CN113820761B - Optical diffusion polyester master batch, optical diffusion polyester film and preparation methods thereof - Google Patents
Optical diffusion polyester master batch, optical diffusion polyester film and preparation methods thereof Download PDFInfo
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- CN113820761B CN113820761B CN202111106780.4A CN202111106780A CN113820761B CN 113820761 B CN113820761 B CN 113820761B CN 202111106780 A CN202111106780 A CN 202111106780A CN 113820761 B CN113820761 B CN 113820761B
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 193
- 230000003287 optical effect Effects 0.000 title claims abstract description 152
- 229920000728 polyester Polymers 0.000 title claims abstract description 66
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920006267 polyester film Polymers 0.000 title abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 115
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 104
- 239000002245 particle Substances 0.000 claims abstract description 80
- 239000003365 glass fiber Substances 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 54
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 52
- 239000006229 carbon black Substances 0.000 claims abstract description 46
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000004005 microsphere Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 109
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 76
- 229910000077 silane Inorganic materials 0.000 claims description 76
- 239000011259 mixed solution Substances 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000000051 modifying effect Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004512 die casting Methods 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 20
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 137
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 239000012756 surface treatment agent Substances 0.000 description 33
- 239000011159 matrix material Substances 0.000 description 17
- 239000003595 mist Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 13
- 239000010954 inorganic particle Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000007493 shaping process Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- -1 polybutylene terephthalate Polymers 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002464 physical blending Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Elements Other Than Lenses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of polymer film materials, and discloses an optical diffusion polyester master batch, an optical diffusion polyester film and a preparation method thereof, wherein the polyester master batch comprises the following raw material components in percentage by mass as per 100 percent: 60-70% of polyester and 30-40% of optical diffusion auxiliary agent; the optical diffusion aid comprises the following raw material components: 30-40% of white carbon black; 45-55% of silicon dioxide microspheres; 6-10% of glass fiber; 5-9% of nano calcium carbonate; 1 to 1.5 percent of surface treating agent; the optical diffusion film comprises silicon dioxide microspheres, white carbon black, nano calcium carbonate and chopped glass fibers, and the obtained optical diffusion film has good effect of uniformly diffusing visible light into a surface light source through the synergistic effect of various materials, and has high tensile strength, good flexibility and excellent dimensional stability, and the technical level is in the international advanced level; solves the technical bottleneck problem of reducing the particle addition amount in the optical diffusion film.
Description
Technical Field
The invention relates to the technical field of polymer film materials, in particular to an optical diffusion polyester master batch, an optical diffusion polyester film and a preparation method thereof.
Background
The optical diffusion film is a film material capable of promoting the uniformity of illumination brightness. When light passes through the film materials, refraction, reflection and scattering phenomena occur in the film materials, and then the light is corrected into a uniform surface light source so as to achieve the effect of optical diffusion. The optical diffusion film is mainly applied to the fields of LCD backlight source modules, planar illumination and the like.
Currently, an optical diffusion film based on a polymer film material can be prepared by the following three methods:
(1) Through processing modes such as electrospray, photoetching or hot-pressing film technology, the surface of the film material is formed with microstructures (including V-groove shapes, hemispheres, cones and the like) which are regularly arranged, and the microstructures display different photophysical properties along different directions. When light passes through the surface of the film material with the microstructure, refraction and reflection actions are carried out for a plurality of times, so that the effect of light diffusion is achieved. The haze and the light transmittance of the diffusion film are adjusted by regulating and controlling the surface microstructure morphology and the distribution density of the film material.
(2) The holographic recording technology is used for forming orderly arranged grains on the surface of the film substrate, diffraction behaviors can be generated when light reaches the surface of the film material, and then the light diffusion direction is accurately controlled, so that the light diffusion effect is achieved. The holographic recording technology can regulate and control the incident light source for most of incident light and the incident light with a wider wavelength range.
(3) The matrix resin and the diffusion particles are subjected to melt mixing, stretching traction, solidification and cooling to form a film after being physically mixed uniformly; or coating the liquid mixture on a transparent film substrate, and solidifying and cooling to form the light diffusion film. When light passes through the interface between the diffusion particles and the matrix resin, scattering and refraction phenomena occur due to the difference of refractive indexes between the two phases, so that the effect of light diffusion is achieved.
The selected diffusion particles are divided into inorganic diffusion particles and organic diffusion particles. The inorganic diffusion particles comprise nano silicon dioxide, nano calcium carbonate, nano titanium dioxide, nano barium sulfate, glass beads and the like, the particles absorb incident light to a certain extent and are easy to agglomerate in the film material, and the light can be transmitted when the light is refracted, scattered or diffracted after encountering the particles, so that the light loss and the haze of the light diffusion film prepared from the inorganic diffusion particles and the resin are high, and the light transmittance is relatively low.
The organic diffusion particles comprise acrylic, polystyrene, polymethacrylate, organic silicon and the like, belong to particles with higher transparency, have small influence on light loss of incident light rays, and can realize the light diffusion requirement under the condition of high light transmittance. However, the light diffusion film prepared from the organic diffusion particles and the resin has poor dimensional stability and low abrasion resistance and tensile resistance.
The preparation of the light diffusion film by adopting the surface microstructure regulation and control and holographic recording technology requires complex process and expensive instruments and equipment, and is not suitable for large-scale and low-cost industrialized production and sales; the preparation process of the light diffusion film prepared by adopting the matrix resin and diffusion particle composite mode is relatively simple, the universality of instruments and equipment is high, and the light diffusion film is suitable for large-scale industrialized production. The method for preparing the matrix resin and the diffusion particles in a compounding way comprises a coating type and a non-coating type. The coating process requires good adhesion between the coating containing the diffusion particles and the matrix resin, and the diffusion particles are uniformly dispersed in the coating, so that the process flow is simple and easy to control, but a thin film coating production line (comprising thin film pretreatment, coating, drying and other processes) is additionally arranged at the rear end of the matrix resin film manufacturing equipment.
CN102167839a discloses a preparation method of a high-performance optical diffusion film, wherein diffusion particles are acrylic or silicon dioxide particles or siloxane particles, a layer of polyethylene glycol methacrylate monomer is coated on the surface layer of polybutylene terephthalate with diffusion particles, which is subjected to hydroxylation and bromination treatment, the monomer is polymerized under a certain thermal environment condition to obtain an oligomer, the polybutylene terephthalate is used as a substrate bottom layer, the polyethylene glycol methacrylate is used as a diffusion layer, and the diffusion particles are regularly arranged on the uppermost layer, so that the high light transmittance and high haze characteristics of the film are realized.
CN105589117a discloses an optical diffusion film with covering rate and light transmittance coordination, wherein the upper layer of the substrate is a diffusion layer, the lower layer is a back coating, and the resin in the diffusion layer coating and the back coating is at least one of acrylic resin, polyurethane and acrylic polyol respectively; the particles in the diffusion layer mainly comprise organic particles such as polymethyl methacrylate, polystyrene, polyethylene, polycarbonate and the like with different particle sizes and inorganic particles such as silicon dioxide, aluminum oxide, titanium dioxide, calcium carbonate, barium sulfate and the like; the particles in the back coating layer mainly consist of anti-adhesion inorganic particles of silica, alumina, titania and the like with small particle sizes.
In comparison, the non-coating process is to directly melt and mix the diffusion particles with a resin base material after surface modification, and then obtain the corresponding optical diffusion film through tape casting film formation and biaxial stretching. The process can be completed on the existing polyester film production line, has high production efficiency, does not need to additionally increase manufacturing equipment, and has higher compatibility requirement on the modified diffusion particles and matrix resin. In order to realize uniform dispersion of diffusion particles in matrix resin in a non-coating process, so that the composite film achieves higher haze and light transmittance, and simultaneously, excellent mechanical property and thermal yield performance of the film are ensured, it is necessary to perform screening combination (including shape, size, specific gravity and the like) on diffusion particles for preparing an optical diffusion film, further modify surface properties of the combined diffusion particles, adjust and optimize material compounding, film stretching process and the like, and prepare the high-performance optical diffusion film based on a polyester substrate at low cost.
Disclosure of Invention
Aiming at the problem that the optical diffusion film prepared by a non-coating process in the prior art cannot have excellent mechanical properties and light diffusion properties, the invention provides a polyester master batch of the optical diffusion film, wherein carbon black, calcium carbonate, silicon dioxide microspheres and chopped glass fibers are adopted as combined diffusion particles in the master batch, and the polyester master batch is obtained by compounding the polyester master batch with a polyester substrate after surface modification, and the master batch is further fused and compounded with a pure polyester chip to prepare the optical diffusion film with high haze, uniform light transmission brightness and excellent mechanical properties, and is applied to the fields of LCD backlight modules, planar illumination and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The optical diffusion polyester master batch comprises the following raw material components in percentage by mass of 100 percent: 60-70% of polyester and 30-40% of optical diffusion auxiliary agent;
The optical diffusion aid comprises the following raw material components in percentage by mass as 100 percent:
The surface treating agent comprises silane A, silane B and silane C;
The silane A comprises any one of bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-mercaptopropyl trimethoxysilane and gamma-mercaptopropyl triethoxysilane;
the silane B comprises one of gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane;
the silane C comprises gamma-aminopropyl triethoxysilane and/or gamma-aminopropyl trimethoxysilane.
The optical diffusion aid comprises white carbon black, silica microspheres, glass fibers, nano calcium carbonate and a surface treatment agent, wherein the white carbon black and the nano calcium carbonate can toughen and stiffen a base material, and the scattering and refraction effects of light rays in a polyester film are improved; the silica microspheres have larger particle size, and the light rays are further corrected into uniform area light sources by changing the transmission line of the light rays through reflection, scattering and refraction at the interface with the substrate; the glass fiber has a certain length-diameter ratio, so that the matrix material can be enhanced, and the other diffusion particles can be promoted to be uniformly dispersed in the matrix material, so that the refraction and reflection effects of light rays in the film can be improved. The surface treating agent modifies the surface properties of white carbon black, silica microspheres, nano calcium carbonate and glass fibers, improves the compatibility among diffusion particles, glass fibers and polyester, enhances the interfacial binding force among the diffusion particles, glass fibers and polyester, realizes the uniform dispersion of the optical diffusion aid in the polyester film, and achieves the effect of uniform light diffusion on a microscopic scale under the condition of high haze. The final product has high haze, uniform light transmission brightness and excellent mechanical properties through the combined action of multiple components.
The polyester comprises one or more than two of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate. When in use, the polyester needs to be dried and heat treated to remove water, and the water content is not more than 500ppm.
Preferably, the optical diffusion film master batch comprises the following raw material components in percentage by mass of 100 percent: 65-70% of polyester and 30-35% of optical diffusion auxiliary agent;
Considering the light transmittance, haze, thermal shrinkage, tensile property and the like of the optical diffusion film comprehensively, more preferably, the optical diffusion film master batch comprises the following raw material components in percentage by mass of 100 percent: 67% of polyester and 33% of optical diffusion auxiliary agent, and the obtained master batch is used for preparing an optical diffusion film with better comprehensive performance.
Preferably, the optical diffusion aid comprises the following raw material components in percentage by mass of 100 percent:
The modified white carbon black and the modified silica microspheres are products of the white carbon black and the silica microspheres modified by silane A; the modified glass fiber is a product of modifying glass fiber by silane B; the modified nano calcium carbonate is a product of modifying nano calcium carbonate by silane C;
The silane A comprises any one of bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-mercaptopropyl trimethoxysilane and gamma-mercaptopropyl triethoxysilane;
the silane B comprises one of gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane;
the silane C comprises gamma-aminopropyl triethoxysilane and/or gamma-aminopropyl trimethoxysilane.
One end of the silane A is a stronger polar group and is used for modifying the white carbon black and the silicon dioxide microspheres with high specific gravity, so that agglomeration among granular modified powder can be prevented; the hydrophobic end of the silane B used for modifying the glass fiber is a reactive group, so that the modified glass fiber, the modified white carbon black and the silica microspheres form chemical bonding, and the glass fiber isolation material is cooperated to uniformly disperse the modified mixed powder in the matrix resin in the film biaxial stretching process; the silane C is used for modifying nano calcium carbonate, and can further improve the compatibility effect between the nano calcium carbonate and the polyester substrate.
The specific steps of the modification process of the silica microsphere and the white carbon black through the silane A include: physically blending silane A with white carbon black and silica microspheres; the specific steps of the glass fiber modified by the silane B comprise: physically blending silane B with glass fibers; the specific steps of the modification process of the nano calcium carbonate by the silane C comprise: silane C was physically blended with nano calcium carbonate.
Preferably, the silane A accounts for 0.1 to 0.3 weight percent of the total mass of the white carbon black and the silica microspheres; the silane B accounts for 0.05 to 0.2 weight percent of the mass of the glass fiber; the silane C accounts for 0.1 to 0.2 weight percent of the mass of the nano calcium carbonate. The surface treating agent has the functions of modifying the surfaces of nano calcium carbonate, white carbon black, silica microspheres and glass fibers, improving the compatibility between modified particles and polyester base materials, but the single silane has poor effect, and silane A is used for improving the compatibility between the white carbon black and the silica microspheres, if the content of the silica microspheres is not improved or is insufficient, the compatibility between the modified particles and the polyester can not be improved; the excessively high proportion results in free silane A, which in turn affects the dispersibility of the modified glass fibers in the polyester film. Likewise, silane C is used for improving nano calcium carbonate, and if the content of the silane C is low, the modifying effect of the calcium carbonate can be reduced, so that the compatibility of the silane C with polyester is not improved; too high a ratio will also produce free silane C, reducing the dispersion of the modified glass fibers in the polyester film. Therefore, various silanes respectively modify other raw materials, and reasonably control the content of the silanes and the proportion of each component to effectively obtain the polyester master batch with excellent comprehensive performance.
The particle size of the white carbon black is 10-30 nanometers; the particle size of the silicon dioxide microsphere is 0.9-1.2 microns; the glass fiber comprises chopped alkali-free glass fiber, the diameter is 10-16 micrometers, and the length-diameter ratio is 12-15:1; the nano calcium carbonate is spindle-shaped and has the particle size of 60-80 nanometers.
The particle size of the nano calcium carbonate and the white carbon black is too small, so that particles are easy to agglomerate, the capability of light penetrating through the film is increased, and the scattering and refraction effects of light in the film are reduced; if the particle sizes of the calcium carbonate and the white carbon black particles are too large, the effect of toughening and reinforcing the matrix material cannot be achieved, the reflection and absorption effects of the film on light rays can be increased, and the transmittance of the light rays can be further reduced.
Preferably, the particle size range of the nano calcium carbonate is 65-75 nanometers, and the particle size range of the white carbon black is 14-20 nanometers.
The silica microspheres have too small particle size to change the transmission path of light, and the luminous flux is increased but the light is not uniformly spread over the whole surface of the film; if the particle size of the silica microspheres is too large, the blocking and reflection of the particles to light are enhanced, the refractive ratio of the particles to the interface of the substrate is reduced, and the uneven distribution of illumination intensity on the film surface light source is shown. Preferably, the silica microspheres have a particle size in the range of 1.05 to 1.15 microns.
The diameter of the glass fiber is too small, and particles such as calcium carbonate, white carbon black and silicon dioxide microspheres cannot be effectively pulled in the biaxially oriented process of the polyester film, so that the particles are not uniformly dispersed in the polyester film, and the refraction and reflection effects of the glass fiber on light rays in the film are weakened; too large a diameter tends to expose the surface of the mylar. Too small an aspect ratio of the glass fiber can not effectively enhance the tensile strength of the film, too large an aspect ratio can cause the fiber ends to be mutually stacked, affect the uniform dispersion of particles in the film, and simultaneously easily expose the surface of the polyester film. Preferably, the glass fibers have a diameter of 13 microns and an aspect ratio of 13:1.
The invention also provides a preparation method of the optical diffusion polyester master batch, which comprises the following steps:
step 1, dissolving silane A in a solvent to form a mixed solution A, and mixing the mixed solution A with white carbon black and silica microspheres to obtain a modified material A;
Step 2, dissolving silane B in a solvent to form a mixed solution B, and mixing the mixed solution B with glass fibers to obtain modified glass fibers;
Step 3, dissolving silane C in a solvent to form a mixed solution C, and mixing the mixed solution C with nano calcium carbonate to obtain modified nano calcium carbonate;
And step 4, blending the modified material A, the modified glass fiber and the modified nano calcium carbonate to obtain the optical diffusion auxiliary agent, melting and blending the optical diffusion auxiliary agent with polyester, granulating and slicing to obtain the optical diffusion polyester master batch.
In the step 1, the temperature of mixing the mixed solution A with the white carbon black and the silica microspheres is 105-120 ℃ and the mixing time is 0.5-2 h;
in the step 2, the temperature of the mixed solution B and the glass fiber is 105-120 ℃ and the mixing time is 15 min-2 h;
In the step 3, the temperature of the mixed solution C and the nano calcium carbonate is 105-120 ℃ and the mixing time is 0.5-2 h.
Preferably, the mixed solution A is firstly mixed with the white carbon black and the silica microspheres at room temperature or 40-65 ℃ for 25-40 min, then the temperature is raised to 105-120 ℃ and the mixture is continuously mixed for 0.5-1 h; mixing the mixed solution B and the glass fiber at room temperature or 40-65 ℃ for 10-20 min, and continuously mixing for 30-60 min after the temperature is raised to 105-120 ℃; mixing the mixed solution C and nano calcium carbonate at room temperature or 40-65 ℃ for 40-50 min, and continuously mixing for 30-60 min after heating to 100-115 ℃; this ensures that the silane is fully contacted with the feed components and the modification is more uniform.
Further preferably, in the steps 1 to 4, the materials are mixed by a high-speed mixer, and the rotating speed is more than 1000 revolutions per minute; wherein the initial mixing temperature of inorganic raw materials such as silica microspheres, white carbon black, nano calcium carbonate and the like and silane is 40-65 ℃; the temperature of the melt blending granulation in the step 4 is 270-280 ℃, and the process can be carried out in a co-directional parallel double-screw extruder.
The solvent for dissolving the silane A, the silane B and the silane C comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether, acetone, a mixed solution of methanol and water, a mixed solution of ethanol and water and a mixed solution of acetone and water;
Preferably, the solvent is a mixed solution of ethanol and water, the ethanol is low in price and good in volatility, the raw material sources are wide, the concentration of silane in the mixed solution of various silanes is 5.5-11.0%, and further preferably, the mixed solution A, the mixed solution B and the mixed solution C comprise the following raw material components in percentage by mass as 100 percent:
silane A, silane B or silane C5.5-11%;
75-88% of ethanol;
6.5 to 14 percent of water.
The pH value ranges of the mixed solution A, the mixed solution B and the mixed solution C are all 5.0-6.5. The pH value of the mixed solution of silane is adjusted by adding acid or alkali, such as acetic acid, sodium hydroxide and the like, and is too low, so that the mixed solution is easy to undergo condensation reaction in advance, and is not beneficial to further carrying out chemical reaction with inorganic particles; the pH value is too high, the product is unstable after the silane is hydrolyzed, and the method is not suitable for the requirement of industrial production.
Further preferably, the mixed solution A, the mixed solution B or the mixed solution C is respectively added into the silicon dioxide microspheres, the white carbon black, the nano calcium carbonate and the glass fiber in an atomizing spray mode, and the surface treatment agent is dispersed more uniformly and can be uniformly attached to the surfaces of modified particles or fibers due to the fact that the amount of the surface treatment agent is small.
The invention also provides an optical diffusion film which comprises the following raw material components in percentage by mass as per 100 percent: 80-90% of polyester and 10-20% of the optical diffusion film master batch.
According to the preparation method of the polyester film, a master batch method is adopted, and the optical diffusion auxiliary agent can be uniformly dispersed in the polyester film through the synergistic material formula design: the optical diffusion auxiliary agent and the polyester are prepared into optical diffusion film master batch in advance, and then the optical diffusion film master batch and the polyester are prepared into the optical diffusion film. The polyester used for preparing the optical diffusion film master batch and the polyester used for preparing the optical diffusion film can be the same or different, preferably the same, and have better compatibility.
Further preferably, the optical diffusion film comprises the following raw material components in percentage by mass of 100 percent: 86-88% of polyester and 12-14% of the optical diffusion film master batch.
Still more preferably, the optical diffusion film comprises the following raw material components in percentage by mass of 100): 87% of polyester and 13% of the optical diffusion film master batch, and the obtained polyester film has the best comprehensive performance in the aspects of tensile strength, haze, dimensional stability and the like.
The invention also provides a preparation method of the optical diffusion film, which comprises the following steps: and (3) carrying out melt blending, die casting, longitudinal drawing, transverse drawing, rolling and forming on the optical diffusion film master batch and polyester to obtain the optical diffusion film.
In the preparation process of the optical diffusion film, the temperatures of the respective stages are set as follows: the temperature of the die casting sheet is 270-280 ℃, and the die casting sheet can be carried out in an anisotropic parallel double-screw extruder; the temperature of the longitudinal pulling preheating section is 59-76 ℃, the temperature of the stretching section is 78-25 ℃, and the temperature of the shaping section is 32-37 ℃; the temperature of the transverse drawing preheating section is 82-105 ℃, the temperature of the stretching section is 110-118 ℃, the temperature of the shaping section is 208-230 ℃, and the temperature of the cooling section is 100-117 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The optical diffusion film comprises silicon dioxide microspheres, white carbon black, nano calcium carbonate and chopped glass fibers, wherein the silicon dioxide microspheres can change the line of light passing through a polyester film, and correct the light into a surface light source through reflection and scattering of the light and refraction of the light at the interface of the light and a substrate; white carbon black and nano calcium carbonate can help to promote the scattering and refracting effects of light in the polyester film, so that the illumination intensity on a surface light source is more uniform and softer, and the polyester matrix material can be toughened and hardened; the chopped glass fibers with a certain length-diameter ratio can strengthen the polyester matrix material, promote the uniform dispersion of other inorganic particles in the matrix material, and assist in improving the refraction and reflection effects of light rays in the film; the surface treating agent modifies silicon dioxide microspheres, white carbon black, nano calcium carbonate and chopped glass fibers, improves the compatibility of the silicon dioxide microspheres, the white carbon black, the nano calcium carbonate and the chopped glass fibers with polyester matrix materials, and further realizes the uniform dispersion of inorganic particles and fibers in the matrix materials. Through the synergistic effect of the materials, the optical diffusion film has the characteristics of high haze and moderate light transmittance, and a soft surface light source with uniform illumination intensity distribution can be formed when visible light passes through the film. Meanwhile, the optical diffusion film has high tensile strength, good flexibility and excellent dimensional stability, and the technical level is in the international advanced level; solves the technical bottleneck problem of reducing the particle addition amount in the optical diffusion film and breaks through international technical monopoly. Meanwhile, the used raw materials are wide in sources, moderate in price and convenient to mold and process.
(2) The preparation method disclosed by the invention is simple to operate, easy to control, high in production efficiency and suitable for industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
Example 1
Preparation of optical diffusion film master batch:
(1) 9.2kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide was added to a mixture of 82kg of ethanol and 8.8kg of water, and the mixture was stirred and adjusted to pH 6 with sodium hydroxide or acetic acid to give a surface-treating agent mixture 1. 50kg of silica microspheres (average particle size 1 micron) and 35kg of white carbon black (average particle size 17 nanometers) are added into a high-speed mixer (1500 revolutions per minute), 10kg of mist surface treatment agent mixed liquid 1 is sprayed, the mixture is mixed at a high speed for 25 minutes at 60 ℃, the mixture is heated to 115 ℃ and mixed at a high speed for 50 minutes, and the mixture is discharged and discharged to obtain modified material 1.
(2) 8Kg of gamma-methacryloxypropyl trimethoxysilane was added to a mixture of 80kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 2. 8kg of chopped glass fibers (with the diameter of 13 micrometers and the length of 170 micrometers) are added into a high-speed mixer (800 revolutions per minute), 0.4kg of mist surface treatment agent mixed solution 2 is sprayed, the mixture is mixed at a high speed for 15min at the temperature of 60 ℃, the mixture is mixed at a high speed for 45min at the temperature of 115 ℃ again, and the mixture is discharged and discharged to obtain modified material 2.
(3) 10Kg of gamma-aminopropyl triethoxysilane was added to a mixture of 78kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 3. Adding 6kg of nano calcium carbonate (with the average particle size of 70 nanometers) into a high-speed mixer (1500 revolutions per minute), spraying 0.48kg of mist surface treatment agent mixed solution 3, mixing at a high speed for 40 minutes at a temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 55 minutes, exhausting and discharging to obtain modified material 3.
(4) And (3) carrying out physical blending (600 revolutions per minute) on the modified material 1, the modified material 2 and the modified material 3 to obtain an optical diffusion auxiliary agent, uniformly mixing 33kg of the optical diffusion auxiliary agent and 67kg of polyester, extruding and granulating the mixture, and extruding and granulating the mixture at 275+/-5 ℃ in a co-rotating parallel double-screw extruder to obtain the master batch of the optical diffusion film.
Preparation of an optical diffusion film:
Taking 90kg of optical diffusion film master batch, drying, mixing with 610kg of polyester, melting and extruding at 275+/-5 ℃ in a different-direction parallel double-screw extruder, casting a die head, longitudinally pulling (the preheating section temperature is 59-76 ℃, the stretching section temperature is 78-25 ℃, and the shaping section temperature is 32-37 ℃), transversely pulling (the preheating section temperature is 82-105 ℃, the stretching section temperature is 110-118 ℃, the shaping section temperature is 208-230 ℃, and the cooling section temperature is 100-117 ℃), and winding and forming to obtain the optical diffusion film (film thickness of 25 micrometers).
Example 2
Preparation of optical diffusion film master batch:
(1) 9.2kg of gamma-mercaptopropyl trimethoxysilane was added to a mixture of 84kg of ethanol and 6.8kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treating agent mixture 1. 50kg of silica microspheres (average particle size 1 micron) and 35kg of white carbon black (average particle size 17 nanometers) are added into a high-speed mixer (1500 revolutions per minute), 10kg of mist surface treatment agent mixed liquid 1 is sprayed, the mixture is mixed at a high speed for 35 minutes at 60 ℃, then the mixture is mixed at a high speed for 50 minutes at a temperature of 110 ℃, and the mixture is discharged after being exhausted, so as to obtain modified material 1.
(2) 8Kg of gamma-glycidoxypropyl trimethoxysilane was added to a mixture of 83kg of ethanol and 9kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 2.8 kg of chopped glass fibers (with the diameter of 13 micrometers and the length of 170 micrometers) are added into a high-speed mixer (800 revolutions per minute), 0.4kg of mist surface treatment agent mixed solution 2 is sprayed, the mixture is mixed at a high speed for 15min at the temperature of 60 ℃, then the mixture is mixed at a high speed for 40min at the temperature of 110 ℃, and the mixture is discharged after being exhausted, so as to obtain modified material 2.
(3) 10Kg of gamma-aminopropyl trimethoxysilane was added to a mixture of 76kg of ethanol and 14kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treating agent mixture 3. Adding 6kg of nano calcium carbonate (with the average particle size of 70 nanometers) into a high-speed mixer (1500 revolutions per minute), spraying 0.48kg of mist surface treatment agent mixed solution 3, mixing at a high speed for 40 minutes at a temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 48 minutes, exhausting and discharging to obtain modified material 3.
The conditions and the process of the step (4) and the preparation of the optical diffusion film were the same as those of example 1, and an optical diffusion film (film thickness: 25 μm) was obtained.
Example 3
Preparation of optical diffusion film master batch:
(1) 9.2kg of gamma-mercaptopropyl-triethoxysilane was added to a mixture of 84kg of ethanol and 6.8kg of water, and the mixture was stirred and adjusted to pH 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 1. 50kg of silica microspheres (average particle size 1 micron) and 35kg of white carbon black (average particle size 17 nanometers) are added into a high-speed mixer (1500 revolutions per minute), 10kg of mist surface treatment agent mixed liquid 1 is sprayed, the mixture is mixed at a high speed for 40 minutes at 60 ℃, the mixture is mixed at a high speed for 50 minutes at a temperature of 120 ℃, and the mixture is discharged after being exhausted, so as to obtain modified material 1.
(2) 8Kg of vinyltriethoxysilane was added to a mixture of 83kg of ethanol and 9kg of water, stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 2. 8kg of chopped glass fibers (with the diameter of 13 micrometers and the length of 170 micrometers) are added into a high-speed mixer (800 revolutions per minute), 0.4kg of mist surface treatment agent mixed solution 2 is sprayed, the mixture is mixed at a high speed for 12 minutes at the temperature of 60 ℃, then the mixture is mixed at a high speed for 45 minutes at the temperature of 115 ℃, and the mixture is discharged after being exhausted, so as to obtain modified material 2.
The conditions and the process of the steps (3) and (4) and the preparation of the optical diffusion film were the same as those of example 1, and an optical diffusion film (film thickness: 25 μm) was obtained.
Example 4
Preparation of optical diffusion film master batch:
(1) 9.2kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide was added to a mixture of 82kg of ethanol and 8.8kg of water, and the mixture was stirred and adjusted to pH 6 with sodium hydroxide or acetic acid to give a surface-treating agent mixture 1. 54kg of silica microspheres (average particle size 1 micron) and 30kg of white carbon black (average particle size 17 nanometers) are added into a high-speed mixer (1500 revolutions per minute), 10kg of mist surface treatment agent mixed liquid 1 is sprayed, the mixture is mixed at a high speed for 25 minutes at 60 ℃, the mixture is heated to 115 ℃ and mixed at a high speed for 50 minutes, and the mixture is discharged and discharged to obtain modified material 1.
(2) 8Kg of gamma-methacryloxypropyl trimethoxysilane was added to a mixture of 80kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 2. 10kg of chopped glass fibers (with the diameter of 13 micrometers and the length of 170 micrometers) are added into a high-speed mixer (800 revolutions per minute), 0.5kg of mist surface treatment agent mixed solution 2 is sprayed, the mixture is mixed at a high speed for 15min at the temperature of 60 ℃, then the mixture is mixed at a high speed for 45min at the temperature of 115 ℃, and the mixture is discharged after being exhausted, so as to obtain modified material 2.
(3) 10Kg of gamma-aminopropyl triethoxysilane was added to a mixture of 78kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 3. Adding 5kg of nano calcium carbonate (with the average particle size of 70 nanometers) into a high-speed mixer (1500 revolutions per minute), spraying 0.38kg of mist surface treatment agent mixed solution 3, mixing at a high speed for 40 minutes at a temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 55 minutes, exhausting and discharging to obtain modified material 3.
The conditions and the process of the step (4) and the preparation of the optical diffusion film were the same as those of example 1, and an optical diffusion film (film thickness: 25 μm) was obtained.
Example 5
Preparation of optical diffusion film master batch:
(1) 9.2kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide was added to a mixture of 82kg of ethanol and 8.8kg of water, and the mixture was stirred and adjusted to pH 6 with sodium hydroxide or acetic acid to give a surface-treating agent mixture 1. 44kg of silica microspheres (average particle size 1 micron) and 40kg of white carbon black (average particle size 17 nanometers) are added into a high-speed mixer (1500 revolutions per minute), 10kg of mist surface treatment agent mixed liquid 1 is sprayed, the mixture is mixed at a high speed for 25 minutes at 60 ℃, the mixture is heated to 115 ℃ and mixed at a high speed for 50 minutes, and the mixture is discharged and discharged to obtain modified material 1.
(2) 8Kg of gamma-methacryloxypropyl trimethoxysilane was added to a mixture of 80kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 2. Adding 6kg of chopped glass fibers (with the diameter of 13 micrometers and the length of 170 micrometers) into a high-speed mixer (800 revolutions per minute), spraying 0.3kg of mist surface treatment agent mixed liquid 2, mixing at a high speed for 15min at the temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 45min, exhausting and discharging to obtain modified material 2.
(3) 10Kg of gamma-aminopropyl triethoxysilane was added to a mixture of 78kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 3. Adding 9kg of nano calcium carbonate (with the average particle size of 70 nanometers) into a high-speed mixer (1500 revolutions per minute), spraying 0.58kg of mist surface treatment agent mixed solution 3, mixing at a high speed for 40 minutes at a temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 55 minutes, exhausting and discharging to obtain modified material 3.
The conditions and the process of the step (4) and the preparation of the optical diffusion film were the same as those of example 1, and an optical diffusion film (film thickness: 25 μm) was obtained.
Example 6
The preparation steps (1), (2) and (3) of the optical diffusion film master batch are the same as the conditions and the process of the embodiment 1.
(4) And (3) carrying out physical blending (600 revolutions per minute) on the modified material 1, the modified material 2 and the modified material 3 to obtain an optical diffusion auxiliary agent, uniformly mixing 30kg of the optical diffusion auxiliary agent with 70kg of polyester, extruding and granulating the mixture, and extruding and granulating the mixture into slices at 275+/-5 ℃ in a homodromous parallel double-screw extruder to obtain the master batch of the optical diffusion film.
Preparation of an optical diffusion film:
50kg of optical diffusion film master batch is taken, dried and mixed with 450kg of polyester, and then the mixture is subjected to melt extrusion at 275+/-5 ℃ in a heterogeneous parallel double-screw extruder, die casting, longitudinal drawing (the preheating section temperature is 59-76 ℃, the stretching section temperature is 78-25 ℃, and the shaping section temperature is 32-37 ℃), transverse drawing (the preheating section temperature is 82-105 ℃, the stretching section temperature is 110-118 ℃, the shaping section temperature is 208-230 ℃, and the cooling section temperature is 100-117 ℃), and winding molding is carried out, so that the optical diffusion film (film thickness of 25 micrometers) is obtained.
Example 7
The preparation steps (1), (2) and (3) of the optical diffusion film master batch are the same as the conditions and the process of the embodiment 1.
(4) And (3) carrying out physical blending (600 revolutions per minute) on the modified material 1, the modified material 2 and the modified material 3 to obtain an optical diffusion auxiliary agent, uniformly mixing 40kg of the optical diffusion auxiliary agent and 60kg of polyester, extruding and granulating the mixture, and extruding and granulating the mixture at 275+/-5 ℃ in a co-rotating parallel double-screw extruder to obtain the master batch of the optical diffusion film.
Preparation of an optical diffusion film:
100kg of optical diffusion film master batch is taken, dried and mixed with 400kg of polyester, and then subjected to melt extrusion at 275+/-5 ℃ in a heterogeneous parallel double screw extruder, die casting, longitudinal drawing (preheating section temperature is 59-76 ℃, stretching section temperature is 78-25 ℃, shaping section temperature is 32-37 ℃), transverse drawing (preheating section temperature is 82-105 ℃, stretching section temperature is 110-118 ℃, shaping section temperature is 208-230 ℃, cooling section temperature is 100-117 ℃) and rolling forming to obtain the optical diffusion film (film thickness is 25 microns).
Comparative example 1
Preparation of optical diffusion film master batch:
(1) 9.2kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide was added to a mixture of 82kg of ethanol and 8.8kg of water, and the mixture was stirred and adjusted to pH 6 with sodium hydroxide or acetic acid to give a surface-treating agent mixture 1. 85kg of silicon dioxide microspheres (with the average particle size of 1 micron) are added into a high-speed mixer (1500 rpm), 10kg of mist surface treatment agent mixed solution 1 is sprayed, the mixture is mixed at a high speed for 25min at the temperature of 60 ℃, then the mixture is mixed at a high speed for 50min at the temperature of 115 ℃, and the mixture is discharged after being exhausted, so as to obtain modified material 1.
The conditions and the process of the steps (2), (3) and (4) and the preparation of the optical diffusion film were the same as those of the example 1, and an optical diffusion film (film thickness: 25 μm) was obtained.
Comparative example 2
Preparation of optical diffusion film master batch:
(1) 9.2kg of bis- (gamma-triethoxysilylpropyl) tetrasulfide was added to a mixture of 82kg of ethanol and 8.8kg of water, and the mixture was stirred and adjusted to pH 6 with sodium hydroxide or acetic acid to give a surface-treating agent mixture 1. Adding 85kg of white carbon black (with the average particle size of 17 nanometers) into a high-speed mixer (1500 revolutions per minute), spraying 10kg of mist surface treatment agent mixed solution 1, mixing at a high speed for 25 minutes at a temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 50 minutes, exhausting and discharging to obtain modified material 1.
The conditions and the process of the steps (2), (3) and (4) and the preparation of the optical diffusion film were the same as those of the example 1, and an optical diffusion film (film thickness: 25 μm) was obtained.
Comparative example 3
Preparation of optical diffusion film master batch:
Steps (1) and (2) are the same as in example 1.
(3) And (3) carrying out physical blending (600 revolutions per minute) on the modified material 1 and the modified material 2 to obtain an optical diffusion auxiliary agent, uniformly mixing 33kg of the optical diffusion auxiliary agent and 67kg of polyester, extruding and granulating the mixture, and extruding and granulating the mixture at 275+/-5 ℃ in a co-directional parallel double-screw extruder to obtain the master batch of the optical diffusion film.
The optical diffusion film was produced under the same conditions and by the same process as in example 1, to obtain an optical diffusion film (film thickness: 25 μm).
Comparative example 4
Preparation of optical diffusion film master batch:
step (1) was carried out under the same conditions and in the same manner as in example 1.
(2) 10Kg of gamma-aminopropyl triethoxysilane was added to a mixture of 78kg of ethanol and 12kg of water, and the mixture was stirred and the pH of the mixture was adjusted to 6 with sodium hydroxide or acetic acid to obtain a surface treatment agent mixture 2. Adding 6kg of nano calcium carbonate (with the average particle size of 70 nanometers) into a high-speed mixer (1500 revolutions per minute), spraying 0.48kg of mist surface treatment agent mixed solution 3, mixing at a high speed for 40 minutes at a temperature of 60 ℃, heating to 115 ℃ and mixing at a high speed for 55 minutes, exhausting and discharging to obtain modified material 2.
(3) And (3) carrying out physical blending (600 revolutions per minute) on the modified material 1 and the modified material 2 to obtain an optical diffusion auxiliary agent, uniformly mixing 33kg of the optical diffusion auxiliary agent and 67kg of polyester, extruding and granulating the mixture, and extruding and granulating the mixture at 275+/-5 ℃ in a co-directional parallel double-screw extruder to obtain the master batch of the optical diffusion film.
The optical diffusion film was produced under the same conditions and by the same process as in example 1, to obtain an optical diffusion film (film thickness: 25 μm).
Comparative example 5
Preparation of optical diffusion film master batch:
50kg of silica microspheres (average particle size: 1 μm), 35kg of white carbon black (average particle size: 17 nm), 8kg of chopped glass fibers (diameter: 13 μm, length: 170 μm) and 6kg of nano calcium carbonate (average particle size: 70 nm) were added to a mixer to perform physical blending (600 rpm) to obtain an optical diffusion aid. And (3) uniformly mixing 33kg of optical diffusion aid and 67kg of polyester, extruding the mixture into granulating slices, and extruding the granulating slices at 275+/-5 ℃ in a co-rotating parallel double-screw extruder to obtain the master batch of the optical diffusion film.
The optical diffusion film was produced under the same conditions and by the same process as in example 1, to obtain an optical diffusion film (film thickness: 25 μm).
Performance testing
The optical diffusion films prepared in examples 1 to 7 were compared with the relevant properties of other optical diffusion films prepared in comparative examples, comparative example 1 (without white carbon black), comparative example 2 (without silica microspheres), comparative example 3 (without nano calcium carbonate), comparative example 4 (without chopped glass fibers), and comparative example 5 (inorganic particles were not treated with a surface treatment agent), the detection criteria were according to GB/T6672-2001 "mechanical measurement for Plastic film and sheet thickness measurement", GB/T1040.3-2006 "determination of tensile Properties of plastics part 3: test conditions for films and sheets, GB/T2410-2008 determination of light transmittance and haze of transparent plastics. The detection results are shown in Table 1.
Table 1 properties of optical diffusion films prepared in examples and comparative examples
From the results of the performance test obtained in table 1, examples 1-3 studied the influence of different silane treatment inorganic particles on the performance of the polyester film, and from the results, it can be seen that the prepared polyester film has balanced performance, haze of 100% and good effect of light correction into uniform surface light source by adopting silane a, silane B and silane C to treat white carbon black, silica microspheres, glass fibers and nano calcium carbonate respectively. In comparative example 5, however, the inorganic particles were directly added to the polyester film without being treated with the surface treatment agent, and various mechanical properties and optical properties of the polyester film were greatly reduced.
By observing examples 1, 4 and 5, it can be seen that the proportion of glass fibers and silica microspheres in the system is increased, the tensile strength and the light transmittance of the polyester film are improved, but the haze is reduced; the results of comparative examples 1 to 4 show that the absence of any auxiliary component results in a significant decrease in the mechanical and optical properties of the product.
Observing examples 1, 6 and 7, the addition amount of the optical diffusion film master batch in example 6 is reduced, and the elongation at break, the thermal shrinkage, the glossiness and the light transmittance of the polyester film are all improved, but the haze is obviously reduced; the amount of the optical diffusion film master batch added in example 7 was increased, and the obtained polyester film had high tensile strength, good dimensional stability, high haze, good optical diffusion effect, but decreased light transmittance and gloss.
In summary, the adoption of a proper surface treating agent to treat different inorganic particles and the addition amount of the master batch of the optical diffusion film respectively plays an important role in the performance of the polyester film, and the improper surface treatment of the inorganic particles or the lack of system components can lead to the reduction of the comprehensive performance of the product. The data in Table 1 show that the optical diffusion films obtained in examples 1-7 have good dimensional stability and higher haze and tensile strength, and can be applied to the fields of LCD backlight modules, planar illumination and the like to modify the light rays of the incident film into uniform surface light sources.
In the invention, any combination of the components within the dosage range defined by the invention can obtain the polyester film with the optical diffusion effect, such as polyester produced by different manufacturers, the change of the surface treatment agent type and the like, and the polyester film with the optical diffusion effect can be obtained. The concentration of the treating agent in the alcohol-water mixed solution of the surface treating agent has no strict requirement, so that the alcohol-water mixed solution is atomized mainly, the dosage and the proportion of the surface treating agent are within the limit range of the invention, the optical diffusion auxiliary agent is uniformly dispersed in the polyester film, and the compatibility and the binding force between the optical diffusion auxiliary agent and the polyester are improved. Thus, any combination within the amount range defined by the present invention is suitable for use in the present invention. And will not be described in detail herein.
Claims (10)
1. The optical diffusion polyester master batch is characterized by comprising the following raw material components in percentage by mass as 100 percent: 60-70% of polyester and 30-40% of optical diffusion auxiliary agent;
The optical diffusion aid comprises the following raw material components in percentage by mass as 100 percent:
；
The surface treating agent comprises silane A, silane B and silane C;
The silane A comprises any one of bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-mercaptopropyl trimethoxysilane and gamma-mercaptopropyl triethoxysilane;
the silane B comprises one of gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane;
the silane C comprises gamma-aminopropyl triethoxysilane and/or gamma-aminopropyl trimethoxysilane.
2. The optical diffusion polyester master batch according to claim 1, wherein the optical diffusion aid comprises the following raw material components in percentage by mass of 100:
；
The modified white carbon black and the modified silica microspheres are products of the white carbon black and the silica microspheres modified by silane A; the modified glass fiber is a product of modifying glass fiber by silane B; the modified nano calcium carbonate is a product of modifying nano calcium carbonate by silane C;
The silane A comprises any one of bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-mercaptopropyl trimethoxysilane and gamma-mercaptopropyl triethoxysilane;
the silane B comprises one of gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane;
the silane C comprises gamma-aminopropyl triethoxysilane and/or gamma-aminopropyl trimethoxysilane.
3. The optical diffusion polyester master batch according to claim 2, wherein the silica microspheres and the white carbon black are modified by silane a, comprising the following specific steps: physically blending silane A with white carbon black and silica microspheres; the specific steps of the glass fiber modified by the silane B comprise: physically blending silane B with glass fibers; the specific steps of the modification process of the nano calcium carbonate by the silane C comprise: silane C was physically blended with nano calcium carbonate.
4. The optical diffusion polyester master batch according to claim 2, wherein silane A accounts for 0.1-0.3 wt% of the total mass of the white carbon black and the silica microspheres; the silane B accounts for 0.05 to 0.2 weight percent of the mass of the glass fiber; the silane C accounts for 0.1 to 0.2 weight percent of the mass of the nano calcium carbonate.
5. The optical diffusion polyester master batch according to claim 1, wherein the particle size of the white carbon black is 10-30 nanometers; the particle size of the silicon dioxide microsphere is 0.9-1.2 microns; the glass fiber comprises chopped alkali-free glass fiber, the diameter is 10-16 micrometers, and the length-diameter ratio is 12-15:1; the nano calcium carbonate is spindle-shaped and has the particle size of 60-80 nanometers.
6. The method for producing an optically diffusing polyester masterbatch according to any one of claims 1 to 5 comprising the steps of:
step 1, dissolving silane A in a solvent to form a mixed solution A, and mixing the mixed solution A with white carbon black and silica microspheres to obtain a modified material A;
Step 2, dissolving silane B in a solvent to form a mixed solution B, and mixing the mixed solution B with glass fibers to obtain modified glass fibers;
Step 3, dissolving silane C in a solvent to form a mixed solution C, and mixing the mixed solution C with nano calcium carbonate to obtain modified nano calcium carbonate;
And step 4, blending the modified material A, the modified glass fiber and the modified nano calcium carbonate to obtain the optical diffusion auxiliary agent, melting and blending the optical diffusion auxiliary agent with polyester, granulating and slicing to obtain the optical diffusion polyester master batch.
7. The preparation method of the optical diffusion polyester master batch according to claim 6, wherein the temperature of mixing the mixed solution A with the white carbon black and the silica microspheres in the step 1 is 105-120 ℃ and the mixing time is 0.5-2 h;
in the step 2, the temperature of the mixed solution B and the glass fiber is 105-120 ℃ and the mixing time is 15 min-2 h;
In the step 3, the temperature of the mixed solution C and the nano calcium carbonate is 105-120 ℃ and the mixing time is 0.5-2 h.
8. The method for producing an optically diffusing polyester masterbatch according to claim 6 wherein the solvent in which silane a, silane B and silane C are dissolved comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether, acetone, a mixture of methanol and water, a mixture of ethanol and water, and a mixture of acetone and water;
The pH value ranges of the mixed solution A, the mixed solution B and the mixed solution C are all 5.0-6.5.
9. An optical diffusion film is characterized by comprising the following raw material components in percentage by mass as 100 percent: 80-90% of polyester and 10-20% of the optical diffusion polyester master batch according to any one of claims 1-5 or the optical diffusion polyester master batch prepared by the preparation method of the optical diffusion polyester master batch according to any one of claims 6-8.
10. The method of manufacturing an optical diffusion film according to claim 9, comprising the steps of: and (3) carrying out melt blending, die casting, longitudinal drawing, transverse drawing, rolling and forming on the optical diffusion film master batch and polyester to obtain the optical diffusion film.
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