CN109661601A

CN109661601A - Polarization plates and its manufacturing method

Info

Publication number: CN109661601A
Application number: CN201780054035.5A
Authority: CN
Inventors: 阪上智惠; 古川达也; 中川弘也
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2016-09-06
Filing date: 2017-09-01
Publication date: 2019-04-19
Anticipated expiration: 2037-09-01
Also published as: KR20230148394A; CN109661601B; JP2022153440A; TWI777973B; WO2018047728A1; JP2018041079A; KR102591351B1; JP7174511B2; KR20190044099A; TW201816043A; JP7406594B2

Abstract

Even if the present invention provides the polarization plates and its manufacturing method for also showing excellent durability under the environment such as high temperature and humidity.A kind of polarization plates, it includes polarizing films and the protective film being laminated at least one face of above-mentioned polarizing film via adhesive layer, above-mentioned adhesive layer is comprising cationically polymerizable compound, the solidfied material of the bonding agent of first acid agent and the second acid agent, above-mentioned first acid agent is ionic compound of the solidification temperature less than 120 DEG C, and be constitute above-mentioned ionic compound counter anion be following formula (1) or (2) shown in anion ionic compound, above-mentioned second acid agent is that solidification temperature is 120 DEG C or more and is generated the ionic compound of acid using active energy beam.

Description

Polarization plates and its manufacturing method

Technical field

The present invention relates to the polarization plates used in liquid crystal display device etc. and its manufacturing methods.

Background technique

As bonding agent used when assembling optical component etc., it is known that it is poly- to be combined with cationically polymerizable resin, light Close the bonding agent (patent document 1 and 2) of initiator and thermal polymerization.Such bonding agent not only has based on light irradiation Solidification also has the solidification based on heating, therefore the part etc. in the assembling of optical component etc. as shadow also can Enough bondings, so as to be used in the assembling of the optical material such as semiconductor laser module.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-95881 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2003-96425 bulletin

Summary of the invention

Subject to be solved by the invention

On the other hand, bonding agent is also used in the polarization plates for being widely used in liquid crystal display device etc., in general, polarization plates The composition of protective film is laminated with via bonding agent with the single or double in polarizing film.In recent years, polarization plates are used in Various uses, such as using smart phone or panel type terminal as the mobile device purposes of representative, be placed on sometimes for example high Under temperature or hot and humid environment.

It is therefore desirable to which the floating of the interface of bonding agent and polarizing film or protective film can be inhibited under such circumstances Rise or removing etc. and deteriorate optical characteristics.Especially since polarization plates strong shrinkage stress in a high temperauture environment, right Bonding agent used in polarization plates requires bonding agent used in the assembling than general optical component etc. higher resistance to Long performance.

Therefore, even if the object of the present invention is to provide also show the inclined of excellent durability under the environment such as high temperature and humidity Vibration plate and its manufacturing method.

Means for solving the problems

The present inventor has made intensive studies in order to solve the above problems, as a result completes the present invention.That is, packet of the present invention Containing following technical scheme.

[1] a kind of polarization plates, it includes polarizing film and at least one face of above-mentioned polarizing film via adhesive layer and The protective film of stacking, above-mentioned adhesive layer are comprising the viscous of cationically polymerizable compound, the first acid agent and the second acid agent The solidfied material of agent is connect,

Above-mentioned first acid agent is ionic compound of the solidification temperature less than 120 DEG C, and is that composition is above-mentioned ionic The counter anion of compound is the ionic chemical combination of anion shown in anion shown in following formula (1) or following formula (2) Object,

[changing 1]

[in formula, R¹For optionally with the C of substituent group_6-14Aryl or the C optionally with substituent group_3-14Aromatic heterocycle, R²~R⁴Independently of one another C_1-18Alkyl, the C optionally with substituent group_6-14Aryl or the C optionally with substituent group_3-14Aromatic series Heterocycle, above-mentioned substituent group are C_1-18Alkyl, halogenated C_1-8Alkyl, C_2-18Alkenyl, C_2-18Alkynyl, C_6-14Aryl, C_3-14Aromatic series is miscellaneous Ring group, nitro, hydroxyl, cyano ,-OR⁵Shown in alkoxy or aryloxy group, R⁶Acyl group, R shown in CO-⁷Acyl-oxygen shown in COO- Base ,-SR⁸Shown in alkylthio group or arylthio ,-NR⁹R¹⁰Shown in amino or halogen atom, above-mentioned R⁵~R⁸For C_1-8Alkyl, C_6-14Aryl or C_3-14Aromatic heterocycle, above-mentioned R⁹And R¹⁰For hydrogen atom, C_1-8Alkyl, C_6-14Aryl or C_3-14Heteroaromatic Base.]

[changing 2]

[(Rf)_aPF_6-a]^- (2)

[in formula, Rf indicate 80% or more of hydrogen be replaced by fluorine atoms after, identical or different alkyl, a be 1~5 it is whole Number.]

Above-mentioned second acid agent is that solidification temperature is 120 DEG C or more and is generated ionicization of acid using active energy beam Close object.

[2] polarization plates according to [1], wherein above-mentioned adhesive layer is by irradiating active energy to above-mentioned bonding agent It is heated and cured adhesive layer after amount ray.

[3] polarization plates according to [1] or [2], wherein the first acid agent is ionicization shown in following formula (3) Close object.

[changing 3]

[in formula, R¹¹And R¹²Alkyl, aralkyl, aryl or aromatic heterocycle, R are indicated independently of each other¹³Indicate optional Phenyl with substituent group, X^-For anion shown in formula (1) described in [1] or formula (2).]

[4] polarization plates according to any one of [1]~[3], wherein the counter anion of the second acid agent is above-mentioned Anion or PF shown in formula (1) or above-mentioned formula (2)₆ ^-。

[5] polarization plates according to any one of [1]~[4], wherein the counter cation of the second acid agent is sulfonium system Cation.

[6] polarization plates according to any one of [1]~[5], wherein cationically polymerizable compound includes to be selected from ring At least one kind of compound in oxygen compound, oxetane compound and vinyl compound.

[7] polarization plates according to any one of [1]~[6], wherein protective film include selected from cellulose-based resin, At least one kind of resin in (methyl) acrylic resin, polyolefin-based resins, polyester based resin and polycarbonate-based resin.

[8] a kind of method is the manufacturing method of polarization plates described in any one of [1]~[7] comprising:

(a) on polarizing film and/or protective film coating adhesive process；

(b) process that polarizing film and protective film are laminated；

(c) to the process of the irradiation active energy beam of laminated body obtained in process (b)；And

(d) process of following heating layer stack.

The effect of invention

According to the present invention it is possible to provide polarization plates under the environment such as high temperature and humidity with excellent durability.

Detailed description of the invention

Fig. 1 is the schematic sectional view for indicating an example of layer structure of polarization plates of the invention.

Specific embodiment

Polarization plates of the invention include polarizing film and at least one face of above-mentioned polarizing film via adhesive layer layer Folded protective film.

Fig. 1 is the schematic sectional view for indicating an example of layer structure of polarization plates of the invention.Polarization plates shown in FIG. 1 are successively It is constituted comprising the first protective film 10, first bonding agents layer 15, polarizing film 30, second bonding agents layer 25 and the second protective film 20. That is, the first protective film 10 is layered on a face of polarizing film 30 via first bonding agents layer 15, the second protective film 20 via Second bonding agents layer 25 and be layered on another face of polarizing film 30.

It is not limited to the example of Fig. 1, polarization plates of the invention may include other layers in addition to the foregoing.If enumerating it The concrete example of his layer, such as are as follows: it is laminated in the adhesive phase of the outer surface of the first protective film 10 and/or the second protective film 20；Layer It is laminated on the isolation film (also referred to as " stripping film ") of the outer surface of the adhesive phase；The first protective film 10 and/or second is laminated in protect The protective film (also referred to as " surface protection film ") of the outer surface of cuticula 20；In the first protective film 10 and/or the second protective film 20 The optical functional film etc. that outer surface is laminated via adhesive layer or adhesive phase.

Polarization plates of the invention can for the bar of the polarization plates constituted with above-mentioned layer or its reel spool, from the length The polarization plates monolithic body is cut into the monolithic body after smaller szie by the polarization plates monolithic body of object and reel spool cutting.

Be explained, in the present specification, durability refers to: under such as hot environment, under hot and humid environment, repeatedly In the environment of high temperature and low temperature etc., it is able to suppress adhesive layer and the interface of polarizing film or protective film that is adjacent floats Or removing characteristic (sometimes referred to as peel resistance), be able to suppress optical characteristics deterioration characteristic (sometimes referred to as resistance to deterioration), And it is able to suppress the characteristic (sometimes referred to as resistance to crimpiness) etc. of polarization slab warping (or curling).

[1] adhesive layer

Constitute polarization plates of the invention adhesive layer be comprising following record defined cationically polymerizable compound, The solidfied material of the bonding agent of first acid agent and the second acid agent is preferably solidified by being heated after irradiation active energy beam Solidfied material constitute.

(1) cationically polymerizable compound

Cationically polymerizable compound is preferably by active energy beam (such as ultraviolet light, visible light, electron ray, X Ray etc.) irradiation and heating and carry out cationic polymerization and cured compound or oligomer.As cationic polymerization Property compound, it can be mentioned, for example in the molecule with 1 or more epoxy group epoxide, in the molecule have 1 or more Oxetane compound, vinyl compound of oxetane etc..These cationically polymerizable compounds can individually make With or two or more is applied in combination.Wherein, it is preferably selected from epoxide, oxetane compound and vinyl compound At least one kind of compound, particularly preferred epoxide and oxetane compound.As epoxide, example can be enumerated Such as cycloaliphatic epoxy, aliphatic epoxy compound, aromatic epoxy compound, hydrogenated epoxy compound, from bonding From the perspective of property and curing rate, preferably cycloaliphatic epoxy, aliphatic epoxy compound etc..In addition, epoxy compound The quantity of epoxy group existing for the intramolecular of object can be such as 1, preferably 2 or more, particularly 2.If using two functions The epoxide of (quantity of epoxy group is 2), then it is also high even for adaptation for the shrinkage stress of polarizing film, because This, is advantageous for forming the excellent polarization plates such as peel resistance.

Cycloaliphatic epoxy can be in the molecule with the change of 1 or more epoxy group for being bonded to ester ring Close object." epoxy group for being bonded to ester ring " refers to 3 member rings in following formula (5) comprising oxygen atom-O-.Following formula (5) In, m can be 2~5 integer.

[changing 4]

Cycloaliphatic epoxy can be the removing (CH of formula (5)₂)_mIn one or more hydrogen atoms after form base Compound made of group is bonded with other chemical structures.Specifically, in the cycloaliphatic epoxy, the removing of formula (5) (CH₂)_mIn hydrogen after form group directly or via straight-chain or branched alkylidene (such as straight-chain or branched C_1-12Alkylidene) it is bonded to the compound of one or more formulas (5).It is explained, constitutes above-mentioned straight-chain or branched alkylidene - CH₂- O- or-CO- can be replaced into.In addition, (CH₂)_mIn one or more hydrogen atoms can be straight by methyl, ethyl etc. Chain or branched-chain alkyl suitably replace.Wherein, from the viewpoint of cementability and curing rate, there is cyclopentane epoxide structure The cycloaliphatic epoxy of (m=3 in above-mentioned formula (5)), 7-oxa-bicyclo[4.1.0 structure (m=4 in above-mentioned formula (5)) is advantageous 's.

Hereinafter, enumerating cycloaliphatic epoxy (the sometimes referred to as two function alicyclic epoxies conjunction of two suitable functions Object) concrete example.Here, enumerating chemical combination name first, later, chemical formula corresponding with each chemical combination name is shown, for chemical combination Name and corresponding chemical formula mark the same symbol.

1A:3,4- 7-oxa-bicyclo[4.1.0 formic acid -3,4- epoxycyclohexanecarboxylate,

2A:3,4- epoxy group -6- cyclohexanecarboxylic acid -3,4- epoxy group -6- methylcyclohexyl methyl esters,

3A: ethylenebis (3,4- 7-oxa-bicyclo[4.1.0 formic acid esters),

4A: bis- (3, the 4- epoxycyclohexyl-methyl) esters of adipic acid,

5A: bis- (3, the 4- epoxy group -6- methylcyclohexylmethyl) esters of adipic acid,

6A: diethylene glycol bis- (3,4- epoxycyclohexyl-methyl ethers),

7A: ethylene glycol bis- (3,4- epoxycyclohexyl-methyl ethers),

8A:2,3,14,15- bicyclic oxygens -7,11,18,21- tetra- oxa-, three spiral shell [5.2.2.5.2.2] heneicosane,

9A:3- (3,4- epoxycyclohexyl) -8,9- epoxy group -1,5- dioxo spiro [5.5] hendecane,

10A: dioxidized 4-vinyl cyclohexene,

11A: limonene dioxide,

12A: bis- (2,3- epoxycyclopentyl) ethers,

13A: titanium dioxide bicyclopentadiene.

[changing 5]

[changing 6]

It as aliphatic epoxy compound, can enumerate: the ring being bonded in the molecule at least one with aliphatic carbon atom The compound of oxidative ethane ring (3 yuan of cyclic ethers), such as aliphatic epoxy compound (such as the butyl glycidyl base of simple function The straight-chains such as ether, 2- ethylhexyl glycidyl ether or branched C_2-12Alkyl glycidyl base ether)；The aliphatic of two functions Epoxide (such as the contracting of 1,4-butanediol diglycidyl ether, 1,6- hexylene glycol diglycidyl ether, neopentyl glycol two The straight-chains such as water glyceryl ether or branched C_2-12Alkyl diglycidyl ether, 1,4-CHDM diglycidyl The cyclic alkyls diglycidyl ether such as ether, preferably straight-chain or branched C_2-6Alkyl diglycidyl ether etc.)；Trifunctional Above aliphatic epoxy compound (such as trimethylolpropane tris glycidyl ether, pentaerythritol tetraglycidyl ether Equal C_1-12Alkyl glycidyl base ether etc.)；Dioxidized 4-vinyl cyclohexene, limonene dioxide etc. have 1 Direct Bonding In ester ring epoxy group and have be bonded to aliphatic carbon atom oxirane ring epoxide etc..

The aliphatic epoxy compound of suitable two functions (quantity of existing epoxy group is 2 in the molecule) is (sometimes Referred to as two functional aliphatic's epoxides) it can for example be indicated with following formula (6).

[changing 7]

In above-mentioned formula (6), Y is the alkylidene (the preferably alkylidene of carbon atom number 2~6) of carbon atom number 2~12, entrainment The divalent alkyl of the alkylidene of the total carbon atom number 4~12 of ehter bond or the carbon atom number 6~18 with alicyclic structure, preferably carbon are former The alkylidene of subnumber 2~6.

Aliphatic di-epoxy compounds shown in above-mentioned formula (6) is specially the diglycidyl ether of alkane diol, repeats Count the diglycidyl ether of the oligo alkylene glycols until being 4 or so or the diglycidyl ether of ester ring type glycol.

It is exemplified below the specific of the glycol (glycol) that can form aliphatic di-epoxy compounds shown in above-mentioned formula (6) Example.As alkane diol, including such as ethylene glycol, propylene glycol, 1,3-PD, 2- methyl-1,3-propanediol, 2- butyl -2- Ethyl -1,3-PD, 1,4-butanediol, neopentyl glycol, 3- methyl -2,4- pentanediol, 2,4- pentanediol, 1,5-PD, 3- methyl-1,5- pentanediol, 2- methyl -2,4- pentanediol, 2,4- diethyl -1,5-PD, 1,6- hexylene glycol, 1,7- heptan two Alcohol, 3,5- heptandiol, 1,8- ethohexadiol, 2- methyl-1,8- ethohexadiol, 1,9- nonanediol etc..As oligo alkylene glycols, packet Include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol etc..As ester ring type glycol, including cyclohexanediol, hexamethylene two Methanol etc..

Aromatic epoxy compound is compound in the molecule with aromatic ring and epoxy group.As its concrete example, It can be mentioned, for example: diglycidyl ether, the diglycidyl ether of Bisphenol F, the diglycidyl ether of bisphenol S of bisphenol-A Equal biphenol type epoxies compound or its oligomer；Phenol novolac type epoxy resin, cresol novalac type epoxy resin, hydroxyl The epoxy resin of the novolac types such as benzaldehyde phenol novolac type epoxy resin；2,2 ', 4,4 '-tetrahydroxy diphenylmethyls The glycidyl ether of alkane, 2,2',4,4'-tetrahydroxybenzophenone the multifunctional type such as glycidyl ether epoxy compound Object；The epoxy resin etc. of the multifunctional type such as epoxidation polyvinylphenol.

Hydrogenated epoxy compound can be the glycidyl ether of the polyalcohol with ester ring, or for virtue Aromatic rings is selectively carried out hydrogenation in the presence of a catalyst and under pressurizeing and will be thus obtained by fragrant race's polyalcohol Core hydrogenated polyol carry out it is glycidyl etherified after compound.As the concrete example of aromatic polyol, can arrange It illustrates such as: bisphenol-A, Bisphenol F, bisphenol S bisphenol type compounds；Phenol linear phenolic resin, cresol novalac resin, hydroxyl The novolac types resins such as benzaldehyde phenol linear phenolic resin；Tetrahydroxy diphenyl methane, tetrahydroxybenzophenone, polyethylene The compound etc. of the multifunctional type such as base phenol.And making epichlorohydrin and to the aromatic rings progress hydrogenation of aromatic polyol The ester ring type polyalcohol obtained reacts, so as to which glycidyl ether is made.In these hydrogenated epoxy compounds, preferably The diglycidyl ether etc. of bisphenol-A after hydrogenation.

The epoxide equivalent of epoxide can be such as 43~1500g/ equivalent, preferably 700~1000g/ equivalent, into One step is preferably 90~500g/ equivalent, particularly preferably 100~300g/ equivalent.If epoxide equivalent be above range in, can To form the excellent polarization plates of peel resistance.

The ratio of epoxide relative to cationically polymerizable compound can be 40~100 mass parts, preferably 60 ~99 mass parts, further preferably 80~98 mass parts, specifically for 90 mass parts~97 mass parts.If being in these ranges, It is then advantageous to adaptation (or cementability).It, can also be in addition, from optimization curing rate, improve the viewpoint grade of adaptation etc. And with cycloaliphatic epoxy and aliphatic epoxy compound.In this case, cycloaliphatic epoxy and aliphatic ring The ratio (mass ratio) of oxygen compound can be such as cycloaliphatic epoxy/aliphatic epoxy compound=95/5~5/ 95, preferably 90/10~10/90, more preferably 80/20~20/80, further preferably 75/25~30/70.If in should Range, then the adhesive layer high for formation adaptation and durability is advantageous.

It can be to contain in the molecule for the oxetane compound as one of cationically polymerizable compound The compound of 1 or more oxetane (hexyloxy), it can be mentioned, for example the oxetane compound of simple function [such as 3- Ethyl -3- hydroxymethyl oxetane (sometimes referred to as oxetanes alcohol), 2- ethylhexyl oxetanes, Isosorbide-5-Nitrae-are bis- ({ (3- Ethyloxetane -3- base) methoxyl group } methyl) benzene (sometimes referred to as xyxylene dioxygen azetidine), 3- ethyl - 3- (phenoxymethyl) oxetanes, 3- (cyclohexyloxy) methyl -3- Ethyloxetane；The oxetanes of two functions Compound [such as 3- ethyl -3 ({ (3- Ethyloxetane -3- base) methoxyl group } methyl) oxetanes etc..In these oxygen Among oxetane compounds, from the viewpoint of cementability and curing rate, the preferred oxetane compound of two functions. The principal component that oxetane compound can be used as cationically polymerizable compound uses, can also be with epoxide simultaneously With.Especially, from the aspect that can be improved curability, raising peel resistance, resistance to crimpiness etc. sometimes, epoxy is preferably used in combination Compound and oxetane compound.In this case, the ratio of oxetane compound is relative to epoxide 100 Mass parts can be such as 0.5~70 mass parts, preferably 1~30 mass parts, further preferably 3~10 mass parts.If oxygen The ratio of oxetane compounds is upper limit value hereinafter, being then advantageous from the viewpoint of adaptation (or cementability), if It more than lower limit value, is then advantageous from the viewpoint of the durability to high temperature etc..

As the vinyl compound that can become cationically polymerizable compound, aromatic series, aliphatic or rouge can be enumerated The vinyl ether compound of ring type, as its concrete example, it can be mentioned, for example: n-pentyl vinyl ethers, isopentyl vinyl ethers, just Hexylvinyl ether, n-octyl vinyl ethers, 2- ethylhexyl vinyl ether, dodecyl vinyl ethers, stearyl ethylene The vinyl ethers of the alkyl or alkenyl alcohol of the carbon atom numbers 5~20 such as base ether, oleyl vinyl ethers；2- hydroxyethylvinyl The vinyl ethers of the hydroxyls such as ether, 3- hydroxypropyl vinyl ethers, 4- hydroxybutyl vinyl ether；Cyclohexyl vinyl ether, 2- Methylcyclohexyl vinyl ethers, cyclohexyl methyl vinyl ethers, benzyl vinyl ether etc. have aliphatic ring or aromatic ring The vinyl ethers of monohydric alcohol；Glycerol mono vinyl ether, 1,4-butanediol mono vinyl ether, 1,4-butanediol divinyl ether, 1, 6- hexylene glycol divinyl ether, neopentyl glycol divinyl ether, pentaerythrite divinyl ether, pentaerythrite tetravinyl ether, Trimethylolpropane divinyl ether, trimethylolpropane tris vinyl ethers, Isosorbide-5-Nitrae-dihydroxy butylcyclohexane mono vinyl ether, Isosorbide-5-Nitrae- Dihydroxy butylcyclohexane divinyl ether, Isosorbide-5-Nitrae-bishydroxymethyl hexamethylene mono vinyl ether, Isosorbide-5-Nitrae-bishydroxymethyl hexamethylene two The list of the polyalcohols such as vinyl ethers~more vinyl ethers；Diethylene glycol divinyl ether, triethyleneglycol divinylether, diethyl two Polyalkylene glycol monos~the divinyl ethers such as alcohol monobutyl mono vinyl ether；Glycidyl vinyl ether, ethylene glycol ethylene Other vinyl ethers such as base ether metacrylic acid ester etc..Vinyl compound can be used as cationically polymerizable compound it is main at Divide and use, can also be used in combination with epoxide or epoxide and oxetane compound.From the low viscous of bonding agent The aspect that degreeization and curing rate can be improved sometimes is set out, and vinyl compound also can be used together.

Cationic polymerization type bonding agent can further include annular lactone compound, cyclic acetal compounds, cyclic annular sulphur Other cations as ether compound, spiro orthoester (Spiro Ortho Ester) compound in addition to the foregoing are poly- Conjunction property compound.

(2) first acid agents

First acid agent be solidification temperature less than 120 DEG C, generate acid at an established temperature and cation can be made poly- The ionic compound of conjunction property compound polymerization.Here, " solidification temperature " of the invention indicate using embodiment < solidification temperature Measurement > mono- in record method measurement, in 3, the 4- 7-oxa-bicyclo[4.1.0 formic acid -3 ' as standard substance, 4 '-epoxide rings Be added in hexyl methyl esters (Daicel corporation, trade name " CEL2021P ") 100 mass parts 1 mass parts of the first acid agent (Gu Body ingredient) obtained by temperature of solidification compound, differential scanning calorimetry (DSC) (DSC) heat when reaching maximum.In addition, the As long as an acid agent has above-mentioned property, the curability based on active energy beam can have.I.e., it is possible to be by viscous Connect the acid agent that agent irradiates active energy beam and generates the acid of specified amount.

As long as solidification temperature less than 120 DEG C, can be such as 50 DEG C~115 DEG C, preferably 70 DEG C~110 DEG C, into One step is preferably 90 DEG C~105 DEG C, and particularly preferably 95 DEG C~105 DEG C, and can be preferably 95 DEG C~117 DEG C, further Preferably 95 DEG C~115 DEG C.

If above range, then cationically polymerizable compound is easy solidification, therefore, from the viewpoint of the durability of polarization plates It sets out and is advantageous, in addition, being also advantageous in terms of appearance since heating temperature is lower.

First acid agent is ionic compound, and the counter anion for constituting above-mentioned ionic compound is following formula (1) Shown in anion shown in anion or following formula (2).

[changing 8]

[in formula, R¹For optionally with the C of substituent group_6-14Aryl or the C optionally with substituent group_3-14Aromatic heterocycle, R²~R⁴Independently of one another C_1-18Alkyl, the C optionally with substituent group_6-14Aryl or the C optionally with substituent group_3-14Aromatic series Heterocycle, above-mentioned substituent group are C_1-18Alkyl, halogenated C_1-8Alkyl, C_2-18Alkenyl, C_2-18Alkynyl, C_6-14Aryl, C_3-14Aromatic series is miscellaneous Ring group, nitro, hydroxyl, cyano ,-OR⁵Shown in alkoxy or aryloxy group, R⁶Acyl group, R shown in CO-⁷Acyl-oxygen shown in COO- Base ,-SR⁸Shown in alkylthio group or arylthio ,-NR⁹R¹⁰Shown in amino or halogen atom, above-mentioned R⁵~R⁸For C_1-8Alkyl, C_6-14Aryl or C_3-14Aromatic heterocycle, above-mentioned R⁹And R¹⁰For hydrogen atom, C_1-8Alkyl, C_6-14Aryl or C_3-14Heteroaromatic Base]

[changing 9]

[(Rf)_aPF_6-a]^- (2)

R in above-mentioned formula (1)²~R⁴In, as C_1-18Alkyl, it can be mentioned, for example: methyl, ethyl, n-propyl, normal-butyl, The straight-chains C such as n-pentyl, n-octyl, positive decyl, dodecyl, n-tetradecane base_1-18Alkyl, preferably straight-chain C_1-8Alkyl； Isopropyl, isobutyl group, sec-butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl, isohesyl, 2- ethylhexyl and 1,1,3,3- The branched such as tetramethyl butyl C_1-18Alkyl, preferably branched C_1-8Alkyl；The C such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl_3-18 Naphthenic base, preferably C_3-8Naphthenic base；Norborny, adamantyl and pinane base (pinanyl) etc. are crosslinked ring type alkyl etc..

R in above-mentioned formula (1)¹~R⁴In, as C_6-14Aryl, it can be mentioned, for example: the monocyclics such as phenyl C_6-14Aryl；Naphthalene The fused polycyclics C such as base, anthryl, phenanthryl, anthraquinonyl, fluorenyl, naphthoquinones base_6-14Aryl etc..

R in above-mentioned formula (1)¹~R⁴In, as C_3-14Aromatic heterocycle can be enumerated: thienyl, furyl, pyrans The monocyclics such as base, pyrrole radicals, oxazolyl, thiazolyl, pyridyl group, pyrimidine radicals, pyrazinyl C_3-14Heterocycle；Indyl, benzofuran Base, isobenzofuran-base, benzothienyl, isobenzo-thienyl, quinolyl, isoquinolyl, quinoxaline base, quinazolyl, click Oxazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthyl, thiophene dislike base, phenoxazine base, phenoxazine thiophene base, chromanyl, different Chromanyl, cumarin base, dibenzothiophene, xanthene ketone group, thioxanthene ketone group, dibenzofuran group etc. are condensed Polycycle C_6-14The C such as heterocycle_3-14Heteroaromatic hydrocarbon etc..As C_3-14Aromatic heterocycle, can be for by monocyclic C_3-5Heterocycle The 1 valence group formed, or by monocyclic C_6-14The 1 valence group that heterocycle is formed.

In addition, the R of above-mentioned formula (1)¹~R⁴In C_6-14Aryl or C_3-14Aromatic heterocycle, which can have substituent group, (to be had When referred to as substituent group (A)).It is explained, as R⁵~R¹⁰C_1-8Alkyl, C_6-14Aryl and C_3-14Aromatic heterocycle can arrange Lift above-mentioned R¹~R⁴The C of middle illustration_1-8Alkyl, C_6-14Aryl or C_3-14Aromatic heterocycle.

As substituent group (A), it can be mentioned, for example: C_1-18Alkyl [such as foregoing illustrative C_1-18Alkyl etc.]；Halogenated C_1-8Alkane Base [such as trifluoromethyl, trichloromethyl, pentafluoroethyl group, 2,2,2- trichloroethyls, 2,2,2- trifluoroethyls, 1,1- bis-fluoro ethyls, It is seven fluorine n-propyls, 1,1- difluoro n-propyl, 3,3,3- trifluoro n-propyls, nine fluorine normal-butyls, 3,3,4,4,4- five fluorine normal-butyls, complete The halogenated straights shape such as fluorine n-pentyl, n-perfluoro-octyl C_1-8Alkyl；Hexafluoro isopropyl, chlordene isopropyl, hexafluoro isobutyl group, nine fluorine The halogenated branched C such as tert-butyl_1-8Alkyl；Five fluorine cyclopropyl, nine fluorine cyclobutyl, perfluor cyclopenta, perfluorocyclohexyl etc. are halogenated C_3-8Naphthenic base]；The carbon atom numbers such as perfluorinated adamantane base C_7-12Halogenated crosslinking ring type alkyl；C_2-18Alkenyl [such as vinyl, allyl Base, 1- acrylic, 2- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- methyl-1-propylene base, 1- methyl -2- propylene Straight-chains or the branched C such as base, 2- methyl-1-propylene base and 2- methyl -2- acrylic_2-18Alkenyl；2- cyclohexenyl group, 3- hexamethylene The C such as alkenyl_2-18Cycloalkenyl；The C such as styryl, cinnamyl_2-18Aryl alkenyl etc.]；C_2-18Alkynyl [such as acetenyl, 1- propine Base, 2-propynyl, 1- butynyl, 2- butynyl, 3- butynyl, 1- methyl -2-propynyl, 1,1- dimethyl -2-propynyl, 1- Pentynyl, valerylene base, 3- pentynyl, 4- pentynyl, 1- methyl-2- butynyl, 3- methyl-1-butynyl, 1- decynyl, 2- Straight-chains or the branched C such as decynyl, 8- decynyl, 1- dodecyne base, 2- dodecyne base, 10- dodecyne base_2-18Alkynyl；Benzene The C such as ethyl-acetylene base_2-18Aromatic yl polysulfide yl etc.]；C_6-14Aryl [such as foregoing illustrative aryl etc.]；C_3-14Aromatic heterocycle [such as Foregoing illustrative aromatic heterocycle etc.]；Nitro；Hydroxyl；Cyano；-OR⁵Shown in alkoxy [such as methoxyl group, ethyoxyl, Positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, neopentyl oxygen, 2- first The C such as base butoxy_1-8Alkoxy etc.]；-OR⁵Shown in the aryloxy group [C such as phenoxy group, naphthoxy_6-14Aryloxy group etc.]；-COR⁶It is shown Acyl group [such as C such as acetyl group, propiono, bytyry, valeryl, benzoyl_1-8Alkyl-carbonyl or C_6-14Aryl carbonyl Deng]；-COOR⁷Shown in acyloxy [such as C such as acetoxyl group, butyryl acyloxy, benzoyloxy_1-8Alkyl carbonyl epoxide or C_6-14 Aryl carbonyl epoxide etc.]；-SR⁸Shown in alkylthio group [such as methyl mercapto, ethylmercapto group, butylthio, own sulfenyl, cyclohexylthio etc. C_1-8Alkylthio group etc.] ,-SR⁸Shown in arylthio [such as C such as thiophenyl, naphthalene sulfenyl_6-14Arylthio etc.]；-NR⁹R¹⁰Shown in ammonia Base [such as methylamino, ethylamino, propylcarbamic, dimethylamino, diethylamino, methylethylamine, dipropyl ammonia Amino such as base, dipropylamino, piperidyl etc.]；Halogen atom [such as fluorine atom, chlorine atom, bromine atom, iodine atom] etc..

In these substituent groups (A), preferably halogenated C_1-8Alkyl, halogen atom, nitro, cyano etc..Especially, from sun from The viewpoints such as the polymerism of sub- polymerizable compound and curability are set out, preferably fluorine atom, fluorination C_1-8Alkyl.

R¹Preferably optionally with the C of substituent group_6-14Aryl more preferably optionally has halogen atom or halogenated C_1-8Alkyl C_6-14Aryl.

R²And R³Separately preferably optionally with the C of substituent group_6-14Aryl more preferably optionally has halogen former Sub or halogenated C_1-8The C of alkyl_6-14Aryl.

R⁴Preferably C_1-18Alkyl or the C optionally with substituent group_6-14Aryl.

It is preferred that making R²And R³For identical group, more preferably make R¹~R³For identical group, further preferably make R¹~R⁴ All identical groups.

As the preferred configuration of the counter anion in above-mentioned formula (1), it can be mentioned, for example: R¹~R⁴Respectively pentafluorophenyl group Anion；R¹~R⁴The anion of bis- (trifluoromethyl) phenyl of respectively 3,5-；R¹~R⁴Respectively 3,4,5- trifluorophenyls Anion；R¹~R³Respectively tetrafluoro phenyl and R⁴For the anion of phenyl；R¹~R³Respectively tetrafluoro phenyl and R⁴For butyl Anion etc..

In above-mentioned formula (2), the alkyl of Rf can enumerate foregoing illustrative alkyl etc..Particularly preferred methyl, ethyl, propyl, The C such as butyl_1-8Alkyl.In formula (2), a can be 1~5 integer, preferably 2~4 integer.

Constitute the first acid agent of the invention counter cation be for example sulfonium (such as triphenylsulfonium cation, 4,4 '-is bis- Triaryl mattes cations such as (diphenyl sulfonium) diphenylsulfide cation etc.), iodine (such as the virtue of diphenyl iodine cation etc. two Base iodine cation etc.), diazonium (such as benzene diazonium cations etc.), oxygen, An, Phosphonium etc..Wherein, from the viewpoint of polymerisation reactivity It sets out, preferably sulfonium, iodine, particularly preferred sulfonium.

Anion shown in the higher formula of acidity (1) or (2) of first acid agent of the invention with conjugate acid is as anti- Weigh anion, therefore, can promote the solidification of cationically polymerizable compound by heating, can be formed even if in high temperature and humidity Lower peel resistance, resistance to deterioration also excellent polarization plates.Especially, anion shown in formula (1) can be effectively facilitated solidification. In addition, with metaantimmonic acid salt anionic (such as SbF₆ ^-) etc. compare, anion shown in formula (1) or (2) in terms of safety also more It is suitable.

As the preferred configuration of the first acid agent of the invention, ionic compound shown in following formula (3) can be enumerated.

[changing 10]

[in formula, R¹¹And R¹²Alkyl, aralkyl, aryl or aromatic heterocycle, R are indicated independently of each other¹³Indicate optional Phenyl with substituent group, X^-For anion shown in above-mentioned formula (1) or above-mentioned formula (2).]

R in above-mentioned formula (3)¹¹And R¹²In, as alkyl, it can be mentioned, for example above-mentioned R²~R⁴The alkyl etc. of middle illustration is made For aralkyl, it can be mentioned, for example the C such as benzyl, 2- methylbenzyl, 1- naphthyl methyl, 2- naphthyl methyl_6-10Aryl C_1-8Alkyl etc., As aryl, it can be mentioned, for example above-mentioned R¹~R⁴The aryl etc. of middle illustration.As aromatic heterocycle, it can be mentioned, for example above-mentioned R¹ ~R⁴The aromatic heterocycle etc. of middle illustration.R¹³In phenyl can be substituted base (B) substitution.

As R¹¹And R¹²Alkyl, the preferably C such as methyl, ethyl, propyl, butyl, amyl_1-8Alkyl, more preferably C_1-4 Alkyl.As R¹¹And R¹²Aralkyl, preferably benzyl, naphthobenzyl, as R¹¹And R¹²Aryl, preferably phenyl, naphthalene Deng.

As substituent group (B), it can be mentioned, for example: alkoxy [such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, fourth The straight-chains such as oxygroup, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy and octadecane epoxide Or branched C_1-18Alkoxy etc.]；Aryl [such as the C such as phenyl, tolyl, 3,5-dimethylphenyl, naphthalene_6-10Aryl, C_1-5Alkyl C_6-10Aryl etc.]；Aromatic heterocycle (the C such as thienyl, furyl, pyrrole radicals, indyl_3-14Aromatic heterocycle)；Aryloxy group [such as the C such as phenoxy group, naphthoxy_6-10Aryloxy group etc.]；Alkyl-carbonyl [such as acetyl group, propiono, bytyry, 2- methyl-prop Acyl group, heptanoyl group, 2- methylbutyryl, 3- methylbutyryl, caprylyl, capryl, dodecane acyl group and octadecanoyl etc. C_2-18Alkyl-carbonyl etc.]；Aryl carbonyl [such as the C such as benzoyl, naphthoyl_7-11Aryl carbonyl etc.]；Aromatic alkyl carbonyl [example Such as benzyloxycarbonyl group, 2- methylbenzyl carbonyl, 1- naphthyl methyl carbonyl, 2- naphthyl methyl carbonyl C_6-10Aryl C_1-8Alkyl-carbonyl Deng]；Alkoxy carbonyl [such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, Isobutoxy carbonyl, s-butoxycarbonyl, tert-butoxycarbonyl, carbonyl octyloxy, tetradecyloxyaniline carbonyl, octadecane epoxide carbonyl The straight-chains such as base or branched C_2-19Alkoxy carbonyl etc.]；Aryloxycarbonyl [the C such as phenyloxycarbonyl and naphthoxycarbonyl_7-11Virtue Epoxide carbonyl etc.] etc..

In addition, as substituent group (B), it can be mentioned, for example: aromatic alkoxy carbonyl [such as benzyloxycarbonyl, 2- methyl benzyloxy The C such as base carbonyl, 1- naphthyl methyl Epoxide carbonyl, 2- naphthyl methyl Epoxide carbonyl_6-10Aryl C_1-8Alkoxy carbonyl；Alkyl-carbonyl Oxygroup [such as acetoxyl group, ethylcarbonyl group oxygroup, propyl carbonyl oxygroup, Isopropylcarbonyl oxygroup, butyl carbonyl oxygroup, isobutyl Base carbonyl oxygroup, sec-butylcarbonyl group oxygroup, tert-butyl carbonyl oxygroup, octyl carbonyl oxygroup, myristyl carbonyl oxygroup, octadecane The C such as base carbonyl oxygroup_2-19Alkyl carbonyl epoxide etc.]；Aryl carbonyl epoxide [such as the C such as benzoyloxy, naphthalene formyloxy_7-11's Aryl carbonyl epoxide etc.], aromatic alkyl carbonyl oxygroup [such as benzyloxycarbonyl group oxygroup, 2- methylbenzyl carbonyl oxygroup, 1- naphthyl methyl The C such as carbonyl oxygroup, 2- naphthyl methyl carbonyl oxygroup_6-10Aryl C_1-8Alkyl-carbonyl etc.], alkoxy-carbonyl oxy [such as methoxyl group Carbonyl oxygroup, ethoxy carbonyl oxygroup, propoxycarbonyl oxygroup, isopropoxy carbonyl oxygroup, butoxy carbonyl oxygroup, isobutyl oxygen Base carbonyl oxygroup, s-butoxycarbonyl oxygroup, tert-butoxycarbonyl oxygroup, carbonyl octyloxy oxygroup, tetradecyloxyaniline ketonic oxygen The straight-chains such as base and octadecane epoxide carbonyl oxygroup or branched C_2-19Alkoxy-carbonyl oxy etc.]；Aryloxycarbonyl epoxide [example Such as phenyloxycarbonyl oxygroup and naphthoxycarbonyl oxygroup C_7-11Aryloxycarbonyl epoxide etc.]；Aromatic alkoxy carbonyl oxygroup [such as Benzyloxycarbonyl oxygroup, 2- methvlbenzyloxvcarbonyl oxygroup, 1- naphthyl methyl Epoxide carbonyl oxygroup, 2- naphthyl methyl Epoxide carbonyl The C such as oxygroup_6-10Aryl C_1-8Alkoxy-carbonyl oxy etc.]；Arylthiocarbonyl [such as thiophenyl carbonyl and naphthoxy sulfenyl carbonyl Equal C_7-11Arylthiocarbonyl etc.]；Arylthio [such as thiophenyl, 2- methylphenyl-sulfanyl, 3- methylphenyl-sulfanyl, 4- methylphenyl-sulfanyl, 2- chlorophenylsulfanyl, 3- chlorophenylsulfanyl, 4- chlorophenylsulfanyl, 2- bromophenylthio, 3- bromophenylthio, 4- bromophenylthio, 2- chlorophenylthio, 3- chlorophenylthio, 4- chlorophenylthio, 2- hydroxy benzenes sulfenyl, 4- hydroxy benzenes sulfenyl, 2- Methoxv-phenylsulfanvl, 4- methoxybenzene sulphur Base, 1- naphthalene sulfenyl, 2- naphthalene sulfenyl, 4- [4- (thiophenyl) benzoyl] thiophenyl, 4- [4- (thiophenyl) phenoxy group] thiophenyl, 4- [4- (thiophenyl) phenyl] thiophenyl, 4- (thiophenyl) thiophenyl, 4- benzoylphenylsulfanyl, 4- benzoyl -2- chlorobenzene Sulfenyl, 4- benzoyl -3- chlorophenylsulfanyl, 4- benzoyl -3- methylthio phenyl sulfenyl, 4- benzoyl -2- methylthio phenyl sulphur Base, 4- (4- methylthio phenyl formoxyl) thiophenyl, 4- (2- methylthio phenyl formoxyl) thiophenyl, 4- (to methyl benzoyl) benzene Sulfenyl, 4- (to ethylamino benzonitrile acyl group) thiophenyl -4- (cumic aldehyde formoxyl) thiophenyl, 4- (to tert-butyl-benzoyl) The C such as thiophenyl_6-20Arylthio etc.]；Alkylthio group [such as methyl mercapto, ethylmercapto group, rosickyite base, isopropyisulfanyl, butylthio, isobutyl sulphur Base, secondary butylthio, tertiary butylthio, penta sulfenyl, isopentylthio, new penta sulfenyl, tertiary penta sulfenyl, pungent sulfenyl, last of the ten Heavenly stems sulfenyl, dodecane sulphur The straight-chains such as base, isooctadecane sulfenyl or branched C_1-18Alkylthio group etc.] etc..

In turn, as substituent group (B), can enumerate: hetero ring type alkyl [such as thienyl, furyl, pyranose, pyrrole radicals, Oxazolyl, thiazolyl, pyridyl group, pyrimidine radicals, pyrazinyl, indyl, benzofuranyl, benzothienyl, quinolyl, isoquinolin Base, quinoxaline base, quinazolyl, carbazyl, acridinyl, phenothiazinyl, phenazinyl, xanthyl, thienyl, phenoxazine base, pheno Dislike thiophene base, chromanyl, isochroman base, dibenzothiophene, xanthene ketone group, thioxanthene ketone group and two The C such as benzofuranyl_3-20Aryl-heterocyclic formula alkyl (aromatic heterocycle) etc.]；Alkyl sulphinyl [such as methylsulfinyl Base, ethylsulfinyl, propylsulfenyl, isopropylsulphinyl, butylsulfinyl, isobutyl group sulfinyl, Zhong Ding Base sulfinyl, terf-butylsulfinyl, pentylsulfinyl, isopentyl sulfinyl, neopentyl sulfinyl, tertiary pentyl are sub- Straight-chains or the branched C such as sulfonyl, octyl sulfinyl and isooctadecane base sulfinyl_1-18Alkyl sulphinyl etc.]；Virtue Base sulfinyl [such as the C such as phenylsufinyl, tolyl sulfinyl and naphthalene sulfinyl_6-10Aryl sulfonyl kia Deng]；Alkyl sulphonyl [such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, butyl sulfonyl, Iso-butylsulfonyl, sec-butylsulfonyl, tert. butylsulfonyl, pentylsulfonyl, isopentyl sulfonyl, neopentyl sulfonyl, The linear chain or branched chains C such as tertiary pentyl sulfonyl, octyl sulfonyl, octadecyl sulfonyl_1-18Alkyl sulphonyl etc.]；Arylsulfonyl Base [such as the C such as phenyl sulfonyl, tolylsulfonyl- base (tosyl) and Naphthylsulfonyl_6-10Aryl sulfonyl etc.]；Hydroxyl Base (poly-) alkylene oxide group [such as the number of repeat unit of alkylene oxide group is 1~6 hydroxyl (poly-) alkylene oxide group etc.]；Amino [such as Methylamino, dimethylamino, ethylamino, methylethylamine, diethylamino, n-propyl amino, methyl n-propyl ammonia Base, ethyl n-propyl amino, n-propyl amino, isopropylamino, isopropylmethylamino, isopropoxyethyl radicals amino, diisopropyl Base amino, phenyl amino, diphenyl amino, MethYlphenylamino, ethylphenyl amino, n-propyl phenyl amino and cumene Substituted-amino and amino of the carbon atom numbers such as base amino 1~15 etc.]；Halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine Atom), hydroxyl etc..

It is explained, as preferred X^-, the preferred configuration of anion shown in above-mentioned formula (1) or (2) can be enumerated.

As the concrete example of the first acid agent shown in above-mentioned formula (3), it can be mentioned, for example: (five fluorine of pheiiyldimetliyl sulfonium four Phenyl) borate, 4- hydroxy phenyl dimethyl sulfonium four (pentafluorophenyl group) borate, 4- methoxycarbonyl phenyl dimethyl sulfonium Four (pentafluorophenyl group) borates, four (pentafluorophenyl group) borate of 4- acetoxyl group phenyl dimethyl sulfonium, 4- benzyloxycarbonyl oxygroup Pheiiyldimetliyl sulfonium four (pentafluorophenyl group) borate, phenylmethyl benzyl sulfonium four (pentafluorophenyl group) borate, 4- hydroxy phenyl first Base benzyl sulfonium four (pentafluorophenyl group) borate, four (pentafluorophenyl group) borate of 4- methoxycarbonyl phenyl methylbenzyl sulfonium, Four (pentafluorophenyl group) borate of 4- acetoxyl group phenyl methyl benzyl sulfonium, 4- benzyloxycarbonyl oxygroup phenylmethyl benzyl sulfonium four (pentafluorophenyl group) borate, four (pentafluorophenyl group) borate of phenyl methyl -2- methylbenzyl sulfonium, 4- hydroxyphenylmethyl -2- first Base benzyl sulfonium four (pentafluorophenyl group) borate, 4- methoxycarbonyl phenyl methyl -2- methylbenzyl sulfonium four (pentafluorophenyl group) Borate, four (pentafluorophenyl group) borate of 4- acetoxyl group phenyl methyl -2- methylbenzyl sulfonium, 4- benzyloxycarbonyl oxygroup phenyl Four (pentafluorophenyl group) borate of methyl -2- methylbenzyl sulfonium, four (pentafluorophenyl group) borate of phenyl methyl -1- naphthyl methyl sulfonium, Four (pentafluorophenyl group) borate of 4- hydroxyphenylmethyl -1- naphthyl methyl sulfonium, 4- hydroxyphenylmethyl -2- naphthyl methyl sulfonium four (pentafluorophenyl group) borate, 4- methoxycarbonyl phenyl methyl-1-naphthyl methyl sulfonium four (pentafluorophenyl group) borate, 4- second Phenyl methyl-1-naphthyl methyl sulfonium four (pentafluorophenyl group) borate, 4- benzyloxycarbonyl oxygroup phenyl methyl-1- naphthalene Methyl sulfonium four (pentafluorophenyl group) borate；The counter anion of these the first acid agents, i.e. four (pentafluorophenyl group) borate is set It is changed to ionic compound obtained by three (pentafluoroethyl group) three fluorophosphates etc..These first acid agents can be used alone or group It closes and uses two or more.

(3) second acid agents

Above-mentioned second acid agent is to pass through active energy beam (such as ultraviolet light, visible light, electron ray, X-ray etc.) Irradiation and generate acid and the ionic compound of above-mentioned cationically polymerizable compound polymerization can be made.Second acid agent Thermal stability it is high, it can be such as 120~350 DEG C that solidification temperature, which is 120 DEG C or more, preferably 150~350 DEG C, more preferably It is 200~320 DEG C, further preferably 250~300 DEG C.It being explained, the definition of solidification temperature is same as the first acid agent, Its using embodiment<method recorded in the measurement of solidification temperature>one measures.

As long as the counter anion for constituting the second acid agent makes 120 DEG C of solidification temperature of the second acid agent or more, simultaneously It is not particularly limited, can be CF₃SO₃ ^-、C₄F₉SO₃ ^-、CH₃SO₃ ^-Equal R-SO₃ ^-(the alkyl or carbon atom of R expression carbon atom number 1~6 The fluoro-alkyl of number 1~6) shown in anion, anion shown in anion, above-mentioned formula (2) shown in above-mentioned formula (1), SbF₆ ^-Or PF₆ ^-.Wherein, in terms of curability, anion shown in preferably above-mentioned formula (1), yin shown in above-mentioned formula (2) from Son or PF₆ ^-.With metaantimmonic acid salt anionic (such as SbF₆ ^-) etc. compare, these anion are more suitable in terms of safety.Separately Outside, the counter anion of the second acid agent can be identical or different with the counter anion of the first acid agent.

For example, anion shown in the above-mentioned formula of the anion of the second acid agent (1) or (2) and the first production acid can be made The anion of agent is PF₆ ^-。

As long as in addition, constitute the second acid agent counter cation make 120 DEG C of solidification temperature of the second acid agent or more, It then can be for such as sulfonium, iodine (such as diaryl iodonium cation diphenyl iodine cation etc.), diazonium (such as benzene diazonium Cation etc.), oxygen, An, Phosphonium etc..Wherein, from the viewpoint of polymerisation reactivity and curability, preferably sulfonium, iodine are especially excellent Select the sulfonium of the good thermal stability of bonding agent.

In terms of the curability of bonding agent, the wavelength region tool of the second acid agent of the invention preferably near 300nm There is Ultraviolet Light, maximum absorption is more preferably shown near 300nm.

As the preferred configuration of the second acid agent, ionic compound shown in following formula (4) can be enumerated.

[changing 11]

[in formula, R¹⁴And R¹⁵Alkyl, aralkyl, aryl or aromatic heterocycle, R are indicated independently of each other¹⁶Indicate optional Phenyl with substituent group, Y^-For anion or PF shown in above-mentioned formula (1) or above-mentioned formula (2)₆ ^-。]

In R¹⁴And R¹⁵In, as alkyl, aralkyl, aryl or aromatic heterocycle, aforementioned R can be illustrated¹¹And R¹²Middle illustration Alkyl, aralkyl, aryl or aromatic heterocycle etc..R¹⁴And R¹⁵It is separately preferably the aryl such as phenyl, naphthalene.

R¹⁶For phenyl, which can have substituent group (C).As substituent group (C), it can be mentioned, for example in substituent group (B) The group of illustration, particularly preferred arylthio etc..

As preferred Y^-, preferred configuration or PF shown in above-mentioned formula (1) or (2) can be enumerated₆ ^-Deng particularly preferably PF₆ ^- Or anion shown in formula (2).

Second acid agent can be commercially available product.As the commercially available product of the second acid agent, it can be mentioned, for example Kayarad PCI- 220 (Japanese chemical drug corporations), Kayarad PCI-620 (Japanese chemical drug corporation), UVI-6990 (UnionCarbide Corporation system), Adeka Optomer SP-150 (ADEKA corporation), (ADEKA is public by Adeka Optomer SP-170 Department's system), CI-5102 (Japanese Cao reach at corporation), CIT-1370 (Japanese Cao reaches corporation), CIT-1682 (Japanese Cao Da company System), CIP-1866S (Japanese Cao reach at corporation), CIP-2048S (Japanese Cao reaches corporation), CIP-2064S (Japanese Cao Dagong Department's system), DPI-101 (greening learn corporation), DPI-102 (corporation is learned in greening), DPI-103 (corporation is learned in greening), DPI- 105 (corporation is learned in greening), MPI-103 (corporation is learned in greening), MPI-105 (corporation is learned in greening), BBI-101 (learn by greening Corporation), BBI-102 (greening learn corporation), BBI-103 (corporation is learned in greening), BBI-105 (corporation is learned in greening), TPS-101 (corporation is learned in greening), TPS-102 (corporation is learned in greening), TPS-103 (corporation is learned in greening), TPS-105 are (green Chemical company's system), MDS-103 (greening learn corporation), MDS-105 (corporation is learned in greening), DTS-102 (green chemical company System), DTS-103 (greening learn corporation), PI-2074 (Rhodia corporation), CPI-100P (San-Apro corporation), CPI- 101A (San-Apro corporation), CPI-200K (San-Apro corporation), CPI-210S (San-Apro corporation) etc..

First acid agent and the second acid agent can be solution obtained by being dissolved in the solvent for not hindering polymerization etc..As molten Agent, it can be mentioned, for example aromatic hydrocarbon [such as toluene, dimethylbenzene etc.]；Carbonates [such as propylene carbonate, carbonic acid Asia second Ester, carbonic acid 1,2- butylene, dimethyl carbonate, diethyl carbonate etc.]；Ketone [such as acetone, methyl ethyl ketone, methyl isoamyl ketone, Ring-type ketone such as the chains such as 2-HEPTANONE ketone, cyclohexanone etc.]；Ether [such as ring-type ethers such as dioxanes etc.]；Esters [such as acetic acid Methyl esters, ethyl acetate, butyl acetate etc.]；Polyalcohols and its derivative [such as ethylene glycol, ethylene glycol acetate, diethyl two Alcohol, diethylene glycol monoacetate, propylene glycol, Propylene glycol monoacetate etc.].

The ratio of solvent is such as 0.1~10 mass parts relative to the first acid agent or 1 mass parts of the second acid agent, preferably For 0.5~5 mass parts or so.

In bonding agent, the ratio of the total amount of the first acid agent and the second acid agent is relative to cationically polymerizable compound 100 mass parts can be such as 0.1~30 mass parts, preferably 0.2~20 mass parts, more preferably 0.5~10 mass parts, into One step is preferably 1~5 mass parts, particularly preferably 2~4 mass parts.If the total amount of the first acid agent and the second acid agent is upper More than the lower limit value stated, then it can be sufficiently carried out the solidification of bonding agent, durability and cementability can be improved.On the other hand, If the total amount of the first acid agent and the second acid agent be above-mentioned upper limit value hereinafter, if can effectively inhibit heating polarization plates When polarization plates xanthochromia.

In addition, the ratio (mass ratio) of the first acid agent and the second acid agent can produce for such as the first acid agent/second Sour agent (mass ratio)=95/5~5/95, preferably 90/10~10/90, more preferably 80/20~20/80, further preferably It 75/25~25/75, particularly preferably 70/30~30/70, is most preferably 60/40~40/60.If the range, then can incite somebody to action Cationically polymerizable compound effectively solidifies, and is capable of forming the polarization plates of excellent in te pins of durability.In addition, going out from the viewpoint of durability Hair is preferably comprised with the first acid agent equal amount or than its further amounts of second acid agent, more preferably comprising than the first acid agent Further amounts of second acid agent.

One kind can be used only in first acid agent, can also be applied in combination different two or more.In addition, the second acid agent One kind can also be used only, can also be applied in combination different two or more.

(4) additive

The bonding agent for forming adhesive layer can according to need and contain additive.As additive, ion can be enumerated and caught Obtain agent (such as inorganic compounds such as powdered bismuth system, antimony system, magnesium system, aluminium system, calcium system, titanium system and their mixed system Deng), antioxidant (such as hindered phenolic antioxidant etc.), chain-transferring agent, polymerization accelerant (polyalcohol etc.), sensitizer, increasing Feel auxiliary agent, light stabilizer, tackifiers, thermoplastic resin, filler, flow modifier, plasticizer, defoaming agent, levelling agent, silane Coupling agent, pigment, antistatic agent, ultraviolet absorbing agent etc..

For adhesive layer of the invention, even if being placed under high temperature and humidity, the adaptation of protective film and polarizing film Also high, there is excellent peel resistance.That is, the peeling force (closing force) of adhesive layer is 300mm/ minutes in fixture movement speed Under conditions of can be such as 1.2~3, preferably 1.5~2.5.It is explained, peeling force (closing force) can use embodiment The method of middle record measures.

It is explained, bonding agent can use customary way at least the above cationically polymerizable compound, above-mentioned One acid agent, the mixing of above-mentioned second acid agent are to prepare.

Storage modulus of the adhesive layer at 80 DEG C is preferably 600MPa or more.If storage modulus is 600MPa or more, The change in size of polarization plates when polarization plates can be inhibited to be placed under hot environment, also, such as cold shock testing that In the endurance test of the application dramatic temperature variation of sample, the rupture of polarizing film can be inhibited.Storage modulus at 80 DEG C is more excellent It is selected as 800MPa or more, further preferably 1000MPa or more.

The adaptation of polarizing film and protective film in polarization plates comprising adhesive layer of the invention and excellent in adhesion, i.e., So that polarizing film is generated strong shrinkage stress, can also effectively inhibit the removing at interface or float.Moreover, even if high in high temperature or high temperature Under wet, it can also inhibit the deterioration (such as radioparent variation of polarization plates etc.) of optical characteristics.In addition, with polarization plates monolithic body Deng form use in the case where, be also not easy when being cut from bar and reel spool cut stress due to polarizing film with Peeling-off between protective film, the monolithic body after making processing is not susceptible to warpage.Therefore, even if polarization plates of the invention are in high temperature High humidity it is inferior it is harsh under conditions of also there is excellent durability, therefore be useful as the polarization plates in liquid crystal display device etc. 's.

[2] polarizing film

Polarizing film is with the film for selectively transmiting this function of the rectilinearly polarized light in some direction from natural light.It can Enumerate that the iodine system polarizing film for for example making iodine be adsorbed in polyvinyl alcohol resin film and being orientated, to be adsorbed in dichroic dye poly- Vinyl alcohol resin film and the dyestuff system polarizing film being orientated and the dichroic dye of coating lysotropic liquid crystal state are simultaneously allowed to Application type polarizing film etc. after orientation and immobilization.These polarizing films selectively transmit the straight line in some direction from natural light Polarised light and the rectilinearly polarized light for absorbing another direction, therefore it is referred to as absorption-type polarizing film.Polarizing film is not limited to inhale Receipts type polarizing film can be selectively to transmit the rectilinearly polarized light in a direction from natural light and reflect another direction The reflection type polarizer of rectilinearly polarized light or scatter another direction rectilinearly polarized light scatter-type polarizing disc, from making to regard Feel that the excellent aspect of identification is set out, preferably absorption-type polarizing film.Wherein, more preferable degree of polarization and transmissivity it is excellent iodine system it is inclined Shake piece.

As polyvinyl alcohol resin, the polyethenol series tree after being saponified polyvinyl acetate system resin can be used Rouge.As polyvinyl acetate system resin, other than homopolymer, that is, polyvinyl acetate of vinyl acetate, second can be also enumerated The copolymer etc. of vinyl acetate and the other monomers that can be copolymerized with it.It can be with the example of the other monomers of vinyl acetate copolymerization Attached bag includes unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and acrylic amide with ammonium etc..

The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of % or so, preferably 98 moles of % or more.Poly- second Enol system resin can be modified, and also can be used for example by the modified polyvinyl formal of aldehydes or polyvinyl alcohol contracting second Aldehyde etc..The average degree of polymerization of polyvinyl alcohol resin is usually 1000~10000 or so, and preferably 1500~5000 or so.It is poly- The average degree of polymerization of vinyl alcohol resin can be acquired according to JIS K 6726.

Film made of such polyvinyl alcohol resin is used as to the former material film of polarizing film.The system of polyvinyl alcohol resin Film method is not particularly limited, and can use well known method.Polyethenol series former material film with a thickness of such as 150 μm hereinafter, Preferably 100 μm or less (such as 50 μm or less).

Polarizing film can use the method including following process to manufacture, that is, carry out polyvinyl alcohol resin film uniaxial The process of stretching；It is set to adsorb the work of dichroism pigment and being dyed polyvinyl alcohol resin film with dichroism pigment Sequence；The process that the polyvinyl alcohol resin film for being adsorbed with dichroism pigment is handled into (crosslinking Treatment) with boric acid aqueous solution； And the process washed after the processing based on boric acid aqueous solution.

Being uniaxially stretched for polyvinyl alcohol resin film can be before the dyeing of dichroism pigment, while dyeing or after dyeing It carries out.In the case where being uniaxially stretched after dyeing, this be uniaxially stretched can boric acid processing before or boric acid processing in into Row.Alternatively, it is also possible to be uniaxially stretched in these multiple stages.

When being uniaxially stretched, can be uniaxially stretched between the different roller of peripheral speed, also can be used hot-rolling into Row is uniaxially stretched.In addition, being uniaxially stretched to be the dry type stretching that is stretched in an atmosphere, or using solvent or Water makes the wet tensile stretched in the state of polyvinyl alcohol resin membrane swelling.Stretching ratio is usually 3~8 times or so.

As the method for dyeing polyvinyl alcohol resin film with dichroism pigment, can be used for example by the film immersion in containing There is the method for the aqueous solution of dichroism pigment.As dichroism pigment, iodine or dichroic organic dye are used.It is explained, gathers Vinyl alcohol resin film preferably implements the impregnation impregnated in water before dyeing processing in advance.

As the dyeing processing based on iodine, it is typically employed in the aqueous solution containing iodine and potassium iodide and impregnates polyethenol series The method of resin film.The content of iodine in the aqueous solution can be 0.01~1 mass parts or so relative to 100 mass parts of water.

The content of potassium iodide can be 0.5~20 mass parts or so relative to 100 mass parts of water.In addition, the aqueous solution Temperature can be 20~40 DEG C or so.On the other hand, it as the dyeing processing based on dichroic organic dye, is typically employed in and contains There is the method that polyvinyl alcohol resin film is impregnated in the aqueous solution of dichroic organic dye.Contain the water-soluble of dichroic organic dye The inorganic salts such as sodium sulphate can be contained in liquid as dyeing assistant.The content of dichroic organic dye in the aqueous solution relative to 100 mass parts of water can be 1 × 10^-4~10 mass parts or so.The temperature of the aqueous solution can be 20~80 DEG C or so.

As the boric acid processing after the dyeing based on dichroism pigment, generally use the polyvinyl alcohol resin after dyeing The method that film impregnates in the aqueous solution of boronic acid containing.In the case where using iodine as dichroism pigment, the boronic acid containing it is water-soluble Liquid preferably comprises potassium iodide.

The amount of boric acid in the aqueous solution of boronic acid containing can be 2~15 mass parts or so relative to 100 mass parts of water.The water The amount of potassium iodide in solution can be 0.1~20 mass parts or so relative to 100 mass parts of water.The temperature of the aqueous solution can be with It is 50 DEG C or more, for example, 50~85 DEG C.

Treated that polyvinyl alcohol resin film usually carries out washing process for boric acid.Washing process for example can be by will be through Treated that polyvinyl alcohol resin film immersion carries out in water for boric acid.The temperature of water in washing process is usually 5~40 DEG C or so.

Implement to be dried after washing, obtains polarizing film.Air drier can be used in drying process or far infrared adds Hot device carries out.By using bonding agent the polarizing film two-sided fitting protective film, so as to obtain polarization plates.

In addition, other examples of the manufacturing method as polarizing film, it can be mentioned, for example Japanese Unexamined Patent Publication 2000-338329 bulletins Or the method recorded in Japanese Unexamined Patent Publication 2012-159778 bulletin.In the method, on the surface of base material film, coating contains poly- second The solution of enol system resin and after resin layer is set, the stacked film comprising base material film and resin layer is stretched, then, is implemented Dyeing processing, crosslinking Treatment etc. form polarizer layer by resin layer.Include this of base material film and polarizer layer polarizability stacked film It can be by the way that after polarizer layer face paste closes protective film, removing removes base material film, then the polarization exposed due to the removing because of base material film Lamella face paste closes another protective film and polarization plates is made.

The thickness of polarizing film can be for 40 μm hereinafter, preferably 30 μm or less (such as 20 μm or less).It is explained, according to The method recorded in Japanese Unexamined Patent Publication 2000-338329 bulletin or Japanese Unexamined Patent Publication 2012-159778 bulletin, can be more easily The polarizing film of film is manufactured, the thickness of polarizing film may be such as 20 μm hereinafter, can be in turn 10 μm or less.Polarizing film Thickness is usually 2 μm or more.The thickness for reducing polarizing film is advantageous the slimming of polarization plates or even image display device.

[3] protective film

Protective film can be for by (preferably optically transparent) thermoplastic resin, such as chain polyolefin with translucency The polyolefin-based resins such as resin (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon system resin (norbornene resin etc.)；Triacetyl The cellulose-based resins such as the cellulose esters such as base cellulose, diacetyl cellulose system resin；Polyethylene terephthalate gathers The polyester based resins such as (ethylene naphthalate), polybutylene terephthalate (PBT)；Polycarbonate-based resin；(methyl) acrylic acid It is resin；Or the film of the formation such as their mixture, copolymer.It is explained, " (methyl) acrylic acid series " refers to metering system Acid system and/or acrylic acid series refer to that " (methyl) " whens " (methyl) acrylate " etc. is also same meaning.Wherein, first Protective film 10 and the second protective film 20 (or principal component of the protective film) are preferably comprised respectively selected from cellulose-based resin, (methyl) At least one kind of resin in acrylic resin, polyolefin-based resins, polyester based resin and polycarbonate-based resin.

Protective film can be for non-stretched film or any one of the film after being stretched uniaxially or biaxially.Twin shaft It can be biaxial stretch-formed while 2 draw directions are stretched simultaneously for stretching, or after prescribed direction stretching again It is stretched in another direction gradually biaxial stretch-formed.Protective film may be to have both the optical function as phase difference film Protective film.Phase difference film be using for the purpose of by compensation of liquid crystal cells bring phase difference as image-displaying member etc. and The optical functional film used.For example, (being uniaxially stretched or twin shaft by being stretched the film formed by above-mentioned thermoplastic resin Stretch etc.), or liquid crystal layer etc. is formed on the film, so as to which the phase difference film for imparting arbitrary phase difference is made.

As chain polyolefin-based resins, it can be mentioned, for example chain olefins as polyvinyl resin, acrylic resin Homopolymer and the copolymer formed by chain olefin of more than two kinds.

Cyclic polyolefin hydrocarbon system resin be comprising with norbornene, tetracyclododecane (alias: dimethano octahydro naphthalene) or it Derivative be typical example cyclic olefin as polymerized unit resin general designation.If enumerating cyclic polyolefin hydrocarbon system resin Concrete example, then be the open loop (co) polymer and its hydride of cyclic olefin, the addition polymer of cyclic olefin, cyclic olefin With the copolymer of the chain olefins such as ethylene, propylene or the aromatic compound with vinyl and by them with unsaturated carboxylic Modified modified (co) polymer of acid or derivatives thereof etc..Wherein, it is preferable to use norbornene resin, the norbornene It is that resin uses the orbornene-baseds monomer such as norbornene or polycyclic orbornene-based monomer as cyclic olefin.

At least part of hydroxyl in cellulose-based resin preferred cellulose cellulose esters system obtained by acid esterification Resin can be a part of by acid esterification and a part of by other Esterification mixed esters.Cellulose esters system resin is preferably Acetylcellulose system resin.As the concrete example of acetylcellulose system resin, it can be mentioned, for example tri acetyl celluloses, two Acetylcellulose, cellulose-acetate propionate, cellulose acetate-butyrate etc..

Polyester based resin is resin with ester bond, other than above-mentioned cellulose esters system resin, generally by polynary The resin that the condensation polymer of carboxylic acid or derivatives thereof and polyalcohol is formed.As the concrete example of polyester based resin, can enumerate poly- to benzene Naphthalate, polyethylene naphthalate, polybutylene naphthalate, gathers polybutylene terephthalate (PBT) Propylene glycol ester terephthalate, polytrimethylene naphthalate, polycyclohexylene's dimethyl ester, poly- naphthalenedicarboxylic acid hexamethylene Alkane dimethyl ester etc..Wherein, from viewpoints such as engineering properties, solvent resistance, scratch resistance, costs, it is preferable to use poly- to benzene two Formic acid glycol ester.Polyethylene terephthalate refers to 80 moles of % or more of repetitive unit by terephthalate The resin that ester is constituted, may include the Component units from other copolymer compositions.

As other copolymer compositions, dicarboxylic acid component, diol component can be enumerated.As dicarboxylic acid component, isophthalic can be enumerated Dioctyl phthalate, 4,4 '-dicarboxylate biphenyls, 4,4 '-benzophenonedicarboxylic acids, bis- (4- carboxyl phenyl) ethane, adipic acid, decanedioic acid, 5-sodium sulfo isophthalate, Isosorbide-5-Nitrae-dicarboxyl butylcyclohexane etc..As diol component, propylene glycol, butanediol, new penta can be enumerated Glycol, diethylene glycol, cyclohexanediol, the ethylene oxide adduct of bisphenol-A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Deng.Dicarboxylic acid component or diol component, which also can according to need to be respectively combined, uses two or more.In addition, also can be by para hydroxybenzene The hydroxycarboxylic acids such as formic acid, p- beta-hydroxy ethoxybenzoic acid are used in combination together with above-mentioned dicarboxylic acid component or diol component.As it His copolymer composition, can be marginally using the dicarboxylic acid component with amido bond, urethane bond, ehter bond, carbonic acid ester bond etc. And/or diol component.

Polycarbonate-based resin is the polyester formed by carbonic acid and glycol or bis-phenol.Wherein, from heat resistance, weatherability and resistance to From the perspective of acidity, it is preferable to use with the aromatic copolycarbonate of diphenyl alkane in strand.As polycarbonate, It can enumerate by bis- (4- hydroxy phenyl) propane (alias bisphenol-A) of 2,2-, bis- (4- hydroxy phenyl) butane of 2,2-, bis- (the 4- hydroxyls of 1,1- Base phenyl) poly- carbon derived from the bis-phenols such as hexamethylene, bis- (4- hydroxy phenyl) iso-butanes of 1,1-, bis- (4- hydroxy phenyl) ethane of 1,1- Acid esters etc..

(methyl) acrylic resin can be (to contain 50 mass % or more using methacrylate as principal monomer ) polymer, the copolymer for being copolymerized it with other a small amount of copolymer compositions.(methyl) acrylic resin is more preferable For the copolymer of methyl methacrylate and methyl acrylate, it can also be made, which to be further copolymerized, third monofunctional monomer.

As third monofunctional monomer, it can be mentioned, for example: ethyl methacrylate, butyl methacrylate, metering system Sour cyclohexyl, phenyl methacrylate, benzyl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid 2- hydroxyl The methyl acrylic ester other than methyl methacrylate such as ethyl ester；Ethyl acrylate, butyl acrylate, acrylate The esters of acrylic acid such as ester, phenyl acrylate, benzyl acrylate, 2-EHA, acrylic acid 2- hydroxy methacrylate；2- (hydroxyl Ylmethyl) methyl acrylate, 2- (1- hydroxyethyl) methyl acrylate, 2- (hydroxymethyl) ethyl acrylate, 2- (hydroxyl first Base) the hydroxy alkyl acrylates class such as butyl acrylate；The unsaturation acids such as methacrylic acid, acrylic acid；Chlorostyrene, bromobenzene The halogenated styrenes class such as ethylene；The substituted phenylethylene class as vinyltoluene, α-methylstyrene；Acrylonitrile, methyl-prop The unsaturated nitriles such as alkene nitrile；The unsaturated acids anhydride such as maleic anhydride, citraconic anhydride；Phenyl maleimide, cyclohexyl Malaysia acyl Unsaturated acyls imines such as imines etc..Third monofunctional monomer can be used alone or two or more is applied in combination.

Polyfunctional monomer can also be made further to be copolymerized with (methyl) acrylic resin.As polyfunctional monomer, can arrange It illustrates such as: ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Ester, tetraethylene glycol two (methyl) acrylate, nine ethylene glycol two (methyl) acrylate, ten tetraethylene glycol two (methyl) acrylic acid Ester etc. two terminal hydroxyls of ethylene glycol or its oligomer are esterified with (methyl) acrylic acid after substance；By propylene glycol or its Two terminal hydroxyls of oligomer be esterified with (methyl) acrylic acid after substance；Neopentyl glycol two (methyl) acrylate, oneself Glycol two (methyl) acrylate, butanediol two (methyl) acrylate etc. carry out the hydroxyl of 2 yuan of alcohol with (methyl) acrylic acid Substance after esterification；By two terminal hydroxyl (first of bisphenol-A, the alkylene oxide addition product of bisphenol-A or their halogen substituents Base) acrylic acid be esterified after substance；The polyalcohols such as trimethylolpropane, pentaerythrite are subjected to ester with (methyl) acrylic acid Substance after change and make on their terminal hydroxyl after the epoxy group of open loop addition (methyl) glycidyl acrylate Substance；Make succinic acid, adipic acid, terephthalic acid (TPA), phthalic acid, their binary acid and their ring such as halogen substituents Substance after the epoxy group of upper open loop addition (methyl) glycidyl acrylate such as oxygen alkane addition product；(methyl) acrylic acid virtue Ester；Divinyl aromatic compounds such as divinylbenzene etc..Wherein, it is preferable to use ethylene glycol dimethacrylate, tetrem Diol dimethacrylate, neopentylglycol dimethacrylate.

(methyl) acrylic resin can for the reaction between functional group possessed by further progress copolymer and by Modified (methyl) acrylic resin.As the reaction, it can be mentioned, for example the carbomethoxies of methyl acrylate and 2- (hydroxyl first Base) methyl acrylate hydroxyl macromolecular chain in separating methanol condensation reaction, the carboxyl of acrylic acid and 2- (hydroxymethyl) propylene Dehydration condensation etc. in the macromolecular chain of the hydroxyl of sour methyl esters.

The glass transition temperature of (methyl) acrylic resin is preferably 80~160 DEG C.Glass transition temperature can Using the polymerization ratio of methacrylate ester monomer and acrylate monomer, the carbon chain length of each ester group and there is each ester group Functional group type and polyfunctional monomer controlled relative to the adjustment of the polymerization ratio of whole monomers.

In addition, the means as the glass transition temperature for improving (methyl) acrylic resin, high molecular It is also effective that ring structure is introduced in main chain.Ring structure is preferably cyclic acid anhydride structure, cyclic imide structure and lactone structure Equal heterocycle structures.Specifically, the cyclic acid anhydrides structures, glutarimide such as glutaric anhydride structure, succinic anhydride structure can be enumerated The lactones ring structures such as cyclic imides structure, butyrolactone and the valerolactones such as structure, succinimide structure.Increase in main chain Ring structure content, can more improve the glass transition temperature of (methyl) acrylic resin.Cyclic acid anhydride structure and ring-type Imide structure can use following methods to introduce, that is, by the way that maleic anhydride and maleimide etc. are had cyclic structure Monomer be copolymerized and the method that introduces；By be dehydrated after polymerization/separating methanol condensation reaction introduces cyclic acid anhydride knot The method of structure；The method etc. for reacting amino-compound and introducing cyclic imide structure.Resin with lactone ring structure is (poly- Close object) it can obtain by the following method, that is, after polymer of the preparation with hydroxyl and ester group in macromolecular chain, in root In the presence of the catalyst such as the organic phosphorus compound according to needs, by heating the hydroxyl and ester group generation ring that make in resulting polymers Change condensation and forms lactone ring structure.

(methyl) acrylic resin can according to need containing additive.As additive, it can be mentioned, for example lubricant, Anti-blocking agent, heat stabilizer, antioxidant, antistatic agent, photostabilizer, impact resistance modifying agent, surfactant etc..

From the viewpoints such as the film formation property of film, the impact resistance of film are made, (methyl) acrylic resin can contain work For the acrylic rubber particle of impact modifying agent.Acrylic rubber particle refers to poly- by the elasticity of acrylate of main body Particle of the object as essential component is closed, the acrylic acid series rubber for the single layer structure being substantially only made of the elastomeric polymer can be enumerated Micelle, using the elastomeric polymer as the acrylic rubber particle of the multilayered structure of 1 layer.As the elastomeric polymer Example can be enumerated using alkyl acrylate as principal component and its copolymerization is made to have other vinyl monomers that can be copolymerized And the crosslinking elastocopolymer of cross-linkable monomer.As the alkyl acrylate for the principal component for becoming elastomeric polymer, can enumerate Such as methyl acrylate (methyl acrylate), ethyl acrylate, butyl acrylate (butyl acrylate), acrylic acid The alkyl acrylate that the carbon atom number of the alkyl such as 2- ethylhexyl is 1~8 or so is, it is preferable to use have 4 or more carbon atom number Alkyl alkyl acrylate.As can be enumerated with other vinyl monomers of the alkyl acrylate copolymer There is intramolecular the compound of 1 polymerism carbon-to-carbon double bond more specifically can enumerate the methyl-props such as methyl methacrylate Vinyl cyanide compounds such as the aromatic ethenyl compounds such as olefin(e) acid ester, styrene, acrylonitrile etc..It, can as cross-linkable monomer More specifically ethylene glycol can be enumerated by enumerating the cross-linked compound at least two polymerism carbon-to-carbon double bond in the molecule (methyl) esters of acrylic acid, (methyl) propylene of the polyalcohols such as two (methyl) acrylate, butanediol two (methyl) acrylate The alkenyl esters, divinylbenzene etc. of allyl propionate etc. (methyl) acrylic acid.

It can also be by the film formed by (methyl) acrylic resin without rubber particles and by comprising rubber particles Protective film is made in the sandwich for the film that (methyl) acrylic resin is formed.Alternatively, it is also possible to will by with (methyl) acrylic acid The single or double for the phase difference presentation layer that the different resin of resinoid is formed forms (methyl) acrylic resin layer and shows The substance of phase difference is made protective film.

Protective film can contain ultraviolet absorbing agent.It is shown polarization plates are applied to image as liquid crystal display device In the case where device, by the way that the protective film containing ultraviolet absorbing agent is configured at image-displaying member (such as liquid crystal cells) Observation side, so as to inhibit image-displaying member because of the deterioration caused by ultraviolet light.As ultraviolet absorbing agent, bigcatkin willow can be enumerated Acid esters based compound, benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex salt Based compound etc..

In Fig. 1, the first protective film 10 and the second protective film 20 can be the film being made of same resin, or by The film that mutually different resin is constituted.In addition, the first protective film 10 and the second protective film 20 in the presence or absence of thickness, additive or add Type, the phase difference characteristics etc. for adding agent may be the same or different.

First protective film 10 and/or the second protective film 20 can be on its outer surfaces (surface with 30 opposite side of polarizing film) With the surface-treated layer as hard conating, antiglare layer, anti-reflection layer, light diffusion layer, antistatic layer, stain-proofing layer, conductive layer (coating layer).

Typically respectively 5~200 μm of the thickness of first protective film 10 and the second protective film 20, preferably 10~120 μm, more Preferably 10~85 μm.The thickness for reducing protective film is advantageous the slimming of polarization plates or even image display device.

Polarization plates of the invention are manufactured using including the method for following process, that is,

(a) on polarizing film and/or protective film coating adhesive process；

(b) process that polarizing film and protective film are laminated；

(d) process of following heating layer stack.

For example, polarization plates shown in FIG. 1 can be formed in the following manner, that is, in a face of polarizing film 30 via One adhesive layer 15 and the first protective film of lamination adhesive 10, and another face of polarizing film 30 via second bonding agents layer 25 and The second protective film of lamination adhesive 20.They (are collectively referred to simply as " protecting by the first protective film 10 and the second protective film 20 sometimes below Cuticula ") lamination adhesive periodically can be carried out by face, it is viscous two-sided protective film can also to be subjected to stacking with a stage It connects.

Specifically, in the binding face of polarizing film 30 and/or the binding face coating adhesive (process (a)) of protective film, warp It is overlapped the film of the two by the coating layer of bonding agent, carries out fitting stacking (process from upper and lower pressing using such as doubling roller etc. (b)).Then, it after irradiating active energy beam (process (c) is referred to as " active energy beam irradiation process "), then is heated (process (d) is referred to as " heating process "), thus adhesive layer is made to be solidified to form polarization plates.It is explained, is forming bonding agent Coating layer before, can one of binding face to polarizing film 30 and protective film or both implement saponification process, corona discharge The easily bonding processing such as processing, corona treatment, flame treatment, prime treatment, anchoring coating process.

In the manufacturing method of polarization plates of the invention, in active-energy irradiation process (c), above-mentioned second acid agent master It plays a role, is cured above-mentioned cationically polymerizable compound.In turn, in heating process (d), the first acid agent master It plays a role, makes uncured in active-energy irradiation process or to solidify insufficient cationically polymerizable compound further Solidification.As described above, in the present invention, by defined cationically polymerizable compound and defined second acid agent combination and Therefore the higher adhesive layer such as adaptation can be formed using active-energy irradiation process, in turn, add by constituting bonding agent In thermal process, the first acid agent of the higher counter anion of acidity with conjugate acid plays a role, and promotes solidification, therefore, It is capable of forming the excellent polarization plates such as peel resistance, resistance to crimpiness and resistance to deterioration (humidity resistance).

In in process (a) and (b), in the formation of the coating layer of bonding agent, such as scraper, bar, die coating can use The various application patterns such as machine, comma coater, gravure coater.Alternatively, it is also possible to use one side by polarizing film 30 and protective film Binding face to make the two continuously feeds on one side curtain coating bonding agent therebetween in a manner of becoming inside in the way of.

From the viewpoint of screening characteristics, preferably make to form the bonding agent of first bonding agents layer 15 and second bonding agents layer 25 Viscosity is low.Specifically, the viscosity at 25 DEG C is preferably 1000mPas hereinafter, more preferably 500mPas is hereinafter, into one Step is preferably 100mPas or less.Bonding agent can be no-solvent type, in order to be adjusted to fit in used application pattern Viscosity and so that it is contained organic solvent.

In process (c), as long as the light source of active energy beam is such as generating ultraviolet light, electron ray, X-ray Light source, preferably ultraviolet light.As ultraviolet light source, there is the light source for the distribution that shines preferably below wavelength 400nm, it can Enumerate such as low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal Halide lamp etc..

The active energy beam exposure intensity of adhesive layer irradiation is determined according to bonding agent, preferably makes to produce for second The photo-irradiation intensity of effective wavelength region reaches 0.1~1000mW/cm for the activation of sour agent².If photo-irradiation intensity is too small, Then the reaction time is too long, on the other hand, if the photo-irradiation intensity is excessive, there is the polymerization of the heat and bonding agent that are radiated by lamp When fever and generate the xanthochromia of adhesive layer, the deterioration of polarizing film 30 or protective film surface it is bad a possibility that.In addition, right The light irradiation time of bonding agent irradiation is also controlled according to bonding agent, according to the shape of photo-irradiation intensity and the product of light irradiation time The accumulated light that formula indicates is such as 10~3000mJ/cm², preferably 10~1000mJ/cm², more preferably 50~500mJ/ cm², further preferably 100~300mJ/cm²Mode set.If accumulated light be upper limit value hereinafter, if light irradiate when Between will not be too long, productivity raising is advantageous, more than lower limit value, then acid agent (especially the second acid agent) can be with Acid is effectively generated, adhesive layer can be cured sufficiently.

Active energy beam can be irradiated from the either side in protective film or polarizing coating, the usually absorption from the second acid agent The high film side irradiation of transmissivity near wavelength.

The present invention and with the first acid agent, therefore, even if being 85% or less (preferably in the transmissivity under such as 320nm Be 70% or less) and 300nm under transmissivity be the low protective film of transmissivity as 50% or less (10% or less preferably) And in the case where irradiating active energy beam, it so that the first acid agent is played a role by heating, make the solidification of bonding agent It sufficiently carries out, and improves the durability of polarization plates.In addition, even if the present invention is in the transmissivity under such as 320nm Transmissivity under 85% or less (70% or less preferably), 300nm is under 50% or less (10% or less preferably) and 350nm Transmissivity be the low protective film of 85% or less such transmissivity and in the case where irradiating active energy beam, durability also can It improves.

In process (d), if at least adhesive layer is heated, such as can to protective film 10 and 20, it is viscous The laminated body for connecing oxidant layer 15 and 25 and polarizing film 30 is heated.As heating means, it can be mentioned, for example the protections for making strip Film or laminated body pass sequentially through the method for the device of the sending radiant heat such as infrared heater, protective film or laminated body to strip Blow the method etc. using the gas after the heating such as pressure fan.Heating temperature can be carried out according to the solidification temperature of the first acid agent Appropriate selection.Specifically, it is preferable that the first acid agent is easy to produce the temperature of acid, and it can be such as solidification temperature ± 30 DEG C, it is excellent It is selected as solidification temperature ± 20 DEG C, further preferably solidification temperature ± 10 DEG C.It, can will be in active-energy if being in the range It is uncured or solidify insufficient cationically polymerizable compound and effectively solidify in irradiation process, therefore can be improved polarizing film With the adaptation of protective film.Specific heating temperature can be such as 50~150 DEG C, preferably 70~120 DEG C, further preferably It is 80~100 DEG C, particularly preferably 85~95 DEG C.If the range, be then able to suppress the heat deterioration of polarization plates, and from sun from It is also advantageous from the perspective of the polymerism and curability of sub- polymerizable compound.

In addition, defined first acid agent has been used in the present invention, therefore curing rate is larger.Therefore, heating process Heating time can be such as 1 second~1 hour, preferably 10 seconds~30 minutes (such as 20 seconds~10 minutes), further it is excellent It is selected as 30 seconds~5 minutes, particularly preferably 50 seconds~2 minutes.

Protective film is laminated in the opportunity of polarizing film 30 via the coating layer of bonding agent 15 or 25 and solidifies coating layer There is no particular restriction opportunity.For example, next coating layer can be made to solidify after a protective film 10 is laminated, and later, stacking Another protective film 20, solidifies coating layer.Alternatively, can also make two-sided after the protective film that the two gradually or is simultaneously laminated Coating layer solidify simultaneously.In addition, the irradiation of active energy beam can be carried out from any protective film side in process (c).

The thickness (such as thickness of first bonding agents layer 15 and second bonding agents layer 25) of adhesive layer after solidification is usual For 20 μm hereinafter, preferably 10 μm hereinafter, further preferably 5 μm hereinafter, particularly preferably 3 μm or less.The thickness of adhesive layer Degree is usually 0.01 μm or more, preferably 0.1 μm or more.It is explained, first bonding agents layer 15 and second bonding agents layer 25 Thickness may be the same or different.

(1) optical functional film

Polarization plates can have other optical functions other than polarizing film 30 for assigning desired optical function Property film, suitable an example be phase difference film.For example, first protective film 10 and/or second is protected in polarization plates shown in Fig. 1 Cuticula 20 can also double as phase difference film, but the phase difference film seperated with protective film can also be laminated.In the latter case, phase Potential difference film can be laminated in the appearance of the first protective film 10 and/or the second protective film 20 via adhesive phase or adhesive layer Face.

The concrete example of phase difference film include the birefringence film formed by the stretched film of the thermoplastic resin with translucency, By film after fixed of discotic mesogenic or nematic liquid crystal orientation, it is formed on base material film the film of above-mentioned liquid crystal layer.Base material film is usual For thermoplastic resin film, as thermoplastic resin, it is preferable to use the cellulose esters such as tri acetyl cellulose system resin.

As the thermoplastic resin for forming birefringence film, the thermoplastic resin described for protective film can be used. For example, if in case where enumerating and using cellulose esters system resin, it can use following methods to obtain birefringence film, That is, forming the method for film by the substance for making cellulose esters system resin contain the compound with phase difference regulatory function, in fibre It ties up the method for compound of the surface coating with phase difference regulatory function of plain ester resin film, carry out cellulose esters system resin The method being stretched uniaxially or biaxially.As the thermoplastic resin for forming birefringence film, also can be used such as polyvinyl alcohol It is other thermoplastic resins as resin, polystyrene resin, polyarylate system resin, polyamide resin.

Phase difference film can for the control of the optical characteristics such as broad in band purpose and be applied in combination 2 or more.In addition, It is not limited to that there is optically anisotropic film, substantial optically isotropic zero-lag film also can be used as phase difference Film.Zero-lag film refers to phase difference value R in face_eAnd thickness direction phase difference value R_thIt is the film of -15~15nm.It is said here Phase difference value R in face_eAnd thickness direction phase difference value R_thFor the value at wavelength 590nm.

Phase difference value R in face_eAnd thickness direction phase difference value R_thIt is defined respectively with following formula.

R_e=(n_x-n_y)×d

R_th=((n_x+n_y)/2-n_z〕×d

In formula, n_xFor the refractive index of the slow-axis direction (x-axis direction) in film surface, n_yIt is the fast axis direction in film surface (in face The y-axis direction orthogonal with x-axis) refractive index, n_zFor the refractive index in film thickness direction (the z-axis direction vertical with film surface), d is film Thickness.

The thermoplastic resin described for protective film or birefringence film can be used in zero-lag film, can be used Such as cellulose esters system resin, the polyolefin-based resins as chain polyolefin-based resins and cyclic polyolefin hydrocarbon system resin, The resin film that the polyester based resin as polyethylene terephthalate is formed.Wherein, from be easy to control phase difference value and The aspect being easy to get is set out, it is preferable to use cellulose esters system resin, polyolefin-based resins.

The example for other optical functional films (optical component) that may include in polarization plates is solar panel, brightness enhancement film, anti- Penetrate layer (reflectance coating), Transflective layer (Transflective film), light diffusion layer (optical diffusion film) etc..They are generally in polarization plates It is configured in the case where the polarization plates of liquid crystal cells back side (backlight side) for configuration.

Solar panel is the substance that uses for the purpose of light path control etc., can be prism array piece, lens array sheet, attached Piece etc. equipped with point (dot).

Brightness enhancement film is used for the purpose for improving the brightness of liquid crystal display device for applying polarization plates.Specifically, It can enumerate the mutually different film stacking of the anisotropy of multi-disc refractive index and be designed to keep reflectivity generation anisotropic The alignment films of cholesteryl liquid crystal polymer or its aligned liquid-crystal layer are supported on base material film and obtain by reflective polarizing light separate sheet Circularly polarizing separation sheet etc..

In order to make polarization plates reflection-type, Semitransmissive, diffused optical component and reflecting layer, half transmitting is respectively set Reflecting layer, light diffusion layer.The polarization plates of reflection-type be used to make the reflection of generation incident light from observation side and carry out display this kind The liquid crystal display device of type, it is convenient to omit the light sources such as backlight, therefore be easy for liquid crystal display device to be thinned.Semitransmissive Polarization plates be used to show with the light from backlight as reflection-type and in the dark in the open the liquid crystal of this type Showing device.In addition, the polarization plates of diffused be used to assign light diffusing and inhibit ripple (moire) etc. display undesirable liquid Crystal device.Reflecting layer, Transflective layer and light diffusion layer can use well known method to be formed.

(2) adhesive phase

Polarization plates of the invention may include for being fitted in the image-displaying members such as liquid crystal cells or other optics The adhesive phase of component.Adhesive phase can be laminated in the outer surface of protective film.

As the adhesive used within the adhesive layer, can be used with (methyl) acrylic resin, silicone-based resin, The adhesive as basic polymer such as polyester based resin, polyurethane series resin, polyether system resin.Wherein, from the transparency, bonding The viewpoints such as power, reliability, weatherability, heat resistance, re-workability are set out, it is preferable to use (methyl) acrylic adhesive.In (first Base) in acrylic adhesive, according to making glass transition temperature be preferably 25 DEG C or less, more preferably 0 DEG C of mode below It is (methyl) alkyl acrylate and (methyl) of 20 alkyl below that cooperating, which has the carbon atom numbers such as methyl, ethyl, butyl, Made of (methyl) acrylic monomer containing functional group such as acrylic acid, (methyl) Hydroxyethyl Acrylate, weight average molecular weight be 100000 or more (methyl) acrylic resin is useful as basic polymer.

Adhesive phase is formed in polarization plates can carry out for example, by following manner, that is, make toluene or ethyl acetate Dissolved in equal organic solvents or dispersible adhesive compositions and prepare the solution of 10~40 mass %, be applied directly to polarization The object surface of plate, and form the mode of adhesive phase；The bonding of sheet is pre-formed on the isolation film for implementing demoulding processing Oxidant layer, and moved the mode etc. for the object surface for being attached to polarization plates.The thickness of adhesive phase is according to its bonding force etc. come certainly It is fixed, it is suitably for 1~50 μm or so of range, preferably 2~40 μm.

Polarization plates may include above-mentioned isolation film.Isolation film can be for by the polyethylene-based resins such as polyethylene, polypropylene The film of the formation such as the polyester based resins such as equal polypropylene-based resins, polyethylene terephthalate.Wherein, preferably poly- terephthaldehyde The stretched film of sour glycol ester.

Can according to need within the adhesive layer and cooperate comprising glass fibre, bead, resin bead, metal powder, other Filler, pigment, colorant, antioxidant, ultraviolet absorbing agent, antistatic agent of inorganic powder etc..

As antistatic agent, it can be mentioned, for example ionic compound, electrically conductive microparticle, electroconductive polymers etc., preferably make Use ionic compound.The cation constituent for constituting ionic compound can be inorganic anion, or organically Anion, from the viewpoint of with the compatibility of (methyl) acrylic resin, preferably organic cation.As it is organic sun from Son can enumerate pyridylium, glyoxaline cation, ammonium cation, sulfonium cation, phosphonium cation etc..On the other hand, as The anion component for constituting ionic compound, can be inorganic anion, or organic anion, it is anti-from assigning It sets out in terms of the excellent ionic compound of antistatic property, preferably comprises the anion component of fluorine atom.As former containing fluorine The anion component of son, can enumerate hexafluorophosphoric acid salt anionic [(PF₆ ^-)], bis- (trifyl) imide anions [(CF₃SO₂)₂N^-] anion, bis- (fluorosulfonyl) imide anion [(FSO₂)₂N^-] anion etc..

(3) protective film

Polarization plates of the invention may include the protective film for temporarily protecting its surface (protection film surface).For example, After being bonded polarization plates on image-displaying member or other optical components, protective film is shelled together with its adhesive phase From removing.

Protective film is made of base material film and the adhesive phase being layered on the base material film.

For adhesive phase, above-mentioned description is quoted.It can be poly- as such as polyethylene for constituting the resin of base material film Polypropylene-based resin as vinylite, polypropylene, polyethylene terephthalate or polyethylene naphthalate The thermoplastic resins such as such polyester based resin, polycarbonate-based resin.The preferably polyester such as polyethylene terephthalate It is resin.

Embodiment

The present invention is further illustrated hereinafter, showing Examples and Comparative Examples, still, the present invention is not by these The restriction of example.In the following examples, as cationically polymerizable compound, the first acid agent and second for constituting bonding agent Acid agent uses substance below.

(cationically polymerizable compound)

Cationically polymerizable compound is by pressing compound below (A-1), compound (A-2) and compound (A-3) According to (A-1): (A-2): the mass ratio of (A-3)=70: 25: 5 mixes to prepare.Resulting cationically polymerizable compound is set as " cationically polymerizable compound A ".

Compound (A-1): 3,4- 7-oxa-bicyclo[4.1.0 formic acid -3 ', 4 '-epoxycyclohexanecarboxylates (Daicel corporation, commodity Name " CEL2021P ", epoxide equivalent: 126~145g/ equivalent)

Compound (A-2): neopentyl glycol diglycidyl ether (Nagase ChemteX corporation, trade name " EX- 211L ", epoxide equivalent: 108~130g/ equivalent),

Compound (A-3): 3- ethyl -3 { ((3- Ethyloxetane -3- base) methoxyl group) methyl } oxetanes (East Asia Synesis Company system, trade name " OXT-221 ")

Cationically polymerizable compound by by compound below (A-1) and compound (A-2) according to (A-1): (A-2) The mass ratio of=40:60 mixes to prepare.Resulting cationically polymerizable compound is set as " cationically polymerizable compound B”。

Compound (A-2): neopentyl glycol diglycidyl ether (Nagase ChemteX corporation, trade name " EX- 211L ", epoxide equivalent: 108~130g/ equivalent)

(the first acid agent)

Compound (B-1): the acid agent of following structures is used.Solidification temperature: 100 DEG C.

[changing 12]

Compound (B-3): the acid agent of following structures is used.Solidification temperature: 113 DEG C.

[changing 13]

(the second acid agent)

Compound (B-2): the acid agent (San-Apro company, trade name " CPI-100P ") of following structures is used.Solidification Temperature: 272 DEG C.

[changing 14]

Compound (B-4): the acid agent of following structures is used.Solidification temperature: 219 DEG C.

[changing 15]

(measurement of the solidification temperature of acid agent)

The solidification temperature of acid agent is measured using the following method.

1 mass parts of the first acid agent (B-1) or the second acid agent (B-2) are added in 100 mass parts of compound (A-1) (solid component), prepares hardening resin composition, is taken 10mg, is put into aluminium gland type container, carry out pressing and it is close It closes, makes measurement sample.Then, the container for having said determination sample will be added to be arranged at differential scanning calorimetry (DSC) (DSC) In (SII Nano Technology corporation, " EXSTAR-6000DSC6220 "), nitrogen cleaning is carried out on one side, on one side with 10 DEG C/min speed be warming up to 300 DEG C from 30 DEG C.According to resulting DSC curve, temperature when heat reaches maximum value will be generated It is set as solidification temperature.It is explained, the DSC obtained from individually taking 10mg " CEL2021P " and operating as described above is bent In line, heat absorption and fever are not shown between 30 DEG C~200 DEG C.In addition, B-2 is 50% solution, solid content is relative to change Conjunction object (A-1) 100 mass parts are 1 mass parts.

First acid agent (B-3) and the second acid agent (B-4) also measure solidification temperature as described above.It is explained, Second acid agent (B-4) is cooperated in the form of 50% polypropylene carbonate ester solution, and solid content is relative to compound (A-1) 100 mass parts are 1 mass parts.

(1) preparation of bonding agent

The mixing ratio (numerical value of table 1 indicates mass parts) recorded according to table 1 measures above-mentioned in the helix tube of 20mL Cationically polymerizable compound, the first acid agent and the second acid agent carry out mixing/deaeration, prepare the ultraviolet light of liquid respectively Curability bonding agent.It is explained, the second acid agent (B-2) and the second acid agent (B-4) are with 50% polypropylene carbonate ester solution Form cooperates, and shows its solid content in table 1.

(2) production of polarization plates

To 80 μm of thickness of acetylcellulose resin film (the Konica Minolta comprising ultraviolet absorbing agent Opto corporation, trade name " Konicatac KC8UX2MW ", the transmission that the transmissivity of wavelength 300nm is 0%, wavelength 320nm Rate is 0%, the transmissivity of wavelength 350nm is that single side 0%) implements Corona discharge Treatment, using bar coater so that after solidification The mode that thickness reaches about 2.5 μm applies bonding agent recorded in table 1 on the Corona discharge Treatment face.Then, in the coating The polyvinyl alcohol (PVA) that 25 μm of face coating thickness-iodine system polarizing coating (polarizing film).Then, to by cyclic polyolefin hydrocarbon system resin (drop Bornylene system resin) formed 50 μm of thickness of phase difference film (Japanese ZEON corporation, trade name " ZEONOR ", wavelength 300nm Transmissivity be 90%, the transmissivity of wavelength 320nm is 90%, the transmissivity of wavelength 350nm is that single side 91%) implements corona Discharge treatment, using bar coater in such a way that the thickness after solidification reaches about 2.5 μm on the Corona discharge Treatment face it is same Ground applies bonding agent recorded in table 1.By the polarizing coating of the subsidiary acetylcellulose resin film made above with polarizing coating Stress to be laminated on the applicator surface, is pressed, is bonded using doubling roller, obtain laminated body.For the laminated body, subsidiary conveying is used The ultraviolet lamp (" D Bulb " that lamp uses Fusion UV Systems corporation) of band, so that accumulated light reaches 200mJ/cm²(UVB) mode then heats 1 at 90 DEG C of temperature from cyclic polyolefin resin film side irradiation ultraviolet light Minute, solidify two-sided adhesive layer, makes polarization plates.

For the laminated body after fitting, ultraviolet light is not irradiated, and is heated 5 minutes at 90 DEG C of temperature, in addition to this, with reality It applies example 1 and similarly makes polarization plates.It is explained, is heated 1 minute at 90 DEG C of temperature, bonding agent is uncured, therefore heats 5 points Clock.

Bonding agent is changed to bonding agent recorded in table 1 respectively, in addition to this, production polarizes similarly to Example 1 Plate.

Bonding agent is changed to bonding agent recorded in table 1, and after irradiating ultraviolet light, by polarization plates at 100 DEG C plus Heat 1 minute, in addition to this, makes polarization plates similarly to Example 1.

Bonding agent is changed to bonding agent recorded in table 1, in addition to this, makes polarization plates similarly to Example 1.

To 80 μm of thickness of acetylcellulose resin film (the Konica Minolta comprising ultraviolet absorbing agent Opto corporation, trade name " Konicatac KC8UX2MW ") single side implement Corona discharge Treatment, using bar coater according to solid The mode that thickness after change reaches about 2.5 μm applies bonding agent recorded in table 1 on the Corona discharge Treatment face.Then, exist 25 μm of coating thickness of polyvinyl alcohol (PVA)-iodine system polarizing coating (polarizing film) in the applicator surface.Then, to by polyester based resin (transmissivity of wavelength 300nm is the saturating of 0%, wavelength 320nm to 25 μm of thickness of the film that (polyethylene terephthalate) is formed The rate of penetrating is 68%, the transmissivity of wavelength 350nm is that single side 83%) implements Corona discharge Treatment, using bar coater according to solidification The mode that thickness afterwards reaches about 2.5 μm similarly applies bonding agent recorded in table 1 on the Corona discharge Treatment face.It will be with The polarizing coating of the subsidiary acetylcellulose resin film of upper production stresses to be laminated on the applicator surface with polarizing coating, using doubling roller into Row pressing, fitting, obtain laminated body.For the laminated body, ultraviolet lamp (the lamp use of subsidiary conveyer belt is used " the D Bulb " of Fusion UV Systems corporation) so that accumulated light reaches 400mJ/cm²(UVB) mode is poly- from it Ester resin film side irradiation ultraviolet light then heats 1 minute at 90 DEG C of temperature, solidifies two-sided adhesive layer, and production is inclined Vibration plate.

To 80 μm of thickness of acetylcellulose resin film (the Konica Minolta comprising ultraviolet absorbing agent Opto corporation, trade name " Konicatac KC8UX2MW ") single side implement Corona discharge Treatment, using bar coater according to solid The mode that thickness after change reaches about 2.5 μm applies bonding agent recorded in table 1 on the Corona discharge Treatment face.Then, exist 25 μm of coating thickness of polyvinyl alcohol (PVA)-iodine system polarizing coating (polarizing film) in the applicator surface.Then, to by acetyl group fiber 40 μm of thickness of the film (trade name: " KC4CR-1 ", Konica Minolta Opto corporation, wavelength that prime system resin is formed The transmissivity of 300nm is 49%, the transmissivity of wavelength 320nm is 90%, the transmissivity of wavelength 350nm is 90%) single side it is real Corona discharge Treatment is applied, using bar coater in the Corona discharge Treatment face in such a way that the thickness after solidification reaches about 2.5 μm On similarly apply bonding agent recorded in table 1.By the polarizing coating of the above made subsidiary acetylcellulose resin film Stress to be laminated on the applicator surface with polarizing coating, is pressed, is bonded using doubling roller, obtain laminated body.For the laminated body, use The ultraviolet lamp (" D Bulb " that lamp uses Fusion UV Systems corporation) of subsidiary conveyer belt, so that accumulation Light quantity reaches 200mJ/cm²(UVB) mode is irradiated ultraviolet from its acetylcellulose resin film (films that 40 μm of thickness) side Line then heats 1 minute at 90 DEG C of temperature, solidifies two-sided adhesive layer, makes polarization plates.

(3) ocular estimate of polarization plates

The monolithic body of the size of 8cm × 8cm is cut from the polarization plates made by above-mentioned (2).By the monolithic body in temperature After placing an evening in the environment of 23 DEG C of degree, relative humidity 60%, the amount of curl of monolithic body is measured.Amount of curl is following numerical value: will Curved monolithic body has occurred to be placed on horizontal platform in downwardly convex mode, is measured from platform to monolithic body respectively with ruler The average value of 4 point values obtained from height until 4 corners.Based on resulting amount of curl, carried out according to benchmark below Determine.The results are shown in Table 2.

4: amount of curl is less than 8nm.

3: amount of curl is 8mm or more and less than 13mm.

2: amount of curl is 13mm or more.

1: polarization plates are curled into tubular or float between protective film and polarizing film.

(4) evaluation of peeling force (closing force)

Corona discharge Treatment is implemented to the protection film surface of gained polarization plates formed by tri acetyl cellulose system resin, Then, it is bonded (methyl) acrylic adhesive piece of 25 μm of commercially available thickness on its Corona discharge Treatment face, is made subsidiary The polarization plates of adhesive phase.The test of cut width 25mm, length about 200mm from the polarization plates that gained is attached to adhesive phase Piece, by its adhesive phase face paste together in soda-lime glass.It is small that the sample is saved to 24 in the environment of 80 DEG C of temperature, relative humidity 90% Shi Hou saves an evening in the environment of 23 DEG C of temperature, relative humidity 55%.Then, by the blade incision polarizing coating of cutter and guarantor Between cuticula, 30mm is removed from end in length direction, with universal tensile testing machine (Shimadzu Seisakusho Ltd.'s system, product name " AG-1 ") Clamp portion clamp the released part.By the test film of the state in the atmosphere of 23 DEG C of temperature and relative humidity 55% foundation JIS K 6854-2:1999 " bonding agent-removing adhesive strength test method-the second: 180 degree removing " is with fixture movement speed Progress 180 degree disbonded test in 300mm/ minutes, the Average peel force of the 170mm long after finding out the 30mm for removing clamp portion.As a result As shown in table 2.

(5) formation of adhesive phase

Use die coating machine will be in the copolymer as butyl acrylate, methyl acrylate, acrylic acid and Hydroxyethyl Acrylate (methyl) acrylic resin in add isocyanates system crosslinking agent, (methyl) acrylic acid series made of silane coupling agent bonds Coated on demoulding is implemented, treated by poly- to benzene in such a way that the thickness after drying reaches 20 μm for the organic solvent solution of agent The demoulding for 38 μm of thickness of the isolation film (LINTEC corporation, trade name " SP-PLR382052 ") that naphthalate is formed Process face makes the sheet adhesive of subsidiary isolation film.Then, by sheet adhesive obtained as above and isolation film opposite side Face (adhesive face) the cyclic polyolefin resin film face of the polarization plates made in above-mentioned (2) is fitted in using laminating machine after, It is conserved 7 days under conditions of 23 DEG C of temperature, relative humidity 65%, obtains the polarization plates with adhesive phase.

(5) formation of adhesive phase

Use die coating machine will be in the copolymer as butyl acrylate, methyl acrylate, acrylic acid and Hydroxyethyl Acrylate (methyl) acrylic resin in add isocyanates system crosslinking agent, (methyl) acrylic acid series made of silane coupling agent bonds Coated on demoulding is implemented, treated by poly- to benzene in such a way that the thickness after drying reaches 20 μm for the organic solvent solution of agent The demoulding for 38 μm of thickness of the isolation film (LINTEC corporation, trade name " SP-PLR382052 ") that naphthalate is formed In process face, the sheet adhesive of subsidiary isolation film is made.Then, by the opposite with isolation film of sheet adhesive obtained as above After the face (adhesive face) of side fits in the polyester based resin film surface of the polarization plates made in above-mentioned (2) using laminating machine, in temperature It is conserved 7 days under conditions of 23 DEG C of degree, relative humidity 65%, obtains the polarization plates with adhesive phase.

(5) formation of adhesive phase

Use die coating machine will be in the copolymer as butyl acrylate, methyl acrylate, acrylic acid and Hydroxyethyl Acrylate (methyl) acrylic resin in add isocyanates system crosslinking agent, (methyl) acrylic acid series made of silane coupling agent bonds Coated on demoulding is implemented, treated by poly- to benzene in such a way that the thickness after drying reaches 20 μm for the organic solvent solution of agent The demoulding for 38 μm of thickness of the isolation film (LINTEC corporation, trade name " SP-PLR382052 ") that naphthalate is formed In process face, the sheet adhesive of subsidiary isolation film is made.Then, by the opposite with isolation film of sheet adhesive obtained as above The face (adhesive face) of side fits in the acetylcellulose resin film face of the polarization plates made in above-mentioned (2) using laminating machine Afterwards, it is conserved 7 days under conditions of 23 DEG C of temperature, relative humidity 65%, obtains the polarization plates with adhesive phase.

(6) evaluation of the wet heat durability of polarization plates

The polarization plates of the subsidiary adhesive phase made in above-mentioned (5) are cut into the size of 30mm × 30mm, and remove every From film, by the adhesive phase face paste of exposing together in glass substrate.Glass substrate has used the alkali-free glass commodity of Corning Incorporated Name " Eagle XG ".For resulting optical laminate, using subsidiary integrating sphere spectrophotometer (Japan's light splitting corporation, Product name " V7100 "), the MD transmissivity and TD transmissivity in wavelength 380~780nm range are measured, the list under each wavelength is calculated Body transmissivity recycles the JIS Z 8701:1999 " representation method-XYZ color specification system and X of color₁₀Y₁₀Z₁₀2 degree of color specification system " The visual field (illuminant-C) carries out visibility correction, and the visibility before acquiring endurance test corrects monomer transmissivity (Ty).It is explained, Optical laminate is according to being set as detector side for the cyclic polyolefin resin film surface side of polarization plates and make light from glass substrate The mode that side enters is set to the spectrophotometer of subsidiary integrating sphere.

Monomer transmissivity formula (λ)=0.5 × (Tp (λ)+Tc (λ)) Lai Dingyi.Tp (λ) is with incident wavelength X (nm) transmissivity (%) for the optical laminate that the relationship of rectilinearly polarized light and parallel-nicol prism measures, Tc (λ) be with The transmissivity of the optical laminate of the relationship measurement of the rectilinearly polarized light and Nicol crossed of incident wavelength X (nm) (%).

Then, by the optical laminate 80 DEG C of temperature, relative humidity 90% hygrothermal environment under place 24 hours, then It is durable using being acquired with method same before endurance test after being placed 24 hours in the environment of 23 DEG C of temperature, relative humidity 60% Ty after test.The increment rate for being calculated Ty based on following formula by the Ty before and after endurance test, is carried out according to benchmark below Determine.The results are shown in Table 2.

The increment rate of Ty={ Ty before (Ty before Ty- endurance test after endurance test)/endurance test } × 100

4: the increment rate (Δ Ty) of monomer transmissivity is less than 6%.

3: the increment rate (Δ Ty) of monomer transmissivity is 6% or more and less than 10%.

2: the increment rate (Δ Ty) of monomer transmissivity is 10% or more and less than 80%.

1: the increment rate (Δ Ty) of monomer transmissivity is 80% or more.

[table 1]

[table 2]

As shown in table 2, compared with may validate that the polarization plates obtained in the comparative example 1, polarization plates obtained in embodiment Adaptation, appearance and wet heat durability are excellent.

Description of symbols

10 ... first protective films, 15 ... first bonding agents layers, 20 ... second protective films, 25 ... second bonding agents layers, 30 ... Polarizing film.

Claims

1. a kind of polarization plates are laminated it includes polarizing film and at least one face of the polarizing film via adhesive layer Protective film, the adhesive layer are the bonding agents comprising cationically polymerizable compound, the first acid agent and the second acid agent Solidfied material,

First acid agent is ionic compound of the solidification temperature less than 120 DEG C, and is to constitute the ionic chemical combination The counter anion of object is the ionic compound of anion shown in anion shown in following formula (1) or following formula (2),

In formula (1), R¹For optionally with the C of substituent group_6-14Aryl or the C optionally with substituent group_3-14Aromatic heterocycle, R²~ R⁴Independently of one another C_1-18Alkyl, the C optionally with substituent group_6-14Aryl or the C optionally with substituent group_3-14Aromatic series is miscellaneous Ring group, the substituent group are C_1-18Alkyl, halogenated C_1-8Alkyl, C_2-18Alkenyl, C_2-18Alkynyl, C_6-14Aryl, C_3-14Heteroaromatic Base, nitro, hydroxyl, cyano ,-OR⁵Shown in alkoxy or aryloxy group, R⁶Acyl group, R shown in CO-⁷Acyl-oxygen shown in COO- Base ,-SR⁸Shown in alkylthio group or arylthio ,-NR⁹R¹⁰Shown in amino or halogen atom, the R⁵~R⁸For C_1-8Alkyl, C_6-14Aryl or C_3-14Aromatic heterocycle, the R⁹And R¹⁰For hydrogen atom, C_1-8Alkyl, C_6-14Aryl or C_3-14Heteroaromatic Base,

[(Rf)_aPF_6-a]^- (2)

In formula (2), Rf indicate 80% or more of hydrogen be replaced by fluorine atoms after, identical or different alkyl, a be 1~5 it is whole Number,

Second acid agent is that solidification temperature is 120 DEG C or more and is generated the ionic chemical combination of acid using active energy beam Object.

2. polarization plates according to claim 1, wherein the adhesive layer is by irradiating active energy to the bonding agent It is heated and cured adhesive layer after amount ray.

3. polarization plates according to claim 1 or 2, wherein the first acid agent is ionic chemical combination shown in following formula (3) Object,

In formula (3), R¹¹And R¹²Alkyl, aralkyl, aryl or aromatic heterocycle, R are indicated independently of each other¹³Indicate optionally tool The phenyl of substituted base, X^-For anion shown in formula described in claim 1 (1) or formula (2).

4. polarization plates described in any one of claim 1 to 3, wherein the counter anion of the second acid agent is described Anion or PF shown in formula (1) or the formula (2)₆ ^-。

5. polarization plates according to any one of claims 1 to 4, wherein the counter cation of the second acid agent is sulfonium system Cation.

6. polarization plates according to any one of claims 1 to 5, wherein cationically polymerizable compound includes to be selected from ring At least one kind of compound in oxygen compound, oxetane compound and vinyl compound.

7. polarization plates described according to claim 1~any one of 6, wherein protective film include selected from cellulose-based resin, At least one kind of resin in (methyl) acrylic resin, polyolefin-based resins, polyester based resin and polycarbonate-based resin.

8. a kind of manufacturing method of polarization plates according to any one of claims 1 to 7 comprising:

(a) on polarizing film and/or protective film coating adhesive process；

(b) process that polarizing film and protective film are laminated；

(d) process of following heating layer stack.