CN102193130B - Polaroid and preparation method thereof - Google Patents
Polaroid and preparation method thereof Download PDFInfo
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- CN102193130B CN102193130B CN201010139563.0A CN201010139563A CN102193130B CN 102193130 B CN102193130 B CN 102193130B CN 201010139563 A CN201010139563 A CN 201010139563A CN 102193130 B CN102193130 B CN 102193130B
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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 use in liquid crystal indicator etc.
Background technology
Polaroid is used as the feed element of polarized light in liquid crystal indicator, is also used as the detecting element of polarized light.At present, as polaroid, be used in containing being mixed with iodine etc. and carrying out at least one side of the polarizer of polyvinyl alcohol (PVA) (PVA) film stretched, bonded the diaphragm containing tri acetyl cellulose (TAC) etc.Now, if protective film self exists birefringence, then the function as polaroid declines to a great extent, therefore in order to prevent this situation, use with solvent cast method make there is no optically anisotropic TAC film.
For this existing polaroid, due to the super drawing of PVA film, thus produce large stress along lax direction.For protective film; it is needed to have the rigidity of this stress of tolerance; but when using TAC as protective film; in the large picture purposes of LCD TV etc.; at film periphery; the differential contraction stress of polarizer is better than the rigidity of TAC and produces distortion, produces with it the birefringence of TAC diaphragm together, thus has the situation of fading.
In Japanese Laid-Open Patent JP 2005-92112 publication, propose and use the solidfied material of actinic energy ray curable resion composition to replace the motion of TAC diaphragm.According to this technology, the polaroid that birefringence is little, humidity resistance is excellent can be obtained.But, be only that birefringence is little, and change in the local birefringence that the differential contraction stress of above-mentioned polarizer is large, damage the function as polaroid.
[patent documentation 1] publication JP 2005-92112 publication
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 if apply polaroid and its preparation method that stress is also difficult to occur birefringence change.
The present inventor to achieve these goals; carry out making great efforts research; found that; with the polaroid of at least one side of the diaphragm protection polarizer of the solidfied material containing actinic energy ray curable resion composition; diaphragm is transparent, birefringence is little; even and if applying stress is also difficult to birefringent change occurs, wherein said actinic energy ray curable resion composition contains specific resin, thus completes the present invention.
Namely; the invention provides the polaroid of the structure of at least one side had with the diaphragm protection polarizer containing 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 the compound and cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton.The above-mentioned compound with unsaturated carboxylic acid acyl group and alicyclic skeleton preferably has the compound of unsaturated carboxylic acid acyl group and bridging alicyclic skeleton, particularly preferably with the compound that following formula (1) represents,
In formula, R1, R2 are identical or different, represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, X1, X2 are identical or different, represent singly-bound, carbon number to be the alkylidene of 1 ~ 8 or the carbon number of more than 1 or 2 or 2 be the divalent group of the alkylidene of 1 ~ 8 and the oxygen atom of more than 1 or 2 or 2 or sulfur atom linkage.M, n represent 0 or 1 separately.
Preferred above-mentioned cellulose derivative is at least a kind that is selected from methylcellulose and ethyl cellulose.
Present invention also offers the preparation method of polaroid; it is characterized in that; on at least one side of polarizer after coat activated energy ray-curable resin combination; this actinic energy ray curable resion composition is solidified and forms diaphragm, wherein said actinic energy ray curable resion composition contains the compound and cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton.
According to polaroid of the present invention; use the diaphragm of solidfied material as polarizer of the actinic energy ray curable resion composition containing specific resin; therefore not only diaphragm is transparent, birefringence is little, even and if apply stress be also difficult to birefringent change occurs.Preparation in accordance with the present invention, can prepare the polaroid with this excellent specific property simply.
Embodiment
The structure that at least one side that polaroid of the present invention has polarizer is protected with the diaphragm containing resin.Polarizer is not particularly limited, and can be used in polyvinyl alcohol (PVA) (PVA), its acetal compound, vinyl-vinyl acetate copolymer, its saponified etc. base material and mix iodine, dichroic dye carry out the film stretched or the film etc. they being carried out crosslinking Treatment.Wherein, particularly preferably in mixing iodine in polyvinyl alcohol (PVA) and the polyvinyl alcohol film containing iodine carrying out stretching or it is crosslinked with boric acid etc.
In the present invention, as the resin forming diaphragm, use the solidfied material of actinic energy ray curable resion composition, described composition contains the compound and cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton.Compound and the cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton can be used alone or 2 kinds or two or more are combinationally used separately.Further, in this manual, actinic energy ray curable resion composition refers to that the irradiation by active energy beam can form the composition of the resin of solidification.
As the compound with unsaturated carboxylic acid acyl group and alicyclic skeleton, as long as have the compound of the radically curing of alicyclic skeleton and more than 1 or 1 unsaturated carboxylic acid acyl group in molecule, be not particularly limited.The unsaturated carboxylic acid acyl group etc. that unsaturated carboxylic acid acyl group can enumerate acryloyl group, methacryl, α-ethyl propylene acyl group, α-propyl group acryloyl group, α-carbon number such as butyl propyleneglycol acyl group, crotonic acid acyl group are about 3 ~ 10.
Alicyclic skeleton can enumerate the naphthenic hydrocarbon ring of such as 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] hexadecane ring, norbornane ring, camphane ring, isoborneol alkane ring, Fourth Ring [4.4.0.12,5.17,10] the bridging alicyclic skeleton of 12 carbon alkane rings, diamantane ring, decahydro naphthalene nucleus, perhydro indenes ring etc.Wherein, preferred bridging alicyclic skeleton, particularly preferably three rings [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] hexadecane ring.Especially preferably three rings [5.2.1.02,6] decane ring.
In the compound with unsaturated carboxylic acid acyl group and alicyclic skeleton, as long as the number of unsaturated carboxylic acid acyl group has 1 at least, be preferably more than 2 or 2 (being such as 2 ~ 4), and then be preferably 2 ~ 3.
Unsaturated carboxylic acid acyl group and bridging alicyclic skeleton can Direct Bonding, also can by linking group bonding.Link group and can enumerate the group represented with following formula (2),
-X-O- (2)
In formula, X represents singly-bound, carbon number to be the alkylidene of 1 ~ 8 or the carbon number of more than 1 or 2 or 2 is the divalent group of the alkylidene of 1 ~ 8 and the oxygen atom of more than 1 or 2 or 2 or sulfur atom linkage.The left side of X and alicyclic skeleton bonding, the right side of O and unsaturated carboxylic acid acyl group bonding.
Carbon number be 1 ~ 8 alkylidene can enumerate such as methylene, ethylidene, methylmethylene, dimethylated methylene base, 1,2-propylidene, 1,3-propylidene, 1,4-butylidene, 1,5-pentylidene, 1,6-hexylidene, 1, the sub-heptyl of 7-, 1,8-sub-octyl group etc.
As the divalent group that the carbon number of more than 1 or 2 or 2 is the alkylidene of 1 ~ 8 and the oxygen atom of more than 1 or 2 or 2 or sulfur atom linkage, can enumerate such as carbon number be 1 ~ 8 oxyalkylene, the carbon number alkylidene oxyalkylene that is 2 ~ 8, the carbon number sulphur alkylidene that is 1 ~ 8, the carbon number alkylidene sulphur alkylidene that is 2 ~ 8, the carbon number polyoxygenated thiazolinyl that is 2 ~ 8, carbon number be 3 ~ 8 the polyoxygenated thiazolinyl of alkylidene etc.
X particularly preferably singly-bound or carbon number is the alkylidene of 1 ~ 8, especially preferably methylene.
The representative example with the compound of unsaturated carboxylic acid acyl group and alicyclic skeleton can enumerate the compound represented with above formula (1).In formula (1), R1, R2 are identical or different, represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, X1, X2 are identical or different, represent singly-bound, carbon number to be the alkylidene of 1 ~ 8 or the carbon number of more than 1 or 2 or 2 be the divalent group of the alkylidene of 1 ~ 8 and the oxygen atom of more than 1 or 2 or 2 or sulfur atom linkage.M, n represent 0 or 1 separately.
Carbon number in R1, R2 be 1 ~ 4 alkyl can enumerate such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group etc.R1, R2 be hydrogen atom or methyl particularly preferably.
As carbon number in X1, X2 be the alkylidene of 1 ~ 8, the carbon number of more than 1 or 2 or 2 is the divalent group of the alkylidene of 1 ~ 8 and the oxygen atom of more than 1 or 2 or 2 or sulfur atom linkage, same with above-mentioned X.X1, X2 are particularly preferably singly-bound separately or carbon number is the alkylidene of 1 ~ 8, is especially preferably methylene.
M, n are particularly preferably 0 separately.
The object lesson of the compound represented by formula (1) can enumerate such as 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] pentadecane glycol two (methyl) acrylate, five rings [6.6.1.13, 6.02, 7.09, 14] 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 the compound of unsaturated carboxylic acid acyl group and alicyclic skeleton can enumerate such as (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 rings [5.2.1.02,6] decane list methyl alcohol (methyl) acrylate, three rings [5.2.1.02,6] decane one alcohol list (methyl) acrylate (=(methyl) acrylic acid bicyclopentyl ester), three rings [4.4.0.12,5] hendecane list methyl alcohol list (methyl) acrylate, three rings [4.4.0.12,5] hendecane one alcohol list (methyl) acrylate, 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] pentadecane one alcohol list (methyl) acrylate, 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] hexadecane one alcohol list (methyl) acrylate etc. has the compound of 1 unsaturated carboxylic acid acyl group, 1, 4-cyclohexyl two (methyl) acrylate, 1, ethylene oxide denatured two (methyl) acrylate of 4-cyclohexanedimethanol two (methyl) acrylate, 1,4-CHDM, diamantane glycol two (methyl) acrylate etc. have the compound of more than 2 or 2 unsaturated carboxylic acid acyl groups.
Cellulose derivative can enumerate the cellulose ether of such as methylcellulose, ethyl cellulose, carboxymethyl cellulose, cyanethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethylcellulose etc.; The cellulose organic ester of cellulose-acetate propionate, cellulose acetate-butyrate, acetic acid cellulose benzoate 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, particularly preferably methylcellulose, ethyl cellulose.
Degree of substitution in cellulose derivative is different according to substituent kind, can have suitably selecting of the compatibility, operability etc. of the solidfied material of the compound of unsaturated carboxylic acid acyl group and alicyclic skeleton from the viewpoint of with above-mentioned.Such as, degree of etherification falling in methylcellulose is preferably the scope of 25% ~ 33%, and the degree of etherification falling in ethyl cellulose is preferably the scope of 46% ~ 51%.
In general; the compatibility of acrylic acid series polymeric compounds and cellulose derivative is low, produces gonorrhoea during mixing, but owing to using the monomer containing alicyclic skeleton in the present invention; the compatibility of polymkeric substance and cellulose derivative thus after solidification is higher, can form the diaphragm of transparency excellence.In addition, gained diaphragm not only birefringence is little, and photoelastic coefficient is low, is also difficult to the such characteristic of birefringent change occurs even if therefore have applying stress.
For the present invention; in actinic energy ray curable resion composition; can only containing the above-mentioned compound with unsaturated carboxylic acid acyl group and alicyclic skeleton as active energy ray-curable compound, but and then also can containing other active energy ray-curable compound.Other active energy ray-curable compound this can enumerate radically curing compound, cation-curable compound.
Radically curing compound can be set forth in molecule has at least 1 olefinic double bond and by compound that the irradiation of active energy beam (such as ultraviolet, visible ray, electron beam, X ray etc.) is carried out being polymerized under the existence of polymerization initiator.Such compound can enumerate such as (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) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylate, (methyl) acryloyl morpholine, (methyl) acrylic ester monomer of the simple functions such as γ-(methyl) acryloxypropyl trimethoxy silane, the ethene base system monomer of styrene, α-methyl styrene, vinyltoluene, vinyl acetate, allyl acetate, propionate, vinyl benzoate, NVP, N-vinyl imidazole, N-caprolactam etc., (methyl) acrylate of 2 functionalities of BDO 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 denatured 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 officials such as 3,5-triacryl six hydrogen-s-triazine can or 3 officials can above multi-functional monomer.Wherein, preferably 2 officials can or 2 officials can above multi-functional monomer.These radically curing compounds can be used alone, or 2 kinds or two or more are combinationally used.
In addition, radically curing compound can also use (methyl) acrylate oligomer of ester (methyl) acrylate, polyurethane (methyl) acrylate, epoxy (methyl) acrylate, propylene (methyl) acrylate etc.
Cation-curable compound can enumerate such as vinyl ether based compound, epoxy compound, oxetanes based compound etc.
Vinyl ether based compound can enumerate such as ethylene oxide denatured bisphenol-A-divinyl ether, ethylene oxide denatured quinhydrones divinyl ether etc.
Epoxy compound can enumerate such as 1,2-epoxy-cyclohexane, limonene diepoxide, 3,4-epoxycyclohexylmethyl-3 ', 4 '-epoxycyclohexane carboxylate, 1,4-butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, two (3,4-epoxy radicals-6-methylcyclohexylmethyl) adipate, bisphenol-A-diglycidyl ether, Bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, hydrogenated bisphenol A-diglycidyl ether etc.
Oxetanes based compound can enumerate 3-ethyl-3-hydroxymethyl oxetane, 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 active energy ray-curable compound, Thermocurable compound can also be contained.
Relative to the whole curability compounds in actinic energy ray curable resion composition; ratio shared by the above-mentioned compound with unsaturated carboxylic acid acyl group and alicyclic skeleton is such as more than 30 % by weight; be preferably more than 50 % by weight; and then preferably more than 70 % by weight, particularly preferably more than 90 % by weight.
In addition, in actinic energy ray curable resion composition, except above-mentioned curability compound, Photoepolymerizationinitiater initiater and light sensitizer as required, light cationic polymerization initiators, hot cationic polymerization initiators, hot radical polymerization initiator, photosensitizer, light stabilizer, ultraviolet light absorber, levelling agent, defoamer etc. can also be coordinated.
Photoepolymerizationinitiater initiater suitably can be selected according to the kind of the active energy beam as solidification means.The example of Photoepolymerizationinitiater initiater can enumerate acetophenone, 3-methyl acetophenone, benzophenone, 4-chloro benzophenone, 4,4-diaminobenzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-2-phenylacetones, 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 alicyclic skeleton; divide totally (comprising the composition becoming solid by solidifying) relative to the solid in actinic energy ray curable resion composition; be such as 1 ~ 98 % by weight; be preferably 5 ~ 93 % by weight; and then preferably 10 ~ 85 % by weight, particularly preferably 20 ~ 75 % by weight.
The content of above-mentioned cellulose derivative in actinic energy ray curable resion composition, divide totally (comprising the composition becoming solid by solidifying) relative to the solid in actinic energy ray curable resion composition, be such as 1 ~ 98 % by weight, be preferably 5 ~ 93 % by weight, and then preferably 10 ~ 85 % by weight, particularly preferably 20 ~ 75 % by weight.
Above-mentioned in actinic energy ray curable resion composition has the compound of unsaturated carboxylic acid acyl group and alicyclic skeleton and the ratio of cellulose derivative; such as the former/the latter's (weight ratio)=1/99 ~ 99/1; be preferably 5/95 ~ 95/5; and then preferably 10/90 ~ 90/10, particularly preferably 20/80 ~ 80/20.
The content of Photoepolymerizationinitiater initiater in actinic energy ray curable resion composition, divide totally (comprising the composition becoming solid by solidifying) relative to the solid in actinic energy ray curable resion composition, be such as 0.1 ~ 10 % by weight, be preferably 1 ~ 8 about % by weight.
Polaroid of the present invention makes this actinic energy ray curable resion composition be solidified to form diaphragm to be prepared after passing through to be coated with above-mentioned actinic energy ray curable resion composition at least one side of polarizer.
The coating process of actinic energy ray curable resion composition is not particularly limited, and can utilize scraper, line rod coating machine, various coating method such as mould painting machine, gravure coater etc.When being coated with, solvent also can be used to regulate the viscosity of hardening resin composition.
The film formed by actinic energy ray curable resion composition solidifies by irradiating active energy beam, forms diaphragm.Active energy beam can enumerate ultraviolet, luminous ray, electron beam, X ray etc.Wherein preferably use ultraviolet.Ultraviolet occurring source can enumerate 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.
Consider from the angle of slim light weight, protectiveness, operability etc., the thickness of diaphragm is such as 10 ~ 200 μm, is preferably 30 ~ 100 μm.
Polaroid of the present invention uses the diaphragm of solidfied material as polarizer of actinic energy ray curable resion composition; therefore have not only transparent, birefringence is little; even if apply stress to be also difficult to the such remarkable advantage of birefringent change occurs, wherein said actinic energy ray curable resion composition contains the compound and cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton.
Embodiment
Below, in more detail the present invention is described based on embodiment, but the present invention is not limited to these embodiments.Further, the photoelastic coefficient of cured film (cured film) and the mensuration of phase differential, the mensuration of glass transition temperature are carried out according to following methods.
[mensuration of photoelastic coefficient and phase differential]
Make the cured film that thickness is 200 μm, 3 dimensions birefringence meter (" KOBRA-WR ") using prince to measure machine Co., Ltd. measure.
[mensuration of glass transition temperature]
At the upper coat activated energy ray-curable resin combination (thickness is 40 μm) of cold-rolled steel sheet (thickness 0.3mm × width 20mm × length 50mm), irradiate from the place of distance 11cm the ultraviolet that accumulative light quantity is 350m 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), obtain the cured film of actinic energy ray curable resion composition.Use rigidity vibrator type determination of viscoelasticity device (Co., Ltd. A & D (Ai Ande) system, " RPT-3000W ") that it is warming up to 200 DEG C from 25 DEG C, measure glass transition temperature (Tg).
Embodiment 1
Three ring [the 5.2.1.02 by the hydroxyl value of 10 % by weight be ethyl acetate solution 500 weight portion of the ethyl cellulose of 32.9mgKOH/g, representing with following formula (1a), 6] decane Dimethanol Diacrylate (Daicel Qing Te Co., Ltd. system, trade name " IRR-214K ") 50 weight portions, 1-hydroxy-cyclohexyl-phenyl ketone 5 weight portion mix, and obtain actinic energy ray curable resion composition 1.Use applicator with the coat activated energy ray-curable resin combination 1 of the thickness of 1000 μm on a glass, 80 DEG C of dryings after 1 hour, to irradiate 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) ultraviolet 3 times that accumulative light quantity is 500m J/cm2 from the place of distance 11cm, obtain the independent cured film (thickness is 188 μm) 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 example 1
Be ethyl acetate solution 500 weight portion of the ethyl cellulose of 32.9mgKOH/g by the hydroxyl value of 10 % by weight, pentaerythritol triacrylate 50 weight portion, 1-hydroxy-cyclohexyl-phenyl ketone 5 weight portion mix, obtain actinic energy ray curable resion composition 2.Use applicator with the coat activated energy ray-curable resin combination 2 of the thickness of 1000 μm on a glass, 80 DEG C of dryings after 1 hour, irradiation ultraviolet radiation similarly to Example 1, obtains the independent cured film (thickness is 189 μm) 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 example 2
Be ethyl acetate solution 500 weight portion of the ethyl cellulose of 32.9mgKOH/g by the hydroxyl value of 10 % by weight, dipentaerythritol acrylate 50 weight portion, 1-hydroxy-cyclohexyl-phenyl ketone 5 weight portion mix, obtain actinic energy ray curable resion composition 3.Use applicator with the coat activated energy ray-curable resin combination 3 of the thickness of 1000 μm on a glass, 80 DEG C of dryings after 1 hour, irradiation ultraviolet radiation similarly to Example 1, obtains the independent cured film (thickness is 191 μm) 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 example 3
Be ethyl acetate solution 500 weight portion of the ethyl cellulose of 32.9mgKOH/g by the hydroxyl value of 10 % by weight, pentaerythrite ethoxy tetraacrylate 50 weight portion, 1-hydroxy-cyclohexyl-phenyl ketone 5 weight portion mix, obtain actinic energy ray curable resion composition 4.Use applicator with the coat activated energy ray-curable resin combination 4 of the thickness of 1000 μm on a glass, 80 DEG C of dryings after 1 hour, irradiation ultraviolet radiation similarly to Example 1, obtains the independent cured film (thickness is 185 μm) 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 example 4
Be ethyl acetate solution 500 weight portion of the ethyl cellulose of 32.9mgKOH/g by the hydroxyl value of 10 % by weight, two (trimethylolpropane) tetraacrylate 50 weight portion, 1-hydroxy-cyclohexyl-phenyl ketone 5 weight portion mix, obtain actinic energy ray curable resion composition 5.Use applicator with the coat activated energy ray-curable resin combination 5 of the thickness of 1000 μm on a glass, irradiation ultraviolet radiation similarly to Example 1, obtains the independent cured film (thickness is 189 μm) 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
Be ethyl acetate solution 700 weight portion of the ethyl cellulose of 32.9mgKOH/g by the hydroxyl value of 10 % by weight, acrylic acid bicyclopentyl ester (Hitachi Chemical Co., Ltd.'s system, trade name " FA-513A ") 30 weight portions that represent with following formula (2), 1-hydroxy-cyclohexyl-phenyl ketone 5 weight portion mix, obtain actinic energy ray curable resion composition 6.Use applicator with the coat activated energy ray-curable resin combination 6 of the thickness of 500 μm on a glass, irradiation ultraviolet radiation similarly to Example 1, obtains the independent cured film (thickness is 76 μm) 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 obtained in embodiment and comparative example, glass transition temperature, photoelastic coefficient and phase differential is shown in table 1.In table, "-" represents and can not measure.Known according to table 1, the cured film obtained in embodiment is transparent, and phase differential and photoelastic coefficient all show as little value, and not only birefringence is little, even and if apply stress be also difficult to birefringent change occurs.
Claims (5)
1. a polaroid; there is the structure of at least one side with the diaphragm protection polarizer containing 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 the compound and cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton
The content of described cellulose derivative in actinic energy ray curable resion composition is, dividing relative to the solid in actinic energy ray curable resion composition is totally 20 ~ 98 % by weight, and the solid in described actinic energy ray curable resion composition divides the composition totally comprising and become solid by solidifying.
2. polaroid according to claim 1, wherein, the compound with unsaturated carboxylic acid acyl group and alicyclic skeleton is the compound with unsaturated carboxylic acid acyl group and bridging alicyclic skeleton.
3. polaroid according to claim 1, wherein, the compound with unsaturated carboxylic acid acyl group and alicyclic skeleton is the compound represented with following formula (1),
In formula, R
1, R
2identical or different, represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, X
1, X
2identical or different, represent singly-bound, carbon number to be the alkylidene of 1 ~ 8 or the carbon number of more than 1 or 2 be the divalent group of the alkylidene of 1 ~ 8 and the oxygen atom of more than 1 or 2 or sulfur atom linkage; M, n represent 0 or 1 separately.
4. the polaroid according to any one of claims 1 to 3, wherein, cellulose derivative is at least a kind that is selected from methylcellulose and ethyl cellulose.
5. the preparation method of a polaroid; it is characterized in that; on at least one side of polarizer after coat activated energy ray-curable resin combination; this actinic energy ray curable resion composition is solidified and forms diaphragm; wherein; described actinic energy ray curable resion composition contains the compound and cellulose derivative with unsaturated carboxylic acid acyl group and alicyclic skeleton
The content of described cellulose derivative in actinic energy ray curable resion composition is, dividing relative to the solid in actinic energy ray curable resion composition is totally 20 ~ 98 % by weight, and the solid in described actinic energy ray curable resion composition divides the composition totally comprising and become solid by solidifying.
Priority Applications (1)
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| CN1582308A (en) * | 2001-11-07 | 2005-02-16 | 大曹株式会社 | Solidified composition excellent in optical characteristics |
| TW200835945A (en) * | 2006-11-10 | 2008-09-01 | Konica Minolta Opto Inc | Polarization plate and liquid crystal display device |
| CN101395507A (en) * | 2006-03-09 | 2009-03-25 | 柯尼卡美能达精密光学株式会社 | Polarizer protection film, polarizing plate and vertically aligned liquid crystal display |
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| JP2005092112A (en) * | 2003-09-19 | 2005-04-07 | Kuraray Co Ltd | Polarizing plate and its manufacturing method |
| JP2006292895A (en) * | 2005-04-07 | 2006-10-26 | Fuji Photo Film Co Ltd | Transparent film, and liquid crystal display element and liquid crystal display using the transparent film |
| JP2006292890A (en) * | 2005-04-07 | 2006-10-26 | Fuji Photo Film Co Ltd | Transparent film, and liquid crystal display element and liquid crystal display using the transparent film |
| JP4967943B2 (en) * | 2007-09-12 | 2012-07-04 | 大日本印刷株式会社 | Optical laminate, polarizing plate, and image display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1582308A (en) * | 2001-11-07 | 2005-02-16 | 大曹株式会社 | Solidified composition excellent in optical characteristics |
| CN101395507A (en) * | 2006-03-09 | 2009-03-25 | 柯尼卡美能达精密光学株式会社 | Polarizer protection film, polarizing plate and vertically aligned liquid crystal display |
| TW200835945A (en) * | 2006-11-10 | 2008-09-01 | Konica Minolta Opto Inc | Polarization plate and liquid crystal display device |
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| JP特开2005-92112A 2005.04.07 * |
| JP特开2006-292890A 2006.10.26 * |
| JP特开2006-292895A 2006.10.26 * |
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