CN109554122A - Polarizing coating curing type adhesive, polarizing coating, optical film and image display device - Google Patents
Polarizing coating curing type adhesive, polarizing coating, optical film and image display device Download PDFInfo
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- CN109554122A CN109554122A CN201811395174.7A CN201811395174A CN109554122A CN 109554122 A CN109554122 A CN 109554122A CN 201811395174 A CN201811395174 A CN 201811395174A CN 109554122 A CN109554122 A CN 109554122A
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Abstract
Polarizing coating containing curability composition of the invention is with curing type adhesive in the case of the pure water 24 that the solidfied material of polarizing coating curing type adhesive is impregnated in 23 DEG C is small, following formula: volume water absorption rate (%)=formula: { (M2-M1)/M1 } × 100 (%), { wherein, in above-mentioned formula, M1 indicates that the weight of solidfied material before dipping, M2 indicate the weight of the solidfied material after dipping } shown in volume water absorption rate be 10 weight % or less.For the polarizing coating curing type adhesive, the cementability of polarizing film and transparent protective film is good, and while can satisfy the optical durability in the harsh environment under high temperature and humidity, and impregnate also has sufficient bonding force in water in prolonged situation.
Description
The application be on 08 29th, 2014 the applying date, application No. is 201480047627.0, entitled " polarization
The divisional application of the application of film curing type adhesive, polarizing coating, optical film and image display device ".
Technical field
The present invention relates in the polarizing coating that polarizing film and transparent protective film are laminated gluing oxidant layer, above-mentioned glue is formed
The polarizing coating curing type adhesive of adhesive layer.The invention also relates to the polarizing coatings for having used above-mentioned gluing oxidant layer.The polarization
Film can be shown individually or by formation liquid crystal display device (LCD), organic EL in the form of the optical film for being laminated with the polarizing coating
The image display devices such as device, CRT, PDP.
Background technique
For clock and watch, mobile phone, PDA, laptop, PC monitor, DVD player, TV etc., liquid crystal
Display device sharply develops on the market.Liquid crystal display device is to make the visible dress of the polarization state as caused by the switch of liquid crystal
It sets, according to its displaying principle, uses polarizing film.In particular, in TV and other uses, increasingly wanting high brightness, high contrast, wide view
Angle also increasingly requires high-transmission rate, high-polarization, high colorrendering quality etc. for polarizing coating.
As polarizing film, from the viewpoint of with high-transmission rate, high-polarization, being most generally widely used adsorbs iodine
In such as polyvinyl alcohol (hereinafter, being also only called " PVA ") and the iodine system polarizing film of structure obtained from being stretched.It is general and
Transparent protective film is fitted in partially by speech, polarizing coating using using by the so-called water system adhesive that polyvinyl alcohol based material is dissolved in water
Shake polarizing coating (following patent documents 1 and patent document 2) obtained from the two sides of piece.As transparent protective film, moisture permeability is used
High triacetyl cellulose etc..Using (so-called wet type lamination) when above-mentioned water system adhesive, make polarizing film and transparency protected
After film fitting, drying process is needed.
On the other hand, active energy ray curable adhesive is proposed to replace above-mentioned water system adhesive.Use active energy
When measuring ray curing adhesive manufacture polarizing coating, drying process is not needed, therefore the productivity of polarizing coating can be improved.It proposes
For example use the N substituted amide system monomer as the active energy ray curable of the radical polymerization mould assembly of curability composition
Adhesive (following patent documents 3 and patent document 4).The adhesive is played in the harsh environment under high temperature at high humidity
Excellent durability out, but in the market, it in fact can be further improved the glue of cementability and/or water resistance in continuous requirement
Stick.
In addition, proposing a kind of active energy ray curable adhesive, it is conceived to the SP value (dissolution of curability composition
Property parameter), by that, using the different free-radical polymerised compound of at least three kinds of SP values, can be formed with defined composition ratio
Improve the gluing oxidant layer (following patent documents 5) of durability and water resistance.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-220732 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2001-296427 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2008-287207 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2010-078700 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2012-144690 bulletin
Summary of the invention
Subject to be solved by the invention
Using the active energy ray curable adhesive recorded in above patent document 5, for the manufacture in polarizing coating
When the various transparent protective films that use can satisfy durability and water resistance.But use the active energy recorded in patent document 5
The obtained polarizing coating of amount ray curing adhesive although can satisfy impregnate in 60 DEG C of warm water 6 hours water resistance it is (warm
Water immersion test), but the optical durability in the harsh environment under further high temperature and humidity is pursued in market.Further,
Above-mentioned polarizing coating is required to impregnate in water, also there is sufficient bonding force in prolonged situation.
The purpose of the present invention is to provide a kind of polarizing coating curing type adhesive, with polarizing film and transparent protective film
Cementability is good, and can satisfy the optical durability in the harsh environment under high temperature and humidity, while when impregnating long in water
Between in the case where also have sufficient bonding force.
The object of the invention is also to provide a kind of polarizing coating, the polarizing coating, which utilizes, uses polarizing coating curing type gluing
Dosage form at gluing oxidant layer, polarizing film is provided with transparent protective film, further, the present invention offer used above-mentioned polarizing coating
Optical film, the present invention also provides the image display devices for having used above-mentioned polarizing coating or optical film.
The method to solve the problem
The inventors of the present invention further investigate in order to solve the above problems and repeatedly, as a result, it has been found that, it is used using following polarizing coatings
Above-mentioned purpose may be implemented in curing type adhesive, to solve the present invention.
That is, the present invention relates to a kind of polarizing coating curing type adhesives, which is characterized in that it contains curability composition,
The polarizing coating is impregnated in 23 DEG C with curing type adhesive solidfied material obtained by the curing type adhesive will be made to solidify
Pure water 24 it is small in the case of, following formula:
Volume water absorption rate (%)={ (M2-M1)/M1 } × 100,
{ wherein, in above-mentioned formula, M1 indicates that the weight of the solidfied material before dipping, M2 indicate the weight of the solidfied material after dipping }
Shown in volume water absorption rate be 10 weight % or less.
The Octanol/water Partition Coefficients (logPow value) of above-mentioned polarizing coating curing type adhesive are preferably 1 or more.
For above-mentioned polarizing coating curing type adhesive, above-mentioned curability composition be active energy ray-curable at
Timesharing can be used as the use of active energy ray curable adhesive.As above-mentioned curability composition, radical polymerization can be contained
Conjunction property compound.As above-mentioned free-radical polymerised compound, (methyl) acrylamide derivative is preferably comprised.In addition, conduct
Above-mentioned free-radical polymerised compound, preferably comprises multi-functional compounds, and the multi-functional compounds have at least two
There is free-radical polymerised functional group.In addition, above-mentioned active energy ray curable adhesive can also cause containing photopolymerization
Agent.
Above-mentioned polarizing coating curing type adhesive can also contain acrylic oligomers (A).
Above-mentioned polarizing coating curing type adhesive can also contain photoacid generator (B).
Above-mentioned polarizing coating curing type adhesive can also contain the compound comprising any one of alkoxy, epoxy group
(C).As the above-mentioned compound (C) comprising any one of alkoxy, epoxy group, the compound of alkoxy is preferably comprised
(C1).Further, the above-mentioned compound (C1) containing alkoxy is preferably the melamine compound containing alkoxy.
In addition, above-mentioned polarizing coating curing type adhesive can also contain isocyanate compound (D).
For above-mentioned polarizing coating curing type adhesive, when above-mentioned curability composition is Thermocurable ingredient, pass through
Also contain thermal polymerization, can be used as the use of thermohardening type adhesive.
The invention also relates to a kind of polarizing coatings, which is characterized in that it is at least one face of polarizing film across gluing
Oxidant layer is provided with the polarizing coating of transparent protective film,
Above-mentioned gluing oxidant layer is formed by the solidified material layer of above-mentioned polarizing coating curing type adhesive.
In above-mentioned polarizing coating, the thickness of above-mentioned adhesive solidified material layer is preferably 0.1~3 μm.
The invention further relates to a kind of optical films, which is characterized in that is laminated at least 1 above-mentioned polarizing coating.
The invention further relates to a kind of image display devices, which is characterized in that has used above-mentioned polarizing coating or above-mentioned optical film.
Invention effect
For polarizing coating curing type adhesive of the invention, solidfied material obtained by solidifying the curing type adhesive
Volume water absorption rate is 10 weight % or less.The volume water absorption rate is shown using by polarizing coating of the invention curing type gluing
Water imbibition when the solidified material layer formation gluing oxidant layer that agent obtains is very low.Therefore, for across including above-mentioned solidified material layer
Gluing oxidant layer is provided with for the polarizing coating of transparent protective film on polarizing film, and the cementability of polarizing film and clear protective film layer is good
It is good, and can satisfy the optical durability in the harsh environment under high temperature and humidity.
For example, having the inclined of the solidified material layer (gluing oxidant layer) formed using polarizing coating of the invention with curing type adhesive
Vibrating diaphragm (85 DEG C × 85%RH) optical durability (humidification durability test) under harsh humidified ambient is also good.Therefore, originally
It, can also be by the transmissivity of polarizing coating, the decline of degree of polarization when the polarizing coating of invention is under the humidified ambient for being placed in above-mentioned harshness
(variation) inhibits smaller.In addition, the present invention provides a kind of polarizing coating, it can also in the case where being impregnated in harsh environment as water
To inhibit the decline of bonding force, impregnate also has sufficient bonding force in water in prolonged situation.
Specific embodiment
<volume water absorption rate>
It is solid obtained by the curing type adhesive will be made to solidify for polarizing coating curing type adhesive of the invention
Compound be impregnated in 23 DEG C pure water 24 it is small in the case of the volume water absorption rate of above-mentioned record that measures be 10 weight % or less.It will
When polarizing coating is placed in the environment of harsh high temperature and humidity (85 DEG C/85%RH etc.), through transparent protective film and gluing oxidant layer
Moisture invades polarizing film, and cross-linked structure hydrolysis causes the orientation of 2 color pigments chaotic, causes transmissivity to rise, degree of polarization decline
Etc. optical durabilities deterioration.By setting 10 weight % for the volume water absorption rate of gluing oxidant layer hereinafter, can inhibit will be inclined
Vibrating diaphragm is placed in the movement of Shi Shuixiang polarizing film, the transmissivity rising for inhibiting polarizing film, polarization in the environment of harsh high temperature and humidity
Degree decline.About above-mentioned volume water absorption rate, for the gluing oxidant layer of polarizing coating, from the harsh environment made under high temperature
From the viewpoint of optical durability is better, preferably 5 weight % hereinafter, further preferably 3 weight % hereinafter, further excellent
1.5 weight % are selected as hereinafter, most preferably 1 weight % or less.On the other hand, when making polarizing film and transparent protective film is bonded,
Polarizing film maintains a certain amount of moisture, and cratering occurs sometimes when the curing type adhesive is with contact with moisture contained in polarizing film
The bad orders such as (Ha ジ キ), bubble.In order to inhibit bad order, a certain amount of water is can be absorbed in the preferably curing type adhesive
Point.More specifically, volume water absorption rate is preferably 0.01 weight % or more, further preferably 0.05 weight % or more.Specifically
For above-mentioned volume water absorption rate measured by the moisture content test method recorded in JISK 7209.
The preferred Octanol/water Partition Coefficients of polarizing coating curing type adhesive (hereinafter, being denoted as logPow value) of the invention are high.
LogPow value is to indicate the lipophilic index of substance, refers to the logarithm of the distribution coefficient of octanol/water.LogPow high means
For lipophilicity, that is, mean that water absorption rate is low.Although can also measure logPow value (the flask impregnating method that JIS-Z-7260 is recorded),
But it also can be using the structure of each compound of the composition point (curability composition etc.) as polarizing coating curing type adhesive as base
Plinth is calculated by calculating.In this specification, use what is calculated using Cambridge Soft corporation ChemDraw Ultra
LogPow value.
The polarizing coating curing type adhesive in the present invention can be calculate by the following formula based on above-mentioned calculated value
LogPow value.
The logPow=∑ (logPowi × Wi) of curing type adhesive
LogPowi: the logPow value of each ingredient of curing type adhesive
The molal quantity of Wi:(i ingredient)/(total mole number of each ingredient of curing type adhesive)
When carrying out above-mentioned calculating, in each ingredient of curing type adhesive, polymerization initiator, photoacid generator etc. do not form solid
The ingredient of the skeleton of compound (gluing oxidant layer) is removed from the ingredient in above-mentioned calculating.Polarizing coating of the invention curing type glue
The logPow value of stick is preferably 1 or more, and more preferably 1.5 or more, most preferably 2 or more.It is possible thereby to which it is water-fast to improve bonding
Property, humidification durability.On the other hand, the logPow value of polarizing coating of the invention curing type adhesive is typically about 8 hereinafter, excellent
5 are selected as hereinafter, more preferably 4 or less.If the logPow value is excessively high, it is easy to produce the appearances such as cratering, bubble as described above not
It is good, therefore not preferably.
It is not particularly limited in addition, setting 10 weight % means below for the above-mentioned volume water absorption rate in the present invention,
But it, can be by body by selecting each ingredient in the case where polarizing coating curing type adhesive is the composition containing Multiple components
Product water absorption rate control is in above range.For example, polarizing coating curing type adhesive is the adhesive compound containing Multiple components
In the case where, pass through the mode system to keep the ratio of the ingredient below of logPow value 1 in the adhesive compound small
It is the methods of standby, volume water absorption rate can be controlled in above range.In order to which the above-mentioned volume water absorption rate in the present invention is adjusted to
10 weight % by the logPow value control of polarizing coating curing type adhesive is 1 or more hereinafter, for example, can be by carrying out.
<cure shrinkage>
In addition, making the curing type since polarizing coating of the invention curing type adhesive has curability composition
In the cured situation of adhesive, it is usually cured contraction.Cure shrinkage is indicated by polarizing coating curing type adhesive shape
The index of the ratio of cure shrinkage when plastic adhesive layer.If the cure shrinkage of gluing oxidant layer becomes larger, use polarizing coating
Curing type adhesive inhibits the generation of interface strain, the generation of poor attachment when being solidified to form gluing oxidant layer, examine from this aspect
Worry is preferred.From above-mentioned viewpoint consider, solidfied material obtained by solidifying polarizing coating curing type adhesive of the invention it is upper
Stating cure shrinkage is preferably 10% or less.It is preferred that above-mentioned cure shrinkage is small, above-mentioned cure shrinkage be preferably 8% hereinafter,
Further preferably 5% or less.Above-mentioned cure shrinkage is measured by the method recorded in Japanese Unexamined Patent Publication 2013-104869,
It is measured in particular by the method using Sentec corporation cure shrinkage sensor recorded in embodiment.
<curability composition>
Polarizing coating curing type adhesive of the invention contains curability composition.Suitably select the curability composition so that
Solidfied material meets above-mentioned volume water absorption rate.
As curability composition, it is living that electronic beam solidified, ultraviolet hardening, visible light curable etc. can be roughly divided into
Property energy ray-curable and thermohardening type.Further, ultraviolet hardening, Visible light curable adhesives can be roughly divided into
Free radical polymerization curing type adhesive and cationic polymerization type adhesive.In the present invention, by wave-length coverage 10nm~be lower than 380nm
Active energy beam be denoted as ultraviolet light, the active energy beam of wave-length coverage 380nm~800nm is denoted as visible light.It is above-mentioned
The curability composition that the curability composition of free radical polymerization curing type adhesive can be used as thermohardening type adhesive uses.
<1: free radical polymerization curing type adhesive>
As above-mentioned curability composition, radical polymerization used in such as free radical polymerization curing type adhesive can be enumerated
Conjunction property compound.Free-radical polymerised compound can enumerate oneself with carbon-to-carbon double bonds such as (methyl) acryloyl group, vinyl
By the compound of the functional group of base polymerism.Monofunctional free radical's polymerizable compound or two can be used in these curability compositions
It is any in multifunctional free-radical polymerised compound more than function.In addition, these free-radical polymerised compounds can be single
1 kind is solely used, or two or more is applied in combination.It is suitably for example with (methyl) third as these free-radical polymerised compounds
The compound of enoyl-.It should be noted that (methyl) acryloyl group refers to acryloyl group and/or metering system in the present invention
Acyl group, hereinafter, " (methyl) " is the same meaning.
" monofunctional free radical's polymerizable compound "
As monofunctional free radical's polymerizable compound, (methyl) for example with (methyl) acrylamido can be enumerated
Acrylamide derivative.(methyl) acrylamide derivative ensure with polarizing film, various transparent protective films cementability in terms of,
And polymerization speed is fast and the excellent aspect of productivity is 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,
The alkyl containing N- such as N- isopropyl (methyl) acrylamide, N- butyl (methyl) acrylamide, N- hexyl (methyl) acrylamide
(methyl) acrylamide derivative；N- methylol (methyl) acrylamide, N- hydroxyethyl (methyl) acrylamide, N- hydroxyl first
(methyl) acrylamide derivative of the hydroxy alkyls containing N- such as base-N- propane (methyl) acrylamide；Amino methyl (methyl) third
(methyl) acrylamide derivative of the aminoalkyls containing N- such as acrylamide, amino-ethyl (methyl) acrylamide；N- methoxy methyl
(methyl) acrylamide derivative of the alkoxies containing N- such as base acrylamide, N- ethoxymethyl acrylamide；Mercapto methyl (first
Base) mercaptoalkyl containing N- such as acrylamide, mercaptoethyl (methyl) acrylamide (methyl) acrylamide derivative；Deng.Separately
Outside, the nitrogen-atoms as (methyl) acrylamido forms (methyl) acrylamide derivative containing heterocycle of heterocycle, can be with
It enumerates for example: N- acryloyl morpholine, N- acryloylpiperidine, N- methacryloylpiperidine, N- acryloyl group nafoxidine
Deng.
In above-mentioned (methyl) acrylamide derivative, from from the aspect of the cementability of polarizing film, various transparent protective films,
It is preferred that (methyl) acrylamide derivative of the hydroxy alkyl containing N-, particularly preferred N- hydroxyethyl (methyl) acrylamide.
In addition, can be enumerated for example as monofunctional free radical's polymerizable compound: with (methyl) acryloxy
Various (methyl) acrylic acid derivatives.Specifically, can enumerate for example: (methyl) methyl acrylate, (methyl) acrylic acid second
Ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2- methyl -2- nitro propyl ester, (methyl)
N-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl)
Acrylic acid n-pentyl ester, (methyl) t-amyl, (methyl) acrylic acid 3- pentyl ester, (methyl) acrylic acid 2,2- dimethyl butyrate
Ester, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid cetyl, (methyl) n-octyl, (methyl) acrylic acid 2- second
(methyl) acrylic acid such as the own ester of base, (methyl) acrylic acid 4- methyl-2-propyl pentyl ester, (methyl) acrylic acid n-octadecane base ester
(carbon atom number 1-20) alkyl esters.
In addition, can be enumerated for example as above-mentioned (methyl) acrylic acid derivative: (methyl) cyclohexyl acrylate, (first
Base) (methyl) the acrylate base ester such as acrylic acid ring pentyl ester；
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester；
Ice drops in (methyl) acrylic acid 2- isobornyl thiocyanoacetate, (methyl) acrylic acid 2- norborny methyl esters, (methyl) acrylic acid 5-
Piece alkene -2- base-methyl esters, (methyl) acrylic acid 3- methyl -2- norborny methyl esters, (methyl) propylene acid dihydride dicyclopentadiene
Ester (bis- Le (メ タ) ア Network リ レ ー ト of ジ シ Network ロ ペ Application テ), (methyl) propylene acid dihydride dicyclopentadiene 2-ethoxyethyl acetate (ジ
Bis- Le オ キ シ エ チ Le (メ タ) ア Network リ レ of シ Network ロ ペ Application テ, mono- ト), (methyl) acrylic acid tetrahydro dicyclopentadiene ester
Polycycles (methyl) acrylate such as (bis- Le (メ タ) ア Network リ レ of ジ シ Network ロ ペ Application タ, mono- ト)；
(methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- methoxy
Ylmethoxy ethyl ester, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic ethyl carbitol, (methyl) acrylic acid benzene
(methyl) acrylate containing alkoxy or phenoxy group such as oxygroup ethyl ester, alkyl phenoxy polyethylene glycol (methyl) acrylate；
Deng.
In addition, can be enumerated as above-mentioned (methyl) acrylic acid derivative: (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl)
Acrylic acid 2- hydroxypropyl acrylate, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxy butyl ester, (methyl) acrylic acid 4- hydroxyl fourth
Ester, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) propylene
(methyl) acrylic acid hydroxy alkyl esters such as sour 12- hydroxylauric ester or acrylic acid [4- (hydroxymethyl) cyclohexyl] methyl esters, hexamethylene
(methyl) propylene of the hydroxyls such as dimethanol list (methyl) acrylate, 2- hydroxyl -3- phenoxy propyl (methyl) acrylate
Acid esters；
(methyl) glycidyl acrylate, 4- hydroxyl butyl (methyl) acrylate glycidyl ether etc. are containing epoxy group
(methyl) acrylate；
2,2,2- trifluoroethyls (methyl) acrylate, 2,2,2- trifluoroethyl ethyl (methyl) acrylate, (methyl)
Acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester, (methyl) acrylic acid octafluoro pentyl ester, the 17 fluorine last of the ten Heavenly stems of (methyl) acrylic acid
Halogen-containing (methyl) acrylate such as chloro- 2- hydroxypropyl (methyl) acrylate of ester, 3-；
(methyl) acrylate etc. (methyl) acrylic acid alkylaminoalkyl ester；
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-
(methyl) acrylate of the oxygen heterocycle butyl such as oxetanyl methyl (methyl) acrylate；
(methyl) tetrahydrofurfuryl acrylate, butyrolactone (methyl) acrylate etc. have heterocycle (methyl) acrylate,
Or 3-hydroxypivalic acid neopentyl glycol (methyl) acrylic acid adduct, p-phenyl phenol (methyl) acrylate etc..
In addition, can be enumerated as monofunctional free radical's polymerizable compound: (methyl) acrylic acid, carboxy ethyl acrylate,
The carboxylic monomer such as carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, iso-crotonic acid.
In addition, can be enumerated for example as monofunctional free radical's polymerizable compound: n-vinyl pyrrolidone, N- second
The lactams system such as alkenyl-epsilon-caprolactams, methyl ethylene pyrrolidones vinyl monomer；Vinylpyridine, vinylpiperidine
Ketone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl
Quinoline etc. has nitrogenous heterocyclic vinyl monomer etc..
In addition, the free radical polymerization of active methylene can be used as monofunctional free radical's polymerizable compound
Property compound.The free-radical polymerised compound of active methylene is in end or in the molecule with (methyl) acryloyl
The compound of base isoreactivity double bond base and active methylene.As active methylene group, can enumerate for example: acetoacetyl
Base, alkoxypropan diacyl or Cyanoacetyl etc..Above-mentioned active methylene group is preferably acetoacetyl.As active
The concrete example of the free-radical polymerised compound of methylene can be enumerated for example: 2- acetoacetoxyethyl (methyl) propylene
Acid esters, 2- acetoacetoxy groups propyl (methyl) acrylate, 2- acetoacetoxy groups -1- Methylethyl (methyl) acrylate
Etc. acetoacetoxy groups alkyl (methyl) acrylate；2- ethoxy-c diacyl oxygroup ethyl (methyl) acrylate, 2- cyanogen
Base Acetoxvethyl (methyl) acrylate, N- (2- cyano-acetoxy ethyl) acrylamide, N- (2- propiono acetyl oxygen
Base butyl) acrylamide, N- (4- acetoacetoxy groups methylbenzyl) acrylamide, N- (2- acetoacetyl amino-ethyl) third
Acrylamide etc..The free-radical polymerised compound of active methylene is preferably acetoacetoxy groups alkyl (methyl) acrylic acid
Ester.
" multifunctional free-radical polymerised compound "
In addition, can be enumerated for example: tripropylene glycol two as multifunctional free-radical polymerised compounds more than two functions
(methyl) acrylate, tetraethylene glycol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol
It is two (methyl) acrylate, 1,10- decanediol diacrylate, two (methyl) acrylate of 2- ethyl -2- butyl propylene glycol, double
Phenol A bis- (methyl) acrylate, bisphenol A epoxy ethane additive product two (methyl) acrylate, bisphenol A propylene oxide addition product two
(methyl) acrylate, bisphenol-A diglycidyl ether two (methyl) acrylate, neopentyl glycol two (methyl) acrylate,
Tricyclodecane Dimethanol two (methyl) acrylate, cyclic trimethylolpropane formal (methyl) acrylate, dioxanes two
Alcohol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, season penta
Tetrol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, EO
Bis- [4- (the 2- (methyl) third of carboxylate, 9,9- of (methyl) acrylic acid and polyalcohol such as modified two glycerol four (methyl) acrylate
Alkene oyloxyethoxy) phenyl] fluorenes.It as concrete example, can enumerate: Aronix M-220, M-306 (East Asia Synesis Company
System), Light Acrylate 1,9ND-A (chemical company, common prosperity society system), LightAcrylate DGE-4A (common prosperity society chemistry
Corporation), Light Acrylate DCP-A (chemical company, common prosperity society system), SR-531 (Sartomer Company system), CD-536
(Sartomer Company system) etc..It according further to needs, can enumerate: various epoxy (methyl) acrylate, carbamate (first
Base) acrylate, polyester (methyl) acrylate or various (methyl) acrylate monomers etc..
In terms of the water absorption rate for controlling above-mentioned solidfied material and to meet optics of the polarizing coating under harsh humidified ambient resistance to
In terms of long property, preferably free-radical polymerised compound contains above-mentioned multifunctional free-radical polymerised compound.It is above-mentioned it is multifunctional from
By in base polymerizable compound, the preferred high free-radical polymerised compound of logPow value.Free-radical polymerised compound
LogPow value is preferably 2 or more, and more preferably 3 or more, most preferably 4 or more.
The free-radical polymerised compound high as logPow value can be enumerated for example: two (first of Tricyclodecane Dimethanol
Base) alicyclic rings (methyl) propylene such as acrylate (logPow=3.05), (methyl) isobornyl acrylate (logPow=3.27)
Acid esters；
1,9- nonanediol two (methyl) acrylate (logPow=3.68), 1,10- decanediol diacrylate (logPow
=4.10) long-chain fats race (methyl) acrylate such as；
3-hydroxypivalic acid neopentyl glycol (methyl) acrylic acid adduct (logPow=3.35), 2- ethyl -2- butyl the third two
Alcohol two (methyl) acrylate (logPow=3.92) etc. highly branched chains (methyl) acrylate；
4 moles of bisphenol-A two (methyl) acrylate (logPow=5.46), bisphenol-A epoxy ethane addition products two (methyl)
2 moles of acrylate (logPow=5.15), bisphenol A propylene oxide (methyl) acrylate of addition product two (logPow=
6.10), the bis- [4- (2- (first of 4 moles of addition product two (methyl) acrylate (logPow=6.43), 9,9- of bisphenol A propylene oxide
Base) acryloyloxyethoxy) phenyl] fluorenes (logPow=7.48), p-phenyl phenol (methyl) acrylate (logPow=
3.98) (methyl) acrylate containing aromatic rings such as；Deng.
For free-radical polymerised compound, from have both with polarizing film, the cementability of various transparent protective films and harshness
In the environment of optical durability from the viewpoint of, preferably by monofunctional free radical's polymerizable compound and multifunctional radical polymerization
Conjunction property compound is used in combination.In general, preferably being polymerize relative to 100 weight % of free-radical polymerised compound with monofunctional free radical
The ratio of 20~97 weight % of property 3~80 weight % of compound and multifunctional free-radical polymerised compound is used in combination.
<form of free radical polymerization curing type adhesive>
About polarizing coating curing type adhesive of the invention, by curability composition with active energy ray-curable at
Point form use in the case where, can be used as the use of active energy ray curable adhesive, in addition, by curability composition
In the form of Thermocurable ingredient in the case where use, the use of thermohardening type adhesive can be used as.Above-mentioned active-energy is penetrated
For line curing type adhesive, whens active energy beam is using electron beam etc., which is not necessarily to
Containing Photoepolymerizationinitiater initiater, but when active energy beam uses ultraviolet light or visible light, the active energy ray curable gluing
Agent preferably comprises Photoepolymerizationinitiater initiater.On the other hand, by the curability composition of above-mentioned adhesive in the form of Thermocurable ingredient
In the case where use, which preferably comprises thermal polymerization.
" Photoepolymerizationinitiater initiater "
Photoepolymerizationinitiater initiater when using free-radical polymerised compound can suitably be selected according to active energy beam.It is logical
Cross ultraviolet light or when visible light is solidified using ultraviolet light or the Photoepolymerizationinitiater initiater of visible photodestruciton.As above-mentioned photopolymerization
Initiator can be enumerated for example: benzil, benzophenone, benzoyl benzoic acid, 3,3 '-dimethyl -4- methoxyl group hexichol first
The benzophenone based compounds such as ketone；4- (2- hydroxyl-oxethyl) phenyl (2- hydroxyl -2- propyl) ketone, Alpha-hydroxy-α, α '-dimethyl
The aromatic ketones compounds such as acetophenone, 2- methyl -2- hydroxypropiophenonepreparation, Alpha-hydroxy cyclohexyl phenyl ketone；Methoxyacetophenone, 2,
2- dimethoxy-2- phenyl acetophenone, 2,2- diethoxy acetophenone, 2- methyl-1-[4- (methylsulfany)-phenyl]-2-
Quinoline is for acetophenones based compounds such as propane -1- ketone；Benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin butyl ether,
The benzoin ethers based compound such as anisoin methyl ether；The aromatic series ketal based compound such as benzil dimethyl ketal；2- naphthalene sulfonyl
The aromatic sulfonyls based compound such as chlorine；The photolytic activities oxime system chemical combination such as 1- phenyl -1,1- propanedione -2- (O- ethoxy carbonyl) oxime
Object；Thioxanthones, 2-chlorothioxanthone, 2- methyl thioxanthones, 2,4- dimethyl thioxanthone, isopropyl thioxanthone, 2,4- dichloro thioxanthene
The thioxanthones based compounds such as ketone, 2,4- diethyl thioxanthone, 2,4- diisopropylthioxanthone, dodecyl thioxanthones；Camphorquinone；
Halogenated ketone；Acylphosphine oxide；Acyl phosphonate etc..In Photoepolymerizationinitiater initiater, the preferred high Photoepolymerizationinitiater initiater of logPow value.
Although the ingredient in the calculating of the logPow value of polarizing coating curing type adhesive does not include Photoepolymerizationinitiater initiater, photopolymerization
The logPow value of initiator is preferably 1 or more, and more preferably 2 or more, most preferably 3 or more.
Total amount 100 of the use level of above-mentioned Photoepolymerizationinitiater initiater relative to curability composition (free-radical polymerised compound)
Parts by weight are 20 parts by weight or less.The use level of Photoepolymerizationinitiater initiater is preferably 0.01~20 parts by weight, further preferably
0.05~10 parts by weight, further preferably 0.1~5 parts by weight.
In addition using contain free-radical polymerised compound as curability composition visible light curable in the form of using this
When the polarizing coating curing type adhesive of invention, particularly preferably drawn using the light to 380nm or more in highly sensitive photopolymerization
Send out agent.It is described below to the light of 380nm or more in highly sensitive Photoepolymerizationinitiater initiater.
As above-mentioned Photoepolymerizationinitiater initiater, preferably exclusive use the following general formula (1) compound represented
[changing 1]
(in formula, R1And R2Expression-H ,-CH2CH3,-iPr or Cl, R1And R2Can be the same or different), or by general formula
(1) compound represented is used in combination with the aftermentioned light to 380nm or more in highly sensitive Photoepolymerizationinitiater initiater.Use general formula
(1) the case where the case where compound represented with being used alone to the light of 380nm or more in highly sensitive Photoepolymerizationinitiater initiater
It compares, cementability is more excellent.In general formula (1) compound represented, particularly preferred R1And R2For-CH2CH3Diethyl thioxanthone.
The composition ratio of general formula (1) compound represented in adhesive is preferably relative to 100 parts by weight of total amount of curability composition
0.1~5 parts by weight, more preferably 0.5~4 parts by weight, further preferably 0.9~3 parts by weight.
Additionally, it is preferred that polymerization trigger auxiliary agent is added as needed.As polymerization trigger auxiliary agent, can enumerate triethylamine,
Diethylamide, N methyldiethanol amine, ethanol amine, 4- dimethylaminobenzoic acid, 4- dimethylaminobenzoic acid methyl esters, 4- bis-
Methylaminobenzoate ethyl ester, 4- dimethylaminobenzoic acid isopentyl ester etc., particularly preferred ethyl 4-dimethylaminobenzoate.
When using polymerization trigger auxiliary agent, total amount 100 parts by weight of the additive amount relative to curability composition, usually 0~5 parts by weight,
Preferably 0~4 parts by weight, most preferably 0~3 parts by weight.
In addition, well known Photoepolymerizationinitiater initiater also can be used together as needed.Transparent protective film with UV absorbability
380nm light below is not transmitted, therefore it is preferable to use the light to 380nm or more in highly sensitive light as Photoepolymerizationinitiater initiater
Polymerization initiator.Specifically, can enumerate: 2- methyl-1-(4- methylsulfanylphenyl)-2- morpholino propane-1- ketone, 2- benzyl
Base -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 oxides, bis- (2,4,6- front threes
Base benzoyl)-phenylphosphine oxide, bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- fluoro- 3- (1H- pyrroles -1-
Base)-phenyl) titanium etc..
Especially as Photoepolymerizationinitiater initiater, other than the Photoepolymerizationinitiater initiater of general formula (1), preferably further under use
State general formula (2) compound represented；
[changing 2]
(in formula, R3、R4And R5Expression-H ,-CH3、-CH2CH3,-iPr or Cl, R3、R4And R5It can be identical or not
Together).As general formula (2) compound represented, 2- methyl-1-(the 4- methylsulfany benzene as commercially available product can be properly used
Base) -2- morpholino propane -1- ketone (trade name: IRGACURE907 manufacturer: BASF).In addition to this, due to 2- benzyl -2- two
Methylamino -1- (4- morphlinophenyl)-butanone -1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino
Base) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone (trade name: IRGACURE379 manufacture
Quotient: BASF) high sensitivity and it is preferred that.
The free-radical polymerised compound (a1) of < active methylene and free radical polymerization with dehydrogenation cause
Agent (a2) >
In above-mentioned active energy ray curable adhesive, active methylene is used as free-radical polymerised compound
When free-radical polymerised compound (a1) of base, preferably combining with the radical polymerization initiator (a2) with dehydrogenation makes
With.According to this constitution, especially just after being taken out in high humidity environment or water (non-dry state), gluing possessed by polarizing coating
The cementability of oxidant layer also significantly improves.Should the reason is not yet clear, but think the reason is as follows that.That is, the freedom of active methylene
Base polymerizable compound (a1) polymerize together with other free-radical polymerised compounds for constituting gluing oxidant layer, is introduced in simultaneously
The main chain and/or side chain of base polymer in gluing oxidant layer form gluing oxidant layer.In the polymerization process, have if it exists de-
The radical polymerization initiator (a2) of hydrogen effect, then from active while forming the base polymer for constituting gluing oxidant layer
The free-radical polymerised compound (a2) of methylene sloughs hydrogen, generates free radicals in methylene.Then, the Asia of free radical is produced
Methyl is reacted with the hydroxyl of the polarizing film of PVA etc., forms covalent bond between gluing oxidant layer and polarizing film.As a result, thus it is speculated that
Especially under non-dry state, the cementability of gluing oxidant layer possessed by polarizing coating is also significantly improved.
In the present invention, as the radical polymerization initiator (a2) with dehydrogenation, such as thioxanthones system can be enumerated
Radical polymerization initiator, benzophenone series radical polymerization initiator etc..Above-mentioned radical polymerization initiator (a2) is preferably
Thioxanthones system radical polymerization initiator.As thioxanthones system radical polymerization initiator, for example above-mentioned general formula (1) can be enumerated
Compound represented.As the concrete example of general formula (1) compound represented, can enumerate for example thioxanthones, dimethyl thioxanthone,
Diethyl thioxanthone, isopropyl thioxanthone, clopenthixal ketone etc..In general formula (1) compound represented, particularly preferred R1And R2For-
CH2CH3Diethyl thioxanthone.
In above-mentioned active energy ray curable adhesive, the free-radical polymerised compound containing active methylene
(a1) and in the case where the radical polymerization initiator with dehydrogenation (a2), the total amount of curability composition is set as 100 weights
When measuring %, preferably: the free-radical polymerised compound (a1) and phase of the above-mentioned active methylene containing 1~50 weight %
100 parts by weight of total amount for curability composition are the radical polymerization initiator (a2) of 0.1~10 parts by weight.
As described above, in the presence of radical polymerization initiator (a2) with dehydrogenation, making to have in the present invention
The methylene of the free-radical polymerised compound (a1) of active methylene group generates free radicals, the polarization of the methylene and PVA etc.
The hydroxyl of piece reacts and forms covalent bond.Therefore, in order to make the free-radical polymerised compound of active methylene
(a1) methylene generates free radicals and is sufficiently formed the covalent bond, and curability composition total amount is preferably being set as 100 weights
When measuring %, the free-radical polymerised compound (a1) of the active methylene containing 1~50 weight % even more preferably contains
There is the free-radical polymerised compound (a1) of the active methylene of 3~30 weight %.In order to improve water resistance sufficiently simultaneously
The cementability under non-dry state is improved, and it is preferred that the free-radical polymerised compound (a1) of active methylene is set as
1 weight % or more.On the other hand, if more than 50 weight %, the solidification that gluing oxidant layer occurs sometimes is bad.Additionally, it is preferred that phase
The radical polymerization initiator that 0.1~10 parts by weight have dehydrogenation is contained for 100 parts by weight of total amount of curability composition
(a2), even more preferably there is containing 0.3~9 parts by weight the radical polymerization initiator (a2) of dehydrogenation.In order to make to take off
Hydrogen reaction sufficiently carries out, it is preferable to use the above radical polymerization initiator of 0.1 parts by weight (a2).On the other hand, if more than 10 weights
Part is measured, then will not be completely dissolved in adhesive sometimes.
" thermal polymerization "
As thermal polymerization, it will not preferably cause the thermal polymerization of polymerization due to thermal cracking when forming gluing oxidant layer
Initiator.For example, 10 hours half life temperatures are 65 DEG C or more, further preferably 75~90 DEG C as thermal polymerization.
It should be noted that half-life period is the index for indicating the decomposition rate of polymerization initiator, refer to that the residual quantity of polymerization initiator is
Time until half.About the decomposition temperature for obtaining half-life period in the arbitrary time, the half-life period at arbitrary temperature
It is time, on the books in manufacturer's catalogue etc., for example, in " the organic peroxide catalogue " the 9th edition of NOF Corp
It is on the books in (in May, 2003) " etc..
It as thermal polymerization, can enumerate for example: lauroyl peroxide (10 hours half life temperatures: 64 DEG C), mistake
Benzoyl Oxide (10 hours half life temperatures: 73 DEG C), bis- (tert-butyl peroxide) -3 1,1-, 3,5- trimethyl-cyclohexanes (10
Hour half life temperature: 90 DEG C), dicetyl peroxydicarbonate two (2- ethylhexyl) ester (10 hours half life temperatures: 49 DEG C), peroxide
Change two carbonic acid two (4- tert-butylcyclohexyl) esters, peroxide-butyl carbonate (10 hours half life temperatures: 51 DEG C), peroxide
Change the neodecanoic acid tert-butyl ester (10 hours half life temperatures: 48 DEG C), the tertiary own ester of peroxidating neopentanoic acid, tert-Butyl peroxypivalate,
Dilauroyl peroxide (10 hours half life temperatures: 64 DEG C), the positive decoyl of peroxidating two, 1,1,3,3- tetramethyl butyl peroxide
Change -2 ethyl hexanoic acid ester (10 hours half life temperatures: 66 DEG C), peroxidating two (4- toluyl), dibenzoyl peroxide
(10 hours half life temperatures: 73 DEG C), peroxidating tert-butyl isobutyrate (10 hours half life temperatures: 81 DEG C), 1,1-, bis- (peroxide
Change tertiary hexyl) the organic systems peroxide such as hexamethylene.
In addition, can be enumerated for example as thermal polymerization: 2,2 '-azobis isobutyronitriles (10 hour half-life period temperature
Degree: 67 DEG C), 2,2 '-azos bis- (2- methylbutyronitriles) (10 hours half life temperatures: 67 DEG C), 1,1- azo bis cyclohexane -1- first
The azo compounds such as nitrile (10 hours half life temperatures: 87 DEG C).
Total amount 100 weight of the use level of thermal polymerization relative to curability composition (free-radical polymerised compound)
Part is 0.01~20 parts by weight.The use level of thermal polymerization is further 0.05~10 parts by weight, further preferably 0.1
~3 parts by weight.
<2: cation polymerization curing type adhesive>
As the curability composition of cation polymerization curing type adhesive, can enumerate with epoxy group, oxetanylmethoxy
Compound.Compound with epoxy group is as long as the compound in the molecule at least two epoxy group without special
Limitation, can be used generally known various curability epoxides.It, as an example can be with as preferred epoxide
Enumerate: in the molecule the compound (aromatic system epoxide) at least two epoxy group and at least one aromatic rings,
There is intramolecular at least two epoxy group, at least one therein to be formed between adjacent 2 carbon atom for constituting ester ring
Compound (cycloaliphatic epoxy) etc..
<light cationic polymerization initiator>
Cation polymerization curing type adhesive contains epoxide and oxetane compound conduct described above
Curability composition, they all pass through it is cation polymerization curing, therefore cooperate light cationic polymerization initiator.The light cationic polymerization
Initiator generates cation kind or Louis by the irradiation of visible light, ultraviolet light, X-ray, electron beam isoreactivity energy-ray
This acid, causes epoxy group, the polymerization reaction of oxetanylmethoxy.
<other compositions>
Curing type adhesive of the invention preferably comprises following compositions.
<acrylic oligomers (A)>
Active energy ray curable adhesive of the invention in addition to above-mentioned free-radical polymerised compound curability at
Other than point, the acrylic oligomers (A) that (methyl) acrylic monomer is polymerized can also be contained.By in active energy
It measures in ray curing adhesive and contains acrylic oligomers (A), can reduce and active energy beam is irradiated to the adhesive
And the interfacial stress for making cure shrinkage when its solidification, can reduce the adherends such as adhesive and polarizing film and transparent protective film.
As a result, it is possible to inhibit the decline of the cementability of gluing oxidant layer and adherend.In order to sufficiently inhibit solidified material layer (adhesive
Layer) cure shrinkage, relative to 100 parts by weight of total amount of curability composition, the content of acrylic oligomers (A) is preferably 20
Parts by weight are hereinafter, below more preferably 15 parts by weight.If the content of the acrylic oligomers (A) in adhesive is excessive, right
The decline of reaction speed when adhesive irradiation active energy beam is violent, causes to solidify sometimes bad.On the other hand, relatively
In 100 parts by weight of total amount of curability composition, the acrylic oligomers (A) of 3 parts by weight or more are preferably comprised, further preferably
Acrylic oligomers (A) more than 5 parts by weight.
When operability of the active energy ray curable adhesive when considering coating, uniformity, preferably low viscosity, because
The acrylic oligomers (A) that (methyl) acrylic monomer is polymerized are preferably also low viscosity by this.As being low
Viscosity and can prevent gluing oxidant layer cure shrinkage acrylic oligomers, preferable weight-average molecular weight (Mw) be 15000 with
Under, more preferably 10000 hereinafter, particularly preferably 5000 or less.On the other hand, in order to sufficiently inhibit solidified material layer (adhesive
Layer) cure shrinkage, preferably the weight average molecular weight (Mw) of acrylic oligomers (A) be 500 or more, more preferably 1000 with
On, particularly preferably 1500 or more.As (methyl) acrylic monomer for constituting acrylic oligomers (A), specifically,
It can enumerate for example: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) propylene
Isopropyl propionate, (methyl) acrylic acid 2- methyl -2- nitro propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate,
(methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) t-amyl,
(methyl) acrylic acid 3- pentyl ester, (methyl) acrylic acid 2,2- dimethyl butyl ester, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid
Cetyl, (methyl) n-octyl, (methyl) 2-EHA, (methyl) acrylic acid 4- methyl-2-propyl penta
(methyl) acrylic acid (carbon atom number 1-20) alkyl esters and, for example, (methyl) such as ester, (methyl) acrylic acid n-octadecane ester
Acrylate base ester (for example, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester etc.), (methyl) acrylic acid aralkyl
Base ester (for example, (methyl) benzyl acrylate etc.), polycycle (methyl) acrylate are (for example, (methyl) acrylic acid 2- isoborneol
Ester, (methyl) acrylic acid 2- norborny methyl esters, (methyl) acrylic acid 5- norbornene -2- base-methyl esters, (methyl) acrylic acid 3-
Methyl -2- norborny methyl esters etc.), (methyl) esters of acrylic acid of hydroxyl is (for example, (methyl) hydroxy-ethyl acrylate, (first
Base) acrylic acid 2- hydroxypropyl acrylate, (methyl) methacrylic acid 2,3- dihydroxypropyl methyl-butyl acrylate etc.), containing alkoxy or phenoxy group
(methyl) esters of acrylic acid ((methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) propylene
Sour 2- methoxymethoxy ethyl ester, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic ethyl carbitol, (methyl)
Phenoxyethyl acrylate etc.), (methyl) esters of acrylic acid containing epoxy group is (for example, (methyl) glycidyl acrylate
Deng), halogen-containing (methyl) esters of acrylic acid (for example, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, (methyl) acrylic acid 2,2,
2- trifluoroethyl ethyl ester, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester, (methyl) acrylic acid octafluoro penta
Ester, 17 fluorine last of the ten Heavenly stems ester of (methyl) acrylic acid etc.), (methyl) alkyl acrylate aminoalkyl ester is (for example, (methyl) acrylic acid diformazan ammonia
Base ethyl ester etc.) etc..These (methyl) acrylate may be used singly or two or more in combination.It is low as acrylic acid series
The concrete example of polymers (A), can enumerate East Asia Synesis Company manufacture " ARUFON ", Soken Chemical Company manufacture " ACTFLOW ",
BASF Japanese firm manufactures " JONCRYL " etc..The acrylic oligomers (A) that (methyl) acrylic monomer is polymerized
In, preferably logPow value is high.Acrylic oligomers (A) are contained in the meter of the logPow value of polarizing coating curing type adhesive
Ingredient in calculation.In the calculating of logPow value, the molal quantity of the ingredient of acrylic oligomers (A), which uses, is scaled composition propylene
The molal quantity of (methyl) acrylic monomer of acid system oligomer (A).The propylene that (methyl) acrylic monomer is polymerized
More than the logPow value preferably 2 of acid system oligomer (A) is, more preferably 3 or more, most preferably 4 or more.
<photoacid generator (B)>
Photoacid generator (B) can be contained in above-mentioned active energy ray curable adhesive.It is penetrated in above-mentioned active-energy
It the case where containing photoacid generator in line curing type adhesive, compared with the case where not containing photoacid generator, can mention tremendously
The water resistance and durability of high gluing oxidant layer.Photoacid generator (B) can be indicated by the following general formula (3).
General formula (3)
[changing 3]
L+X-
(wherein, L+Indicate arbitrary cation.In addition, X-It indicates selected from by PF66 -、SbF6 -、AsF6 -、SbCl6 -、
BiCl5 -、SnCl6 -、ClO4 -, dithiocar-bamate anion, SCN- composition group in counter anion)
About preferably as the cationic L for constituting general formula (3)+Cation structure, can enumerate selected from following
Cation in general formula (4)~general formula (12).
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]
Ar4-I+-Ar5
(in above-mentioned general formula (4)-(12), wherein R1、R2And R3It each independently represents selected from hydrogen atom, replace or do not take
The alkyl in generation, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, substitution or not
Substituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyl
Group in base, substituted or unsubstituted carbonyl oxygroup, substituted or unsubstituted Epoxide carbonyl or halogen atom.R4Expression and R1、
R2And R3The identical group of the group of middle record.R5Indicate substituted or unsubstituted alkyl, substituted or unsubstituted alkyl sulfenyl.
R6And R7Each independently represent substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy.R indicates halogen atom, hydroxyl
Base, carboxyl, sulfydryl, cyano, nitro, substituted or unsubstituted carbamoyl, substituted or unsubstituted alkyl, substitution do not take
The alkenyl in generation, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, substituted or unsubstituted alkoxy, substitution or
It is unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted
Artyl sulfo, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyl oxygroup, takes substituted or unsubstituted heterocyclethio
Generation or unsubstituted Epoxide carbonyl in any one.Ar4、Ar5Indicate substituted or unsubstituted aryl, substituted or unsubstituted
Any one in heterocycle.X indicates oxygen or sulphur atom.I indicates 0~5 integer.J indicates 0~4 integer.K indicates 0~3
Integer.Furthermore it is possible between adjacent R, Ar4With Ar5、R2With R3、R2With R4、R3With R4、R1With R2、R1With R3、R1With R4、
R1With R or R1With R5Cyclic structure made of being mutually bonded.)
The cation (sulfonium cation) for meeting general formula (4) can be enumerated:
3,5-dimethylphenyl sulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (chlorphenyl) sulfonium, dimethyl (p-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 are (to sulfydryl benzene
Base) sulfonium, dimethyl (to methylsulfinylphenyl) sulfonium, dimethyl (to methylsulfonyl phenyl) sulfonium, dimethyl (adjacent acetyl group
Phenyl) 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-
Naphthalene) sulfonium, dimethyl (9- anthryl) sulfonium, diethyl phenyl sulfonium, Methylethyl phenyl sulfonium, methyldiphenyl base sulfonium, triphenylsulfonium, two
Isopropyl phenyl sulfonium, diphenyl (4- phenylsulfartyl-phenyl)-sulfonium, 4,4 '-bis- (diphenyl sulfonium) diphenylsulfides, 4,4 '-is bis-
[two [(4- (2- Hydroxy-ethoxy)-phenyl)] sulfoniums]] diphenylsulfide, 4,4 '-bis- (diphenyl sulfoniums) Asia biphenyl, diphenyl are (adjacent
Fluorophenyl) sulfonium, diphenyl (chlorphenyl) sulfonium, diphenyl (p-bromophenyl) sulfonium, diphenyl (to cyano-phenyl) sulfonium, diphenyl
(m-nitro base) sulfonium, diphenyl (2,4,6- tribromo phenyl) sulfonium, diphenyl (pentafluorophenyl group) sulfonium, diphenyl are (to (fluoroform
Base) phenyl) sulfonium, diphenyl (p-hydroxybenzene) sulfonium, diphenyl (to mercaptophenyl) sulfonium, diphenyl is (to methylsulfinyl benzene
Base) sulfonium, diphenyl (to methylsulfonyl phenyl) sulfonium, diphenyl (adjacent acetylphenyl) sulfonium, diphenyl (o-benzoyl base benzene
Base) sulfonium, diphenyl (p-methylphenyl) sulfonium, diphenyl (p-isopropyl phenyl) sulfonium, diphenyl (to octadecylphenyl) sulfonium, two
Phenyl (to cyclohexyl phenyl) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, diphenyl (O-methoxy carbonyl phenyl) sulfonium, diphenyl
(to phenylsulfartyl phenyl) sulfonium, (7- methoxyl group -2- oxo -2H- chromene -4- base) diphenyl sulfonium, (4- methoxynaphthalene -1-
Base) diphenyl sulfonium, diphenyl (to isopropoxy carbonyl phenyl) sulfonium, diphenyl (2- naphthalene) sulfonium, diphenyl (9- anthryl) sulfonium, second
Base diphenyl sulfonium, Methylethyl (o-tolyl) sulfonium, methyl two (p-methylphenyl) sulfonium, three (p-methylphenyl) sulfoniums, diisopropyl (4-
Phenylsulfartyl phenyl) sulfonium, diphenyl (2- thienyl) sulfonium, diphenyl (2- furyl) sulfonium, diphenyl (9- ethyl -9H carbazole -3-
Base) sulfonium etc., but not limited to this.
The cation (oxidation sulfonium cation) for meeting general formula (5) can be enumerated:
3,5-dimethylphenyl sulfoxonium, dimethyl (o-fluorophenyl) sulfoxonium, dimethyl (chlorphenyl) sulfoxonium, dimethyl
(p-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, two
Methyl (p-hydroxybenzene) sulfoxonium, dimethyl (to mercaptophenyl) sulfoxonium, dimethyl (to methylsulfinylphenyl) oxygen
Change sulfonium, dimethyl (to methylsulfonyl phenyl) sulfoxonium, dimethyl (adjacent acetylphenyl) sulfoxonium, dimethyl (adjacent benzene first
Aminosulfonylphenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-isopropyl phenyl) sulfoxonium, dimethyl be (right
Octadecylphenyl) sulfoxonium, dimethyl (to cyclohexyl phenyl) sulfoxonium, dimethyl (p-methoxyphenyl) sulfoxonium, two
Methyl (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 is (to isopropoxy
Carbonyl phenyl) sulfoxonium, dimethyl (2- naphthalene) sulfoxonium, dimethyl (9- anthryl) sulfoxonium, diethyl phenyl sulfoxonium, first
Base ethylphenyl sulfoxonium, methyldiphenyl base sulfoxonium, triphenyl sulfoxonium, diisopropyl phenyl sulfoxonium, diphenyl (4- benzene
Base sulfenyl-phenyl)-sulfoxonium, 4,4 '-bis- (diphenyl sulfoxonium) diphenylsulfides, 4,4 '-bis- [two [(4- (2- hydroxyls-second
Oxygroup)-phenyl)] sulfoxonium] diphenylsulfide, 4,4 '-bis- (diphenyl sulfoxoniums) Asia biphenyl, diphenyl (o-fluorophenyl) oxygen
Change sulfonium, diphenyl (chlorphenyl) sulfoxonium, diphenyl (p-bromophenyl) sulfoxonium, diphenyl (to cyano-phenyl) sulfoxonium,
Diphenyl (m-nitro base) sulfoxonium, diphenyl (2,4,6- tribromo phenyl) sulfoxonium, diphenyl (pentafluorophenyl group) sulfoxonium,
Diphenyl (to (trifluoromethyl) phenyl) sulfoxonium, diphenyl (p-hydroxybenzene) sulfoxonium, diphenyl (to mercaptophenyl) oxygen
Change sulfonium, diphenyl (to methylsulfinylphenyl) sulfoxonium, diphenyl (to methylsulfonyl phenyl) sulfoxonium, diphenyl
(adjacent acetylphenyl) sulfoxonium, diphenyl (o-benzoyl base phenyl) sulfoxonium, diphenyl (p-methylphenyl) sulfoxonium, two
Phenyl (p-isopropyl phenyl) sulfoxonium, diphenyl (to octadecylphenyl) sulfoxonium, diphenyl (to cyclohexyl phenyl) oxygen
Change sulfonium, diphenyl (p-methoxyphenyl) sulfoxonium, diphenyl (O-methoxy carbonyl phenyl) sulfoxonium, diphenyl (to phenyl
Sulfenyl phenyl) sulfoxonium, (7- methoxyl group -2- oxo -2H- chromene -4- base) diphenyl sulfoxonium, (4- methoxynaphthalene -1-
Base) diphenyl sulfoxonium, diphenyl (to isopropoxy carbonyl phenyl) sulfoxonium, diphenyl (2- naphthalene) sulfoxonium, diphenyl
(9- anthryl) sulfoxonium, ethyl diphenyl sulfoxonium, Methylethyl (o-tolyl) sulfoxonium, methyl two (p-methylphenyl) oxidation
Sulfonium, three (p-methylphenyl) sulfoxoniums, diisopropyl (4- phenylsulfartyl phenyl) sulfoxonium, diphenyl (2- thienyl) sulfoxonium,
Diphenyl (2- furyl) sulfoxonium, diphenyl (9- ethyl -9H carbazole -3- base) sulfoxonium etc., but not limited to this.
The cation (phosphonium cation) for meeting general formula (6) can be to arrange the example for phosphonium cation:
Trimethyl benzene base Phosphonium, triethyl group phenyl Phosphonium, tetraphenylphosphoniphenolate, triphenyl (p-fluorophenyl) Phosphonium, triphenyl (adjacent chlorobenzene
((to cyano-phenyl) Phosphonium, triphenyl, (m-nitro base) Phosphonium, triphenyl are (right for m-bromophenyl) Phosphonium, triphenyl for base) Phosphonium, triphenyl
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, triphen
Base is (to isopropyl phenyl) Phosphonium, triphenyl (O-methoxy carbonyl phenyl) Phosphonium, triphenyl (1- naphthalene) Phosphonium, triphenyl (9- anthracene
Base) Phosphonium, triphenyl (2- thienyl) Phosphonium, triphenyl (2- furyl) Phosphonium, triphenyl (9- ethyl -9H carbazole -3- base) Phosphonium etc., but
It is without being limited thereto.
The cation (pyridylium) for meeting general formula (7) can enumerate the example of pyridylium:
N- phenylpyridine, N- (Chloro-O-Phenyl) pyridine, N- (chlorphenyl) pyridine, N- (to cyano-phenyl) pyridine
, N- (O-Nitrophenylfluorone) pyridine, N- (to acetylphenyl) pyridine, N- (p-isopropyl phenyl) pyridine, N- is (to ten
Eight alkyl oxy phenyl) pyridine, N- (to methoxycarbonyl-phenyl) pyridine, N- (9- anthryl) pyridine, 2- chloro-1-phenyl
Pyridine, 2- cyano-1- phenylpyridine, 2- methyl-1-phenylpyridine, 2- vinyl-1- phenylpyridine, 2- phenyl-
1- phenylpyridine, 1,2- hexichol yl pyridines, 2- methoxyl group -1- phenylpyridine, 2- phenoxy group -1- phenylpyridine, 2-
Acetyl group -1- (p-methylphenyl) pyridine, 2- methoxycarbonyl -1- (p-methylphenyl) pyridine, the fluoro- 1- naphthlypyridine of 3-,
4- methyl-1-(2- furyl) pyridine, N- picoline, N- ethylpyridine etc., but not limited to this.
The cation (quinoline cation) for meeting general formula (8) can enumerate the example of quinoline cation:
N- methylquinoline, N- ethyl quinolinium, N- phenylchinoline, N- naphthalene quinoline, N- (Chloro-O-Phenyl) quinoline
, N- (chlorphenyl) quinoline, N- (to cyano-phenyl) quinoline, N- (O-Nitrophenylfluorone) quinoline, N- is (to acetylbenzene
Base) quinoline, N- (p-isopropyl phenyl) quinoline, N- (to octadecyl phenyl) quinoline, N- is (to methoxycarbonyl
Phenyl) quinoline, N- (9- anthryl) quinoline, 2- chloro-1-phenyl quinoline, 2- cyano-1- phenylchinoline, 2- methyl-1-
Phenylchinoline, 2- vinyl -1- phenylchinoline, 2- phenyl -1- phenylchinoline, 1,2- diphenylquinoline, 2- methoxy
Base -1- phenylchinoline, 2- phenoxy group -1- phenylchinoline, 2- acetyl group -1- phenylchinoline, 2- methoxycarbonyl -1- benzene
The fluoro- 1- phenylchinoline of base quinoline, 3-, 4- methyl-1-phenylchinoline, 2- methoxyl group-1- (p-methylphenyl) quinoline, 2-
Phenoxy group -1- (2- furyl) quinoline, 2- acetyl group -1- (2- thienyl) quinoline, 2- methoxycarbonyl -1- methylquinoline
, the fluoro- 1- ethyl quinolinium of 3-, 4- methyl-1-isopropyl quinoline etc., but not limited to this.
The cation (isoquinoline cation moiety) for meeting general formula (9) can enumerate the example of isoquinoline cation moiety:
N- phenyl isoquinolin quinoline, N- methylisoquinolinium, N- ethyl isoquinolin, N- (Chloro-O-Phenyl) isoquinolin, N-
(chlorphenyl) isoquinolin, N- (to cyano-phenyl) isoquinolin, N- (O-Nitrophenylfluorone) isoquinolin, N- are (to acetyl group
Phenyl) isoquinolin, N- (p-isopropyl phenyl) isoquinolin, N- (to octadecyl phenyl) isoquinolin, N- is (to first
Epoxide carbonyl phenyl) isoquinolin, N- (9- anthryl) isoquinolin, 1,2- diphenyl isoquinolin, N- (2- furyl) isoquinoline
Quinoline, N- (2- thienyl) isoquinolin, N- naphthalene isoquinolin etc., but not limited to this.
The cation (benzoxazoles cation, benzothiazole cation) for meeting general formula (10) can enumerate benzo
The example of oxazole cation:
N- methylbenzoxazole, N- ethyl benzoxazoles, N- naphthalene benzoxazoles, N- phenyl benzoxazoles,
N- (p-fluorophenyl) benzoxazoles, N- (rubigan) benzoxazoles, N- (to cyano-phenyl) benzoxazoles, N- are (adjacent
Methoxycarbonyl-phenyl) benzoxazoles, N- (2- furyl) benzoxazoles, N- (o-fluorophenyl) benzoxazoles, N- be (right
Cyano-phenyl) benzoxazoles, N- (m-nitro base) benzoxazoles, N- (to isopropoxy carbonyl phenyl) benzoxazoles
, N- (2- thienyl) benzoxazoles, N- (carboxyl phenyl) benzoxazoles, 2- sulfydryl -3- phenyl benzoxazoles, 2-
Methyl -3- phenyl benzoxazoles, 2- methylsulfany -3- (4- phenylsulfartyl phenyl) benzoxazoles, 6- hydroxyl -3- are (to first
Phenyl) benzoxazoles, 7- sulfydryl -3- phenyl benzoxazoles, the fluoro- 3- ethyl benzoxazoles of 4,5- bis- etc., but be not limited to
This.
The example of benzothiazole cation can be enumerated:
N- methylbenzothiazole, N- ethyl-benzothiazole, N- phenylbenzothiazol, N- (1- naphthalene) benzothiazole
, N- (p-fluorophenyl) benzothiazole, N- (rubigan) benzothiazole, N- (to cyano-phenyl) benzothiazole, N-
(O-methoxy carbonyl phenyl) benzothiazole, N- (p-methylphenyl) benzothiazole, N- (o-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- naphthalene) benzo thiophene
Azoles, 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 not limited to this.
The cation (furyl or thienyl iodine cation) for meeting general formula (11) can be enumerated:
Difuryl iodine, dithienyl iodine, bis- (4,5- dimethyl -2- furyl) iodine, bis- (chloro- 2- thiophene of 5-
Base) iodine, bis- (5- cyano -2- furyl) iodine, bis- (5- nitro -2- thienyl) iodine, bis- (5- acetyl group -2- furyls)
Iodine, bis- (5- carboxyl -2- thienyl) iodine, bis- (5- methoxycarbonyl -2- furyl) iodine, bis- (5- phenyl -2- furans
Base) iodine, bis- (5- (p-methoxyphenyl) -2- thienyl) iodine, bis- (5- vinyl -2- furyl) iodine, bis- (5- acetylene
Base -2- thienyl) iodine, bis- (5- cyclohexyl -2- furyl) iodine, bis- (5- hydroxyl -2- thienyl) iodine, bis- (5- benzene oxygen
Base -2- furyl) iodine, bis- (5- sulfydryl -2- thienyl) iodine, bis- (5- butyl sulfenyl -2- thienyl) iodine, bis- (5- benzene
Base sulfenyl -2- thienyl) iodine etc., but not limited to this.
The cation (diaryl iodonium cation) for meeting general formula (12) can be enumerated:
Diphenyl iodine, bis- (p-methylphenyl) iodine, bis- (to octyl phenyl) iodine, bis- (to octadecylphenyl) iodine
, bis- (to octyl phenyl) iodine, bis- (to octadecyl phenyl) iodine, phenyl (to octadecyl phenyl)
It is iodine, 4- isopropyl -4 '-methyldiphenyl base iodine, (4- isobutyl phenenyl)-p-methylphenyl iodine, bis- (1- naphthalene) iodine, double
(4- phenylsulfartyl phenyl) iodine, phenyl (6- benzoyl -9- ethyl -9H- carbazole -3- base) iodine, (7- methoxyl group -2- oxygen
Generation -2H- chromene -3- base) -4 '-isopropyl phenyl iodine etc., but not limited to this.
Then, the counter anion X- in mutual-through type (3) is illustrated.
Counter anion X- in general formula (3) is not particularly limited in principle, but preferred non-nucleophilic anion.Anti-
In the case that the anion X- that weighs is non-nucleophilic anion, it is not easy to cause the various materials of the cation coexisted in the molecule
Therefore as a result the necleophilic reaction of material can be improved photoacid generator itself shown in general formula (2), the gluing using the photoacid generator
The ageing stability of agent.Non-nucleophilic anion described herein refers to the anion for causing the ability of necleophilic reaction low.As
Such anion can be enumerated: PF6 -、SbF6 -、AsF6 -、SbCl6 -、BiCl5 -、SnCl6 -、ClO4 -, dithiocar-bamate
Anion, SCN-Deng.
In above-mentioned Exemplary anions, as the counter anion X in general formula (3)-, as it is particularly preferred contend with yin from
Son can enumerate PF6 -、SbF6 -And AsF6 -, can particularly preferably enumerate PF6 -、SbF6 -。
Therefore, the concrete example as the preferred salt for constituting photoacid generator (B), for by foregoing illustrative general formula (3)~logical
The concrete example of cationic structure shown in formula (12) and be selected from PF6 -、SbF6 -、AsF6 -、SbCl6 -、BiCl5 -、SnCl6 -、
ClO4 -, dithiocar-bamate anion, SCN-In anion constitute salt.
Specifically, the preferred concrete example as photoacid generator (B), can enumerate " Cyracure UVI-6992 ",
" Cyracure UVI-6974 " (more than, DOW Chemical Japanese firm system), " Adekaoptomer SP150 ",
" Adekaoptomer SP152 ", " Adekaoptomer SP170 ", " Adekaoptomer SP172 " (more than, Co., Ltd.
ADEKA system), " IRGACURE250 " (Ciba Specialty Chemicals' system), " CI-5102 ", " CI-2855 " (more than, Japanese Cao Da company
System), " San-aid SI-60L ", " San-aid SI-80L ", " San-aid SI-100L ", " San-aid SI-110L ",
" San-aid SI-180L " (more than, three new chemical company's systems), " CPI-100P ", " CPI-100A " (more than, San-Apro plants
Formula commercial firm system), " WPI-069 ", " WPI-113 ", " WPI-116 ", " WPI-041 ", " WPI-044 ", " WPI-054 ", " WPI-
055 ", " WPAG-281 ", " WPAG-567 ", " WPAG-596 " (more than, He Guangchun medicine corporation).
The content of photoacid generator (B) is 10 parts by weight hereinafter, preferably relative to 100 parts by weight of total amount of curability composition
0.01~10 parts by weight, more preferably 0.05~5 parts by weight, particularly preferably 0.1~3 parts by weight.
<compound (C) comprising any one of alkoxy, epoxy group>
In above-mentioned active energy ray curable adhesive, it can contain and include any one of alkoxy, epoxy group
Compound (C).For example, the compound (C1) containing alkoxy carries out alkoxy with the relationship of the hydroxyl of PVA system polarizing film
With the condensation reaction of hydroxyl, the compound (C2) containing epoxy group carries out the addition reaction of epoxy group and hydroxyl, can be to activity
Energy ray-curable adhesive assigns stronger cementability.When using compound (C2) containing epoxy group, pass through epoxy
The addition reaction of base and hydroxyl, generates secondary hydroxyl after the reaction, there is a possibility that increase volume water absorption rate of the invention, because
This is more preferably using the compound (C1) with alkoxy.That is, using photoacid generator (B) and the compound with alkoxy is contained
(C1) polarizing film and transparent protective film are laminated active energy ray curable adhesive, irradiate active energy beam, thus
Acid is generated by photoacid generator (B), by the acid, the alkoxy of the compound (C1) with alkoxy and the hydroxyl of polarizing film are carried out
Condensation reaction shows the good cementability of polarizing film and transparent protective film.In addition, passing through the compound with alkoxy
(C1) condensation reaction between and form the lower gluing oxidant layer of water absorption rate, can satisfy under the harsh environment under high temperature and humidity
Optical durability.
In above-mentioned active energy ray curable adhesive, the compound (C) comprising any one in alkoxy, epoxy group can
To be used alone a kind, can also be applied in combination a variety of.In addition, the compound (C) comprising any one in alkoxy, epoxy group
Can by the compound (C1) containing alkoxy and the compound (C2) containing epoxy group and with use.In addition, comprising alkoxy,
The compound (C) of any one in epoxy group can with photoacid generator (B) and with and not and be used to use, but from promote PVA
It is the chemical combination comprising any one in alkoxy, epoxy group from the viewpoint of hydroxyl and the alkoxy of polarizing film, the reacting of epoxy group
Object (C) is preferably used in combination with photoacid generator (B).
(compound (C1) with alkoxy)
As the compound (C1) in the molecule with alkoxy, as long as there is 1 or more alkoxy in the molecule
It is not particularly limited, the well known compound with alkoxy can be used.It can enumerate for example: there is general formula :-(CH2)n-O-
(in formula, the integer that n is 1~3, R indicates the alkyl or H of carbon atom number 1~4 to R.R in above-mentioned formula is preferably methyl.) shown in
Compound of the alkoxy as substituent group.Specifically, can enumerate for example: (methyl) alkoxyalkyl acrylate, alcoxyl
Free-radical polymerised compound, melamine methylol, the alkoxy methyls containing alkoxy such as base alkyl (methyl) acrylamide
Change melamine compounds, amino resins and the silane coupling agents such as melamine.As free-radical polymerisedization containing alkoxy
The concrete example for closing object, can enumerate: wild emerging mono- 2MA of ワ ス マ, mono- 3MA of ワ ス マ, ワ ス マ mono- IBM, N- for producing corporation of large bamboo hat with a conical crown and broad brim
Isobutoxymethyl acrylamide, mono- EMA of ワ ス マ, mono- A of N-MAM-PC, MM90, ワ ス マ etc..As melamine compound
Concrete example, may be exemplified M-3, MK, M-6, M-100, MC of Sumitex resin series of sumitomo chemical company etc., strain
Nikalac MW-30 of formula commercial firm three and chemical company, MW-100LM, MX-750LM, MX-280, MX-270 etc..In them
, it is preferable to use ワ ス マ mono- 2MA, N-MAM-PC, MX-750LM etc. from the viewpoint of reactivity.It should be noted that counting
When calculating the glass transition temperature Tg of gluing oxidant layer, compound and macromolecule (C1) with alkoxy are not counted in calculating.
(compound (C2) with epoxy group)
As the compound (C2) with epoxy group, can be used in the molecule with 1 or more epoxy group compound,
Or in the molecule with the macromolecule (epoxy resin) of 2 or more epoxy groups.When using macromolecule (epoxy resin), it can be used together
There is with 2 or more with epoxy group the compound of reactive functional group in the molecule.Herein, there is reactivity with epoxy group
Functional group can enumerate for example: carboxyl, phenolic hydroxyl group, sulfydryl, primary or secondary aromatic series amino etc..Consider 3 dimension curability, especially
It is preferred that having 2 the above functional groups in a molecule.
Macromolecule as intramolecular with 1 or more epoxy group, can enumerate such as epoxy resin, have: by bisphenol-A
Bisphenol A type epoxy resin, the bisphenol f type epoxy resin by Bisphenol F and epichlorohydrin derived, bisphenol S type ring with epichlorohydrin derived
Oxygen 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, diphenyl ether type epoxy, hydroquinone type epoxy resin, naphthalene type
More officials such as epoxy resin, biphenyl type epoxy resin, fluorenes type epoxy resin, trifunctional type epoxy resin, tetrafunctional type epoxy resin
It can type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, different
Cyanurate ester type epoxy resin, aliphatic chain epoxy resin etc., these epoxy resin can carry out halogenation, can also carry out hydrogen
Change.It as commercially available epoxy resin product, can enumerate for example: the JER Coat (U of Japanese epoxy resin Co., Ltd. manufacture
One ト) 828,1001,801N, 806,807,152,604,630,871, YX8000, YX8034, YX4000, Dainippon Ink Chemicals's system
Epiclon 830, EXA835LV, HP4032D, the HP820, the EP4100 series of Asahi Denka Co., Ltd.'s manufacture, EP4000 system made
Celloxide serial (2021,2021P, 2083,2085,3000 that column, EPU series, Daicel Chemical Co., Ltd. manufacture
Deng), Epolead series, EHPE series, chemical company, Nippon Steel manufacture YD series, YDF series, YDCN series, YDB series,
(Polyhydroxypolyether synthesized by bisphenols and epichlorohydrin has epoxy group in two ends to phenoxy resin；YP series etc.), length it is rapids
The Epolight series etc. that the Denacol series of chemical conversion company manufacture, chemical company, common prosperity society manufacture, but not limited to this.These
Epoxy resin can be used together two or more.It should be noted that being counted when calculating the glass transition temperature Tg of gluing oxidant layer
The compound (C2) with epoxy group is not counted in calculation.
Total amount 100 of the use level of compound (C) comprising any one in alkoxy, epoxy group relative to curability composition
Parts by weight are usually 30 parts by weight hereinafter, if the content mistake of the above compound (C) in active energy ray curable adhesive
It is more, then cementability decline sometimes, the impact resistance deterioration to shatter test.It is above-mentioned in active energy ray curable adhesive
The content of compound (C) is more preferably 20 parts by weight or less.On the other hand, from the aspect of water resistance, active energy beam is solid
In change type adhesive, the above compound (C) of 2 parts by weight or more, above-mentionedization more than further preferably 5 parts by weight are preferably comprised
It closes object (C)
<isocyanate compound (D)>
Active energy ray curable adhesive of the invention can contain isocyanate compound (D).Isocyanation esterification
Closing object (D) is compound in the molecule at least one isocyanate group.Active energy ray curable adhesive contains different
It when cyanate esters (D), is interacted, polarizing coating can be assigned more by the hydroxyl and isocyanate group on polarizing film surface
Firm cementability, water resistance.In addition, active energy ray curable adhesive contains (methyl) propylene of the hydroxy alkyl containing N-
When amide derivatives are as free-radical polymerised compound, if the content of (methyl) acrylamide derivative of the hydroxy alkyl containing N-
Become it is more, then due in gluing oxidant layer include hydroxyl and there are the tendencies that volume water absorption rate is got higher, as a result, exist harshness humidification
The tendency of optical durability decline under environment.By that will contain (methyl) acrylamide derivative of N- hydroxy alkyl and have different
The compound of cyanic acid ester group is used in combination, and is helpless to bonding hydroxyl and isocyanate group with polarizing film and forms urethane bond,
Volume water absorption rate can be made to decline while keeping cementability.
It as isocyanate compound (D), can enumerate: polyfunctional isocyanate compound, active energy ray-curable
Type isocyanate compound etc..It as polyfunctional isocyanate compound, can enumerate for example: 1,2- ethylene isocyanic acid
The lower aliphatics polyisocyanates such as ester, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate；Sub- ring penta
Group diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenation two
The alicyclic polyisocyanates class such as toluene di-isocyanate(TDI)；2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI), 4,
Aromatic polyisocyanates class such as 4 '-methyl diphenylene diisocyanates, xylene diisocyanate etc..As above-mentioned isocyanic acid
Ester compounds (D) can also be enumerated for example: [the Japanese polyurethane industry strain of trimethylolpropane/toluene di-isocyanate(TDI) addition product
Formula commercial firm system, trade name " Coronate L "], trimethylolpropane/hexamethylene diisocyanate addition product [Japanese polyurethane
Industrial Co., Ltd's system, trade name " Coronate HL "], trade name " Coronate HX " (Japanese polyurethane industry strain formula meeting
Society), trimethylolpropane/xylene diisocyanate addition product [Mitsui Chemicals, Inc's system, trade name
" Takenate110N "] etc. commercially available products.As active energy ray curable isocyanate compound (D), it can enumerate: have
The isocyanates of (methyl) acryloyl group can be enumerated for example: Karenz AOI (Showa Denko K. K's system), Karenz
The commercially available products such as BEI (Showa Denko K. K's system), Laromer LR9000 (BASF AG's system).
The use level of isocyanate compound (D) is usually 30 weight relative to 100 parts by weight of total amount of curability composition
Part is hereinafter, if the content of the above compound (D) in active energy ray curable adhesive group is excessive, sometimes under cementability
Drop deteriorates the impact resistance of shatter test.The content of above compound (D) in active energy ray curable adhesive is more
Below preferably 20 parts by weight.On the other hand, from the aspect of water resistance, in active energy ray curable adhesive, preferably
Above compound (D) containing above compounds (D) more than 0.1 parts by weight, more than further preferably 1 parts by weight.
<silane coupling agent (E)>
When polarizing coating of the invention with curing type adhesive is active energy ray-curable curing type, silane coupling agent
(E) it is preferable to use the compounds of active energy ray-curable, even if not being that active energy ray-curable can also assign
Same water resistance.
It can be enumerated: second as the concrete example of silane coupling agent (E) as the compound of active energy ray-curable
Alkenyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyl front three
Oxysilane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl diethoxy silane, 3- epoxy
Propoxypropyl triethoxysilane, to styryltrimethoxysilane, 3- methacryloyloxypropyl methyl dimethoxy
Base silane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl methyl diethoxysilane,
3- methacryloxypropyl, 3- acryloyloxypropyltrimethoxysilane etc..
Preferably 3- methacryloxypropyl trimethoxy silane, 3- acryloyloxypropyltrimethoxysilane.
The concrete example of silane coupling agent as nonactive energy ray-curable, preferably with the silane coupling agent of amino
(E1).As the concrete example of the silane coupling agent (E1) with amino, can enumerate: gamma-amino propyl trimethoxy silicane,
γ aminopropyltriethoxy silane, three isopropoxy silane of gamma-amino propyl, gamma-amino hydroxypropyl methyl dimethoxy silicon
Alkane, gamma-amino hydroxypropyl methyl diethoxy silane, γ-(2- amino-ethyl) TSL 8330, γ-(2- amino
Ethyl) aminopropylmethyldimethoxysilane, γ-(2- amino-ethyl) aminopropyltriethoxywerene werene, γ-(2- amino
Ethyl) amino propyl methyl diethoxy silane, three isopropoxy silane of γ-(2- amino-ethyl) aminopropyl, γ-(2- (2-
Amino-ethyl) amino-ethyl) TSL 8330, γ-(6- Aminohexyl) TSL 8330,3-
(N- ethylamino) -2- trimethoxysilyl propyl methacrylate oxysilane, γ-urea propyl trimethoxy silicane, γ-urea propyl-triethoxysilicane
Alkane, N- phenyl-gamma-amino propyl trimethoxy silicane, N- benzyl-gamma-amino propyl trimethoxy silicane, N- vinyl benzyl
Base-γ aminopropyltriethoxy silane, N- Cyclohexylaminomethyl triethoxysilane, N- Cyclohexylaminomethyl diethyl
Oxygroup methyl-monosilane, N- phenvlaminomethvl trimethoxy silane, (2- amino-ethyl) amino methyl trimethoxy silane, N,
The amino-containing silanes such as bis- [3- (trimethoxysilyl) propyl] ethylenediamines of N '-；N- (1,3- dimethyl butane) -3-
The ketimides type silanes such as (triethoxysilyl) -1- propylamine.
Silane coupling agent (E1) with amino can be used only a kind, can also be applied in combination a variety of.Wherein, in order to true
Protect good cementability, preferably gamma-amino propyl trimethoxy silicane, γ-(2- amino-ethyl) aminopropyl trimethoxy silicon
Alkane, γ-(2- amino-ethyl) aminopropylmethyldimethoxysilane, γ-(2- amino-ethyl) aminopropyl triethoxysilicane
Alkane, γ-(2- amino-ethyl) amino propyl methyl diethoxy silane, N- (1,3- dimethyl butane) -3- (triethoxy first
Silylation) -1- propylamine.
The use level of silane coupling agent (E) is preferably 0.01~20 weight relative to 100 parts by weight of total amount of curability composition
Measure the range of part, more preferably 0.05~15 parts by weight, further preferably 0.1~10 parts by weight.This is because more than 20 weights
When measuring part, the storage stability of adhesive deteriorates, and the effect of water-fast cementability is unable to give full play when in addition, being lower than 0.1 parts by weight
Fruit.It should be noted that being not counted in silane coupling agent (E) in calculating when calculating the glass transition temperature Tg of gluing oxidant layer.
As it is other than the above be not active energy ray-curable silane coupling agent concrete example, can enumerate: 3-
Urea propyl-triethoxysilicane, 3- r-chloropropyl trimethoxyl silane, 3- mercapto propyl methyl dimethoxy silane, 3- mercaptopropyi
Trimethoxy silane, bis- (triethoxysilylpropyltetrasulfide) four thioethers, 3- isocyanate propyl triethoxysilane, imidazoles silicon
Alkane etc..
Compound (C), isocyanation esterification about above-mentioned photoacid generator (B), comprising any one of alkoxy, epoxy group
Object (D), silane coupling agent (E) are closed, the logPow value of each ingredient is preferably 1 or more, and more preferably 2 or more.It should be noted that
Ingredient in the calculating of the logPow value of polarizing coating curing type adhesive does not include photoacid generator (B), silane coupling agent (E).
On the other hand, the ingredient in the calculating of the logPow value of polarizing coating curing type adhesive includes comprising in alkoxy, epoxy group
The compound of any one (C), isocyanate compound (D).
<additive other than the above>
In addition, in polarizing coating curing type adhesive of the invention, in the range for not damaging the purpose of the present invention, effect
It is interior, various additives can be cooperated as any other ingredient.As the additive, can enumerate: polyamide, polyamide acyl are sub-
Amine, polyurethane, polybutadiene, polychlorobutadiene, polyethers, polyester, styrene-butadiene block copolymer, Petropols, diformazan
The polymer or low such as benzene resin, ketone resin, celluosic resin, fluorine system oligomer, silicone-based oligomer, polythiaether system oligomer
Polymers；The polymerization inhibitors such as phenthazine, 2,6- di-tert-butyl-4-methy phenol；Polymerization trigger auxiliary agent；Levelling agent；Wetability modifying agent；
Surfactant；Plasticizer；Ultraviolet absorbing agent；Inorganic filler；Pigment；Dyestuff etc..In various additives, preferably logPow
Value is high.The logPow value of various additives is preferably 2 or more, and more preferably 3 or more, most preferably 4 or more.It needs to illustrate
It is that the ingredient in the calculating of the logPow value of polarizing coating curing type adhesive does not include these additives.
Above-mentioned additive is usually 0~10 parts by weight, preferably 0~5 relative to 100 parts by weight of total amount of curability composition
Parts by weight, most preferably 0~3 parts by weight.
<viscosity of adhesive>
Polarizing coating curing type adhesive of the invention contains above-mentioned curability composition, should from the viewpoint of screening characteristics
The viscosity of adhesive preferably 100cp or less at 25 DEG C.On the other hand, polarizing coating curing type adhesive of the invention is 25
DEG C when be more than 100cp in the case where, can also coating time control preparing adhesive temperature and be adjusted to 100cp or less.Viscosity
More preferable range is 1~80cp, most preferably 10~50cp.The E type viscosimeter TVE22LT of Dong Ji industry companies can be used
To measure viscosity.
In addition, considering from a security point, it is preferable to use pierce to skin with curing type adhesive for polarizing coating of the invention
Small material is swashed as above-mentioned curability composition.Skin irritation can be judged with the index of P.I.I.As expression skin irritatin
The index of degree P.I.I is widely used, measured by Draize method.With 0~8 Range Representation measured value, value is smaller then
Judge that irritation is lower, since the error of measured value is big, is understood as reference value.P.I.I be preferably 4 hereinafter,
More preferably 3 hereinafter, most preferably 2 or less.
<polarizing coating>
For polarizing coating of the invention, polarizing film at least single side across by above-mentioned polarizing coating curing type adhesive
Solidified material layer formed gluing oxidant layer be bonded transparent protective film.As above-mentioned solidified material layer gluing oxidant layer as described above,
Volume water absorption rate is 10 weight % or less.
<gluing oxidant layer>
It is preferred that being 0.1~3 μm by the thickness control of the gluing oxidant layer formed by above-mentioned curing type adhesive.Gluing oxidant layer
Thickness is more preferably 0.3~2 μm, further preferably 0.5~1.5 μm.Inhibiting bonding not by the cohesiveness of gluing oxidant layer
Good generation inhibits in terms of generating bad order (bubble) in lamination, preferably by the thickness of gluing oxidant layer be set as 0.1 μm with
On.On the other hand, if gluing oxidant layer is than 3 μ m-thicks, possible polarizing coating is unable to satisfy durability.
In addition, curing type adhesive preferably selects in such a way that the Tg for the gluing oxidant layer being consequently formed is 60 DEG C or more, into
One step is preferably 70 DEG C or more, further preferably 75 DEG C or more, further preferably 100 DEG C or more, further preferably 120
DEG C or more.On the other hand, the bendability of polarizing coating declines if the Tg of gluing oxidant layer is excessively high, therefore preferably: the Tg of gluing oxidant layer
300 DEG C are set as hereinafter, being further arranged to 240 DEG C hereinafter, being further arranged to 180 DEG C or less.Use TA
Instruments dynamic determination of viscoelasticity device RSAIII measures Tg < glass transition temperature according to determination condition below
>。
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Mode determination: it stretches, frequency: 1Hz, heating rate: 5 DEG C/min
The measurement of dynamic viscoelastic is carried out, the temperature Tg of the summit as tan δ is used.
In addition, the storage elastic modulus for the gluing oxidant layer being consequently formed is below at 70 DEG C for curing type adhesive
Region is preferably 1.0 × 106Pa or more.It is even more preferably 1.0 × 107Pa or more.The storage elastic modulus pair of gluing oxidant layer
Polarizing film rupture when applying thermal cycle (- 40 DEG C~80 DEG C etc.) to polarizing coating has an impact, and when storage elastic modulus is low, holds
The unfavorable condition of polarizing film rupture easily occurs.More preferable 80 DEG C of temperature region with high storage elastic modulus are hereinafter, most preferably
90 DEG C or less.Measurement with Tg<glass transition temperature>simultaneously uses TA instruments dynamic determination of viscoelasticity to fill
It sets RSAIII and measures storage elastic modulus in same determination condition.The measurement for carrying out dynamic viscoelastic, using storage springform
Measure the value of (E ' ').
Polarizing coating of the invention has following processes: in the face that form gluing oxidant layer of polarizing film and/or transparency protected
After the face coating curing type adhesive that form gluing oxidant layer of film, the process that is bonded polarizing film and transparent protective film, then
The process that curing type adhesive is solidified to form gluing oxidant layer.
For polarizing film, transparent protective film, before applying above-mentioned curing type adhesive, it can carry out at the modification of surface
Reason.As specific processing, can enumerate based on sided corona treatment, corona treatment, processing of saponification process etc..
The application pattern of curing type adhesive is suitably selected according to the viscosity of the curing type adhesive, target thickness.As
The example of application pattern can be enumerated for example: reversion coating machine, gravure coater (directly, reversion or hectograph), scraper reversion apply
Cloth machine, roll coater, die coating machine, metering bar coater, rod coater etc..In addition to this, it can be properly used dipping side in coating
The modes such as formula.
Using the curing type adhesive as above applied, it is bonded polarizing film and transparent protective film.It can use layer of rolls press
Deng the fitting for carrying out polarizing film and transparent protective film.
<solidification of adhesive>
Polarizing coating curing type adhesive of the invention is with active energy ray curable adhesive or thermohardening type gluing
The form of agent uses.For active energy ray curable adhesive, can with electronic beam solidified, ultraviolet hardening, can
The form of light-exposed curing type uses.From the viewpoint of productivity, compared with thermohardening type adhesive, above-mentioned curing type adhesive
The preferred active energy ray curable adhesive of form, active energy ray curable adhesive is further used as, from production
Preferred Visible light curable adhesives from the viewpoint of rate.
" active energy ray curable "
For active energy ray curable adhesive, after being bonded polarizing film and transparent protective film, active energy is irradiated
It measures ray (electron beam, ultraviolet light, visible light etc.), active energy ray curable adhesive is solidified to form gluing oxidant layer.
For the direction of illumination of active energy beam (electron beam, ultraviolet light, visible light etc.), it can be shone from arbitrary direction appropriate
It penetrates.It is preferred that being irradiated from transparent protective film side.If from polarizing film side irradiate, sometimes polarizing film because active energy beam (electron beam,
Ultraviolet light, visible light etc.) and deteriorate.
" electronic beam solidified "
In electronic beam solidified, about the irradiation condition of electron beam, as long as above-mentioned active energy ray-curable can be made
The cured condition of type adhesive, so that it may use arbitrary felicity condition.For example, acceleration voltage is preferably in electron beam irradiation
5kV~300kV, further preferably 10kV~250kV.When acceleration voltage is lower than 5kV, electron beam will not reach adhesive, can
It can solidify deficiency, when acceleration voltage is more than 300kV, the penetration passed through from sample is too strong, may be to transparent protective film, inclined
Vibration piece brings damage.It is 5~100kGy, further preferably 10~75kGy as exposure.When exposure is lower than 5kGy, glue
Stick can solidify deficiency, when more than 100kGy, bring damage to transparent protective film, polarizing film, generate reduction, the Huang of mechanical strength
Become, is unable to get defined optical characteristics.
Electron beam irradiation in, be usually irradiated in inactive gas, but if desired then can also in an atmosphere or
It is imported under conditions of a small amount of oxygen and carries out.Although depending on the material of transparent protective film, by suitably importing oxygen, and exist first
The transparency protected film surface of irradiating electron beam generates oxygen and hinders, and can prevent the damage to transparent protective film, can be only to adhesive
Effectively irradiating electron beam.
" ultraviolet hardening, visible light curable "
, it is preferable to use visible light comprising wave-length coverage 380nm~450nm in the manufacturing method of polarizing coating of the invention
Active energy beam is as active energy beam, particularly preferably using the exposure of the visible light of wave-length coverage 380nm~450nm
Most active energy beams are as active energy beam.In ultraviolet hardening, visible light curable, purple is imparted in use
In the case where the transparent protective film (ultraviolet light not transmission-type transparent protective film) of outside line absorbability, absorbs and be shorter than about 380nm's
The light of short wavelength, therefore, the light that wavelength is shorter than 380nm will not reach active energy ray curable adhesive, therefore poly- to it
Reaction is closed not contribute.In addition, being changed into heat by the light that the wavelength that transparent protective film absorbs is shorter than 380nm, make transparent protective film
Self-heating causes curling, fold of polarizing coating etc. bad.Therefore, in the present invention, using ultraviolet hardening, visible light
When curing type, as active energy beam generation device, it is preferable to use not issuing the device that wavelength is shorter than the light of 380nm, more
For body, the ratio between accumulated illumination and the accumulated illumination of 250~370nm of wave-length coverage of 380~440nm of wave-length coverage are preferably
100: 0~100:50, more preferably 100: 0~100: 40.As active energy beam of the invention, the metal of preferably enclosed gallium
Halide lamp, issue 380~440nm of wave-length coverage light LED light source.Alternatively, low pressure mercury lamp, middle pressure mercury also can be used
Lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium
Lamp, excimer laser or sunlight etc. include the light source of ultraviolet light and visible light, bandpass filter can be used also to block
Wavelength is shorter than the ultraviolet light of 380nm.In order to improve the gluing oxidant layer between polarizing film and transparent protective film adhesive property and
The curling of polarizing coating is prevented, it is preferable to use enclosing the metal halide lamp of gallium and utilizing the light that wavelength can be blocked to be shorter than 380nm
The obtained active energy beam of bandpass filter or the wavelength 405nm obtained using LED light source active energy beam.
For ultraviolet hardening or visible light curable, preferably to active-energy before irradiation ultraviolet light or visible light
Ray curing adhesive is heated (heating before irradiation), at this point, being preferably heated to 40 DEG C or more, is more preferably heated to 50 DEG C
More than.It is also preferable to be heated (irradiation to active energy ray curable adhesive after irradiation ultraviolet light or visible light
Heat afterwards), at this point, being preferably heated to 40 DEG C or more, more preferably it is heated to 50 DEG C or more.
Active energy ray curable adhesive of the invention can formed particularly preferably by polarizing film and wavelength 365nm
Light transmittance less than 5% transparent protective film bonding gluing oxidant layer in the case where use.Herein, active-energy of the invention is penetrated
Line curing type adhesive contains the Photoepolymerizationinitiater initiater of above-mentioned general formula (1), and thereby, it is possible to across with the saturating of UV absorbability
Bright protective film irradiates ultraviolet light and is formed by curing gluing oxidant layer.Therefore, it is laminated with even for the two sides in polarizing film with UV
For the polarizing coating of the transparent protective film of absorbability, gluing oxidant layer can also solidified.But do not have UV for being laminated with
For the polarizing coating of the transparent protective film of absorbability, naturally it is also possible to solidify gluing oxidant layer.It should be noted that having UV
The transparent protective film of absorbability refers to the transparent protective film to the transmissivity of the light of 380nm less than 10%.
It as the method for assigning UV absorbability to transparent protective film, can enumerate: containing ultraviolet in transparent protective film
The method of light absorbers, the method that the surface-treated layer containing ultraviolet absorbing agent is laminated on the transparent protective film surface.
As specific examples of ultraviolet absorbers, it can enumerate for example: conventionally known epoxide benzophenone based compound,
Benzotriazole based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel network
Close object based compound, triazine based compound etc..
After being bonded polarizing film with transparent protective film, active energy beam (electron beam, ultraviolet light, visible light are irradiated
Deng), so that active energy ray curable adhesive is solidified to form gluing oxidant layer.It is (electron beam, ultraviolet about active energy beam
Line, visible light etc.) direction of illumination, can be irradiated from arbitrary appropriate direction.It is preferred that being irradiated from transparent protective film side.From polarization
When piece side is irradiated, polarizing film may be deteriorated due to active energy beam (electron beam, ultraviolet light, visible light etc.).
" thermohardening type "
On the other hand, if thermohardening type adhesive, after being bonded polarizing film and transparent protective film, pass through heating, benefit
Caused with thermal polymerization and polymerize, forms solidified material layer.Heating temperature is set according to thermal polymerization, but preferably 60
~200 DEG C or so, preferably 80~150 DEG C.
In the case where manufacturing polarizing coating of the invention using tinuous production, when linear velocity depends on the solidification of adhesive
Between, but preferably 1~500m/min, more preferably 5~300m/min, further preferably 10~100m/min.Linear speed is spent
Hour, undercapacity, or it is excessive to the damage of transparent protective film, the polarization for being resistant to durability test etc. can not be made
Film.When linear velocity is excessive, the solidification of adhesive is become inadequate, and is unable to get target cementability sometimes.
It should be noted that polarizing film and transparent protective film pass through using by above-mentioned active energy in polarizing coating of the invention
It measures the gluing oxidant layer of the solidified material layer formation of ray curing adhesive and is bonded, but can be in transparent protective film and gluing oxidant layer
Between adhesive layer is set.Adhesive layer can use for example with polyester backbone, polyether skeleton, polycarbonate backbone, poly- ammonia
The various resins of ester skeleton, silicone-based, polyamide backbone, polyimide backbone, polyvinyl alcohol skeleton etc. are formed.These polymer
Resin can be used alone or be applied in combination two or more.In addition, other can be added in the formation of adhesive layer
Additive.Specifically, stabilizers such as tackifier, ultraviolet absorbing agent, antioxidant, heat-resisting stabilizing agent etc. can also be used.
Adhesive layer is usually pre-set at transparent protective film, by the adhesive layer side of the transparent protective film and polarizing film benefit
It is bonded with gluing oxidant layer.The formation of adhesive layer is by utilizing well-known technique to be coated with the formation of adhesive layer on transparent protective film
Material is simultaneously dried to carry out.The forming material of adhesive layer usually consider it is dry after thickness, coating fairness etc. and
It is adjusted in the form of the solution for being diluted to debita spissitudo.Thickness after the drying of adhesive layer is preferably 0.01~5 μm, into
One step is preferably 0.02~2 μm, and further preferably 0.05~1 μm.It should be noted that multilayer can be set in adhesive layer,
But in this case, it is also preferred that the overall thickness of adhesive layer is above range.
<polarizing film>
Polarizing film is not particularly limited, and various polarizing films can be used.As polarizing film, can enumerate for example in polyethylene
The hydrophilic macromolecules such as alcohol mesentery, part formolation polyvinyl alcohol mesentery, the partly-hydrolysed film of vinyl-vinyl acetate copolymer system
Film absorption iodine, the dichroic materials such as dichroic dye and film, polyvinyl alcohol obtained from being uniaxially stretched dehydration treatment,
Polyene system alignment films such as the dehydrochlorinated products of polyvinyl chloride etc..In them, two color such as polyvinyl alcohol mesentery and iodine is preferably comprised
The polarizing film of property substance.The thickness of these polarizing films is not particularly limited, and typically about 80 μm or less.
By polyvinyl alcohol mesentery iodine staining and polarizing film obtained from being uniaxially stretched for example can be by by poly- second
Enol is impregnated into the aqueous solution of iodine and dyes, and is stretched to 3~7 times of former length to make.Also it can according to need and be impregnated into boron
The aqueous solution of acid, potassium iodide etc..Water is carried out further, it is also possible to which polyvinyl alcohol mesentery is impregnated into water before dyeing as needed
It washes.By washing to polyvinyl alcohol mesentery, the dirt of polyvinyl alcohol mesentery surface, anti-sticking agent can be cleaned, except this with
Outside, also there is the unequal non-uniform effect that dyeing is prevented and making polyethenol series membrane swelling.Stretching can be with iodine
It carries out, can also be stretched while dyeing, furthermore it is also possible to be dyed after the stretch with iodine after dyeing.It can also be with
In aqueous solutions of boric acid, potassium iodide, etc., it is stretched in water-bath.
In addition curing type adhesive of the invention is using with a thickness of 10 μm of slim polarizing films below as polarizing film
When, it can significantly show its effect (meeting the optical durability in the harsh environment under high temperature and humidity).It is above-mentioned with a thickness of
The influence of 10 μm of polarizing films below moisture compared with thickness is more than 10 μm of polarizing film is relatively large, the environment under high temperature and humidity
Middle optical durability is insufficient, easily causes transmissivity rising, degree of polarization decline.That is, being 10 with volume water absorption rate of the invention
The ring under high temperature and humidity when above-mentioned 10 μm of polarizing films below are laminated weight % gluing oxidant layer below, by inhibiting harshness
Movement of the water to polarizing film in border can significantly inhibit the optical durabilities such as transmissivity rising, the degree of polarization decline of polarizing coating
Deteriorate.From the viewpoint of slimming, the thickness of polarizing film is preferably 1~7 μm.The uneven thickness of such slim polarizing film
Few, observation property is excellent, and change in size is few, and can also realize slimming as the thickness of polarizing coating, in these areas preferably.
It as slim polarizing film, can typically enumerate: Japanese Unexamined Patent Application 51-069644 bulletin, Japanese Unexamined Patent Publication
2000-338329 bulletin, WO2010/100917 pamphlet, the specification of PCT/JP2010/001460 or Japanese Patent Application
The slim polarizing coating recorded in 2010-269002 specification, Japanese Patent Application 2010-263692 specification.These are slim partially
Vibrating diaphragm can be by including that polyvinyl alcohol resin (hereinafter also referred to PVA system resin) layer and stretching resin base material are being laminated
The preparation method of process that the state of body is stretched and the process dyed obtains.If it is the preparation method, even if then PVA system tree
Rouge layer is relatively thin, can will not also produced fracture etc. in undesirable situation due to stretching and being supported by stretching with resin base material
It is stretched.
It is including the process that is stretched of state and the process that is dyed in laminated body as above-mentioned slim polarizing coating
Preparation method in, from can be stretched to high magnification and from the viewpoint of improving polarization property, preferably by No. WO2010/100917 small
Book, the specification of PCT/JP2010/001460 or Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-
What is recorded in No. 263692 specifications includes that the preparation method of the process stretched in boric acid aqueous solution obtains, and is particularly preferably passed through
Recorded in Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-263692 specification to be included in boric acid water-soluble
The preparation method of the process auxiliarily stretched in the air before being stretched in liquid obtains.
The slim high function polarizing coating recorded in the specification of above-mentioned PCT/JP2010/001460 is integrated film forming in tree
Aliphatic radical material, comprising the PVA system resin that is orientated dichroic substance and with a thickness of 7 μm of slim high functions polarizations below
Film has the optical characteristics that monomer transmissivity is 42.0% or more and degree of polarization is 99.95% or more.
Above-mentioned slim high function polarizing coating can manufacture by the following method: in the resin base of the thickness at least 20 μm
Material coating PVA system resin simultaneously makes it dry, and thus generates PVA resin, the PVA resin of generation is impregnated into dichroism
It in the dyeing liquor of substance, is adsorbed on dichroic substance in PVA resin, the PVA system resin of dichroic substance will have been adsorbed
Layer is integrally stretched in boric acid aqueous solution with resin base material, so that total stretching ratio reaches 5 times or more of former length.
In addition, in the side of laminate film of the manufacture comprising the slim high function polarizing coating for being orientated dichroic substance
In method, by the inclusion of following processes, above-mentioned slim high function polarizing coating, the process can be manufactured are as follows: generate laminate film, institute
State the resin base material and contain by the one side coating in resin base material that laminate film includes the thickness at least 20 μm
The aqueous solution of PVA system resin and make it dry and the PVA resin that is formed；Comprising resin base material and resin base material will be formed in
The above-mentioned laminate film of PVA resin of single side be impregnated into the dyeing liquor containing dichroic substance, thus make dichroism
Substance is adsorbed onto the PVA resin contained in laminate film；It will be comprising the PVA resin that has adsorbed dichroic substance
Above-mentioned laminate film is stretched in boric acid aqueous solution, so that total stretching ratio reaches 5 times or more of former length；Two will have been adsorbed
The PVA resin of color substance is integrally stretched with resin base material, and the single side thus manufactured in resin base material is formed with
Comprising be orientated dichroic substance PVA resin, with a thickness of 7 μm or less and have monomer transmissivity
42.0% or more and degree of polarization be 99.95% or more optical characteristics slim high function polarizing coating laminate film.
Above-mentioned Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-263692 specification it is slim partially
Vibrating diaphragm is the continuous band-shaped polarizing coating comprising the PVA system resin for being orientated dichroic substance, by that will include shape
It is drawn in by aerial assisting tension and boric acid water at the laminated body of the PVA resin in amorphism ester based thermoplastic resin base material
It stretches and is stretched in the two stages stretching process of composition and form 10 μm of thickness below.The slim polarizing coating preferably has such as
Lower optical characteristics meets P >-(10 when monomer transmissivity to be set as T, degree of polarization is set as P0.929T-42.4-1(its of) × 100
In, T < 42.3) and P >=99.9 (wherein, T >=42.3) condition.
Specifically, above-mentioned slim polarizing coating can be made by the manufacturing method of the slim polarizing coating comprised the following steps
It makes: aerial drawing by high temperature is carried out to the PVA resin for being formed in continuous band-shaped amorphism ester based thermoplastic resin base material, by
This generates the stretching intermediate product comprising the PVA resin after orientation；Suction to intermediate product progress dichroic substance is stretched
It is attached, thus generate the PVA system tree comprising being orientated dichroic substance (the preferably mixture of iodine or iodine and organic dyestuff)
The coloring intermediate product of rouge layer；Stretch in boric acid water with to coloring intermediate product, thus generate comprising making dichroic substance
The PVA resin being orientated with a thickness of 10 μm of polarizing coatings below.
In the manufacturing method, amorphism ester system thermoplastic is formed in preferably by what is stretched in aerial drawing by high temperature and boric acid water
Property resin base material PVA resin total stretching ratio be 5 times or more.Liquid for the boric acid aqueous solution stretched in boric acid water
Temperature can be set as 60 DEG C or more.It is preferred that before being stretched in boric acid aqueous solution to coloring intermediate product, it is intermediate to coloring
Product carries out insoluble processing, in this case, it is preferred that above-mentioned by impregnating in boric acid aqueous solution of the liquid temperature no more than 40 DEG C
Color intermediate product carries out.Above-mentioned amorphism ester based thermoplastic resin base material is preferably capable being formed comprising being total to M-phthalic acid
Copolymerization polyethylene terephthalate obtained from poly- is copolymerized poly terephthalic acid obtained from being copolymerized cyclohexanedimethanol
Glycol ester or other copolymerization polyethylene terephthalates amorphism polyethylene terephthalate and include transparent
The substrate of resin, thickness can be set as being formed by 7 times of the thickness of PVA resin or more.In addition, aerial high temperature is drawn
The stretching ratio stretched is preferably 3.5 times hereinafter, the draft temperature of aerial drawing by high temperature is preferably the glass transition of PVA system resin
More than temperature, specifically, it is preferable that being 95 DEG C~150 DEG C of range.Aerial high temperature drawing is carried out being uniaxially stretched by free end
In the case where stretching, be formed in the PVA resin of amorphism ester based thermoplastic resin base material total stretching ratio be preferably 5 times with
It is upper and 7.5 times or less.In addition, being formed in amorphism in the case where being uniaxially stretched the aerial drawing by high temperature of progress by fixing end
Total stretching ratio of the PVA resin of ester based thermoplastic resin base material is preferably 5 times or more and 8.5 times or less.
More specifically, slim polarizing coating can be manufactured by method as described below.
The copolymerization polyethylene terephthalate of M-phthalic acid made of production is copolymerized 6mol% M-phthalic acid is (non-
Crystalline substance PET) continuous band-shaped substrate.The glass transition temperature of amorphism PET is 75 DEG C.Include continuous net-shaped amorphism
The laminated body of PET base material and polyvinyl alcohol (PVA) layer makes in the following manner.It may be mentioned that the glass transition temperature of PVA
It is 80 DEG C.
Prepare the amorphism PET base material of 200 μ m-thicks and makes the PVA powder of 1000 or more the degree of polymerization, 99% or more saponification degree
It is dissolved in the PVA aqueous solution that concentration obtained from water is 4~5%.Then, PVA is coated in the amorphism PET base material of 200 μ m-thicks
Aqueous solution obtains being formed with the laminated body of the PVA layer of 7 μ m-thicks in amorphism PET base material in 50~60 DEG C of at a temperature of drying.
The laminated body of PVA layer comprising 7 μ m-thicks is passed through into the two stages comprising stretching in aerial assisting tension and boric acid water
Following processes of stretching process manufacture the slim high function polarizing coatings of 3 μ m-thicks.Pass through the aerial assisting tension work of first stage
Sequence integrally stretches the laminated body of the PVA layer comprising 7 μ m-thicks with amorphism PET base material, generates the PVA layer comprising 5 μ m-thicks
Stretch laminated body.Specifically, the stretching laminated body be by by include 7 μ m-thicks PVA layer laminated body be placed in configure setting
Due to carried out in the stretching device in the baking oven of 130 DEG C of draft temperature environment and in a manner of making 1.8 times of stretching ratio from
Laminated body obtained from being uniaxially stretched as end.By the stretch processing, make to stretch the PVA layer variation contained in laminated body to be PVA
The PVA layer for 5 μ m-thicks that molecule is orientated.
Then, by dyeing process, generate adsorbed in the PVA layer for 5 μ m-thicks that PVA molecule is orientated iodine
Chromatograph stack.Specifically, the coloring laminated body will be by that will stretch dye containing iodine and potassium iodide of the laminated body at 30 DEG C of liquid temperature
Impregnated in color liquid the arbitrary time to constitute the monomer transmissivity of the PVA layer of high function polarizing coating ultimately generated for 40~
44% has adsorbed the laminated body of iodine to the PVA layer contained in stretching laminated body.In this process, dyeing liquor is using water as molten
Agent, for iodine concentration in the range of 0.12~0.30 weight %, iodate potassium concn is in the range of 0.7~2.1 weight %.Iodine and iodine
The concentration ratio for changing potassium is 1 to 7.It may be mentioned that needing potassium iodide when iodine is dissolved in water.More specifically, by that will stretch
Laminated body impregnates 60 seconds in the dyeing liquor that iodine concentration is 0.30 weight %, iodate potassium concn is 2.1 weight %, generates in PVA
The coloring laminated body of iodine has been adsorbed in the PVA layer for 5 μ m-thicks that molecule is orientated.
It further, further will coloring laminated body and amorphism PET base by stretching process in the boric acid water of second stage
Material is integrally stretched, and the optical film laminate of the PVA layer of the high function polarizing coating of composition comprising 3 μ m-thicks is generated.It is specific and
Speech, the optical film laminate are to contain boric acid and potassium iodide by that will colour laminated body and be placed in configure and be set in liquid temperature range
It is carried out in stretching device in the processing unit of 60~85 DEG C of boric acid aqueous solution and in a manner of making 3.3 times of stretching ratio certainly
Laminated body obtained from being uniaxially stretched as end.More specifically, the liquid temperature of boric acid aqueous solution is 65 DEG C.In addition, by boric acid content
It is set as 4 parts by weight relative to 100 parts by weight of water, iodate potassium content is set as 5 parts by weight relative to 100 parts by weight of water.This
In process, the coloring laminated body for having adjusted iodine absorption number is impregnated 5~10 seconds in boric acid aqueous solution first.Then, it will be somebody's turn to do
Chromatograph stack directly passed through between the different multiple groups roller of stretching device, that is, peripheral speed in processing unit from configuration, with 30~90 seconds
Free end is carried out in a manner of making 3.3 times of stretching ratio to be uniaxially stretched.By the stretch processing, makes to colour and contain in laminated body
The variation of PVA layer carried out in the form of more iodide ion complex compounds 3 μ m-thicks of high order orientation in one direction for the iodine of absorption
PVA layers.The high function polarizing coating of the PVA layers of composition optical film laminate.
Although not being required process in the manufacture of optical film laminate, preferably optical film is laminated by cleaning process
Body takes out from boric acid aqueous solution, uses the boric acid of the surface attachment of the PVA layer in 3 μ m-thicks for being formed in amorphism PET base material
Potassium iodide aqueous solution is cleaned.Then, the optical film laminate after cleaning is passed through into the drying process of the warm wind using 60 DEG C
It is dried.In addition, cleaning process is the process for eliminating the bad orders such as boric acid precipitation.
It equally, can also be by being bonded and/or transferring although not being required process in the manufacture of optical film laminate
Process the PVA layer for 3 μ m-thicks for being formed in amorphism PET base material surface coating binder, and be bonded 80 μ m-thicks three second
Then acyl cellulose membrane can also be needed on the triacetyl of 80 μ m-thicks by the removing of amorphism PET base material, by the PVA layer of 3 μ m-thicks
Cellulose membrane.
[other processes]
It can also include other processes other than above-mentioned operation in the manufacturing method of above-mentioned slim polarizing coating.As it
His process, can enumerate such as insoluble process, cross-linking process step, drying (adjusting of moisture rate) process.Other processes can be with
It is carried out in arbitrary opportune moment.
Typically, above-mentioned insoluble process can be carried out by the way that PVA resin to be impregnated into boric acid aqueous solution.
By implementing insoluble processing, water resistance can be assigned to PVA resin.The concentration of the boric acid aqueous solution is relative to water 100
Parts by weight are preferably 1 parts by weight~4 parts by weight.The liquid temperature of insoluble bath (boric acid aqueous solution) is preferably 20 DEG C~50 DEG C.It is insoluble
Chemical industry sequence carries out before stretching process preferably after laminated body production, in dyeing process or water.
Typically, above-mentioned cross-linking process step is carried out by the way that PVA resin to be impregnated into boric acid aqueous solution.Pass through reality
Crosslinking Treatment is applied, water resistance can be assigned to PVA resin.The concentration of the boric acid aqueous solution is excellent relative to 100 parts by weight of water
It is selected as 1 parts by weight~4 parts by weight.In addition, preferably further cooperating in the case where carrying out cross-linking process step after above-mentioned dyeing process
Iodide.By cooperating iodide, it is able to suppress the dissolution of the iodine adsorbed in PVA resin.The use level of iodide is opposite
In 100 parts by weight of water be preferably 1 parts by weight~5 parts by weight.The concrete example of iodide is as described above.Crosslinking bath (boric acid aqueous solution)
Liquid temperature be preferably 20 DEG C~50 DEG C.Cross-linking process step preferably carries out before stretching process in above-mentioned second boric acid water.It is preferred real
It applies in mode, successively stretching process in progress dyeing process, cross-linking process step and the second boric acid water.
<transparent protective film>
As the material for the transparent protective film that the one or two sides for being formed in above-mentioned polarizing film is arranged, preferably clear, machine
The excellent material such as tool intensity, thermal stability, water preventing ability, isotropism.Such as polyethylene terephthalate can be enumerated
Or the cellulose-based polymerization such as the polyester based polymers such as polyethylene naphthalate, diacetyl cellulose or triacetyl cellulose
The benzene such as the acrylic acid series polymeric compounds such as object, polymethyl methacrylate, polystyrene or acrylonitritrile-styrene resin (AS resin)
Ethylene-based polymer, polycarbonate based polymer etc..Alternatively, it is also possible to enumerate polyethylene, polypropylene, ring system or there is norborneol
Polyolefin polymer, vinyl chloride-based polymer, nylon or fragrance as the polyolefin of alkene structure, ethylene-propylene copolymer
The amides such as polyamide based polymer, imide series polymer, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone system are poly-
Close object, polyphenylene sulfide based polymer, vinyl alcohol system polymer, vinylidene chloride based polymer, vinyl butyral based polymer,
Acrylic acid series polymeric compounds, polyformaldehyde based polymer, blend etc. of epoxy based polymer or above-mentioned polymer are above-mentioned as being formed
The example of the polymer of transparent protective film.It may include a kind of any of the above additive appropriate in transparent protective film.As adding
Add agent, can enumerate for example: is ultraviolet absorbing agent, antioxidant, lubricant, plasticizer, release agent, coloring agent, fire-retardant
Agent, nucleating agent, antistatic agent, pigment, colorant etc..The content of above-mentioned thermoplastic resin in transparent protective film is preferably 50~
100 weight %, more preferably 50~99 weight %, further preferably 60~98 weight %, particularly preferably 70~97 weights
Measure %.When the content of above-mentioned thermoplastic resin in transparent protective film is 50 weight % or less, it is unable to fully show heat sometimes
Plastic resin originally possessed by high transparency etc..
In addition, note in Japanese Unexamined Patent Publication 2001-343529 bulletin (WO01/37007) can be enumerated as transparent protective film
The polymer film of load, such as in side chain there is the thermoplastic resin of substitution and/or unsubstituted imide and (B) to exist containing (A)
Side chain has the resin combination of the thermoplastic resin of substitution and/or unsubstituted phenyl and itrile group.As concrete example, Ke Yilie
Lift the resin combination for containing the alternate copolymer comprising isobutene and N- methylmaleimido and acrylonitritrile-styrene resin
The film of object.The film of mixing extrusion pin comprising resin combination etc. can be used in film.The phase difference of these films is small, photoelastic coefficient
It is small, therefore a problem that the unevenness as caused by the strain of polarizing coating can be eliminated, it is small additionally, due to moisture permeability, therefore humidify resistance to
Long property is excellent.
In above-mentioned polarizing coating, the moisture permeability of above-mentioned transparent protective film is preferably 150g/m2/ following for 24 hours.According to this constitution,
Moisture in air is difficult to enter in polarizing coating, and the moisture rate of polarizing coating itself can be inhibited to change.As a result, it is possible to inhibit
By the curling of the polarizing coating of Conservation environment generation, change in size.
As the material for the transparent protective film that the one or two sides for being formed in above-mentioned polarizing film is arranged, preferably clear, machine
The excellent material such as tool intensity, thermal stability, water preventing ability, isotropism, especially more preferable moisture permeability are 150g/m2/ for 24 hours with
Under material, particularly preferred 140g/m2/ material below for 24 hours, further preferred 120g/m2/ material below for 24 hours.Pass through reality
It applies the method recorded in example and finds out moisture permeability.
As the forming material for the transparent protective film for meeting above-mentioned low moisture permeability, such as poly terephthalic acid second can be used
The polyester resin such as diol ester or polyethylene naphthalate；Polycarbonate resin；Acrylic resin；Nylon or fragrant adoption
The amides such as amide system resin；Polyethylene, polypropylene, polyolefin polymer as ethylene-propylene copolymer, ring system or have
The annular ethylene series resin of norbornene structure, (methyl) acrylic resin or their mixture.It is excellent in above-mentioned resin
Select polycarbonate-based resin, cyclic polyolefin hydrocarbon system resin, (methyl) acrylic resin, particularly preferred cyclic polyolefin hydrocarbon system tree
Rouge, (methyl) acrylic resin.
It can suitably determine the thickness of transparent protective film, but usually from the workability such as intensity or operability, thin layer etc.
It is thought of as 1~100 μm or so.Particularly preferred 1~80 μm, more preferable 3~60 μm.
It should be noted that can be used in its table back comprising identical when transparent protective film is arranged in the two sides of polarizing film
Polymer material transparent protective film, the transparent protective film comprising different polymer material etc. also can be used.
The surface for not being bonded polarizing film of above-mentioned transparent protective film can be set hard conating, anti-reflection layer, antiblocking layers,
The functional layers such as diffusing layer or antiglare layer.It should be noted that above-mentioned hard conating, anti-reflection layer, antiblocking layers, diffusing layer or anti-dazzle
The functional layers such as layer can also be separately provided separately with transparent protective film in addition to can be set in transparent protective film itself.
<optical film>
Polarizing coating of the invention can use in the form of with the optical film of other optics layer stackups in actual use.It closes
In the optical layer, be not particularly limited, can be used 1 layer or 2 layers or more for example sometimes in reflecting plate or half transmitting plate, phase
Optical layer used in the formation of the liquid crystal display devices such as poor plate (including 1/2,1/4 equiwavelength's plate), compensation film for angular field of view etc..Especially
It is preferred that being further laminated with the reflective polarizing film or Semitransmissive of reflecting plate or Transflective plate in polarizing coating of the invention
Polarizing coating is further laminated with the elliptical polarization film of phase plate in polarizing coating or circular polarization film, is further laminated in polarizing coating
There is the wide viewing angle polarizing coating of compensation film for angular field of view or is further laminated with the polarizing coating of brightness enhancement film in polarizing coating.
The optical film that polarizing film is laminated with above-mentioned optical layer can also be by the manufacturing process in liquid crystal display device etc.
In the mode that is successively laminated individually formed, but stacking in advance and stability of the optical film with quality, assembling behaviour is made
The advantages of manufacturing process that is excellent and liquid crystal display device being improved etc. such as making.It is appropriate that adhesive layer etc. can be used in stacking
Adhesion means.Above-mentioned polarizing coating, other optical films bonding when, their optic axis can be according to target phase difference characteristic etc.
And form arrangement angles appropriate.
It also can be set in above-mentioned polarizing coating, the optical film for being laminated at least 1 layer polarizing coating for liquid crystal cells etc.
The adhesive layer of other components bonding.The adhesive for forming adhesive layer is not particularly limited, and can suitably select use with such as third
The polymer conduct of olefin(e) acid based polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyethers, fluorine system or rubber series etc.
The adhesive of base polymer.In particular, can that it is preferable to use the optical transparences as acrylic adhesive be excellent, shows
The excellent adhesive of the adhesion characteristic and weatherability, heat resistance etc. of appropriate wetability, coherency and cementability.
Adhesive layer can also be used as the overlapping layer of the layer of different composition or type etc. and polarizing coating, optical film be arranged in
One or two sides.In addition, in the case of being arranged at two sides, difference can also be formed in the surface back side of polarizing coating, optical film
Composition, type, thickness etc. adhesive layer.The thickness of adhesive layer can be according to using purpose, bonding force etc. suitably to determine, usually
It is 1~500 μm, preferably 1~200 μm, particularly preferably 1~100 μm.
For the exposed surface of adhesive layer, during until for practical, the temporarily adhesion such as its pollution in order to prevent
Partition and protected.Thus, it is possible to prevent from contacting under common processing status with adhesive layer.As partition, above-mentioned thickness is removed
Other than degree condition, can use for example by plastic foil, sheet rubber, paper, cloth, non-woven fabrics, mesh, foamed sheet or metal foil, they
The sheet-like article appropriate such as layered product etc. use the stripping appropriate such as silicone or chain alkyl class, fluorine system or molybdenum sulfide as needed
From partition that agent has carried out coating process etc. according to previous partition appropriate.
<image display device>
Polarizing coating or optical film of the invention can be used preferably in formation of the various devices such as liquid crystal display device etc..
The formation of liquid crystal display device can be carried out according to previous mode.That is, liquid crystal display device is generally by by liquid crystal cells and partially
Driving circuit etc. is arranged after being suitably assembled to be formed in the component parts such as vibrating diaphragm or optical film and lighting system as needed,
But in the present invention, other than using polarizing coating or optical film of the invention, be not particularly limited, can according to existing way into
Row.For liquid crystal cells, the arbitrary type such as TN type or STN type, π type also can be used.
Can be formed in liquid crystal display device configured with polarizing coating or optical film of the unilateral side or two sides of liquid crystal cells or
The liquid crystal display device appropriate of backlight or reflecting plate etc. has been used in lighting system.In this case, polarization of the invention
Film or optical film can be set in the unilateral side or two sides of liquid crystal cells.Polarizing coating is set in two sides or when optical film, they can be with
It is identical to can also be different.Further, when forming liquid crystal display device, one or two layers or more can be configured in position
The portion appropriate such as diffusing panel, antiglare layer, antireflection film, protection board, prism array, lens array sheet, light diffusing board, backlight
Part.
Embodiment
Hereinafter, recording the embodiment of the present invention, but embodiments of the present invention are not limited to these.
<production of polarizing film>
75 μm of thickness of polyvinyl alcohol film of 99.9 moles of average degree of polymerization 2400, saponification degree % is impregnated in 30 DEG C of temperature
In water 60 seconds and make its swelling.Then, it is impregnated in the aqueous solution of the concentration 0.3% of iodine/potassium iodide (weight ratio=0.5/8),
Film is dyed when being stretched to 3.5 times.Later, in 65 DEG C of boric acid ester solution in such a way that total stretching ratio is 6 times
It is stretched.After stretching, drying in 3 minutes is carried out with 40 DEG C of baking ovens, obtains PVA system polarizing film X (23 μm of thickness).
<transparent protective film>
Transparent protective film 1: using be not saponified, 60 μm of thickness of tri acetyl cellulose membrane (moisture-inhibiting of sided corona treatment etc.
Spend 530g/m2/ for 24 hours) (in table 1, being denoted as TAC).
Transparent protective film 2: to 40 μm of thickness of (methyl) acrylic resin (moisture permeability 96g/ with lactone ring structure
m2/ for 24 hours) implement use (in table 1, being denoted as acrylic acid series) after sided corona treatment.
Transparent protective film 3: to 55 μm of thickness of cyclic polyolefin films (Nippon Zeon Co., Ltd.'s system: ZEONOR, moisture permeability 11g/
m2/ for 24 hours) implement use (in table 1, being denoted as COP) after sided corona treatment.
<moisture permeability of transparent protective film>
The measurement of moisture permeability is carried out according to the moisture permeability test (agar diffusion method) of JIS Z0208.The sample of diameter 60mm will be cut to
Product are set in the moisture vapor transmission cup for having put into the calcium chloride of about 15g, are put into the constant temperature machine of 40 DEG C of temperature, humidity 90%R.H., measurement
The weight for placing the calcium chloride of 24 hours front and backs increases, and thus finds out moisture permeability (g/m2/24h)。
<active energy beam>
Use visible light (gallium encloses metal halide lamp) irradiation unit: Fusion UV Systems, Inc corporation
Light HAMMER10 light bulb: V-arrangement light bulb peak illumination: 1600mW/cm2, add up exposure 1000/mJ/cm2(wavelength 380~
440nm) it is used as active energy beam.It should be noted that visible using Solatell corporation Sola-Check system measurement
The illumination of light.
Examples 1 to 4 and the Comparative Examples 1 to 5
(preparation of active energy ray curable adhesive)
According to cooperation table recorded in table 1, each ingredient is mixed and is stirred 1 hour at 50 DEG C, embodiment 1 is obtained and compares
The active energy ray curable adhesive of example 1.It should be noted that the active energy ray curable adhesive of embodiment 1
Viscosity be 95cp (25 DEG C), the viscosity of the active energy ray curable adhesive of comparative example 1 is 45cp (25 DEG C).
(production of polarizing coating)
Using MCD coating machine (Mechanology Inc., Fuji system), (cell configuration: gravure roll line number: honeycomb 1000 pieces/inch, revolves
Rotary speed 140%/opposite line speed), above-mentioned reality is applied in a manner of reaching 0.7 μm of thickness on above-mentioned transparent protective film
The active energy ray curable adhesive of example or comparative example is applied, the two sides of above-mentioned polarizing film X is fitted in roller machine.Later, from
The transparent protective film side (two sides) of fitting, is heated to 50 DEG C using IR heater, irradiates above-mentioned visible light to two sides and makes above-mentioned
After the solidification of the active energy ray curable adhesive of embodiment or comparative example, in 70 DEG C of progress, 3 minutes heated-air dryings, obtain
The two sides of polarizing film have the polarizing coating of transparent protective film.It is carried out so that the line speed of fitting is 25m/min.
The production of polarizing coating is carried out respectively according to 3 kinds of above-mentioned transparent protective film 1~3.
The polarizing coating obtained by above-described embodiment and comparative example is conducted the following evaluation.Evaluation result is shown in table 1.
It should be noted that separately making same polarizing coating respectively when humidifying durability and being bonded the evaluation of water resistance.
<volume water absorption rate>
Using polarizing coating curing type adhesive used in each example, pressed from both sides with 2 sheet glass of the spacer provided with 100 μm
Firmly, solidified and prepared 100 μm of thickness of gluing oxidant layer (solidfied material) with active-energy condition same as embodiment.By its
As sample.The weight of sample is set as M1g.Sample M1g is impregnated 24 hours in 23 DEG C of pure water.Later, it is taken from pure water
Measure the weight (M2g) of sample after being wiped out and with the cloth after drying again within 1 point.According to these as a result, by formula:
{ (M2-M1)/M1 } × 100 (%) calculates volume water absorption rate.
<cure shrinkage>
It is measured by Sentec corporation cure shrinkage sensor " resin solidification shrinkage stress measurement device EU201C ".Tool
For body, cure shrinkage is calculated by the method that Japanese Unexamined Patent Publication 2013-104869 is recorded.It should be noted that by embodiment 1
Active energy ray curable adhesive formed solidfied material cure shrinkage be 8.9%, by the active-energy of comparative example 1
The cure shrinkage for the solidfied material that ray curing adhesive is formed is 11.9%.
<bonding force>
It is 200mm, orthogonal side that the polarizing coating obtained by each example, which is cut into the direction parallel with the draw direction of polarizing film,
To the size for 20mm, notch is marked with cutter between transparent protective film and polarizing film, polarizing coating is made to fit in glass plate.
Using Tensilon, transparent protective film and polarizing film are removed with peeling rate 500mm/min along 90 degree of directions, measure its removing
Intensity.In addition, by the infrared absorption spectrum of the release surface after the measurement removing of ATR method, according to following benchmark to removing interface
It is evaluated.
A: the cohesion of transparent protective film destroys
B: transparent protective film/adhesive interlayer interface peel
C: the interface peel between gluing oxidant layer/polarizing film
D: the cohesion of polarizing film destroys
In said reference, the bonding force of A and D indicate that bonding force is very excellent more than the cohesiveness of film.Another party
The bonding force at the transparent protective film of face, B and C/gluing oxidant layer (gluing oxidant layer/polarizing film) interface is insufficient (bonding force is poor).In view of
This, bonding force when by for A or D be denoted as zero, A-B (while occur " cohesion of transparent protective film destroys " and " transparent protective film/
The interface peel of adhesive interlayer ") or A-C (while " cohesion of transparent protective film destroys " and " gluing oxidant layer/polarization occurs
Interface peel between piece ") when bonding force be denoted as △, bonding force when by B or C is denoted as ×.
<humidification durability: the measurement that monomer transmissivity, degree of polarization change>
By method same as embodiment and comparative example 1 will be laminated respectively as transparency protected on the two sides of polarizing film
Sample is made in the polarizing coating of the transparent protective film 2 and 3 of film.The polarizing coating (sample) is put into the constant temperature and humidity of 85 DEG C/85%RH
500 hours in machine.It is measured and is thrown using the spectral transmission analyzer (Dot-3c of color technical research institute in village) with integrating sphere
The monomer transmissivity and degree of polarization of polarizing coating before entering and after investment, ask calculation as follows:
The variable quantity (Δ T:%) of monomer transmissivity=(the monomer transmissivity (%) after investment)-(monomer before investment is saturating
Penetrate rate (%)),
The variable quantity (Δ P:%) of degree of polarization=(degree of polarization (%) after investment)-(degree of polarization (%) before investment).
It should be noted that degree of polarization P is by applying in following formula with the axis of homology of 2 identical polarizing coatings
Transmissivity (parallel transmission: Tp) when parallel mode is overlapped 2 identical polarizing coatings and orthogonal with the axis of homology of the two
Transmissivity (orthogonal transmission: Tc) of mode when being overlapped and the value that finds out.Degree of polarization P (%)={ (Tp-Tc)/(Tp+Tc) }1/2
×100
Each transmissivity is passed through being set as 100% from Glan-Taylor prism polarizing film complete polarized light as obtained from
2 degree of visual fields (illuminant-C) of JIS Z8701 be worth shown in the Y value after brightness correction.
<bonding water resistance (warm water immersion experiment)>
By method same as embodiment and comparative example 1 will be laminated respectively as transparency protected on the two sides of polarizing film
Sample is made in the polarizing coating of the transparent protective film 1 and 3 of film.It is by the draw direction that the polarizing coating (sample) is cut into polarizing film
50mm, the rectangle that vertical direction is 25mm.It is visual with magnifying glass after the polarizing coating is impregnated 6 hours in 60 DEG C of warm water
Measure the length of removing.Measured value will be used as from the maximum value of the vertical range in the section of peeling-off part (mm).
<bonding water resistance (water-fast peeling force)>
By method same as embodiment and comparative example 1 will be laminated respectively as transparency protected on the two sides of polarizing film
Sample is made in the polarizing coating of the transparent protective film 1 and 3 of film.The polarizing coating (sample) is cut into flat with the draw direction of polarizing film
The size that capable direction is 200mm, orthogonal direction is 20mm.After the polarizing coating is impregnated 24 hours in 23 DEG C of pure water, from
After taking out and wiped with the cloth after drying in pure water, notch is marked with cutter between transparent protective film and polarizing film, it will be inclined
Vibrating diaphragm fits in glass plate.Operation until carrying out being fetched into evaluation from pure water within 1 point.After, it carries out and above-mentioned < viscous
Relay > same evaluation.
<calculating of logPow>
Using the logPow value of each compound obtained by Chem DrawUltra (Cambridge Soft corporation),
It is calculated by following formula.It should be noted that removing polymerization initiator and photoacid generator from calculating.
The logPow=∑ (logPowi × Wi) of curing type adhesive
LogPowi: the logPow value of each ingredient of curing type adhesive
The molal quantity of Wi:(i ingredient)/(total mole number of each ingredient of curing type adhesive)
[table 1]
In table 1, free-radical polymerised compound is shown:
HEAA: hydroxyethyl acrylamide, logPow=-0.56, Tg=123 DEG C of homopolymer, emerging people's corporation；
ACMO: acryloyl morpholine, logPow=-0.20, Tg=150 DEG C of homopolymer, emerging people's corporation；
FA-THFM:(methyl) tetrahydrofurfuryl acrylate, logPow=1.13, Tg=45 DEG C of homopolymer, Hitachi's chemical conversion is public
Department's system；
Light Acrylate DCP-A: Tricyclodecane Dimethanol diacrylate, logPow=3.05, the Tg of homopolymer
=134 DEG C, chemical company, common prosperity society system；
Light Acrylate 1,9ND-A:1,9- nonanediol diacrylate, logPow=3.68, the Tg=of homopolymer
68 DEG C, chemical company, common prosperity society system；
Aronix M-220: tripropylene glycol diacrylate, logPow=1.68, Tg69 DEG C of homopolymer, East Asia synthesis
Corporation；
Aronix M-306: three/tetraacrylate of pentaerythrite, logPow=1.04, Tg=250 DEG C of homopolymer with
On, East Asia Synesis Company system.
Acrylic oligomers are shown: the East Asia ARUFON UP-1190, logPow=1.95 Synesis Company system,
Compound containing alkoxy is shown: Carbide industrial group, Nikalac MX-750LM, logPow=0.8 Japan
System,
Compound containing epoxy group is shown: JER828, logPow=4.76 Japan epoxy resin corporation,
Isocyanate compound is shown: Karenz AOI, logPow=1.6 Showa Denko K. K system).
Photoepolymerizationinitiater initiater is shown:
IRGACURE907 (2- methyl-1-(4- methylsulfanylphenyl)-2- morpholino propane-1- ketone), logPow=
2.09, BASF AG's system
KAYACURE DETX-S (diethyl thioxanthone), logPow=5.12, Japanese chemical drug corporation.
Photoacid generator shows CPI-100P (using triaryl matte hexafluorophosphate as the carbonic acid of the effective component 50% of principal component
Sub- propyl ester solution), San-Apro corporation.
Claims (17)
1. a kind of polarizing coating curing type adhesive, which is characterized in that be the polarizing coating curing type glue containing curability composition
Stick,
The polarizing coating is impregnated in 23 DEG C pure with curing type adhesive solidfied material obtained by the curing type adhesive will be made to solidify
In the case of water 24 is small, volume water absorption rate shown in following formula be 10 weight % hereinafter,
Volume water absorption rate (%)={ (M2-M1)/M1 } × 100,
Wherein, in the formula, M1 indicates the weight of the solidfied material before dipping, and M2 indicates the weight of the solidfied material after dipping,
The polarizing coating curing type adhesive also contains the compound (C) comprising any one of alkoxy, epoxy group.
2. polarizing coating curing type adhesive according to claim 1, which is characterized in that Octanol/water Partition Coefficients are
LogPow value is 1 or more.
3. polarizing coating curing type adhesive according to claim 1 or 2, which is characterized in that the curability composition is
Active energy ray-curable ingredient.
4. polarizing coating curing type adhesive according to claim 3, which is characterized in that the active energy ray-curable
Property ingredient contains free-radical polymerised compound.
5. polarizing coating curing type adhesive according to claim 4, which is characterized in that the free-radical polymerised chemical combination
Object contains (methyl) acrylamide derivative.
6. polarizing coating curing type adhesive according to claim 4 or 5, which is characterized in that described free-radical polymerised
Compound contains multi-functional compounds, and the multi-functional compounds have free-radical polymerised function at least two
Group.
7. the polarizing coating curing type adhesive according to any one of claim 3~6, which is characterized in that also contain light
Polymerization initiator.
8. the polarizing coating curing type adhesive according to any one of claim 3~7, which is characterized in that also contain third
Olefin(e) acid system oligomer (A).
9. the polarizing coating curing type adhesive according to any one of claim 3~8, which is characterized in that also contain light
Acid agent (B).
10. polarizing coating curing type adhesive according to claim 1, which is characterized in that described includes alkoxy, epoxy
The compound (C) of any one of base is the compound (C1) containing alkoxy.
11. polarizing coating curing type adhesive according to claim 10, which is characterized in that the change containing alkoxy
Closing object (C1) is the melamine compound containing alkoxy.
12. the polarizing coating curing type adhesive according to any one of claim 3~11, which is characterized in that also contain
Isocyanate compound (D).
13. polarizing coating curing type adhesive according to claim 1 or 2, which is characterized in that the curability composition is
Thermocurable ingredient, also contains thermal polymerization.
14. a kind of polarizing coating, which is characterized in that be provided at least one face of polarizing film across gluing oxidant layer transparency protected
Film,
The solidified material layer shape of gluing oxidant layer polarizing coating curing type adhesive as described in any one of claim 1~13
At.
15. polarizing coating according to claim 14, which is characterized in that the adhesive solidified material layer with a thickness of 0.1~3
μm。
16. a kind of optical film, which is characterized in that be laminated with polarizing coating described at least 1 claims 14 or 15.
17. a kind of image display device, which is characterized in that used polarizing coating described in claims 14 or 15 or right
It is required that optical film described in 16.
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| WO2018030210A1 (en) * | 2016-08-10 | 2018-02-15 | 昭和電工株式会社 | Chloroprene graft copolymer latex, method for producing same, bonding agent and adhesive |
| KR102409278B1 (en) * | 2016-09-30 | 2022-06-15 | 닛토덴코 가부시키가이샤 | A liquid crystal panel and an image display device |
| JP7195041B2 (en) * | 2017-02-08 | 2022-12-23 | 住友化学株式会社 | Polarizing film, circularly polarizing plate and display device |
| JP7027003B2 (en) * | 2017-09-21 | 2022-03-01 | 日東電工株式会社 | Laminated optical film and its manufacturing method, and image display device |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329246A (en) * | 2000-05-25 | 2001-11-27 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition for adhesive improved in moisture resistance, cured item obtained therefrom, and production method thereof |
| JP2008249885A (en) * | 2007-03-29 | 2008-10-16 | Jsr Corp | Polarizing plate and its manufacturing method |
| CN102326105A (en) * | 2009-03-05 | 2012-01-18 | 日东电工株式会社 | Highly functional thin polarizing film and process for producing same |
| CN102471642A (en) * | 2009-07-28 | 2012-05-23 | 东亚合成株式会社 | Actinic-energy-ray-curable adhesive composition for plastic film or sheet |
| CN102516462A (en) * | 2010-08-02 | 2012-06-27 | 新日铁化学株式会社 | Curable resin composition and cured product thereof |
| CN102639663A (en) * | 2010-01-21 | 2012-08-15 | 日本合成化学工业株式会社 | Adhesive agent, adhesive agent for optical member, optical member having adhesive layer attached thereto, image display device, active-energy-ray- and/or heat-curable adhesive agent composition, and adhesive agent composition |
| CN102884147A (en) * | 2010-06-28 | 2013-01-16 | 日东电工株式会社 | Pressure-sensitive adhesive layer for optical films, pressure-sensitive optical film and image display device |
| JP2013112715A (en) * | 2011-11-28 | 2013-06-10 | Toagosei Co Ltd | Active energy ray-curing type adhesive composition |
| JP2013112693A (en) * | 2011-11-25 | 2013-06-10 | Toagosei Co Ltd | Curing type adhesive composition |
| CN104024294A (en) * | 2011-12-01 | 2014-09-03 | 东亚合成株式会社 | Active energy beam-cured composition for optical film, optical film, polarizer protective film, and polarizing plate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4744496B2 (en) * | 2007-04-16 | 2011-08-10 | 日東電工株式会社 | Polarizing plate, optical film and image display device |
| JP5326315B2 (en) * | 2008-03-21 | 2013-10-30 | Ｊｓｒ株式会社 | Radiation curable composition for adhesive, polarizing plate, and manufacturing method of polarizing plate |
| JP5552338B2 (en) * | 2010-03-12 | 2014-07-16 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| JP6128576B2 (en) * | 2011-04-22 | 2017-05-17 | 日東電工株式会社 | Optical laminate |
-
2014
- 2014-08-29 CN CN201811395174.7A patent/CN109554122B/en active Active
- 2014-08-29 CN CN201480047627.0A patent/CN105492564B/en active Active
- 2014-08-29 CN CN201811394795.3A patent/CN109536046B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329246A (en) * | 2000-05-25 | 2001-11-27 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition for adhesive improved in moisture resistance, cured item obtained therefrom, and production method thereof |
| JP2008249885A (en) * | 2007-03-29 | 2008-10-16 | Jsr Corp | Polarizing plate and its manufacturing method |
| CN102326105A (en) * | 2009-03-05 | 2012-01-18 | 日东电工株式会社 | Highly functional thin polarizing film and process for producing same |
| CN102471642A (en) * | 2009-07-28 | 2012-05-23 | 东亚合成株式会社 | Actinic-energy-ray-curable adhesive composition for plastic film or sheet |
| CN102639663A (en) * | 2010-01-21 | 2012-08-15 | 日本合成化学工业株式会社 | Adhesive agent, adhesive agent for optical member, optical member having adhesive layer attached thereto, image display device, active-energy-ray- and/or heat-curable adhesive agent composition, and adhesive agent composition |
| CN102884147A (en) * | 2010-06-28 | 2013-01-16 | 日东电工株式会社 | Pressure-sensitive adhesive layer for optical films, pressure-sensitive optical film and image display device |
| CN102516462A (en) * | 2010-08-02 | 2012-06-27 | 新日铁化学株式会社 | Curable resin composition and cured product thereof |
| JP2013112693A (en) * | 2011-11-25 | 2013-06-10 | Toagosei Co Ltd | Curing type adhesive composition |
| JP2013112715A (en) * | 2011-11-28 | 2013-06-10 | Toagosei Co Ltd | Active energy ray-curing type adhesive composition |
| CN104024294A (en) * | 2011-12-01 | 2014-09-03 | 东亚合成株式会社 | Active energy beam-cured composition for optical film, optical film, polarizer protective film, and polarizing plate |
Non-Patent Citations (3)
| Title |
|---|
| CHUN, HYUNAEE 等: "Effect of the stress relaxation property of acrylic pressure-sensitive adhesive on light-leakage phenomenon of polarizer in liquid crystal display", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| LIU JIE 等: "Defect Related to Polarizer in TFT-LCD", 《CHINESE JOURNAL OF LIQUID CRYSTALS AND DISPLAYS》 * |
| 赖延清等: "液晶显示器用偏光片", 《激光与光电子学进展》 * |
Also Published As
| Publication number | Publication date |
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| CN109554122B (en) | 2022-03-01 |
| CN109536046B (en) | 2021-06-11 |
| CN105492564A (en) | 2016-04-13 |
| CN109536046A (en) | 2019-03-29 |
| CN105492564B (en) | 2018-12-11 |
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