CN102193130A - Polaroid and preparation method thereof - Google Patents
Polaroid and preparation method thereof Download PDFInfo
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- CN102193130A CN102193130A CN2010101395630A CN201010139563A CN102193130A CN 102193130 A CN102193130 A CN 102193130A CN 2010101395630 A CN2010101395630 A CN 2010101395630A CN 201010139563 A CN201010139563 A CN 201010139563A CN 102193130 A CN102193130 A CN 102193130A
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- 0 CCC(C)(C)CC1C2C3C(C4)C5C6C(C)NC*(*)CCC6C5C4C3C2*C1 Chemical compound CCC(C)(C)CC1C2C3C(C4)C5C6C(C)NC*(*)CCC6C5C4C3C2*C1 0.000 description 1
Abstract
The invention provides a polaroid. The polaroid is transparent and low in dual refraction, and dual-refraction change is hard to generate in the polaroid even under a stress. The polaroid has a structure for protecting at least one surface of a polarizer by using a resin-containing protection film, and is characterized in that: the resin is a cured substance of an active energy ray cured resin composition; and the active energy ray cured resin composition contains a compound having unsaturated carboxylic acid acyl and an alicyclic framework, and a cellulose derivative. The compound having the unsaturated carboxylic acid acyl and the alicyclic framework is shown by the formula in specifications, wherein R1 and R2 are the same or different and represent alkyl in which the number of hydrogen atoms or carbon atoms is 1 to 4; X1 and X2 are the same or different and represent alkylene in which the number of single bonds or carbon atoms is 1 to 8, or divalent perssad bonded by 1, 2 or more pieces of alkylene in which the number of carbon atoms is 1 to 8 and 1, 2 or more oxygen atoms or sulfur atoms; and m and n independently represent 0 and 1.
Description
Technical field
The present invention relates to the polaroid and its preparation method that in liquid crystal indicator etc., use.
Background technology
Polaroid also is used as the detecting element of polarized light as the feed element of polarized light in the liquid crystal indicator.At present,, use on the single face at least of the polarizer that contains polyvinyl alcohol (PVA) (PVA) film that has mixed iodine etc. and stretched as polaroid, the bonding diaphragm that contains tri acetyl cellulose (TAC) form etc.At this moment, if there is birefringence in protective film self, then the function as polaroid declines to a great extent, and therefore in order to prevent this situation, uses the optically anisotropic TAC film that do not have with the making of solvent cast method.
For this existing polaroid, because the super drawing of PVA film, thereby along the lax big stress of direction generation.For protective film; need it to have the rigidity of this stress of tolerance; but when using TAC as protective film; in the big picture purposes of LCD TV etc.; at the film periphery; the differential contraction stress of polarizer is better than the rigidity of TAC and produces distortion, produces the birefringence of TAC diaphragm with it together, thereby the situation of fading is arranged.
Open in the 2005-92112 communique Japanese publication spy, the solidfied material that has proposed the use actinic energy ray curable resion composition replaces the motion of TAC diaphragm.According to this technology, can obtain the polaroid that birefringence is little, humidity resistance is excellent.But, only be that birefringence is little, and change in the big local birefringence of the differential contraction stress of above-mentioned polarizer, diminish function as polaroid.
[patent documentation 1] publication spy opens the 2005-92112 communique
Summary of the invention
The object of the present invention is to provide that a kind of diaphragm is transparent, birefringence is little, even and stress application also be difficult to take place polaroid and its preparation method that birefringence changes.
The inventor to achieve these goals; carried out making great efforts research; found that; the polaroid that forms with the single face at least of the diaphragm of the solidfied material that contains actinic energy ray curable resion composition protection polarizer; diaphragm is transparent, birefringence is little; even and stress application also is difficult to take place birefringent variation, wherein said actinic energy ray curable resion composition contains specific resin, thereby has finished the present invention.
Promptly; the invention provides the polaroid of structure with single face at least of using the diaphragm protection polarizer that contains resin; it is characterized in that; above-mentioned resin is the solidfied material of actinic energy ray curable resion composition, and described actinic energy ray curable resion composition contains compound and the cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton.Above-mentioned compound with unsaturated carboxylic acid acyl group and ester ring type skeleton is preferably the compound with unsaturated carboxylic acid acyl group and bridging ester ring type skeleton, especially preferably uses the compound of following formula (1) expression,
In the formula, R1, R2 are identical or different, expression hydrogen atom or carbon number are 1～4 alkyl, X1, X2 are identical or different, and expression singly-bound, carbon number are that 1～8 alkylidene or the carbon number more than 1 or 2 or 2 are the divalent group that 1～8 alkylidene and the oxygen atom more than 1 or 2 or 2 or sulfur atom linkage form.M, n represent 0 or 1 separately.
Preferred above-mentioned cellulose derivative is to be selected from methylcellulose and ethyl cellulose at least a kind.
The present invention also provides the preparation method of polaroid; it is characterized in that; behind coating actinic energy ray curable resion composition on the single face at least of polarizer; this actinic energy ray curable resion composition is solidified form diaphragm, wherein said actinic energy ray curable resion composition contains compound and the cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton.
According to polaroid of the present invention; use contains the solidfied material of actinic energy ray curable resion composition of specific resin as the diaphragm of polarizer; therefore not only diaphragm is transparent, birefringence is little, even and stress application also be difficult to take place birefringent variation.Preparation in accordance with the present invention can prepare the polaroid with this excellent specific property simply.
Embodiment
Polaroid of the present invention has the structure of the single face at least of polarizer with the diaphragm protection that contains resin.Polarizer limits especially, can use and mix iodine, dichroic dye and the film that stretches or they are carried out film that crosslinking Treatment forms etc. in polyvinyl alcohol (PVA) (PVA), its acetalation thing, vinyl-vinyl acetate copolymer, its saponified etc. base material.Wherein, particularly preferably in mixing iodine and the polyvinyl alcohol film that contains iodine that stretches in the polyvinyl alcohol (PVA) or it being formed with boric acid etc. is crosslinked.
In the present invention, as the resin that constitutes diaphragm, use the solidfied material of actinic energy ray curable resion composition, described composition contains compound and the cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton.Compound and cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton can use separately separately or will be used in combination more than 2 kinds or 2 kinds.And in this manual, actinic energy ray curable resion composition is meant the composition that can form the resin of curing by the irradiation of active energy beam.
As compound with unsaturated carboxylic acid acyl group and ester ring type skeleton, get final product so long as in molecule, have the compound of the radically curing of ester ring type skeleton and 1 or 1 above unsaturated carboxylic acid acyl group, do not limit especially.It is unsaturated carboxylic acid acyl group of about 3～10 etc. that the unsaturated carboxylic acid acyl group can be enumerated carbon numbers such as acryloyl group, methacryl, α-ethyl propylene acyl group, α-propyl group acryloyl group, α-butyl acryloyl group, crotonic acid acyl group.
The ester ring type skeleton can be enumerated for example naphthenic hydrocarbon ring of cyclopentane ring, cyclohexane ring, cyclooctane ring, cyclodecane ring, cyclododecane ring etc.; Three ring [5.2.1.02,6] decane ring, three ring [4.4.0.12,5] hendecane ring, five rings [6.5.1.13,6.02,7.09,13] pentadecane ring, five rings [6.6.1.13,6.02,7.09,14] and hexadecane ring, norbornane ring, camphane ring, isoborneol alkane ring, Fourth Ring [4.4.0.12,5.17,10] and the bridging ester ring type skeleton of 12 carbon alkane rings, diamantane ring, decahydro naphthalene nucleus, perhydro indenes ring etc.Wherein, preferred bridging ester ring type skeleton, preferred especially three ring [5.2.1.02,6] decane rings, three ring [4.4.0.12,5] hendecane rings, five rings [6.5.1.13,6.02,7.09,13] pentadecane ring, five rings [6.6.1.13,6.02,7.09,14] hexadecane ring.Especially preferred three ring [5.2.1.02,6] decane rings.
In compound, as long as the number of unsaturated carboxylic acid acyl group has 1 at least, be preferably more than 2 or 2 and (for example be 2～4), and then be preferably 2～3 with unsaturated carboxylic acid acyl group and ester ring type skeleton.
Unsaturated carboxylic acid acyl group and bridging ester ring type skeleton can Direct Bonding, also can be by linking group bonding.Link group and can enumerate the group of representing with following formula (2),
-X-O- (2)
In the formula, X represents that singly-bound, carbon number are that 1～8 alkylidene or the carbon number more than 1 or 2 or 2 are the divalent group that 1～8 alkylidene and the oxygen atom more than 1 or 2 or 2 or sulfur atom linkage form.The left side of X and ester ring type skeleton bonding, the right side of O and unsaturated carboxylic acid acyl group bonding.
Carbon number is that 1～8 alkylidene can be enumerated for example methylene, ethylidene, methyl methylene, dimethylated methylene base, 1,2-propylidene, 1,3-propylidene, 1,4-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1, the inferior heptyl, 1 of 7-, the inferior octyl group of 8-etc.
As the carbon number more than 1 or 2 or 2 is the divalent group that 1～8 alkylidene and the oxygen atom more than 1 or 2 or 2 or sulfur atom linkage form, and can enumerate carbon number for example and be 1～8 oxyalkylene, carbon number and be 2～8 alkylidene oxyalkylene, carbon number and be 1～8 sulphur alkylidene, carbon number and be 2～8 alkylidene sulphur alkylidene, carbon number and be 2～8 polyoxy thiazolinyl, carbon number is alkylidene polyoxy thiazolinyl of 3～8 etc.
Preferred especially singly-bound of X or carbon number are 1～8 alkylidene, especially preferred methylene.
Representative example with compound of unsaturated carboxylic acid acyl group and ester ring type skeleton can be enumerated the compound of representing with following formula (1).In the formula (1), R1, R2 are identical or different, expression hydrogen atom or carbon number are 1～4 alkyl, X1, X2 are identical or different, and expression singly-bound, carbon number are that 1～8 alkylidene or the carbon number more than 1 or 2 or 2 are the divalent group that 1～8 alkylidene and the oxygen atom more than 1 or 2 or 2 or sulfur atom linkage form.M, n represent 0 or 1 separately.
Carbon number among R1, the R2 is that 1～4 alkyl can be enumerated for example methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group etc.Preferred especially hydrogen atom of R1, R2 or methyl.
As carbon number among X1, the X2 be 1～8 alkylidene, carbon number more than 1 or 2 or 2 is the divalent group that 1～8 alkylidene and the oxygen atom more than 1 or 2 or 2 or sulfur atom linkage form, and is same with above-mentioned X.It is 1～8 alkylidene that X1, X2 are preferably singly-bound or carbon number separately especially, especially is preferably methylene.
M, n are preferably 0 separately especially.
Object lesson with the compound of formula (1) expression can be enumerated for example three ring [5.2.1.02,6] decane dimethanol two (methyl) acrylate, three ring [5.2.1.02,6] decanediol two (methyl) acrylate, three ring [4.4.0.12,5] hendecane dimethanol two (methyl) acrylate, three ring [4.4.0.12,5] hendecane glycol two (methyl) acrylate, five rings [6.5.1.13,6.02,7.09,13] pentadecane dimethanol two (methyl) acrylate, five rings [6.5.1.13,6.02,7.09,13] and pentadecane glycol two (methyl) acrylate, five rings [6.6.1.13,6.02,7.09,14] and hexadecane dimethanol two (methyl) acrylate, five rings [6.6.1.13,6.02,7.09,14] hexadecane glycol two (methyl) acrylate etc.
Other examples with compound of unsaturated carboxylic acid acyl group and ester ring type skeleton for example can be enumerated (methyl) cyclohexyl acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen ethyl ester, (methyl) acrylic acid norborneol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester, three ring [5.2.1.02,6] decane list methyl alcohol (methyl) acrylate, three ring [5.2.1.02,6] single (methyl) acrylate (=(methyl) acrylic acid two cyclopentyl esters) of decane one alcohol, three ring [4.4.0.12,5] hendecane list methyl alcohol list (methyl) acrylate, three ring [4.4.0.12,5] single (methyl) acrylate of hendecane one alcohol, five rings [6.5.1.13,6.02,7.09,13] pentadecane list methyl alcohol list (methyl) acrylate, five rings [6.5.1.13,6.02,7.09,13] single (methyl) acrylate of pentadecane one alcohol, five rings [6.6.1.13,6.02,7.09,14] hexadecane list methyl alcohol list (methyl) acrylate, five rings [6.6.1.13,6.02,7.09,14] and single (methyl) acrylate etc. of hexadecane one alcohol has 1 unsaturated carboxylic acid acylated compound; 1; 4-cyclohexyl two (methyl) acrylate, 1; ethylene oxide modification two (methyl) acrylate, diamantane glycol two (methyl) acrylate etc. of 4-cyclohexanedimethanol two (methyl) acrylate, 1,4 cyclohexane dimethanol have 2 or 2 above unsaturated carboxylic acid acylated compound.
Cellulose derivative can be enumerated for example cellulose ether of methylcellulose, ethyl cellulose, carboxymethyl cellulose, cyanethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethylcellulose etc.; The cellulose organic ester of cellulose-acetate propionate, cellulose acetate-butyrate, acetate benzoic acid cellulose etc.; The cellulose inorganic acid ester of cellulose nitrate, sulfate cellulose etc.; The cellulose carbamate of cellulose carbanilate etc.; Cellulose acetal etc.
Wherein, preferred cellulose ether, special preferable methyl cellulose, ethyl cellulose.
Degree of substitution in the cellulose derivative is according to substituent kind and different, can be from considering suitably to select with the aspect of the compatibility of the solidfied material of above-mentioned compound with unsaturated carboxylic acid acyl group and ester ring type skeleton, operability etc.For example the degree of etherification falling in the methylcellulose is preferably 25%～33% scope, and the degree of etherification falling in the ethyl cellulose is preferably 46%～51% scope.
In general; the compatibility of acrylic acid series polymeric compounds and cellulose derivative is low, produces gonorrhoea during mixing, but contains the monomer of ester ring type skeleton among the present invention owing to use; thereby the compatibility of polymkeric substance after solidifying and cellulose derivative is higher, can form the excellent diaphragm of the transparency.In addition, gained diaphragm not only birefringence is little, and photoelastic coefficient is low, even therefore having stress application also is difficult to take place the such characteristic of birefringent variation.
For the present invention; in actinic energy ray curable resion composition; can only contain above-mentioned compound as the active energy ray-curable compound, but and then also can contain other active energy ray-curable compound with unsaturated carboxylic acid acyl group and ester ring type skeleton.This other active energy ray-curable compound can be enumerated radically curing compound, cation-curable compound.
The radically curing compound can be set forth in to have at least 1 olefinic double bond and can carry out polymeric compounds by the irradiation of active energy beam (for example ultraviolet ray, visible light, electron beam, X ray etc.) in the presence of polymerization initiator in the molecule.Such compound for example can be enumerated (methyl) acrylic acid; (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) benzyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid ethoxy ethyl ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid phenoxy ethyl, (methyl) acryloyl morpholine, (methyl) acrylic ester monomer of γ-simple functions such as (methyl) acryloxy propyl trimethoxy silicane; The ethene base system monomer of styrene, α-Jia Jibenyixi, vinyltoluene, vinyl acetate, allyl acetate, propionate, vinyl benzoate, N-vinyl pyrrolidone, N-vinyl imidazole, N-caprolactam etc.; 1, (methyl) acrylate of 2 functionalities of 4-butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, bisphenol-A-diglycidyl ether two (methyl) acrylate, ethylene oxide modified bisphenol A-two (methyl) acrylate etc.; Three (methyl) acrylate of trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite five (methyl) acrylate, pentaerythrite six (methyl) acrylate, ethylene oxide addition trimethylolpropane, dipentaerythritol five (methyl) acrylate, triallyl cyanurate, triallyl isocyanurate, 1; 3,5-triacryl six hydrogen-3 officials such as s-triazine can or 3 officials can be above multi-functional monomer.Wherein, preferred 2 officials can or 2 officials can be above multi-functional monomer.These radically curing compounds can use separately, perhaps will be used in combination more than 2 kinds or 2 kinds.
In addition, the radically curing compound can also use (methyl) acrylate oligomer of ester (methyl) acrylate, polyurethane (methyl) acrylate, epoxy (methyl) acrylate, propylene (methyl) acrylate etc.
The cation-curable compound can be enumerated for example vinyl ether based compound, epoxy based compound, oxetanes based compound etc.
The vinyl ether based compound can be enumerated for example ethylene oxide modified bisphenol A-divinyl ether, ethylene oxide modification quinhydrones divinyl ether etc.
The epoxy based compound for example can enumerate 1,2-epoxy-cyclohexane, limonene diepoxide, 3,4-epoxy radicals cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylate, 1,4-butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, two (3,4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, bisphenol-A-diglycidyl ether, Bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, hydrogenated bisphenol A-diglycidyl ether etc.
The oxetanes based compound can be enumerated 3-ethyl-3-hydroxymethyl oxetanes, 3-ethyl-3-(phenoxymethyl) oxetanes, two [(3-ethyl-3-oxetanyl) methyl] ether etc.
In the present invention, in actinic energy ray curable resion composition, except the active energy ray-curable compound, can also contain the Thermocurable compound.
With respect to the whole curable compounds in the actinic energy ray curable resion composition; the above-mentioned shared ratio of compound with unsaturated carboxylic acid acyl group and ester ring type skeleton for example is more than the 30 weight %; be preferably more than the 50 weight %; and then more than the preferred 70 weight %, more than the preferred especially 90 weight %.
In addition, in actinic energy ray curable resion composition, except above-mentioned curable compound, can also cooperate Photoepolymerizationinitiater initiater and light sensitizer as required, light cationic polymerization initiators, hot cationic polymerization initiators, hot radical polymerization initiator, light promoter, light stabilizer, ultraviolet light absorber, levelling agent, defoamer etc.
Photoepolymerizationinitiater initiater can be according to suitably selecting as the kind of the active energy beam that solidifies means.The example of Photoepolymerizationinitiater initiater can be enumerated acetophenone, 3-methyl acetophenone, benzophenone, 4-chloro benzophenone, 4,4-diaminobenzophenone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2,2-dimethoxy-2-phenylacetone, yellow Fluorenone, benzaldehyde, anthraquinone, benzoin ethyl ether, benzoin propyl ether, benzyldimethylketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 4-hydroxyl anthrone, camphorquinone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone etc.
The above-mentioned content of compound in actinic energy ray curable resion composition with unsaturated carboxylic acid acyl group and ester ring type skeleton; divide overall (comprising the composition that becomes solid by curing) with respect to the solid shape in the actinic energy ray curable resion composition; for example be 1～98 weight %; be preferably 5～93 weight %; and then preferred 10～85 weight %, preferred especially 20～75 weight %.
The content of above-mentioned cellulose derivative in actinic energy ray curable resion composition, divide overall (comprising the composition that becomes solid by curing) with respect to the solid shape in the actinic energy ray curable resion composition, for example be 1～98 weight %, be preferably 5～93 weight %, and then preferred 10～85 weight %, preferred especially 20～75 weight %.
Above-mentioned in actinic energy ray curable resion composition has the compound of unsaturated carboxylic acid acyl group and ester ring type skeleton and the ratio of cellulose derivative; for example for the former/latter's (weight ratio)=1/99～99/1; be preferably 5/95～95/5; and then preferred 10/90～90/10, preferred especially 20/80～80/20.
The content of Photoepolymerizationinitiater initiater in actinic energy ray curable resion composition, divide overall (comprising the composition that becomes solid by curing) with respect to the solid shape in the actinic energy ray curable resion composition, for example be 0.1～10 weight %, be preferably about 1～8 weight %.
Polaroid of the present invention makes this actinic energy ray curable resion composition be solidified to form diaphragm and is prepared by behind the above-mentioned actinic energy ray curable resion composition of coating on the single face at least of polarizer.
The coating process of actinic energy ray curable resion composition does not limit especially, can utilize scraper, line rod coating machine, mould to be coated with various coating methods such as machine, intaglio plate coating machine.When coating, also can use solvent to regulate the viscosity of hardening resin composition.
Solidify by the irradiation active energy beam by filming of forming of actinic energy ray curable resion composition, form diaphragm.Active energy beam can be enumerated ultraviolet ray, luminous ray, electron beam, X ray etc.Wherein preferred use ultraviolet ray.Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, xenon lamp, black lamp, metal halide lamp etc. can be enumerated in ultraviolet generation source.
Consider that from the angle of slim light weight, protectiveness, operability etc. the thickness of diaphragm for example is 10～200 μ m, is preferably 30～100 μ m.
Polaroid of the present invention uses the diaphragm of the solidfied material of actinic energy ray curable resion composition as polarizer; therefore have not only transparent, birefringence is little; even stress application also is difficult to take place the such remarkable advantage of birefringent variation, wherein said actinic energy ray curable resion composition contains compound and the cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton.
Embodiment
Below, based on embodiment the present invention is described in more detail, but the present invention is not limited to these embodiment.And the mensuration of the photoelastic coefficient of cured film (cured film) and the mensuration of phase differential, glass transition temperature is carried out according to following method.
[mensuration of photoelastic coefficient and phase differential]
Making thickness is the cured film of 200 μ m, uses 3 dimension birefringence meters (" KOBRA-WR ") of prince's instrumentation machine Co., Ltd. system to measure.
[mensuration of glass transition temperature]
Go up coating actinic energy ray curable resion composition (thickness is 40 μ m) at cold-rolled steel sheet (thickness 0.3mm * width 20mm * length 50mm), shining the accumulative total light quantity with small-sized UV irradiating machine (Eye graphics (ア イ グ ラ Off イ Star Network) Co., Ltd.'s system, " ECS-401GX ", rated voltage 200V, high-pressure mercury-vapor lamp) from the place of distance 11cm is the ultraviolet ray of 350m J/cm2, obtains the cured film of actinic energy ray curable resion composition.Use the rigidity vibrator type determination of viscoelasticity device (A﹠amp of Co., Ltd.; D (Ai Ande) system, " RPT-3000W ") it is warming up to 200 ℃, mensuration glass transition temperature (Tg) from 25 ℃.
Embodiment 1
With the hydroxyl value of 10 weight % is ethyl acetate solution 500 weight portions of the ethyl cellulose of 32.9mgKOH/g, the three ring [5.2.1.02 that use following formula (1a) to represent, 6] decane dimethanol diacrylate (the special Co., Ltd. of Daicel cyanogen system, trade name " IRR-214K ") 50 weight portions, 1-hydroxyl-cyclohexyl-phenyl ketone 5 weight portions mix, and obtain actinic energy ray curable resion composition 1.On glass plate, use the thickness coating actinic energy ray curable resion composition 1 of applicator with 1000 μ m, 80 ℃ of dryings after 1 hour, is the ultraviolet ray 3 times of 500m J/cm2 with small-sized UV irradiating machine (Eye graphics (ア イ グ ラ Off イ Star Network) Co., Ltd.'s system, " ECS-401GX ", rated voltage 200V, high-pressure mercury-vapor lamp) from the place of distance 11cm irradiation accumulative total light quantity, obtains the independent cured film (thickness is 188 μ m) of actinic energy ray curable resion composition 1.By the outward appearance of visual observations gained cured film, and measure photoelastic coefficient and phase differential.
Comparative Examples 1
With the hydroxyl value of 10 weight % is that ethyl acetate solution 500 weight portions, pentaerythritol triacrylate 50 weight portions, 1-hydroxyl-cyclohexyl-phenyl ketone 5 weight portions of the ethyl cellulose of 32.9mgKOH/g mix, and obtains actinic energy ray curable resion composition 2.On glass plate, use the thickness coating actinic energy ray curable resion composition 2 of applicator with 1000 μ m, 80 ℃ of dryings after 1 hour, irradiation ultraviolet radiation similarly to Example 1 obtains the independent cured film (thickness is 189 μ m) of actinic energy ray curable resion composition 2.By the outward appearance of visual observations gained cured film, and measure photoelastic coefficient and phase differential.
Comparative Examples 2
With the hydroxyl value of 10 weight % is that ethyl acetate solution 500 weight portions, dipentaerythritol acrylate 50 weight portions, 1-hydroxyl-cyclohexyl-phenyl ketone 5 weight portions of the ethyl cellulose of 32.9mgKOH/g mix, and obtains actinic energy ray curable resion composition 3.On glass plate, use the thickness coating actinic energy ray curable resion composition 3 of applicator with 1000 μ m, 80 ℃ of dryings after 1 hour, irradiation ultraviolet radiation similarly to Example 1 obtains the independent cured film (thickness is 191 μ m) of actinic energy ray curable resion composition 3.By the outward appearance of visual observations gained cured film, and measure photoelastic coefficient and phase differential.
Comparative Examples 3
With the hydroxyl value of 10 weight % is that ethyl acetate solution 500 weight portions, pentaerythrite ethoxy tetraacrylate 50 weight portions, 1-hydroxyl-cyclohexyl-phenyl ketone 5 weight portions of the ethyl cellulose of 32.9mgKOH/g mix, and obtains actinic energy ray curable resion composition 4.On glass plate, use the thickness coating actinic energy ray curable resion composition 4 of applicator with 1000 μ m, 80 ℃ of dryings after 1 hour, irradiation ultraviolet radiation similarly to Example 1 obtains the independent cured film (thickness is 185 μ m) of actinic energy ray curable resion composition 4.By the outward appearance of visual observations gained cured film, and measure photoelastic coefficient and phase differential.
Comparative Examples 4
With the hydroxyl value of 10 weight % is that ethyl acetate solution 500 weight portions, two (trimethylolpropane) tetraacrylate, 50 weight portions, 1-hydroxyl-cyclohexyl-phenyl ketone 5 weight portions of the ethyl cellulose of 32.9mgKOH/g mix, and obtains actinic energy ray curable resion composition 5.Use the thickness coating actinic energy ray curable resion composition 5 of applicator with 1000 μ m on glass plate, irradiation ultraviolet radiation similarly to Example 1 obtains the independent cured film (thickness is 189 μ m) of actinic energy ray curable resion composition 5.By the outward appearance of visual observations gained cured film, and measure photoelastic coefficient and phase differential.
Embodiment 2
With the hydroxyl value of 10 weight % is that ethyl acetate solution 700 weight portions of the ethyl cellulose of 32.9mgKOH/g, acrylic acid two cyclopentyl esters (Hitachi Chemical Co., Ltd.'s system, trade name " FA-513A ") 30 weight portions, 1-hydroxyl-cyclohexyl-phenyl ketone 5 weight portions of representing with following formula (2) mix, and obtains actinic energy ray curable resion composition 6.Use the thickness coating actinic energy ray curable resion composition 6 of applicator with 500 μ m on glass plate, irradiation ultraviolet radiation similarly to Example 1 obtains the independent cured film (thickness is 76 μ m) of actinic energy ray curable resion composition 6.By the outward appearance of visual observations gained cured film, and measure photoelastic coefficient and phase differential.
The measurement result of the outward appearance of the cured film that obtains in embodiment and the Comparative Examples, glass transition temperature, photoelastic coefficient and phase differential is shown in table 1.In the table, "-" expression can not be measured.According to table 1 as can be known, the cured film that obtains among the embodiment is transparent, and phase differential and photoelastic coefficient all show as little value, and not only birefringence is little, even and stress application also be difficult to take place birefringent variation.
Claims (5)
1. polaroid; has structure with the single face at least of the diaphragm protection polarizer that contains resin; it is characterized in that; above-mentioned resin is the solidfied material of actinic energy ray curable resion composition; wherein, described actinic energy ray curable resion composition contains compound and the cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton.
2. polaroid according to claim 1, wherein, the compound with unsaturated carboxylic acid acyl group and ester ring type skeleton is the compound with unsaturated carboxylic acid acyl group and bridging ester ring type skeleton.
3. polaroid according to claim 1, wherein, the compound with unsaturated carboxylic acid acyl group and ester ring type skeleton is the compound with following formula (1) expression,
In the formula, R1, R2 are identical or different, expression hydrogen atom or carbon number are 1～4 alkyl, X1, X2 are identical or different, and expression singly-bound, carbon number are that 1～8 alkylidene or the carbon number more than 1 or 2 or 2 are the divalent group that 1～8 alkylidene and the oxygen atom more than 1 or 2 or 2 or sulfur atom linkage form; M, n represent 0 or 1 separately.
4. according to each described polaroid in the claim 1～3, wherein, cellulose derivative is to be selected from methylcellulose and ethyl cellulose at least a kind.
5. the preparation method of a polaroid; it is characterized in that; behind coating actinic energy ray curable resion composition on the single face at least of polarizer; this actinic energy ray curable resion composition is solidified form diaphragm; wherein, described actinic energy ray curable resion composition contains compound and the cellulose derivative with unsaturated carboxylic acid acyl group and ester ring type skeleton.
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| CN111417878A (en) * | 2017-11-24 | 2020-07-14 | 株式会社Lg化学 | Polarizing plate, image display device including the same, and photocurable composition for protective layer of polarizing plate |
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