Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily to understandOpen content.A large amount of terms can be referred in following description and claims, these terms are defined as following meanings.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise.
" optionally " or " any one " refer to that the item described thereafter or event may or may not occur, and shouldDescription includes the situation that the situation that event occurs and event do not occur.
Expressing a range includes all integers and its score within the scope of this.Expressing a range further includes the rangeEndpoint, do not consider that the range indicates whether certain numerical value "inner" or a numerical value of " between " or " ".In the disclosureHold and the intention of range described in claim particularly including full scope and not just one or more endpoints.For example, 0 toRange illustrated by 10 is intended to disclose all integers between 0 and 10, such as 1,2,3,4 etc., all scores between 0 and 10,Such as 1.5,2.3,4.57,6.1113 etc. and endpoint 0 and 10.
Equally, for chemical substituents, such as, for example, " C1To C5The related range of hydrocarbon " is intended to particularly including and public affairsOpen C1And C5Hydrocarbon and C2、C3And C4Hydrocarbon.
As used herein, term " copolyesters " is understood to mean that more kinds of by one or more bifunctional carboxylic acids and twoThe synthetic polymer of difunctional hydroxyl compound's polycondensation preparation.Typically, bifunctional carboxylic acid is dicarboxylic acids and bifunctional hydroxyizationConjunction object is dihydric alcohol, for example, for example glycols (glycol) and glycols (diol).
As used herein, term " residue " is indicated by being related to being introduced into polymer and corresponding to the polycondensation reaction of monomerAny organic structure.As used herein, term " repetitive unit " indicates have the dicarboxylic acids being bonded via carbonyl oxygroup residualThe organic structure of base and diol residue.Therefore, dicarboxylic acid residue can be derived from dicarboxylic acid monomer or its acyl halide combined,Ester, salt, or mixtures thereof acid anhydrides.Therefore, as used herein, term dicarboxylic acids is intended to include the polycondensation side that can be used for glycolMethod is to generate the dicarboxylic acids of high molecular weight copolyester and any derivative of dicarboxylic acids, the acyl halide including its combination, ester, and halfOr mixtures thereof ester, salt, half salt, acid anhydrides, mixed acid anhydride,.
One aspect of the present invention provides a kind of light polarizing products, comprising:
The first outer membrane containing amorphous copolyester, film thickness are 0.09-1.9 millimeters；
First gluing oxidant layer, thickness are 1 micron -2 millimeters；
Interlayer film containing PVA, film thickness are 0.2-0.4 millimeters；
Second gluing oxidant layer, thickness are 1 micron -2 millimeters；And
The second outer membrane containing amorphous copolyester, film thickness are 0.09-1.9 millimeters；
These layers are successively bonded by said sequence；
In first outer membrane and the second outer membrane, the amorphous copolyester includes the residue of following components:
(a) acid constituents comprising at least residue of the residue or derivates of the terephthalic acid (TPA) of 80mol%；With
(b) comprising the accumulative at least residue of the neopentyl glycol of 80mol% and 2,2,4,4- tetraalkyl -1,3- cyclobutanediolHydroxy component；
Based on the acid constituents residue of the 100mol% in copolyesters and the hydroxy component residues of 100mol%.
Preferably, the film thickness of first outer membrane and the second outer membrane is 0.1-1.5 millimeters, more preferably 0.5-1.2 millimeters, most preferably 1 millimeter.
Preferably, the film thickness of the interlayer film containing PVA is 0.3 millimeter.
Preferably, the thickness of the first gluing oxidant layer and the second gluing oxidant layer be 50 microns -1 millimeter, more preferably 80- 300 microns, most preferably 150 microns of micron.
Amorphous copolyester
Amorphous copolyester of the present invention indicates the polyester substantially and includes the disordered regions of polymer.Amorphous copolymerizationEster usually not fusing point.
Amorphous copolyester of the invention shows at least 90 DEG C of glass transition temperature (being abbreviated as " Tg " herein), such as byWell-known technique, for example, for example differential scanning calorimetry (" DSC "), uses the TA DSC for being purchased from TA Instruments2920 with the scan rate measurement of 20 DEG C/min.
It is desirable that the Tg of amorphous copolyester shows at least 92 DEG C, or at least 94 DEG C, or at least 96 DEG C, or at least 98 DEG C,Or at least 100 DEG C, or at least 102 DEG C, or at least 104 DEG C, or at least 106 DEG C, or at least 108 DEG C, or at least 110 DEG C, or extremelyIt is 112 DEG C few, or at least 144 DEG C, or at least 116 DEG C, or at least 118 DEG C, or at least 120, and at most 185 DEG C, or be at most less than170 DEG C, or at most 160 DEG C, or less than 150 DEG C, or less than 140 DEG C, or less than 138 DEG C, or less than 136 DEG C, or less than 134DEG C, or less than 132 DEG C, or less than 130 DEG C, or less than 128 DEG C, or less than 126 DEG C, or less than 124 DEG C, or less than 122 DEG C, orLess than 120 DEG C, or less than 118 DEG C, or the Tg less than 116 DEG C.
The example of range is included in 90 to 185 DEG C；90 to 180 DEG C；90 to 170 DEG C；90 to 160 DEG C；90 to 155 DEG C；90To 150 DEG C；90 to 145 DEG C；90 to 140 DEG C；90 to 138 DEG C；90 to 135 DEG C；90 to 130 DEG C；90 to 125 DEG C；90 to 120℃；90 to 115 DEG C；90 to 110 DEG C；90 to 105 DEG C；90 to 100 DEG C；90 to 95 DEG C；92 to 185 DEG C；92 to 180 DEG C；92 to170℃；92 to 160 DEG C；92 to 155 DEG C；92 to 150 DEG C；92 to 145 DEG C；92 to 140 DEG C；92 to 138 DEG C；92 to 136 DEG C；92 to 134 DEG C；92 to 132 DEG C；92 to 130 DEG C；92 to 128 DEG C；92 to 126 DEG C；92 to 124 DEG C；100 to 185 DEG C；100 to160℃；100 to 150 DEG C；100 to 145 DEG C；100 to 140 DEG C；100 to 138 DEG C；100 to 136 DEG C；100 to 134 DEG C；100 to132℃；100 to 130 DEG C；100 to 128 DEG C；100 to 126 DEG C；105 to 185 DEG C；105 to 160 DEG C；105 to 150 DEG C；105 to145℃；105 to 140 DEG C；105 to 136 DEG C；105 to 132 DEG C；105 to 128 DEG C；110 to 185 DEG C；110 to 160 DEG C；110 to150℃；110 to 145 DEG C；110 to 140 DEG C；110 to 136 DEG C；110 to 132 DEG C；With the Tg within the scope of 110 to 128 DEG C.
Preferably, amorphous copolyester polymer of the invention repeats in polymer chain containing terephthalic acids alkylene esterUnit.
Amorphous copolyester can be by making the C of NPG and TACD and terephthalic acid (TPA)1-C4Dialkyl ester reaction generates ester listThen body and/or oligomer make its polycondensation generate copolyesters to prepare.It can make during this method more than one containing oneOr the compound or one or more derivatives reaction of multiple carboxylic acid groups.The entrance for becoming a part of copolyester product shouldAll compounds containing one or more carboxylic acid groups or one or more derivative in method constitute " acid constituents ".Contain" residue " of the one or more compounds or one or more derivative that have one or more carboxylic acid groups indicates allizationThe copolyester polymer chain for closing object condensation and polycondensation formation different length remains in one of copolyester product or a variety of laterThe part of compound.
More than one compound containing one or more hydroxyls or derivatives thereof can become one or more copolyestersThe part of polymer product.Become containing one or more hydroxyls in the access method of the part of one or more copolyester productsAll compounds of base or derivatives thereof constitute hydroxy component.Become one or more hydroxyl-functionals of the part of copolyester productThe residue of compound or derivatives thereof indicates, in the compound and one or more chemical combination containing one or more carboxylic acid groupsObject or one or more derivative are condensed an one-step polycondensation of going forward side by side and are formed after the copolyester polymer chain of different length, remain inThe part of one of copolyester product or multiple compounds.
The mol% of OH residues and carboxylic acid residues in one or more products can be by proton NMR or gas chromatographyMeasurement.
Preferably, which includes:
(a) acid constituents, it includes at least 80mol%, or at least 85mol%, or at least 90mol%, or at least92mol%, or the terephthalic acid (TPA) of at least 96mol%, or the ideally C of terephthalic acid (TPA)1-C4The residue of dialkyl ester, orAt least 85mol% in any case, or at least 90mol%, or at least 92mol%, or at least 96mol%'s includes being bonded to virtueThe terephthalate unit of-C (O) O- group of race's ring；With
(b) hydroxy component, it includes at least 85mol%, or at least 90mol%, or at least 92mol%, or at leastThe residue of the TACD and NPG of 96mol%；
Based on the acid constituents residue of 100mol% in copolyester polymer and the hydroxy component residues of 100mol%.
The acid constituents for preparing copolyester polymer is not limited to the mole percent with reacting for hydroxy component, becauseIt can be with the hydroxy component of excessive addition during manufacture.But described sour group will be contained by reacting copolyester polymer obtainedDivide the amount with hydroxy component.
The derivative of terephthalic acid (TPA) includes terephthalic acid (TPA) C1-C4Dialkyl ester, such as dimethyl terephthalate (DMT).ReasonThink ground, the amount of acid constituents is the C of terephthalic acid (TPA)1-C4The residue of dialkyl ester or dimethyl terephthalate (DMT).
Except the C of terephthalic acid (TPA) and terephthalic acid (TPA)1-C4Except dialkyl ester, TACD and NPG, other acid constituents and hydroxylComponent may be used as modifying agent, as long as the Tg of polymer is maintained at least 90 DEG C of level.
The example of sour modifying agent includes aromatic dicarboxylic acid, preferably has 8 to 14 carbon atoms, aliphatic dicarboxylic acid, excellentChoosing has 4 to 12 carbon atoms or alicyclic dicarboxylic acid, preferably has 8 to 12 carbon atoms.It can be used as one or more acidThe more particular example of the modifying agent dicarboxylic acids of component be phthalic acid, M-phthalic acid, naphthalene -2,6- dioctyl phthalate, hexamethylene -1,4- dioctyl phthalate, cyclohexanediacetic, diphenyl -4,4'- dioctyl phthalate, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid,Decanedioic acid, dimeric dibasic acid, sulfoisophthalic acid, fumaric acid, maleic acid, itaconic acid, 1,3- cyclohexane cyclohexanedimethanodibasic, diglycolic acid,2,5- norbornane dioctyl phthalate, diphenic acid, 4,4'- oxygen dibenzoic acid, 4,4'- sulfonyl dibenzoic acid, mixture etc..It answersUnderstand and is included in term " carboxylic acid " using correspondence acid anhydrides, ester and the acyl chlorides of these acid.Three carboxyl compounds and have it is higherThe compound of carboxylic acid group number equally can be with modified copolyester.
In addition to the hydroxy component comprising NPG and TACD, the hydroxy component of copolyesters of the present invention may include modifying agent.HydroxylBase modifying agent is any hydroxyl compound in addition to NPG and TACD.Hydroxyl modification agent includes single methanol, glycol, or as branchChange the compound with higher hydroxyl value of monomer.The example of modifying agent hydroxy compounds includes alicyclic diol, preferred to haveThere are 6 to 20 carbon atoms and/or aliphatic diol, preferably there are 2 to 20 carbon atoms.The more particular example of this glycol includesEthylene glycol, diethylene glycol (DEG)；Triethylene glycol；1,2- cyclohexanedimethanol；1,3- cyclohexanedimethanol；1,4 cyclohexane dimethanol；1,2-Propylene glycol；1,3- propylene glycol；1,4- butanediol；1,5- pentanediol；1,6-HD；3- methyl -2,4-PD；2- methyl-1,4- pentanediol；2,2,4- trimethylpentane -1,3- glycol；2,5- ethyl hexane -1,3- glycol；2,2- diethyl -1,3- thirdGlycol；1,3- hexylene glycol；1,4- bis--(hydroxyl-oxethyl)-benzene；2,2- bis--(4- hydroxy-cyclohexyl)-propane；2,4- dihydroxy-1,1,3,3- tetramethyl-cyclobutane；2,2- bis--(3- hydroxyethoxyphenyl)-propane；2,2- bis--(4- hydroxy propyloxy group benzeneBase)-propane；2- butyl -2- ethyl -1,3-PD, 2- ethyl -2- isobutyl group -1,3-PD, 2,2,4,4- tetramethyls -1,6- hexylene glycol, 1,10- decanediol, Isosorbide-5-Nitrae-benzene dimethanol, hydrogenated bisphenol A, different de- two water D-sorbites, propylene glycol, dipropyl are sweetAlcohol, polytetramethylene glycol, tetraethylene glycol, polyethylene glycol, and may be used as the higher functional hydroxy compounds of hyperbranched compounds, including 1,1,1- trimethylolpropane, 1,1,1- trimethylolethane, glycerol, pentaerythrite, antierythrite, threitol, dipentaerythritol, mountainPears sugar alcohol, mixture etc..
One example of modifying agent includes the M-phthalic acid or naphthalenedicarboxylic acid as the addition of sour modifying agent, and as hydroxylThe cyclohexanedimethanol of base modifying agent addition, ethylene glycol or diethylene glycol (DEG).
In addition to NPG and TACD, hydroxyl modifying agent can be to be less than 40mol%, or is less than 20mol%, or be less than10mol%, or it is less than 8mol%, or be less than 5mol%, or be less than 3mol%, or be less than 2mol%, or be less than 1mol% or smallAmount addition in 0.5mol%, or less than 0.25mol%, and do not add completely ideally, based in polymerIts each component of 100mol%, acid or hydroxyl.In addition to NPG and TACD, hydroxyl modifying agent is also ideally to be less than20mol%, or it is less than 10mol%, or be less than 5mol%, or be less than 4mol%, or be less than 2mol%, or be less than 1mol%, orAmount less than 0.5mol% is present in polymer, and (it includes hydroxyl by definition to the molal quantity based on residues all in copolyestersThe residue of base and acid constituents).
It is desirable that removing terephthalate, other than the part NGP and TACD, the amount of all parts, is wrapped present in copolyestersIt those of is formed in situ during including those of the modifying agent for being attributed to addition and melt phase polymerization, for less than 12mol%, or notMore than 10mol%, or it is no more than 8mol%, or is no more than 6mol%, or is no more than or is less than 5mol%, or be no more than5mol%, or it is no more than 4mol%, or be no more than 2mol%, or be no more than 1mol%, or be no more than and be less than 0.5mol%, or notMore or less than 0.25mol%, or it is no more than or is less than 0.1mol%, or be 0mol%, based on residues all in copolyestersMolal quantity.
It is desirable that copolyesters of the invention includes being less than 5mol%, or be less than 4mol%, or be less than 3mol%, or be less than2mol%, or the glycol residue less than 1mol%, the molal quantity based on residues all in copolyesters.It is desirable that not adding secondGlycol, unless adding it as the carrier of catalyst metal compound.Optionally, ethylene glycol is not added.
Polyester of the invention may include at least one chain extender.The suitable including but not limited to multifunctional (packet of chain extenderInclude but be not limited to difunctionality) isocyanates, multi-functional epoxy's compound, including such as epoxidised novolaks and phenoxy group treeRouge.In certain embodiments, chain extender can add at the end of polymerization or after polymerization.If poly-It is added after conjunction method, chain extender can draw during method for transformation (such as injection molding or extrusion) by being kneaded or by addingEnter.The amount of the chain extender used can be different, depending on the specific monomer composition used and required physical property, but it is logicalChang Weiyue 0.1wt% to about 10wt%, for example, about 0.1wt% are to about 5wt%, the total weight based on polyester.
In one embodiment, in the amorphous copolyester, described 2,2,4,4- tetraalkyl -1,3- cyclobutanediolsResidue includes by the residue of the compound of following representation:
Wherein R1, R2, R3And R4Each independently represent the alkyl with 1 to 8 carbon atom.Alkyl can be it is linear,Branching, or linear and branched-alkyl combination, it is desirable that R1, R2, R3And R4At least one be methyl, preferably R1, R2, R3And R4Each be methyl.
The corresponding 2,2,4,4- tetraalkyl -1,3- cyclobutanediol that may be used as TACD compound includes 2,2,4,4- tetramethylBase -1,3- cyclobutanediol (" TMCD "), 2,2,4,4- tetraethyl -1,3- cyclobutanediols, 2,2,4,4- tetra--n-propyl -1,3- ringsButanediol, 2,2,4,4- tetra--normal-butyl -1,3- cyclobutanediols, 2,2,4,4- tetra--n-pentyl -1,3- cyclobutanediols, 2,2,4,4-Four-n-hexyl -1,3- cyclobutanediols, 2,2,4,4- tetra--n-heptyl -1,3- cyclobutanediols, 2,2,4,4- tetra--n-octylcyclams, 3-Cyclobutanediol, 2,2- dimethyl -4,4- diethyl -1,3- cyclobutanediols, 2- ethyl -2,4,4- trimethyl -1,3- cyclobutanediol,2,4- dimethyl -2,4- diethyl -1,3- cyclobutanediols, 2,4- dimethyl -2,4- diη-propyl -1,3- cyclobutanediols, 2,4-Positive dibutyl -2,4- diethyl -1,3- cyclobutanediol, 2,4- dimethyl -2,4- diisobutyl -1,3- cyclobutanediols and 2,4-Diethyl -2,4- diisoamyl -1,3- cyclobutanediol.It is desirable that TACD compound includes 2,2,4,4- tetramethyl -1,3- ring fourthsGlycol.
Hydroxy component based on 100mol%, the molal quantity of TACD residue can be at least 20mol%, or at least30mol%, or at least 40mol%, or at least 50mol%, or at least 60mol%, or at least 70mol%, or at least80mol%, and it is less than 90mol%, or be less than 85mol%, or be less than 80mol%, or be less than 75mol%, or be less than70mol%, or it is less than 65mol%, whole molal quantitys of the hydroxy component based on addition.Suitable range includes 20-90, or20-85 or 20-80 or 20-75 or 20-70 or 20-65 or 30-90 or 30-85 or 30-80 or 30-75 or 30-70 or 30-65 or 30-60 or 40-90 or 40-85 or 40-80 or 40-75 or 40-70 or 40-65 or 40-60, or50-90 or 50-85 or 50-80 or 50-75 or 50-70 or 50-65 or 50-60 or 60-90 or 60-85 or 60-80 or 60-75 or 60-70 or 60-65 or 70-90 or 70-85 or 70-80 or 70-75 or 80-90 or 80-85,It is the mol% form based on hydroxy component molal quantity in each situation.
Based on the molal quantity of residues all in copolyesters, the mol% of TACD residue present in copolyesters can be at least10mol%, or at least 15mol%, or at least 20mol%, or at least 25mol%, or at least 30mol%, or at least35mol%, or at least 40mol%, and it is less than 45mol%, or be less than 40mol%, or be less than 35mol%, or be less than30mol%.Suitable range includes 10-45 or 15-45 or 20-45 or 25-45 or 30-45 or 35-45 or 40-45,Or 10-40 or 15-40 or 20-40 or 25-40 or 30-40 or 35-40 or 10-35 or 15-35 or 20-35 or 25-35 or 30-35 or 10-30 or 15-30 or 20-30 or 25-30 or 10-25 or 15-25 or 20-25 or 15-20,Molal quantity based on residues all in copolyesters in each situation.
Copolyesters also contains the residue of neopentyl glycol (or 2,2- dimethyl -1,3- propylene glycol) (" NPG ").It is based onThe amount of the hydroxy component of 100mol%, the amount of the NPG of addition are at least 10mol%, or at least 15mol%, or at least20mol%, or at least 30mol%, or at least 40mol%, or at least 50mol%, or at least 60mol%, or at least70mol%, and it is less than 80mol%, or be less than 75mol%, or be less than 70mol%, or be less than 65mol%, or be less than60mol%, or it is less than 55mol%, or be less than 50mol%, or be less than 45mol%.Suitable range includes 10-80 or 10-75 or 10-70 or 10-65 or 10-60 or 10-60 or 10-55 or 10-50 or 10-45 or 20-80 or 20-75, or20-70 or 20-65 or 20-60 or 20-65 or 20-60 or 20-55 or 20-50 or 20-45 or 30-80 or 30-75 or 30-70 or 30-65 or 30-60 or 30-55 or 30-50 or 30 45 or 40-80 or 40-75 or 40-70, or40-65 or 40-60,40-55 or 40-50 or 40 45 or 50-80 or 50-75 or 50-70 or 50-65 or 50-60,Or 60-80 or 60-75 or 60-70 or 60-65 or 70-80 or 70-75 or 80-90 or 80-85, in every case forMol% form based on hydroxy component molal quantity.
Based on the molal quantity of residues all in copolyesters, the mol% of NPG residue present in copolyesters can be at least5mol%, or at least 7mol%, or at least 8mol%, or at least 10mol%, or at least 15mol%, or at least 20mol%, orAt least 25mol%, or at least 30mol%, or at least 35mol%, or at least 40mol%, and it is less than 40mol%, or be less than35mol%, or it is less than 30mol%.Suitable range includes 5-40 or 7-40 or 8-40 or 10-40 or 15-40 or 20-40 or 25-40 or 30-40 or 35-40,5 to 35 or 7 to 35 or 8 to 35 or 10-35 or 15-35 or 20-35, or25-35 or 30-35 or 5 to 30 or 7 to 30 or 8 to 30 or 10-30 or 15-30 or 20-30 or 25-30 or 5-25,Or 7-25 or 8-25 or 10-25 or 15-25 or 20-25 or 5-20 or 7-20 or 8-20 or 15-20, in every caseFor the mol% form based on residue molal quantitys all in copolyesters.
In one embodiment, the amorphous copolyester has following one or more features:
(1) light transmittance>90%, mist degree<1%；
(2) low pressure heat distortion temperature (HDT@0.455MPa) is between 94 DEG C -109 DEG C；
(3) test condition is under the conditions of 2.16kgf pressure, 280 DEG C of melt temperatures, and melting means (MI) is between 15.3-29.5；(4) at least 90 DEG C of glass transition temperature.
In one embodiment, first outer membrane and the second outer membrane after longitudinal stretching extends with PVAThe phase difference of interlayer film is 1000-2500.
Adhesive
Adhesive for the application is not particularly limited, and can be commercially available or experiment synthesis.Such as selected from propyleneAny one in esters of gallic acid adhesive, epoxy resin tackifier, polyurethane tackifier and polyimide adhesiveOr it is a variety of.
Preferably, adhesive used in the present invention is esters of acrylic acid adhesive, and the esters of acrylic acid adhesive,Preparing raw material includes:
The acrylate copolymer of 100 parts by weight；
The ester plasticiser of 0.01~20 parts by weight；
The alkali metal salt of 0.001~7 parts by weight；
Amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound of 0.01~10 parts by weight and
The epoxy-capped polyetheramine of 0.01~10 parts by weight；
The weight average molecular weight Mw of the acrylate copolymer is 100000~2000000, and dispersion degree Mw/Mn is 4~20,It can directly buy and also test synthesis；
The ester plasticiser is selected from-two 2 ethyl hexanoic acid ester of diethylene glycol, two -2 ethyl hexanoic acid of tetraethylene glycol ester, poly- secondTwo -2 ethyl hexanoic acid of glycol ester, triethylene glycol diethyl butyrate, polyethylene glycol diethyl butyrate, polypropylene glycol diethylCapronate, triethylene glycol dibenzoate, polyethylene glycol dibenzoate, dibenzonate and polyethylene glycol -2-Any one or more in ethyl hexyl hydrochlorate benzoic ether；
Any one or more of the alkali metal salt in lithium perchlorate, trifluoromethanesulfonic acid lithium and sodium perchlorate.
In one embodiment, the acrylate copolymer is to cause comonomer by radical initiator by moltenWhat liquid polymerize；Initiator is one of azo-bis-isobutyl cyanide or dibenzoyl peroxide, the total weight that initiator is addedIt is the 0.03%~0.6% of total monomer weight；Copolymerization temperature is 50 DEG C~100 DEG C；Polymerization process uses N2Protection；Polymerisation in solutionThe middle solvent used is aromatic hydrocarbon, esters, the mixture of one or more of alcohols and ketone for organic solvent.
In one embodiment, the amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compoundIt is prepared by following methods:
1) by 0.16 mole 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s are first dissolved in 1000 containing 85wt% phosphorus pentoxideIn gram polyphosphoric acids, then benzenetricarboxylic acid between the 1 of 0.1 mole, 3,5- is added in reaction solution, after 200 DEG C are reacted 20 hours,It is down to room temperature, then precipitating is neutralized into water with ammonium hydroxide, filtering is dried in vacuo at 100 DEG C, obtains amino-terminated hyperbranchedPolybenzimidazoles；
2) after 10 grams of beta-cyclodextrins being completely dissolved in acetum, amino-terminated over-expense described in 10 grams of steps 1) is addedChange polybenzimidazoles, 3 grams of graphene oxides, 3 grams of amino silicane coupling agent KH-550,2 grams of glutaraldehydes and 2 grams of 1,3- dibromos thirdAlkane and ultrasonic disperse adjust pH value of solution between 8.0~9.0；1.5~2.5h is stirred at 55~65 DEG C, obtains sediment, is cleanedTo neutral and drying, amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound is obtained.
In one embodiment, the epoxy-capped polyetheramine is prepared by following methods:
100 grams of epoxy resin E51 and 0.23 mole of benzylamine are dissolved in 2000 grams of propylene glycol monomethyl ethers, nitrogen is protectedUnder shield, 100 DEG C after reaction 4 hours, it is down to room temperature and with after deionized water repeatedly washed product, 50 DEG C of dryings in vacuum drying oven5 hours, obtain the epoxy-capped polyetheramine.
PVA
PVA for the application is not particularly limited, and can be commercially available or experiment synthesis.
The method that another aspect of the present invention offer prepares light polarizing products, comprising:
Interlayer film containing PVA is provided；
By adhesive coated in the two sides of the interlayer film, the first gluing oxidant layer and the second gluing oxidant layer are formed；And
Make the first outer membrane containing amorphous copolyester and the second outer membrane respectively with the first gluing oxidant layer and secondThe contact of gluing oxidant layer.
Another aspect of the invention provides application of the light polarizing products in glasses, display equipment or communication equipment.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only usedIn the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the fieldThe some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, and number used in following material is weightPart.Wherein, 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s and 1, benzenetricarboxylic acid is purchased from Sigma-Aldrich, graphene oxide purchase between 3,5-From Suzhou Tan Feng graphene Science and Technology Ltd., model GR-005-2, other raw materials are purchased from Aladdin reagent Co., Ltd.
Raw material:
A1: VF-PX is uniaxially stretched by interlayer film using the VF-PX of Kuraray, blue with the absorption of polyazo systemThe dyestuff of color is dyed, and drying is allowed to, and film thickness is 0.2 millimeter
A2: VF-PX is uniaxially stretched by interlayer film using the VF-PX of Kuraray, blue with the absorption of polyazo systemThe dyestuff of color is dyed, and drying is allowed to, and film thickness is 0.4 millimeter
A3: VF-PX is uniaxially stretched by interlayer film using the VF-PX of Kuraray, blue with the absorption of polyazo systemThe dyestuff of color is dyed, and drying is allowed to, and film thickness is 0.3 millimeter
B1: gluing oxidant layer, using the happy pine Technomelt Q 8783 of Henkel Thailand, thickness is 150 microns
B2: gluing oxidant layer, using esters of acrylic acid adhesive, thickness is 150 microns, the esters of acrylic acid adhesiveThe preparation method comprises the following steps:
By the butyl polyacrylate of 100 parts by weight, two -2 ethyl hexanoic acid of tetraethylene glycol ester of 5 parts by weight, 4 parts by weight heightLithium chlorate, amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound of 5 parts by weight and 5 parts by weightEpoxy-capped polyetheramine is uniformly mixed up to the esters of acrylic acid adhesive；
Wherein, the butyl polyacrylate the preparation method comprises the following steps:
In 500mL round-bottomed flask, butyl acrylate 20g, dibenzoyl peroxide 0.3g and dimethyl are sequentially addedSulfoxide 100g, N2It protects and heats up 80 DEG C, poured into deionized water after reacting 5h, after washing repeatedly, be dried in vacuo to obtain polypropyleneAcid butyl ester；
Amino silane modified beta-cyclodextrin-graphene oxide-the polybenzimidazole compound the preparation method comprises the following steps:
1) by 0.16 mole 3,3 ', 4,4 '-tetramino diphenyl sulphone (DPS)s are first dissolved in 1000 containing 85wt% phosphorus pentoxideIn gram polyphosphoric acids, then benzenetricarboxylic acid between the 1 of 0.1 mole, 3,5- is added in reaction solution, after 200 DEG C are reacted 20 hours,It is down to room temperature, then precipitating is neutralized into water with ammonium hydroxide, filtering is dried in vacuo at 100 DEG C, obtains amino-terminated hyperbranchedPolybenzimidazoles；
2) after 10 grams of beta-cyclodextrins being completely dissolved in acetum, amino-terminated over-expense described in 10 grams of steps 1) is addedChange polybenzimidazoles, 3 grams of graphene oxides, 3 grams of amino silicane coupling agent KH-550,2 grams of glutaraldehydes and 2 grams of 1,3- dibromos thirdAlkane and ultrasonic disperse adjust pH value of solution between 8.0~9.0；1.5~2.5h is stirred at 55~65 DEG C, obtains sediment, is cleanedTo neutral and drying, amino silane modified beta-cyclodextrin-graphene oxide-polybenzimidazole compound is obtained；
The epoxy-capped polyetheramine is prepared by following methods:
100 grams of epoxy resin E51 and 0.23 mole of benzylamine are dissolved in 2000 grams of propylene glycol monomethyl ethers, nitrogen is protectedUnder shield, 100 DEG C after reaction 4 hours, it is down to room temperature and with after deionized water repeatedly washed product, 50 DEG C of dryings in vacuum drying oven5 hours, obtain the epoxy-capped polyetheramine.
C1: the first outer membrane and the second outer membrane, using NPG-TMCD copolyesters, film thickness is 0.09 millimeter, describedNPG-TMCD copolyesters the preparation method comprises the following steps:
In 500mL round-bottomed flask, dimethyl terephthalate (DMT) (0.40mol)=77.7g, neopentyl glycol is added(0.30mol)=31.3g, 2,2,4,4- tetramethyl -1,3- cyclobutanediol (TMCD) (0.30mol)=43.3g, three -2- ethylsCaproic acid butyl tin 0.02g, lithium hydroxide monohydrate 0.05g, isopropyl aluminum oxide 0.03g, Triphenyl phosphate 0.03g, thenIt heats up 290 DEG C to react 4 hours and obtain.
C2: the first outer membrane and the second outer membrane, using NPG-TMCD copolyesters, film thickness is 1.9 millimeters, the NPG-The same C1 of the preparation method of TMCD copolyesters.
C3: the first outer membrane and the second outer membrane, using NPG-TMCD copolyesters, film thickness is 1 millimeter, the NPG-The same C1 of the preparation method of TMCD copolyesters.
C4: the first outer membrane and the second outer membrane, using NPG-TMCD copolyesters, after longitudinal stretching, with A3Phase difference be 2000, film thickness be 1 millimeter, the same C1 of preparation method of the NPG-TMCD copolyesters.
C5: the first outer membrane and the second outer membrane, using the Tritan TX-1001 of Yi Shiman, film thickness is 1 millimeter.
C6: the first outer membrane and the second outer membrane, using polycarbonate, film thickness is 1 millimeter.
C7: the first outer membrane and the second outer membrane, using Triafol T, film thickness is 1 millimeter.