CN105492564A - Curable adhesive for polarizing films, polarizing film, optical film and image display device - Google Patents
Curable adhesive for polarizing films, polarizing film, optical film and image display device Download PDFInfo
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- CN105492564A CN105492564A CN201480047627.0A CN201480047627A CN105492564A CN 105492564 A CN105492564 A CN 105492564A CN 201480047627 A CN201480047627 A CN 201480047627A CN 105492564 A CN105492564 A CN 105492564A
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Abstract
This curable adhesive for polarizing films, which contains a curable component, has a bulk water absorption of 10% by weight or less in cases where a cured product of this curable adhesive for polarizing films is immersed in pure water at 23 DEG C for 24 hours, said bulk water absorption being represented by the following formula. Bulk water absorption (%)=(M2-M1)/M1*100 (%) (In this formula, M1 represents the weight of the cured product before immersion, and M2 represents the weight of the cured product after immersion.) This curable adhesive for polarizing films provides excellent adhesion between a polarizer and a transparent protective film, and is able to have satisfactory optical durability in a harsh environment at high temperature and high humidity. In addition, this curable adhesive for polarizing films exhibits sufficient adhesive power even if immersed in water for a long period of time.
Description
Technical field
The present invention relates to across adhesive layer by polaroid and the stacked polarizing coating of transparent protective film, form the polarizing coating curing type adhesive of above-mentioned adhesive layer.The present invention relates to the polarizing coating employing above-mentioned adhesive layer in addition.This polarizing coating can form the image display device such as liquid crystal indicator (LCD), organic EL display, CRT, PDP separately or with the form of the blooming being laminated with this polarizing coating.
Background technology
For clock and watch, mobile phone, PDA, notebook computer, PC watch-dog, DVD player, TV etc., liquid crystal indicator commercially sharply develops.Liquid crystal indicator is the polarization state visible device making to be caused by the switch of liquid crystal, according to its displaying principle, uses polaroid.Particularly, in the purposes such as TV, more and more want high brightness, high-contrast, wide viewing angle, for polarizing coating, also more and more require high-transmission rate, high-polarization, high colorrendering quality etc.
As polaroid, from the viewpoint of having high-transmission rate, high-polarization, widely using the most at large and making iodine be adsorbed in such as polyvinyl alcohol (following, to be also only called " PVA ") and the iodine system polaroid of the structure of carrying out stretching and obtaining.Generally speaking, polarizing coating uses and utilizes two sides transparent protective film being fitted in by so-called water system tackiness agent water-soluble for polyvinyl alcohol based material polaroid and the polarizing coating (following patent documentation 1 and patent documentation 2) obtained.As transparent protective film, use the triacetyl cellulose etc. that Water Vapour Permeability is high.When using above-mentioned water system tackiness agent (so-called wet type lamination), after making polaroid and transparent protective film laminating, need drying process.
On the other hand, propose active energy ray curable tackiness agent and replace above-mentioned water system tackiness agent.When using active energy ray curable tackiness agent to manufacture polarizing coating, do not need drying process, therefore can improve the productivity of polarizing coating.Propose and such as employ the active energy ray curable tackiness agent (following patent documentation 3 and patent documentation 4) of N substituted amide system monomer as the radical polymerization mould assembly of solidified nature composition.This tackiness agent has given play to excellent weather resistance at high humidity with in the environment of the harshness under high temperature, but in the market, in fact can improve the tackiness agent of cementability and/or water tolerance further in continuous requirement.
In addition, propose a kind of active energy ray curable tackiness agent, it is conceived to the SP value (solubility parameter) of solidified nature composition, by using with the composition ratio of regulation the free-radical polymerised compound that at least 3 kinds of SP values are different, the adhesive layer (following patent documentation 5) that improve weather resistance and water tolerance can be formed.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-220732 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-296427 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2008-287207 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-078700 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-144690 publication
Summary of the invention
The problem that invention will solve
Utilize the active energy ray curable tackiness agent recorded in above-mentioned patent documentation 5, weather resistance and water tolerance can be met for the various transparent protective films used when the manufacture of polarizing coating.But, although the polarizing coating using the active energy ray curable tackiness agent recorded in patent documentation 5 to obtain can meet the water tolerance (warm water immersion test) of to flood in the warm water of 60 DEG C 6 hours, pursue in market further hot and humid under harshness environment in optical durability.Further, under above-mentioned polarizing coating being required to flood long situation in water, also there is sufficient bonding force.
The object of the present invention is to provide a kind of polarizing coating curing type adhesive; the cementability of itself and polaroid and transparent protective film is good; and can meet hot and humid under harshness environment in optical durability, under simultaneously flooding long situation in water, also there is sufficient bonding force.
The present invention also aims to provide a kind of polarizing coating; described polarizing coating utilizes the adhesive layer using polarizing coating curing type adhesive to be formed; polaroid is provided with transparent protective film; further; the invention provides the blooming employing above-mentioned polarizing coating, the present invention also provides the image display device employing above-mentioned polarizing coating or blooming.
Solve the method for problem
The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, found that, utilize following polarizing coating curing type adhesive, can realize above-mentioned purpose, thus solve the present invention.
That is, the present invention relates to a kind of polarizing coating curing type adhesive, it is characterized in that, it contains solidified nature composition,
This polarizing coating curing type adhesive when by making this curing type adhesive solidify, the cured article that obtains impregnated in the pure water 24 hours of 23 DEG C, following formula:
Volume water absorption rate (%)=(M2-M1)/M1} × 100,
Volume water absorption rate shown in { wherein, in above-mentioned formula, the weight of the cured article before M1 represents dipping, M2 represent the weight of the cured article after dipping } is less than 10 % by weight.
The Octanol/water Partition Coefficients (logPow value) of above-mentioned polarizing coating curing type adhesive is preferably more than 1.
For above-mentioned polarizing coating curing type adhesive, when above-mentioned solidified nature composition is active energy ray-curable composition, can use as active energy ray curable tackiness agent.As above-mentioned solidified nature composition, free-radical polymerised compound can be contained.As above-mentioned free-radical polymerised compound, preferably containing (methyl) acrylamide derivative.In addition, as above-mentioned free-radical polymerised compound, preferably containing multi-functional compounds, described multi-functional compounds has at least 2 and has free-radical polymerised functional group.In addition, above-mentioned active energy ray curable tackiness agent also can contain Photoepolymerizationinitiater initiater.
Above-mentioned polarizing coating curing type adhesive also can contain acrylic oligomers (A).
Above-mentioned polarizing coating curing type adhesive also can contain light acid producing agent (B).
Above-mentioned polarizing coating curing type adhesive can also containing the compound of any one (C) comprised in alkoxyl group, epoxy group(ing).As the above-mentioned compound of any one (C) comprised in alkoxyl group, epoxy group(ing), the compound (C1) preferably containing alkoxyl group.Further, the above-mentioned compound (C1) containing alkoxyl group is preferably the melamine compound containing alkoxyl group.
In addition, above-mentioned polarizing coating curing type adhesive also can contain isocyanate compound (D).
For above-mentioned polarizing coating curing type adhesive, when above-mentioned solidified nature composition is Thermocurable composition, by also containing thermal polymerization, can use as thermohardening type tackiness agent.
The present invention relates to a kind of polarizing coating in addition, it is characterized in that, it is the polarizing coating being provided with transparent protective film at least one face of polaroid across adhesive layer,
Above-mentioned adhesive layer is formed by the solidification nitride layer of above-mentioned polarizing coating curing type adhesive.
In above-mentioned polarizing coating, the thickness of above-mentioned adhesive solidification nitride layer is preferably 0.1 ~ 3 μm.
The invention still further relates to a kind of blooming, it is characterized in that, be laminated with at least 1 above-mentioned polarizing coating.
The invention still further relates to a kind of image display device, it is characterized in that, employ above-mentioned polarizing coating or above-mentioned blooming.
Invention effect
With regard to polarizing coating curing type adhesive of the present invention, this curing type adhesive is solidified and the volume water absorption rate of cured article that obtains is less than 10 % by weight.The water-absorbent that this volume water absorption rate demonstrates when utilizing the solidification nitride layer obtained by polarizing coating curing type adhesive of the present invention to form adhesive layer is very low.Therefore, for being provided with for the polarizing coating of transparent protective film on polaroid across the adhesive layer comprising above-mentioned solidification nitride layer, the cementability of polaroid and clear protective film layer is good, and can meet hot and humid under harshness environment in optical durability.
Such as, polarizing coating (85 DEG C × 85%RH) optical durability (humidification endurance test) under the humidified ambient of harshness with the solidification nitride layer (adhesive layer) using polarizing coating curing type adhesive of the present invention to be formed is also good.Therefore, when polarizing coating of the present invention is under the humidified ambient being placed in above-mentioned harshness, also can the decline of the transmissivity of polarizing coating, degree of polarization (change) be suppressed less.In addition, the invention provides a kind of polarizing coating, it also can suppress the decline of bonding force under the environment that impregnated in the such harshness of water, also has sufficient bonding force under flooding long situation in water.
Embodiment
< volume water absorption rate >
For polarizing coating curing type adhesive of the present invention, the volume water absorption rate of the above-mentioned record measured when the cured article that obtains impregnated in the pure water 24 hours of 23 DEG C by making this curing type adhesive solidify is less than 10 % by weight.When polarizing coating being placed under the environment of harsh hot and humid (85 DEG C/85%RH etc.); moisture through transparent protective film and adhesive layer invades polaroid; crosslinking structure is hydrolyzed; cause the orientation of 2 look pigments chaotic, cause that transmissivity rises, the deterioration of degradation optical durability under degree of polarization.By the volume water absorption rate of adhesive layer is set to less than 10 % by weight, when can suppress to be placed in by polarizing coating under harsh hot and humid environment, water is to the movement of polaroid, the transmissivity rising suppressing polaroid, degree of polarization decline.About above-mentioned volume water absorption rate, for the adhesive layer of polarizing coating, better from the viewpoint of the optical durability in the environment of the harshness made under high temperature, be preferably less than 5 % by weight, more preferably less than 3 % by weight, more preferably less than 1.5 % by weight, most preferably be less than 1 % by weight.On the other hand, when making polaroid and transparent protective film laminating, polaroid maintains a certain amount of moisture, during contact with moisture contained by this curing type adhesive and polaroid, the bad orders such as cratering (Ha ジ キ), bubble occurs sometimes.In order to suppress bad order, preferably this curing type adhesive can absorb a certain amount of moisture.More specifically, volume water absorption rate is preferably more than 0.01 % by weight, and more preferably more than 0.05 % by weight.Above-mentioned volume water absorption rate is measured in particular by the moisture content test method recorded in JISK7209.
The preferred Octanol/water Partition Coefficients of polarizing coating curing type adhesive of the present invention (following, to be designated as logPow value) is high.LogPow value is the oil loving index representing material, refers to the logarithmic value of the partition ratio of octanol/water.LogPow is high to be meaned for lipophilicity, that is, mean that water-intake rate is low.Although logPow value (the flask impregnating method that JIS-Z-7260 records) also can be measured, also can calculate to divide as the formation of polarizing coating curing type adhesive based on the structure of each compound of (solidified nature composition etc.) by calculating.In this specification sheets, use the logPow value utilizing CambridgeSoft Inc. ChemDrawUltra to calculate.
Based on above-mentioned calculated value, the logPow value of the polarizing coating curing type adhesive in the present invention can be calculated by following formula.
The logPow=Σ (logPowi × Wi) of curing type adhesive
LogPowi: the logPow value of each composition of curing type adhesive
The mole number of Wi:(i composition)/(total mole number of each composition of curing type adhesive)
When carrying out above-mentioned calculating, in each composition of curing type adhesive, the composition that polymerization starter, light acid producing agent etc. do not form the skeleton of cured article (adhesive layer) is removed by from the composition in above-mentioned calculating.The logPow value of polarizing coating curing type adhesive of the present invention is preferably more than 1, is more preferably more than 1.5, most preferably is more than 2.Bonding water tolerance, humidification weather resistance can be improved thus.On the other hand, the logPow value of polarizing coating curing type adhesive of the present invention is generally about less than 8, is preferably less than 5, is more preferably less than 4.If this logPow value is too high, then easily produce the bad order such as cratering, bubble as mentioned above, therefore not preferred.
In addition, the means that above-mentioned volume water absorption rate in the present invention is set to less than 10 % by weight are not particularly limited, but when polarizing coating curing type adhesive is the composition containing Multiple components, by selecting each composition, volume water absorption rate can be controlled in above-mentioned scope.Such as, when polarizing coating curing type adhesive is the adhesive compound containing Multiple components, by to make the logPow value in this adhesive compound be that mode that the ratio of the composition of less than 1 is little such as to be prepared at the method, volume water absorption rate can be controlled in above-mentioned scope.In order to the above-mentioned volume water absorption rate in the present invention is adjusted to less than 10 % by weight, such as, can by being more than 1 to carry out the logPow value control of polarizing coating curing type adhesive.
< cure shrinkage >
In addition, because polarizing coating curing type adhesive of the present invention has solidified nature composition, therefore when making this curing type adhesive solidify, usually there is cure shrinkage.Cure shrinkage is the index of the ratio of the cure shrinkage represented when forming adhesive layer by polarizing coating curing type adhesive.If the cure shrinkage of adhesive layer becomes large, then suppressing the generation of interface strain, the generation of poor attachment when making polarizing coating curing type adhesive be solidified to form adhesive layer, is preferred from this side considerations.Consider from above-mentioned viewpoint, polarizing coating curing type adhesive of the present invention is solidified and the above-mentioned cure shrinkage of cured article that obtains is preferably less than 10%.Preferred above-mentioned cure shrinkage is little, and above-mentioned cure shrinkage is preferably less than 8%, and more preferably less than 5%.Measure above-mentioned cure shrinkage by the method recorded in No. 2013-104869, Japanese Unexamined Patent Publication, measure in particular by the method for Sentec Inc. cure shrinkage sensor that utilizes recorded in embodiment.
< solidified nature composition >
Polarizing coating curing type adhesive of the present invention contains solidified nature composition.This solidified nature composition of suitable selection meets above-mentioned volume water absorption rate to make cured article.
As solidified nature composition, electronic beam solidified, ultraviolet hardening, visible light curable isoreactivity energy ray-curable and thermohardening type can be roughly divided into.Further, ultraviolet hardening, Visible light curable adhesives can be roughly divided into radical polymerization curing type adhesive and cationic polymerization type tackiness agent.In the present invention, by wavelength region 10nm ~ be designated as ultraviolet lower than the active energy beam of 380nm, the active energy beam of wavelength region 380nm ~ 800nm is designated as visible ray.The solidified nature composition of above-mentioned radical polymerization curing type adhesive can use as the solidified nature composition of thermohardening type tackiness agent.
<1: radical polymerization curing type adhesive >
As above-mentioned solidified nature composition, the free-radical polymerised compound used in such as radical polymerization curing type adhesive can be enumerated.Free-radical polymerised compound can enumerate the compound of the free-radical polymerised functional group with carbon-to-carbon double bond such as (methyl) acryl, vinyl etc.These solidified nature compositions can use any one in the multifunctional free-radical polymerised compound of more than monofunctional free radical's polymerizable compound or two senses.In addition, these free-radical polymerised compounds can be used alone a kind, or combinationally use two or more.As these free-radical polymerised compounds, be suitably the compound such as with (methyl) acryl.It should be noted that, in the present invention, (methyl) acryl refers to acryl and/or methacryloyl, and below, " (methyl) " is the same meaning.
<< monofunctional free radical polymerizable compound >>
As monofunctional free radical's polymerizable compound, (methyl) acrylamide derivative such as with (methyl) acrylamido can be enumerated.(methyl) acrylamide derivative guarantee with the cementability of polaroid, various transparent protective film in and the fast and productivity of polymerization velocity excellent in preferred.As the concrete example of (methyl) acrylamide derivative, can enumerate such as: N-methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-hexyl (methyl) acrylamide etc. are containing (methyl) acrylamide derivative of N-alkyl; N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N-methylol-N-propane (methyl) acrylamide etc. are containing (methyl) acrylamide derivative of N-hydroxyalkyl; Amino methyl (methyl) acrylamide, amino-ethyl (methyl) acrylamide etc. are containing (methyl) acrylamide derivative of N-aminoalkyl group; N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide etc. are containing (methyl) acrylamide derivative of N-alkoxyl group; Mercapto methyl (methyl) acrylamide, mercaptoethyl (methyl) acrylamide etc. are containing (methyl) acrylamide derivative of N-mercaptoalkyl; Deng.In addition; nitrogen-atoms as (methyl) acrylamido defines (methyl) acrylamide derivative containing heterocycle of heterocycle, can enumerate such as: N-acryloyl morpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryl Pyrrolidine etc.
In above-mentioned (methyl) acrylamide derivative; from the viewpoint of the cementability with polaroid, various transparent protective film; preferably containing (methyl) acrylamide derivative of N-hydroxyalkyl, particularly preferably N-hydroxyethyl (methyl) acrylamide.
In addition, as monofunctional free radical's polymerizable compound, can enumerate such as: various (methyl) acrylic acid derivative with (methyl) acryloxy.Specifically, can enumerate such as: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) vinylformic acid 2-methyl-2-nitro propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) t-amyl, (methyl) vinylformic acid 3-pentyl ester, (methyl) vinylformic acid 2, 2-dimethyl butyl ester, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, (methyl) n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid 4-methyl-2-propyl pentyl ester, (methyl) vinylformic acid (carbonatoms 1-20) alkyl esters such as (methyl) vinylformic acid Octadecane base ester.
In addition, as above-mentioned (methyl) acrylic acid derivative, can enumerate such as: (methyl) acrylate base esters such as (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring pentyl ester;
(methyl) vinylformic acid aralkyl esters such as (methyl) benzyl acrylate;
(methyl) vinylformic acid 2-isobornyl thiocyanoacetate, (methyl) vinylformic acid 2-norcamphyl methyl esters, (methyl) vinylformic acid 5-norbornylene-2-base-methyl esters, (methyl) vinylformic acid 3-methyl-2-norcamphyl methyl esters, (methyl) vinylformic acid dihydro dicyclopentadiene ester (ジ シ Network ロ ペ Application テ ニ Le (メ タ) ア Network リ レ ー ト), (methyl) vinylformic acid dihydro dicyclopentadiene 2-ethoxyethyl acetate (ジ シ Network ロ ペ Application テ ニ Le オ キ シ エ チ Le (メ タ) ア Network リ レ ー ト), polycycle (methyl) acrylate such as (methyl) vinylformic acid tetrahydrochysene dicyclopentadiene ester (ジ シ Network ロ ペ Application タ ニ Le (メ タ) ア Network リ レ ー ト),
(methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-methoxymethoxy ethyl ester, (methyl) vinylformic acid 3-methoxybutyl, (methyl) acrylic acid ethyl carbitol ester, (methyl) acrylate, alkyl phenoxy polyoxyethylene glycol (methyl) acrylate etc. contain (methyl) acrylate of alkoxyl group or phenoxy group; Deng.
In addition, as above-mentioned (methyl) acrylic acid derivative, can enumerate: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid hydroxy alkyl esters such as (methyl) vinylformic acid 12-hydroxylauric ester, or vinylformic acid [4-(hydroxymethyl) cyclohexyl] methyl esters, cyclohexanedimethanol list (methyl) acrylate, (methyl) acrylate of the hydroxyls such as 2-hydroxyl-3-phenoxy propyl (methyl) acrylate,
(methyl) glycidyl acrylate, 4-hydroxyl butyl (methyl) acrylate glycidyl ether etc. are containing (methyl) acrylate of epoxy group(ing);
2,2,2-trifluoroethyl (methyl) acrylate, 2, halogen-containing (methyl) acrylate such as 2,2-trifluoroethyl ethyl (methyl) acrylate, (methyl) vinylformic acid tetrafluoro propyl ester, (methyl) vinylformic acid hexafluoro propyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid 17 fluorine ester in the last of the ten Heavenly stems, 3-chloro-2-hydroxypropyl (methyl) acrylate;
(methyl) acrylic acid alkyl aminoalkyl esters such as (methyl) acrylate;
(methyl) acrylate of the oxygen heterocyclic ring butyl such as 3-oxetanyl methyl (methyl) acrylate, 3-methyl-oxetanyl methyl (methyl) acrylate, 3-ethyl-oxetanyl methyl (methyl) acrylate, 3-butyl-oxetanyl methyl (methyl) acrylate, 3-hexyl-oxetanyl methyl (methyl) acrylate;
(methyl) tetrahydrofurfuryl acrylate, butyrolactone (methyl) acrylate etc. have (methyl) acrylate or hydroxypivalic acid neopentyl glycol (methyl) acrylic acid adduct, p-phenyl phenol (methyl) acrylate etc. of heterocycle.
In addition, as monofunctional free radical's polymerizable compound, can enumerate: the carboxylic monomers such as (methyl) vinylformic acid, carboxy ethyl acrylate, carboxypentyl acrylate, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid.
In addition, as monofunctional free radical's polymerizable compound, can enumerate such as: the lactan system vinyl monomers such as NVP, N-vinyl-Epsilon-caprolactam, methyl ethylene pyrrolidone; Vinyl pyridine, vinylpiperidone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, second alkene base oxazole, polyvinyl morpholinone etc. have nitrogenous heterocyclic ethene base system monomer etc.
In addition, as monofunctional free radical's polymerizable compound, the free-radical polymerised compound with active methylene group can be used.The free-radical polymerised compound with active methylene group is at end or has (methyl) acryl isoreactivity double bond base in the molecule and have the compound of active methylene group.As active methylene group, can enumerate such as: acetoacetyl, alkoxypropan diacyl or Cyanoacetyl etc.Above-mentioned active methylene group is preferably acetoacetyl.As the concrete example of free-radical polymerised compound with active methylene group, can enumerate such as: acetoacetoxy groups alkyl (methyl) acrylate such as 2-acetoacetoxyethyl (methyl) acrylate, 2-acetoacetoxy groups propyl group (methyl) acrylate, 2-acetoacetoxy groups-1-methylethyl (methyl) acrylate; 2-ethoxy-c diacyl oxygen base ethyl (methyl) acrylate, 2-cyano-acetoxy ethyl (methyl) acrylate, N-(2-cyano-acetoxy ethyl) acrylamide, N-(2-propionyl Acetoxybutyl) acrylamide, N-(4-acetoacetoxy groups methyl-benzyl) acrylamide, N-(2-acetoacetyl amino-ethyl) acrylamide etc.The free-radical polymerised compound with active methylene group is preferably acetoacetoxy groups alkyl (methyl) acrylate.
The multifunctional free-radical polymerised compound >> of <<
In addition, as multifunctional free-radical polymerised compounds more than two senses, can enumerate such as: tripropylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, decamethylene-glycol diacrylate, 2-ethyl-2-butyl propylene glycol two (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate, bisphenol A epoxy ethane additive product two (methyl) acrylate, bisphenol A propylene oxide affixture two (methyl) acrylate, dihydroxyphenyl propane diglycidyl ether two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, cyclic trimethylolpropane formal (methyl) acrylate, diox glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, the carboxylate of (methyl) vinylformic acid such as EO modification two glycerine four (methyl) acrylate and polyvalent alcohol, two [4-(2-(methyl) acryloyloxyethoxy) phenyl] fluorenes of 9,9-.As concrete example, can enumerate: AronixM-220, M-306 (East Asia Synesis Company system), LightAcrylate1,9ND-A (chemical company of common prosperity society system), LightAcrylateDGE-4A (chemical company of common prosperity society system), LightAcrylateDCP-A (chemical company of common prosperity society system), SR-531 (Sartomer Inc.), CD-536 (Sartomer Inc.) etc.In addition as required, can enumerate: various epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate or various (methyl) acrylic ester monomer etc.
In the water-intake rate controlling above-mentioned cured article and in the optical durability meeting under the humidified ambient of polarizing coating in harshness, preferred free-radical polymerised compound contains above-mentioned multifunctional free-radical polymerised compound.In above-mentioned multifunctional free-radical polymerised compound, the free-radical polymerised compound that preferred logPow value is high.The logPow value of free-radical polymerised compound is preferably more than 2, is more preferably more than 3, most preferably is more than 4.
As the free-radical polymerised compound that logPow value is high, can enumerate such as: alicyclic ring (methyl) acrylate such as Tricyclodecane Dimethanol two (methyl) acrylate (logPow=3.05), (methyl) isobornyl acrylate (logPow=3.27);
Long-chain fat race (methyl) acrylate such as 1,9-nonanediol two (methyl) acrylate (logPow=3.68), decamethylene-glycol diacrylate (logPow=4.10);
Higly branched chain (methyl) acrylate such as hydroxypivalic acid neopentyl glycol (methyl) acrylic acid adduct (logPow=3.35), 2-ethyl-2-butyl propylene glycol two (methyl) acrylate (logPow=3.92);
Dihydroxyphenyl propane two (methyl) acrylate (logPow=5.46), bisphenol-A epoxy ethane 4 moles of affixtures two (methyl) acrylate (logPow=5.15), bisphenol A propylene oxide 2 moles of affixtures two (methyl) acrylate (logPow=6.10), bisphenol A propylene oxide 4 moles of affixtures two (methyl) acrylate (logPow=6.43), 9, two [4-(2-(methyl) acryloyloxyethoxy) phenyl] fluorenes (logPow=7.48) of 9-, (methyl) acrylate containing aromatic nucleus such as p-phenyl phenol (methyl) acrylate (logPow=3.98), Deng.
With regard to free-radical polymerised compound; from the viewpoint of having concurrently and the optical durability under polaroid, the cementability of various transparent protective film and the environment of harshness, preferably monofunctional free radical's polymerizable compound and multifunctional free-radical polymerised compound are used.Usually, relative to free-radical polymerised compound 100 % by weight, preferably use with the ratio of monofunctional free radical's polymerizable compound 3 ~ 80 % by weight and multifunctional free-radical polymerised compound 20 ~ 97 % by weight.
The form > of < radical polymerization curing type adhesive
About polarizing coating curing type adhesive of the present invention, when solidified nature composition is used with the form of active energy ray-curable composition, can use as active energy ray curable tackiness agent, in addition, when solidified nature composition is used with the form of Thermocurable composition, can use as thermohardening type tackiness agent.With regard to above-mentioned active energy ray curable tackiness agent, when active energy beam uses electron beam etc., this active energy ray curable tackiness agent is without the need to containing Photoepolymerizationinitiater initiater, but when active energy beam use ultraviolet or visible ray, this active energy ray curable tackiness agent is preferably containing Photoepolymerizationinitiater initiater.On the other hand, when being used with the form of Thermocurable composition by the solidified nature composition of above-mentioned tackiness agent, this tackiness agent is preferably containing thermal polymerization.
<< Photoepolymerizationinitiater initiater >>
Use Photoepolymerizationinitiater initiater during free-radical polymerised compound suitably can select according to active energy beam.The Photoepolymerizationinitiater initiater of ultraviolet or visible ray cracking is used when being cured by ultraviolet or visible ray.As above-mentioned Photoepolymerizationinitiater initiater, can enumerate such as: benzil, benzophenone, benzoyl phenylformic acid, 3, the benzophenone based compounds such as 3 '-dimethyl-4-methoxy benzophenone; The aromatic ketone compounds such as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2-methyl-2-hydroxypropiophenonepreparation, Alpha-hydroxy cyclohexyl-phenyl ketone; The methyl phenyl ketone based compounds such as methoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones, 2-methyl isophthalic acid-[4-(methylsulfany)-phenyl]-2-morpholino propane-1-ketone; The benzoin ether based compounds such as benzoin methylether, ethoxybenzoin, benzoin iso-propylether, benzoin butyl ether, anisoin methyl ether; The aromatic series ketal based compounds such as benzil dimethyl ketal; The aromatic sulfonyl based compounds such as 2-naphthalic sulfonic chloride; The photolytic activity oxime compounds such as 1-phenyl-1,1-propanedione-2-(O-ethoxy carbonyl) oxime; The thioxanthone based compounds such as thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketones, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone, dodecyl thioxanthone; Camphorquinone; Halogenated ketone; Acylphosphine oxide; Acyl phosphonate etc.In Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater that preferred logPow value is high.Although the composition in the calculating of the logPow value of polarizing coating curing type adhesive does not comprise Photoepolymerizationinitiater initiater, the logPow value of Photoepolymerizationinitiater initiater is preferably more than 1, is more preferably more than 2, most preferably is more than 3.
The use level of above-mentioned Photoepolymerizationinitiater initiater is below 20 weight parts relative to total amount 100 weight part of solidified nature composition (free-radical polymerised compound).The use level of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 20 weight part, more preferably 0.05 ~ 10 weight part, more preferably 0.1 ~ 5 weight part.
Time in addition to use polarizing coating curing type adhesive of the present invention containing free-radical polymerised compound as the form of the visible light curable of solidified nature composition, particularly preferably using the light of more than 380nm is highly sensitive Photoepolymerizationinitiater initiater.Describing the light of more than 380nm is later highly sensitive Photoepolymerizationinitiater initiater.
As above-mentioned Photoepolymerizationinitiater initiater, be preferably used alone the compound shown in following general formula (1)
[changing 1]
(in formula, R
1and R
2represent-H ,-CH
2cH
3,-iPr or Cl, R
1and R
2can be the same or different), or the compound shown in general formula (1) and the light to more than 380nm described later are highly sensitive Photoepolymerizationinitiater initiater and use.Use the situation of the compound shown in general formula (1) to be compared with the situation of highly sensitive Photoepolymerizationinitiater initiater with being used alone the light of more than 380nm, cementability is more excellent.In compound shown in general formula (1), particularly preferably R
1and R
2for-CH
2cH
3diethyl thioxanthone.The composition ratio of the compound shown in general formula (1) in tackiness agent is preferably 0.1 ~ 5 weight part relative to total amount 100 weight part of solidified nature composition, is more preferably 0.5 ~ 4 weight part, more preferably 0.9 ~ 3 weight part.
In addition, preferably add polymerization as required and cause auxiliary agent.Auxiliary agent is caused as polymerization, triethylamine, diethylamide, N methyldiethanol amine, thanomin, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester etc. can be enumerated, particularly preferably EDMAB.When using polymerization to cause auxiliary agent, its addition, relative to total amount 100 weight part of solidified nature composition, is generally 0 ~ 5 weight part, is preferably 0 ~ 4 weight part, most preferably is 0 ~ 3 weight part.
In addition, also can be used together known Photoepolymerizationinitiater initiater as required.Have the light of transparent protective film not transmission below the 380nm of UV receptivity, therefore preferably using the light of more than 380nm as Photoepolymerizationinitiater initiater is highly sensitive Photoepolymerizationinitiater initiater.Specifically, can enumerate: 2-methyl isophthalic acid-(4-methylsulfanylphenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide, two (2, 4, 6-trimethylbenzoyl)-phenylphosphine oxide, two (η 5-2, 4-cyclopentadiene-1-base)-bis-(2, the fluoro-3-of 6-bis-(1H-pyrroles-1-base)-phenyl) titanium etc.
Particularly as Photoepolymerizationinitiater initiater, except the Photoepolymerizationinitiater initiater of general formula (1), preferably use the compound shown in following general formula (2) further;
[changing 2]
(in formula, R
3, R
4and R
5represent-H ,-CH
3,-CH
2cH
3,-iPr or Cl, R
3, R
4and R
5can be the same or different).As the compound shown in general formula (2), 2-methyl isophthalic acid-(4-methylsulfanylphenyl)-2-morpholino propane-1-ketone (trade(brand)name: IRGACURE907 manufacturers: BASF) of commercially available product can be used as aptly.In addition, because 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1 (trade(brand)name: IRGACURE369 manufacturers: BASF), 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone (trade(brand)name: IRGACURE379 manufacturers: BASF) are highly sensitive and preferred.
< has the free-radical polymerised compound (a1) of active methylene group and has radical polymerization initiator (a2) > of dehydrogenation
In above-mentioned active energy ray curable tackiness agent, when there is free-radical polymerised compound (a1) of active methylene group as free-radical polymerised compound use, preferably combinationally use with the radical polymerization initiator (a2) with dehydrogenation.According to this formation, particularly firm taking-up rear (non-dry state) from high humidity environment or water, the cementability of the adhesive layer that polarizing coating has also significantly improves.This reason is still not clear, but thinks that reason is as follows.Namely, the free-radical polymerised compound (a1) with active methylene group is polymerized together with forming other free-radical polymerised compounds of adhesive layer, be introduced in main chain and/or the side chain of the base polymer in adhesive layer simultaneously, form adhesive layer.In this polymerization process, if there is the radical polymerization initiator (a2) with dehydrogenation, then while forming the base polymer forming adhesive layer, slough hydrogen from the free-radical polymerised compound (a2) with active methylene group, produce free radical at methylene radical.Then, create the hydroxyl reaction of the polaroid of the methylene radical and PVA etc. of free radical, between adhesive layer and polaroid, form covalent linkage.Consequently, infer particularly under non-dry state, the cementability of the adhesive layer that polarizing coating has also significantly improves.
In the present invention, as the radical polymerization initiator (a2) with dehydrogenation, such as thioxanthone system radical polymerization initiator, benzophenone series radical polymerization initiator etc. can be enumerated.Above-mentioned radical polymerization initiator (a2) is preferably thioxanthone system radical polymerization initiator.As thioxanthone system radical polymerization initiator, the such as compound shown in above-mentioned general formula (1) can be enumerated.As the concrete example of the compound shown in general formula (1), such as thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, isopropyl thioxanthone, clopenthixal ketone etc. can be enumerated.In compound shown in general formula (1), particularly preferably R
1and R
2for-CH
2cH
3diethyl thioxanthone.
In above-mentioned active energy ray curable tackiness agent, containing when there is the free-radical polymerised compound (a1) of active methylene group and there is radical polymerization initiator (a2) of dehydrogenation, when the total amount of solidified nature composition is set to 100 % by weight, preferably: containing 1 ~ 50 % by weight above-mentioned there is active methylene group free-radical polymerised compound (a1) and be the radical polymerization initiator (a2) of 0.1 ~ 10 weight part relative to total amount 100 weight part of solidified nature composition.
As mentioned above, in the present invention, under the existence of radical polymerization initiator (a2) with dehydrogenation, make the methylene radical of the free-radical polymerised compound (a1) with active methylene group produce free radical, the hydroxyl of the polaroid of described methylene radical and PVA etc. reacts and forms covalent linkage.Therefore, produce free radical to make the methylene radical of the free-radical polymerised compound (a1) with active methylene group and fully form described covalent linkage, preferably when solidified nature composition total amount is set to 100 % by weight, containing the free-radical polymerised compound (a1) with active methylene group of 1 ~ 50 % by weight, more preferably contain the free-radical polymerised compound (a1) with active methylene group of 3 ~ 30 % by weight further.Fully improve to make water tolerance and the cementability under non-dry state is improved, and preferably the free-radical polymerised compound (a1) with active methylene group being set to more than 1 % by weight.On the other hand, if more than 50 % by weight, then the solidification that adhesive layer occurs sometimes is bad.In addition, preferably contain relative to total amount 100 weight part of solidified nature composition the radical polymerization initiator (a2) that 0.1 ~ 10 weight part has dehydrogenation, more preferably there is containing 0.3 ~ 9 weight part the radical polymerization initiator (a2) of dehydrogenation further.In order to make dehydrogenation reaction fully carry out, preferably use the above radical polymerization initiator of 0.1 weight part (a2).On the other hand, if more than 10 weight parts, then sometimes can not dissolve completely in tackiness agent.
<< thermal polymerization >>
As thermal polymerization, preferably when forming adhesive layer can not due to thermo-cracking the thermal polymerization of initiated polymerization.Such as, as thermal polymerization, 10 hr half-life temperature are more than 65 DEG C, more preferably 75 ~ 90 DEG C.It should be noted that, the transformation period is the index of the decomposition rate representing polymerization starter, refers to that the residual quantity of polymerization starter is the time till half.About the half-life at the decomposition temperature for obtaining the transformation period in the arbitrary time, arbitrary temperature, on the books in manufacturers's catalogue etc., such as, in " the organo-peroxide catalogue " the 9th edition (in May, 2003) of NOF Corp " etc. on the books.
As thermal polymerization, can enumerate such as: lauroyl peroxide (10 hr half-life temperature: 64 DEG C), benzoyl peroxide (10 hr half-life temperature: 73 DEG C), 1,1-two (tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane (10 hr half-life temperature: 90 DEG C), peroxy dicarbonate two (2-ethylhexyl) ester (10 hr half-life temperature: 49 DEG C), peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxide-butyl carbonate (10 hr half-life temperature: 51 DEG C), new peroxide tert-butyl caprate (10 hr half-life temperature: 48 DEG C), the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), tert-Butyl peroxypivalate, dilauroyl peroxide (10 hr half-life temperature: 64 DEG C), the positive decoyl of peroxidation two, 1，1，3，3-tetra-methylbutyl peroxy-2-ethylhexanoate (10 hr half-life temperature: 66 DEG C), peroxidation two (4-toluyl), dibenzoyl peroxide (10 hr half-life temperature: 73 DEG C), peroxidation tert-butyl isobutyrate (10 hr half-life temperature: 81 DEG C), the organic system superoxide such as 1,1-bis-(the tertiary hexyl of peroxidation) hexanaphthene.
In addition, as thermal polymerization, can enumerate such as: 2,2 '-azobis isobutyronitrile (10 hr half-life temperature: 67 DEG C), 2, the two Azo such as (2-methylbutyronitrile) (10 hr half-life temperature: 67 DEG C), 1,1-azo bis cyclohexane-1-formonitrile HCN (10 hr half-life temperature: 87 DEG C) of 2 '-azo.
The use level of thermal polymerization is 0.01 ~ 20 weight part relative to total amount 100 weight part of solidified nature composition (free-radical polymerised compound).The use level of thermal polymerization is 0.05 ~ 10 weight part, more preferably 0.1 ~ 3 weight part further.
<2: cation polymerization curing type tackiness agent >
As the solidified nature composition of cation polymerization curing type tackiness agent, the compound with epoxy group(ing), oxetanylmethoxy can be enumerated.As long as the compound that the compound with epoxy group(ing) has at least 2 epoxy group(ing) in molecule is just not particularly limited, usually known various solidified nature epoxy compoundss can be used.As preferred epoxy compounds, can enumerate as an example: there is the compound (fragrant family epoxy compounds) of at least 2 epoxy group(ing) and at least 1 aromatic nucleus in molecule, there are at least 2 epoxy group(ing) in molecule, wherein at least 1 forming the compound (cycloaliphatic epoxy) etc. formed between 2 adjacent carbon atoms of ester ring type ring.
< light cationic polymerization initiators >
Cation polymerization curing type tackiness agent contains epoxy compounds described above and oxetane compound as solidified nature composition, and they all pass through cation polymerization curing, therefore coordinates light cationic polymerization initiators.This light cationic polymerization initiators produces positively charged ion kind or Lewis acid by the irradiation of visible ray, ultraviolet, X-ray, electron beam isoreactivity energy-ray, causes the polyreaction of epoxy group(ing), oxetanylmethoxy.
Other compositions of < >
Curing type adhesive of the present invention is preferably containing following compositions.
< acrylic oligomers (A) >
Active energy ray curable tackiness agent of the present invention, can also containing the acrylic oligomers (A) be polymerized by (methyl) acrylic monomer except the solidified nature composition of above-mentioned free-radical polymerised compound.By containing acrylic oligomers (A) in active energy ray curable tackiness agent, cure shrinkage when this tackiness agent is irradiated to active energy beam and makes it solidify can be reduced, the interfacial stress of tackiness agent and the adherend such as polaroid and transparent protective film can be reduced.Consequently, the decline of the cementability of adhesive layer and adherend can be suppressed.In order to fully suppress the cure shrinkage of solidifying nitride layer (adhesive layer), relative to total amount 100 weight part of solidified nature composition, the content of acrylic oligomers (A) is preferably below 20 weight parts, is more preferably below 15 weight parts.If the content of the acrylic oligomers in tackiness agent (A) is too much, then violent to the decline of speed of response during this tackiness agent irradiation active energy beam, sometimes cause solidification bad.On the other hand, relative to total amount 100 weight part of solidified nature composition, preferably containing acrylic oligomers (A) more than 3 weight parts, more preferably containing acrylic oligomers (A) more than 5 weight parts.
Active energy ray curable tackiness agent, when considering operability, homogeneity when being coated with, is preferably low viscosity, and therefore, the acrylic oligomers (A) of being carried out by (methyl) acrylic monomer being polymerized also is preferably low viscosity.As preventing the acrylic oligomers of the cure shrinkage of adhesive layer for low viscosity, preferable weight-average molecular weight (Mw) is less than 15000, is more preferably less than 10000, is particularly preferably less than 5000.On the other hand, in order to fully suppress the cure shrinkage of solidifying nitride layer (adhesive layer), the weight-average molecular weight (Mw) of preferred acrylic oligomers (A) is more than 500, is more preferably more than 1000, is particularly preferably more than 1500.As (methyl) acrylic monomer forming acrylic oligomers (A), specifically, can enumerate such as: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) vinylformic acid 2-methyl-2-nitro propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) t-amyl, (methyl) vinylformic acid 3-pentyl ester, (methyl) vinylformic acid 2,2-dimethyl butyl ester, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, (methyl) n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid 4-methyl-2-propyl pentyl ester, (methyl) vinylformic acid (carbonatoms 1-20) alkyl esters such as (methyl) vinylformic acid Octadecane ester, and such as (methyl) acrylate base ester (such as, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring pentyl ester etc.), (methyl) vinylformic acid aralkyl ester (such as, (methyl) benzyl acrylate etc.), polycycle (methyl) acrylate (such as, (methyl) vinylformic acid 2-isobornyl thiocyanoacetate, (methyl) vinylformic acid 2-norcamphyl methyl esters, (methyl) vinylformic acid 5-norbornylene-2-base-methyl esters, (methyl) vinylformic acid 3-methyl-2-norcamphyl methyl esters etc.), (methyl) esters of acrylic acid (such as, (methyl) Hydroxyethyl acrylate of hydroxyl, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) methacrylic acid 2,3-dihydroxypropyl methyl-butyl acrylate etc.), containing (methyl) esters of acrylic acid ((methyl) vinylformic acid 2-methoxy acrylate of alkoxyl group or phenoxy group, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-methoxymethoxy ethyl ester, (methyl) vinylformic acid 3-methoxybutyl, (methyl) acrylic acid ethyl carbitol ester, (methyl) acrylate etc.), containing (methyl) esters of acrylic acid (such as, (methyl) glycidyl acrylate etc.) of epoxy group(ing), halogen-containing (methyl) esters of acrylic acid (such as, (methyl) vinylformic acid 2,2,2-trifluoro ethyl ester, (methyl) vinylformic acid 2,2,2-trifluoroethyl ethyl ester, (methyl) vinylformic acid tetrafluoro propyl ester, (methyl) vinylformic acid hexafluoro propyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid 17 fluorine ester in the last of the ten Heavenly stems etc.), (methyl) alkyl acrylate aminoalkyl ester (such as, (methyl) dimethylaminoethyl acrylate etc.) etc.These (methyl) acrylate may be used singly or two or more in combination.As the concrete example of acrylic oligomers (A), East Asia Synesis Company can be enumerated and manufacture " ARUFON ", Soken Chemical Company manufacture " ACTFLOW ", BASF Japanese firm manufacture " JONCRYL " etc.In the acrylic oligomers (A) be polymerized by (methyl) acrylic monomer, preferred logPow value is high.Acrylic oligomers (A) is contained in the composition in the calculating of the logPow value of polarizing coating curing type adhesive.In the calculating of logPow value, the mole number of the composition of acrylic oligomers (A) adopts the mole number being scaled (methyl) acrylic monomer forming acrylic oligomers (A).The logPow value of the acrylic oligomers (A) that (methyl) acrylic monomer is polymerized preferably 2 be more than, be more preferably more than 3, most preferably be more than 4.
< light acid producing agent (B) >
Light acid producing agent (B) can be contained in above-mentioned active energy ray curable tackiness agent.Situation containing light acid producing agent in above-mentioned active energy ray curable tackiness agent, compared with the situation not containing light acid producing agent, can improve water tolerance and the weather resistance of adhesive layer tremendously.Light acid producing agent (B) can be represented by following general formula (3).
General formula (3)
[changing 3]
L
+X
-
(wherein, L
+represent arbitrary positively charged ion.In addition, X
-represent and be selected from by PF6
6 -, SbF
6 -, AsF
6 -, SbCl
6 -, BiCl
5 -, SnCl
6 -, ClO
4 -, dithiocar-bamate negatively charged ion, SCN-composition group in counter anion)
About the preferred positively charged ion L as forming general formula (3)
+cationic structure, the positively charged ion be selected from following general formula (4) ~ general formula (12) can be enumerated.
General formula (4)
[changing 4]
General formula (5)
[changing 5]
General formula (6)
[changing 6]
General formula (7)
[changing 7]
General formula (8)
[changing 8]
General formula (9)
[changing 9]
General formula (10)
[changing 10]
General formula (11)
[changing 11]
General formula (12)
[changing 12]
Ar
4-I
+-Ar
5
(in above-mentioned general formula (4)-(12), wherein, R
1, R
2and R
3represent the group be selected from hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted thiazolinyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic radical, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyl group, substituted or unsubstituted ketonic oxygen base, substituted or unsubstituted oxygen base carbonyl or halogen atom independently of one another.R
4represent and R
1, R
2and R
3the group that the group of middle record is identical.R
5represent substituted or unsubstituted alkyl, substituted or unsubstituted alkyl sulfenyl.R
6and R
7represent substituted or unsubstituted alkyl, substituted or unsubstituted alkoxyl group independently of one another.R represents halogen atom, hydroxyl, carboxyl, sulfydryl, cyano group, nitro, substituted or unsubstituted formamyl, substituted or unsubstituted alkyl, substituted or unsubstituted thiazolinyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic radical, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted heterocyclethio, substituted or unsubstituted acyl group, substituted or unsubstituted ketonic oxygen base, any one in substituted or unsubstituted oxygen base carbonyl.Ar
4, Ar
5represent in substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic radical any one.X represents oxygen or sulphur atom.I represents the integer of 0 ~ 5.J represents the integer of 0 ~ 4.K represents the integer of 0 ~ 3.In addition, can be between adjacent R, Ar
4with Ar
5, R
2with R
3, R
2with R
4, R
3with R
4, R
1with R
2, R
1with R
3, R
1with R
4, R
1with R or R
1with R
5the ring texture of mutual bonding.)
The positively charged ion (sulfonium cation) meeting general formula (4) can be enumerated:
3,5-dimethylphenyl sulfonium, dimethyl (adjacent fluorophenyl) sulfonium, dimethyl (chloro-phenyl-) sulfonium, dimethyl (to bromophenyl) sulfonium, dimethyl (to cyano-phenyl) sulfonium, dimethyl (m-nitro base) sulfonium, dimethyl (2,4,6-tribromo phenyl) sulfonium, dimethyl (pentafluorophenyl group) sulfonium, dimethyl (to (trifluoromethyl) phenyl) sulfonium, dimethyl (p-hydroxybenzene) sulfonium, dimethyl (to mercaptophenyl) sulfonium, dimethyl (to methylsulfinylphenyl) sulfonium, dimethyl (to methylsulfonyl phenyl) sulfonium, dimethyl (adjacent acetylphenyl) sulfonium, dimethyl (o-benzoyl base phenyl) sulfonium, dimethyl (p-methylphenyl) sulfonium, dimethyl (p-isopropyl phenyl) sulfonium, dimethyl (to octadecylphenyl) sulfonium, dimethyl (to cyclohexyl phenyl) sulfonium, dimethyl (p-methoxyphenyl) sulfonium, dimethyl (O-methoxy carbonyl phenyl) sulfonium, dimethyl (to phenylsulfartyl phenyl) sulfonium, (7-methoxyl group-2-oxo-2H-chromene-4-base) dimethyl sulfonium, (4-methoxynaphthalene-1-base) dimethyl sulfonium, dimethyl (to isopropoxy carbonyl phenyl) sulfonium, dimethyl (2-naphthyl) sulfonium, dimethyl (9-anthryl) sulfonium, diethyl phenyl sulfonium, methylethyl phenyl sulfonium, methyldiphenyl base sulfonium, triphenylsulfonium, diisopropyl phenyl sulfonium, phenylbenzene (4-phenylsulfartyl-phenyl)-sulfonium, 4,4 '-bis-(phenylbenzene sulfonium) diphenylsulfide, 4,4 '-bis-[two [(4-(2-Hydroxy-ethoxy)-phenyl)] sulfonium]] diphenylsulfide, 4,4 '-bis-(phenylbenzene sulfonium) sub-biphenyl, phenylbenzene (adjacent fluorophenyl) sulfonium, phenylbenzene (chloro-phenyl-) sulfonium, phenylbenzene (to bromophenyl) sulfonium, phenylbenzene (to cyano-phenyl) sulfonium, phenylbenzene (m-nitro base) sulfonium, phenylbenzene (2,4,6-tribromo phenyl) sulfonium, phenylbenzene (pentafluorophenyl group) sulfonium, phenylbenzene (to (trifluoromethyl) phenyl) sulfonium, phenylbenzene (p-hydroxybenzene) sulfonium, phenylbenzene (to mercaptophenyl) sulfonium, phenylbenzene (to methylsulfinylphenyl) sulfonium, phenylbenzene (to methylsulfonyl phenyl) sulfonium, phenylbenzene (adjacent acetylphenyl) sulfonium, phenylbenzene (o-benzoyl base phenyl) sulfonium, phenylbenzene (p-methylphenyl) sulfonium, phenylbenzene (p-isopropyl phenyl) sulfonium, phenylbenzene (to octadecylphenyl) sulfonium, phenylbenzene (to cyclohexyl phenyl) sulfonium, phenylbenzene (p-methoxyphenyl) sulfonium, phenylbenzene (O-methoxy carbonyl phenyl) sulfonium, phenylbenzene (to phenylsulfartyl phenyl) sulfonium, (7-methoxyl group-2-oxo-2H-chromene-4-base) phenylbenzene sulfonium, (4-methoxynaphthalene-1-base) phenylbenzene sulfonium, phenylbenzene (to isopropoxy carbonyl phenyl) sulfonium, phenylbenzene (2-naphthyl) sulfonium, phenylbenzene (9-anthryl) sulfonium, ethyl diphenyl sulfonium, methylethyl (o-tolyl) sulfonium, methyl two (p-methylphenyl) sulfonium, three (p-methylphenyl) sulfonium, di-isopropyl (4-phenylsulfartyl phenyl) sulfonium, phenylbenzene (2-thienyl) sulfonium, phenylbenzene (2-furyl) sulfonium, phenylbenzene (9-ethyl-9H carbazole-3-base) sulfonium etc., but be not limited thereto.
The positively charged ion (sulfoxonium positively charged ion) meeting general formula (5) can be enumerated:
3,5-dimethylphenyl sulfoxonium, dimethyl (adjacent fluorophenyl) sulfoxonium, dimethyl (chloro-phenyl-) sulfoxonium, dimethyl (to bromophenyl) sulfoxonium, dimethyl (to cyano-phenyl) sulfoxonium, dimethyl (m-nitro base) sulfoxonium, dimethyl (2,4,6-tribromo phenyl) sulfoxonium, dimethyl (pentafluorophenyl group) sulfoxonium, dimethyl (to (trifluoromethyl) phenyl) sulfoxonium, dimethyl (p-hydroxybenzene) sulfoxonium, dimethyl (to mercaptophenyl) sulfoxonium, dimethyl (to methylsulfinylphenyl) sulfoxonium, dimethyl (to methylsulfonyl phenyl) sulfoxonium, dimethyl (adjacent acetylphenyl) sulfoxonium, dimethyl (o-benzoyl base phenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-isopropyl phenyl) sulfoxonium, dimethyl (to octadecylphenyl) sulfoxonium, dimethyl (to cyclohexyl phenyl) sulfoxonium, dimethyl (p-methoxyphenyl) sulfoxonium, dimethyl (O-methoxy carbonyl phenyl) sulfoxonium, dimethyl (to phenylsulfartyl phenyl) sulfoxonium, (7-methoxyl group-2-oxo-2H-chromene-4-base) dimethyl sulfonium, (4-methoxynaphthalene-1-base) dimethyl sulfonium, dimethyl (to isopropoxy carbonyl phenyl) sulfoxonium, dimethyl (2-naphthyl) sulfoxonium, dimethyl (9-anthryl) sulfoxonium, diethyl phenyl sulfoxonium, methylethyl phenyl sulfoxonium, methyldiphenyl base sulfoxonium, triphenyl sulfoxonium, diisopropyl phenyl sulfoxonium, phenylbenzene (4-phenylsulfartyl-phenyl)-sulfoxonium, 4,4 '-bis-(phenylbenzene sulfoxonium) diphenylsulfide, 4,4 '-bis-[two [(4-(2-Hydroxy-ethoxy)-phenyl)] sulfoxonium] diphenylsulfide, 4,4 '-bis-(phenylbenzene sulfoxonium) sub-biphenyl, phenylbenzene (adjacent fluorophenyl) sulfoxonium, phenylbenzene (chloro-phenyl-) sulfoxonium, phenylbenzene (to bromophenyl) sulfoxonium, phenylbenzene (to cyano-phenyl) sulfoxonium, phenylbenzene (m-nitro base) sulfoxonium, phenylbenzene (2,4,6-tribromo phenyl) sulfoxonium, phenylbenzene (pentafluorophenyl group) sulfoxonium, phenylbenzene (to (trifluoromethyl) phenyl) sulfoxonium, phenylbenzene (p-hydroxybenzene) sulfoxonium, phenylbenzene (to mercaptophenyl) sulfoxonium, phenylbenzene (to methylsulfinylphenyl) sulfoxonium, phenylbenzene (to methylsulfonyl phenyl) sulfoxonium, phenylbenzene (adjacent acetylphenyl) sulfoxonium, phenylbenzene (o-benzoyl base phenyl) sulfoxonium, phenylbenzene (p-methylphenyl) sulfoxonium, phenylbenzene (p-isopropyl phenyl) sulfoxonium, phenylbenzene (to octadecylphenyl) sulfoxonium, phenylbenzene (to cyclohexyl phenyl) sulfoxonium, phenylbenzene (p-methoxyphenyl) sulfoxonium, phenylbenzene (O-methoxy carbonyl phenyl) sulfoxonium, phenylbenzene (to phenylsulfartyl phenyl) sulfoxonium, (7-methoxyl group-2-oxo-2H-chromene-4-base) phenylbenzene sulfoxonium, (4-methoxynaphthalene-1-base) phenylbenzene sulfoxonium, phenylbenzene (to isopropoxy carbonyl phenyl) sulfoxonium, phenylbenzene (2-naphthyl) sulfoxonium, phenylbenzene (9-anthryl) sulfoxonium, ethyl diphenyl sulfoxonium, methylethyl (o-tolyl) sulfoxonium, methyl two (p-methylphenyl) sulfoxonium, three (p-methylphenyl) sulfoxonium, di-isopropyl (4-phenylsulfartyl phenyl) sulfoxonium, phenylbenzene (2-thienyl) sulfoxonium, phenylbenzene (2-furyl) sulfoxonium, phenylbenzene (9-ethyl-9H carbazole-3-base) sulfoxonium etc., but be not limited thereto.
Meet the positively charged ion (phosphonium cation of general formula (6)) can Lie for the example of phosphonium cation:
Trimethyl Ben Ji Phosphonium, triethyl phenyl Phosphonium, tetraphenylphosphoniphenolate, triphenyl is (to fluorophenyl) Phosphonium, triphenyl (Chloro-O-Phenyl) Phosphonium, a triphenyl (bromophenyl) Phosphonium, triphenyl is (to cyano-phenyl) Phosphonium, triphenyl (m-nitro base) Phosphonium, triphenyl is (to phenylsulfartyl phenyl) Phosphonium, (7-methoxyl group-2-oxo-2H-chromene-4-base) triphenyl phosphonium, triphenyl (o-hydroxy-phenyl) Phosphonium, triphenyl (adjacent acetylphenyl) Phosphonium, triphenyl (benzoylphenyl) Phosphonium, triphenyl (p-methylphenyl) Phosphonium, triphenyl is (to isopropyl phenyl) Phosphonium, triphenyl (O-methoxy carbonyl phenyl) Phosphonium, triphenyl (1-naphthyl) Phosphonium, triphenyl (9-anthryl) Phosphonium, triphenyl (2-thienyl) Phosphonium, triphenyl (2-furyl) Phosphonium, triphenyl (9-ethyl-9H carbazole-3-base) Phosphonium etc., but be not limited thereto.
The positively charged ion (pyridylium) meeting general formula (7) can enumerate the example of pyridylium:
N-phenylpyridine, N-(Chloro-O-Phenyl) pyridine, N-(chloro-phenyl-) pyridine, N-(to cyano-phenyl) pyridine, N-(O-Nitrophenylfluorone) pyridine, N-(to acetylphenyl) pyridine, N-(p-isopropyl phenyl) pyridine, N-(to octadecyl oxygen base phenyl) pyridine, N-(to methoxycarbonyl-phenyl) pyridine, N-(9-anthryl) pyridine, 2-chloro-1-phenyl pyridine, 2-cyano group-1-phenylpyridine, 2-methyl isophthalic acid-phenylpyridine, 2-vinyl-1-phenylpyridine, 2-phenyl-1-phenylpyridine, 1, 2-phenylbenzene pyridine, 2-methoxyl group-1-phenylpyridine, 2-phenoxy group-1-phenylpyridine, 2-ethanoyl-1-(p-methylphenyl) pyridine, 2-methoxycarbonyl-1-(p-methylphenyl) pyridine, the fluoro-1-naphthlypyridine of 3-, 4-methyl isophthalic acid-(2-furyl) pyridine, N-picoline, N-ethylpyridine etc., but be not limited thereto.
The positively charged ion (quinoline positively charged ion) meeting general formula (8) can enumerate the cationic example of quinoline:
N-toluquinoline, N-ethyl quinolinium, N-phenylquinoline, N-naphthyl quinoline, N-(Chloro-O-Phenyl) quinoline, N-(chloro-phenyl-) quinoline, N-(to cyano-phenyl) quinoline, N-(O-Nitrophenylfluorone) quinoline, N-(to acetylphenyl) quinoline, N-(p-isopropyl phenyl) quinoline, N-(to octadecyl oxygen base phenyl) quinoline, N-(to methoxycarbonyl-phenyl) quinoline, N-(9-anthryl) quinoline, 2-chloro-1-phenyl quinoline, 2-cyano group-1-phenylquinoline, 2-methyl isophthalic acid-phenylquinoline, 2-vinyl-1-phenylquinoline, 2-phenyl-1-phenylquinoline, 1,2-diphenylquinoline, 2-methoxyl group-1-phenylquinoline, 2-phenoxy group-1-phenylquinoline, 2-ethanoyl-1-phenylquinoline, 2-methoxycarbonyl-1-phenylquinoline, the fluoro-1-phenylquinoline of 3-, 4-methyl isophthalic acid-phenylquinoline, 2-methoxyl group-1-(p-methylphenyl) quinoline, 2-phenoxy group-1-(2-furyl) quinoline, 2-ethanoyl-1-(2-thienyl) quinoline, 2-methoxycarbonyl-1-toluquinoline, the fluoro-1-ethyl quinolinium of 3-, 4-methyl isophthalic acid-isopropyl quinoline etc., but be not limited thereto.
The positively charged ion (isoquinoline 99.9 positively charged ion) meeting general formula (9) can enumerate the cationic example of isoquinoline 99.9:
N-phenyl isoquinolin quinoline, N-methylisoquinolinium, N-ethyl isoquinoline 99.9, N-(Chloro-O-Phenyl) isoquinoline 99.9, N-(chloro-phenyl-) isoquinoline 99.9, N-(to cyano-phenyl) isoquinoline 99.9, N-(O-Nitrophenylfluorone) isoquinoline 99.9, N-(to acetylphenyl) isoquinoline 99.9, N-(p-isopropyl phenyl) isoquinoline 99.9, N-(to octadecyl oxygen base phenyl) isoquinoline 99.9, N-(to methoxycarbonyl-phenyl) isoquinoline 99.9, N-(9-anthryl) isoquinoline 99.9, 1, 2-phenylbenzene isoquinoline 99.9, N-(2-furyl) isoquinoline 99.9, N-(2-thienyl) isoquinoline 99.9, N-naphthyl isoquinoline 99.9 etc., but be not limited thereto.
Meet positively charged ion (benzoxazole positively charged ion, the benzothiazole positively charged ion of general formula (10)) the cationic example of benzoxazole can be enumerated:
N-Jia base benzoxazole, N-ethyl benzoxazole, N-naphthyl benzoxazole, N-Ben base benzoxazole, N-is (to fluorophenyl) benzoxazole, N-(rubigan) benzoxazole, N-is (to cyano-phenyl) benzoxazole, N-(O-methoxy carbonyl phenyl) benzoxazole, N-(2-furyl) benzoxazole, N-(adjacent fluorophenyl) benzoxazole, N-is (to cyano-phenyl) benzoxazole, N-(m-nitro base) benzoxazole, N-is (to isopropoxy carbonyl phenyl) benzoxazole, N-(2-thienyl) benzoxazole, a N-(carboxyl phenyl) benzoxazole, 2-sulfydryl-3-Ben base benzoxazole, 2-methyl-3-Ben base benzoxazole, 2-methylsulfany-3-(4-phenylsulfartyl phenyl) benzoxazole, 6-hydroxyl-3-(p-methylphenyl) benzoxazole, 7-sulfydryl-3-Ben base benzoxazole, 4,5-bis-fluoro-3-ethyl benzoxazole etc., but be not limited thereto.
The cationic example of benzothiazole can be enumerated:
N-methylbenzothiazole, N-ethyl-benzothiazole, N-phenylbenzothiazol, N-(1-naphthyl) benzothiazole, N-(to fluorophenyl) benzothiazole, N-(rubigan) benzothiazole, N-(to cyano-phenyl) benzothiazole, N-(O-methoxy carbonyl phenyl) benzothiazole, N-(p-methylphenyl) benzothiazole, N-(adjacent fluorophenyl) benzothiazole, N-(m-nitro base) benzothiazole, N-(to isopropoxy carbonyl phenyl) benzothiazole, N-(2-furyl) benzothiazole, N-(4-methylsulfanylphenyl) benzothiazole, N-(4-phenylsulfartyl phenyl) benzothiazole, N-(2-naphthyl) benzothiazole, N-(carboxyl phenyl) benzothiazole, 2-sulfydryl-3-phenylbenzothiazol, 2-methyl-3-phenylbenzothiazol, 2-methylsulfany-3-phenylbenzothiazol, 6-hydroxyl-3-phenylbenzothiazol, 7-sulfydryl-3-phenylbenzothiazol, the fluoro-3-phenylbenzothiazol of 4,5-bis-etc., but be not limited thereto.
The positively charged ion (furyl or thienyl iodine positively charged ion) meeting general formula (11) can be enumerated:
Difuryl iodine, dithienyl iodine, two (4, 5-dimethyl-2-furyl) iodine, two (the chloro-2-thienyl of 5-) iodine, two (5-cyano group-2-furyl) iodine, two (5-nitro-2-thienyl) iodine, two (5-ethanoyl-2-furyl) iodine, two (5-carboxyl-2-thienyl) iodine, two (5-methoxycarbonyl-2-furyl) iodine, two (5-phenyl-2-furyl) iodine, two (5-(p-methoxyphenyl)-2-thienyl) iodine, two (5-vinyl-2-furyl) iodine, two (5-ethynyl-2-thienyl) iodine, two (5-cyclohexyl-2-furyl) iodine, two (5-hydroxyl-2-thienyl) iodine, two (5-phenoxy group-2-furyl) iodine, two (5-sulfydryl-2-thienyl) iodine, two (5-butyl sulfenyl-2-thienyl) iodine, two (5-phenylsulfartyl-2-thienyl) iodine etc., but be not limited thereto.
The positively charged ion (diaryl iodonium cation) meeting general formula (12) can be enumerated:
Phenylbenzene iodine, two (p-methylphenyl) iodine, two (to octyl phenyl) iodine, two (to octadecylphenyl) iodine, two (to octyl group oxygen base phenyl) iodine, two (to octadecyl oxygen base phenyl) iodine, phenyl (to octadecyl oxygen base phenyl) iodine, 4-sec.-propyl-4 '-methyldiphenyl base iodine, (4-isobutyl phenenyl)-p-methylphenyl iodine, two (1-naphthyl) iodine, two (4-phenylsulfartyl phenyl) iodine, phenyl (6-benzoyl-9-ethyl-9H-carbazole-3-base) iodine, (7-methoxyl group-2-oxo-2H-chromene-3-base)-4 '-isopropyl phenyl iodine etc., but be not limited thereto.
Then, the counter anion X in mutual-through type (3)
-be described.
Counter anion X-in general formula (3) is not particularly limited in principle, but preferred non-nucleophilic negatively charged ion.When counter anion X-is non-nucleophilic negatively charged ion, not easily cause the positively charged ion that coexists in molecule and the nucleophilic reaction of various materials, therefore, result can improve the light acid producing agent self shown in general formula (2), use the ageing stability of the tackiness agent of this light acid producing agent.Non-nucleophilic negatively charged ion described herein refers to the negatively charged ion causing the ability of nucleophilic reaction low.As such negatively charged ion, can enumerate: PF
6 -, SbF
6 -, AsF
6 -, SbCl
6 -, BiCl
5 -, SnCl
6 -, ClO
4 -, dithiocar-bamate negatively charged ion, SCN
-deng.
In above-mentioned Exemplary anions, as the counter anion X in general formula (3)
-, as particularly preferred counter anion, can PF be enumerated
6 -, SbF
6 -and AsF
6 -, particularly preferably can enumerate PF
6 -, SbF
6 -.
Therefore, as the concrete example of preferably salt forming light acid producing agent (B), for by the cationic structure shown in above-mentioned illustrative general formula (3) ~ general formula (12) concrete example and be selected from PF
6 -, SbF
6 -, AsF
6 -, SbCl
6 -, BiCl
5 -, SnCl
6 -, ClO
4 -, dithiocar-bamate negatively charged ion, SCN
-in negatively charged ion form salt.
Specifically, as the preferred concrete example of light acid producing agent (B), can enumerate " CyracureUVI-6992 ", " CyracureUVI-6974 " (more than, DOW Chemical Japanese firm system), " AdekaoptomerSP150 ", " AdekaoptomerSP152 ", " AdekaoptomerSP170 ", " AdekaoptomerSP172 " (more than, Asahi Denka Co., Ltd.'s system), " IRGACURE250 " (Ciba Specialty Chemicals's system), " CI-5102 ", " CI-2855 " (more than, Japanese Cao Da Inc.), " San-aidSI-60L ", " San-aidSI-80L ", " San-aidSI-100L ", " San-aidSI-110L ", " San-aidSI-180L " (more than, three new chemical company systems), " CPI-100P ", " CPI-100A " (more than, San-Apro Co., Ltd. system), " WPI-069 ", " WPI-113 ", " WPI-116 ", " WPI-041 ", " WPI-044 ", " WPI-054 ", " WPI-055 ", " WPAG-281 ", " WPAG-567 ", " WPAG-596 " (more than, and Guang Chun medicine Inc.).
The content of light acid producing agent (B) is below 10 weight parts relative to total amount 100 weight part of solidified nature composition, is preferably 0.01 ~ 10 weight part, is more preferably 0.05 ~ 5 weight part, is particularly preferably 0.1 ~ 3 weight part.
< comprises the compound of any one (C) > in alkoxyl group, epoxy group(ing)
In above-mentioned active energy ray curable tackiness agent, can containing the compound of any one (C) comprised in alkoxyl group, epoxy group(ing).Such as, in the relation of the hydroxyl with PVA system polaroid, compound (C1) containing alkoxyl group carries out the condensation reaction of alkoxyl group and hydroxyl, compound (C2) containing epoxy group(ing) carries out the addition reaction of epoxy group(ing) and hydroxyl, can give more firmly cementability to active energy ray curable tackiness agent.When using compound (C2) containing epoxy group(ing), by the addition reaction of epoxy group(ing) and hydroxyl, generate secondary hydroxyl after the reaction, there is the possibility making volume water absorption rate of the present invention increase, therefore more preferably use the compound (C1) with alkoxyl group.Namely; utilize containing light acid producing agent (B) and have alkoxyl group compound (C1) active energy ray curable tackiness agent by polaroid and transparent protective film stacked; irradiate active energy beam; acid is produced thus by light acid producing agent (B); by this acid; the alkoxyl group of compound (C1) and the hydroxyl of polaroid with alkoxyl group carry out condensation reaction, show the good cementability of polaroid and transparent protective film.In addition, form the lower adhesive layer of water-intake rate by the condensation reaction between the compound (C1) with alkoxyl group, can meet hot and humid under harshness environment under optical durability.
In above-mentioned active energy ray curable tackiness agent, comprise the compound (C) of any one in alkoxyl group, epoxy group(ing) and can be used alone a kind, also can combinationally use multiple.In addition, the compound (C) comprising in alkoxyl group, epoxy group(ing) any one also can by the compound (C1) containing alkoxyl group and the compound (C2) containing epoxy group(ing) and with using.In addition, to comprise in alkoxyl group, epoxy group(ing) any one compound (C) can with light acid producing agent (B) and with also can not and be used for using, but from the viewpoint of promoting the reaction of the hydroxyl of PVA system polaroid and alkoxyl group, epoxy group(ing), the compound (C) that to comprise in alkoxyl group, epoxy group(ing) any one is preferably used with light acid producing agent (B).
(there is the compound (C1) of alkoxyl group)
As the compound (C1) in molecule with alkoxyl group, as long as the alkoxyl group in molecule with more than 1 is just not particularly limited, the known compound with alkoxyl group can be used.Can enumerate such as: there is general formula :-(CH
2)
n(in formula, n is the integer of 1 ~ 3 to-O-R, and R represents alkyl or the H of carbonatoms 1 ~ 4.R in above-mentioned formula is preferably methyl.) shown in the compound of alkoxyl group alternatively base.Specifically, can enumerate such as: (methyl) alkoxyalkyl acrylate, alkoxyalkyl (methyl) acrylamide etc. are containing melamine compound, aminoresin and the silane coupling agent such as free-radical polymerised compound, melamine methylol, alkoxymethylated melamine of alkoxyl group.As the concrete example of the free-radical polymerised compound containing alkoxyl group, can enumerate: ワ ス マ ー 2MA, the ワ ス マ ー 3MA, ワ ス マ ー IBM, N-isobutoxymethyl acrylamide, ワ ス マ ー EMA, N-MAM-PC, MM90, ワ ス マ ー A etc. of Li Yexingchan Inc..As the concrete example of melamine compound, M-3, MK, M-6, M-100, MC etc. of the Sumitexresin series of sumitomo chemical company, NikalacMW-30, MW-100LM, MX-750LM, MX-280, MX-270 etc. of chemical company of Sanwa Co., Ltd. can be illustrated.Consider from reactive viewpoint in them, preferably use ワ ス マ ー 2MA, N-MAM-PC, MX-750LM etc.It should be noted that, when calculating the glass transition temperature Tg of adhesive layer, being not counted in the compound and polymer (C1) with alkoxyl group in the calculation.
(there is the compound (C2) of epoxy group(ing))
As the compound (C2) with epoxy group(ing), the compound with more than 1 epoxy group(ing) or the polymer in molecule with more than 2 epoxy group(ing) (epoxy resin) can be used in molecule.When using polymer (epoxy resin), can be used together and there is the compound that more than 2 and epoxy group(ing) have reactive functional group in molecule.Herein, there is reactive functional group can enumerate such as with epoxy group(ing): carboxyl, phenolic hydroxyl group, sulfydryl, uncle or secondary aromatic series are amino.Consider 3 dimension solidified nature, particularly preferably in having more than 2 these functional groups in a part.
As the polymer of epoxy group(ing) in molecule with more than 1, such as epoxy resin can be enumerated, have: by the bisphenol A type epoxy resin of dihydroxyphenyl propane and epichlorohydrin derived, by the bisphenol f type epoxy resin of Bisphenol F and epichlorohydrin derived, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, Bisphenol F novolac type epoxy resin, alicyclic epoxy resin, phenylbenzene ether type epoxy, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorenes type epoxy resin, trifunctional type epoxy resin, the multifunctional type epoxy resin such as four functional-type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycolylurea type epoxy resin, isocyanuric acid ester type epoxy resin, aliphatics chain epoxy resin etc., these epoxy resin can carry out halogenation, also hydrogenation can be carried out.As commercially available epoxy resin product, can enumerate such as: the JERCoat (コ ー ト that japan epoxy resin Co., Ltd. manufactures) 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, the Epiclon830 that Dainippon Ink Chemicals manufactures, EXA835LV, HP4032D, HP820, the EP4100 series that Asahi Denka Co., Ltd. manufactures, EP4000 series, EPU series, the Celloxide series (2021 that Daicel KCC manufactures, 2021P, 2083, 2085, 3000 etc.), Epolead series, EHPE series, the YD series that chemical company of Nippon Steel manufactures, YDF series, YDCN series, YDB series, phenoxy resin (the Polyhydroxypolyether synthesized by bisphenols and Epicholorohydrin, at two ends, there is epoxy group(ing), YP series etc.), long rapidsly change into Denacol series that company manufactures, Epolight series etc. that chemical company of common prosperity society manufactures, but to be not limited thereto.These epoxy resin can be used together two or more.It should be noted that, when calculating the glass transition temperature Tg of adhesive layer, being not counted in the compound (C2) with epoxy group(ing) in the calculation.
The use level comprising the compound (C) of any one in alkoxyl group, epoxy group(ing) is generally below 30 weight parts relative to total amount 100 weight part of solidified nature composition, if the content of the above-claimed cpd (C) in active energy ray curable tackiness agent is too much, then cementability declines, worsens the shock-resistance of shatter test sometimes.The content of the above-claimed cpd (C) in active energy ray curable tackiness agent is more preferably below 20 weight parts.On the other hand, from the viewpoint of water tolerance, in active energy ray curable tackiness agent, preferably containing above-claimed cpds (C) more than 2 weight parts, more preferably containing above-claimed cpds (C) more than 5 weight parts
< isocyanate compound (D) >
Active energy ray curable tackiness agent of the present invention can contain isocyanate compound (D).Isocyanate compound (D) is the compound in the molecule with at least 1 isocyanate group.When active energy ray curable tackiness agent contains isocyanate compound (D), interacted by the hydroxyl on polaroid surface and isocyanate group, more firmly cementability, water tolerance can be given to polarizing coating.In addition, when active energy ray curable tackiness agent contains (methyl) acrylamide derivative containing N-hydroxyalkyl as free-radical polymerised compound, if contain the many containing quantitative change of (methyl) acrylamide derivative of N-hydroxyalkyl, the tendency that volume water-intake rate uprises then is there is owing to comprising hydroxyl in adhesive layer, as a result, there is the tendency that the optical durability under harsh humidified ambient declines.By will (methyl) acrylamide derivative of N-hydroxyalkyl be contained and there is the compound of isocyanate group and use, be helpless to form amino-formate bond with the bonding hydroxyl of polaroid and isocyanate group, can while maintenance cementability, volume water absorption rate declined.
As isocyanate compound (D), can enumerate: polyfunctional isocyanate compound, active energy ray curable isocyanate compound etc.As polyfunctional isocyanate compound, can enumerate such as: the lower aliphatic polyisocyanates such as ethylene vulcabond, tetramethylene vulcabond, 1,6-hexamethylene diisocyanate; The alicyclic polyisocyanates classes such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; The aromatic polyisocyanate classes etc. such as 2,4 toluene diisocyanate, 2,6-tolylene diisocyanates, 4,4'-diphenylmethanediisocyanates, Xylene Diisocyanate.As above-mentioned isocyanate compound (D), also can enumerate such as: TriMethylolPropane(TMP)/tolylene diisocyanate affixture [Nippon Polyurethane Industry Co., Ltd.'s system, trade(brand)name " CoronateL "], TriMethylolPropane(TMP)/hexamethylene diisocyanate affixture [Nippon Polyurethane Industry Co., Ltd.'s system, trade(brand)name " CoronateHL "], trade(brand)name " CoronateHX " (Nippon Polyurethane Industry Co., Ltd.), TriMethylolPropane(TMP)/Xylene Diisocyanate affixture [Mitsui Chemicals, Inc's system, trade(brand)name " Takenate110N "] etc. commercially available product.As active energy ray curable isocyanate compound (D); can enumerate: the isocyanates with (methyl) acryl, can enumerate such as: the commercially available products such as KarenzAOI (Showa Denko K. K's system), KarenzBEI (Showa Denko K. K's system), LaromerLR9000 (BASF AG's system).
The use level of isocyanate compound (D) is generally below 30 weight parts relative to total amount 100 weight part of solidified nature composition, if the content of the above-claimed cpd (D) in active energy ray curable tackiness agent group is too much, then cementability declines, worsens the shock-resistance of shatter test sometimes.The content of the above-claimed cpd (D) in active energy ray curable tackiness agent is more preferably below 20 weight parts.On the other hand, from the viewpoint of water tolerance, in active energy ray curable tackiness agent, preferably containing above-claimed cpd (D) more than 0.1 weight part, more preferably containing above-claimed cpd (D) more than 1 weight part.
< silane coupling agent (E) >
When polarizing coating curing type adhesive of the present invention is active energy ray-curable curing, silane coupling agent (E) preferably uses the compound of active energy ray-curable, even if but be not that active energy ray-curable also can give same water tolerance.
As the concrete example of silane coupling agent (E), as the compound of active energy ray-curable, can enumerate: vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-(3, 4 epoxycyclohexyls) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxyl silane, to styryl Trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane etc.
Be preferably 3-methacryloxypropyl trimethoxy silane, 3-acryloxypropyl Trimethoxy silane.
As the concrete example of the silane coupling agent of nonactive energy ray-curable, preferably there is amino silane coupling agent (E1).As the concrete example with amino silane coupling agent (E1), can enumerate: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, gamma-amino propyl group three isopropoxy silane, gamma-amino hydroxypropyl methyl dimethoxysilane, gamma-amino hydroxypropyl methyl diethoxy silane, γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) amino propyl methyl dimethoxysilane, γ-(2-amino-ethyl) aminopropyltriethoxywerene werene, γ-(2-amino-ethyl) amino propyl methyl diethoxy silane, γ-(2-amino-ethyl) aminopropyl three isopropoxy silane, γ-(2-(2-amino-ethyl) amino-ethyl) TSL 8330, γ-(6-Aminohexyl) TSL 8330, 3-(N-ethylamino)-2-trimethoxysilyl propyl methacrylate TMOS, γ-urea propyl trimethoxy silicane, γ-urea propyl-triethoxysilicane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-benzyl-gamma-amino propyl trimethoxy silicane, N-vinyl benzyl-γ aminopropyltriethoxy silane, N-Cyclohexylaminomethyl triethoxyl silane, N-Cyclohexylaminomethyl diethoxymethylsilane, N-phenvlaminomethvl Trimethoxy silane, (2-amino-ethyl) amino methyl Trimethoxy silane, N, N '-bis-[3-(trimethoxysilyl) propyl group] quadrol etc. is containing amino silicane, the ketoimine type silicane such as N-(1,3-dimethyl butyrate fork base)-3-(triethoxysilyl)-1-propylamine.
There is amino silane coupling agent (E1) and can only use a kind, also can combinationally use multiple.Wherein, in order to ensure good cementability, preferred gamma-amino propyl trimethoxy silicane, γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) amino propyl methyl dimethoxysilane, γ-(2-amino-ethyl) aminopropyltriethoxywerene werene, γ-(2-amino-ethyl) amino propyl methyl diethoxy silane, N-(1,3-dimethyl butyrate fork base)-3-(triethoxysilyl)-1-propylamine.
The use level of silane coupling agent (E) is preferably the scope of 0.01 ~ 20 weight part relative to total amount 100 weight part of solidified nature composition, be more preferably 0.05 ~ 15 weight part, more preferably 0.1 ~ 10 weight part.This is because during more than 20 weight part, the storage stability of tackiness agent worsens, in addition, lower than the effect that cannot give full play to water-fast cementability during 0.1 weight part.It should be noted that, when calculating the glass transition temperature Tg of adhesive layer, be not counted in silane coupling agent (E) in the calculation.
As other than the above be not the concrete example of the silane coupling agent of active energy ray-curable, can enumerate: 3-urea propyl-triethoxysilicane, 3-r-chloropropyl trimethoxyl silane, 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi Trimethoxy silane, two (triethoxysilylpropyltetrasulfide) four thioether, 3-isocyanic ester propyl-triethoxysilicane, imidizole silane etc.
About above-mentioned light acid producing agent (B), the compound of any one (C) comprised in alkoxyl group, epoxy group(ing), isocyanate compound (D), silane coupling agent (E), the logPow value of each composition is preferably more than 1, is more preferably more than 2.It should be noted that, the composition in the calculating of the logPow value of polarizing coating curing type adhesive does not comprise light acid producing agent (B), silane coupling agent (E).On the other hand, the composition in the calculating of the logPow value of polarizing coating curing type adhesive comprises the compound of any one (C) comprised in alkoxyl group, epoxy group(ing), isocyanate compound (D).
< additive > other than the above
In addition, in polarizing coating curing type adhesive of the present invention, in the scope not damaging object of the present invention, effect, various additive can be coordinated as other any compositions.As this additive, can enumerate: polymkeric substance or the oligopolymer such as polymeric amide, polyamidoimide, urethane, polyhutadiene, sovprene, polyethers, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, celluosic resin, fluorine system oligopolymer, silicone-based oligopolymer, polythioether system oligopolymer; The stopper such as thiodiphenylamine, 2,6 di tert butyl 4 methyl phenol; Polymerization causes auxiliary agent; Flow agent; Wettability modifying agent; Tensio-active agent; Softening agent; UV light absorber; Inorganic filler; Pigment; Dyestuff etc.In various additive, preferred logPow value is high.The logPow value of various additive is preferably more than 2, is more preferably more than 3, most preferably is more than 4.It should be noted that, the composition in the calculating of the logPow value of polarizing coating curing type adhesive does not comprise these additives.
Above-mentioned additive is generally 0 ~ 10 weight part relative to total amount 100 weight part of solidified nature composition, is preferably 0 ~ 5 weight part, most preferably is 0 ~ 3 weight part.
The viscosity > of < tackiness agent
Polarizing coating curing type adhesive of the present invention contains above-mentioned solidified nature composition, and from the viewpoint of screening characteristics, the viscosity of this tackiness agent is preferably below 100cp 25 DEG C time.On the other hand, polarizing coating curing type adhesive of the present invention when 25 DEG C time more than 100cp, also can be adjusted to below 100cp in the temperature of coating time control preparing adhesive.More preferably the scope of viscosity is 1 ~ 80cp, most preferably is 10 ~ 50cp.The E type viscometer TVE22LT of Dong Ji industry companies can be used to measure viscosity.
In addition, from the viewpoint of security, polarizing coating curing type adhesive of the present invention preferably uses the little material of skin irritation as above-mentioned solidified nature composition.Skin irritation can be judged by the index of P.I.I.As representing that the index of skin irritant degree widely uses P.I.I, it is measured by Draize method.With the Range Representation measured value of 0 ~ 8, be worth and littlely then judge that pungency is lower, because the error of measured value is large, be therefore understood as reference value.P.I.I is preferably less than 4, is more preferably less than 3, most preferably is less than 2.
< polarizing coating >
With regard to polarizing coating of the present invention, to fit transparent protective film across the adhesive layer that the solidification nitride layer by above-mentioned polarizing coating curing type adhesive is formed at least one side of polaroid.Adhesive layer as above-mentioned solidification nitride layer is described above, and volume water absorption rate is less than 10 % by weight.
< adhesive layer >
It is preferably 0.1 ~ 3 μm by the gauge control of the adhesive layer formed by above-mentioned curing type adhesive.The thickness of adhesive layer is more preferably 0.3 ~ 2 μm, more preferably 0.5 ~ 1.5 μm.Produce in bad order (bubble) suppressing the generation of poor attachment by the cohesive force of adhesive layer, when suppressing at lamination, preferably the thickness of adhesive layer is set to more than 0.1 μm.On the other hand, if adhesive layer is thicker than 3 μm, then may cannot meet weather resistance by polarizing coating.
In addition, curing type adhesive is preferably the way selection of more than 60 DEG C with the Tg of the adhesive layer formed thus, more preferably more than 70 DEG C, more preferably more than 75 DEG C, more preferably more than 100 DEG C, more preferably more than 120 DEG C.On the other hand, if the Tg of adhesive layer is too high, the bendability of polarizing coating declines, therefore preferably: the Tg of adhesive layer is set to less than 300 DEG C, is set to less than 240 DEG C further, is set to less than 180 DEG C further.TAinstruments Measurement of Dynamic Viscoelasticity device RSAIII is used to measure Tg< second-order transition temperature > according to following condition determination.
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Mode determination: stretch, frequency: 1Hz, heat-up rate: 5 DEG C/min
Carry out the mensuration of dynamic viscoelastic, the temperature Tg as the summit of tan δ adopts.
In addition, with regard to curing type adhesive, the region of storage elastic modulus below 70 DEG C of the adhesive layer formed thus is preferably 1.0 × 10
6more than Pa.Be more preferably 1.0 × 10 further
7more than Pa.The storage elastic modulus of adhesive layer breaks to the polaroid when applying thermal cycling (-40 DEG C ~ 80 DEG C etc.) to polarizing coating and has an impact, and when storage elastic modulus is low, the unfavorable condition that polaroid breaks easily occurs.There is the temperature province more preferably less than 80 DEG C of high storage elastic modulus, most preferably less than 90 DEG C.TAinstruments Measurement of Dynamic Viscoelasticity device RSAIII is side by side used to measure storage elastic modulus at same condition determination with the mensuration of Tg< second-order transition temperature >.Carry out the mensuration of dynamic viscoelastic, adopt the value of storage elastic modulus (E ' ').
Polarizing coating of the present invention has following operation: the face that will form adhesive layer of polaroid and/or transparent protective film to form the face coating curing type tackiness agent of adhesive layer after, make the operation of polaroid and transparent protective film laminating, then curing type adhesive be solidified to form the operation of adhesive layer.
With regard to polaroid, transparent protective film, before the above-mentioned curing type adhesive of coating, surface modification treatment can be carried out.As concrete process, the process etc. based on corona treatment, Cement Composite Treated by Plasma, saponification process can be enumerated.
The application pattern of curing type adhesive is suitably selected according to the viscosity of this curing type adhesive, target thickness.As the example of application pattern, can enumerate such as: reversion coating machine, gravure coater (directly, reversion or hectograph), scraper reversion coating machine, roller coating machine, mould are coated with machine, metering bar coater, rod coater etc.In addition, suitably the modes such as impregnation method can be used in coating.
Utilize the curing type adhesive as above applied, make polaroid and transparent protective film laminating.Layer of rolls press etc. can be utilized to carry out the laminating of polaroid and transparent protective film.
The solidification > of < tackiness agent
Polarizing coating curing type adhesive of the present invention uses with the form of active energy ray curable tackiness agent or thermohardening type tackiness agent.With regard to active energy ray curable tackiness agent, can use with the form of electronic beam solidified, ultraviolet hardening, visible light curable.From the viewpoint of productivity, compared with thermohardening type tackiness agent, the preferred active energy ray curable tackiness agent of form of above-mentioned curing type adhesive, is further used as active energy ray curable tackiness agent, from the viewpoint of the preferred Visible light curable adhesives of productivity.
<< active energy ray curable >>
With regard to active energy ray curable tackiness agent, after making polaroid and transparent protective film laminating, irradiate active energy beam (electron beam, ultraviolet, visible ray etc.), active energy ray curable adhesive solidification is formed adhesive layer.With regard to the direction of illumination of active energy beam (electron beam, ultraviolet, visible ray etc.), can irradiate from direction suitable arbitrarily.Preferably irradiate from transparent protective film side.If irradiate from polaroid side, then polaroid is deteriorated because of active energy beam (electron beam, ultraviolet, visible ray etc.) sometimes.
The electronic beam solidified >> of <<
In electronic beam solidified, about the illuminate condition of electron beam, as long as the condition of above-mentioned active energy ray curable adhesive solidification can be made, just arbitrary felicity condition can be adopted.Such as, in electron beam irradiation, acceleration voltage is preferably 5kV ~ 300kV, more preferably 10kV ~ 250kV.When acceleration voltage is lower than 5kV, electron beam can not arrive tackiness agent, may solidify deficiency, and when acceleration voltage is more than 300kV, the seepage force passed through from sample is excessively strong, may bring damage to transparent protective film, polaroid.As irradiation dose, be 5 ~ 100kGy, more preferably 10 ~ 75kGy.When irradiation dose is lower than 5kGy, tackiness agent can solidify deficiency, during more than 100kGy, brings damage to transparent protective film, polaroid, produces the reduction of physical strength, xanthochromia, cannot obtain the optical characteristics specified.
In electron beam irradiation, usually irradiate in inactive gas, but if desired then also can carry out in an atmosphere or under the condition being imported with a small amount of oxygen.Although depend on the material of transparent protective film, by suitably importing oxygen, and first producing oxygen obstruction at the transparency protected face of irradiating electron beam, the damage to transparent protective film can be prevented, can only to tackiness agent irradiating electron beam effectively.
<< ultraviolet hardening, visible light curable >>
In the manufacture method of polarizing coating of the present invention, preferred use comprises the active energy beam of the visible ray of wavelength region 380nm ~ 450nm as active energy beam, particularly preferably uses the active energy beam that the irradiation dose of the visible ray of wavelength region 380nm ~ 450nm is maximum as active energy beam.In ultraviolet hardening, visible light curable; when use imparts transparent protective film (ultraviolet is the transmission-type transparent protective film not) of ultraviolet absorption ability; absorb the light being shorter than the short wavelength of about 380nm; therefore; the light that wavelength is shorter than 380nm can not arrive active energy ray curable tackiness agent, does not therefore contribute its polyreaction.In addition, the light that the wavelength absorbed by transparent protective film is shorter than 380nm changes heat into, makes transparent protective film self-heating, causes curling, fold of polarizing coating etc. bad.Therefore, in the present invention, when adopting ultraviolet hardening, visible light curable, as active energy beam generation device, preferred use does not send the device that wavelength is shorter than the light of 380nm, more specifically, the accumulated illumination of wavelength region 380 ~ 440nm is preferably 100:0 ~ 100:50 with the ratio of the accumulated illumination of wavelength region 250 ~ 370nm, is more preferably 100:0 ~ 100:40.As active energy beam of the present invention, preferably enclose the metal halide lamp of gallium, send the LED light source of the light of wavelength region 380 ~ 440nm.Or, also low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, incandescent light, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, luminescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight etc. can be used to comprise the light source of ultraviolet and visible ray, bandpass filter also can be used to block the ultraviolet that wavelength is shorter than 380nm.In order to improve the adhesiveproperties of the adhesive layer between polaroid and transparent protective film and prevent the curling of polarizing coating, preferably use the metal halide lamp enclosing gallium and utilize the active energy beam that can block the active energy beam that bandpass filter that wavelength is shorter than the light of 380nm obtains or the wavelength 405nm using LED light source to obtain.
For ultraviolet hardening or visible light curable, preferably before irradiation ultraviolet radiation or visible ray, active energy ray curable tackiness agent is heated (pre-irradiation heating), now, be preferably heated to more than 40 DEG C, be more preferably heated to more than 50 DEG C.In addition, also preferably after irradiation ultraviolet radiation or visible ray, active energy ray curable tackiness agent to be heated (irradiation post-heating), now, be preferably heated to more than 40 DEG C, be more preferably heated to more than 50 DEG C.
Active energy ray curable tackiness agent of the present invention can use particularly preferably in when forming the bonding adhesive layer of the transparent protective film that polaroid and the transmittance of wavelength 365nm is less than 5%.Herein, active energy ray curable tackiness agent of the present invention contains the Photoepolymerizationinitiater initiater of above-mentioned general formula (1), thereby, it is possible to solidify to form adhesive layer across the transparent protective film irradiation ultraviolet radiation with UV receptivity.Therefore, even if for the polarizing coating that the two sides at polaroid is laminated with the transparent protective film with UV receptivity, adhesive layer also can be made to solidify.But, for being laminated with the polarizing coating of the transparent protective film without UV receptivity, adhesive layer can certainly be made to solidify.It should be noted that, the transparent protective film with UV receptivity refers to the transparent protective film transmissivity of the light of 380nm being less than to 10%.
As the method for transparent protective film being given to UV receptivity, can enumerate: in transparent protective film, contain the method for UV light absorber, in the stacked method containing the surface-treated layer of UV light absorber in transparent protective film surface.
As the concrete example of UV light absorber, can enumerate such as: existing known oxygen base benzophenone based compound, benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex based compound, triazine based compound etc.
After polaroid and transparent protective film are fitted, irradiate active energy beam (electron beam, ultraviolet, visible ray etc.), make active energy ray curable adhesive solidification and form adhesive layer.About the direction of illumination of active energy beam (electron beam, ultraviolet, visible ray etc.), can irradiate from arbitrary suitably direction.Preferably irradiate from transparent protective film side.When irradiating from polaroid side, may there is deterioration in polaroid due to active energy beam (electron beam, ultraviolet, visible ray etc.).
<< thermohardening type >>
On the other hand, thermohardening type tackiness agent, after making polaroid and transparent protective film laminating, by heating, utilizes thermal polymerization initiated polymerization, forms solidification nitride layer.Heating temperature sets according to thermal polymerization, but is preferably about 60 ~ 200 DEG C, is preferably 80 ~ 150 DEG C.
When utilizing tinuous production to manufacture polarizing coating of the present invention, linear velocity depends on the set time of tackiness agent, but is preferably 1 ~ 500m/min, is more preferably 5 ~ 300m/min, more preferably 10 ~ 100m/min.When linear velocity is too small, undercapacity, or excessive to the damage of transparent protective film, the polarizing coating that can tolerate endurance test etc. cannot be made.When linear velocity is excessive, the solidification of tackiness agent becomes insufficient, sometimes cannot obtain target cementability.
It should be noted that; in polarizing coating of the present invention; polaroid and transparent protective film are fitted by utilizing the adhesive layer that formed by the solidification nitride layer of above-mentioned active energy ray curable tackiness agent, but can arrange easy adhesive linkage between transparent protective film and adhesive layer.Easy adhesive linkage can utilize the various resin formation such as with polyester backbone, polyether skeleton, polycarbonate backbone, polyurethane skeleton, silicone-based, polyamide backbone, polyimide backbone, polyvinyl alcohol skeleton etc.These fluoropolymer resins can be used alone one or combinationally use two or more.In addition, other additives can be added in the formation of easy adhesive linkage.Specifically, the stablizers etc. such as tackifier, UV light absorber, antioxidant, heat-resisting stabilizing agent can also be used.
Easy adhesive linkage is pre-set at transparent protective film usually, utilizes adhesive layer to fit the easy adhesive linkage side of this transparent protective film and polaroid.The formation of easy adhesive linkage is undertaken by the formation material being dried utilizing known technology be coated with easy adhesive linkage on transparent protective film.The formation material of easy adhesive linkage usually consider dried thickness, coating fairness etc. and regulate with the form of the solution being diluted to proper concn.The dried thickness of easy adhesive linkage is preferably 0.01 ~ 5 μm, more preferably 0.02 ~ 2 μm, more preferably 0.05 ~ 1 μm.It should be noted that, easy adhesive linkage can arrange multilayer, but in this case, also preferably easily the total thickness of adhesive linkage is above-mentioned scope.
< polaroid >
Polaroid is not particularly limited, and can use various polaroid.As polaroid, can enumerate and such as adsorb the dichroic material such as iodine, dichroic dye and the polyene system alignment films etc. such as the desalination acid treatment thing of the processed thing of the film carrying out uniaxial extension and obtain, polyvinyl alcohol, polyvinyl chloride at hydrophilic macromolecule films such as polyvinyl alcohol mesentery, part formolation polyvinyl alcohol mesentery, the partly-hydrolysed films of vinyl-vinyl acetate copolymer system.In them, preferably comprise the polaroid of the dichroic substance such as polyvinyl alcohol mesentery and iodine.The thickness of these polaroids is not particularly limited, and is generally less than about 80 μm.
By polyvinyl alcohol mesentery iodine staining and the polaroid carrying out uniaxial extension and obtain such as can by dyeing in the aqueous solution that polyvinyl alcohol is impregnated into iodine, 3 ~ 7 times that are stretched to former length make.Also the aqueous solution of boric acid, potassiumiodide etc. can be impregnated into as required.In addition, before dyeing, polyvinyl alcohol mesentery can also be impregnated in water as required and wash.By washing polyvinyl alcohol mesentery, the dirt on polyvinyl alcohol mesentery surface, antiseized agent can being cleaned, in addition, also there is the unequal uneven effect preventing from by making polyvinyl alcohol mesentery swelling dyeing.Stretching can be carried out after with iodine staining, also can stretch while dyeing, in addition, can also dye with iodine after the stretch.Also can in the aqueous solution of boric acid, potassiumiodide etc., stretch in water-bath.
In addition curing type adhesive of the present invention use thickness be the slim polaroid of less than 10 μm as polaroid time, can significantly show its effect (meet hot and humid under harshness environment in optical durability).Above-mentioned thickness is that the impact of moisture is relatively large compared with polaroid and the thickness of less than the 10 μm polaroid more than 10 μm, and in the environment under hot and humid, optical durability is insufficient, easily causes that transmissivity rises, degree of polarization declines.Namely, be that the adhesive layer of less than 10 % by weight is by time stacked for the polaroid of above-mentioned less than 10 μm by volume water absorption rate of the present invention, by suppress harsh hot and humid under environment in water to the movement of polaroid, significantly can suppress that the transmissivity of polarizing coating rises, the deterioration of degradation optical durability under degree of polarization.From the viewpoint of slimming, the thickness of polaroid is preferably 1 ~ 7 μm.The uneven thickness of slim polaroid is like this few, and observation property is excellent, and dimensional change is few, and also can realize slimming as the thickness of polarizing coating, in these areas preferably.
As slim polaroid, can enumerate typically: the slim polarizing coating recorded in the specification sheets of Japanese Laid-Open Patent Publication 51-069644 publication, Japanese Unexamined Patent Publication 2000-338329 publication, WO2010/100917 brochure, PCT/JP2010/001460 or Japanese Patent Application 2010-269002 specification sheets, Japanese Patent Application 2010-263692 specification sheets.These slim polarizing coatings can be obtained with the method for making of carrying out the operation dyeed by the operation comprised polyvinyl alcohol resin (hereinafter also referred to PVA system resin) layer and stretching resin base material carry out stretching in the state of duplexer.If this method for making, even if then PVA resin is thinner, also can by by stretching resin base material support and when can not due to stretch produce fracture etc. bad stretch.
As above-mentioned slim polarizing coating, carry out in the state being included in duplexer the operation that stretches and carry out in the method for making of the operation dyeed, polarization property is improved from the viewpoint of high magnification can be stretched to, preferably by WO2010/100917 brochure, the specification sheets of PCT/JP2010/001460, or Japanese Patent Application 2010-269002 specification sheets, the method for making of carrying out the operation stretched in boric acid aqueous solution that is included in recorded in Japanese Patent Application 2010-263692 specification sheets obtains, particularly preferably by Japanese Patent Application 2010-269002 specification sheets, the method for making of auxiliarily carrying out the aerial operation stretched before being included in of recording in Japanese Patent Application 2010-263692 specification sheets stretches in boric acid aqueous solution obtains.
The slim high function polarizing coating recorded in the specification sheets of above-mentioned PCT/JP2010/001460 be integrated film forming in resin base material, comprise and make dichroic substance carry out the PVA system resin of orientation and thickness is the slim high function polarizing coating of less than 7 μm, there is monomer transmissivity and be more than 42.0% and degree of polarization is the optical characteristics of more than 99.95%.
Above-mentioned slim high function polarizing coating can manufacture by the following method: be coated with PVA system resin at the resin base material of the thickness with at least 20 μm and make it dry, generate PVA resin thus, the PVA resin of generation is impregnated in the staining fluid of dichroic substance, dichroic substance is made to be adsorbed in PVA resin, the PVA resin having adsorbed dichroic substance is stretched integratedly with resin base material in boric acid aqueous solution, makes total stretching ratio reach more than 5 times of former length.
In addition, comprising in manufacture makes dichroic substance carry out in the method for the laminate film of the slim high function polarizing coating of orientation, by comprising following operation, above-mentioned slim high function polarizing coating can be manufactured, described operation is: generate laminate film, and described laminate film comprises the resin base material of the thickness with at least 20 μm and makes it dry and the PVA resin of formation by the aqueous solution that contains PVA system resin at the single spreading of resin base material; The above-mentioned laminate film of PVA resin of the one side comprising resin base material and be formed in resin base material is impregnated in the staining fluid containing dichroic substance, in the PVA resin making dichroic substance be adsorbed onto thus to contain in laminate film; The above-mentioned laminate film comprising the PVA resin having adsorbed dichroic substance is stretched in boric acid aqueous solution, makes total stretching ratio reach more than 5 times of former length; The PVA resin and resin base material that have adsorbed dichroic substance are stretched integratedly, the one side being manufactured on resin base material is thus formed to comprise and makes that dichroic substance has carried out the PVA resin of orientation, thickness is less than 7 μm and have monomer transmissivity to be more than 42.0% and degree of polarization is the laminate film of the slim high function polarizing coating of the optical characteristics of more than 99.95%.
Above-mentioned Japanese Patent Application 2010-269002 specification sheets, the slim polarizing coating of Japanese Patent Application 2010-263692 specification sheets are comprise the continuous band-shaped polarizing coating making dichroic substance carry out the PVA system resin of orientation, carry out stretching and form the thickness of less than 10 μm in its two benches stretching process formed by being stretched in by aerial assisting tension and boric acid water by the duplexer comprising the PVA resin being formed in amorphism ester based thermoplastic resin base material.Described slim polarizing coating preferably has following optical characteristics, when monomer transmissivity being set to T, degree of polarization being set to P, meets P >-(10
0.929T-42.4-1the condition of) × 100 (wherein, T < 42.3) and P>=99.9 (wherein, T>=42.3).
Specifically, above-mentioned slim polarizing coating can be manufactured by the manufacture method of the slim polarizing coating comprising following operation: carry out aerial drawing by high temperature to the PVA resin being formed in continuous band-shaped amorphism ester based thermoplastic resin base material, generates the stretching intermediate product of the PVA resin after comprising orientation thus; Stretching intermediate product is carried out to the absorption of dichroic substance, generate thus and comprise the painted intermediate product making dichroic substance (mixture of preferred iodine or iodine and organic dye) carry out the PVA resin of orientation; Stretching in boric acid water with carrying out painted intermediate product, generating thus and comprising the polarizing coating that the thickness making dichroic substance carry out the PVA resin of orientation is less than 10 μm.
In this manufacture method, the total stretching ratio being formed in the PVA resin of amorphism ester based thermoplastic resin base material stretched in aerial drawing by high temperature and boric acid water is preferably utilized to be more than 5 times.Liquid temperature for the boric acid aqueous solution stretched in boric acid water can be set as more than 60 DEG C.Before preferably painted intermediate product being stretched in boric acid aqueous solution, insoluble process is carried out to painted intermediate product, in this situation, flood above-mentioned painted intermediate product to carry out preferably by the boric acid aqueous solution being no more than 40 DEG C in liquid temperature.Above-mentioned amorphism ester based thermoplastic resin base material preferably can be formed to comprise and makes m-phthalic acid copolymerization and the copolymerization polyethylene terephthalate obtained, make cyclohexanedimethanol copolymerization and the amorphism polyethylene terephthalate of the copolymerization polyethylene terephthalate obtained or other copolymerization polyethylene terephthalates and comprise the base material of transparent resin, and its thickness can be set as more than 7 times of the thickness of formed PVA resin.In addition, the stretching ratio of aerial drawing by high temperature is preferably less than 3.5 times, and the draft temperature of aerial drawing by high temperature is preferably more than the second-order transition temperature of PVA system resin, specifically, is preferably the scope of 95 DEG C ~ 150 DEG C.When carrying out aerial drawing by high temperature by free end uniaxial extension, the total stretching ratio being formed in the PVA resin of amorphism ester based thermoplastic resin base material is preferably more than 5 times and less than 7.5 times.In addition, when carrying out aerial drawing by high temperature by inboardend uniaxial extension, the total stretching ratio being formed in the PVA resin of amorphism ester based thermoplastic resin base material is preferably more than 5 times and less than 8.5 times.
More specifically, slim polarizing coating can be manufactured by method as described below.
Make the continuous band-shaped base material making the m-phthalic acid copolymerization polyethylene terephthalate (amorphism PET) of 6mol% m-phthalic acid copolymerization.The second-order transition temperature of amorphism PET is 75 DEG C.The duplexer comprising continuous net-shaped amorphism PET base material and polyvinyl alcohol (PVA) layer makes in the following manner.By the way, the second-order transition temperature of PVA is 80 DEG C.
Prepare 200 μm of thick amorphism PET base material and make the polymerization degree more than 1000, concentration that the PVA powder dissolution of saponification deg more than 99% obtains in water be 4 ~ 5% the PVA aqueous solution.Then, at 200 μm of thick amorphism PET base material coating PVA aqueous solution, dry at the temperature of 50 ~ 60 DEG C, obtain the duplexer being formed with 7 μm of thick PVA layers in amorphism PET base material.
The duplexer comprising 7 μm of thick PVA layers is manufactured 3 μm of thick slim high function polarizing coatings through the following operation comprising the two benches stretching process stretched in aerial assisting tension and boric acid water.By the aerial assisting tension operation of first stage, the duplexer and amorphism PET base material that comprise 7 μm of thick PVA layers are stretched integratedly, generate the stretching duplexer comprising 5 μm of thick PVA layers.Specifically, this stretching duplexer is stretching device by the duplexer comprising 7 μm of thick PVA layers being placed in the baking oven being configured in the draft temperature environment being set in 130 DEG C and to make stretching ratio be the duplexer that the mode of 1.8 times is carried out free end uniaxial extension and obtained.By this stretch processing, make the PVA layer contained in stretching duplexer be changed to PVA molecule and carried out the thick PVA layer of 5 μm of orientation.
Then, by dyeing process, the painted duplexer that PVA molecule has carried out having adsorbed in the thick PVA layer of 5 μm of orientation iodine is created on.Specifically, this painted duplexer by by stretching duplexer liquid temperature 30 DEG C containing the staining fluid of iodine and potassiumiodide in flood the arbitrary time and make the monomer transmissivity of the PVA layer forming the final high function polarizing coating generated be 40 ~ 44% thus the PVA layer contained in stretching duplexer has adsorbed the duplexer of iodine.In this operation, staining fluid is using water as solvent, and iodine concentration is in the scope of 0.12 ~ 0.30 % by weight, and potassiumiodide concentration is in the scope of 0.7 ~ 2.1 % by weight.Iodine is 1 to 7 with the concentration ratio of potassiumiodide.By the way, when iodine is water-soluble, potassiumiodide is needed.More specifically, by by stretching duplexer iodine concentration be 0.30 % by weight, potassiumiodide concentration is flood 60 seconds in the staining fluid of 2.1 % by weight, is created on the painted duplexer that PVA molecule has carried out having adsorbed in the thick PVA layer of 5 μm of orientation iodine.
Further, by stretching process in the boric acid water of subordinate phase, further painted duplexer and amorphism PET base material are stretched integratedly, generate the optical film laminate of the PVA layer comprising 3 μm of thick high function polarizing coatings of formation.Specifically, this optical film laminate be by painted duplexer is placed in be configured in containing boric acid and potassiumiodide and be set in the treatment unit of the boric acid aqueous solution of liquid temperature scope 60 ~ 85 DEG C stretching device and to make stretching ratio be the duplexer that the mode of 3.3 times is carried out free end uniaxial extension and obtained.More specifically, the liquid temperature of boric acid aqueous solution is 65 DEG C.In addition, boric acid content is set as 4 weight parts relative to water 100 weight part, potassiumiodide content is set as 5 weight parts relative to water 100 weight part.In this operation, first the painted duplexer that have adjusted iodine absorption number is flooded 5 ~ 10 seconds in boric acid aqueous solution.Then, directly being passed through between the stretching device be configured in treatment unit and the different many groups roller of peripheral speed by this painted duplexer, was that the mode of 3.3 times carries out free end uniaxial extension with 30 ~ 90 seconds to make stretching ratio.By this stretch processing, the iodine making the PVA layer contained in painted duplexer be changed to absorption to have carried out the thick PVA layer of 3 μm of high order orientation with the form of many iodide ions complex compound along a direction.This PVA layer forms the high function polarizing coating of optical film laminate.
Although be not operation required in the manufacture of optical film laminate, but preferably by matting, optical film laminate is taken out from boric acid aqueous solution, the boric acid potassium iodide aqueous solution of the surface attachment at 3 μm that are formed at amorphism PET base material thick PVA layers is cleaned.Then, the optical film laminate after cleaning is carried out drying by the drying process of the warm air utilizing 60 DEG C.In addition, matting is the operation for eliminating the bad orders such as boric acid precipitation.
Equally, although be not operation required in the manufacture of optical film laminate, but also can by laminating and/or the transfer printing process surface coated tackiness agent at 3 μm that are formed in amorphism PET base material thick PVA layers, and 80 μm of thick tri acetyl cellulose membranes of fitting, then, also amorphism PET base material can be peeled off, 3 μm of thick PVA layers are needed on 80 μm of thick tri acetyl cellulose membranes.
[other operations]
In the manufacture method of above-mentioned slim polarizing coating, beyond above-mentioned operation, can also comprise other operations.As other operations, such as insoluble operation, cross-linking process step, drying (adjustment of moisture rate) operation etc. can be enumerated.Other operations can be carried out in arbitrary opportune moment.
Typically, above-mentioned insoluble operation can be undertaken by being impregnated in boric acid aqueous solution by PVA resin.By implementing insoluble process, water tolerance can be given to PVA resin.The relative concentration of this boric acid aqueous solution is preferably 1 weight part ~ 4 weight part in water 100 weight part.The liquid temperature of insoluble bath (boric acid aqueous solution) is preferably 20 DEG C ~ 50 DEG C.Insoluble operation is preferably carried out before stretching process after duplexer makes, in dyeing process or water.
Typically, above-mentioned cross-linking process step is undertaken by being impregnated in boric acid aqueous solution by PVA resin.By implementing crosslinking Treatment, water tolerance can be given to PVA resin.The relative concentration of this boric acid aqueous solution is preferably 1 weight part ~ 4 weight part in water 100 weight part.In addition, when carrying out cross-linking process step after above-mentioned dyeing process, preferably iodide are coordinated further.By coordinating iodide, the stripping of the iodine adsorbed in PVA resin can be suppressed.The use level of iodide is preferably 1 weight part ~ 5 weight part relative to water 100 weight part.The concrete example of iodide is described above.The liquid temperature of crosslinked bath (boric acid aqueous solution) is preferably 20 DEG C ~ 50 DEG C.Cross-linking process step preferably carries out before stretching process in above-mentioned second boric acid water.Preferred embodiment, carry out stretching process in dyeing process, cross-linking process step and the second boric acid water successively.
< transparent protective film >
As the material of the transparent protective film that the one or two sides being formed in above-mentioned polaroid is arranged, the material that preferably transparent, physical strength, thermostability, water preventing ability, isotropy etc. are excellent.Styrenic, the polycarbonate based polymers etc. such as the acrylic acid polymer such as the such as cellulose-based polymkeric substance such as the Polyester such as polyethylene terephthalate or PEN polymkeric substance, diacetyl cellulose or triacetyl cellulose, polymethylmethacrylate, polystyrene or acrylonitritrile-styrene resin (AS resin) can be enumerated.In addition, also polyethylene can be enumerated, polypropylene, ring system or there is the polyolefine of norbornylene structure, the polyolefin polymkeric substance that ethylene-propylene copolymer is such, vinyl chloride-based polymer, the acid amides such as nylon or aromatic polyamide based polymer, imide series polymkeric substance, sulfone based polymer, polyethersulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol system polymer, vinylidene chloride based polymer, vinyl butyral based polymer, acrylic acid polymer, polyoxymethylene based polymer, epoxy polymkeric substance, or the blend of above-mentioned polymkeric substance etc. is as the example of polymkeric substance forming above-mentioned transparent protective film.More than a kind arbitrary suitable additive can be comprised in transparent protective film.As additive, can enumerate such as: UV light absorber, antioxidant, lubricant, softening agent, releasing agent, painted preventing agent, fire retardant, nucleator, antistatic agent, pigment, tinting material etc.The content of the above-mentioned thermoplastic resin in transparent protective film is preferably 50 ~ 100 % by weight, is more preferably 50 ~ 99 % by weight, and more preferably 60 ~ 98 % by weight, be particularly preferably 70 ~ 97 % by weight.When the content of the above-mentioned thermoplastic resin in transparent protective film is below 50 % by weight, sometimes fully cannot show original the had high transparent etc. of thermoplastic resin.
In addition; as transparent protective film; the polymeric film recorded in Japanese Unexamined Patent Publication 2001-343529 publication (WO01/37007) can be enumerated, such as, at side chain, there is the thermoplastic resin of replacement and/or non-substituted imides base and (B) to have the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group resin combination at side chain containing (A).As concrete example, the film of the resin combination containing the alternating copolymer and acrylonitritrile-styrene resin comprising iso-butylene and N-methylmaleimido can be enumerated.Film can use the film of the mixing extrusion pin comprising resin combination etc.The phase differential of these films is little, and photoelastic coefficient is little, therefore can eliminate the unequal unfavorable condition caused by the strain of polarizing coating, in addition because Water Vapour Permeability is little, and therefore humidification excellent in te pins of durability.
In above-mentioned polarizing coating, the Water Vapour Permeability of above-mentioned transparent protective film is preferably 150g/m
2/ below 24h.According to this formation, the moisture in air is difficult to enter in polarizing coating, and the moisture rate of polarizing coating itself can be suppressed to change.Consequently, curling, the dimensional change of the polarizing coating produced by Conservation environment can be suppressed.
As the material of the transparent protective film that the one or two sides being formed in above-mentioned polaroid is arranged, the material that preferably transparent, physical strength, thermostability, water preventing ability, isotropy etc. are excellent, particularly more preferably Water Vapour Permeability is 150g/m
2the material of/below 24h, particularly preferably 140g/m
2the material of/below 24h, further preferred 120g/m
2the material of/below 24h.Water Vapour Permeability is obtained by the method recorded in embodiment.
As the formation material of transparent protective film meeting above-mentioned low Water Vapour Permeability, the such as vibrin such as polyethylene terephthalate or PEN can be used; Polycarbonate resin; Acrylic resin; The acid amides such as nylon or aromatic polyamide system resin; The polyolefin polymkeric substance that polyethylene, polypropylene, ethylene-propylene copolymer are such, ring system or there is the annular ethylene series resin of norbornylene structure, (methyl) acrylic resin or their mixture.In above-mentioned resin, optimization polycarbonate system resin, cyclic polyolefine hydrocarbon system resin, (methyl) acrylic resin, particularly preferably cyclic polyolefine hydrocarbon system resin, (methyl) acrylic resin.
Suitably can determine the thickness of transparent protective film, but usually be thought of as about 1 ~ 100 μm from aspects such as the workability such as intensity or operability, thin layers.Particularly preferably 1 ~ 80 μm, more preferably 3 ~ 60 μm.
It should be noted that, when the two sides of polaroid arranges transparent protective film, can use at its table back of the body the transparent protective film comprising identical polymer materials, also can use the transparent protective film comprising different polymer materials etc.
On the surface of the not bonding polaroid of above-mentioned transparent protective film, the functional layers such as hard coat, anti-reflection layer, antiblocking layers, diffusing layer or antiglare layer can be set.It should be noted that, the functional layers such as above-mentioned hard coat, anti-reflection layer, antiblocking layers, diffusing layer or antiglare layer, except being arranged on transparent protective film itself, also can be arranged with transparent protective film separately dividually.
< blooming >
Polarizing coating of the present invention can use with the form of the blooming stacked with other optical layers when reality uses.About this optical layers, be not particularly limited, the optical layers such as sometimes used in the formation of the liquid crystal indicators such as reflector or half transmitting plate, polarizer (comprising 1/2,1/4 equiwavelength's plate), compensation film for angular field of view etc. of more than 1 layer or 2 layers can be used.Be laminated with the reflective polarizing film of reflector or Transflective plate or Semitransmissive polarizing coating further particularly preferably in polarizing coating of the present invention, be laminated with the elliptical polarization film of polarizer or circular polarization film further at polarizing coating, be laminated with the wide viewing angle polarizing coating of compensation film for angular field of view further at polarizing coating or be laminated with the polarizing coating of brightness enhancement film at polarizing coating further.
The blooming being laminated with above-mentioned optical layers at polarizing coating also can by the manufacturing processed at liquid crystal indicator etc. in carry out stacked mode to be formed individually successively, but stacked in advance and make blooming to have the stability, assembly operation etc. of quality excellent and can improve the advantage of the manufacturing process of liquid crystal indicator etc.The stacked adhesion means that bonding coat etc. can be used suitable.During above-mentioned polarizing coating, other bloomings bonding, their optic axis can form suitable arrangement angles according to target phase difference characteristic etc.
Also can arrange for the bonding coat bonding with other components such as liquid crystal cells at above-mentioned polarizing coating, the blooming that is laminated with at least 1 layer of polarizing coating.Form the tackiness agent of bonding coat to be not particularly limited, can the tackiness agent of suitable choice for use polymkeric substance based on the polymkeric substance of such as acrylic acid polymer, silicone-based polymer, polyester, urethane, polymeric amide, polyethers, fluorine system or rubber series etc.Particularly, the adhesion characteristic of optical transparence excellence, the wettability demonstrating appropriateness, coherency and cementability as acrylic adhesive can preferably be used and the tackiness agent of the excellence such as weathering resistance, thermotolerance.
Bonding coat also can be arranged on the one or two sides of polarizing coating, blooming as the overlapping layer of the layer of different compositions or kind etc.In addition, when being arranged at two sides, also can form the bonding coat of different compositions, kind, thickness etc. at the surface back side of polarizing coating, blooming.The thickness of bonding coat suitably can determine according to application target, bonding force etc., is generally 1 ~ 500 μm, is preferably 1 ~ 200 μm, is particularly preferably 1 ~ 100 μm.
For the exposed surface of bonding coat, until during for practicality, the temporarily adhesion partition and protecting such as to pollute to prevent it.Thus, can prevent from contacting with bonding coat under common treated state.As partition, except above-mentioned thickness condition, can use and such as sheet-like article suitable to plastic film, sheet rubber, paper, cloth, non-woven fabrics, reticulation, foamed sheet or tinsel, their layered product etc. etc. carried out being coated with the partition of process etc. according to suitable partition in the past with the stripper that silicone or chain alkyl class, fluorine system or moly-sulfide etc. are suitable as required.
< image display device >
Polarizing coating of the present invention or blooming can preferably use in the formation etc. of the various devices such as liquid crystal indicator.The formation of liquid crystal indicator can be carried out according to mode in the past.Namely, liquid crystal indicator is generally formed by arranging driving circuit etc. after liquid crystal cells and polarizing coating or the component parts such as blooming and lighting system as required suitably being assembled, but in the present invention, except using polarizing coating of the present invention or blooming, be not particularly limited, can carry out according to existing mode.For liquid crystal cells, arbitrary type such as such as TN type or STN type, π type etc. also can be used.
The one-sided of liquid crystal cells can be formed in or both sides are configured with the liquid crystal indicator of polarizing coating or blooming or employ the suitable liquid crystal indicator of backlight or reflector etc. in the illumination system.In this case, polarizing coating of the present invention or blooming can be arranged on the one-sided of liquid crystal cells or both sides.When arranging polarizing coating or blooming in both sides, they can be the same or different.Further, when forming liquid crystal indicator, one deck or the suitable parts of two-layer above diffusing panel, antiglare layer, antireflection film, protecting sheet, prism array, lens array sheet, light diffusing board, backlight etc. can be configured in position.
Embodiment
Below, notebook inventive embodiment, but embodiments of the present invention are not limited to these.
The making > of < polaroid
The polyvinyl alcohol film of the thickness 75 μm of mean polymerisation degree 2400, saponification deg 99.9 % by mole be impregnated in 60 seconds in the warm water of 30 DEG C and make it swelling.Then, impregnated in the aqueous solution of the concentration 0.3% of iodine/potassiumiodide (weight ratio=0.5/8), while be stretched to 3.5 times of limits, film is dyeed.Afterwards, the mode being 6 times with total stretching ratio in the boric acid ester aqueous solution of 65 DEG C stretches.After stretching, carry out drying in 3 minutes with the baking ovens of 40 DEG C, obtain PVA system polaroid X (thickness 23 μm).
< transparent protective film >
Transparent protective film 1: use tri acetyl cellulose membrane (the Water Vapour Permeability 530g/m not carrying out the thickness 60 μm of saponification, corona treatment etc.
2/ 24h) (in table 1, being designated as TAC).
Transparent protective film 2: to (methyl) acrylic resin (Water Vapour Permeability 96g/m with lactonic ring structure of thickness 40 μm
2/ 24h) implement corona treatment after use (in table 1, being designated as acrylic acid series).
Transparent protective film 3: to cyclic polyolefin film (Nippon Zeon Co., Ltd.'s system: ZEONOR, the Water Vapour Permeability 11g/m of thickness 55 μm
2/ 24h) implement corona treatment after use (in table 1, being designated as COP).
The Water Vapour Permeability > of < transparent protective film
Water Vapour Permeability according to JISZ0208 tests the mensuration that (agar diffusion method) carries out Water Vapour Permeability.Be arranged in the moisture vapor transmission cup of the calcium chloride having dropped into about 15g by the sample being cut to diameter 60mm, put into the constant temperature machine of temperature 40 DEG C, humidity 90%R.H., the weight measuring the calcium chloride of placement 24 hours front and back increases, and obtains Water Vapour Permeability (g/m thus
2/ 24h).
< active energy beam >
Use visible ray (gallium inclosure metal halide lamp) irradiating unit: FusionUVSystems, Inc Inc. LightHAMMER10 bulb: V-arrangement bulb peak illumination: 1600mW/cm
2, accumulative irradiation dose 1000/mJ/cm
2(wavelength 380 ~ 440nm) is as active energy beam.It should be noted that, use the illumination of Solatell Inc. Sola-Check systems measurement visible ray.
Embodiment 1 ~ 4 and comparative example 1 ~ 5
(preparation of active energy ray curable tackiness agent)
According to the cooperation table recorded in table 1, be incorporated in 50 DEG C of stirrings 1 hour by mixed for each composition, obtain the active energy ray curable tackiness agent of embodiment 1 and comparative example 1.It should be noted that, the viscosity of the active energy ray curable tackiness agent of embodiment 1 is 95cp (25 DEG C), and the viscosity of the active energy ray curable tackiness agent of comparative example 1 is 45cp (25 DEG C).
(making of polarizing coating)
Use MCD coating machine (Mechanology Inc. of Fuji system) (cell configuration: honeycomb; gravure roll line number: 1000 pieces/inch; speed of rotation 140%/line speed relatively); above-mentioned transparent protective film applies in the mode reaching thickness 0.7 μm the active energy ray curable tackiness agent of above-described embodiment or comparative example, fits in the two sides of above-mentioned polaroid X with roller machine.Afterwards; from the transparent protective film side (both sides) of laminating; use IR heater heats to 50 DEG C; above-mentioned visible ray is irradiated to two sides and after making the active energy ray curable adhesive solidification of above-described embodiment or comparative example; carry out 3 minutes warm air dryings at 70 DEG C, obtain the polarizing coating in the both sides of polaroid with transparent protective film.With the line speed of laminating for 25m/min carries out.
The making of polarizing coating is carried out respectively according to 3 kinds of above-mentioned transparent protective film 1 ~ 3.
Following evaluation is carried out to the polarizing coating obtained by above-described embodiment and comparative example.In Table 1 evaluation result is shown.It should be noted that, when the evaluation of humidification weather resistance and bonding water tolerance, make same polarizing coating respectively separately.
< volume water absorption rate >
Use the polarizing coating curing type adhesive used in each example, clamp with 2 sheet glass of the distance piece being provided with 100 μm, be cured with the active-energy condition same with embodiment and prepare the adhesive layer (cured article) of thickness 100 μm.It can be used as sample.The weight of sample is set to M1g.Sample M1g is flooded 24 hours in the pure water of 23 DEG C.Afterwards, from pure water take out and with after dried cloth wiping within 1 point the weight (M2g) of working sample again.According to these results, by formula: { (%) calculates volume water absorption rate in (M2-M1)/M1} × 100.
< cure shrinkage >
Measured by Sentec Inc. cure shrinkage sensor " resin solidification string stress determinator EU201C ".Specifically, the method recorded by Japanese Unexamined Patent Publication 2013-104869 calculates cure shrinkage.It should be noted that, the cure shrinkage of the cured article formed by the active energy ray curable tackiness agent of embodiment 1 is 8.9%, and the cure shrinkage of the cured article formed by the active energy ray curable tackiness agent of comparative example 1 is 11.9%.
< bonding force >
The polarizing coating obtained by each example is cut into the direction parallel with the draw direction of polaroid is 200mm, orthogonal directions is the size of 20mm, between transparent protective film and polaroid, marks otch with cutters, make polarizing coating fit in sheet glass.Utilize Tensilon, with peeling rate 500mm/min, transparent protective film and polaroid are peeled off along 90 degree of directions, measure its stripping strength.In addition, measured the infrared absorption spectrum of the release surface after peeling off by ATR method, according to following benchmark, stripping interface is evaluated.
A: the cohesion of transparent protective film destroys
B: the interface peel between transparent protective film/adhesive layer
C: the interface peel between adhesive layer/polaroid
D: the cohesion of polaroid destroys
In said reference, the bonding force of A and D, more than the cohesive force of film, therefore represents that bonding force is very excellent.On the other hand, the bonding force deficiency (bonding force is poor) at transparent protective film/adhesive layer (adhesive layer/polaroid) interface of B and C.Given this; zero is designated as by for bonding force during A or D; bonding force when A-B (" cohesion of transparent protective film destroys " and " interface peel between transparent protective film/adhesive layer " occur simultaneously) or A-C (" cohesion of transparent protective film destroys " and " interface peel between adhesive layer/polaroid " occur simultaneously) is designated as △, bonding force during B or C is designated as ×.
< humidification weather resistance: the mensuration > of monomer transmissivity, degree of polarization change
By the method same with embodiment and comparative example using the two sides at polaroid respectively stacked 1 polarizing coating as the transparent protective film 2 and 3 of transparent protective film make sample.This polarizing coating (sample) to be dropped in the constant temperature and humidity machine of 85 DEG C/85%RH 500 hours.The monomer transmissivity of the polarizing coating before using the spectral transmission tester Dot-3c of color technical institute (in the village) of band integrating sphere to measure to drop into and after dropping into and degree of polarization, ask calculation as follows:
Variable quantity (Δ T:%)=(the monomer transmissivity (%) after input)-(the monomer transmissivity (%) before input) of monomer transmissivity,
Variable quantity (Δ P:%)=(degree of polarization (%) after input)-(degree of polarization (%) before input) of degree of polarization.
It should be noted that, degree of polarization P be transmissivity (parallel transmission: Tp) by applying in following formula when making 2 identical polarizing coatings overlap in the mode that the axis of homology of 2 identical polarizing coatings is parallel and overlap in the mode that both axis of homology are orthogonal time transmissivity (orthogonal transmission: Tc) and the value obtained.Degree of polarization P (%)={ (Tp-Tc)/(Tp+Tc) }
1/2× 100
Each transmissivity is that the complete polarized light obtained passing through from Glan-Taylor prism polaroid is set to 100%, carries out the value shown in the Y value after apparent brightness correction by 2 degree of visual fields (illuminant-C) of JISZ8701.
The bonding water tolerance of < (warm water immersion test) >
By the method same with embodiment and comparative example using the two sides at polaroid respectively stacked 1 polarizing coating as the transparent protective film 1 and 3 of transparent protective film make sample.The draw direction this polarizing coating (sample) being cut into polaroid is 50mm, vertical direction is the rectangle of 25mm.After this polarizing coating is flooded 6 hours in the warm water of 60 DEG C, measure with magnifying glass is visual the length peeled off.Using the maximum value (mm) of the vertical range in the cross section of the part from generation stripping as measured value.
The bonding water tolerance of < (water-fast peeling force) >
By the method same with embodiment and comparative example using the two sides at polaroid respectively stacked 1 polarizing coating as the transparent protective film 1 and 3 of transparent protective film make sample.This polarizing coating (sample) is cut into the direction parallel with the draw direction of polaroid is 200mm, orthogonal directions is the size of 20mm.After this polarizing coating is flooded 24 hours in the pure water of 23 DEG C, take out from pure water and with after dried cloth wiping, between transparent protective film and polaroid, mark otch with cutters, polarizing coating is fitted in sheet glass.Operation carry out being fetched into evaluation from pure water within 1 point till.After, carry out the evaluation same with above-mentioned < bonding force >.
The calculating > of <logPow
Use the logPow value of each compound obtained by ChemDrawUltra (CambridgeSoft Inc.), calculated by following formula.It should be noted that, from calculating, remove polymerization starter and light acid producing agent.
The logPow=Σ (logPowi × Wi) of curing type adhesive
LogPowi: the logPow value of each composition of curing type adhesive
The mole number of Wi:(i composition)/(total mole number of each composition of curing type adhesive)
[table 1]
In table 1, free-radical polymerised compound illustrates:
HEAA: hydroxyethyl acrylamide, logPow=-0.56, the Tg=123 DEG C of homopolymer, Xing Ren Inc.;
ACMO: acryloyl morpholine, logPow=-0.20, the Tg=150 DEG C of homopolymer, Xing Ren Inc.;
FA-THFM:(methyl) tetrahydrofurfuryl acrylate, logPow=1.13, the Tg=45 DEG C of homopolymer, Hitachi changes into Inc.;
LightAcrylateDCP-A: Tricyclodecane Dimethanol diacrylate, logPow=3.05, the Tg=134 DEG C of homopolymer, chemical company of common prosperity society system;
LightAcrylate1,9ND-A:1,9-nonanediol diacrylate, logPow=3.68, the Tg=68 DEG C of homopolymer, chemical company of common prosperity society system;
AronixM-220: tripropylene glycol diacrylate, logPow=1.68, the Tg69 DEG C of homopolymer, East Asia Synesis Company system;
AronixM-306: tetramethylolmethane three/tetraacrylate, logPow=1.04, more than Tg=250 DEG C of homopolymer, East Asia Synesis Company system.
Acrylic oligomers illustrates: ARUFONUP-1190, logPow=1.95 East Asia Synesis Company system,
Compound containing alkoxyl group illustrates: Carbide industrial of NikalacMX-750LM, logPow=0.8 Japan system,
Compound containing epoxy group(ing) illustrates: JER828, logPow=4.76 japan epoxy resin Inc.,
Isocyanate compound illustrates: KarenzAOI, logPow=1.6 Showa Denko K. K system).
Photoepolymerizationinitiater initiater illustrates:
IRGACURE907 (2-methyl isophthalic acid-(4-methylsulfanylphenyl)-2-morpholino propane-1-ketone), logPow=2.09, BASF AG's system
KAYACUREDETX-S (diethyl thioxanthone), logPow=5.12, Japanese chemical drug Inc..
Light acid producing agent illustrates CPI-100P (the polypropylene carbonate ester solution of the effective constituent 50% being principal constituent with triaryl matte hexafluorophosphate), San-Apro Inc..
Claims (18)
1. a polarizing coating curing type adhesive, is characterized in that, is the polarizing coating curing type adhesive containing solidified nature composition,
This polarizing coating curing type adhesive is when by making this curing type adhesive solidify, the cured article that obtains impregnated in the pure water 24 hours of 23 DEG C, and the volume water absorption rate shown in following formula is less than 10 % by weight,
Volume water absorption rate (%)=(M2-M1)/M1} × 100,
Wherein, in described formula, M1 represents the weight of the cured article before dipping, and M2 represents the weight of the cured article after dipping.
2. polarizing coating curing type adhesive according to claim 1, is characterized in that, Octanol/water Partition Coefficients and logPow value are more than 1.
3. polarizing coating curing type adhesive according to claim 1 and 2, is characterized in that, described solidified nature composition is active energy ray-curable composition.
4. polarizing coating curing type adhesive according to claim 3, is characterized in that, described active energy ray-curable composition contains free-radical polymerised compound.
5. polarizing coating curing type adhesive according to claim 4, is characterized in that, described free-radical polymerised compound contains (methyl) acrylamide derivative.
6. the polarizing coating curing type adhesive according to claim 4 or 5, is characterized in that, described free-radical polymerised compound contains multi-functional compounds, and described multi-functional compounds has at least 2 and has free-radical polymerised functional group.
7. the polarizing coating curing type adhesive according to any one of claim 3 ~ 6, is characterized in that, also containing Photoepolymerizationinitiater initiater.
8. the polarizing coating curing type adhesive according to any one of claim 3 ~ 7, is characterized in that, also containing acrylic oligomers (A).
9. the polarizing coating curing type adhesive according to any one of claim 3 ~ 8, is characterized in that, also containing light acid producing agent (B).
10. the polarizing coating curing type adhesive according to any one of claim 3 ~ 9, is characterized in that, also containing the compound of any one (C) comprised in alkoxyl group, epoxy group(ing).
11. polarizing coating curing type adhesives according to claim 10, is characterized in that, described in the compound of any one (C) comprised in alkoxyl group, epoxy group(ing) be compound (C1) containing alkoxyl group.
12. polarizing coating curing type adhesives according to claim 11, is characterized in that, the described compound (C1) containing alkoxyl group is the melamine compound containing alkoxyl group.
13. polarizing coating curing type adhesives according to any one of claim 3 ~ 12, is characterized in that, also containing isocyanate compound (D).
14. polarizing coating curing type adhesives according to claim 1 and 2, is characterized in that, described solidified nature composition is Thermocurable composition, and it is also containing thermal polymerization.
15. 1 kinds of polarizing coatings, is characterized in that, at least one face of polaroid, adhesive layer are provided with transparent protective film,
The solidification nitride layer of the polarizing coating curing type adhesive of described adhesive layer according to any one of claim 1 ~ 14 is formed.
16. polarizing coatings according to claim 15, is characterized in that, the thickness of described adhesive solidification nitride layer is 0.1 ~ 3 μm.
17. 1 kinds of bloomings, is characterized in that, are laminated with the polarizing coating described at least 1 claim 15 or 16.
18. 1 kinds of image display devices, is characterized in that, employ the polarizing coating described in claim 15 or 16 or blooming according to claim 17.
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| CN201811394795.3A CN109536046B (en) | 2013-08-30 | 2014-08-29 | Curing adhesive for polarizing film, optical film, and image display device |
| CN201811395174.7A CN109554122B (en) | 2013-08-30 | 2014-08-29 | Curing adhesive for polarizing film, optical film, and image display device |
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| CN111149026A (en) * | 2017-09-21 | 2020-05-12 | 日东电工株式会社 | Laminated optical film, method for producing same, and image display device |
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| CN111149026A (en) * | 2017-09-21 | 2020-05-12 | 日东电工株式会社 | Laminated optical film, method for producing same, and image display device |
| CN111149026B (en) * | 2017-09-21 | 2021-02-26 | 日东电工株式会社 | Laminated optical film, method for producing same, and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109554122B (en) | 2022-03-01 |
| CN109536046A (en) | 2019-03-29 |
| CN105492564B (en) | 2018-12-11 |
| CN109554122A (en) | 2019-04-02 |
| CN109536046B (en) | 2021-06-11 |
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