CN1311248C - Method for making optical devices from homopolymers - Google Patents
Method for making optical devices from homopolymers Download PDFInfo
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- CN1311248C CN1311248C CNB018171311A CN01817131A CN1311248C CN 1311248 C CN1311248 C CN 1311248C CN B018171311 A CNB018171311 A CN B018171311A CN 01817131 A CN01817131 A CN 01817131A CN 1311248 C CN1311248 C CN 1311248C
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
Abstract
An improved optical film having a continuous/disperse phase morphology and a method for making the same is provided. At least one of the continuous and disperse phases comprises a blend of homopolymers which are inter-reacted, as by transesterification. The resulting films exhibit a higher degree of birefringence for a given level of strain than analogous films in which the blend is replaced by a random copolymer.
Description
Invention field
The present invention relates generally to a kind of optical device such as polarizer, diffusing globe and catoptron, more particularly, relate to improvement in order to the material of making these devices.
Background of invention
Known in the art have multiple optical thin film and device to depend on refractive index difference (causing that by strain birefringence produces sometimes) to realize certain optical effect, such as the random polarization polarisation of light.This film and device can be multilayer laminated forms, wherein stacked in refractive index difference between the adjacent layer can produce certain optical characteristics, as disclosed film among US5882774 people such as () Jonza.Other optical device have disperse phase, be positioned on the successive substrates, and its optical characteristics stem from continuously and the refractive index difference between the disperse phase.Disclosed material is the representative of this system among the US5825543 (people such as Ouderkirk).The various combinations of aforementioned system also are known, disclosed multilayer optical film among the US5867316 (people such as Carlson) for example, and wherein said film comprises having the multilayer laminated of supersequence, wherein one deck has continuously/the disperse phase structure at least.This area is also known multiple other optical thin films and device, at US5831375 (Benson, Jr.), US5825542 (Cobb, Jr. wait the people), US5808794 (people such as Weber), US5783120 (people such as Ouderkirk), US5751388 (Larson), US5940211 (people such as Hikmet), US3213753 (Rogers), US2604817 (Schupp Jr.), Aphonin, O.A.: " Optical Properties of Stretched Polymer DispersedLiquid Crystal Films:Angle-Dependent Polarized Light Scattering " (Liquid Crystals, Vol.19, No.4, pp.469-480 (1995)), Land, E.H.: " Some Aspects of the Development of Sheet Polarizers " ( 1951 OpticalSociety of America, Reprinted from Journal of the Optical Society ofAmerica, Vol.41 (12), 957-963, (Dec nineteen fifty-one), pp.45-51) and " Polarizer " (2244 Research Disclosure (1993), July, No.351, Emsworth, GB has description in pp.452-453).
In the past few years, material science particularly field of block copolymers has obtained many progress, the method that this has caused developing new noticeable material and has made these materials and use it for various uses.In some cases, these progressive application that caused in optical thin film and devices field.Therefore, for example at people such as Urbas " One-Dimensional PeriodicReflectors from Self-Assembly Block Copolymer-Homopolymer Blends " (Macromolecules, Vol.32, pp.4748-50 (1999)) proposes in to make to be similar to the stacked well-ordered photonic crystal of multilayer quarter wave plate, comprise the optional self assembly admixture that contains the segmented copolymer of homopolymer.The making of narrowband reflection device has been described among embodiment.Multipolymer conduct periodic means of generation in block copolymer material of using pure segmented copolymer and containing liquid crystal material have also briefly been described.
Disclose to improving having a definite purpose of interlayer adhesion among United States serial US08/904325 people such as () Weber (corresponding to WO9906203), the polyester that is arranged in the stacked adjacent layer of multilayer optical has been carried out ester interchange or reaction.Suppose that the interfacial thickness that comprises reaction material is enough thin, so that can not produce opposite influence to the stacked optical characteristics except that the interface of optics.
Disclose among United States serial US09/006455 people such as () Merrill (corresponding to WO9936812) to making the purpose of optical device, in the stacked one deck of multilayer optical, used the transesterification admixture of PEN and PET such as polarizer and catoptron.
US3546320 (people such as Duling) discloses the ester exchange method that is used to prepare the miocrystalline composition, miocrystalline composition wherein contain 94 to 60 percentage by weights polyalkylene terephthalates, 6 to 40 percentage by weights poly-2,6-naphthalenedicarboxylic acid alkylidene diol ester, and at least 5 percentage by weight contain polyalkylene terephthalates and poly-2, the segmented copolymer of the discrete polymer segment of 6-naphthalenedicarboxylic acid alkylidene diol ester.This segmented copolymer prepares by the fusing ester interchange to single homopolymer, controls the transesterification degree by incorporation time.Duling shows and depends on its component, and the crystallinity of segmented copolymer completely loses after abundant transesterification.
US3937754 people such as () Sagamihara discloses the poly-2 of a kind of biaxial orienting, and 6-(ethylene naphthalate) (PEN) film also contains the vibrin of with good grounds PEN weight meter 0.5% to 10% outside PEN, with and preparation method thereof.The document points out, when PEN resin (1) during with molten state and vibrin (2) fusion, the softening point of blended mixture is reduced gradually by the softening point of PEN, until finally reaching a specified point, is called balanced softening point.The document is also instructed, and this softening point is with consistent by the softening point that makes the resulting PEN multipolymer of following monomer copolymerizable, and wherein said monomer has identical component and ratio with the monomer that constitutes PEN resin (1) and vibrin (2).In view of the above, the document infers through a stage that forms segmented copolymer and reacts, if this moment in given enough reaction time then can obtain multipolymer.
Research Disclosure 28340 and 29410 discloses PEN, PET and other contain the ester exchange offspring of dibasic acid multipolymer.Typical dibasic acid comprises isophthalic acid, hexane diacid, glutaric acid, azelaic acid and decanedioic acid etc.Polymkeric substance based on PEN all is based on 2 usually, the 6-naphthalenedicarboxylic acid, but also can be based on 1,4-, 1,5-or 2,7-isomeride or these mixture of isomers.These instructions are primarily aimed at control machinery and the physical characteristics ability such as modulus, gas penetration potential and glass temperature.
WO92/02584 people such as () Cox discloses and has adopted the phosphite material to control transesterification speed in the solid-state polymerization process, and physics and mechanical property when mainly being intended to improve final product and using are such as gaseous diffusion.The document discloses the admixture of PEN and PET homopolymer pellets, preserves in the temperature range between higher glass temperature and lower melt temperature.
Although obtained above-mentioned many progress at optical thin film and devices field, still there are many problems in this area.For example, owing to can on the spreader of laboratory, be orientated film easily in a controlled manner, cause that birefringence realizes required optical characteristics in optical thin film so need depend on strain usually according to perfect technology and the principle of development.Yet these technologies are selected material for all and not all are equally useful.Especially, adopting the little thermodynamics of boundary strength often not encounter problems during the phase mixed polymer, because the gained film always can not be stretched to sufficiently high draw ratio to reach best birefringence level.Under the situation of for example continuous/disperse phase system, making this thin film alignment is that the required draw ratio of optimized birefringent can cause the hole of generation at the interface between two phases, thereby has damaged the required optical characteristics (for example polarization characteristic) of system.This hole has description in US5811493 (Kent), it is used for making can irreflexive paper shape film to whole two kinds of polarized lights.Regrettably, if adopt lower draw ratio to prevent to produce hole, then the gained film can have lower birefringence degree and less than the optical characteristics of the best.
Therefore this area needs a kind of method to realize that in optical thin film or device required birefringence degree is reduced to the required birefringence degree of realization and common required draw ratio simultaneously.This area also needs a kind of by the little thermodynamics of the boundary strength phase mixed polymer method of making optical thin film and device not, and wherein said film and device can be oriented to realizing than high birefringence degree and optimised optical properties required higher draw ratio usually.The present invention has satisfied these and other demands, will describe below.
Brief description of drawings
Fig. 1 is the curve map that engineering stress changes with apparent draw ratio;
The curve map that Fig. 2 changes with actual draw ratio along the refractive index Nx of main draw direction for the positive birefringence material;
Fig. 3 is that axle is gone up the curve map that gain increase % changes with degree of randomness %; And
Fig. 4 is the curve map that engineering stress changes with apparent draw ratio.
Summary of the invention
In one aspect, the present invention relates to the method for a kind of the making continuously/disperse phase optical device, and relate to the optical device of making like this such as catoptron, polarizer or diffusing globe.According to this method, allowing homopolymer to react to each other under the condition of (for example shifting (transamidization) effect) by ester interchange or acylamino-, make continuously and disperse phase one at least by the admixture of homopolymer, can be used in the multipolymer of the optical device of making physics and optical characteristics improvement with formation.
In another aspect of the present invention, the present invention relates to by homopolymer admixture that can interreaction make continuously/optical device of disperse phase, these devices and homopolymer admixture are wherein substituted by the multipolymer of the same monomer of same ratio but are not to be compared by the similar system of homopolymer manufacturing, have better physics and optical characteristics.In this system, observe the physics of some improvement and the gain that optical effect comprises raising, higher limiting viscosity and the strain hardening (also promptly, optical device of the present invention presents higher levels of birefringence with the strain that its random copolymers analog is compared for given amplitude) that more early begins.Continuous therein and discrete state material has in the more low-viscosity system, back one characteristic advantageous particularly, because this makes this kind system realize required birefringence degree with lower draw ratio, thereby avoid or reduce the hole that between two phases, produces to greatest extent.Can control the degree of interreaction such as residence time by the control processing conditions, thereby in the gained optical device, realize required characteristic, but its degree of randomness generally is lower than 70%.
Make the method for oriented film, comprise: form the potpourri have external phase and disperse phase at least, wherein comprise one of at least the admixture of first and second homopolymer that can react to each other by ester exchange reaction or acyl ammonia transfer reaction in external phase and the disperse phase; First and second homopolymer are reacted to each other by ester exchange reaction or acyl ammonia transfer reaction and obtain casting film by the described potpourri of extrusion molding; With the described casting film of stretching, extension at least one direction, form oriented film thus.
Make the method for oriented film, comprise the steps: to provide continuously and in the disperse phase at least one comprise the admixture that constitutes by first and second homopolymer at least, described first and second homopolymer can pass through ester exchange reaction or acyl ammonia transfer reaction and react each other; Described first and second homopolymer are reacted to each other by ester exchange reaction or acyl ammonia transfer reaction, and the extrusion molding potpourri obtain casting film; And described casting film at least one direction orientation, the birefringence degree Δ n that shows up to casting film is greater than Δ n
Max, Δ n wherein
MaxFor under same alignment conditions, for wherein said admixture with the random copolymers of the same monomeric unit that contains same ratio of an analog quantity part that substitute, same size continuous/the obtainable greatest birefringence degree of discrete state material.
Make the method for optical device, comprise the steps: to provide the material that contains external phase and disperse phase, wherein continuously and disperse phase at least one comprise the admixture that constitutes by first and second homopolymer at least; First and second homopolymer are reacted to each other to produce the material of modification by ester exchange reaction or acyl ammonia transfer reaction; And the material of described modification is made optical device.
Admixture according to the inventive method employing homopolymer can reach the higher molecular weight (thereby having higher limiting viscosity) of molecular weight that the multipolymer analog more random than aforementioned statistics can be realized.Be unexpectedly, compare the gain that presents raising by continuous/disperse phase optical device that this admixture is made with the random analog of its statistics, although do not observe by the average particle size particle size of disperse phase in the system of this admixture material average particle size particle size, and under the limiting viscosity of final film exists than the situation of big-difference, can estimate so originally less than disperse phase in the random copolymers analog made system.
In yet another aspect, the present invention relates to a kind of by continuously/the disperse phase system make to improve the method for optical device such as catoptron, polarizer or diffusing globe, and the optical device of so making.Be that the applicant has been found that when continuously and disperse phase when one comprises segmented copolymer at least, the degree of randomness that can control the polymer monomers unit causes birefringence with accessible strain in the raising system to greatest extent unexpectedly.Especially, by the degree of randomness in the suitable control multipolymer, can under the same stretch condition, obtain the birefringence degree of the similar system attainable birefringence Du Genggao more random than the statistics of monomeric unit sequence length wherein.
In a related aspect, the present invention relates to a kind of the raising continuously/physics of disperse phase optical object and the method for optical characteristics, wherein at least one comprises the statistics random copolymers of two or more monomers mutually in this continuous/disperse phase optical object, in the optical device that is applied to make according to this method.According to this method, substitute the statistics random copolymers with the homopolymer admixture of same monomer, make monomer ratio remain unchanged.
Detailed description of the invention
Following abbreviation used herein has following implication:
" T " represents dimethyl terephthalate (DMT).
" N " represents naphthalate.
" E " represents ethylene glycol.
" coPEN " expression is based on the multipolymer of naphthalate and dimethyl terephthalate (DMT) and ethylene glycol.
" PEN " represents PEN.
" PET " represents polyethylene terephthalate.
" NDC " represents naphthalate.
" DMT " represents dimethyl terephthalate (DMT).
" EG " represents ethylene glycol.
" I.V. " characterization viscosity.
" Δ n " expression birefringence degree, the refractive index that is defined as main draw direction deducts the refractive index of vertical direction.In view of refractive index owing to chromatic dispersion generally along with wavelength reduce increase, so the refractive index of indication is the refractive index that records at 632.8nm herein.
Except being applied to make the segmented copolymer, the solid-state polymerization effect also is the method that is used for improving the common employing of molecular weight institute of the polyester that comprises PEN (PEN) and polyethylene terephthalate (PET).As describe continuously and the aforementioned application of disperse phase optical device such as instructing among U.S. Pat 5825543 people such as () Ouderkirk, US5783120 people such as () Ouderkirk and the US5867316 people such as () Carlson, the particle size of disperse phase is an important control parameter of these devices of optimization.Making the viscosity coupling of two phases is a kind of approach that reduce and control dispersed phase particle size to greatest extent.In the solid-state polymerization process, make the crystallization of polymer particle that contains described kind of kind polyester, under vacuum condition, be warmed up to 235 ℃ to 255 ℃ usually then less than 5 torrs, with separation polycondensation accessory substance ethylene glycol, thereby improve its molecular weight.Be lower than under 210 ℃ the temperature, thereby the solid-state polymerization of aromatic polyester can not be practical because the extremely low polymerization time of its reaction velocity is oversize.Long polymerization time can make because of technology and/or material cost infeasible.Because the fusing point of some random copolymers is lower than 210 ℃, so adopt higher temperature will make particle condense into unwanted solid.Therefore, the random copolymerization (ethylene naphthalate) with the naphthalenedicarboxylic acid ester content that is lower than about 75 molar percentages being carried out solid-state polymerization is unrealistic and the cost prevention.Yet, have polyethylene naphthalate copolymers that the naphthalenedicarboxylic acid ester content is lower than 75 molar percentages and be used in optical device such as being favourable in polarizer and the catoptron, because its color improves, chromatic dispersion is lower, comprise that by the light beam of about 380nm to 400nm scope degeneration that ultraviolet light causes is less and cost is lower.The advantage of low naphthalate content resin has description in applicant's common unsettled U.S. Patent application No.09/416462 (applying date is same day, and attorney docket is 55028USA1A).
High molecular copolymerization (ethylene naphthalate) with the naphthalate that is lower than about 75 molar percentages can make by high molecular polyethylene terephthalate (PET) and high molecular PEN (PEN) are pushed fusion and carry out transesterification.Owing to can adopt solid-state polymerization PET with viscosity higher and PEN, PET and PEN multipolymer are realized than the higher viscosity of gained viscosity in the traditional reactor method polymerization process as initial homopolymer.According to the present invention, contain the single monomer of same ratio but its degree of randomness is lower than the multipolymer of statistics random copolymers by random or approximate random copolymers is replaced with, can improve the random or approximate random copolymers of the statistics that contains two or more monomers continuously/birefringence degree and other optics and the physical characteristics of disperse phase system.Preferably, substitute multipolymer and be the admixture of the condensation homopolymer of single monomer that can interreaction (for example shifting or similar reaction by transesterification, acylamino-), wherein the interreaction degree of monomer can be controlled with the acquisition degree of randomness and be lower than the multipolymer of adding up the random copolymers degree of randomness.
By the present invention continuously/polarizer, catoptron or other optical elements that the disperse phase system makes have plurality of advantages than the similar system that adopts the statistics random copolymers.Especially, can when extruding, control the degree that monomer ratio and transesterification or other react to each other easily, thereby make and to carry out optimization to accessible double refraction amount under given one group of stretching condition.In addition, can by make than the more cheap generally speaking of traditional multipolymer and the homopolymer that under high molecular more, is easier to obtain of the present invention continuously/the disperse phase system.In addition, the method for making copolymer material with needs in advance is opposite, owing to can easily controlling when pushing or changing component, so method of the present invention allows multipolymer to have bigger component dirigibility.
In the optical device that is containing continuous/disperse phase system, one of method that improves the device optical property is maximization along three orthogonal directionss birefringence degree of at least one phase of one at least, minimizes simultaneously along these orthogonal directionss degree that do not match of the refractive index between these two phases of another direction at least.The present invention has been found that with the situation of adding up the random copolymers analog and compares, the segmented copolymer of mentioned kind and/or add up non-random copolymers and can reach given birefringence degree level quickly.When needs adopt boundary strength little continuously and disperse phase thermodynamics not mutually during mixed polymer, it is particularly advantageous can reaching given birefringence degree with lower draw ratio, because adopt lower draw ratio to be not easy to damage two interface contacts (for example by causing hole) between the phase.
For the present invention, transesterification mean comprise condensation polymer such as the reaction of polyester, polyamide, copolyesteramide and specific methine group in order to color, UV stability or other desirable characteristics to be provided.Available material comprises for example those materials described in the U.S. Pat 4617373 (people such as Pruett) of polyester, polyamide, copolyesteramide and other materials among the present invention.
In many embodiment of the present invention, continuously/the thermoplasticity composition of at least one phase of disperse phase optical device in control transesterification degree, make the degree of adding up the preferred interreaction of non-random copolymers for making its degree of randomness less than about 70%, preferably, more preferably about below 40% less than about 50%.The method that can realize required degree of randomness comprises smelting process, and the solid-state polymerization process that can carry out before smelting process.Can adopt various parameters to control the speed that reacts to each other, include but not limited to, the molecular weight of single block and whole segmented copolymer, temperature of reaction, the state of the material that wherein reacts (for example, be reflected at solid-state still molten state and carry out), and the time that allows reaction to finish.Preferably, arbitrary method can adopt adjuvant such as stabilizing agent and antioxidant with further acceleration or postpone the speed of interreaction.
For example, the optical device that can be used as polarizer comprises external phase and disperse phase.Substantially mate by making along the external phase of three at least one first directions of orthogonal directions and the refractive index between the disperse phase, and do not match substantially along the external phase of three at least one second directions of orthogonal directions and the refractive index between the disperse phase, operate this optical device.Make refractive index mate substantially and be known in the art along the unmatched substantially mechanism of second direction at least along first direction at least, and for example U.S. Pat 5783129 and United States serial 09/006455 (people such as Merrill, on January 13rd, 1998 application is corresponding to WO9936812) in description is arranged.
Briefly, by careful selection material and process technology, can realize making refractive index to mate substantially to a great extent.For example, material can change in the direction refractive index with other directions along the orientation of first direction, and its change amount depends on the temperature and the speed of orientation.Therefore, for the refractive index that makes external phase and the refractive index of disperse phase are complementary, parent material must be the material that nominal index of refraction has suitable difference each other, makes the birefringence degree that develops in orientation process during a phase or two are mutually produce basic coupling.
Yet, when external phase or discrete state material when one comprises multipolymer at least-especially can strain cause and/or during stationary crystallization when this multipolymer, the inventor determines, outside degree, temperature and the speed of orientation, birefringent recruitment also depends on the degree of randomness of the single monomeric unit that constitutes multipolymer or depends on homopolymer and the limiting viscosity of the multipolymer that generates.
In one embodiment, but the phase mixed polymer that contains single monomer is considered to can be used for the present invention.At least a should can the development ideally of used polymkeric substance goes out higher birefringence degree.The difference of birefringence degree may be because of multiple factor.At least some this category feature comprises crystallinity and the intrinsic birefringence degree that forms between random copolymers and the segmented copolymer in orientation process, but is not limited thereto.For given molecular weight and the multipolymer that contains two kinds of equivalent monomers, statistics random copolymers and diblock copolymer define the ultimate value that can reach degree of randomness.
In an exemplary embodiments, continuous state material is a polyester, and monomer wherein comprises dimethyl terephthalate (DMT) (T), naphthalate (N) and ethylene glycol (E).The homopolymer of these monomers is known as polyethylene terephthalate (PET) and PEN (PEN).That is to say that PET is corresponding to sequence TE-TE-TE ..., PEN is corresponding to sequence NE-NE-NE ...The degree of randomness of NE or TE block can be similar to by the ratio of viewed NET tlv triple mark with the random probability of the statistics of NET tlv triple, supposes that keyed jointing is at random.The program of determining tlv triple has description in the Polymer of Stewart and Cox one literary composition (Vol.34, pp.4060-67 (1993)).Can prove that the random probability of the statistics of NET tlv triple is provided by product: 2 * Wt * Wn, wherein Wt is the mole fraction of T monomer, and Wn is the mole fraction of N monomer.Degree of randomness is defined as the ratio of viewed NET tlv triple mark and the theoretical mark of NET tlv triple in the statistics random copolymers.
For example, the high molecular block of the diblock copolymer of 50 molar percentage T and 50 molar percentage N has a NET tlv triple in each molecule, thereby presents the not detectable NET tlv triple mark of reality in heavy polymer.The ratio of definition degree of randomness is approximately zero.For random copolymers, the theoretical probability of NET tlv triple is 0.5.For this actual random copolymers, the ratio of definition degree of randomness is approximately 1.0 (100%).
The degree of randomness of NE-or TE-sequence can be similar to following theoretical method, supposes that the reaction ratio of two kinds of monomer materials equates.For unequal those situations of reaction ratio of monomeric unit wherein, can carry out more complicated analysis.The purpose of Tao Luning for this reason, order:
Wn=is by the indicated or measured NE mole fraction of nuclear magnetic resonance spectroscopy (nmr);
Wt=is by the indicated or measured TE mole fraction of nmr;
Pnn=is by the measured NEN sequence mark of nmr;
Pnt=is by the measured NET sequence mark of nmr; And
Ptt=is by the measured TET sequence mark of nmr.
Thus
Wt+Wn＝1
And
Pnn+Pnt+Ptt＝1。
And, make P (j|i) equal on copolymer chain, to find when current selected monomer is for " i " sequence monomer on given copolymer chain the next conditional probability of " j " monomer that is.In the amount of these back, there are four kinds, P (n|n), P (n|t), P (t|n) and P (t|t).Under the restrictive condition of high molecular, the probability of end group is mainly zero, thus:
P(n|t)+P(t|t)＝1
And
P(n|n)+P(t|n)＝1
By defining of this conditional probability:
Pnn＝P(n|n)*Wn，
Ptt=P (t|t) * Wt, and
Pnt＝P(n|t)*Wt+P(t|n)*Wn。
Therefore, above-mentioned equation has defined the measurable conditional probability of NMR.In the special case of random copolymers, find that the probability of next " j " monomer and " i " are irrelevant, thereby P (j|i) only is Wj.Therefore, for random copolymers:
Pnn＝Wn*Wn，
Ptt＝Wt*Wt，
And
Pnt＝2*Wn*Wt，
As previously described.Under this high molecular restriction, generally can be applicable in the reality, the definition of % degree of randomness is deferred to now:
% degree of randomness=Pnt/ (2*Wn*Wt)=Pnt (observation)/Pnt (random)
Draw by the nmr curve map of different characteristic although should be pointed out that Wj and Pij, have further relation therebetween.Usually, also have following relation:
0.5*Pnt+Pnn=Wn, and
0.5*Pnt+Ptt＝Wt。
Special under the situation of low-level degree of randomness, experimental error can cause the little deviation of these relations.Given these deviations, the best of number percent degree of randomness definition is based on Pnt experiment (observation) value of as above providing in the reality.The probability of the k length sequences of j monomeric unit (only at＜k〉effective when not being in the magnitude of amount of monomer in the single chain, therefore supposition has the high molecular restriction) be when " j " monomer occurring the given first time k-1 time continuously the probability of appearance multiply by the k+1 monomer and be not the probability of " j " monomer.Because each sequence must have certain-length, so have:
The quantity average length of j monomer is
Reduce to
＝1/(1-P(j|j))
＝{Pjj/(Wj-Pjj)}+1。
Under the situation of random copolymers, the further amount of reducing to (1-Wj)
-1
Frensdorff has provided the more generalized case of finite chain in Macromolecules (4,369 (1971)) literary composition.Its conditional probability deducts the probability of chain termination a little, for example, (Pj/j) multiply by and directly joins scope near 1.People such as Lopez-Serrano have provided a kind of substituting " recurrence " method with similar results in Polymer (21,263 (1980)) literary composition.Under any circumstance, characteristic method described herein can be applicable to contain the segmented copolymer of unit " A " and " B ", is not limited to the illustration situation of A=NE and B=TE.In following example, the random copolymers of 70%NE block monomer component has only about 3 quantity average N E block sequence length.The random copolymers of 50%NE block monomer component has only about 2 quantity average N E block sequence length.Although bound by theory should not believed, when average sequence length is longer, can improve various physics, optics or mechanical property.For example, crystallinity can improve under given stretching condition, thereby causes higher birefringence or spatial stability.Fusing point also can improve, when being created in temperature and improving than film more stable under the random situation.Because refractive index is a key factor of optical device performance, can improve and/or keep in the drawing process and the molecular orientation afterwards that stretches so improve block length, all the more so for carry out heat-staple optical device by annealing when the high temperature or heat setting especially.One of the mechanism that can stablize or keep molecular orientation is to form crystallite in drawing process.The beginning crystallization can cause the increase of tensile force usually in the drawing process.Consequently, any set point of being increased in the similar drawing process of the stress that presents of segmented copolymer that can crystallization in orientation process has all surpassed the statistics random copolymers that contains same monomer; That is to say that segmented copolymer tends to than the statistics random copolymers strain hardening take place quickly, but identical aspect other.With strain hardening faster accompany be the positive birefringence material along the more high index of refraction of draw direction and in given drawing process the more high birefringence degree of set point.When every other amount remained unchanged, higher birefringence degree can cause higher gain usually.
In fact, several factors can change the variation that stress with stretching shape is, thereby can cause changing the beginning of strain hardening.Outside the number percent degree of randomness, increase the molecular weight or the I.V. of external phase, increase the segmented copolymer monomeric unit with respect to the relative formation of high glass transition temperature and/or faster crystallised component (for example NE) more, and the mark of disperse phase (for example syndiotactic polystyrene (sPS)) can quicken the beginning of strain hardening usually before the increase commutation.These factors only are exemplary, and should not think restrictive.On the contrary, for one group of given processing conditions, arbitrary these factors can improve the birefringence and the optical gain of normal incidence direction.
In following example, external phase comprises that the balanced attitude after its transesterification is random or is bordering on random polyester at least: transesterification number percent is more than 98%.
Comparative Examples 1
Extrusion technique with type described in the U.S. Pat 5783120 (people such as Ouderkirk) carries out extrusion molding and casts film polymer blend.This admixture contains the coPEN (PET of the PEN of 70 moles of % and 30 moles of %) of 57.6 weight % as external phase, Questra MA 405 syndiotactic polystyrenes of 40 weight % (can be by Dow ChemicalCo. (Midland, Michigan) buy) as disperse phase, and Dylark 332 bulking agents of 2.4 weight % (can buy by Nova Chemicals).The limiting viscosity that coPEN has (I.V.) is 0.57 (recording in 60% phenol, 40% dichloro-benzenes).
At Polymer, the proton nmr of describing among the Vol.34, pp.4060-4067 (1993) is carried out sequential analysis on above-mentioned cast film according to people such as Stewart.Observe three sharp-pointed resonance peaks, corresponding to ethylene glycol (E) proton in NEN, NET and the TET tlv triple sequence.The probability of the NET tlv triple sequence that observes is defined as degree of randomness with the ratio (representing with number percent) of its theoretical probability.The degree of randomness that records is 98.1%, this means that multipolymer is actually the random copolymers of PEN and PET.
At first with traditional length orientation instrument make cast film along machine direction be orientated to draw ratio be about 1.3: 1.Make described thin slice along horizontal uniaxial orientation with traditional stenter then.According to the track setting at stenter entrance and exit place, final cross directional stretch ratio is about 5.4: 1.Draft temperature is 118 ℃ (245 ).After orientation, film is carried out heat setting at 163 ℃ (325 ).
Detect the optical characteristics of film with the Perkin-ElmerLambda-19 ultraviolet-visible spectrophotometer that is provided with integrating sphere and Glans-Thompson cube polarizer.For the optical wavelength between polarization direction and the 400-700nm that the film transmission direction is aimed at, average transmittance is 83.5%.The polarization direction is 16.3% with the average transmittance of the light that film blocking-up direction is aimed at.Measure its gain by film being placed C12P cavity backlight.The axle of cavity was gone up brightness ratio when film was in place does not have the same device of film big by 40.2%.The measurement brightness of the same device when becoming the brightness ratio at 40 ° of angles not have film with respect to normal when film is in place is big by 28.5%.
Comparative Examples 2
CoPEN to Comparative Examples 1 carries out extrusion molding and casts film, and recording its degree of randomness is 99.1%.Therefore, the existence of Questra MA 405 resins does not show the measurement that can influence the polyester degree of randomness in the Comparative Examples 1.The limiting viscosity of final copolymer is measured as 0.526.In the spreader described casting system thin slice uniaxial orientation to nominal is stretched than 6: 1 at 115 ℃ in batches in the laboratory.In orientation process, measure the strain-stress relation of thin slice, and it is expressed as curve A among Fig. 1.For actual draw ratio 5.30: 1, determine that 632.8nm wavelength place is 1.766 along the refractive index of direction of extension.Along direction in another no extension plane, determine that refractive index is 1.600.With its crystallinity of determine with dsc method, recording its apparent heat is 25.0J/g, and the peak value melt temperature is 205 ℃.
Except draft temperature is 120 ℃,, described casting system thin slice further is orientated to several different uniaxial tensions ratios according to above-mentioned condition.Utilization is in the reference mark of delineating before the orientation on casting system thin slice, can by the mark spacing after orientation be orientated before ratio determine actual draw ratio simply.For each actual draw ratio, measure refractive index, and in Fig. 2, be drawn as open circles along main draw direction.As estimating, observed the function that increases to draw ratio along the draw direction refractive index for this positive birefringence material.
Embodiment 1-2
The polymer blend that contains 70 moles of %PEN homopolymer and 30 moles of %PET homopolymer is carried out extrusion molding and casts film.In embodiment 1, the I.V. of PEN is 0.56, and the I.V. of PET is 0.60.The I.V. that records final copolymer is 0.535.Degree of randomness is 23.4%.The I.V. of PEN is 0.56 in embodiment 2, and the I.V. of PET is 0.85.The I.V. that records final copolymer is 0.560.Degree of randomness is 30.9%.Thin slice among the embodiment 1 and 2 all is transparent.
Be orientated with the mode of the film that is similar to Comparative Examples 2 thin slice, and determine its corresponding stress-strain curve embodiment 1-2. Embodiment 1 and 2 strain-stress relation are expressed as curve B and C respectively in Fig. 1.The multipolymer of embodiment 1 has low slightly limiting viscosity and lower degree of randomness than the multipolymer of embodiment 2, and shows strain hardening slightly early.The difference of curve B and C may be inapparent on statistics.Yet the strain hardening behavior of these curves is significantly different with the corresponding behavior of the statistics random copolymers of Comparative Examples 1 (curve A), and wherein strain hardening is in order to describe the variation of stress with the strain of apply orientation.
Described in Comparative Examples 2, the casting system flake orientation that makes embodiment 1 and 2 is to each actual draw ratio.Measure its refractive index, and be drawn among Fig. 2 as sealing square and hollow triangle respectively at main draw direction.Embodiment 1 and 2 presents refractive index along draw direction to be increased.In addition, with strain hardening early begin consistently, for any given stretching, extension condition, embodiment 1 and 2 refractive index all are higher than the corresponding refractive index of Comparative Examples 2.
Measure crystallinity with differential scanning calorimetry.In embodiment 1, record apparent fusion heat and be 35.9J/g, the peak value melt temperature is 251 ℃.In embodiment 2, record apparent fusion heat and be 35.3J/g, the peak value melt temperature is 244 ℃.
Under 120 ℃ draft temperature, carry out similar serial ess-strain experiment.For embodiment 1 and 2, strain hardening appears when high slightly draw ratio.Refractive index under all three kinds of situations all reduces about 0.01 in direction of extension.
Be not limited to any theory especially, as can be seen, will change the improvement of optical characteristics into greater than its stress increase in about 3 o'clock at apparent uniaxial tension ratio.For example, when draw ratio is identical,, in the continuous state material that presents the strain hardening behavior, can realize the more big-difference of refractive index between external phase and the disperse phase with respect to the continuous state material that does not present the strain hardening behavior.
For optical device such as reflection type polarizer, its optical characteristics partly depends on along the refractive index difference between at least one axial external phase and the disperse phase, the raising that illustrative segmented copolymer can show optical characteristics among the embodiment 1 and 2 as combination of materials described in the Comparative Examples 1 a part of the time.
Method according to Comparative Examples 1 prepares film, and different is to substitute the coPEN multipolymer with the PEN of embodiment 2 and the admixture of PET homopolymer.The degree of randomness of cast film is 8.7%.At first with traditional length orientation instrument make cast film along machine direction orientation to stretching than being 1.25: 1.Then 118 ℃ (245 ) along cross directional stretch to stretching than being 5.1: 1.Gain is 43.8% on the axle.40 ° of gains are 20.1%.
With respect to Comparative Examples 1, this embodiment shows that the potpourri that can adopt homopolymer and/or lower degree of randomness realize that axle goes up the increase of gain.
Method according to embodiment 3 is made film, and different is that PEN and PET homopolymer are PEN and PET homopolymer among the embodiment 1.The degree of randomness of this sample is 10.8%.Gain is 42.8% on the axle.40 ° of gains are 19.2%.
By comparing embodiment 4 and embodiment 3, as can be seen, at fixing degree of randomness, be close under the identical composition and process conditions, increase I.V. and promptly increase gain.
Method according to embodiment 3 prepares film, and different is by additional filtration unit being set in melt-flow, making the fused mass residence time compare substantive increasing with embodiment 3.Embodiment 5 adopts two filtrators in melt-flow, and embodiment 3 only adopts a filtrator, thereby residence time is approximate double.By increasing residence time, degree of randomness is increased.The control residence time can be used to control degree of randomness.Degree of randomness is 27.9%; Gain is 43.2% on the axle; 40 ° of gains are 18.1%.
This embodiment shows that the residence time relevant with fused mass can influence degree of randomness.This embodiment illustrates that also optical property needn't linear dependence with respect to degree of randomness.
Fig. 3 is that the axle of Comparative Examples 1 and embodiment 3,4 and 5 is gone up gain and degree of randomness graph of a relation, illustrate continuously/at least one block structure (blockiness) in mutually of disperse phase reflection type polarizer has positive role.
Embodiment 6
Method according to embodiment 5 prepares film, and different is that 135 ℃ (275 ) is in a ratio of 140 ℃ (285 ) among stenter preheat temperature and the embodiment 5.The degree of randomness of this sample is 28.5%, and presenting the last gain of axle is 41.9%.
Embodiment 7
The present embodiment explanation can be used for another scope of limiting viscosity of the present invention.Method according to embodiment 6 prepares film, and different is that the PEN limiting viscosity is 0.48, and the PET limiting viscosity is 0.72.The degree of randomness of this sample is 25.2%, and presenting the last gain of axle is 40.4%.By comparing comparative example 7 and embodiment 6, as can be seen, be close under the identical degree of randomness and process conditions, the viscosity that improves the polymers that is mixed mutually can increase gain.
Embodiment 8-10
These embodiment explanations, the different compositions to PEN and PET can obtain different degree of randomness.
Film among the embodiment 8-10 is according to the method preparation of embodiment 4, and different is that PEN is respectively 65/35,60/40 and 55/45 to the PET proportion of composing.Degree of randomness among the embodiment 8,9 and 10 is respectively 11.7%, 9.4% and 10.1%.Axle among the embodiment 8,9 and 10 is gone up gain and is respectively 40.2%, 44.2% and 43.9%.Should be pointed out that 65/35 sample stretches for about 10 ℃ in the temperature that is higher than 60/40 and 55/45 sample, cause its gain to be lower than the expection gain, thereby the yield value of gained not directly compares.8,9 and 10,40 ° of gains are respectively 27.0%, 24.8% and 28.7% for embodiment.
Embodiment 11
The present embodiment explanation increases the influence of degree of randomness to gain.Method according to Comparative Examples 1 prepares continuously/the disperse phase admixture, that different is the coPEN that this admixture contains the PEN/PET with 70/30 mole of % of 34.8 weight %, 22.8 the I.V. of weight % is 0.85 PET, the Questra MA 405 of 40 weight %, and the Dylark of 2.4 weight %, thereby the ratio of the effective PEN that generates and PET is 55/45.Then with among the embodiment 4 similarly method this admixture is carried out extrusion molding and film is made in casting.Recording degree of randomness is 71.0%.Gain is 37.9% on the axle.40 ° of gains are 27.6%.
Wherein degree of randomness is 10.1% embodiment 10, and the film of present embodiment has 71.0% degree of randomness, and the gain that direction and 40 ° of directions present on axle all reduces to some extent.
Comparative Examples 3
Cast film by Comparative Examples 1 prepares film sample, and different is is orientated operation on the spreader in batches in the laboratory, and wherein orientation temperature is 115 ℃, and final nominal is stretched than being 6.0: 1.In orientation process, measure engineering stress, shown in curve D among Fig. 4.By curve A in the comparison diagram 1 and the curve D among Fig. 4, can obviously find out, add disperse phase and changed the strain hardening behavior, and irrelevant with the degree of randomness of external phase.
Embodiment 12
Method according to Comparative Examples 3 prepares film, and different is that it is made by the casting system thin slice of making as embodiment 3 parts.Its stress-strain measured value is shown in curve F among Fig. 4.
Embodiment 13
According to the method for Comparative Examples 3, prepare film with being similar to the casting net that embodiment 3 makes, different is that its % degree of randomness is 40%.Its stress-strain measured value is shown in curve E among Fig. 4.
Three curves among Fig. 4 are compared show,,, have continuous decline in the apparent draw ratio when strain hardening begins along with the reduction of degree of randomness although the strain hardening behavior may be changed owing to the existence of disperse phase.
As previously mentioned, than the increase greater than about 3 o'clock stress, for the very fast rather than slower combination of materials of those strain hardenings, produce bigger difference by making its refractive index as the draw ratio function at apparent uniaxial tension, expectation should improve optical characteristics.
Of the present inventionly noted earlierly only be exemplary but not be intended to limit.For example, in whole application, often quote film.Yet, one skilled in the art will readily appreciate that the given instruction of this paper can be applied to other optical elements outside the optical thin film, such as the on-plane surface optical lens.Therefore, scope of the present invention should be explained with reference to claims individually.
Claims (11)
1. make the method for oriented film, comprising:
Form the potpourri that has external phase and disperse phase at least, wherein external phase comprises the admixture of first and second homopolymer that can react to each other by ester exchange reaction, first homopolymer comprises that the PEN and second homopolymer comprise polyethylene terephthalate;
First and second homopolymer are reacted to each other by ester exchange reaction and obtain casting film by the described potpourri of extrusion molding; With
On at least one direction, stretch described casting film, form oriented film thus.
2. method according to claim 1, wherein first and second homopolymer react to each other before described potpourri forms.
3. method according to claim 1, wherein first and second homopolymer react to each other after described potpourri forms.
4. the oriented film of making according to the described method of claim 1, wherein make with second multipolymer by the same monomer with same ratio but not compared by the respective orientation film that homopolymer makes, described oriented film shows the birefringence degree of appointment under lower strain.
5. the oriented film of making according to the described method of claim 1, wherein make but not compare by the respective orientation film that homopolymer makes with second multipolymer by same monomer with same ratio, for the strain of appointment, described oriented film shows higher birefringence degree.
6. the oriented film of making according to the described method of claim 1 wherein makes with second multipolymer by the same monomer with same ratio but not is compared by the respective orientation film that homopolymer makes, and described oriented film shows higher axle and goes up gain.
7. the polarizer of making according to the described method of claim 1.
8. the forward scattering diffusing globe of making according to the described method of claim 1.
9. method according to claim 1, wherein said first and second homopolymer reaction generate degree of randomness less than about 70% multipolymer.
10. method according to claim 1, wherein said first and second homopolymer reaction generate degree of randomness less than about 50% multipolymer.
11. method according to claim 1, wherein said first and second homopolymer reaction generate degree of randomness less than about 40% multipolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/686,498 | 2000-10-11 | ||
| US09/686,498 US6673275B1 (en) | 1999-10-12 | 2000-10-11 | Method for making optical devices from homopolymers |
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| Publication Number | Publication Date |
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| CN1468380A CN1468380A (en) | 2004-01-14 |
| CN1311248C true CN1311248C (en) | 2007-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018171311A Expired - Fee Related CN1311248C (en) | 2000-10-11 | 2001-10-01 | Method for making optical devices from homopolymers |
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| EP (1) | EP1327165A2 (en) |
| JP (1) | JP4347562B2 (en) |
| KR (1) | KR20030045823A (en) |
| CN (1) | CN1311248C (en) |
| AU (1) | AU2001296447A1 (en) |
| WO (1) | WO2002031541A2 (en) |
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| US7583440B2 (en) * | 2006-06-05 | 2009-09-01 | Skc Haas Display Films Co., Ltd. | Diffusely-reflecting polarizer having nearly isotropic continuous phase |
| US9046656B2 (en) * | 2008-11-18 | 2015-06-02 | 3M Innovative Properties Company | Isotropic layer of multilayer optical film comprising birefringent thermoplastic polymer |
| CN110845711B (en) * | 2019-07-19 | 2021-10-29 | 江建明 | Control method and application of PET average sequence length in PET-PA6 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3937754A (en) * | 1972-07-25 | 1976-02-10 | Teijin Ltd | Biaxially oriented polyethylene-2,6-naphthalate film containing another polyester resin and process for its production |
| US5695710A (en) * | 1995-05-09 | 1997-12-09 | Hoechst Celanese Corp. | Transesterified pet/pen via melt extrusion |
| WO1998024844A1 (en) * | 1996-12-06 | 1998-06-11 | Continental Pet Technologies, Inc. | Process for making pen/pet blends and transparent articles therefrom |
| WO1999036812A1 (en) * | 1998-01-13 | 1999-07-22 | Minnesota Mining And Manufacturing Company | An optical film and process for manufacture thereof |
| WO2000007043A1 (en) * | 1998-07-31 | 2000-02-10 | 3M Innovative Properties Company | Post-forming continuous/disperse phase optical bodies |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546320A (en) * | 1968-03-25 | 1970-12-08 | Sun Oil Co | Polyalkylene terephthalate molding composition |
| JPH05508682A (en) * | 1990-07-30 | 1993-12-02 | イーストマン ケミカル カンパニー | Blends of poly(ethylene terephthalate) and poly(ethylene naphthalene dicarboxylate) containing phosphorus stabilizers |
-
2001
- 2001-10-01 AU AU2001296447A patent/AU2001296447A1/en not_active Abandoned
- 2001-10-01 KR KR10-2003-7005054A patent/KR20030045823A/en not_active Application Discontinuation
- 2001-10-01 EP EP01977319A patent/EP1327165A2/en not_active Withdrawn
- 2001-10-01 CN CNB018171311A patent/CN1311248C/en not_active Expired - Fee Related
- 2001-10-01 JP JP2002534873A patent/JP4347562B2/en not_active Expired - Fee Related
- 2001-10-01 WO PCT/US2001/030681 patent/WO2002031541A2/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3937754A (en) * | 1972-07-25 | 1976-02-10 | Teijin Ltd | Biaxially oriented polyethylene-2,6-naphthalate film containing another polyester resin and process for its production |
| US5695710A (en) * | 1995-05-09 | 1997-12-09 | Hoechst Celanese Corp. | Transesterified pet/pen via melt extrusion |
| WO1998024844A1 (en) * | 1996-12-06 | 1998-06-11 | Continental Pet Technologies, Inc. | Process for making pen/pet blends and transparent articles therefrom |
| WO1999036812A1 (en) * | 1998-01-13 | 1999-07-22 | Minnesota Mining And Manufacturing Company | An optical film and process for manufacture thereof |
| WO2000007043A1 (en) * | 1998-07-31 | 2000-02-10 | 3M Innovative Properties Company | Post-forming continuous/disperse phase optical bodies |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2001296447A1 (en) | 2002-04-22 |
| WO2002031541A2 (en) | 2002-04-18 |
| EP1327165A2 (en) | 2003-07-16 |
| JP2004511628A (en) | 2004-04-15 |
| WO2002031541A3 (en) | 2002-10-31 |
| CN1468380A (en) | 2004-01-14 |
| KR20030045823A (en) | 2003-06-11 |
| JP4347562B2 (en) | 2009-10-21 |
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