CN116178869A - Ultrathin PMMA film and preparation method thereof - Google Patents
Ultrathin PMMA film and preparation method thereof Download PDFInfo
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- CN116178869A CN116178869A CN202211607827.XA CN202211607827A CN116178869A CN 116178869 A CN116178869 A CN 116178869A CN 202211607827 A CN202211607827 A CN 202211607827A CN 116178869 A CN116178869 A CN 116178869A
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 71
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000012745 toughening agent Substances 0.000 claims abstract description 19
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 63
- 238000001125 extrusion Methods 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 25
- 238000003490 calendering Methods 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 92
- 230000001681 protective effect Effects 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 17
- 238000004804 winding Methods 0.000 description 14
- 238000004049 embossing Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000005062 Polybutadiene 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
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention discloses an ultrathin PMMA film and a preparation method thereof, comprising the following steps: the components in parts by weight are as follows: 60-80 parts of polymethyl methacrylate, 1-10 parts of glutarimide, 20-40 parts of styrene resin, 1-10 parts of toughening agent, 5-18 parts of compatibilizer and 0.05-0.75 part of anti-adhesion particles, wherein after the anti-adhesion particles are extruded and stretched into a film, the particles partially expose the surface of the film, the toughening agent is a thermoplastic elastomer, the thermoplastic elastomer has a butyl acrylate or two-phase structure at normal temperature, and the toughness, the outstanding high temperature resistance and the good chemical stability are improved by adding the toughening agent, the compatibilizer and the anti-adhesion particles in the PMMA film preparation raw material to modify the common PMMA raw material.
Description
Technical Field
The invention relates to the field of optical films, in particular to an ultrathin PMMA film and a preparation method thereof.
Background
PMMA is used as a protective film to be adhered on two sides of a polarizing PVA film in a polaroid, so that the polarizing PVA film has supporting and protecting effects, PMMA is used as a hydrophobic material, has extremely low moisture permeability, has good durability in a high-humidity environment, and is thinner and better along with the requirement of thinning of a display technology, in particular to a small-and-medium-sized polarizing plate, while the PMMA film used as a raw film of the polaroid is ensured to have toughness and stiffness.
Although PMMA has very high light transmittance, extremely low water absorption, high mechanical strength and good chemical stability, is one of the most ideal optical materials, the traditional PMMA has a glass transition temperature of less than 110 ℃, poor high temperature resistance and poor toughness, is extremely fragile in processing engineering, and cannot realize ultrathin.
Typically, the acrylic film is formed of only acrylic resin and has a relatively large surface friction value. Therefore, such an acrylic film is difficult to roll up due to blocking (blocking) phenomenon.
In order to solve the above problems, the prior art generally coats a primer containing particles on line in the process of PMMA film, but the problems of increased production cost and contamination of rollers by the primer are caused, so that defects of the optical film are increased, and an ultrathin PMMA film and a preparation method thereof are proposed to solve the above problems.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides an ultrathin PMMA film and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is an ultrathin PMMA film, which comprises the following components in parts by weight: 60-80 parts of polymethyl methacrylate, 1-10 parts of glutarimide, 20-40 parts of styrene resin, 1-10 parts of toughening agent, 5-18 parts of compatibilizer and 0.05-0.75 part of anti-adhesion particles;
after the anti-adhesion particles are extruded and stretched into a film, the particle parts are exposed out of the surface of the film;
the toughening agent is a thermoplastic elastomer, and the thermoplastic elastomer has butyl acrylate or a two-phase structure at normal temperature.
In a preferred embodiment of the present invention, the toughening agent is one or a mixture of two or more of butyl acrylate, methyl acrylate-butadiene-styrene copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, and styrene-butadiene-styrene block copolymer.
In a preferred embodiment of the present invention, the compatibilizer is one or a mixture of two or more of SBS grafted maleic anhydride, SBS grafted glycidyl methacrylate, SEBS grafted maleic anhydride, SEBS grafted glycidyl methacrylate.
In a preferred embodiment of the present invention, the anti-blocking particles are nano-sized or micro-sized particles, including nano/micro silica, nano/micro titania, nano/micro styrene particles, nano/micro PMMA particles, and nano/micro rubber particles.
In a preferred embodiment of the present invention, the styrene resin is one or a mixture of SAN and ABS.
In a preferred embodiment of the present invention, the addition amount x of the anti-blocking particles and the haze y of the prepared PMMA film conform to a quadratic polynomial y=ax under a fixed extension rate 2 +bx, wherein the quadratic coefficient a is negative and satisfies the relation b 2 ≤-12a，b≥-1.5a。
In a preferred embodiment of the present invention, the PMMA resin has a Tg of 115-135 ℃.
The preparation method of the ultrathin PMMA film comprises the following steps of:
(1) Mixing the raw materials: 60-80 parts of polymethyl methacrylate, 1-10 parts of glutarimide, 20-40 parts of styrene resin, 1-10 parts of toughening agent and 5-18 parts of compatibilizer are put into a high-speed mixer to be stirred at a set temperature at a high speed to obtain a mixture;
(2) Granulating: putting the mixture prepared in the step (1) into a first extruder, extruding the mixture into a second extruder at the extrusion pressure of 16-25MPa and the temperature of 230-270 ℃, granulating the extrudate at the extrusion temperature of 230-275 ℃ and the extrusion pressure of 16-25MPa to obtain PMMA resin particles;
(3) Extrusion calendaring: drying the raw material particles prepared in the step (2), calendaring and forming by extrusion calendaring equipment to prepare a film with the thickness of 0.14-0.18 mm, and performing MD and TD biaxial stretching to prepare a film with the thickness of 0.035-0.045 mm, wherein the MD stretching multiplying power is 1.0-3.5, and the TD stretching multiplying power is 1.0-3.5;
and (3) adding 0.05-0.75 part of anti-blocking particles in the step (1) or the step (2).
In a preferred embodiment of the invention, under the condition of a certain addition amount of the anti-sticking particles, the total extension multiplying power x is in the range of 1-6, and accords with the second order polynomial y=ax with the haze y of the PMMA film 2 +bx+c, where the quadratic coefficient a is negative and satisfies the relation c= - (a+b), b 2 ≤-12a，[(4ac-b2)/4a]≦3。
In a preferred embodiment of the present invention, the ultraviolet absorber is fed into the second extruder in the step (2).
In a preferred embodiment of the present invention, the step (3) further includes: the drying temperature of the raw material particles is 80-120 ℃, and the drying time is controlled to be 3-5h; the temperature of the extrusion screw is controlled at 250-275 ℃, the temperature of the conveying section is controlled at 255-265 ℃, the extrusion pressure is 6-10MPa, and the extrusion calendaring production speed is 16-22m/min.
In a preferred embodiment of the present invention, the extrusion calendaring apparatus in the step (3) includes a resin dryer, an extruder, a metal filter, a T-Die, a mirror roller, an MD extending nip roller, a corona, a coater, a drying, a TD extending apparatus, a trimming embossing, and a rolling in order.
In a preferred embodiment of the invention, the T-Die lip is made of carbon steel and is subjected to tungsten carbide spraying treatment between the first mirror roller and the second mirror roller below the T-Die outlet, the mirror rollers are three smooth rollers with the same diameter and fixed on a base, and the surface roughness Ra is less than 0.002mm.
The invention solves the defects existing in the background technology, and has the following beneficial effects:
(1) According to the invention, anti-adhesion particles are added in the film preparation components, the anti-adhesion particles are added in the resin mixture, after the film is formed by extrusion and stretching, the particles are partially exposed out of the surface of the film, the roughness of the film surface is increased, the contact area between film layers can be reduced after rolling, the smoothness is increased, thus anti-adhesion is realized, compared with the online coating priming mode adopted in the prior art, the production process is shortened, the raw material cost is reduced, the problem that the roller is polluted due to the fact that particles added in coating liquid are easy to adhere to the roller when coating is abnormal is avoided, and the anti-adhesion particles are directly added in the resin mixture, compared with the prior art that the particles are arranged in the coating, the phenomenon that a coiled material is separated between two films under the influence of road conditions to cause concave-convex indentation can be avoided, meanwhile, due to the anti-adhesion particles are contained on both sides of the film, one surface is adhered with UV adhesive when producing a polaroid, the other surface is anti-adhesion, rolling is not used for compounding PE protective films to prevent adhesion, and the production cost of the polaroid is reduced.
(2) The toughening agent is added into the film preparation component, and is a thermoplastic elastomer, the toughening agent has butyl acrylate or a two-phase structure at normal temperature, the two-phase structure comprises a rubber continuous phase of polybutadiene and a resin micro-region of polystyrene, the continuous phase polybutadiene has elasticity of the rubber and good low temperature resistance, polystyrene chain segments are gathered together to form a disperse phase, the functions of crosslinking and reinforcing the rubber are achieved, and when the temperature is increased, the polystyrene micro-region is heated and melted, and the crosslinking point is melted to generate good fluidity; butyl acrylate can increase the steric hindrance of the molten resin and increase the elasticity; therefore, the common PMMA raw material is modified to improve the toughness and the high temperature resistance, so that the PMMA film with high toughness is prepared.
(3) The compatibilizer is added in the film preparation components, and different resins are blended to form the polymer alloy which is not enough to have the properties of single resin, so that the application of the material is greatly widened, the polar parameters of different resins are greatly different, a homogeneous system is difficult to form during blending.
(4) According to the invention, in the preparation of the PMMA film, the common PMMA raw material is modified by mixing and adding various raw materials, so that the toughness, the outstanding high temperature resistance and the good chemical stability are improved, and the PMMA film with high transmittance, high toughness, ultra-thin flatness is manufactured by limiting the relative positions of the T-Die and the mirror roller, the roughness of the mirror roller, the stretching multiplying power, the temperature and other production and manufacturing procedures during the preparation.
(5) According to the invention, the requirements of high transparency and low fog of the PMMA film are ensured by setting parameter range values, and under a fixed extension multiplying power, the addition amount x of anti-adhesion particles and the fog y of the prepared PMMA film accord with a quadratic polynomial y=ax 2 +bx, wherein the quadratic coefficient a is negative and satisfies the relation b 2 The total extension multiplying power x is within the range of 1-6 and is less than or equal to-12 a, b is more than or equal to-1.5 a, and the haze y of the PMMA film accords with a quadratic polynomial y=ax 2 +bx+c, wherein the secondary coefficient a is negative and satisfies the relationship c= - (a+b), b2 is less than or equal to-12 a, [ (4 ac-b 2)/4 a]Less than or equal to 3, a is a negative value, represents that the haze y value increases with the increase of the addition amount x of the anti-blocking particles, and simultaneously limits b 2 The two relations of less than or equal to-12 a and b is more than or equal to-1.5 a define the approximate shape of a quadratic curve, namely a value range, so that the haze of the invention can be ensured to be within certain data, under certain condition of the addition amount of anti-sticking particles, a is negative and represents that the haze y is increased along with the increase of the elongation x, and the relation c= - (a+b), b 2 ≤-12a，[(4ac-b2)/4a]And the control range of haze values in the elongation range of the invention is limited by the range of less than or equal to 3, so that the ultra-thin high-transparency low-haze requirement of the PMMA film is met.
Detailed Description
In order that the above-recited objects, features and advantages of the invention will be more clearly understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Example 1
S1, firstly, mixing raw materials: 60 parts of polymethyl methacrylate, 2 parts of glutarimide, 22 parts of styrene resin, 2 parts of toughening agent butyl acrylate, 5 parts of compatibilizer SBS grafted maleic anhydride and 0.5 part of anti-adhesion particle silicon dioxide (particle size of 2 mu m) are put into a high-speed mixer to be stirred at a high speed for 10min, the stirring temperature is controlled at 65 ℃ to obtain a mixture, and the mixture is cooled to 40 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and the temperature of 240 ℃, putting ultraviolet absorbent benzophenone into the second extruder, granulating the extrudate at the extrusion temperature of 240 ℃ and the extrusion pressure of 18MPa to obtain PMMA resin particles with the Tg of 118 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at the drying temperature of 80 ℃ for 5 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.14mm, and biaxially stretching the film with the thickness of 0.040mm through MD and TD, wherein the temperature of an extruding screw is controlled at 250 ℃, the temperature of a conveying section is controlled at 255 ℃, the extruding pressure is 6MPa, and the extruding and calendaring production speed is 16m/min. MD stretch ratio is 1.8, TD stretch ratio is 2.0;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) taking the original film in the step (4) as an upper protective film to be attached to the polarizer, attaching a lower protective film to the other surface of the polarizer, and rolling to obtain the original inverse polarizer.
Example 2
S1, firstly, mixing raw materials: 80 parts of polymethyl methacrylate, 5 parts of glutarimide, 38 parts of styrene resin, 8 parts of toughening agent methyl acrylate-butadiene-styrene copolymer and 12 parts of compatibilizer SBS grafted glycidyl methacrylate are put into a high-speed mixer to be stirred at a high speed for 15min, the stirring temperature is controlled at 75 ℃ to obtain a mixture, and the mixture is cooled to 45 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and at the temperature of 260 ℃, putting 0.7 part of anti-adhesion particle silica (with the particle size of 80 nm) into the second extruder, granulating the extrudate at the extrusion temperature of 270 ℃ and the extrusion pressure of 16MPa to obtain PMMA resin particles with the Tg of 122 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at a drying temperature of 100 ℃ for 4 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.18mm, and biaxially stretching the film with the thickness of 0.045mm through MD and TD, wherein the temperature of an extruding screw is controlled at 265 ℃, the temperature of a conveying section is controlled at 258 ℃, the extruding pressure is 7MPa, and the extruding and calendaring production speed is 18m/min; MD stretch ratio is 2.0, TD stretch ratio is 2.0;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) bonding the original film in the step (4) as a lower protective film with a polarizer, bonding an upper protective film on the other surface of the polarizer, and rolling to obtain the original inverse polarizer.
Example 3
S1, firstly, mixing raw materials: 70 parts of polymethyl methacrylate, 9 parts of glutarimide, 32 parts of styrene resin, 5 parts of toughening agent ethylene-butyl acrylate-glycidyl methacrylate and 17 parts of compatibilizer SEBS grafted maleic anhydride are put into a high-speed mixer to be stirred at a high speed for 12min, the stirring temperature is controlled at 70 ℃ to obtain a mixture, and the mixture is cooled to 50 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and at the temperature of 250 ℃, putting an ultraviolet absorbent and 0.2 part of anti-adhesion particle titanium dioxide (with the particle size of 200 nm) into the second extruder, granulating the extrudate at the extrusion temperature of 250 ℃ and the extrusion pressure of 22MPa to obtain PMMA resin particles with the Tg of 124 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at 90 ℃ for 5 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.18mm, and biaxially stretching the film with the thickness of 0.037mm through MD and TD, wherein the temperature of an extruding screw is controlled at 260 ℃, the temperature of a conveying section is controlled at 255 ℃, the extruding pressure is 10MPa, and the extruding and calendaring production speed is 22m/min. MD stretch ratio is 1.8, TD stretch ratio is 2.7;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) taking the original film in the step (4) as an upper protective film to be attached to the polarizer, attaching a lower protective film to the other surface of the polarizer, and rolling to obtain the original inverse polarizer.
Example 4
S1, firstly, mixing raw materials: 60 parts of polymethyl methacrylate, 4 parts of glutarimide, 25 parts of styrene resin, 3 parts of flexibilizer SBS (styrene-butadiene-styrene block copolymer), 2 parts of compatibilizer SEBS grafted glycidyl methacrylate and 0.3 part of anti-adhesion styrene particles (particle size 1.0 mu m) are put into a high-speed mixer to be stirred at a high speed for 10min, the stirring temperature is controlled at 65 ℃ to obtain a mixture, and the mixture is cooled to 43 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and the temperature of 260 ℃, putting an ultraviolet absorbent into the second extruder, granulating the extrudate at the extrusion temperature of 255 ℃ and the extrusion pressure of 18MPa to obtain PMMA resin particles with the Tg of 130 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at a drying temperature of 120 ℃ for 2 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.18mm, and biaxially stretching the film with the thickness of 0.040mm through MD and TD, wherein the temperature of an extruding screw is controlled at 260 ℃, the temperature of a conveying section is controlled at 255 ℃, the extruding pressure is 8MPa, and the extruding and calendaring production speed is 16m/min. MD stretch ratio is 1.8, TD stretch ratio is 2.5;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) taking the original film in the step (4) as an upper protective film to be attached to the polarizer, attaching a lower protective film to the other surface of the polarizer, and rolling to obtain the original inverse polarizer.
Comparative example 1 without anti-sticking particles
S1, firstly, mixing raw materials: 60 parts of polymethyl methacrylate, 2 parts of glutarimide, 22 parts of styrene resin, 2 parts of toughening agent butyl acrylate and 5 parts of compatibilizer SBS grafted maleic anhydride are put into a high-speed mixer to be stirred at a high speed for 10min, the stirring temperature is controlled at 65 ℃ to obtain a mixture, and the mixture is cooled to 40 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and the temperature of 240 ℃, putting an ultraviolet absorbent into the second extruder, granulating the extrudate at the extrusion temperature of 240 ℃ and the extrusion pressure of 18MPa to obtain PMMA resin particles with the Tg of 118 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at the drying temperature of 80 ℃ for 5 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.14mm, stretching the film through MD, coating a bottom coating on line, drying, entering a TD oven, and stretching the film in the TD direction to prepare the film with the thickness of 0.040mm, wherein the temperature of an extruding screw is controlled at 250 ℃, the temperature of a conveying section is controlled at 255 ℃, the extruding pressure is 6MPa, and the extrusion calendaring production speed is 16m/min. MD stretch ratio is 1.8, TD stretch ratio is 2.0;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) bonding the original film in the step (4) as an upper protective film with a polarizer, bonding a PE protective film on the surface of the prepared original film as the upper protective film, bonding a lower protective film on the other surface of the polarizer, and rolling to obtain the original counter-polarizer.
Comparative example 2 without modified toughening agent
S1, firstly, mixing raw materials: 80 parts of polymethyl methacrylate, 5 parts of glutarimide, 38 parts of styrene resin and 12 parts of compatibilizer SBS grafted maleic anhydride are put into a high-speed mixer to be stirred at a high speed for 15min, the stirring temperature is controlled at 75 ℃ to obtain a mixture, and the mixture is cooled to 45 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and at the temperature of 260 ℃, putting 0.7 part of anti-adhesion particle silica (with the particle size of 80 nm) into the second extruder, granulating the extrudate at the extrusion temperature of 270 ℃ and the extrusion pressure of 16MPa to obtain PMMA resin particles with the Tg of 122 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at a drying temperature of 100 ℃ for 4 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.18mm, and biaxially stretching the film by MD and TD to prepare the film with the thickness of 0.060mm, wherein the temperature of an extruding screw is controlled at 265 ℃, the temperature of a conveying section is controlled at 258 ℃, the extruding pressure is 7MPa, and the extruding and calendaring production speed is 18m/min. MD stretch ratio is 1.55, TD stretch ratio is 1.93;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) bonding the original film in the step (4) as a lower protective film with a polarizer, bonding an upper protective film on the other surface of the polarizer, and rolling to obtain the original inverse polarizer.
Comparative example 3 when the process parameters exceeded the defined range values
S1, firstly, mixing raw materials: 70 parts of polymethyl methacrylate, 9 parts of glutarimide, 32 parts of styrene resin, 5 parts of toughening agent ethylene-butyl acrylate-glycidyl methacrylate and 17 parts of compatibilizer SEBS grafted maleic anhydride are put into a high-speed mixer to be stirred at a high speed for 12min, the stirring temperature is controlled at 70 ℃ to obtain a mixture, and the mixture is cooled to 50 ℃ by a cold mixer;
s2, granulating: putting the mixture prepared in the step (1) into a tandem screw extruder, extruding the mixture into a second extruder at the extrusion pressure of 18MPa and the temperature of 280 ℃, putting an ultraviolet absorbent and 0.2 part of anti-adhesion particle titanium dioxide (with the particle size of 200 nm) into the second extruder, granulating the extrudate at the extrusion temperature of 280 ℃ and the extrusion pressure of 13MPa to obtain PMMA resin particles with the Tg of 124 ℃ for later use;
s3, extrusion calendaring: drying the raw material particles prepared in the step (2) at 90 ℃ for 5 hours; extruding the molten blend resin from the lip to T-Die through a metal filter after drying, falling the molten blend resin between a first mirror roller and a second mirror roller, rolling the molten blend resin through the first mirror roller, the second mirror roller and a third mirror roller to prepare a film with the thickness of 0.18mm, and biaxially stretching the film with the thickness of 0.037mm through MD and TD, wherein the temperature of an extruding screw is controlled at 285 ℃, the temperature of a conveying section is controlled at 280 ℃, the extruding pressure is 10MPa, and the extruding and calendaring production speed is 22m/min. MD stretch ratio is 1.8, TD stretch ratio is 2.7;
s4, winding a finished product: the biaxially oriented film obtained in the step (3) is rolled after edge cutting and embossing to obtain a finished product;
s5, winding the polaroid: and (3) taking the original film in the step (4) as an upper protective film to be attached to the polarizer, attaching a lower protective film to the other surface of the polarizer, and rolling to obtain the original inverse polarizer.
Table 1: performance table
In summary, the invention improves the toughness, the outstanding high temperature resistance and the good chemical stability after modifying the common PMMA raw material by mixing and adding various raw materials in the preparation of the PMMA film, and prepares the PMMA film with high transmittance, high toughness, ultra-thin flatness by limiting the relative positions of the T-Die and the mirror roller, the roughness of the mirror roller, the stretching multiplying power, the temperature and other production and manufacturing procedures during the preparation.
The requirements of high transparency and low fog of the PMMA film are ensured by setting parameter range values, and under the condition of fixed extension multiplying power, the addition amount x of anti-adhesion particles and the fog y of the prepared PMMA film accord with a quadratic polynomial y=ax 2 +bx, a total draw ratio x in the range of 1 to 6, and a haze y of the PMMA film in accordance with a quadratic polynomial y=ax 2 +bx+c, ensuring that the haze is within a certain data, the relation c= - (a+b), b 2 ≤-12a，[(4ac-b2)/4a]Less than or equal to 3 limits the control range of haze values in the elongation range of the invention, meets the high-permeability low-haze requirement of the PMMA film, and simultaneously avoids the influence of excessively high or excessively low parameters on the appearance of the film in the preparation process。
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The ultrathin PMMA film is characterized by comprising the following components in parts by weight: 60-80 parts of polymethyl methacrylate, 1-10 parts of glutarimide, 20-40 parts of styrene resin, 1-10 parts of toughening agent, 5-18 parts of compatibilizer and 0.05-0.75 part of anti-adhesion particles;
after the anti-adhesion particles are extruded and stretched into a film, the particle parts are exposed out of the surface of the film;
the toughening agent is a thermoplastic elastomer, and the thermoplastic elastomer has butyl acrylate or a two-phase structure at normal temperature.
2. An ultra thin PMMA film of claim 1 characterized by: the toughening agent is one or a mixture of more than two of butyl acrylate, methyl acrylate-butadiene-styrene copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer and styrene-butadiene-styrene block copolymer.
3. An ultra thin PMMA film of claim 1 characterized by: the compatibilizer is one or a mixture of two or more of SBS grafted maleic anhydride, SBS grafted glycidyl methacrylate, SEBS grafted maleic anhydride and SEBS grafted glycidyl methacrylate.
4. An ultra thin PMMA film of claim 1 characterized by: the anti-adhesion particles are nano or micron particles, and comprise nano/micron silicon dioxide, nano/micron titanium dioxide, nano/micron styrene particles, nano/micron PMMA particles and nano/micron rubber particles.
5. An ultra thin PMMA film of claim 1 characterized by: the styrene resin is one or a mixture of SAN and ABS.
6. An ultra thin PMMA film according to claim 1 characterized in that: under the condition of fixed extension multiplying power, the addition amount x of the anti-adhesion particles and the haze y of the prepared PMMA film accord with a quadratic polynomial y=ax 2 +bx, wherein the quadratic coefficient a is negative and satisfies the relation b 2 ≤-12a，b≥-1.5a。
7. An ultra thin PMMA film according to claim 1 characterized in that: the Tg of the PMMA resin is 115-135 ℃.
8. A method for producing an ultra-thin PMMA film according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing the raw materials: 60-80 parts of polymethyl methacrylate, 1-10 parts of glutarimide, 20-40 parts of styrene resin, 1-10 parts of toughening agent and 5-18 parts of compatibilizer are put into a high-speed mixer to be stirred at a set temperature at a high speed to obtain a mixture;
(2) Granulating: putting the mixture prepared in the step (1) into a first extruder, extruding the mixture into a second extruder at the extrusion pressure of 16-25MPa and the temperature of 230-270 ℃, granulating the extrudate at the extrusion temperature of 230-275 ℃ and the extrusion pressure of 16-25MPa to obtain PMMA resin particles;
(3) Extrusion calendaring: drying the raw material particles prepared in the step (2), calendaring and forming by extrusion calendaring equipment to prepare a film with the thickness of 0.14-0.18 mm, and performing MD and TD biaxial stretching to prepare a film with the thickness of 0.035-0.045 mm, wherein the MD stretching multiplying power is 1.0-3.5, and the TD stretching multiplying power is 1.0-3.5;
and (3) adding 0.05-0.75 part of anti-blocking particles in the step (1) or the step (2).
9. The method for preparing an ultrathin PMMA film according to claim 8, wherein the method comprises the following steps: under the condition of a certain addition amount of the anti-sticking particles, the total extension multiplying power x is in the range of 1-6, and accords with the second order polynomial y=ax with the haze y of the PMMA film 2 +bx+c, where the quadratic coefficient a is negative and satisfies the relation c= - (a+b), b 2 ≤-12a，[(4ac-b2)/4a]≤3。
10. The method for preparing an ultrathin PMMA film according to claim 8, wherein the method comprises the following steps: and (3) feeding an ultraviolet absorber into the second extruder in the step (2).
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| WO2010061917A1 (en) * | 2008-11-27 | 2010-06-03 | 株式会社日本触媒 | Optical film and method for producing same |
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| WO2010061917A1 (en) * | 2008-11-27 | 2010-06-03 | 株式会社日本触媒 | Optical film and method for producing same |
| JP2010275434A (en) * | 2009-05-29 | 2010-12-09 | Nippon Shokubai Co Ltd | Method for producing optical film |
| JP2012118479A (en) * | 2010-12-03 | 2012-06-21 | Nippon Shokubai Co Ltd | Method for manufacturing optical film |
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