CN113150191A - Modified polymethyl methacrylate, optical thin film material, preparation method of optical thin film material and polarizer - Google Patents
Modified polymethyl methacrylate, optical thin film material, preparation method of optical thin film material and polarizer Download PDFInfo
- Publication number
- CN113150191A CN113150191A CN202110357546.2A CN202110357546A CN113150191A CN 113150191 A CN113150191 A CN 113150191A CN 202110357546 A CN202110357546 A CN 202110357546A CN 113150191 A CN113150191 A CN 113150191A
- Authority
- CN
- China
- Prior art keywords
- polymethyl methacrylate
- modified
- film material
- polycarbonate
- optical film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 113
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000003287 optical effect Effects 0.000 title description 10
- 239000010409 thin film Substances 0.000 title description 6
- 239000010408 film Substances 0.000 claims abstract description 48
- 239000004417 polycarbonate Substances 0.000 claims abstract description 43
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 43
- 239000012788 optical film Substances 0.000 claims abstract description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- UXUFTKZYJYGMGO-CMCWBKRRSA-N (2s,3s,4r,5r)-5-[6-amino-2-[2-[4-[3-(2-aminoethylamino)-3-oxopropyl]phenyl]ethylamino]purin-9-yl]-n-ethyl-3,4-dihydroxyoxolane-2-carboxamide Chemical compound O[C@@H]1[C@H](O)[C@@H](C(=O)NCC)O[C@H]1N1C2=NC(NCCC=3C=CC(CCC(=O)NCCN)=CC=3)=NC(N)=C2N=C1 UXUFTKZYJYGMGO-CMCWBKRRSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- YTJXGDYAEOTOCG-UHFFFAOYSA-N lithium;di(propan-2-yl)azanide;oxolane Chemical compound [Li+].C1CCOC1.CC(C)[N-]C(C)C YTJXGDYAEOTOCG-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C08F8/00—Chemical modification by after-treatment
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Abstract
The invention is applicable to the technical field of materials, and provides a modified polymethyl methacrylate, an optical film material, a preparation method thereof and a polarizer, wherein the modified polymethyl methacrylate is obtained by taking polymethyl methacrylate as a matrix and introducing a phenyl functional group on a molecular chain of the polymethyl methacrylate. The modified polymethyl methacrylate obtained by the invention not only can improve the high temperature resistance of polymethyl methacrylate, but also is beneficial to promoting the compatibility with polycarbonate; in addition, the modified polymethyl methacrylate and the polycarbonate are compounded to form a film, and the benzene ring structure and the positive birefringence characteristic of the polycarbonate are combined, so that the bottleneck problems of poor high-temperature resistance and high retardation value of the conventional polymethyl methacrylate can be well solved, and the preparation requirement of the acrylate film for the polyvinyl alcohol protective film for the polarizer is met.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a modified polymethyl methacrylate, an optical film material, a preparation method of the optical film material and a polarizer.
Background
A polyvinyl alcohol film (PVA film) of a device, which plays a leading role in a polarizer, often needs a protective film due to its weak mechanical properties and susceptibility to temperature and humidity. The traditional PVA protective film uses TAC film which has excellent optical transparency and good hydrophilic property, but the industrial production of the TAC film usually adopts a solution casting method, and the raw material source is highly concentrated in Japan manufacturers, so the production cost is high and the manufacturing difficulty is large. In recent years, the development of a new PVA protective film for a polarizer on the market to replace the TAC film is becoming a trend, particularly an acrylate-based film.
Compared with a TAC film, the acrylate film has more excellent optical performance and mechanical performance. However, when it is used as a polarizer protective film, it is liable to cause poor dimensional stability of the polarizer during use at high temperatures due to its low glass transition temperature; in addition, when the acrylate-based film is prepared by a stretching process, the refractive index in the direction perpendicular to the stretching direction is increased, a negative refractive index characteristic is exhibited, and a high out-of-plane retardation value is brought, which may affect the optical effect of the polarizer. The research and development of modified acrylate resin are completed by the Japanese catalyst and the Brillouin chemistry respectively from the chemical synthesis perspective, the monomer copolymerization ratio, the post-treatment condition and the film-making process need to be strictly controlled, the process is complex and is completely confidential at home. Therefore, the preparation of the acrylate film with high temperature resistance and low retardation value has important scientific significance for the development of the optical field in China.
Therefore, the characteristics of poor high temperature resistance and negative refractive index of the conventional domestic common acrylate film material can not meet the performance requirements of high temperature resistance and low retardation value of the PVA protective film for the polarizer in the current market.
Disclosure of Invention
The embodiment of the invention provides modified polymethyl methacrylate, and aims to solve the problems that the existing acrylate film material has the characteristics of poor high temperature resistance and negative refractive index, and cannot meet the requirements of the market on high temperature resistance and low retardation value of a PVA protective film for a polarizer at present.
The embodiment of the invention is realized by adopting the modified polymethyl methacrylate, wherein the modified polymethyl methacrylate is obtained by taking the polymethyl methacrylate as a matrix and introducing a phenyl functional group on a molecular chain of the polymethyl methacrylate.
The embodiment of the invention also provides a preparation method of the modified polymethyl methacrylate, which comprises the following steps:
dissolving polymethyl methacrylate in an organic solvent, and controlling the solid content to be 5-15% to prepare a first mixed solution;
uniformly stirring phenol or homologues of phenol and an organic solvent in an ice-water bath in an anhydrous and oxygen-free environment to obtain a second mixed solution;
and adding lithium diisopropylamide into the second mixed solution, mixing, continuously adding the first mixed solution, continuously mixing and reacting at the temperature of 70-120 ℃, adjusting the pH value of the solution to be neutral after the reaction is finished, precipitating, extracting and cleaning to obtain the lithium diisopropylamide aqueous solution.
The embodiment of the invention also provides an optical film material, which is prepared by compounding the modified polymethyl methacrylate and polycarbonate and extruding the mixture to form a film.
The embodiment of the invention also provides a preparation method of the optical film material, which comprises the following steps:
blending the modified polymethyl methacrylate and polycarbonate, conveying the blended mixture to a double-screw extruder for melt blending extrusion to obtain a blended material; the mass ratio of the modified polymethyl methacrylate to the polycarbonate is 8: 2-6: 4;
and conveying the blend to a single-screw extruder to be extruded into a film to obtain the optical film material.
The embodiment of the invention also provides a polaroid, which comprises a component prepared from the optical thin film material.
The modified polymethyl methacrylate provided by the embodiment of the invention is obtained by taking polymethyl methacrylate as a raw material to carry out chemical grafting modification and introducing a functional group with a phenyl ester group on a side chain of the polymethyl methacrylate, so that the high temperature resistance of the polymethyl methacrylate can be improved, and the compatibility with polycarbonate can be promoted; in addition, the modified polymethyl methacrylate and the polycarbonate are compounded to form a film, and the benzene ring structure and the positive birefringence characteristic of the polycarbonate are combined, so that the bottleneck problems of poor high-temperature resistance and high retardation value of the conventional polymethyl methacrylate can be well solved, and the preparation requirement of the acrylate film for the polyvinyl alcohol protective film for the polarizer is met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Polycarbonate (PC) not only has positive birefringence, but also has good toughness and high refractive index, can form good complementation with polymethyl methacrylate (PMMA) resin in performance, and is an ideal modifier for preparing acrylate films with low retardation values. However, it is difficult to form a transparent film after blending both PMMA and PC due to poor compatibility of both and difference in refractive index of each. Therefore, through extensive research, the invention modifies PMMA, carries out chemical grafting reaction on the molecular chain of PMMA polymer, and introduces a phenyl ester functional group. The result shows that the obtained modified PMMA can not only improve the high temperature resistance of PMMA, but also is beneficial to improving the blending performance with PC, and the preparation of the acrylate film with low retardation value is completed.
The embodiment of the invention provides modified PMMA which is obtained by taking polymethyl methacrylate as a matrix and introducing a phenyl ester functional group on a molecular chain of the polymethyl methacrylate.
In the examples of the present invention, the structural formula of the modified PMMA is as follows:
wherein R is phenyl or functional groups of its homologues, including but not limited to tolyl, xylyl, chlorophenyl, and the like; the modified PMMA is soluble in methylpyrrolidone (NMP), Dimethylformamide (DMF), dichloroethane (EDC), and the like, and insoluble in methanol, ethanol, and water.
The embodiment of the invention provides a preparation method of modified PMMA, and the involved preparation reaction equation is as follows:
the preparation method of the modified PMMA comprises the following steps:
step S101: dissolving polymethyl methacrylate in an organic solvent, and controlling the solid content to be 5-15% to prepare a first mixed solution.
In the embodiment of the present invention, the polymethyl methacrylate raw material is a resin material having good transparency. Preferably, the polymethyl methacrylate is a copolymer type polymethyl methacrylate, and the average molecular weight thereof is 7 to 13 ten thousand. The copolymer-type polymethyl methacrylate includes, but is not limited to, an alicyclic structure, a heterocyclic structure, or a structure containing an aromatic group in the constituent unit. For example, a copolymer PMMA brand of R100 of Japan Electrochemistry may be used.
Step S102: and uniformly stirring the phenol or the homologue of the phenol and the organic solvent in an ice-water bath under an anhydrous and oxygen-free environment to obtain a second mixed solution.
In the present embodiment, the organic solvent used in step S101 and step S102 includes, but is not limited to, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP).
Specifically, phenol or a homologue of phenol (such as methyl phenol) and an organic solvent are weighed and placed in a three-necked bottle, and the mass fraction is controlled to be 10-25%; stirring in ice water bath; during stirring, vacuumizing and introducing nitrogen gas into the three-mouth bottle are alternately performed to ensure that the three-mouth bottle is in an anhydrous and anaerobic environment.
Step S103: and adding lithium diisopropylamide into the second mixed solution, mixing, continuously adding the first mixed solution, continuously mixing and reacting at the temperature of 70-120 ℃, adjusting the pH value of the solution to be neutral after the reaction is finished, precipitating, extracting and cleaning to obtain the lithium diisopropylamide aqueous solution.
In the embodiment of the present invention, lithium diisopropylamide should preferably be 2M lithium diisopropylamide tetrahydrofuran/n-heptane/ethylbenzene solution; because the water-soluble organic silicon compound is easy to decompose in water and has high activity, the water-free and oxygen-free environment is ensured in the using process.
In the embodiment of the invention, the molar ratio of the polymethyl methacrylate (based on the structural unit of the methyl methacrylate in the polymer), the phenol or the homologue of the phenol and the lithium diisopropylamide is 1-5: 1-2.5.
Specifically, Lithium Diisopropylamide (LDA) was injected into a three-necked flask with a syringe; after stirring for 30-60min, pouring the first mixed solution into a three-mouth bottle; wherein, the three-mouth bottle is kept in an anhydrous and oxygen-free environment during the process of adding the medicine. Removing the ice water bath, continuously stirring the mixed solvent in the three-neck flask for 10-60min, increasing the reaction temperature to 70-120 ℃, and reacting for 2-5 h; after the reaction is finished, neutralizing the pH value of the reaction solution to 7 by using HCl; and the modified PMMA is mainly precipitated in methanol and is extracted by water or normal hexane for continuous cleaning.
The embodiment of the invention also provides an optical film material, which is prepared by compounding the modified polymethyl methacrylate and polycarbonate and extruding the compounded mixture to form a film. .
The embodiment of the invention also provides a preparation method of the optical film material, which comprises the following steps:
step S201, the modified polymethyl methacrylate and polycarbonate of claim 1 or 2 are blended and conveyed to a double-screw extruder for melt blending and extrusion to obtain a blend.
In the embodiment of the invention, the blending mass ratio of the modified PMMA to the PC is 8: 2-6: 4, the temperature of the double-screw extruder is 225-.
In embodiments of the present invention, the positive birefringence characteristics of the polycarbonate itself can be utilized to achieve low retardation values, and it has a higher glass transition temperature. In the present invention, it is preferable to use a copolymerized polycarbonate having low water absorption, excellent heat resistance, low temperature characteristics and surface hardness, a glass transition temperature of not less than 160 ℃ and an average molecular weight of 4.5 to 9.0 ten thousand. For example, APEC 2097, available under the trade mark bayer, germany, may be used.
And S202, conveying the blend to a single-screw extruder to be extruded into a film, so as to obtain the optical film material.
In the embodiment of the invention, the temperature of the single-screw extruder is 225-285 ℃, and the extrusion rotating speed is 10-100 r/min; the temperature of the winding cold roll is 30-80 ℃. The thickness of the resulting optical film material can be appropriately adjusted as needed, and is preferably 10 μm to 100 μm.
The embodiment of the invention also provides a polaroid, which comprises a component prepared from the optical thin film material.
Examples of certain embodiments of the invention are given below, which are not intended to limit the scope of the invention. Unless otherwise indicated, the starting materials used in the examples of the present invention are either commercially available or prepared by conventional methods.
Example 1
This example provides a modified PMMA having a polymer formula as follows:
the reaction equation for preparing the modified PMMA is as follows:
weighing 5 parts of PMMA resin by molar weight, and dissolving the PMMA resin in an organic solvent DMF to prepare a PMMA-DMF organic solution; controlling the solid content to be 5 percent; weighing 1 part (molar weight) of phenol in a three-necked bottle containing DMF, preparing a solution with the mass fraction of 10%, and uniformly stirring in an ice-water bath; during stirring, vacuumizing and introducing nitrogen into the three-mouth bottle are alternately performed to ensure that the three-mouth bottle is in an anhydrous and anaerobic environment; 2 parts (molar weight) of Lithium Diisopropylamide (LDA) are injected into a three-neck flask by using a syringe; after stirring for 60min, pouring PMMA-DMF organic solution into a three-necked bottle; the three-mouth bottle is in an anhydrous and oxygen-free environment; removing the ice water bath, continuously stirring the mixed solvent in the three-mouth bottle for 30min, increasing the reaction temperature to 120 ℃, and reacting for 2 h; after the reaction is finished, neutralizing the reaction solution by using HCl until the pH value is 7; the modified PMMA is mainly precipitated in methanol and is extracted by water or normal hexane for continuous cleaning.
The preparation method of the optical film material comprises the following main steps:
and drying the modified PMMA resin, blending the dried modified PMMA resin with PC, and conveying the mixture to a double-screw extruder for melt blending and extrusion to obtain a blend material. Wherein the blending mass ratio of the modified PMMA to the PC is 8:2, the temperature of the double-screw extruder is 245 ℃, and the rotating speed is 70 r/min; conveying the blend to a single-screw extruder to extrude the blend into a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 255 ℃, and the extrusion speed is 60 r/min; the temperature of the rolling cold roll is 70 ℃; the thickness of the optical film was 60 μm.
Example 2
This example provides a modified PMMA having a polymer formula as follows:
the reaction equation for preparing the modified PMMA is as follows:
weighing PMMA resin with the molar weight of 2.5 parts, and dissolving the PMMA resin in an organic solvent DMF to prepare a PMMA-DMF organic solution; controlling the solid content to be 10 percent; weighing 2.5 parts (molar weight) of phenol in a DMF (dimethyl formamide) -containing three-necked bottle to prepare a solution with the mass fraction of 10%, and uniformly stirring in an ice-water bath; during stirring, vacuumizing and introducing nitrogen into the three-mouth bottle are alternately performed to ensure that the three-mouth bottle is in an anhydrous and anaerobic environment; injecting 1 part (molar weight) of Lithium Diisopropylamide (LDA) into a three-neck flask by using a syringe; after stirring for 30min, pouring PMMA-DMF organic solution into a three-necked bottle; the three-mouth bottle is in an anhydrous and oxygen-free environment; removing the ice water bath, continuously stirring the mixed solvent in the three-mouth bottle for 60min, increasing the reaction temperature to 120 ℃, and reacting for 5 h; after the reaction is finished, neutralizing the reaction solution by using HCl until the pH value is 7; the modified PMMA is mainly precipitated in methanol and extracted in water or normal hexane for continuous cleaning;
the preparation method of the optical film material comprises the following main steps:
and drying the modified PMMA resin, blending the dried modified PMMA resin with PC, and conveying the mixture to a double-screw extruder for melt blending and extrusion to obtain a blend material. Wherein the blending mass ratio of PMMA to PC is 8:2, the temperature of a double-screw extruder is 290 ℃, and the rotating speed is 15 r/min; conveying the blend to a single-screw extruder to extrude the blend into a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 285 ℃, and the extrusion speed is 100 r/min; the temperature of the rolling cold roll is 80 ℃; the thickness of the optical film was 10 μm.
Example 3
This example provides a modified PMMA having a polymer formula as follows:
the reaction equation for preparing the modified PMMA is as follows:
weighing 1 part of PMMA resin in molar weight, and dissolving the PMMA resin in an organic solvent DMF to prepare a PMMA-DMF organic solution; controlling the solid content to be 15 percent; weighing 5 parts (by mol) of phenol in a DMF (dimethyl formamide) -containing three-necked bottle, preparing a solution with the mass fraction of 15%, and uniformly stirring in an ice-water bath; during stirring, vacuumizing and introducing nitrogen into the three-mouth bottle are alternately performed to ensure that the three-mouth bottle is in an anhydrous and anaerobic environment; 2.5 parts (molar weight) of Lithium Diisopropylamide (LDA) are injected into a three-mouth bottle by using a syringe; after stirring for 45min, pouring PMMA-DMF organic solution into a three-necked bottle; the three-mouth bottle is in an anhydrous and oxygen-free environment; removing the ice water bath, continuously stirring the mixed solvent in the three-neck flask for 10min, increasing the reaction temperature to 90 ℃, and reacting for 2.5 h; after the reaction is finished, neutralizing the reaction solution by using HCl until the pH value is 7; the modified PMMA is mainly precipitated in methanol and extracted in water or normal hexane for continuous cleaning;
the preparation method of the optical film material comprises the following main steps:
and drying the modified PMMA resin, blending the dried modified PMMA resin with PC, and conveying the mixture to a double-screw extruder for melt blending and extrusion to obtain a blend material. Wherein the blending mass ratio of PMMA to PC is 8:2, the temperature of a double-screw extruder is 225 ℃, and the rotating speed is 100 r/min; conveying the blend to a single-screw extruder to extrude the blend into a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 225 ℃, and the extrusion speed is 10 r/min; the temperature of the rolling cold roll is 30 ℃; the thickness of the optical film was 100. mu.m.
Example 4
This example provides a modified PMMA having a polymer formula as follows:
the reaction equation for preparing the modified PMMA is as follows:
weighing 5 parts of PMMA resin by molar weight, and dissolving the PMMA resin in an organic solvent DMF to prepare a PMMA-DMF organic solution; controlling the solid content to be 5 percent; weighing 1 part (molar weight) of methylphenol in a DMF (dimethyl formamide) -containing three-necked bottle, preparing a solution with the mass fraction of 25%, and uniformly stirring in an ice-water bath; during stirring, vacuumizing and introducing nitrogen into the three-mouth bottle are alternately performed to ensure that the three-mouth bottle is in an anhydrous and anaerobic environment; 2 parts (molar weight) of Lithium Diisopropylamide (LDA) are injected into a three-neck flask by using a syringe; after stirring for 60min, pouring PMMA-DMF organic solution into a three-necked bottle; the three-mouth bottle is in an anhydrous and oxygen-free environment; removing the ice water bath, continuously stirring the mixed solvent in the three-mouth bottle for 30min, increasing the reaction temperature to 70 ℃, and reacting for 2 h; after the reaction is finished, neutralizing the reaction solution by using HCl until the pH value is 7; the modified PMMA is mainly precipitated in methanol and is extracted by water or normal hexane for continuous cleaning.
The preparation method of the optical film material comprises the following main steps:
and drying the modified PMMA resin, blending the dried modified PMMA resin with PC, and conveying the mixture to a double-screw extruder for melt blending and extrusion to obtain a blend material. Wherein the blending mass ratio of the modified PMMA to the PC is 8:2, the temperature of the double-screw extruder is 245 ℃, and the rotating speed is 70 r/min; conveying the blend to a single-screw extruder to extrude the blend into a film to obtain an optical film material, wherein the temperature of the single-screw extruder is 255 ℃, and the extrusion speed is 60 r/min; the temperature of the rolling cold roll is 70 ℃; the thickness of the optical film was 60 μm.
Comparative example 1
Commercially available PMMA (polymethylmethacrylate) material.
Comparative example 2
Modified PMMA was prepared using example 1, without blending with PC, and was directly film extruded through a single screw extruder to prepare an optical film material.
Comparative example 3
The unmodified commercial PMMA is directly blended with PC in a double-screw extruder according to the proportion of 8:2, and then the blend is extruded by a single-screw extruder to prepare the optical film material.
Comparative example 4
The raw materials and the preparation process conditions were the same as those of example 1 except that the same amounts of the raw material copolymerized polymethyl methacrylate and polycarbonate used in example 1 were replaced with non-copolymerized polymethyl methacrylate and polycarbonate.
The following performance tests were performed on the optical film materials obtained in the above examples 1 to 4 and comparative examples 1 to 4, and the results are shown in Table 1 below. The test method comprises the following steps: the density is tested according to the test standard of ISO 1183; the water absorption is tested according to the test standard of ISO 62; the surface hardness is tested according to the test standard GB/T6739-86; flexural modulus was tested according to ISO 178 test standard; the tensile strength is tested according to the test standard of ISO 527; the glass transition temperature is tested according to a DSC test method, and the specific test method comprises the following steps: putting the sample to be tested in N2Under protection, heating from normal temperature to 230 ℃ at the speed of 10 ℃/min, keeping the temperature at 230 ℃ for 3min to eliminate thermal history, then cooling to 30 ℃ at the speed of 10 ℃/min, staying at 30 ℃ for 3min, and then heating to 230 ℃ at the temperature-rising speed of 10 ℃/min; the refractive index is tested according to the test standard of ISO 489; the light transmittance was measured according to the test method of ISO 13468.
In addition, when a film is produced by stretching an acrylate-based resin, the stretched film has a negative birefringence characteristic in which the refractive index increases in the direction perpendicular to the stretching, and the film has a retardation value. Therefore, before testing the retardation value, the optical film material of the invention needs to be stretched in the MD direction and the TD direction, wherein the stretching in the MD direction is 1.5 times to 2.5 times, and the stretching in the TD direction is 1.5 times to 3.0 times; the stretching temperature used should be close to the glass transition temperature.
The retardation value of the optical film material of the present invention is characterized by:
Rin＝|nx-ny|*d (1-1)
wherein nx, ny, nz represent refractive indices in an x-axis direction, a y-axis direction, and a z-axis direction, respectively, and d represents a thickness (nm) of the optical film after stretching.
TABLE 1
According to the test results of examples 1-4 and comparative examples 1-4 in table 1, it can be seen that, in examples 1-4 of the present invention, the polymethyl methacrylate is used as a raw material to perform chemical grafting modification, a functional group having a phenyl ester group is introduced to a side chain of the polymethyl methacrylate, and the side chain is blended with a polycarbonate polymer, so that not only can the high temperature resistance of the polymethyl methacrylate-based resin be improved, but also the glass transition temperature of the film in examples 1-4 is obviously improved; but also facilitates the compatibility with polycarbonate, and is particularly characterized in that the film has high light transmittance, while the film of comparative example 3 has low light transmittance because the film is not modified; in addition, the modified polymethyl methacrylate and the polycarbonate are compounded to form a film, and the positive birefringence characteristic and the benzene ring structure of the polycarbonate are combined, so that the problem that the current polymethyl methacrylate is high in retardation value can be well solved, and the specific expression is that the Rin and Rth values of the optical films in examples 1-4 are obviously reduced relative to the value in comparative example 1. Comparing example 1 with comparative example 4, it can be seen that the use of the copolymerized polymethylmethacrylate and polycarbonate is advantageous in improving the flexural modulus, tensile strength, glass transition temperature, and light transmittance of the material. In general, the acrylate optical film prepared in the embodiment of the invention meets the preparation requirement of the polyvinyl alcohol protective film for the polarizer.
Further, in order to verify the influence of the PC content on the low retardation value acrylate-based film, the invention only adjusts the blending mass ratio of the modified PMMA and the PC to 9:1, 7:3, 6:4 and 5:5 respectively based on the above example 1, and the corresponding performance test results are shown in table 2.
TABLE 2
| Mass ratio of modified PMMA to PC | 9:1 | 7:3 | 6:4 | 5:5 |
| Density (g/cm)3) | 1.18 | 1.17 | 1.19 | 1.17 |
| Water absorption (%) | 0.23 | 0.24 | 0.23 | 0.22 |
| Surface hardness (Pencil) | 3H | 2H | H | H |
| Flexural modulus (MPa) | 3260 | 3450 | 3500 | 3705 |
| Tensile Strength (MPa) | 79 | 86 | 89 | 88 |
| Glass transition temperature (. degree. C.) | 126 | 129 | 132 | 136 |
| Refractive index | 1.51 | 1.52 | 1.53 | 1.53 |
| Light transmittance (%) | 95 | 93 | 92 | 90 |
| Rin(nm) | 17 | 6.5 | 8.1 | 28 |
| Rth(nm) | 24 | 7.2 | 3.4 | 12 |
Overall, the change in the polycarbonate content has a large effect on the Rin and Rth values of the optical film; when the total content is less than 10% or more than 50%, it is difficult to obtain an optical film having a low retardation value because of insufficient compensation or too large positive birefringence characteristics.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The modified polymethyl methacrylate is characterized in that the modified polymethyl methacrylate is obtained by taking polymethyl methacrylate as a matrix and introducing a phenyl functional group on a molecular chain of the polymethyl methacrylate.
2. The modified polymethylmethacrylate of claim 1 wherein the modified polymethylmethacrylate has the following structural formula:
wherein R is phenyl or functional group of homologous series thereof.
3. A preparation method of modified polymethyl methacrylate is characterized by comprising the following steps:
dissolving polymethyl methacrylate in an organic solvent, and controlling the solid content to be 5-15% to prepare a first mixed solution;
uniformly stirring phenol or homologues of phenol and an organic solvent in an ice-water bath in an anhydrous and oxygen-free environment to obtain a second mixed solution;
and adding lithium diisopropylamide into the second mixed solution, mixing, continuously adding the first mixed solution, continuously mixing and reacting at the temperature of 70-120 ℃, adjusting the pH value of the solution to be neutral after the reaction is finished, precipitating, extracting and cleaning to obtain the lithium diisopropylamide aqueous solution.
4. The method according to claim 3, wherein the molar ratio of the polymethyl methacrylate to the phenol or the homologue of the phenol to the lithium diisopropylamide is 1-5: 1-2.5.
5. The process for producing a modified polymethyl methacrylate according to claim 3 or 4, wherein the polymethyl methacrylate is a copolymer type polymethyl methacrylate and has an average molecular weight of 7 to 13 ten thousand.
6. An optical film material, which is obtained by compounding the modified polymethyl methacrylate according to claim 1 or 2 with polycarbonate and extruding the compounded product to form a film.
7. A method for preparing an optical film material, comprising:
blending the modified polymethyl methacrylate as claimed in claim 1 or 2 with polycarbonate, conveying the blend to a double-screw extruder, and performing melt blending extrusion to obtain a blend; the mass ratio of the modified polymethyl methacrylate to the polycarbonate is 8: 2-6: 4;
and conveying the blend to a single-screw extruder to be extruded into a film to obtain the optical film material.
8. The method for preparing optical film material as claimed in claim 7, wherein the temperature of the twin-screw extruder is 225-290 ℃, and the rotation speed is 15-100 r/min; the temperature of the single-screw extruder is 225-285 ℃, the extrusion rotating speed is 10-100r/min, and the temperature of the winding cold roll is 30-80 ℃.
9. The method for producing an optical film material according to claim 7, wherein the polycarbonate is a copolymer polycarbonate having a glass transition temperature of not less than 160 ℃ and an average molecular weight of 4.5 to 9.0 ten thousand.
10. A polarizer comprising a device prepared from the optical film material of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110357546.2A CN113150191A (en) | 2021-04-01 | 2021-04-01 | Modified polymethyl methacrylate, optical thin film material, preparation method of optical thin film material and polarizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110357546.2A CN113150191A (en) | 2021-04-01 | 2021-04-01 | Modified polymethyl methacrylate, optical thin film material, preparation method of optical thin film material and polarizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113150191A true CN113150191A (en) | 2021-07-23 |
Family
ID=76886135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110357546.2A Pending CN113150191A (en) | 2021-04-01 | 2021-04-01 | Modified polymethyl methacrylate, optical thin film material, preparation method of optical thin film material and polarizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113150191A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094533A (en) * | 2022-08-26 | 2022-09-23 | 汕头市超越织造有限公司 | Nano-modified high-strength polypropylene fiber filament and preparation method and application thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5280070A (en) * | 1992-06-01 | 1994-01-18 | Enichem S.P.A. | Polycarbonate-polymethyl methacrylate blends |
| US5336725A (en) * | 1991-06-21 | 1994-08-09 | Mitsubishi Rayon Co., Ltd. | Method for preparing graft copolymer |
| US5721321A (en) * | 1995-09-21 | 1998-02-24 | Th. Goldschmidt Ag | Polymethacrylic esters whose ester groups in position and differ from those in the chain |
| US20040063887A1 (en) * | 2002-09-30 | 2004-04-01 | Tosoh Corporation | Transparent heat-resistant resin optical material and film |
| CN101323570A (en) * | 2008-07-25 | 2008-12-17 | 中国科学院上海有机化学研究所 | Functional acrylic ester monomer containing atom transfer free radical polymerization initiating group, synthetic method and use thereof |
| CN101336257A (en) * | 2005-11-29 | 2008-12-31 | 巴斯夫欧洲公司 | Method for the reesterification or esterification of side chains in polymers |
| WO2009089006A1 (en) * | 2008-01-11 | 2009-07-16 | The Board Of Trustees Of The University Of Illinois | Label-free biosensors based upon distributed feedback laser |
| KR20100026927A (en) * | 2008-08-28 | 2010-03-10 | 주식회사 엘지화학 | Retardation films and liquid crystal display comprising the sames |
| CN102317333A (en) * | 2009-02-18 | 2012-01-11 | Lg化学株式会社 | Acrylic resin composition, and optical film comprising same |
| CN102933624A (en) * | 2010-06-08 | 2013-02-13 | Lg化学株式会社 | Acryl-based copolymers with heatresistance and high strength, and an optical film comprising the same |
| CN102985454A (en) * | 2010-06-30 | 2013-03-20 | Lg化学株式会社 | Acryl-based copolymers and optical film including the same |
| CN103492479A (en) * | 2011-10-05 | 2014-01-01 | Lg化学株式会社 | Resin composition for an optical film, and retardation film using same |
| CN103649223A (en) * | 2011-10-04 | 2014-03-19 | Lg化学株式会社 | Resin composition and optical film formed by using same |
| US20140128546A1 (en) * | 2011-10-04 | 2014-05-08 | Lg Chem, Ltd. | Resin composition and optical compensation film formed using the same |
| CN107189302A (en) * | 2017-06-20 | 2017-09-22 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of the polymethyl methacrylate nano composite of high rigidity |
| CN108137897A (en) * | 2016-08-09 | 2018-06-08 | 株式会社Lg化学 | Resin composition for optical material and the optical film for including it |
| CN112063146A (en) * | 2020-09-02 | 2020-12-11 | 广州华新科智造技术有限公司 | PC/PMMA alloy and preparation method and application thereof |
-
2021
- 2021-04-01 CN CN202110357546.2A patent/CN113150191A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336725A (en) * | 1991-06-21 | 1994-08-09 | Mitsubishi Rayon Co., Ltd. | Method for preparing graft copolymer |
| US5280070A (en) * | 1992-06-01 | 1994-01-18 | Enichem S.P.A. | Polycarbonate-polymethyl methacrylate blends |
| US5721321A (en) * | 1995-09-21 | 1998-02-24 | Th. Goldschmidt Ag | Polymethacrylic esters whose ester groups in position and differ from those in the chain |
| US20040063887A1 (en) * | 2002-09-30 | 2004-04-01 | Tosoh Corporation | Transparent heat-resistant resin optical material and film |
| CN101336257A (en) * | 2005-11-29 | 2008-12-31 | 巴斯夫欧洲公司 | Method for the reesterification or esterification of side chains in polymers |
| WO2009089006A1 (en) * | 2008-01-11 | 2009-07-16 | The Board Of Trustees Of The University Of Illinois | Label-free biosensors based upon distributed feedback laser |
| CN101323570A (en) * | 2008-07-25 | 2008-12-17 | 中国科学院上海有机化学研究所 | Functional acrylic ester monomer containing atom transfer free radical polymerization initiating group, synthetic method and use thereof |
| KR20100026927A (en) * | 2008-08-28 | 2010-03-10 | 주식회사 엘지화학 | Retardation films and liquid crystal display comprising the sames |
| CN102317333A (en) * | 2009-02-18 | 2012-01-11 | Lg化学株式会社 | Acrylic resin composition, and optical film comprising same |
| CN102933624A (en) * | 2010-06-08 | 2013-02-13 | Lg化学株式会社 | Acryl-based copolymers with heatresistance and high strength, and an optical film comprising the same |
| CN102985454A (en) * | 2010-06-30 | 2013-03-20 | Lg化学株式会社 | Acryl-based copolymers and optical film including the same |
| CN103649223A (en) * | 2011-10-04 | 2014-03-19 | Lg化学株式会社 | Resin composition and optical film formed by using same |
| US20140128546A1 (en) * | 2011-10-04 | 2014-05-08 | Lg Chem, Ltd. | Resin composition and optical compensation film formed using the same |
| CN103492479A (en) * | 2011-10-05 | 2014-01-01 | Lg化学株式会社 | Resin composition for an optical film, and retardation film using same |
| CN108137897A (en) * | 2016-08-09 | 2018-06-08 | 株式会社Lg化学 | Resin composition for optical material and the optical film for including it |
| CN107189302A (en) * | 2017-06-20 | 2017-09-22 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of the polymethyl methacrylate nano composite of high rigidity |
| CN112063146A (en) * | 2020-09-02 | 2020-12-11 | 广州华新科智造技术有限公司 | PC/PMMA alloy and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CAROLIN FLEISCHMANN等: ""Direct Access to Functional (Meth)Acrylate Copolymers Through Transesterification with Lithium Alkoxides"", 《JOURNAL OF POLYMER SCIENCE,PART A: POLYMER CHEMISTRY》 * |
| 周其凤等主编: "《高分子化学》", 31 October 2001, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094533A (en) * | 2022-08-26 | 2022-09-23 | 汕头市超越织造有限公司 | Nano-modified high-strength polypropylene fiber filament and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6389261B2 (en) | Optical film resin composition, optical film formed using the same, polarizing plate including the same, and image display device | |
| CN108884292B (en) | Resin composition, molded article thereof, and film | |
| KR102356921B1 (en) | Stretched film and method for producing stretched film | |
| JP5770374B2 (en) | Resin composition, optical film formed using the same, polarizing plate including the same, and liquid crystal display device | |
| CN104672698A (en) | Stone and plastic composite material | |
| CN103347952A (en) | Resin composition for optical film and optical film using the same | |
| CN105492473A (en) | (meth)acrylic resin | |
| CN101395502B (en) | Layered polarization film, phase difference film, and liquid crystal display device | |
| CN113150191A (en) | Modified polymethyl methacrylate, optical thin film material, preparation method of optical thin film material and polarizer | |
| CN111454517B (en) | Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof | |
| WO2022127860A1 (en) | Modified polypropylene material, preparation method therefor, and application thereof | |
| JPH03175404A (en) | Polarizing film and production thereof | |
| JP6310351B2 (en) | Optical film | |
| JP2020509115A (en) | Transparent film based on resin component with high glass transition temperature | |
| CN103946284A (en) | Acrylic resin film having good transparency and impact resistance and method for manufacturing same | |
| CN114106501B (en) | Optical film, blended resin, preparation method and application | |
| JP2016071218A (en) | Optical film | |
| CN103459490B (en) | Blooming resin combination and use the blooming of this resin combination | |
| CN106147063A (en) | PVC heat shrink films | |
| CN109880253B (en) | PVC (polyvinyl chloride) heat shrinkable film and preparation method thereof | |
| KR102612870B1 (en) | Method for making polarizer protective film | |
| JP2022164227A (en) | Transparent conductive film, and manufacturing method of transparent conductive film | |
| WO2022001018A1 (en) | Anti-floating fiber agent and anti-floating fiber polypropylene reinforced composite material | |
| JP2017181823A (en) | Polarizer protective film | |
| JP5553580B2 (en) | Resin composition, molded body, optical film, polarizer protective film, polarizing plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210723 |