CN106661386A - Laminate optical film production method - Google Patents

Abstract

The invention provides a laminate optical film production method. The laminate optical film production method wherein at least a first optical film and a second optical film are laminated via an adhesive layer that is formed by curing an active-energy-ray-curable adhesive composition, the production method using an active-energy-ray-curable adhesive composition that contains at least two different active-energy-ray-curable adhesive compositions, including a first active-energy-ray-curable adhesive composition and a second active-energy-ray-curable adhesive composition. The production method includes the execution of a coating step wherein a bonding surface of the first optical film is coated with the first active-energy-ray-curable adhesive composition and a bonding surface of the second optical film is coated with the second active-energy-ray-curable adhesive composition.

Description

The manufacture method of laminated optical film

Technical field

The present invention relates to press from both sides across gluing by be solidified to form active energy ray curable adhesive compound Oxidant layer is at least by the first blooming and the manufacture method of laminated optical film obtained by the stacking of the second blooming.The laminated optical film can To form the image display devices such as liquid crystal indicator (LCD), organic EL display, CRT, PDP.

Background technology

Liquid crystal indicator is broadcast in clock and watch, portable phone, PDA, notebook personal computer, PC monitor, DVD Put the market demand in device, TV etc. hastily to expand.Liquid crystal indicator is to make to be caused by the conversion (switching) of liquid crystal The visualization device of polarization state, according to its displaying principle, polarizer is used at present.Especially in the purposes such as TV, All the more high brightness, high-contrast, wide viewing angle are required, polarizing coating also begins to require high-transmission rate, high-polarization, high color weight all the more Existing property etc..

As polarizer, due to high-transmission rate, high-polarization, therefore what be typically the most to be widely used and for example make poly- second Enol (hereinafter also referred to as " PVA ") adsorbs the iodine system polarizer of iodine and structure obtained by stretching.Generally polarizing coating is used It is transparency protected in the two sides laminating of polarizer using so-called water system adhesive obtained by the material of polyethylene dissolving alcohol system in water The polarizing coating (following patent documents 1 and patent document 2) of film.As transparent protective film, using the high triacetyl of moisture permeability Cellulose etc..In the case where the water system adhesive has been used (so-called wet type lamination), make polarizer with it is transparency protected After film laminating, drying process is needed.

On the other hand, the water system adhesive is replaced, it is proposed that active energy ray curable adhesive.Using activity In the case of energy ray-curable adhesive manufacture polarizing coating, it is not necessary to drying process, therefore the life of polarizing coating can be improved Yield.For example, proposed using N substituted amide system monomer as curability composition, radical polymerization by the present inventor etc. The active energy ray curable adhesive (following patent documents 3 and patent document 4) of type.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2006-220732 publications

Patent document 2：Japanese Unexamined Patent Publication 2001-296427 publications

Patent document 3：Japanese Unexamined Patent Publication 2012-052000 publications

Patent document 4：Japanese Unexamined Patent Publication 2012-068593 publications

The content of the invention

Invent problem to be solved

The gluing oxidant layer that use active energy ray curable adhesive described in patent document 3 and 4 is formed can fill Divide the Water Resistance Test of the presence or absence of decolouring, peeling of the ground for example, by evaluating after impregnating 6 hours in 60 DEG C of warm water.But, closely Nian Lai, for laminated optical film adhesive, gradually requires the further raising of the resistance to water of following degree, i.e. can pass through For example evaluating is carrying out the harsher resistance to water examination of the presence or absence of peeling when end nail is peeled off after impregnating (saturation) in water Test.Thus, actual conditions are, including including the active energy ray curable adhesive described in patent document 3 and 4, for The laminated optical film adhesive reported so far, the leeway for having further improvement in terms of resistance to water.

But, in recent years for high-molecular organic material, also often require that the characteristic for contradicting (antinomy), actual feelings Condition is, if single high-molecular organic material is then difficult to meet this and requires characteristic.In order to meet it is conflicting require characteristic, Propose in many fields add in high-molecular organic material there is foreign material of different nature, by the skill of its Composite Art.In bonding technique, such as in the case where making different 2 kind adherend gluing, in order to improve the glue with each adherend Viscosity, it may be considered that gluing oxidant layer is made into 2 Rotating fields.But, in the case where gluing oxidant layer is made into 2 Rotating fields, stress Its interface can be concentrated on, the adhesive tension of gluing oxidant layer is likely to decrease.Especially for the stacking for being required to be thinned in recent years For blooming adhesive, it is difficult to the technology that gluing oxidant layer is set to 2 Rotating fields is established, it is only known with regard to the present inventor etc., do not have There is this kind of report example.

As described above, in the field of the laminated optical film adhesive of special requirement slimming, actual conditions are to make When 2 kinds of different bloomings are gluing, it is difficult to develop the technology that resistance to water is improved while adhesivity is improved.

The present invention is developed to solve the above problems, and be its object is to, there is provided a kind of layer for possessing gluing oxidant layer The manufacture method of folded blooming, the gluing oxidant layer shows high adhesive tension when different 2 kind blooming is laminated, and resistance to It is aqueous excellent.

For the method for solve problem

In the case where the blooming being laminated is different from each other, for example, also show that from from the viewpoint of hydrophily different Characteristic, therefore from improving from the viewpoint of the adhesive tension between blooming, by the gluing oxidant layer for being laminated these bloomings It is favourable to make 2 Rotating fields, but as previously mentioned, it is possible to because interface peel in gluing oxidant layer etc. on the contrary drops adhesive tension It is low.

On the other hand, the discovery such as the present inventor, according to following manufacture method, i.e. in folder across comprising the first active energy Amount ray curing adhesive compound and the second active energy ray curable adhesive compound and containing at least 2 kinds with The active energy ray curable adhesive compound of upper different active energy ray curable adhesive compound makes 2 light Learn film laminating after, irradiate active energy beam, make the first blooming and the second blooming gluing, though using two or more not In the case of same active energy ray curable adhesive compound, it is also difficult to cause the interface peel in gluing oxidant layer.This Invention is completed based on the discovery, possesses following compositions.

That is, the present invention relates to a kind of manufacture method of laminated optical film, it is characterised in that pressed from both sides across by making active energy The gluing oxidant layer that amount ray curing adhesive compound is solidified to form at least is laminated the first blooming and the second blooming Obtained by laminated optical film manufacture method, the active energy ray curable adhesive compound include the first active-energy Ray curing adhesive compound and the second active energy ray curable adhesive compound, and containing at least two or more Different active energy ray curable adhesive compounds, including：Painting process, applies in the binding face of first blooming First active energy ray curable adhesive compound described in cloth, then in the binding face coating described the of second blooming Two active energy ray curable adhesive compounds；Bonding process, makes first blooming and second blooming patch Close；With gluing operation, from the first blooming surface side or the second blooming surface side irradiation active energy beam, make described Active energy ray curable adhesive compound solidifies, and presss from both sides across the described gluing oxidant layer being consequently formed, and makes first light Learn film and second blooming is gluing.

According to the manufacture method of above-mentioned laminated optical film, the first active-energy for coating the binding face of the first blooming is penetrated Line curing type adhesive composition and coat the second blooming binding face the second active energy ray curable adhesive Composition is fitted in the state of with mobility.Even if as a result, the first active energy ray curable adhesive group Compound and the composition that the second active energy ray curable adhesive compound is different compositions, also can be carried out in this 2 interlayer A certain degree of compatibilized, therefore gluing oxidant layer is not to form 2 Rotating fields, but forming component incline structure.Accordingly, it is difficult to draw Rise between the first active energy ray curable adhesive compound and the second active energy ray curable adhesive compound Interface peel.Thus, it is gluing by the first active energy ray curable for properly selecting high with the first blooming compatibility Agent composition, and properly select the second active energy ray curable adhesive composition high with the second blooming compatibility Thing, it is possible to which manufacture has while the splitting in gluing oxidant layer is prevented, between the first blooming and the second blooming There is the laminated optical film of good adhesivity.

In addition, the manufacture method of the laminated optical film of the present invention is related to the manufacture method of following laminated optical film, it is special Levy and be, be to press from both sides at least will across the gluing oxidant layer by being solidified to form active energy ray curable adhesive compound The manufacture method of the first blooming and laminated optical film obtained by the stacking of the second blooming, the active energy ray curable glue Adhesive composition is gluing comprising the first active energy ray curable adhesive compound and the second active energy ray curable Agent composition, and containing at least two or more different active energy ray curable adhesive compound, including：Painting process, The first active energy ray curable adhesive compound is coated with the binding face of first blooming, in coating The coated face of the first active energy ray curable adhesive compound is stated, then carries out second active energy ray curable The face of adhesive compound applies coating；Bonding process, from the second active energy ray curable coated on the first blooming Coating surface side laminating second blooming of adhesive compound；With gluing operation, from the first blooming surface side or institute The second blooming surface side irradiation active energy beam is stated, solidifies the active energy ray curable adhesive compound, folder Across the described gluing oxidant layer being consequently formed, make first blooming and second blooming gluing.

According to the manufacture method of above-mentioned laminated optical film, in the first active-energy of the binding face for coating the first blooming On ray curing adhesive compound, the face for carrying out the second active energy ray curable adhesive compound applies coating.This Afterwards, coat the first active energy ray curable adhesive compound of the binding face of the first blooming and coat coating There is the second active energy ray curable adhesive group of the coated face of the first active energy ray curable adhesive compound Compound is contacted in the state of with mobility.Thus, even if the first active energy ray curable adhesive compound and Two active energy ray curable adhesive compounds are the compositions of different compositions, and at their interface certain journey can be also carried out The compatibilized of degree, forming component incline structure.Accordingly, it is difficult to cause the first active energy ray curable adhesive compound and Interface peel between the second active energy ray curable adhesive compound.Thus, by properly selecting and the first optics The first high active energy ray curable adhesive compound of film compatibility, and properly select affine with the second blooming Property high the second active energy ray curable adhesive compound, it is possible to manufacture is preventing the splitting in gluing oxidant layer While, the first blooming and the second blooming there is the laminated optical film of good adhesivity.

In the manufacture method of above-mentioned laminated optical film, the liquid of the first active energy ray curable adhesive compound Viscosity is preferably above the fluid viscosity of the second active energy ray curable adhesive compound.Coating the first blooming Binding face the first active energy ray curable adhesive compound on, carry out the second active energy ray curable gluing In the case of the coating of the face of agent composition, if the fluid viscosity of the first active energy ray curable adhesive compound is higher than The fluid viscosity of the second active energy ray curable adhesive compound, then can be gluing by the second active energy ray curable Agent composition is reliably coated on the first active energy ray curable adhesive compound.

In the manufacture method of above-mentioned laminated optical film, the active energy ray curable adhesive compound and described The contact angle of one blooming and second blooming is preferably 5～50 degree.According to this composition, due to active energy ray-curable Type adhesive compound is excellent for the wetability of the first blooming and the second blooming, therefore can fully guarantee final obtaining The interlayer adhesivity of the laminated optical film for arriving.

In the manufacture method of above-mentioned laminated optical film, first blooming and second blooming are preferably selected from gathering In ethenol system polarizer, acrylic resin film, cycloolefin resin film, polyester resin film and polyolefin resin film at least 1 Blooming is planted, first blooming and second blooming are preferably selected from the acrylic resin film, the cyclenes At least a kind blooming in hydrocarbon resin film, the polyester resin film and the polyolefin resin film.If the blooming being laminated It is the blooming above recorded, then can produces and possess the glue that high adhesive tension and excellent water resistance are shown in stacking The laminated optical film of adhesive layer.

In the manufacture method of above-mentioned laminated optical film, in the acrylic resin film, cycloolefin resin film, described The binding face of polyester resin film and the polyolefin resin film is formed with containing selected from acrylic resin, polyurethane resin, poly- Vinyl alcohol resin, melmac Ji in the case of the easy adhesive layer of at least a kind resin in the resin of Han oxazolinyls, layer The adhesivity of folded blooming is further improved, therefore preferably.

It is selected from described in first blooming and second blooming in the manufacture method of above-mentioned laminated optical film At least a kind light in acrylic resin film, the cycloolefin resin film, the polyester resin film and the polyolefin resin film In the case of learning film, and the SP values for containing 25～98 weight % in the active energy ray curable adhesive compound are 18～21 (MJ/m³)^1/2Free-radical polymerised compound in the case of, following effect can be played.Specifically, make In the case of with the specific blooming, and contain the aobvious of specified rate in active energy ray curable adhesive compound In the case that the free-radical polymerised compound of given SP values is shown, between gluing oxidant layer and blooming compatibility layer is formed. As a result, the adhesivity of laminated optical film is further improved, therefore preferably.

In the manufacture method of above-mentioned laminated optical film, a side of preferably first blooming and second blooming is The polyethenol series polarizer, coats the active energy ray-curable of the binding face of the polyethenol series polarizer Type adhesive compound contains the polymerizable compound of hydroxyl free radical.According to this composition, polyethenol series polarizer and glue The adhesive tension of adhesive layer is further improved, therefore preferably.

Description of the drawings

Fig. 1 is the schematic diagram of the evaluation method of the composition incline structure for representing the gluing oxidant layer that make use of TOF-SIMS.

Specific embodiment

The present invention laminated optical film be press from both sides across by make active energy ray curable adhesive compound solidify and , at least by the first blooming and laminated optical film obtained by the stacking of the second blooming, gluing oxidant layer is to work for the gluing oxidant layer for being formed Property solidified material layer obtained by energy ray-curable adhesive compound irradiation active energy beam formed.

Active energy ray curable adhesive compound can generally be divided into electronic beam solidified, ultraviolet curing Type, luminous ray curing type etc..Additionally, ultraviolet hardening, luminous ray curing type adhesive can be divided into radical polymerization Curing type adhesive and cationic polymerization type adhesive.In the present invention, by wave-length coverage 10nm～less than 380nm active-energy Ray is expressed as ultraviolet, and the active energy beam of wave-length coverage 380nm～800nm is expressed as into luminous ray.

As the compound for constituting radical polymerization curing type adhesive, free-radical polymerised compound can be enumerated.From Can be enumerated with the free-radical polymerised of the carbon-to-carbon double bonds such as (methyl) acryloyl group, vinyl by base polymerizable compound The compound of functional group.These curability compositions can be using more than monofunctional free radical's polymerizable compound or two senses more Sense free-radical polymerised compound it is any number of.In addition, these free-radical polymerised compounds can be used alone, or Person is applied in combination two or more.As these free-radical polymerised compounds, for example, it is suitably for the change with (methyl) acryloyl group Compound.Active energy ray curable adhesive compound used in the present invention is preferably comprised with (methyl) acryloyl group Compound as principal component, specifically, the total amount of active energy ray curable adhesive compound is being set to into 100 weights During amount %, preferably comprise the compounds with (methyl) acryloyl group more than 50 weight %, further preferably 80 weight % with On.And, in the present invention, so-called (methyl) acryloyl group refers to acryloyl group and/or methylacryloyl, and " (methyl) " exists The following is identical meaning.

＜ monofunctional free radical polymerizable compound ＞

As monofunctional free radical's polymerizable compound, for example, can enumerate (methyl) with (methyl) acrylamido Acrylamide derivative.(methyl) acrylamide derivative not only guarantees the adhesivity with polarizer or various transparent protective films, In addition, polymerization speed is fast, productivity ratio is excellent, from this starting point preferably.As the concrete example of (methyl) acrylamide derivative, N- methyl (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) can for example be enumerated Acrylamide, N- isopropyls (methyl) acrylamide, N- butyl (methyl) acrylamide, N- hexyls (methyl) acrylamide Deng (methyl) acrylamide derivative containing N- alkyl；N- methylols (methyl) acrylamide, N- ethoxys (methyl) third (methyl) acrylamide derivatives containing N- hydroxyalkyls such as acrylamide, N- methylol-N- propane (methyl) acrylamides； (methyl) acryloyl containing N- aminoalkyls such as amino methyl (methyl) acrylamide, amino-ethyl (methyl) acrylamide Amine derivative；(methyl) third containing N- alkoxyls such as N- methoxy acrylamides, N- ethoxymethyl acrylamides Alkenylamide derivative；Mercapto methyl (methyl) acrylamide, mercaptoethyl (methyl) acrylamide etc. are containing N- mercaptoalkyls (methyl) acrylamide derivative；Deng.In addition, as (methyl) acrylamido nitrogen-atoms formed heterocycle containing heterocycle (methyl) acrylamide derivative, for example, can enumerate N- acryloyl morpholines, N- acryloylpiperidines, N- metering systems Acylpiperidine, N- acryloyl group pyrrolidines etc..

In the middle of (methyl) acrylamide derivative, from the side with polarizer or the adhesivity of various transparent protective films Face is set out, and (methyl) acrylamide derivative of N- hydroxyalkyls is preferably comprised, in addition, as monofunctional free radical's polymerism Compound, for example, can enumerate various (methyl) acrylic acid derivatives with (methyl) acryloxy.Specifically, for example may be used To enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid isopropyl Ester, (methyl) acrylic acid 2- methyl -2- nitro propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (first Base) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) t-amyl, (first Base) acrylic acid 3- pentyl esters, (methyl) acrylic acid 2,2- dimethyl butyl esters, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid Cetyl ester, (methyl) n-octyl, (methyl) 2-EHA, (methyl) acrylic acid 4- methyl- (methyl) acrylic acid (carbon number 1-20) alkyl esters such as 2- propyl group pentyl esters, (methyl) acrylic acid n-octadecane base ester.

In addition, as (methyl) acrylic acid derivative, such as (methyl) cyclohexyl acrylate, (methyl) can be enumerated Acrylic acid ring pentyl ester etc. (methyl) acrylate base ester；(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester；(first Base) acrylic acid 2- isobornyl thiocyanoacetates, (methyl) acrylic acid 2- norborny methyl esters, (methyl) acrylic acid 5- ENB -2- Base-methyl esters, (methyl) acrylic acid 3- methyl -2- norborny methyl esters, (methyl) acrylic acid dicyclopentenyl ester, (methyl) third Polycycle (methyl) acrylate such as olefin(e) acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid bicyclopentane ester；(methyl) third Olefin(e) acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 2- methoxymethoxy ethyl esters, (methyl) acrylic acid 3- methoxybutyls, (methyl) acrylic acid ethyl carbitol ester, (methyl) acrylate, alkane (methyl) acrylate containing alkoxyl or phenoxy group such as phenoxyl polyethylene glycol (methyl) acrylate；Deng.

In addition, as (methyl) acrylic acid derivative, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) can be enumerated Acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 3- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxy butyl esters, (methyl) acrylic acid 4- hydroxyls Butyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 8- hydroxyl monooctyl esters, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems esters, (first Base) (methyl) acrylic acid hydroxy alkyl ester or acrylic acid [4- (hydroxymethyl) cyclohexyl] first such as acrylic acid 12- hydroxylauric esters The hydroxyls such as base ester, cyclohexanedimethanol list (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls (methyl) acrylate；(methyl) glycidyl acrylate, 4- hydroxyl butyl (methyl) acrylate glycidol ethers etc. contain There is (methyl) acrylate of epoxy radicals；(methyl) acrylic acid 2,2,2- trifluoro ethyl esters, (methyl) acrylic acid 2,2,2- trifluoros Diethyl acetamidomalonate, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester, (methyl) acrylic acid octafluoro pentyl ester, (first Base) (methyl) acrylate containing halogen such as the fluorine last of the ten Heavenly stems ester of acrylic acid 17, the chloro- 2- hydroxypropyl acrylates of (methyl) acrylic acid 3-； (methyl) acrylate etc. (methyl) acrylic acid alkylaminoalkyl ester；(methyl) acrylic acid 3- oxa- rings Butane group methyl esters, (methyl) acrylic acid 3- methy oxetane base methyl esters, (methyl) acrylic acid 3- Ethyloxetanes Base methyl esters, (methyl) acrylic acid 3- butyl oxetanyl methyl esters, (methyl) acrylic acid 3- hexyl oxetanyl first (methyl) acrylate containing oxetanyl such as ester；(methyl) tetrahydrofurfuryl acrylate, butyrolactone (methyl) acrylic acid (methyl) acrylate with heterocycle such as ester or 3-hydroxypivalic acid neopentyl glycol (methyl) acrylic acid adduct, to phenyl benzene Phenol (methyl) acrylate etc..

In addition, as monofunctional free radical's polymerizable compound, (methyl) acrylic acid, acrylic acid carboxyl second can be enumerated The monomers containing carboxyl such as ester, acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid, crotonic acid, iso-crotonic acid.

In addition, as monofunctional free radical's polymerizable compound, such as NVP, N- second can be enumerated The lactams system such as thiazolinyl-epsilon-caprolactams, methyl ethylene pyrrolidones vinyl monomer；Vinylpyridine, vinyl piperazine Pyridine ketone, vinyl pyrimidine, vinyl piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, Yi Xi Ji oxazoles, vinyl Vinyl monomer with nitrogenous heterocycle such as morpholine etc..

In addition, as monofunctional free radical's polymerizable compound, it is possible to use the radical polymerization of active methylene Property compound.The free-radical polymerised compound of active methylene is that have (methyl) acryloyl group in end or molecule The compound of isoreactivity double bond base and active methylene.As active methylene group, for example, can enumerate acetoacetyl Base, alkoxypropan diacyl or Cyanoacetyl etc..The active methylene group is preferably acetoacetyl.As active The concrete example of the free-radical polymerised compound of methylene, for example, can enumerate (methyl) acrylic acid 2- acetoacetoxy groups second Ester, (methyl) acrylic acid 2- acetoacetoxy groups propyl ester, (methyl) acrylic acid 2- acetoacetoxy groups -1- Methylethyls etc. (methyl) acrylic acid acetoacetoxy groups Arrcostab；The acyloxy ethyl ester of (methyl) acrylic acid 2- ethoxy-cs two, (methyl) propylene Sour 2- cyano-acetoxies ethyl ester, N- (2- cyano-acetoxy ethyls) acrylamide, N- (2- propiono acetoxyl groups Butyl) acrylamide, N- (4- acetoacetoxy groups methyl-benzyls) acrylamide, N- (2- acetoacetyl amino-ethyls) Acrylamide etc..The free-radical polymerised compound of active methylene is preferably (methyl) acrylic acid acetoacetoxy groups alkane Base ester.

The multifunctional free-radical polymerised compound ＞ of ＜

In addition, as multifunctional free-radical polymerised compounds more than two senses, such as tripropylene glycol two can be enumerated (methyl) acrylate, TEG two (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, 1,9- nonyls two Alcohol two (methyl) acrylate, 1,10- decanediol diacrylates, (methyl) propylene of 2- ethyl -2- butyl propane diols two Acid esters, bisphenol-A two (methyl) acrylate, bisphenol A epoxy ethane additive product two (methyl) acrylate, bisphenol A propylene oxide Addition product two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, neopentyl glycol two (methyl) propylene Acid esters, Tricyclodecane Dimethanol two (methyl) acrylate, cyclic trimethylolpropane dimethoxym ethane (methyl) acrylate, dioxy Azacyclohexane glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third Olefin(e) acid ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) The carboxylate of (methyl) acrylic acid such as modified two glycerine four (methyl) acrylate of acrylate, EO and polyalcohol, 9,9- are double [4- (2- (methyl) acryloyloxyethoxy) phenyl] fluorenes.As concrete example, Aronix M-220 (East Asia can be enumerated Synesis Company's system), LIGHT ACRYLATE 1,9ND-A (chemical company of common prosperity society system), LIGHT ACRYLATE DGE-4A (chemical company of common prosperity society system), LIGHT ACRYLATE DCP-A (chemical company of common prosperity society system), (Sartomer is public for SR-531 Department's system), CD-536 (Sartomer Company system) etc..According further to needs, can enumerate various epoxies (methyl) acrylate, Carbamate (methyl) acrylate, polyester (methyl) acrylate or various (methyl) acrylic ester monomers etc..

And, it is selected from acrylic resin film, cycloolefin resin film, polyester in gluing blooming in the present invention The blooming of at least a kind in resin film and polyolefin resin film, and by active energy ray curable adhesive compound Total amount when being set to 100 weight %, the SP values that active energy ray curable adhesive compound contains 25～98 weight % are 18～21 (MJ/m³)^1/2Free-radical polymerised compound, further preferably 30～90 weight %, further preferably 40～ 80 weight %, in this case, between gluing oxidant layer and blooming compatibility layer are formed.As a result, laminated optical film Adhesivity is further improved, therefore preferably.

Herein, the method that calculates of the SP values (solubility parameter) of the present invention is described as follows.

(the calculating method of solubility parameter (SP values))

In the present invention, the solubility parameter (SP of free-radical polymerised compound or polarizer, various transparent protective films etc. Value) can utilize FEDORS's to calculate method [reference《POLYMER ENG.&SCI.》, volume 14, No. second (1974), the 148th～ Page 154] calculate and obtain, i.e.

[number 1]

(wherein, Δ EI is evaporation energy when belonging to 25 DEG C of atom or group, molal volume when Δ VI is 25 DEG C).

Δ EI and Δ VI in above-mentioned mathematical expression represents what is contributed by the i-th atom and group in main molecule Certain numerical value.In addition, the typical example of the numerical value of the Δ E contributed for atom or group and Δ V is shown in table 1 below In.

[table 1]

【Table 1】

Atom or group	Δe(J/mol)	Δv(cm3/mol)
			CH3	4086	33.5
C	1465	-19.2
			Phenyl	31940	71.4
Phenylene	31940	52.4
			COOH	27628	28.5
CONH2	41861	17.5
			NH2	12558	19.2
- N=	11721	5.0
			CN	25535	24.0
NO2(aliphatic acid)	29302	24.0
			NO3(aromatic series)	15363	32.0
O	3349	3.8
			OH	29805	10.0
S	14149	12.0
			F	4186	18.0
Cl	11553	24.0
			Br	15488	30.0

It is 18～21 (MJ/m as SP values³)^1/2Free-radical polymerised compound concrete example, can for example enumerate three The propylene glycol diacrylate ((MJ/m of SP values 19.0³)^1/2), 1,9- nonanediol the diacrylates ((MJ/m of SP values 19.2³)^1/2), three Cyclodecane the Dimethanol Diacrylate ((MJ/m of SP values 20.3³)^1/2), cyclic trimethylolpropane dimethoxym ethane acrylate (SP values 19.1(MJ/m³)^1/2), dioxane glycol the diacrylate ((MJ/m of SP values 19.4³)^1/2), modified two glycerine 4 third of EO Olefin(e) acid the ester ((MJ/m of SP values 20.9³)^1/2) etc..And, it is 18～21 (MJ/m as SP values³)^1/2Free-radical polymerised chemical combination Thing, it is also possible to suitably using commercially available product, for example, can enumerate Aronix M-220 (East Asia Synesis Company system, SP values 19.0 (MJ/m³)^1/2), LIGHT ACRYLATE 1,9ND-A (chemical company of common prosperity society the system, (MJ/m of SP values 19.2³)^1/2)、LIGHT ACRYLATE DGE-4A (chemical company of common prosperity society the system, (MJ/m of SP values 20.9³)^1/2), LIGHT ACRYLATE DCP-A (altogether Rong She chemical companies the system, (MJ/m of SP values 20.3³)^1/2), SR-531 (SARTOMER the company systems, (MJ/m of SP values 19.1³)^1/2)、 CD-536 (SARTOMER the company systems, (MJ/m of SP values 19.4³)^1/2) etc..

In the manufacture method of the laminated optical film of the present invention, it is characterised in that the active energy ray curable for being used Adhesive compound includes the first active energy ray curable adhesive compound and the second active energy ray curable glue Adhesive composition and containing different activities energy ray-curable adhesive compound at least of more than two kinds.So-called " active energy Amount ray curing adhesive compound is different ", refer to that contained free-radical polymerised compound and ratio of components are different, thus For example from from the viewpoint of hydrophilic/hydrophobic so that active energy ray curable adhesive compound has different spies Property.The laminated optical film manufactured in the manufacture method of the present invention is for example, pressed from both sides across gluing oxidant layer at least one side of polarizer In the case of being laminated with the polarizing coating of transparent protective film, polarizer shows hydrophilic trend, and transparent protective film has aobvious Hydrophobic trend is shown.Thus, it is polarizer, the second blooming for transparent protective film in the first blooming in the present invention In the case of, in order to improve adhesivity, it is configured at the first active energy ray curable adhesive compound of the first blooming side Preferably hydrophily, the second active energy ray curable adhesive compound is preferably hydrophobicity.

In the present invention, as free-radical polymerisedization evaluated contained by active energy ray curable adhesive compound The hydrophily of compound and hydrophobic index, can enumerate logPow.Octanol/water Partition Coefficients (logPow) represent material Oil loving index, refers to the logarithm value of the Fen Pei Department numbers of octanol/water.LogPow height is intended to fall within lipophile, i.e. mean Water absorption rate is low.(the flask osmosis that JIS-Z-7260 is recorded) can be measured to logPow values, but can also be utilized It is calculated by.In this specification, using the logPow calculated using CambridgeSoft company system Chem Draw Ultra Value.

Particularly in the present invention, the first blooming be polarizer, the second blooming be transparent protective film in the case of, The the first active energy ray curable adhesive compound for being configured at the first blooming side preferably comprises logPow for -1～1 A compositions, the second active energy ray curable adhesive compound preferably comprises the B component that logPow is 2～7.This kind of structure Cheng Zhong, (i) the first blooming binding face be coated with the first active energy ray curable adhesive compound, again in the second light In the case of learning the binding face second active energy ray curable adhesive compound of coating of film, or (ii) is in the first optics The binding face of film is coated with the first active energy ray curable adhesive compound, is being coated with the first active energy ray-curable The coated face of type adhesive compound carries out again the feelings that the face of the second active energy ray curable adhesive compound applies coating Under condition, be located in gluing oxidant layer between polarizer and transparent protective film have polarizer side show the A of high-hydrophilic into The composition incline structure that the concentration divided is uprised.Therefore, it can to manufacture polarizer and transparent protective film show excellent adhesivity, And possess the polarizing coating of the gluing oxidant layer of excellent water resistance.

And, such as the composition that the concentration with A compositions in the gluing oxidant layer of polarizing coating changes in a thickness direction The confirmation method of incline structure, for example, can enumerate using time-of-flight type SIMS analysis method (Time of Flight Secondary Ion Mass Spectrometry：TOF-SIMS method).The principle of TOF-SIMS is to work as Primary ions beam (such as 1E12ions/cm is irradiated under ultrahigh vacuum to sample²When below), the outmost surface only from sample is (deep NumberLeft and right) secondary ion is released, by the way that secondary ion is imported into time-of-flight type (TOF types) mass spectrograph, it is possible to obtain matter Spectrum.Using the principle, can obtain being present in element composition, the information of the chemical constitution of compound of sample outmost surface.This It is outer in the present invention, in order to confirm the gluing oxidant layer being located between transparent protective film and polarizer in thickness direction on into Divide incline structure, it is possible to use cluster ions etching method.

Hereinafter, " cluster ions etching method " is illustrated.For example utilizing monatomic ion beam (Ar⁺、Cs⁺Deng) make The general etching method used for etch ion come in the case of the surface for etching gluing oxidant layer, the molecule knot of adhesive layer side Structure is destroyed, and is formed and is damaged layer.In this case, even if being intended to obtain the mass spectrum on the surface using TOF-SIMS, also can be because damaging Hinder the impact of layer, and the correct mass spectrum on the surface of gluing oxidant layer cannot be determined.On the other hand, using will " Ar air mass cluster from Son (Arn⁺) " in the case of " the cluster ions etching method " that use as etch ion, to etching after gluing oxidant layer surface The damage step-down of applying, will not form damage layer, therefore the surface of the gluing oxidant layer after etching maintains the surface before etching Molecular structure.Thus, by using TOF-SIMS, can correctly determine the mass spectrum on the surface of gluing oxidant layer.

Be given in Fig. 1 and represent commenting for the composition incline structure that make use of the thickness direction in the gluing oxidant layer of TOF-SIMS The schematic diagram of valency method.(I) of Fig. 1 provides of the polarizing coating as the laminated optical film that can be manufactured in the present invention, should In polarizing coating, transparent protective film 2 is laminated with across gluing oxidant layer 3 in the two sides folder of polarizer 1.First, ultramicrotome water is used The transparent protective film 2 (in (I) of Fig. 1 be upside transparent protective film 2) of the polarizing coating be given in (I) is cut in truncation, it is thinning with it is gluing The thickness ((II)) of the transparent protective film 2 of the contact of oxidant layer 3.Then, as shown in (III), using TOF-SIMS, measure is cut The mass spectrum on the surface of thin transparent protective film 2, thus analyzing the composition on the surface.Then, as shown in (IV), " group is utilized Cluster ion etching method ", after etching the surface of transparent protective film 2 for having been cut thin, using TOF-SIMS, analyzes the composition on the surface. In addition as shown in (V), utilize " cluster ions etching method ", thus etching transparent protective film 2 surface makes the transparent of gluing oxidant layer 3 The surface of the side of diaphragm 2 separates out, and using TOF-SIMS, analyzes the composition on the surface.Henceforth, it is repeated and make use of " group The analysis of the etch processes of cluster ion etching method " and the composition on the surface of gluing oxidant layer 3 using TOF-SIMS to separating out, The analysis processed with the composition on the surface of gluing oxidant layer 3 (entering but polarizer 1) is persistently etched, until eventually arriving at polarization Piece surface.Method using foregoing describing, can confirm that the glue being located in the present invention between transparent protective film and polarizer Composition incline structure on the thickness direction of adhesive layer.

As the A compositions that logPow is -1～1, can free-radical polymerised compound that arbitrarily use is above recorded Central logPow is -1～1 compound, specifically for example can enumerate hydroxyethyl acrylamide (trade name " HEAA ", Emerging people's company system, LogPow：- 0.56), N- vinyl formamides (trade name " Beamset 770 ", Huang Chuan chemical companies system, LogPow：- 0.25), acryloyl morpholine (trade name " ACMO ", emerging people's company system, LogPow：- 0.20), gamma-butyrolacton Acrylate (trade name " GBLA ", Osaka Organic Chemical Industry company system, LogPow：0.19), acrylic acid dimer (trade name " β-CEA ", Daicel company systems, LogPow：0.2), NVP (trade name " NVP ", Japanese catalyst company System, LogPow：0.24), acetoacetoxyethyl methacrylate (trade name " AAEM ", Japan's synthesis chemical company system, LogPow：0.27), acrylic acid 2- hydroxyl ethyl esters (trade name " HEA ", Osaka Organic Chemical Industry company system, LogPow：0.28)、 GMA (trade name " Light Ester G ", common prosperity society chemistry system, LogPow：0.57), dimethyl propylene Acrylamide (trade name " DMAA ", emerging people's company system, LogPow：0.58), acrylic acid tetrahydrofurfuryl alcohol polymer ester (trade name " Viscoat#150D ", Osaka Organic Chemical Industry company system, LogPow：0.60), acrylic acid 4- hydroxy butyl esters (trade name " 4- HBA ", Osaka Organic Chemical Industry company system, LogPow：0.68), acrylic acid (trade name " acrylic acid ", Mitsubishi Chemical Ind System, LogPow：0.69), (trade name " LIGHT ACRYLATE 3EG-A ", common prosperity society chemistry are public for triethylene glycol diacrylate Department's system, LogPow：0.72) etc..In the middle of them, as the A compositions that logPow in the present invention is -1～1, preferably use (methyl) Acrylamide derivative, more preferably using hydroxyethyl acrylamide, acryloyl morpholine or DMAA.In (first Base) beyond acrylamide derivative, preferably use acrylic acid 4- hydroxy butyl esters.

In the case where the first blooming is polarizer, the first active energy ray curable adhesive compound preferably contains There are the A compositions that logPow is -1～1.Additionally, the adhesive tension and resistance to water in order to improve gluing oxidant layer, by the first active energy When the total amount of amount ray curing adhesive compound is set to 100 weight %, logPow is that the content of -1～1 A compositions is preferred For 5～95 weight %, more preferably 30～80 weight %.

It is being that 2～7 when B component is divided into, the B component shows high hydrophobicity by logPow in the present invention.As LogPow is 2～7 B component, and logPow that can be in the middle of the free-radical polymerised compound that arbitrarily use is above recorded is 2 ～7 compound, specifically can for example enumerate acrylic acid dicyclopentenyl ester (trade name " FANCRYL FA-511AS ", day Vertical chemical conversion company system, LogPow：2.26), butyl acrylate (trade name " ACRYLIC ACID BUTYL ", Mitsubishi Chemical Ind System, LogPow：2.35), 1,6- hexanediyl esters (trade name " LIGHT ACRYLATE 1.6HX-A ", common prosperity society Chemical company's system, LogPow：2.43), the ring pentyl ester of acrylic acid two (trade name " FANCRYL FA-513AS ", chemical conversion company of Hitachi System, LogPow：2.58), dihydroxymethyl tristane diacrylate (trade name " LIGHT ACRYLATE DCP-A ", common prosperity Chemical company of society system, LogPow：3.05), isobornyl acrylate (trade name " LIGHT ACRYLATE IB-XA ", common prosperity society Chemical company's system, LogPow：3.27), 3-hydroxypivalic acid neopentyl glycol acrylic acid adduct (trade name " LIGHT ACRYLATE HPP-A ", chemical company of common prosperity society system, LogPow：3.35), 1,9- nonanediols diacrylate (trade name " LIGHT ACRYLATE 1,9ND-A ", chemical company of common prosperity society system, LogPow：3.68), o-phenyl phenol EO modification acrylates (business The name of an article " FANCRYL FA-301A ", Hitachi's chemical conversion company system, LogPow：3.98), 2- ethylhexyls oxetanes (commodity Name " Aron Oxetane OXT-212 ", East Asia Synesis Company system, LogPow：4.24), bisphenol A diglycidyl ether (commodity Name " JER828 ", Mitsubishi Chemical Ind's system, LogPow：4.76), bisphenol-A EO6 moles diacrylate (trade name " FA-326A ", Hitachi chemical conversion company system, LogPow：4.84), bisphenol-A EO4 moles diacrylate (trade name " FA-324A ", Hitachi chemical conversion company system, LogPow：5.15), bisphenol-A PO2 moles diacrylate (trade name " FA-P320A ", Hitachi chemical conversion company system, LogPow：6.10), bisphenol-A PO3 moles diacrylate (trade name " FA-P323A ", Hitachi chemical conversion company system, LogPow：6.26), bisphenol-A PO4 moles diacrylate (trade name " FA-P324A ", Hitachi chemical conversion company system, LogPow：6.43) etc..It is 2～7 as logPow in the present invention in the middle of them B component, preferably uses multifunctional (methyl) acrylate, more preferably using 1,6- hexanediyl esters), dihydroxymethyl Tristane diacrylate, 3-hydroxypivalic acid neopentyl glycol acrylic acid adduct, 1,9- nonanediol diacrylates, 2- second Base hexyl oxetanes, bisphenol A diglycidyl ether, bisphenol-A EO6 mole diacrylates, EO4 mole of bisphenol-A Modified diacrylate, bisphenol-A PO2 mole diacrylates, bisphenol-A PO3 moles diacrylate or bis-phenol A PO4 mole diacrylates.

In the case where the second blooming is transparent protective film, the second active energy ray curable adhesive compound is excellent Choosing is containing the B component that logPow is 2～7.Additionally, the adhesive tension and resistance to water in order to improve gluing oxidant layer, active by second When the total amount of energy ray-curable adhesive compound is set to 100 weight %, logPow is that the content of 2～7 B component is preferred For 30～95 weight %, more preferably 50～80 weight %.

For active energy ray curable adhesive compound, when active energy beam uses electron beam, The active energy ray curable adhesive compound need not contain Photoepolymerizationinitiater initiater, purple used in active energy beam In the case of outside line or luminous ray, Photoepolymerizationinitiater initiater is preferably comprised.

＜ Photoepolymerizationinitiater initiater ＞

Can be properly selected according to active energy beam using Photoepolymerizationinitiater initiater during free-radical polymerised compound. In the case where solidification is allowed to using ultraviolet or luminous ray, it is possible to use the photopolymerization of ultraviolet or luminous ray cracking is drawn Send out agent.The Photoepolymerizationinitiater initiater can be used alone, but in the case where various Photoepolymerizationinitiater initiaters are used in mixed way, can be with Adjustment curing rate, curability, therefore preferably.As the Photoepolymerizationinitiater initiater, for example, can enumerate benzil, hexichol first Ketone, benzoyl benzoic acid, 3, the benzophenone based compound such as 3 '-dimethyl -4- methoxy benzophenones；4- (2- hydroxyls Base oxethyl) phenyl (2- hydroxyl -2- propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2- methyl -2- hydroxyls Base propiophenone, 1- hydroxycyclohexyl phenyl ketones, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxyl -2- first Base -1- acetone, 2- hydroxyl -1- { 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl] phenyl } -2- first The aromatic ketone compounds such as base -1- acetone；Methoxyacetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- bis- The acetophenone systems such as acetophenone, 2- methyl isophthalic acids-[4- (methyl mercapto)-phenyl] -2- morpholinyl -1- acetone Compound；The benzoin ether such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin butyl ether, anisoin methyl ether system Compound；The aromatic series ketal based compound such as dibenzoyl dimethyl ketal；The aromatic sulfonyl based compound such as 2- naphthalene sulfonyl chlorides； The photolytic activity oxime compounds such as 1- phenyl-1,1-propanedione-2- (O- ethoxy carbonyls) oxime；Thioxanthones, 2- diuril tons Ketone, 2- methyl thioxanthones, 2,4- dimethyl thioxanthones, isopropyl thioxanthone, the clopenthixal ketones of 2,4- bis-, 2,4- diethyl thiophenes The thioxanthones based compounds such as ton ketone, 2,4- diisopropylthioxanthones, dodecyl thioxanthones；Camphorquinone；Halogenated ketone；Acyl group phosphorus Oxide；Acyl phosphate etc..

For the use level of the Photoepolymerizationinitiater initiater, by the total amount of active energy ray curable adhesive compound It is below 20 weight % when being set to 100 weight %.The use level of Photoepolymerizationinitiater initiater is preferably 0.01～20 weight %, more excellent Elect 0.05～10 weight %, more preferably 0.1～5 weight % as.

In addition, using this using the luminous ray curing type that contains free-radical polymerised compound as curability composition It is high sensitivity particularly preferably using the light for more than 380nm in the case of bright laminated optical film curing type adhesive Photoepolymerizationinitiater initiater.For the light to more than 380nm will be described later for highly sensitive Photoepolymerizationinitiater initiater.

As the Photoepolymerizationinitiater initiater, the compound represented with following formulas (1) is preferably used alone：

[changing 1]

(in formula, R¹And R²Represent-H ,-CH₂CH₃,-iPr or Cl, R¹And R²Can be with identical, it is also possible to different), or The compound represented with formula (1) is used in combination with the light to more than 380nm described later as highly sensitive Photoepolymerizationinitiater initiater. It is poly- for highly sensitive light with the light to more than 380nm is used alone in the case of having used the compound represented with formula (1) The situation for closing initiator is compared, and adhesivity is excellent.In the middle of the compound represented with formula (1), particularly preferred R¹And R²For- CH₂CH₃Diethyl thioxanthone.The composition ratio of the compound represented with formula (1) in for adhesive, by active energy When the total amount of amount ray curing adhesive compound is set to 100 weight %, preferably 0.1～5 weight %, more preferably 0.5 ～4 weight %, more preferably 0.9～3 weight %.

In addition, as needed preferred addition polymerization causes auxiliary agent.As polymerization cause auxiliary agent, can enumerate triethylamine, two Ethamine, N methyldiethanol amine, monoethanolamine, 4- dimethylaminobenzoic acids, 4- dimethylaminobenzoic acid methyl esters, 4- bis- Methylaminobenzoate ethyl ester, 4- dimethylaminobenzoic acid isopentyl ester etc., particularly preferred 4- dimethylaminobenzoic acids second Ester.In the case where auxiliary agent is caused using polymerization, its addition relative to curability composition the weight portion of total amount 100, usually 0 ～5 weight portions, preferably 0～4 weight portion, most preferably 0～3 weight portion.

In addition, known Photoepolymerizationinitiater initiater can be used together as needed.Transparent protective film with UV absorbabilities is not The light of below 380nm can be transmitted, therefore used as Photoepolymerizationinitiater initiater, it is highly sensitive to preferably use the light to more than 380nm Photoepolymerizationinitiater initiater.Specifically, 2- methyl isophthalic acids-(4- methyl mercapto phenyl) -2- morpholinyls -1- third can be enumerated Ketone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyls) -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone, 2,4,6- trimethylbenzoyls - Diphenyl phosphine oxide, double (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, double (η 5-2,4- cyclopentadiene -1- Base)-bis- (2,6- bis- fluoro- 3- (1H- pyrroles's -1- bases)-phenyl) titaniums etc..

Particularly, as Photoepolymerizationinitiater initiater, preferably in addition to the Photoepolymerizationinitiater initiater of formula (1), also using following State the compound of formula (2) expression：

[changing 2]

(in formula, R³、R⁴And R⁵Represent-H ,-CH₃,-CH₂CH₃,-iPr or Cl, R³、R⁴And R⁵Can be with identical, it is also possible to It is different).As the compound represented with formula (2), can suitably using the 2- methyl isophthalic acids-(4- for falling within commercially available product Methyl mercapto phenyl) -2- morpholinyl -1- acetone (trade names：IRGACURE907 manufacturers：BASF).In addition, 2- benzyls Base -2- dimethylamino -1- (4- morpholino phenyls) -1- butanone (trade names：IRGACURE369 manufacturers： BASF), 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- fourths Ketone (trade name：IRGACURE379 manufacturers：BASF) because sensitivity is high, therefore preferably.

In the present invention, in the middle of above-mentioned Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater of hydroxyl is preferably used.In active energy In the case that amount ray curing adhesive compound contains the Photoepolymerizationinitiater initiater of hydroxyl as polymerization initiator, to polarization Dissolubility in the high gluing oxidant layer of the concentration of the A compositions of piece side is improved, and the curability of gluing oxidant layer is improved.As with hydroxyl Photoepolymerizationinitiater initiater, (trade name " DAROCUR1173 ", BASF are public can for example to enumerate 2- methyl -2- hydroxypropiophenonepreparations Department system), 1- hydroxycyclohexyl phenyl ketones (trade name " IRGACURE184 ", BASF AG's system), 1- [4- (2- hydroxyl second Epoxide)-phenyl] -2- hydroxy-2-methyl -1-1- acetone (trade name " IRGACURE2959 ", BASF AG's system), 2- hydroxyl -1- { 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl] phenyl } -2- methyl isophthalic acids-acetone (trade name " IRGACURE127 ", BASF AG's system) etc..Particularly 1- hydroxycyclohexyl phenyl ketones are high to the concentration of A compositions Gluing oxidant layer in dissolubility it is especially excellent, therefore more preferably.

The free-radical polymerised compound and the radical polymerization initiator with dehydrogenation of the active methylene of ＜ ＞

In above-mentioned active energy ray curable adhesive compound, as free-radical polymerised compound tool is being used In the case of the free-radical polymerised compound of active methylene, preferably with the radical polymerization initiator with dehydrogenation It is applied in combination.According to this composition, even after just taking out from the environment or water of special high humility (non-dry state), partially The adhesivity of the gluing oxidant layer that vibrating diaphragm has also can be significantly improved.Although its reason is not clear, but can consider following The reason for.I.e., it is possible to speculate, the free-radical polymerised compound of active methylene with constitute gluing oxidant layer other from While polymerization together by base polymerizable compound, in the main chain and/or side chain of the base polymer being imported in gluing oxidant layer, Form gluing oxidant layer.In the polymerization process, if there is the radical polymerization initiator with dehydrogenation, will formed While constituting the base polymer of gluing oxidant layer, hydrogen is sloughed from the free-radical polymerised compound of active methylene, Free radical is produced in methylene.Hereafter, the hydroxyl for generating the polarizers such as the methylene of free radical and PVA reacts, in glue Covalent bond is formed between adhesive layer and polarizer.As a result, particularly under non-dry state, it is gluing that polarizing coating has The adhesivity of oxidant layer also can be significantly improved.

In the present invention, as the radical polymerization initiator with dehydrogenation, for example, thioxanthones system freedom can be enumerated Base polymerization initiator, benzophenone series radical polymerization initiator etc..The radical polymerization initiator is preferably thioxanthones system Radical polymerization initiator.As thioxanthones system radical polymerization initiator, for example, can enumerate what is represented with above-mentioned formula (1) Compound.As the concrete example of the compound represented with formula (1), for example, can enumerate thioxanthones, dimethyl thioxanthone, diethyl Base thioxanthones, isopropyl thioxanthone, clopenthixal ketone etc..In the middle of the compound represented with formula (1), particularly preferred R¹And R² For-CH₂CH₃Diethyl thioxanthone.

In above-mentioned active energy ray curable adhesive compound, in the radical polymerization containing active methylene In the case of conjunction property compound and the radical polymerization initiator with dehydrogenation, the total amount of curability composition is being set to During 100 weight %, the free-radical polymerised compound of the described active methylene of 1～50 weight % is preferably comprised, in addition Contain the radical polymerization initiator of 0.1～10 weight portion relative to the weight portion of total amount 100 of curability composition.

As described above, in the present invention, in the presence of the radical polymerization initiator with dehydrogenation, making active The methylene of the free-radical polymerised compound of methylene produces the hydroxyl of the polarizers such as free radical, the methylene and PVA to be occurred Reaction, forms covalent bond.Thus, in order that the methylene of the free-radical polymerised compound of active methylene is produced freely Base, is adequately formed the covalent bond, when the total amount of curability composition is set to into 100 weight %, preferably comprises 1～50 weight % Active methylene free-radical polymerised compound, further preferably 3～30 weight %.Resistance to water is set fully to carry It is high and improve the adhesivity under non-dry state, preferably the free-radical polymerised compound of active methylene is set to into 1 weight Amount more than %.On the other hand, if greater than 50 weight %, then the bad situation of the solidification of the gluing oxidant layer of generation is had.In addition, excellent Phase selection contains the radical polymerization with dehydrogenation of 0.1～10 weight portion for the weight portion of total amount 100 of curability composition Initiator, further preferably 0.3～9 weight portion.Dehydrogenation reaction is sufficiently carried out, is preferably used more than 0.1 weight portion Radical polymerization initiator.On the other hand, if greater than 10 weight portions, then the not exclusively situation of dissolving is had in the composition.

The cation polymerization curing type adhesive ＞ of ＜

As the curability composition of cation polymerization curing type adhesive, can enumerate with epoxy radicals or oxetanes The compound of base.As long as the compound with epoxy radicals has the compound of at least 2 epoxy radicals in intramolecular, just without spy Do not limit, it is possible to use commonly known various curability epoxides.As preferred epoxide, can be used as example Son enumerates the compound (fragrant family epoxide) for having at least 2 epoxy radicals and at least one aromatic rings in intramolecular； Intramolecular have at least 2 epoxy radicals and at least one therein be with constitute ester ring type ring 2 adjacent carbon atoms it Between the compound (cycloaliphatic epoxy) etc. that formed.But in gluing oxidant layer, realize that composition is inclined to be directed to A compositions Structure, even if in the situation using cation polymerization curing type adhesive, active energy ray curable adhesive compound Need the A compositions that the logPow containing expression Octanol/water Partition Coefficients is -1～1 and the B component that logPow is 2～7.

＜ light cationic polymerization initiators ＞

Cation polymerization curing type adhesive contains epoxide described above and oxa- ring as curability composition Butane compound, because they are the compound solidified by cationic polymerization, therefore causes with closing light cationic polymerization Agent.The light cationic polymerization initiator is produced because of luminous ray, ultraviolet, X-ray, the irradiation of electron beam isoreactivity energy-ray Raw cation kind or lewis acid, cause the polymerisation of epoxy radicals or oxetanyl.

＜ other compositions ＞

The active energy ray curable adhesive compound of the present invention can also contain following compositions.

＜ acrylic compounds oligomer ＞

Active energy ray curable adhesive compound used in the present invention can be except containing the free radical Beyond the curability composition of polymerizable compound or cation polymerization curing type adhesive, also containing making (methyl) acrylic compounds The acrylic compounds oligomer that monomer is polymerized.Containing in active energy ray curable adhesive compound makes non-polymerization In the case of the acrylic compounds oligomer that (methyl) acrylic monomer is polymerized, easily propulsion is located in polarizer and transparent The composition of the intermembranous adhesive compound of protection it is inclined, it is easier to obtain that the concentration of A compositions changes in a thickness direction into Divide incline structure.Thus, gluing oxidant layer is further improved with the adhesivity and resistance to water of polarizer and transparent protective film, therefore excellent Choosing.Additionally, by containing acrylic compounds oligomer composition in active energy ray curable adhesive compound, it is possible to reduce Said composition is irradiated and active energy beam and is allowed to cure shrinkage when solidifying, adhesive and polarizer and transparent can be reduced The interfacial stress of the adherends such as diaphragm.As a result, it is possible to suppress the reduction of gluing oxidant layer and the adhesivity of adherend.In order to The composition incline structure of solidified material layer (gluing oxidant layer) is more reliably obtained, in addition in order to be adequately suppressed cure shrinkage, When the total amount of active energy ray curable adhesive compound is set to into 100 weight %, preferably by acrylic compounds oligomer Content is set to 5～30 weight %, is more preferably set to 10～20 weight %.

In the case of operability and uniformity when in view of coating, active energy ray curable adhesive compound Preferably low viscosity, therefore it is low viscous to be preferably also the acrylic compounds oligomer (A) that (methyl) acrylic monomer is polymerized Degree.Used as low viscous acrylic compounds oligomer, preferable weight-average molecular weight (Mw) is less than 15000 oligomer, more preferably Less than 10000 oligomer, particularly preferred less than 5000 oligomer.On the other hand, in order to be pushed further into being located in polarization The composition of piece and transparency protected intermembranous adhesive compound it is inclined in the weight average molecular weight (Mw) of acrylic compounds oligomer (A) Preferably more than 500, more preferably more than 1000, particularly preferably more than 1500.As composition acrylic compounds oligomer (A) (methyl) acrylic monomer, specifically can for example enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2- methyl -2- nitro propyl ester, (methyl) third Olefin(e) acid N-butyl, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid n-pentyl ester, (methyl) t-amyl, (methyl) acrylic acid 3- pentyl esters, (methyl) acrylic acid 2,2- dimethyl butyrates Ester, (methyl) the just own ester of acrylic acid, (methyl) aliphatic acrylate, (methyl) n-octyl, (methyl) acrylic acid (methyl) such as 2- Octyl Nitrites, (methyl) acrylic acid 4- methyl-2-propyl pentyl esters, (methyl) acrylic acid n-octadecane base esters Acrylic acid (carbon number 1-20) alkyl esters and such as (methyl) acrylate base ester (such as (methyl) acrylic acid ring Own ester, (methyl) acrylic acid ring pentyl ester etc.), it is (methyl) acrylic acid aralkyl ester (such as (methyl) benzyl acrylate etc.), polycyclic Formula (methyl) acrylate (such as (methyl) acrylic acid 2- isobornyl thiocyanoacetates, (methyl) acrylic acid 2- norborny methyl esters, (first Base) acrylic acid 5- ENBs -2- bases-methyl esters, (methyl) acrylic acid 3- methyl -2- norborny methyl esters etc.), contain (methyl) esters of acrylic acid (such as (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 2- hydroxy propyl esters, (first of hydroxyl Base) acrylic acid 2,3- dihydroxypropyl methylbutyl butenoates etc.), (methyl) esters of acrylic acid ((methyl) containing alkoxyl or phenoxy group Acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 2- methoxymethoxy second Ester, (methyl) acrylic acid 3- methoxybutyls, ethyl carbitol (methyl) acrylate, (methyl) acrylate Deng), (methyl) esters of acrylic acid (such as (methyl) glycidyl acrylate etc.) containing epoxy radicals, halogen-containing (methyl) third Olefin(e) acid esters (such as (methyl) acrylic acid 2,2,2- trifluoro ethyl esters, (methyl) acrylic acid 2,2,2- trifluoroethyl ethyl esters, (first Base) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid 17 Fluorine last of the ten Heavenly stems ester etc.), (methyl) acrylic acid alkylaminoalkyl ester (such as (methyl) acrylate etc.) etc..These (methyl) acrylate may be used singly or in combination of two or more kinds.As the concrete example of acrylic compounds oligomer (A), Ke Yiju Go out East Asia Synesis Company system " ARUFON ", Soken Chemical Company system " ACT FLOW ", BASF JAPAN company systems " JONCRYL " Deng.

In the case where acrylic compounds oligomer (A) is liquid, it is not necessary to consider the dissolubility in adhesive compound, Therefore can suitably use.Acrylic compounds oligomer (A) is usual in the case where glass transition temperature (Tg) is less than 25 DEG C For liquid.In addition, inclined acrylic compounds are low with the composition in the compatibility of adhesive compound and gluing oxidant layer in order to take into account Polymers (A) preferably comprises polar functional group.Hydroxyl, epoxy radicals, carboxyl, alkoxy silicane can be enumerated as polar functional group Base etc..Specifically, for example can enumerate " ARUFON UH are serial ", " ARUFON UC are serial ", " ARUFON UF are serial ", " ARUFON UG are serial ", " ARUFON US are serial " (being East Asia Synesis Company system) etc..Wherein, due to it is also envisioned that by with The raising of the adhesivity that the interaction of polarizer is caused, therefore preferably comprise epoxy radicals.Specifically for example can enumerate " ARUFON UG-4000 ", " ARUFON UG-4010 " (are East Asia Synesis Company system).

＜ photoacid generator ＞

In above-mentioned active energy ray curable adhesive compound, photoacid generator can be contained.In above-mentioned active-energy Containing in the case of photoacid generator in ray curing resin composition, compared with the situation for not containing photoacid generator, Ke Yi great Amplitude improves the resistance to water and durability of gluing oxidant layer.Photoacid generator can be represented with following formulas (3).

Formula (3)

[changing 3]

L⁺X^-

(wherein, L⁺Represent arbitrary cation.In addition, X^-Represent and be selected from PF6₆ ^-、SbF₆ ^-、AsF₆ ^-、SbCl₆ ^-、 BiCl₅ ^-、SnCl₆ ^-、ClO₄ ^-, dithiocar-bamate anion, the counter anion in SCN-.)

As the cation L for being preferably used as composition formula (3)⁺Cation structure, can enumerate selected from following Cation in formula (4)～formula (12).

Formula (4)

[changing 4]

Formula (5)

[changing 5]

Formula (6)

[changing 6]

Formula (7)

[changing 7]

Formula (8)

[changing 8]

Formula (9)

[changing 9]

Formula (10)

[changing 10]

Formula (11)

[changing 11]

Formula (12)

[changing 12]

Ar⁴-I⁺-Ar⁵

(in above-mentioned formula (4)-(12), wherein, R¹、R²And R³Independently of one another represent selected from hydrogen atom, replace or not Substituted alkyl, substituted or unsubstituted thiazolinyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic radical, replacement or Unsubstituted alkoxyl, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyl Group in base, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted Epoxide carbonyl or halogen atom.R⁴Represent and R¹、 R²And R³Described in group identical group.R⁵Represent substituted or unsubstituted alkyl, substituted or unsubstituted alkylthio group.R⁶ And R⁷Substituted or unsubstituted alkyl, substituted or unsubstituted alkoxyl are represented independently of one another.R represent halogen atom, hydroxyl, Carboxyl, sulfydryl, cyano group, nitro, substituted or unsubstituted carbamoyl, substituted or unsubstituted alkyl, replacement or unsubstituted Thiazolinyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic radical, substituted or unsubstituted alkoxyl, replacement or not Substituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted fragrant sulphur Base, substituted or unsubstituted heterocyclethio, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, replacement do not take The Epoxide carbonyl in generation it is any number of.Ar⁴、Ar⁵Represent substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic radical it is any Kind.X represents oxygen or sulphur atom.I represents 0～5 integer.J represents 0～4 integer.K represents 0～3 integer.In addition, also may be used To be between adjacent R, Ar⁴With Ar⁵、R²With R³、R²With R⁴、R³With R⁴、R¹With R²、R¹With R³、R¹With R⁴、R¹With R or R¹With R⁵Phase Circulus obtained by being mutually bonded.)

Corresponding to the cation (sulfonium cation) of formula (4)：

3,5-dimethylphenyl sulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (chlorphenyl) sulfonium, dimethyl can be enumerated (right Bromophenyl) sulfonium, dimethyl (to cyano-phenyl) sulfonium, dimethyl (m-nitro base) sulfonium, dimethyl (2,4,6- tribromo phenyl) Sulfonium, dimethyl (pentafluorophenyl group) sulfonium, dimethyl (to (trifluoromethyl) phenyl) sulfonium, dimethyl (p-hydroxybenzene) sulfonium, dimethyl (to mercaptophenyl) sulfonium, dimethyl (to methylsulfinylphenyl) sulfonium, dimethyl (to methylsulfonyl phenyl) sulfonium, dimethyl (adjacent acetylphenyl) sulfonium, dimethyl (o-benzoyl base phenyl) sulfonium, dimethyl (p-methylphenyl) sulfonium, dimethyl are (to isopropyl Base phenyl) sulfonium, dimethyl (to octadecylphenyl) sulfonium, dimethyl (to cyclohexyl phenyl) sulfonium, dimethyl is (to methoxybenzene Base) sulfonium, dimethyl (O-methoxy carbonyl phenyl) sulfonium, dimethyl (to phenylsulfartyl phenyl) sulfonium, (7- methoxyl group -2- oxygen Generation -2H- BaPs are muttered -4- bases) dimethyl sulfonium, (4- methoxynaphthalene -1- bases) dimethyl sulfonium, dimethyl is (to isopropyl oxygen Base carbonyl phenyl) sulfonium, dimethyl (2- naphthyls) sulfonium, dimethyl (9- anthryls) sulfonium, diethyl phenyl sulfonium, Methylethyl phenyl Sulfonium, methyldiphenyl base sulfonium, triphenylsulfonium, diisopropyl phenyl sulfonium, diphenyl (4- phenylsulfartyls-phenyl)-sulfonium, 4,4 '- Double (diphenyl sulfonium) diphenylsulfides, 4,4 '-bis- [two [(4- (2- Hydroxy-ethoxies)-phenyl)] sulfoniums]] diphenyl sulphur Ether, 4,4 '-bis- (diphenyl sulfonium) biphenyls, diphenyl (o-fluorophenyl) sulfonium, diphenyl (chlorphenyl) sulfonium, diphenyl are (to bromine Phenyl) sulfonium, diphenyl (to cyano-phenyl) sulfonium, diphenyl (m-nitro base) sulfonium, diphenyl (2,4,6- tribromo phenyl) sulfonium, Diphenyl (pentafluorophenyl group) sulfonium, diphenyl (to (trifluoromethyl) phenyl) sulfonium, diphenyl (p-hydroxybenzene) sulfonium, diphenyl are (right Mercaptophenyl) sulfonium, diphenyl (to methylsulfinylphenyl) sulfonium, diphenyl (to methylsulfonyl phenyl) sulfonium, diphenyl be (adjacent Acetylphenyl) sulfonium, diphenyl (o-benzoyl base phenyl) sulfonium, diphenyl (p-methylphenyl) sulfonium, diphenyl (cumic aldehyde Base) sulfonium, diphenyl (to octadecylphenyl) sulfonium, diphenyl (to cyclohexyl phenyl) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, Diphenyl (O-methoxy carbonyl phenyl) sulfonium, diphenyl (to phenylsulfartyl phenyl) sulfonium, (7- methoxyl group -2- oxo -2H- BaP is muttered -4- bases) diphenyl sulfonium, (4- methoxynaphthalene -1- bases) diphenyl sulfonium, diphenyl is (to isopropoxy carbonyl benzene Base) sulfonium, diphenyl (2- naphthyls) sulfonium, diphenyl (9- anthryls) sulfonium, ethyl diphenyl sulfonium, Methylethyl (o-tolyl) sulfonium, Methyl two (p-methylphenyl) sulfonium, three (p-methylphenyl) sulfoniums, diisopropyl (4- phenylsulfartyl phenyl) sulfonium, diphenyl (2- thiophene Base) sulfonium, diphenyl (2- furyls) sulfonium, diphenyl (9- ethyl -9H- carbazole -3- bases) sulfonium etc., but be not limited to They.

Corresponding to the cation (oxidation sulfonium cation) of formula (5)：

3,5-dimethylphenyl sulfoxonium, dimethyl (o-fluorophenyl) sulfoxonium, dimethyl (chlorphenyl) oxidation can be enumerated Sulfonium, dimethyl (p-bromophenyl) sulfoxonium, dimethyl (to cyano-phenyl) sulfoxonium, dimethyl (m-nitro base) sulfoxonium, Dimethyl (2,4,6- tribromo phenyl) sulfoxonium, dimethyl (pentafluorophenyl group) sulfoxonium, dimethyl (to (trifluoromethyl) phenyl) Sulfoxonium, dimethyl (p-hydroxybenzene) sulfoxonium, dimethyl (to mercaptophenyl) sulfoxonium, dimethyl are (to methylsulfinyl Base phenyl) sulfoxonium, dimethyl (to methylsulfonyl phenyl) sulfoxonium, dimethyl (adjacent acetylphenyl) sulfoxonium, diformazan Base (o-benzoyl base phenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-isopropyl phenyl) sulfoxonium, Dimethyl (to octadecylphenyl) sulfoxonium, dimethyl (to cyclohexyl phenyl) sulfoxonium, dimethyl (p-methoxyphenyl) Sulfoxonium, dimethyl (O-methoxy carbonyl phenyl) sulfoxonium, dimethyl (to phenylsulfartyl phenyl) sulfoxonium, (7- methoxies Base -2- oxo -2H- chromene -4- bases) dimethyl sulfonium, (4- methoxynaphthalene -1- bases) dimethyl Sulfonium, dimethyl (to isopropoxy carbonyl phenyl) sulfoxonium, dimethyl (2- naphthyls) sulfoxonium, dimethyl (9- anthryls) oxidation Sulfonium, diethyl phenyl sulfoxonium, Methylethyl phenyl sulfoxonium, methyldiphenyl base sulfoxonium, triphenyl sulfoxonium, diisopropyl Phenyl sulfoxonium, diphenyl (4- phenylsulfartyls-phenyl)-sulfoxonium, 4,4 '-bis- (diphenyl sulfoxonium) diphenyl sulphur Ether, 4,4 '-bis- [two [(4- (2- Hydroxy-ethoxies)-phenyl)] sulfoxoniums] diphenylsulfides, 4,4 '-bis- (diphenyl Sulfoxonium) biphenyl, diphenyl (o-fluorophenyl) sulfoxonium, diphenyl (chlorphenyl) sulfoxonium, diphenyl (p-bromophenyl) Sulfoxonium, diphenyl (to cyano-phenyl) sulfoxonium, diphenyl (m-nitro base) sulfoxonium, diphenyl (2,4,6- tribromo-benzenes Base) sulfoxonium, diphenyl (pentafluorophenyl group) sulfoxonium, diphenyl (to (trifluoromethyl) phenyl) sulfoxonium, diphenyl is (to hydroxyl Phenyl) sulfoxonium, diphenyl (to mercaptophenyl) sulfoxonium, diphenyl (to methylsulfinylphenyl) sulfoxonium, diphenyl (to methylsulfonyl phenyl) sulfoxonium, diphenyl (adjacent acetylphenyl) sulfoxonium, diphenyl (o-benzoyl base phenyl) oxygen Change sulfonium, diphenyl (p-methylphenyl) sulfoxonium, diphenyl (p-isopropyl phenyl) sulfoxonium, diphenyl (to octadecyl benzene Base) sulfoxonium, diphenyl (to cyclohexyl phenyl) sulfoxonium, diphenyl (p-methoxyphenyl) sulfoxonium, diphenyl (adjacent methoxy Base carbonyl phenyl) sulfoxonium, diphenyl (to phenylsulfartyl phenyl) sulfoxonium, (7- methoxyl group -2- oxo -2H- benzos Pyrans -4- bases) diphenyl sulfoxonium, (4- methoxynaphthalene -1- bases) diphenyl sulfoxonium, diphenyl is (to isopropoxy carbonyl Base phenyl) sulfoxonium, diphenyl (2- naphthyls) sulfoxonium, diphenyl (9- anthryls) sulfoxonium, ethyl diphenyl sulfoxonium, first Base ethyl (o-tolyl) sulfoxonium, methyl two (p-methylphenyl) sulfoxonium, three (p-methylphenyl) sulfoxoniums, diisopropyl (4- Phenylsulfartyl phenyl) sulfoxonium, diphenyl (2- thienyls) sulfoxonium, diphenyl (2- furyls) sulfoxonium, diphenyl (9- ethyl -9H- carbazole -3- bases) sulfoxonium etc., but it is not limited to them.

Corresponding to the cation (phosphonium cations of formula (6))：

The example of phosphonium cation：

Trimethyl benzene base Phosphonium, triethyl group phenyl Phosphonium, tetraphenylphosphoniphenolate, triphenyl (p-fluorophenyl) Phosphonium, triphenyl can be enumerated (Chloro-O-Phenyl) Phosphonium, triphenyl (m-bromophenyl) Phosphonium, triphenyl (to cyano-phenyl) Phosphonium, triphenyl (m-nitro base) Phosphonium, three Phenyl is (to phenylsulfartyl phenyl) Phosphonium, (7- methoxyl group -2- oxo -2H- chromene -4- bases) triphenyl phosphonium, triphen Base (o-hydroxy-phenyl) Phosphonium, triphenyl (adjacent acetylphenyl) Phosphonium, triphenyl (benzoylphenyl) Phosphonium, triphenyl are (to first Base phenyl) Phosphonium, triphenyl are (to isopropyl phenyl) Phosphonium, triphenyl (O-methoxy carbonyl phenyl) Phosphonium, triphenyl (1- naphthyls) Phosphonium, triphenyl (9- anthryl) Phosphonium, triphenyl (2- thienyl) Phosphonium, triphenyl (2- furyl) Phosphonium, triphenyl (9- ethyls- 9H- carbazole -3- base) Phosphonium etc., but it is not limited to them.

Corresponding to the cation (pyridylium) of formula (7)：

The example of pyridylium：

N- phenylpyridines, N- (Chloro-O-Phenyl) pyridine, N- (chlorphenyl) pyridine, N- can be enumerated (right Cyano-phenyl) pyridine, N- (O-Nitrophenylfluorone) pyridine, N- (to acetylphenyl) pyridine, N- (cumic aldehydes Base) pyridine, N- (to octadecyloxyphenyl group) pyridine, N- (to methoxycarbonyl-phenyl) pyridine, N- (9- anthracenes Base) pyridine, 2- chloro-1-phenyl pyridines, 2- cyano group -1- phenylpyridines, 2- methyl isophthalic acids-phenylpyridine, 2- vinyl -1- phenylpyridines, 2- phenyl -1- phenylpyridines, 1,2- hexichol yl pyridines, 2- methoxyl groups - 1- phenylpyridines, 2- phenoxy group -1- phenylpyridines, 2- acetyl group -1- (p-methylphenyl) pyridines, 2- methoxies Base carbonyl -1- (p-methylphenyl) pyridine, the fluoro- 1- naphthlypyridines of 3-, 4- methyl isophthalic acids-(2- furyls) pyridine , N- picolines, N- ethylpyridines etc., but be not limited to them.

Corresponding to the cation (quinoline cation) of formula (8)：

The example of quinoline cation：

N- methylquinolines, N- ethyl quinoliniums, N- phenylchinolines, N- naphthyl quinoline, N- can be enumerated (Chloro-O-Phenyl) quinoline, N- (chlorphenyl) quinoline, N- (to cyano-phenyl) quinoline, N- (O-Nitrophenylfluorone) quinoline Quinoline, N- (to acetylphenyl) quinoline, N- (p-isopropyl phenyl) quinoline, N- (to octadecyloxyphenyl group) quinoline Quinoline, N- (to methoxycarbonyl-phenyl) quinoline, N- (9- anthryls) quinoline, 2- chloro-1-phenyl quinoline, 2- Cyano group -1- phenylchinolines, 2- methyl isophthalic acids-phenylchinoline, 2- vinyl -1- phenylchinolines, 2- phenyl - 1- phenylchinolines, 1,2- diphenylquinolines, 2- methoxyl group -1- phenylchinolines, 2- phenoxy group -1- phenyl quinazolines Quinoline, 2- acetyl group -1- phenylchinolines, 2- methoxycarbonyl -1- phenylchinolines, the fluoro- 1- phenylchinolines of 3- , 4- methyl isophthalic acids-phenylchinoline, 2- methoxyl group -1- (p-methylphenyl) quinoline, 2- phenoxy group -1- (2- furans Mutter base) quinoline, 2- acetyl group -1- (2- thienyls) quinoline, 2- methoxycarbonyl -1- methylquinolines, 3- Fluoro- 1- ethyl quinoliniums, 4- methyl isophthalic acids-isopropyl quinoline etc., but it is not limited to them.

Corresponding to the cation (isoquinoline cation moiety) of formula (9)：

The example of isoquinoline cation moiety：

N- phenyl isoquinolin quinolines, N- methylisoquinoliniums, N- ethyl isoquinolin, N- (Chloro-O-Phenyl) can be enumerated Isoquinolin, N- (chlorphenyl) isoquinolin, N- (to cyano-phenyl) isoquinolin, N- (O-Nitrophenylfluorone) isoquinolin , N- (to acetylphenyl) isoquinolin, N- (p-isopropyl phenyl) isoquinolin, N- (to octadecyloxyphenyl group) Isoquinolin, N- (to methoxycarbonyl-phenyl) isoquinolin, N- (9- anthryls) isoquinolin, 1,2- diphenyl isoquinolin , N- (2- furyls) isoquinolin, N- (2- thienyls) isoquinolin, N- naphthyl isoquinolin etc., but do not limit Due to them.

Corresponding to cation (benzoxazole cations, the benzothiazole cation of formula (10))：

The example of benzoxazole cation：

N- first base benzoxazoles, N- ethyl benzoxazoles, N- naphthyl benzoxazoles, N- phenyl can be enumerated Benzoxazole, N- (p-fluorophenyl) benzoxazole, N- (rubigan) benzoxazoles, N- (to cyano-phenyl) benzene Bing oxazoles, N- (O-methoxy carbonyl phenyl) benzoxazoles, N- (2- furyl) benzoxazoles, N- (adjacent fluorobenzene (to cyano-phenyl) benzoxazoles, N-, (m-nitro base) benzoxazoles, N- are (to isopropyl for base) benzoxazoles, N- Epoxide carbonyl phenyl) benzoxazoles, N- (2- thienyl) benzoxazoles, N- (a carboxyl phenyl) benzoxazole, 2- sulfydryl -3- Ben base benzoxazoles, 2- methyl -3- Ben base benzoxazoles, 2- methyl mercapto -3- (4- phenyl Sulfenyl phenyl) benzoxazoles, 6- hydroxyl -3- (p-methylphenyl) benzoxazoles, 7- sulfydryl -3- Ben base benzoxazoles , fluoro- 3- ethyls benzoxazoles of 4,5- bis- etc., but be not limited to them.

The example of benzothiazole cation：

N- methylbenzothiazoles, N- ethyl-benzothiazoles, N- phenylbenzothiazols, N- (1- can be enumerated Naphthyl) benzothiazole, N- (p-fluorophenyl) benzothiazole, N- (rubigan) benzothiazole, N- is (to cyano group benzene Base) benzothiazole, N- (O-methoxy carbonyl phenyl) benzothiazole, N- (p-methylphenyl) benzothiazole, N- be (adjacent Fluorophenyl) benzothiazole, N- (m-nitro base) benzothiazole, N- (to isopropoxy carbonyl phenyl) benzothiazole , N- (2- furyls) benzothiazole, N- (4- methyl mercapto phenyl) benzothiazole, N- (4- phenylsulfartyl phenyl) Benzothiazole, N- (2- naphthyls) benzothiazole, N- (carboxyl phenyl) benzothiazole, 2- sulfydryl -3- phenyl Benzothiazole, 2- methyl -3- phenylbenzothiazols, 2- methyl mercapto -3- phenylbenzothiazols, 6- hydroxyls - 3- phenylbenzothiazols, 7- sulfydryl -3- phenylbenzothiazols, the fluoro- 3- phenylbenzothiazols of 4,5- bis- etc., But it is not limited to them.

Corresponding to the cation (furyl or thienyl iodine cation) of formula (11)：

Difuryl iodine, dithienyl iodine, double (4,5- dimethyl -2- furyls) iodine, double can be enumerated (the chloro- 2- thienyls of 5-) iodine, double (5- cyano group -2- furyls) iodine, double (5- nitro -2- thienyls) iodine, Double (5- acetyl group -2- furyls) iodine, double (5- carboxyl -2- thienyls) iodine, double (5- methoxycarbonyl -2- Furyl) iodine, double (5- phenyl -2- furyls) iodine, double (5- (p-methoxyphenyl) -2- thienyls) iodine, Double (5- vinyl -2- furyls) iodine, double (5- acetenyl -2- thienyls) iodine, double (5- cyclohexyl -2- furans Mutter base) iodine, double (5- hydroxyl -2- thienyls) iodine, double (5- phenoxy group -2- furyls) iodine, double (5- mercaptos Base -2- thienyls) iodine, double (5- butylthio -2- thienyls) iodine, double (5- thiophenyl -2- thienyls) iodine Deng, but it is not limited to them.

Corresponding to the cation (diaryl iodonium cation) of formula (12)：

Diphenyl iodine, double (p-methylphenyl) iodine, double (to octyl phenyl) iodine, double (to octadecyl can be enumerated Phenyl) iodine, double (to octyloxyphenyl) iodine, double (to octadecyloxyphenyl group) iodine, phenyl is (to octadecane epoxide benzene Base) iodine, 4- isopropyl -4 '-methyldiphenyl base iodine, (4- isobutyl phenenyls)-p-methylphenyl iodine, double (1- naphthalenes Base) iodine, double (4- phenylsulfartyl phenyl) iodine, phenyl (6- benzoyl -9- ethyl -9H- carbazole -3- bases) iodine , (7- methoxyl group -2- oxo -2H- chromene -3- bases) -4 '-isopropyl phenyl iodine etc., but do not limit Due to them.

Below, counter anion X in mutual-through type (3)^-Illustrate.

Counter anion X in formula (3)^-It is not particularly limited in principle, preferred non-nucleophilic anion.Contending with Anion X^-In the case of for non-nucleophilic anion, it is difficult to cause the various materials of the cation that intramolecular coexists Necleophilic reaction, as a result, it is possible to when improving with the Jing of formula (2) photoacid generator for representing itself or the composition for having used it Stability.Non-nucleophilic anion described herein, refers to the anion for causing the ability of necleophilic reaction low.As it is this kind of it is cloudy from Son, can enumerate PF₆ ^-、SbF₆ ^-、AsF₆ ^-、SbCl₆ ^-、BiCl₅ ^-、SnCl₆ ^-、ClO₄ ^-, dithiocar-bamate anion, SCN^-Deng.

In the middle of above-mentioned Exemplary anions, as particularly preferably as counter anion X in formula (3)^-Anion, PF can be enumerated₆ ^-、SbF₆ ^-And AsF₆ ^-, particularly preferably enumerate PF₆ ^-、SbF₆ ^-。

Thus, it is by above-mentioned as the concrete example of the preferred salt of the composition photoacid generator that can be used in the present invention Illustrate the cation represented with formula (3)～formula (12) structure concrete example and selected from PF₆ ^-、SbF₆ ^-、AsF₆ ^-、 SbCl₆ ^-、BiCl₅ ^-、SnCl₆ ^-、ClO₄ ^-, dithiocar-bamate anion, SCN^-In anion constitute salt.

Specifically, " CYRACURE UVI- can be enumerated as the preferred concrete example of the photoacid generator of the present invention 6992 ", " CYRACURE UVI-6974 " (being above DOW CHEMICAL Amada Co., Ltd.s system), " Adeka Optomer SP150 ", " Adeka Optomer SP152 ", " Adeka Optomer SP170 ", " Adeka Optomer SP172 " (more than For Asahi Denka Co., Ltd.'s system), " IRGACURE250 " (Ciba Specialty Chemicals company systems), " CI-5102 ", " CI-2855 " (reaching company system for Japanese Cao above), " Sunaid SI-60L ", " Sunaid SI-80L ", " Sunaid SI-100L ", " Sunaid SI-110L ", " Sunaid SI-180L " (being above three new chemical company's systems), " CPI- 100P ", " CPI-100A " (being above Sun-Apro Co. Ltd. systems), " WPI-069 ", " WPI-113 ", " WPI- 116 ", " WPI-041 ", " WPI-044 ", " WPI-054 ", " WPI-055 ", " WPAG-281 ", " WPAG-567 ", " WPAG-596 " (is above and the pure medicine company system of light).

The content of photoacid generator is below 10 weight portions, preferably relative to the weight portion of total amount 100 of curability composition 0.01～10 weight portion, more preferably 0.05～5 weight portion, particularly preferably 0.1～3 weight portion.

＜ includes alkoxyl, any number of compound ＞ of epoxy radicals

In above-mentioned active energy ray curable adhesive compound, can be by photoacid generator and comprising alkoxyl, epoxy Any number of compound of base is used in combination.

(there is the compound and macromolecule of epoxy radicals)

There is the epoxy of more than 2 in the compound using the epoxy radicals in intramolecular with more than 1 or in intramolecular In the case of the macromolecule (epoxy resin) of base, it is also possible to and used in intramolecular there is two or more to have the reaction with epoxy radicals The compound of the functional group of property.Herein the so-called reactive functional group with epoxy radicals, for example, can enumerate carboxyl, phenol Hydroxyl, sulfydryl, aromatic series amino of 1 grade or 2 grades etc..In view of three-dimensional curability, there are 2 particularly preferably in a molecule The above functional group.

As the macromolecule of the epoxy radicals in intramolecular with more than 1, for example, epoxy resin can be enumerated, be had by bis-phenol The bisphenol A type epoxy resin of A and epichlorohydrin derived, the bisphenol f type epoxy resin by Bisphenol F and epichlorohydrin derived, bisphenol S type ring Oxygen tree fat, phenol novolac type epoxy resin, cresol novalac type epoxy resin, bisphenol A novolak type epoxy resin, Bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy, hydroquinones type epoxy resin, Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorenes type epoxy resin, 3 functional-type epoxy resin or 4 functional-type epoxy resin etc. are more Functional-type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, Isocyanurate type epoxy resin, aliphatic chain epoxy resin etc., these epoxy resin can be by halogenation, it is also possible to added Hydrogen.As commercially available epoxy resin product, for example, can enumerate the JER Epicoat of Japanese epoxy resin Co. Ltd. system , 828th, 1001 801N, 806,807,152,604,630,871, YX8000, YX8034, YX4000, Dainippon Ink Chemicals Epiclon 830, EXA835LV, HP4032D, HP820, the EP4100 series of Asahi Denka Co., Ltd., EP4000 series, EPU Series, Ceroxide series (2021,2021P, 2083,2085,3000 etc.) of Daicel KCCs, EPOLEAD Series, EHPE series, chemical company of Nippon Steel YD series, YDF series, YDCN series, YDB series, phenoxy resin (by Bisphenols and epichlorohydrin synthesis multi-hydroxy polyether and there is epoxy radicals two ends；YP series etc.), Nagase ChemteX Denacol series, Epolite series of chemical company of common prosperity society of company system etc., but it is not limited to them.These rings Oxygen tree fat and can also use two or more.And, when the glass transition temperature Tg of gluing oxidant layer is calculated, will not be with epoxy The compound and macromolecule of base is counted.

(there is the compound and macromolecule of alkoxyl)

As the compound in intramolecular with alkoxyl, as long as there is the change of the alkoxyl of more than 1 in intramolecular Compound, is just not particularly limited, it is possible to use known compound.As the representative of this kind of compound, melamine can be enumerated Amines, amino resins, silane coupler etc..And, when the glass transition temperature Tg of gluing oxidant layer is calculated, will not tool The compound and macromolecule for having alkoxyl is counted.

Comprising alkoxyl, any number of compound of epoxy radicals use level relative to curability composition the weight of total amount 100 Amount part, usually below 30 weight portions, if the content of the compound in composition is excessive, adhesivity is reduced, have for The situation that the resistance to impact of shatter test deteriorates.The content of the compound in composition is more preferably below 20 weight portions.It is another Aspect, from resistance to water aspect, preferably comprises compounds more than 2 weight portions, further preferably 5 weight portions in composition More than.

＜ silane coupler ＞

In the case where the polarizing coating curing type adhesive of the present invention is active energy ray-curable curing type, silane Coupling agent preferably uses the compound of active energy ray-curable, even if but be not active energy ray-curable, also may be used To give identical resistance to water.

As the concrete example of silane coupler, the vinyl of the compound as active energy ray-curable can be enumerated Trichlorosilane, vinyltrimethoxy silane, VTES, 2- (3,4- expoxycyclohexyl) ethyl front three TMOS, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl diethoxy silanes, 3- Glycidoxypropyl group triethoxysilane, to styryl trimethoxy silane, 3- methacryloyloxypropyl methyls two Methoxy silane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloyloxypropyl methyl diethoxies Base silane, 3- methacryloxypropyls, 3- acryloxypropyl trimethoxy silanes etc..

Preferably 3- methacryloxypropyl trimethoxy silanes, 3- acryloxypropyl trimethoxy silicon Alkane.

As the concrete example of the silane coupler of not active energy ray-curable, preferably with the silane coupled of amino Agent (D1).As the concrete example of the silane coupler (D1) with amino, can enumerate gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, the isopropoxy silane of gamma-amino propyl group three, gamma-amino hydroxypropyl methyl dimethoxy Silane, gamma-amino hydroxypropyl methyl diethoxy silane, γ-(2- amino-ethyls) TSL 8330, γ- (2- amino-ethyls) amino propyl methyl dimethoxysilane, γ-(2- amino-ethyls) aminopropyltriethoxywerene werene, γ-(2- amino-ethyls) amino propyl methyl diethoxy silane, γ-(2- amino-ethyls) isopropoxy of aminopropyl three Silane, γ-(2- (2- amino-ethyls) amino-ethyl) TSL 8330, γ-(6- Aminohexyls) amino Propyl trimethoxy silicane, 3- (N- ethylaminos) -2- trimethoxysilyl propyl methacrylate TMOSs, γ-ureido-propyl trimethoxy Base silane, γ-ureidopropyltriethoxysilane, N- phenyl-gamma-amino propyl trimethoxy silicane, N- benzyls- Gamma-amino propyl trimethoxy silicane, N- vinyl benzyls-γ aminopropyltriethoxy silane, N- cyclohexyl ammonia Ylmethyl triethoxysilane, N- Cyclohexylaminomethyl diethoxymethylsilanes, N- phenvlaminomethvl trimethoxies Silane, (2- amino-ethyls) amino methyl trimethoxy silane, N, N '-bis- [3- (trimethoxysilyl) propyl group] second The silanes containing amino such as diamines；N- (1,3- dimethylbutylene) -3- (triethoxysilyl) -1- propylamine etc. Ketimide type silanes.

Silane coupler (D1) with amino can only use a kind, it is also possible to be applied in combination various.In the middle of them, it is Guarantee good adhesivity, preferred gamma-amino propyl trimethoxy silicane, γ-(2- amino-ethyls) aminopropyl front three TMOS, γ-(2- amino-ethyls) amino propyl methyl dimethoxysilane, γ-(2- amino-ethyls) aminopropyl Triethoxysilane, γ-(2- amino-ethyls) amino propyl methyl diethoxy silane, N- (1,3- dimethyl Aden Base) -3- (triethoxysilyl) -1- propylamine.

The use level of silane coupler relative to curability composition the weight portion of total amount 100, preferably 0.01～20 weight The scope of part, more preferably more preferably 0.05～15 weight portion, 0.1～10 weight portion.This is because, more than 20 weights In the case of the use level of amount part, the storage stability of adhesive deteriorates, in addition in the case of less than 0.1 weight portion, it is impossible to Fully play the effect of water-fast adhesivity.And, when the glass transition temperature Tg of gluing oxidant layer is calculated, not by silane idol Connection agent is counted.

As the concrete example of the silane coupler of not active energy ray-curable other than the above, 3- can be enumerated Ureidopropyltriethoxysilane, 3- r-chloropropyl trimethoxyl silanes, 3- mercaptopropyi methyl dimethoxysilanes, 3- mercaptos Base propyl trimethoxy silicane, double (triethoxysilylpropyltetrasulfide) tetrasulfides, 3- NCO propyl triethoxies Silane, imidizole silane etc..

＜ additive ＞ other than the above

In addition, in the active energy ray curable adhesive compound for being used in the present invention, not damaging this In bright purpose, the scope of effect, various additives can be coordinated as other any conditions.As the additive, Ke Yiju Go out epoxy resin, polyamide, polyamidoimide, polyurethane, polybutadiene, polychlorobutadiene, polyethers, polyester, styrene- Butadiene block copolymer, Petropols, xylene resin, ketone resin, celluosic resin, fluorine system oligomer, silicon-type are low Polymer or the oligomer such as polymers, polythiaether system oligomer；Phenthazine, 2,6- di-tert-butyl-4-methy phenols etc. are inhibited Agent；Polymerization causes auxiliary agent；Levelling agent；Wetability modifying agent；Surfactant；Plasticizer；Ultra-violet absorber；Inorganic fill Agent；Pigment；Dyestuff etc..

Above-mentioned additive relative to curability composition the weight portion of total amount 100, usually 0～10 weight portion, preferably 0 ～5 weight portions, most preferably 0～3 weight portion.

Viscosity ＞ of ＜ adhesive

Active energy ray curable adhesive compound used in the present invention contains the curability composition, from painting From the viewpoint of cloth, the viscosity of the adhesive compound is preferably below 100cp at 25 DEG C.On the other hand, the present invention's In the case that polarizing coating curing type adhesive is more than 100cp at 25 DEG C, it is also possible in the temperature of coating time control preparing adhesive, adjust It is whole to use after below 100cp.The preferred scope of viscosity is 1～80cp, most preferably 10～50cp.Viscosity can be used The E type viscosimeters TVE22LT of Dong Ji industry companies is determined.

In addition, set out from a security point, the active energy ray curable adhesive composition used in the present invention Thing uses the low material of skin irritatin preferably as the curability composition.Skin irritation can refer to using P.I.I is such Mark to judge.P.I.I is widely used by the index as the degree for representing skin barrier, is determined using Draize methods.Measured value With 0～8 Range Representation, value is more little then to judge that excitant is lower, big yet with the error of measured value, therefore preferably as ginseng Examine value to understand.P.I.I is preferably less than 4, more preferably less than 3, most preferably less than 2.

Using the laminated optical film of the manufacture method manufacture of the present invention pressed from both sides across by making active energy ray curable Gluing oxidant layer that adhesive compound is solidified to form, at least by the first blooming and optics obtained by the stacking of the second blooming Film.

Gluing oxidant layer ＞ of ＜

It is preferred that being 0.1 by the THICKNESS CONTROL of the gluing oxidant layer formed using active energy ray curable adhesive compound ～3 μm.The thickness of gluing oxidant layer is more preferably 0.3～2 μm, more preferably 0.5～1.5 μm.From suppression by gluing oxidant layer Cohesiveness cause gluing bad generation, suppress to be set out in terms of producing bad order (bubble) in lamination, preferably will The thickness of gluing oxidant layer is set to more than 0.1 μm.On the other hand, if the thickness of gluing oxidant layer is more than 3 μm, polarizing coating is possible to Durability cannot be met.

In addition, active energy ray curable adhesive compound is preferably so that the gluing oxidant layer formed by said composition Tg is that more than 60 DEG C of mode is selected, more preferably more than 70 DEG C, more preferably more than 75 DEG C, still more preferably for More than 100 DEG C, then be still more preferably more than 120 DEG C.On the other hand, if the Tg of gluing oxidant layer is too high, polarizing coating Bendability reduce, therefore preferably make gluing oxidant layer Tg be less than 300 DEG C, more preferably less than 240 DEG C, more preferably Less than 180 DEG C.Tg (glass transition temperature) is existed using TA Instruments dynamic determination of viscoelasticity device RSAIII Determine under following condition determination.

Sample size：Wide 10mm, long 30mm,

Clamp distance 20mm,

Mode determination：Stretching, frequency：1Hz, programming rate：5 DEG C/min

The measure of dynamic viscoelastic is carried out, temperature Tg of the summit of tan δ is employed.

Additionally, it is preferred that active energy ray curable adhesive compound is designed as, by said composition formed it is gluing The storage modulus of oxidant layer is 1.0 × 10 in 70 DEG C of area below⁶More than Pa.More preferably 1.0 × 10⁷More than Pa.Adhesive The storage modulus of layer produces impact when thermal cycle (- 40 DEG C to 80 DEG C etc.) are applied on polarizing coating on polarizer crackle, in energy storage In the case that modulus is low, the not good situation of polarizer crackle is easily produced.Temperature province with high storage modulus is more preferably Less than 80 DEG C, most preferably less than 90 DEG C.It is simultaneously viscous using TAInstruments dynamics with Tg (glass transition temperature) Elasticity measurement device RSAIII determines storage modulus under identical condition determination.The measure of dynamic viscoelastic is carried out, is employed The value of storage modulus (E ').

The manufacture method of the laminated optical film of the present invention is characterised by, is pressed from both sides across by making active energy ray-curable The gluing oxidant layer that type adhesive compound is solidified to form at least will be laminated obtained by the first blooming and the stacking of the second blooming The manufacture method of blooming, the active energy ray curable adhesive compound includes the first active energy ray curable Adhesive compound and the second active energy ray curable adhesive compound, and containing at least two or more different activity Energy ray-curable adhesive compound, including：Painting process, in the binding face of first blooming described first is coated with Active energy ray curable adhesive compound, then in binding face coating second active-energy of second blooming Ray curing adhesive compound；Bonding process, makes first blooming and second blooming laminating；With gluing work Sequence, from the first blooming surface side or the second blooming surface side irradiation active energy beam, penetrates the active-energy Line curing type adhesive composition solidifies, and presss from both sides across the described gluing oxidant layer being consequently formed, and makes first blooming and described Second blooming is gluing.

The manufacture method of other laminated optical film of the invention is characterised by, is to press from both sides across being penetrated by making active-energy First blooming and the second blooming are at least laminated and are obtained by the gluing oxidant layer that line curing type adhesive composition is solidified to form Laminated optical film manufacture method, the active energy ray curable adhesive compound include the first active energy beam Curing type adhesive composition and the second active energy ray curable adhesive compound, and containing at least two or more difference Active energy ray curable adhesive compound, including：Painting process, in the binding face of first blooming institute is coated with The first active energy ray curable adhesive compound is stated, the first active energy ray curable adhesive is being coated with The coated face of composition, then carry out the face painting coating of the second active energy ray curable adhesive compound；Laminating work Sequence, the coating surface side laminating from the second active energy ray curable adhesive compound coated on the first blooming is described Second blooming；Bonding process, makes first blooming and second blooming laminating；Gluing operation, from described first Blooming surface side or the second blooming surface side irradiation active energy beam, make the active energy ray curable adhesive Composition solidifies, and presss from both sides across the described gluing oxidant layer being consequently formed, and makes first blooming and second blooming gluing.

In the manufacture method of the laminated optical film of the present invention, in the case where the laminated optical film is polarizing coating, it is also possible to Before above-mentioned active energy ray curable adhesive compound is coated with, surface is carried out to polarizer, transparent protective film and is modified Process.As specific process, can enumerate by sided corona treatment, corona treatment, process of saponification process etc..

The coating method of active energy ray curable adhesive compound can be according to the viscosity of composition, required thickness Spend and properly select.As the example of coating method, for example, can enumerate reverse coating machine, gravure coater (directly, reversely Or hectograph), reverse bar coater, roll coater, die coating machine, bar coater, rod coater etc..In addition, in coating The modes such as impregnation method can be suitably used.

Folder makes 2 kinds of different optics across the active energy ray curable adhesive compound being coated with as described above Film, such as polarizer are fitted with transparent protective film.Polarizer can be entered with fitting for transparent protective film using layer of rolls press etc. OK.

The solidification ＞ of ＜ adhesive

Active energy ray curable adhesive compound used in the present invention can be with electronic beam solidified, ultraviolet Line curing type, the form of luminous ray curing type are used.As active energy ray curable adhesive compound, from productivity ratio From the viewpoint of, preferred luminous ray curing type adhesive composition.

For active energy ray curable adhesive compound, such as after making polarizer fit with transparent protective film, Irradiation active energy beam (electron beam, ultraviolet, luminous ray etc.), consolidates active energy ray curable adhesive compound Change and form gluing oxidant layer.The direction of illumination of active energy beam (electron beam, ultraviolet, luminous ray etc.) can be from any Proper orientation irradiation.It is preferred that from the irradiation of transparent protective film side.If from the irradiation of polarizer side, polarizer is possible to because of activity Energy-ray (electron beam, ultraviolet, luminous ray etc.) and deteriorate.

In electronic beam solidified, as long as the irradiation condition of electron beam can make above-mentioned active energy ray curable gluing The condition of agent composition solidification, then can adopt arbitrary appropraite condition.For example, the accelerating potential of electron beam irradiation is preferably 5kV～300kV, more preferably 10kV～250kV.In the case where accelerating potential is less than 5kV, electron beam is possible to reach Adhesive and cause solidification not enough, if accelerating potential is higher than 300kV, the penetration through sample is too strong, it is possible to saturating Bright diaphragm, polarizer cause to damage.As exposure dose, more preferably preferably 5～100kGy, 10～75kGy.In irradiation Less than in the case of 5kGy, adhesive can solidify deficiency to dosage, if above 100kGy, then can be to transparent protective film, polarizer Cause to damage, produce reduction, the xanthochromia of mechanical strength, it is impossible to obtain given optical characteristics.

Electron beam irradiation is typically irradiated in non-active gas, if required, it is also possible in an atmosphere or import Carry out under conditions of a small amount of oxygen.Although depending on will be according to the material of transparent protective film, but by being properly directed into oxygen, intentionally Make the transparency protected face that electron beam is got at first produce oxygen to hinder, the damage to transparent protective film can be prevented, can be only To adhesive effectively irradiating electron beam.

In the manufacture method of the laminated optical film of the present invention, the particularly manufacture method of polarizing coating, penetrate as active-energy Line, preferably use the luminous ray comprising wave-length coverage 380nm～450nm ray, particularly wave-length coverage 380nm～ The most active energy beam of the exposure of the luminous ray of 450nm.In ultraviolet hardening, luminous ray curing type, Using in the case of the transparent protective film (not transmitting UV type transparent protective film) for imparting ultraviolet absorption ability, due to big The absorbing wavelength light shorter than 380nm in cause, thus the short light of wavelength ratio 380nm will not to reach active energy ray curable gluing Agent, is not involved in its polymerisation.Additionally, being converted into heat by the short light of wavelength ratio 380nm of transparent protective film absorption, make transparent Diaphragm itself generates heat, become the curling, the fold that cause polarizing coating etc. it is bad the reason for.Therefore, using ultraviolet in the present invention In the case of line curing type, luminous ray curing type, preferably use as active energy beam generating means and do not send wavelength ratio The device of 380nm short light, more specifically, cumulative illuminancc and the 250～370nm of wave-length coverage of 380～440nm of wave-length coverage The ratio of cumulative illuminancc be preferably 100：0～100：50, more preferably 100：0～100：40.As the active-energy of the present invention Ray, the metal halide lamp for preferably enclosing gallium, the LED/light source of the light for sending 380～440nm of wave-length coverage.Or can make With Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, incandescent lamp, xenon lamp, Halogen lamp LED, carbon arc lamp, gold The light sources comprising ultraviolet and luminous ray such as category halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunshine, Can also be using using after the short ultraviolet of passband filter blocks wavelength ratio 380nm.In order to improve polarizer and transparent guarantor While the glueability of the gluing oxidant layer between cuticula, the curling of polarizing coating is prevented, preferably use and make use of the gold for enclosing gallium Category halide lamp and through can stop active energy beam that the bandpass filter of the short light of wavelength ratio 380nm is obtained or The active energy beam of the wavelength 405nm obtained using LED/light source.

In ultraviolet hardening or luminous ray curing type, it is also preferred that to activity after irradiation ultraviolet radiation or luminous ray Energy ray-curable adhesive is heated (heat after irradiation), is in this case preferably warmed to more than 40 DEG C, is more preferably added Temperature is to more than 50 DEG C.

Active energy ray curable adhesive used in the present invention can especially be suitably used for being formed and being polarized The situation of the gluing gluing oxidant layer of transparent protective film of the piece with the light transmittance of wavelength 365nm less than 5%.Herein, the present invention Active energy ray curable adhesive contain the Photoepolymerizationinitiater initiater of above-mentioned formula (1), it is possible thereby to pass through with UV The transparent protective film of absorbability gets over irradiation ultraviolet radiation, solidify to form gluing oxidant layer.Thus, have in the two sides stacking of polarizer In polarizing coating obtained by the transparent protective film of UV absorbabilities, it is also possible to solidify gluing oxidant layer.But, there is no UV in stacking In polarizing coating obtained by the transparent protective film of absorbability, naturally it is also possible to solidify gluing oxidant layer.And, it is so-called to inhale with UV The transparent protective film of receipts ability, refers to the transparent protective film that the transmissivity of the light for 380nm is less than 10%.

Method as UV absorbabilities are given to transparent protective film, can enumerate makes to contain ultraviolet in transparent protective film The method of absorbent, the method for being laminated the surface-treated layer containing ultra-violet absorber on transparent protective film surface.

As the concrete example of ultra-violet absorber, for example can enumerate known epoxide benzophenone based compound, BTA based compound, salicylate based compound, benzophenone based compound, cyanoacrylate based compound, nickel network Compound based compound, triazine based compound etc..

After making 2 kinds of different bloomings, such as polarizers fit with transparent protective film, irradiation active energy beam (electricity Beamlet, ultraviolet, luminous ray etc.), make active energy ray curable adhesive be solidified to form gluing oxidant layer.Make polarizer The moisture rate of polarizer when fitting with transparent protective film is usually more than 1%, preferably more than 3%, more preferably 5% with On.In addition, in the case where polarizer moisture rate is too high, the moisture in laminating rear polarizer is moved to gluing oxidant layer, gluing LogPOW in agent composition is that 2～7 B component genetic horizon is separated, and thus produces bad order, therefore not preferred.Polarizer Moisture rate is preferably less than 18%, more preferably less than 15%, most preferably less than 12%.Polarizer moisture rate is obtained as follows, That is, the sample of 180mm × 500mm is cut out from the polarizer of gained, its initial stage weight (W (g)) is determined.The sample is existed After placing 6 hours in 120 DEG C of drying machine, weight (D (g)) after being dried is determined.According to these measured values, obtained using following formula Moisture rate.

Moisture rate (%)={ (W-D)/W } × 100

The direction of illumination of active energy beam (electron beam, ultraviolet, luminous ray etc.) can be from arbitrary proper orientation Irradiation.It is preferred that from the irradiation of transparent protective film side.If from the irradiation of polarizer side, polarizer is possible to because of active energy beam (electron beam, ultraviolet, luminous ray etc.) and deteriorate.

In the case where the laminated optical film of the present invention is manufactured using tinuous production, line speed is according to adhesive Depending on hardening time, but preferably 1～500m/min, more preferably 5～300m/min, more preferably 10～100m/ min.In the case where line speed is too small, undercapacity, or it is excessive to the damage of transparent protective film, it is impossible to making can The polarizing coating of tolerance endurancing etc..In the case where line speed is excessive, the solidification of adhesive is insufficient, and having cannot The situation of the adhesivity needed for obtaining.

And, in the manufacture method of the laminated optical film of the present invention, in the case where the laminated optical film is polarizing coating, will Polarizer is pressed from both sides across the gluing of the solidified material layer formation using above-mentioned active energy ray curable adhesive with transparent protective film Oxidant layer is fitted, and between transparent protective film and gluing oxidant layer, can arrange easy adhesive layer.Easily adhesive layer can for example be utilized and had It is polyester backbone, polyether skeleton, polycarbonate backbone, polyurethane skeleton, silicon-type, polyamide backbone, polyimide backbone, poly- The various resins of ethene ol skeleton etc. are formed.These fluoropolymer resins can be used alone, or be applied in combination two or more. In addition, other additives can also be added in the formation of easy adhesive layer.Tackifier, ultraviolet specifically can be also used to inhale Receive stabilizers such as agent, antioxidant, heat-resisting stabilizing agent etc..

Easily adhesive layer is generally located on transparent protective film in advance, and using gluing oxidant layer the easy adhesive layer of the transparent protective film is made Fit with polarizer side.Easily technology known to the formation material use being formed by easy adhesive layer of adhesive layer is coated on On bright diaphragm and be dried and carry out.Easily adhesive layer forms material typically as in view of dried thickness, coating Smoothness etc. is diluted to the solution of debita spissitudo and prepares.The dried thickness of easily adhesive layer is preferably 0.01～5 μm, more preferably For 0.02～2 μm, more preferably 0.05～1 μm.Furthermore, it is possible to multiple easy adhesive layers are set, in this case, it is also preferred that The gross thickness for making easy adhesive layer is above range.

＜ polarizer ＞

The manufacture method of the present invention especially can serve as the manufacture method of polarizing coating.The polarization used during manufacture polarizing coating Piece is not particularly limited, it is possible to use various polarizers.Used as polarizer, for example can enumerate makes polyvinyl alcohol mesentery, part The hydrophilic macromolecule films such as dimethoxym ethane polyvinyl alcohol mesentery, the partly-hydrolysed film of EVAc system adsorb iodine Or the dichroic material such as dichroic dye and polarizer, the processed thing of polyvinyl alcohol or polyvinyl chloride obtained by uniaxial tension Polyene system alignment films such as desalination acid treatment thing etc..It is suitably in the middle of them comprising the dichroic substance such as polyvinyl alcohol mesentery and iodine Polarizer.The thickness of these polarizers is not particularly limited, but generally 80 μm or so following.

By polyvinyl alcohol mesentery is with iodine staining and polarizer obtained by uniaxial tension for example can be made by following operation Make, i.e. during polyvinyl alcohol mesentery impregnated in the aqueous solution of iodine, thus dyeed, and elongation is made for 3～7 times of former length Make.During the aqueous solution of boric acid or KI etc. can also be impregnated in as needed.Can also be before dyeing further according to needs Polyvinyl alcohol mesentery impregnated in water and washed.By washing to polyvinyl alcohol mesentery, except poly- second can be cleaned Beyond dirt, the anti-blocking agent on enol mesentery surface, can also make polyethenol series membrane swelling, thus with prevent dyeing it is unequal Inhomogenous effect.Stretching can be carried out after with iodine staining, it is also possible to which an Edge Coloring is stretched on one side, it can in addition contain stretch After use iodine staining.Can also be stretched in the aqueous solution of boric acid or KI etc. or in water-bath.

In addition, the active energy ray curable adhesive compound used in the present invention is being used as polarizer In the case that thickness is less than 10 μm of slim polarizer, can significantly embody its effect (meet it is hot and humid under Optical durability in harsh and unforgiving environments).Above-mentioned thickness be less than 10 μm of polarizer compared with thickness is more than 10 μm of polarizer, The impact of moisture is relative to become big, and optical durability is not abundant enough in hot and humid lower environment, easily cause transmissivity rising, Degree of polarization is reduced.That is, the volume water absorption rate in the polarizer present invention by above-mentioned less than 10 μm is the glue of below 10 weight % In the case of stick layer stackup, it is harsh it is hot and humid under environment in water be inhibited to the movement of polarizer, thus may be used Raised with the transmissivity for significantly suppressing polarizing coating, degree of polarization reduce etc. optical durability deterioration.Go out from the viewpoint of slimming Send out, the thickness of polarizer is preferably 1～7 μm.The uneven thickness of this kind of slim polarizer is few, and observation property is excellent, in addition size It is with low uncertainty, but also the slimming of thickness as polarizing coating can be realized, from this starting point preferably.

As the representative of slim polarizer, Japanese Unexamined Patent Application 51-069644 publication or Japanese Unexamined Patent Publication can be enumerated 2000-338329 publications, WO2010/100917 pamphlets, the specification of PCT/JP2010/001460 or Japanese Patent Application Slim polarizing coating described in 2010-269002 specifications or Japanese Patent Application 2010-263692 specification.These are slim Polarizing coating can be utilized to be included polyvinyl alcohol resin (being also referred to as PVA systems resin below) layer and stretching resin base material in layer The operation stretched in the state of stack and the preparation method of the operation of dyeing are obtained.If the preparation method, even if then PVA resins It is thin, due to by stretching with resin base material support, thus the not good situation such as fracture that can not also occur to be caused by stretching carry out Stretching.

As the slim polarizing coating, the operation stretched in the state of duplexer is included in and the operation of dyeing In preparation method, from polarization property this point can be improved with high magnification stretching, preferably as WO2010/100917 brochures Son, the specification of PCT/JP2010/001460 or Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010- There is the preparation method that the utilization as recording is included in the operation stretched in boric acid aqueous solution to obtain in No. 263692 specifications The polarizing coating for arriving, particularly preferably as Japanese Patent Application 2010-269002 specification, No. 2010-263692 explanation of Japanese Patent Application There is the utilization recorded to include secondarily carrying out the operation of aerial stretching before being stretched in boric acid aqueous solution in book The polarizing coating that preparation method is obtained.

Slim high function polarizing coating described in the specification of above-mentioned PCT/JP2010/001460 is and resin base material one Body masking, the slim high function polarization that the thickness comprising the PVA systems resin for being orientated dichroic substance is less than 7 μm Film, the optical characteristics that with monomer transmissivity be more than 42.0% and degree of polarization is more than 99.95%.

Above-mentioned slim high function polarizing coating can be manufactured by following operation, i.e. in the thickness at least with 20 μm On resin base material, the coating and dry generation PVA resins using PVA systems resin, by the PVA resins for being generated dipping In the dyeing liquor of dichroic substance, make PVA resins adsorb dichroic substance, the PVA systems of dichroic substance will be adsorbed with Resin bed is integrally stretched in boric acid aqueous solution with resin base material so that total stretching ratio is more than 5 times of former length.

It is to manufacture to include to make dichroism thing in addition, using following method, above-mentioned slim high function polarizing coating can be manufactured The method of the laminate film of the slim high function polarizing coating that matter has been orientated, methods described includes：Generate comprising at least with 20 μm Thickness resin base material and by the coated on one side in resin base material comprising PVA systems resin the aqueous solution and drying and formed PVA resins laminate film operation；By the PVA systems by resin base material and the one side for being formed at resin base material is included The laminate film of resin bed impregnated in the dyeing liquor comprising dichroic substance and make PVA systems tree contained in laminate film Lipid layer adsorbs the operation of dichroic substance；The laminate film comprising the PVA resins for being adsorbed with dichroic substance is existed Operation in boric acid aqueous solution to make total stretching ratio stretch as in the way of more than 5 times of former length；By the way that dichroism will be adsorbed with The PVA resins stretching integrated with resin base material of material, and manufacture has slim high function in the one side film forming of resin base material The operation of the laminate film of polarizing coating, the slim high function polarizing coating includes the PVA systems resin for being orientated dichroic substance Layer, thickness be less than 7 μm have monomer transmissivity be more than 42.0% and degree of polarization be more than 99.95% optical characteristics.

Above-mentioned Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-263692 specification it is slim Polarizing coating is the continuous band-shaped polarizing coating comprising the PVA systems resin for being orientated dichroic substance, is included in amorphism ester system The duplexer of the PVA resins of film forming stretches what is constituted in by aerial assisting tension and boric acid water on thermoplastic resin base material It is stretched in 2 sections of stretching process, thus makes less than 10 μm of thickness.Monomer transmissivity is being set to into T, degree of polarization is being set to into P When, the slim polarizing coating is preferably to be made with and meets P ＞-(10^{0.929T-42.4-1}) × 100 (wherein, T ＜ 42.3) and P >=99.9 (wherein, the polarizing coating of the optical characteristics of the condition of T >=42.3).

Specifically, the slim polarizing coating can be made using the manufacture method of the slim polarizing coating for including following operation Make, i.e. using the aerial high temperature to the PVA resins of film forming on continuous band-shaped amorphism ester based thermoplastic resin base material Stretching, generates the operation of the stretching intermediate product comprising the PVA resins through orientation；Using dichroic substance to stretching Absorption on intermediate product, generating to include makes what dichroic substance (mixture of preferred iodine or iodine and organic dyestuff) had been orientated The operation of the coloring intermediate product of PVA resins；Using to stretching in the boric acid water for colouring intermediate product, generation is included The thickness for making the PVA resins that dichroic substance has been orientated is the operation of less than 10 μm of polarizing coating.

In the manufacture method, expect so that using in aerial drawing by high temperature and boric acid water stretching obtain in amorphism ester system Total stretching ratio of the PVA resins of film forming is more than 5 times on thermoplastic resin base material.For the boric acid stretched in boric acid water The liquid temperature of the aqueous solution can be set to more than 60 DEG C.Before stretching to coloring intermediate product in boric acid aqueous solution, expect Implement insoluble process to colouring intermediate product, in this case, be expected that by for the coloring intermediate product impregnated in liquid Carry out in the boric acid aqueous solution that not higher than 40 DEG C of temperature.Above-mentioned amorphism ester based thermoplastic resin base material can be using comprising copolymerization The copolymerization polyethylene terephthalate of M-phthalic acid, the copolymerization copolymerization poly terephthalic acid second of cyclohexanedimethanol The amorphism polyethylene terephthalate of diol ester or other copolymerization polyethylene terephthalates, preferably by saturating The base material that ming tree fat is constituted, its thickness can be set to more than 7 times of the thickness of the PVA resins of institute's film forming.In addition, aerial high The stretching ratio of temperature stretching is preferably less than 3.5 times, and the draft temperature of aerial drawing by high temperature is the glass transition of PVA systems resin It is more than temperature, specifically preferably 95 DEG C～150 DEG C of scope.Aerial drawing by high temperature is being carried out using free end uniaxial tension In the case of, on amorphism ester based thermoplastic resin base material total stretching ratio of the PVA resins of film forming be preferably 5 times with Go up and less than 7.5 times.In addition, in the case where aerial drawing by high temperature is carried out using fixing end uniaxial tension, in amorphism ester system Total stretching ratio of the PVA resins of film forming is preferably more than 5 times and less than 8.5 times on thermoplastic resin base material.

More specifically, using method as follows, slim polarizing coating can be manufactured.

Make the copolymerization M-phthalic acid copolymerization polyethylene terephthalate (amorphous of the M-phthalic acid of 6mol% Property PET) continuous band-shaped base material.The glass transition temperature of amorphism PET is 75 DEG C.Make as shown below comprising continuous The duplexer of the amorphism PET base material of banding and polyvinyl alcohol (PVA) layer.Additionally, the glass transition temperature of PVA For 80 DEG C.

Prepare the amorphism PET base material of 200 μ m-thicks and the saponification degree more than 99% of the degree of polymerization more than 1000 is dissolved with water PVA powder 4～5% concentration the PVA aqueous solution.Then, PVA is coated with the amorphism PET base material of 200 μ m-thicks water-soluble Liquid, is dried in 50～60 DEG C of temperature, and obtaining the film forming in amorphism PET base material has the duplexer of PVA layers of 7 μ m-thicks.

Duplexer to the PVA layers comprising 7 μ m-thicks, through 2 sections of drawings for including being stretched in aerial assisting tension and boric acid water The following operation of operation is stretched, the slim high function polarizing coating of 3 μ m-thicks is manufactured.Using the aerial assisting tension operation of first paragraph, By the stretching integrated with amorphism PET base material of the duplexer of the PVA layers comprising 7 μ m-thicks, the drawing of the PVA layers comprising 5 μ m-thicks is generated Stretch duplexer.Specifically, the stretching duplexer is obtained as follows, i.e. is loaded the duplexer of the PVA layers comprising 7 μ m-thicks and is equipped with It is to carry out in the way of 1.8 times to make stretching ratio in the stretching device being set as in the baking oven of 130 DEG C of draft temperature environment Free end uniaxial tension and obtain.Using the stretch processing, make PVA layers contained in stretching duplexer be changed into PVA molecules and be oriented 5 μ m-thicks PVA layers.

Then, using dyeing process, the PVA layers for generating 5 μ m-thicks for being oriented PVA molecules are adsorbed with the dyed layer of iodine Stack.Specifically, the coloring duplexer is obtained as follows, i.e. by stretching duplexer in 30 DEG C of liquid temperature comprising iodine and KI Dyeing liquor in impregnate the arbitrary time so that the monomer transmissivity of the PVA layers of the high function polarizing coating of composition for ultimately generating is 40～44%, thus make PVA layers contained in stretching duplexer adsorb iodine.In this operation, dyeing liquor with water as solvent, by iodine Concentration is set in the range of 0.12～0.30 weight %, and iodate potassium concn is set in the range of 0.7～2.1 weight %.Iodine with The ratio of the concentration of KI is 1 to 7.Additionally, iodine is dissolved in the water and is necessarily required to KI.It is more specific and Speech, by the way that stretching duplexer is impregnated 60 seconds in weight % of iodine concentration 0.30, the dyeing liquor of weight % of iodate potassium concn 2.1, And the PVA layers for generating 5 μ m-thicks for being oriented PVA molecules are adsorbed with the coloring duplexer of iodine.

Then, using stretching process in the boric acid water of second segment, by coloring duplexer with amorphism PET base material integrally Further stretching, generates the optical film laminate of the PVA layers of the high function polarizing coating of composition comprising 3 μ m-thicks.Specifically, the light Learn film laminated body to obtain as follows, i.e. load coloring duplexer and be provided to the liquid temperature scope being set as comprising boric acid and KI In stretching device in the processing meanss of 60～85 DEG C of boric acid aqueous solution, by make stretching ratio be carry out in the way of 3.3 times from Obtained by end uniaxial tension.More specifically, the liquid temperature of boric acid aqueous solution is 65 DEG C.Additionally, by boric acid content be set to relative to The weight portion of water 100 is 4 weight portions, and it is 5 weight portions that iodate potassium content is set to relative to the weight portion of water 100.In this operation, will adjust The coloring duplexer of whole iodine absorption number first impregnates 5～10 seconds in boric acid aqueous solution.Afterwards, the coloring duplexer is made as former state not Between the different multigroup roller of stretching device, i.e. peripheral speed in becoming ground by being provided to processing meanss, with 30～90 seconds so as to draw Stretching the mode that multiplying power is 3.3 times carries out free end uniaxial tension.Using the stretch processing, PVA contained in coloring duplexer is made Layer is changed into adsorbed iodine as the PVA layers of many iodide ion complex compounds 3 μ m-thicks that high order has been orientated in one direction.The PVA layers Constitute the high function polarizing coating of optical film laminate.

Although not necessary operation in the manufacture of optical film laminate, but preferably by matting, by optics Film laminated body takes out from boric acid aqueous solution, and be attached to the film forming in amorphism PET base material 3 μm are cleaned with potassium iodide aqueous solution The boric acid on the surface of thick PVA layers.Afterwards, the optical film laminate through cleaning is entered using the drying process of 60 DEG C of warm braw Row drying.And matting is the operation for eliminating the bad orders such as boric acid precipitation.

Although same not necessary operation in the manufacture of optical film laminate, however can also using laminating and/or Transfer printing process, while the surface coating binder of the PVA layers of 3 μ m-thicks in film forming in amorphism PET base material, while laminating 80 The tri acetyl cellulose membrane of μ m-thick, peels off afterwards amorphism PET base material, and the PVA layers of 3 μ m-thicks are transferred to into the triacetyl of 80 μ m-thicks On cellulose membrane.

[other operations]

The manufacture method of above-mentioned slim polarizing coating can include other operations beyond above-mentioned operation.As other works Sequence, for example, can enumerate insoluble operation, cross-linking process step, drying (regulation of moisture rate) operation etc..Other operations can be with office Suitable opportunity of anticipating is carried out.

Above-mentioned insoluble operation in the case of representational, is impregnated in boric acid aqueous solution by making PVA resins And carry out.By implementing insoluble process, resistance to water can be given to PVA resins.The concentration of the boric acid aqueous solution is relative 1 weight portion～4 weight portion is preferably in the weight portion of water 100.The liquid temperature of insoluble bath (boric acid aqueous solution) is preferably 20 DEG C～50 ℃.It is preferred that carrying out insoluble operation before stretching process after duplexer makes, in dyeing process or water.

Above-mentioned cross-linking process step in the case of representational, be by making PVA resins impregnated in boric acid aqueous solution and Carry out.By implementing crosslinking Treatment, resistance to water can be given to PVA resins.The concentration of the boric acid aqueous solution is relative to water 100 weight portions are preferably 1 weight portion～4 weight portion.In addition, in the case of carrying out cross-linking process step after above-mentioned dyeing process, it is excellent Choosing also coordinates iodide.By coordinating iodide, the dissolution of the iodine that can suppress to be adsorbed PVA resins.Iodide Use level is preferably 1 weight portion～5 weight portion relative to the weight portion of water 100.The concrete example of iodide is as described above.Crosslinking bath The liquid temperature of (boric acid aqueous solution) is preferably 20 DEG C～50 DEG C.It is preferred that carrying out crosslinking work before stretching process in above-mentioned second boric acid water Sequence.In a preferred embodiment, stretching process in dyeing process, cross-linking process step and the second boric acid water is carried out successively.

＜ transparent protective film ＞

As the material of the transparent protective film for forming the one or both sides located at above-mentioned polarizer, preferably clear, machinery The excellent material such as intensity, heat endurance, water-resisting property, isotropism.For example can enumerate polyethylene terephthalate or The cellulose-based polymer such as the polyester based polymer such as PEN, diacetyl cellulose or triacetyl cellulose, The benzene second such as the acrylic polymers such as polymethyl methacrylate, polystyrene or acrylonitrile styrene copolymer (AS resins) Alkene based polymer, Merlon based polymer etc..In addition, polyethylene, polypropylene, the polyene with ring system or ENB structure The acyls such as the polyolefin polymer of hydrocarbon, ethylene propylene copolymer etc, vinyl chloride-based polymer, nylon or aromatic polyamide Amine system polymer, imide series polymer, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide Based polymer, vinyl alcohol system polymer, vinylidene chloride based polymer, vinyl butyral based polymer, aromatic ester based polymer, Blend of polyformaldehyde based polymer, epoxy based polymer or above-mentioned polymer etc. can also be above-mentioned transparency protected as being formed The example of the polymer of film is enumerated.More than a kind of any appropriate additive can also be included in transparent protective film.As adding Plus agent, for example can enumerate ultra-violet absorber, antioxidant, lubricant, plasticizer, releasing agent, anti-coloring agent, fire retardant, Nucleator, anti-static electricity interference agent, pigment, colouring agent etc..The content of the above-mentioned thermoplastic resin in transparent protective film is preferably 50 ～100 weight %, more preferably 50～99 weight %, more preferably 60～98 weight %, particularly preferably 70～97 weights Amount %.The content of the above-mentioned thermoplastic resin in transparent protective film be 50 weight % below in the case of, it is possible to Wu Fachong Embody thermoplastic resin high transparent inherently etc. with dividing.

In addition, as transparent protective film, during Japanese Unexamined Patent Publication 2001-343529 publications (WO01/37007) can be enumerated The polymer film of record, such as (A) containing in side chain have replace and/or unsubstituted imide thermoplastic resin and There is the resin combination of the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group in side chain.Can as concrete example To enumerate containing the alternate copolymer and acrylonitrile styrene copolymer being made up of isobutene and N- methylmaleimidos The film of resin combination.Film can use the film being made up of mixing extrusion pin of resin combination etc..These films are due to phase difference Little, photoelastic coefficient is little, therefore can eliminate the unequal not good situation caused by the deformation of polarizing coating, additionally, due to moisture permeability It is little, therefore humidify excellent in te pins of durability.

In above-mentioned polarizing coating, the moisture permeability of the transparent protective film is preferably 150g/m²/ below 24h.According to this composition, Moisture in air is difficult to enter in polarizing coating, and the moisture rate that can suppress polarizing coating itself changes.As a result, it is possible to suppress The curling of the polarizing coating produced because of Conservation environment, change in size.

As the material of the transparent protective film for forming the one or both sides located at above-mentioned polarizer, preferably clear, machinery The excellent material such as intensity, heat endurance, water-resisting property, isotropism, particularly more preferably moisture permeability is 150g/m²/ below 24h Material, particularly preferred 140g/m²The material of/below 24h, further preferred 120g/m²The material of/below 24h.Moisture permeability can To be obtained using the method described in embodiment.

As the formation material of the transparent protective film for meeting the low moisture permeability, for example, can use poly terephthalic acid second The polyester resin such as diol ester or PEN；Polycarbonate resin；Aromatic ester system resin；Nylon or aromatic series polyamides The acid amides such as amine system resin；The polyolefin polymer of polyethylene, polypropylene, ethylene propylene copolymer etc, with ring system or The annular ethylene series resin of ENB structure, (methyl) acrylic resin or their mixture.Work as in the resin In, preferred polycarbonate-based resin, cyclic polyolefin hydrocarbon system resin, (methyl) acrylic resin, particularly preferred cyclic polyolefin It is resin, (methyl) acrylic resin.

The thickness of transparent protective film can suitably determine, but general from operability, the thin layers such as intensity, the property disposed etc. Aspect is set out, and is 1～100 μm or so.It is particularly preferably 1～80 μm, more preferably 3～60 μm.

And, when the two sides of polarizer arranges transparent protective film, can use by identical polymer at its table back side The transparent protective film that material is constituted, it is also possible to using the transparent protective film being made up of different polymeric material etc..As transparent The combination of diaphragm, from from the viewpoint of moisture permeability, preferred polyethylene terephthalate film and cyclic polyolefin hydrocarbon system resin Film, (methyl) acrylic resin film and cyclic polyolefin resin film, (methyl) acrylic resin film and (methyl) propylene The combination of sour resin film.By arranging the little transparent protective film of moisture permeability on the two sides of polarizer, moisture is just difficult to into partially In vibrating diaphragm, the especially excellent polarizing coating of resistance to water can be obtained.

Can in the face of the non-glued polarizer of above-mentioned transparent protective film, arrange hard conating, anti-reflection layer, antiblocking layers, The functional layer such as diffusion layer or antiglare layer.And, the function such as above-mentioned hard conating, anti-reflection layer, antiblocking layers, diffusion layer or antiglare layer Layer is in addition to can be located at transparent protective film itself, it is also possible to separately arrange as the component different from transparent protective film.

＜ blooming ＞

Polarizing coating can be used as using when actually used with blooming obtained by other optics layer stackups.For the light Learn layer be not particularly limited, but for example can use 1 layer or more than 2 layers reflecting plate or half transmitting plate, polarizer (including 1/2nd, 1/4 equiwavelength's plate), the optical layers that use sometimes in the formation of the liquid crystal indicator such as compensation film for angular field of view etc..Particularly, it is excellent It is selected on the polarizing coating of the present invention and is laminated reflecting plate again or the reflective polarizing film or Semitransmissive of Transflective plate are inclined Vibrating diaphragm, on polarizing coating again the elliptical polarization film or circular polarization film of laminated phase-difference plate, be laminated on polarizing coating visual angle again The wide viewing angle polarizing coating of compensation film is laminated again the polarizing coating that brightness improves film on polarizing coating.

State blooming obtained by optical layers and can utilize manufacture in liquid crystal indicator etc. polarizing coating upper strata is stacked on The mode being laminated one by one successively in journey carries out being laminated stability, group of the mode for making blooming because of quality in advance being formed Dress operability etc. is excellent and there is the manufacturing process that can improve liquid crystal indicator etc..Can be using bonding in stacking The appropriate bonding methods such as layer.Above-mentioned polarizing coating or other bloomings it is gluing when, their optic axis can be according to institute Phase difference characteristics for needing etc. are set to appropriate arrangement angles.

It is laminated with aforesaid polarizing coating or at least in the blooming of 1 layer of polarizing coating, it is also possible to be provided for and liquid crystal list The gluing adhesive layer of other components such as unit.The adhesive for forming adhesive layer is not particularly limited, and for example can properly select makes It is polymerized to acrylic polymer, silicon-type polymer, polyester, polyurethane, polyamide, polyethers, fluorine system or rubber series etc. The adhesive of polymer based on thing.The particularly preferred optical transparence using acrylic adhesives etc is excellent, display Go out the excellent adhesive such as adhesion characteristic, weatherability, the heat resistance of appropriate wetability, coherency and adhesivity.

Adhesive layer can also be located at the one of polarizing coating or blooming as the overlapping layer of the material of different compositions or species etc. Face or two sides.In addition, in the case of the two sides, it is also possible to the table back side of polarizing coating or blooming using different compositions, The adhesive layer of species, thickness etc..The thickness of adhesive layer can suitably determine according to application target, adhesive tension etc., generally 1～ 500 μm, preferably 1～200 μm, particularly preferably 1～100 μm.

For the exposed surface of adhesive layer, for during for before actually used, the purposes such as its pollution are prevented, temporarily Attach distance piece and cover.Thus, it is possible to prevent from being contacted with adhesive layer under common place's configuration state.As distance piece, except Beyond above-mentioned thickness condition, for example, can use plastic foil, sheet rubber, paper, cloth, non-woven fabrics, net, foamed sheet or metal The appropriate sheet thing such as paper tinsel, their layered product uses as needed silicon-type or chain alkyl system, fluorine system or molybdenum sulfide etc. Appropriate remover is coated the appropriate material that material etc. obtained by process is obtained according to previous methods.

＜ image display device ＞

The polarizing coating or blooming of the present invention can be preferred in formation of the various devices such as liquid crystal indicator etc..Liquid The formation of crystal device can be carried out according to previous methods.That is, liquid crystal indicator generally by by liquid crystal cells and The component parts such as polarizing coating or blooming and the illuminator that uses as needed suitably assembles and loads drive circuit etc. And formed, it is not particularly limited in addition to polarizing coating or blooming this point using the present invention in the present invention, can be according to Previous methods.For liquid crystal cells, for example, can also use any type of liquid crystal cells such as TN types or STN types, π types.

Can be formed in liquid crystal cells one or both sides be configured with polarizing coating or blooming liquid crystal indicator or The appropriate liquid crystal indicator such as liquid crystal indicator of backlight or reflecting plate used in illuminator.In this case, originally The polarizing coating or blooming of invention can be located at the one or both sides of liquid crystal cells.When both sides arrange polarizing coating or blooming, They both can be with identical, it is also possible to different.Additionally, in the formation of liquid crystal indicator, can in position configure 1 layer Or more than 2 layers of such as diffuser plate, antiglare layer, antireflection film, protection board, prism array, lens array sheet, light diffusing sheet, the back of the body The appropriate part such as light lamp.

[embodiment]

Embodiments of the invention will be below described, but embodiments of the present invention are not limited to these embodiments.

Production Example 1

The making ＞ of the slim polarizer of ＜ polyethenol series (corresponding to the first blooming)

In order to make slim polarizer, first, by the PVA layers that have 24 μ m-thicks to the film forming in amorphism PET base material Duplexer carries out the aerial assisting tension of 130 DEG C of draft temperature, generates stretching duplexer, then, by the way that stretching duplexer is contaminated Color and generate coloring duplexer, then by stretching in the boric acid water that 65 degree of draft temperature is carried out to dyed layer stack, and generate PVA layers comprising 10 μ m-thicks for having stretched integrated with amorphism PET base material in the way of making total stretching ratio be 5.94 times Optical film laminate.The PVA molecule high orders of the PVA layers of the film forming in amorphism PET base material are taken using this kind of 2 sections stretchings To, the optical film laminate comprising thick 10 μm PVA layers can be generated, the optical film laminate is constituted will be inhaled by dyeing The slim polarizer of polyethenol series that attached iodine has been orientated in one direction high order as many iodide ion complex compounds.

Production Example 2

The making ＞ of ＜ transparent protective films (corresponding to the second blooming)

By the weight portion of imidizate MS resins 100 described in the Production Example 1 of Japanese Unexamined Patent Publication 2010-284840 publications And triazine system ultra-violet absorber (ADEKA company systems, trade name：T-712) 0.62 weight portion utilizes 2 axle kneading machines at 220 DEG C Mixing, produces resin particle.The resin particle of gained is made in 100.5kPa, 100 DEG C of dryings 12 hours, using the extrusion of single shaft Machine is extruded from T-shaped mould head in 270 DEG C of mold temperature and is configured to membranaceous (thick 160 μm).The film is existed along its carriage direction again (thick 80 μm) is stretched under 150 DEG C of atmosphere, then after easy adhesive of the coating comprising aqueous urethane resin, edge and film are transported Send the orthogonal direction in direction to stretch under 150 DEG C of atmosphere, obtain thick 40 μm of (moisture permeabilitys 58g/m²/ 24h) acrylic films (transparent protective film).

Moisture permeability ＞ of ＜ transparent protective films

The measure of moisture permeability is determined according to the moisture permeability test (cup type method) of JIS Z0208.Diameter 60mm will be cut into Sample be placed in the moisture vapor transmission cup of the calcium chloride for adding about 15g, be put into 40 DEG C of temperature, the constant temperature machine of humidity 90%R.H. In, the weight increase for standing 24 hours calcium chloride in front and back is determined, thus obtain moisture permeability (g/m²/24h)。

＜ active energy beam ＞

As active energy beam, luminous ray (enclosing the metal halide lamp of gallium) irradiation unit has been used：Fusion UV Sysyems, Inc company system Light HAMMER10 fluorescent tubes：V fluorescent tube peak illuminations：1600mW/cm², cumulative exposure 1000/mJ/cm²(380～440nm of wavelength).And, it is seen that the illumination of light is to use Solatell company systems Sola- Check system measurements.

Embodiment 1

Prepare the active energy ray curable adhesive compound containing following compound.

First active energy ray curable adhesive compound (350mPas/25 DEG C of fluid viscosity)；The weights of HEAA 94 Weight % of 3 weight %, KAYACURE DETX-S of amount %, IRGACURE907 3

Second active energy ray curable adhesive compound (10mPas/25 DEG C of fluid viscosity)；LIGHT Weight % of 94 weight %, IRGACURE907 of ACRYLATE 1,9ND-A, 3 weight %, KAYACURE DETX-S 3

The compound for being used is：

HEAA：Hydroxyethyl acrylamide, logPow=-0.56, emerging people's company system,

LIGHT ACRYLATE 1,9ND-A：1,9- nonanediol diacrylate, logPow=3.68, common prosperity society chemistry Company system,

IRGACURE907；2- methyl isophthalic acids-(4- methyl mercapto phenyl) -2- morpholinyl -1- acetone, BASF AG System,

KAYACURE DETX-S；Diethyl thioxanthone, Japanese chemical drug company system,

(making of polarizing coating)

In the PVA aspects of the slim polarizer corresponding to the first blooming, coating is warmed to 40 DEG C and adjusts fluid viscosity For the first active energy ray curable adhesive compound (0.3 μm of adhesive layer thickness) of 80cp.In addition, corresponding to the The binding face of the transparent protective film of two bloomings, is coated with the second active energy ray curable adhesive compound (gluing oxidant layer 0.7 μm of thickness), hereafter make them fit using roll squeezer.First active energy ray curable adhesive compound and second The ratio of active energy ray curable adhesive compound is 30：70.Thereafter, irradiate above-mentioned luminous ray to two sides and make the One and second active energy ray curable adhesive compound solidification after, 3 minutes heated-air dryings are carried out at 70 DEG C, obtain inclined The shake both sides of piece have the polarizing coating (laminated optical film) of transparent protective film.The line speed of laminating is 25m/min.

To the polarizing coating obtained in above-described embodiment 1, carry out and the adhesive tension of slim polarizer and transparent protective film Evaluate.In addition, having carried out contact angle, Yi Ji of the first active energy ray curable adhesive compound with slim polarizer The evaluation of the contact angle of two active energy ray curable adhesive compounds and transparent protective film.And, for contact angle Evaluate, carried out based on JIS-K 6768.Evaluation result is shown in table 2.

Embodiment 2

Consolidate except the binding face for being substituted in the transparent protective film corresponding to the second blooming is coated with the second active energy beam The painting process of change type adhesive compound, and implement the binding face coating in the slim polarizer corresponding to the first blooming It is gluing that the coated face for having the first active energy ray curable adhesive compound carries out again the second active energy ray curable Beyond the painting process of the face of agent composition coating, using method same as Example 1 the both sides tool in polarizer is obtained There is the polarizing coating (laminated optical film) of transparent protective film.

Comparative example 1

Except corresponding to the first blooming slim polarizer binding face, coating containing weight % of HEAA 47, Weight % of 47 weight %, IRGACURE907 of LIGHT ACRYLATE 1,9ND-A, 3 weight %, KAYACURE DETX-S 3 The first active energy ray curable adhesive compound (21mPas/25 DEG C of fluid viscosity), fit thereon corresponding to Beyond the transparent protective film of two bloomings, obtain that there is transparent guarantor in the both sides of polarizer using method same as Example 1 The polarizing coating (laminated optical film) of cuticula.

Polarizing coating to obtaining in above-described embodiment and comparative example has carried out following evaluation.Evaluation result is shown in into table In 2.

＜ adhesive tensions ＞

By the polarizing coating obtained in each example with the direction parallel with the draw direction of polarizer as 200mm, it is orthogonal Size on direction for 20mm cuts out, and otch is carved with cutting knife between transparent protective film and polarizer, fits in polarizing coating On glass plate.Using stenter, transparent protective film and polarizer are surveyed with the stripping of 500mm/min peeling rates along 90 degree of directions Make its peel strength.In addition, the infrared absorption spectroscopy of the release surface after stripping is measured using ATR methods, based on following Benchmark evaluation stripping interface.

A：The cohesion destruction of transparent protective film

B：The interface peel of transparent protective film/adhesive interlayer

C：Interface peel between gluing oxidant layer/polarizer

D：The cohesion destruction of polarizer

In said reference, A and D due to adhesive tension for film cohesiveness more than, therefore, it is intended that adhesive tension is very excellent. On the other hand, B and C mean that the adhesive tension at transparent protective film/gluing oxidant layer (gluing oxidant layer/polarizer) interface is not enough (gluing Power is poor).In view of these situations, adhesive tension during A or D is set to into zero, by AB (while there is the " cohesion of transparent protective film Destruction " and " interface peel of transparent protective film/adhesive interlayer ") or AC (while occurring that " cohesion of transparent protective film is broken It is bad " and " interface peel between gluing oxidant layer/polarizer ") when adhesive tension be set to △, adhesive tension during B or C is set to ×.

[table 2]

【Table 2】

Claims (9)

1. a kind of manufacture method of laminated optical film, it is characterised in that be folder across by making active energy ray curable glue The gluing oxidant layer that adhesive composition is solidified to form at least will be laminated optics obtained by the first blooming and the stacking of the second blooming The manufacture method of film,

The active energy ray curable adhesive compound includes the first active energy ray curable adhesive compound And the second active energy ray curable adhesive compound, and containing at least two or more different active energy ray-curable Type adhesive compound,

The manufacture method of the laminated optical film includes：

Painting process, in the binding face of first blooming the first active energy ray curable adhesive composition is coated with Thing, then in binding face coating the second active energy ray curable adhesive compound of second blooming；

Bonding process, makes first blooming and second blooming laminating；And

Gluing operation, from the first blooming surface side or the second blooming surface side irradiation active energy beam, makes described Active energy ray curable adhesive compound solidifies, and presss from both sides across the described gluing oxidant layer being consequently formed, and makes first light Learn film and second blooming is gluing.

2. a kind of manufacture method of laminated optical film, it is characterised in that be folder across by making active energy ray curable glue The gluing oxidant layer that adhesive composition is solidified to form at least will be laminated optics obtained by the first blooming and the stacking of the second blooming The manufacture method of film,

The active energy ray curable adhesive compound includes the first active energy ray curable adhesive compound And the second active energy ray curable adhesive compound, and containing at least two or more different active energy ray-curable Type adhesive compound,

The manufacture method of the laminated optical film includes：

Painting process, in the binding face of first blooming the first active energy ray curable adhesive composition is coated with Thing, being coated with the coated face of the first active energy ray curable adhesive compound, then to carry out described second active The face of energy ray-curable adhesive compound applies coating；

Bonding process, from the coated face of the second active energy ray curable adhesive compound coated on the first blooming Side laminating second blooming；And

Gluing operation, from the first blooming surface side or the second blooming surface side irradiation active energy beam, makes described Active energy ray curable adhesive compound solidifies, and presss from both sides across the described gluing oxidant layer being consequently formed, and makes first light Learn film and second blooming is gluing.

3. the manufacture method of laminated optical film according to claim 2, wherein,

The fluid viscosity of the first active energy ray curable adhesive compound is solid higher than second active energy beam The fluid viscosity of change type adhesive compound.

4. the manufacture method of the laminated optical film according to any one of claims 1 to 3, wherein,

Active energy ray curable adhesive compound contact with first blooming and second blooming Angle is 5～50 degree.

5. the manufacture method of the laminated optical film according to any one of Claims 1 to 4, wherein,

First blooming and second blooming are selected from polyethenol series polarizer, acrylic resin film, cyclenes At least a kind blooming in hydrocarbon resin film, polyester resin film and polyolefin resin film.

6. the manufacture method of laminated optical film according to claim 5, wherein,

First blooming and second blooming be selected from the acrylic resin film, the cycloolefin resin film, At least a kind blooming in the polyester resin film and the polyolefin resin film.

7. the manufacture method of the laminated optical film according to claim 5 or 6, wherein,

The acrylic resin film, the cycloolefin resin film, the polyester resin film and the polyolefin resin film are at it Binding face be formed with containing selected from acrylic resin, polyurethane resin, polyvinyl alcohol resin, melmac Ji Han oxazoles The easy adhesive layer of at least a kind resin in the resin of quinoline base.

8. the manufacture method of the laminated optical film according to claim 6 or 7, wherein,

The SP values that the active energy ray curable adhesive compound contains 25～98 weight % are 18～21 (MJ/m³)^1/2 Free-radical polymerised compound.

9. the manufacture method of the laminated optical film according to any one of claim 1～8, wherein,

One side of first blooming and second blooming is the polyethenol series polarizer, coats the poly- second The active energy ray curable adhesive compound of the binding face of enol system polarizer contains the poly- of hydroxyl free radical Conjunction property compound.