate, siloxane and 1, 3-dioxane acrylic ester monomers are added into a reaction kettle according to the corresponding proportion, and an initiator and a chain transfer agent are added.
The initiator is preferably a peroxide, as a specific example of which may be selected: one or more of dibenzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxyacetate, 1-bis- (t-butylperoxy) -3,3, 5-trimethylcyclohexane, t-butyl peroxy-3, 5, 5-trimethylhexanoate. The amount of the initiator to be added is 0.03 to 3% of the amount of the raw material to be used, and more preferably 0.5 to 2%.
The chain transfer agent is selected from one or more of n-butyl mercaptan, tert-butyl mercaptan, n-octyl mercaptan, isooctyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, and the amount of the chain transfer agent is 0.05-0.5% of the amount of the raw materials, and more preferably 0.15-0.5%. The present invention enables control of the molecular weight of the polymer by the use of a chain transfer agent, and when the amount of the chain transfer agent falls within the above range, the weight average molecular weight of the polymer can be controlled to 50000 to 150000, more preferably 80000 to 12000. When the molecular weight is too large, the melt fluidity is poor, the processing is difficult, and when the molecular weight is too low, the use requirement cannot be met.
Polymerization: under the protection of nitrogen, the reaction kettle is heated to 150-200 ℃ and reacts for 6-10 h at the temperature.
Extrusion dechucking: and (3) feeding the polymer after the polymerization reaction into a de-excitation type extruder, removing unreacted monomers and other byproducts, controlling the temperature of a de-excitation port to be 200-300 ℃ and the vacuum degree to be-0.095 MPa to-0.07 MPa.
Granulating: and (3) sending the polymer obtained after the dechucking into a screw for extrusion and granulation to obtain the modified polymethacrylic resin.
(II) ultraviolet absorber
The ultraviolet absorber can be N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine, 2 '-methylenebis (4-tert-octyl-6-benzotriazole phenol) or 2- (2' -hydroxy-3 '5' -dipentylphenyl) benzotriazole. Further preferred is N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine. The invention can make the blocking rate of the polymer to ultraviolet light with wave band of 300 nm-380 nm reach more than 90% by adding proper ultraviolet absorber into the modified polymethacrylic resin, and has excellent ultraviolet resistance.
(III) dispersants
The dispersants to which the invention relates may employ organosilicon leveling agents, such as polydimethylsiloxanes or polymethylalkylsiloxanes.
(IV) dimethyl ether
The solvent in the formula of the invention can be replaced by other organic solvents with the same function.
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1: modified polymethacrylic acid resin
80 parts of methyl methacrylate, 15 parts of vinyl trimethoxy silane and 5 parts of 1, 3-dioxane cycloacrylate monomer shown in the following formula (2) are sequentially added into a reaction kettle, and then 2 parts of initiator and 0.5 part of chain transfer agent are added into the reaction kettle. Nitrogen is introduced into the reaction kettle, the reaction kettle is heated to 200 ℃ under the protection of the nitrogen, and the reaction is carried out for 8 hours at the temperature. After the reaction is finished, the polymer material obtained by the reaction is sent into a devolatilizing extruder, the devolatilizing port temperature is controlled to be 255 ℃, the vacuum degree is controlled to be minus 0.090MPa, unreacted monomers and other byproducts are removed, and then the polymer obtained after the deamination is sent into a screw extrusion for extrusion granulation, thus obtaining the modified polymethacrylic resin. The relative molecular weight was 61500 as measured by Gel Permeation Chromatography (GPC).
(2)
Example 2: modified polymethacrylic acid resin
82 parts of methyl methacrylate, 15 parts of vinyl trimethoxy silane and 3 parts of 1, 3-dioxane cyclic acrylate monomer shown in the following formula (3) are sequentially added into a reaction kettle, and then 0.5 part of initiator and 0.15 part of chain transfer agent are added into the reaction kettle. Nitrogen is introduced into the reaction kettle, the reaction kettle is heated to 180 ℃ under the protection of the nitrogen, and the reaction is carried out for 10 hours at the temperature. After the reaction is finished, the polymer material obtained by the reaction is sent into a devolatilizing extruder, the devolatilizing port temperature is controlled to be 300 ℃, the vacuum degree is controlled to be minus 0.085MPa, unreacted monomers and other byproducts are removed, and then the polymer obtained after the deamination is sent into a screw extrusion for extrusion granulation, thus obtaining the modified polymethacrylic resin, and the relative molecular weight of the modified polymethacrylic resin is measured to be 98000 by adopting a Gel Permeation Chromatography (GPC) method.
(3)
Example 3: zero phase difference protective film
15 parts of the modified polymethacrylic resin of example 1, 1 part of N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine, 0.5 part of a dispersing agent and 83.5 parts of dimethyl ether were stirred and mixed uniformly until no particles were formed. Filtering the mixed solution through a filter, selecting a filter element with the specification of 500 meshes, adjusting the solid content to 30%, and then coating the filtered solution on an intermediate carrier (PET release film) through a gap coater. The thickness of the wet film after coating is 800 mu m, then the wet film passes through a baking oven, the temperature of the baking oven is 80-100 ℃, the length of the baking oven is 20m, the speed of the coated film passing through the baking oven is 10m/min, and the thickness of the dry film after drying is 350 mu m. Separating the dry film from the carrier by a film tearing machine after the dry film is discharged out of the oven, and stretching the separated dry film by a biaxial stretching device, wherein the preheating temperature is 120-150 ℃, the stretching temperature is 140-160 ℃, the heat setting temperature is 160-80 ℃, the transverse and longitudinal stretching ratio is 1:1, and the stretching multiplying power is 3.0 times. The stretched film is the zero phase difference protective film, and the thickness of the film is 80 mu m.
Example 4: zero phase difference protective film
18 parts of the modified polymethacrylic resin of example 1, 2 parts of N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylmethyl, 1.6 parts of a dispersing agent and 79.2 parts of dimethyl ether were stirred and mixed uniformly until no particles were formed. Filtering the mixed solution through a filter, selecting a filter element with the specification of 500 meshes, adjusting the solid content to 25%, and then coating the filtered solution on an intermediate carrier (PET release film) through a gap coater. The thickness of the wet film after coating is 600 mu m, then the wet film passes through a baking oven, the temperature of the baking oven is 80-100 ℃, the length of the baking oven is 20m, the speed of the coated film passing through the baking oven is 8m/min, and the thickness of the dry film after drying is 180 mu m. Separating the dry film from the carrier by a film tearing machine after the dry film is discharged out of the oven, and stretching the separated dry film by a biaxial stretching device, wherein the preheating temperature is 120-150 ℃, the stretching temperature is 140-160 ℃, the heat setting temperature is 160-80 ℃, the transverse and longitudinal stretching ratio is 1:1, and the stretching multiplying power is 2.5 times. The stretched film is the zero phase difference protective film, and the thickness of the film is 50 mu m.
Example 5: zero phase difference protective film
20 parts of the modified polymethacrylic resin of example 2, 5 parts of N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylmethyl, 1 part of a dispersing agent and 74 parts of dimethyl ether were stirred and mixed uniformly until no particles were formed. Filtering the mixed solution through a filter, selecting a filter element with the specification of 500 meshes, adjusting the solid content to 25%, and then coating the filtered solution on an intermediate carrier (PET release film) through a gap coater. The thickness of the wet film after coating is 100 mu m, then the wet film passes through a baking oven, the temperature of the baking oven is 80-100 ℃, the length of the baking oven is 20m, the speed of the coated film passing through the baking oven is 10m/min, and the thickness of the dry film after drying is 30-80 mu m. Separating the dry film from the carrier by a film tearing machine after the dry film is discharged out of the oven, and stretching the separated dry film by a biaxial stretching device, wherein the preheating temperature is 120-150 ℃, the stretching temperature is 140-160 ℃, the heat setting temperature is 160-80 ℃, the transverse and longitudinal stretching ratio is 1:1, and the stretching multiplying power is 1.5 times. The film thickness after stretching was 20. Mu.m.
Comparative example 1: protective film
The modified polymethyl methacrylate (PMMA) was substituted for the common PMMA to prepare a protective film by the same process and procedure as in example 1.
The protective films prepared in the above-described processes of example 3, example 4, example 5 and comparative example 1 were subjected to respective related tests of retardation, water blocking property and uv blocking property, as shown in table 1 below.
TABLE 1 characterization data for protective films
In table 1, re refers to the in-plane retardation, re= (nx-ny) x d, where nx is the refractive index along the retardation axis direction of the film, nx is the refractive index along the transmission axis direction of the film, and d is the film thickness.
Rth refers to the vertical direction retardation, rth= [ (nx+ny)/2-nz ]. D, where nx is the refractive index along the retardation axis direction of the film, nx is the refractive index along the transmission axis direction of the film, nz is the refractive index in the plane perpendicular to the film, and d is the film thickness. The smaller the Re and Rth values, the better the effect of improving the color shift of the liquid crystal.
Re and Rth are measured by Axoscan equipment, and the measurement wavelength is 550nm.
The measurement wavelength of the UV transmittance is 380nm, the smaller the index is, the lower the UV transmittance is, and the more favorable for protecting the liquid crystal layer
The water resistance measurement condition is that the temperature is 38 ℃, the relative humidity is 10% RH, and the smaller the index is, the stronger the hydrophobic property is represented, and the larger the display size is suitable.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (9)
1. A zero phase difference protection film is characterized in that: comprises the following components in parts by weight: 15 to 20 parts of modified polymethacrylic resin, 1 to 5 parts of ultraviolet absorber, 0.5 to 1 part of dispersing agent and 70 to 80 parts of dimethyl ether,
the modified polymethacrylic resin is prepared by taking methyl methacrylate, siloxane and 1, 3-dioxane acrylic ester monomers as raw materials and polymerizing the raw materials in the presence of an initiator and a chain transfer agent,
the structural formula of the modified polymethacrylic resin is shown in the following formula (1):
（1）
in the formula (1), x is 300-1000; y is 20-200; z is 10 to 160; n is an integer of 1 to 4; m is an integer of 0 to 4; r is R 2 And R is 3 Are respectively selected from alkyl with 1-6C atoms or cycloalkyl with 5-12C atoms; r is R 4 Is H or methyl.
2. The zero phase difference protective film according to claim 1, characterized in that: 60-95 parts of methyl methacrylate, 0.1-20 parts of siloxane and 0.1-10 parts of 1, 3-dioxane acrylic ester monomer in the modified polymethacrylic resin.
3. The zero phase difference protective film according to claim 1, characterized in that: the addition amount of the initiator is 0.03-3% of the raw material consumption, and the initiator is one or more selected from dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxyacetate, 1-bis- (tert-butylperoxy) -3, 5-trimethylcyclohexane and tert-butyl peroxy-3, 5-trimethylhexanoate.
4. The zero phase difference protective film according to claim 1, characterized in that: the addition amount of the chain transfer agent is 0.05-0.5% of the raw material dosage, and the chain transfer agent is one or more selected from n-butyl mercaptan, tert-butyl mercaptan, n-octyl mercaptan, isooctyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan.
5. The zero phase difference protective film according to claim 1, characterized in that: the ultraviolet absorbent is selected from N- (ethoxycarbonylphenyl) -N '-ethyl-N' -phenylformamidine, 2 '-methylenebis (4-tert-octyl-6-benzotriazol phenol) or 2- (2' -hydroxy-3 '5' -dipentylphenyl) benzotriazol.
6. The zero phase difference protective film according to claim 1, characterized in that: the dispersing agent is selected from one of organosilicon leveling agents.
7. A preparation method of a zero phase difference protective film is characterized by comprising the following steps: according to the component proportion of claim 1, the modified polymethacrylic resin, the ultraviolet absorbent, the dispersing agent and the dimethyl ether are stirred and mixed uniformly to prepare a coating liquid, and then the coating liquid is coated, dried and biaxially stretched to obtain the zero phase difference protective film.
8. A polarizer comprising the zero phase contrast protective film according to any one of claims 1 to 7.
9. An image display assembly, characterized by: a polarizer according to claim 8.
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