CN107533253A

CN107533253A - Liquid crystal disply device and its preparation method with contact panel

Info

Publication number: CN107533253A
Application number: CN201680027241.2A
Authority: CN
Inventors: 森井里志
Original assignee: Konica Minolta Opto Inc
Current assignee: Konica Minolta Inc; Konica Minolta Opto Inc
Priority date: 2015-05-13
Filing date: 2016-04-15
Publication date: 2018-01-02
Anticipated expiration: 2036-04-15
Also published as: KR20190096444A; JP6627869B2; KR20170125098A; KR102011587B1; KR102057017B1; WO2016181756A1; JPWO2016181756A1; CN107533253B

Abstract

The problem of the present invention is to provide a kind of excellent Liquid crystal disply device and its preparation method with contact panel with VA mode-type liquid crystal cells of front contrast.The liquid crystal display device with contact panel of the present invention is that possess the liquid crystal display device with contact panel for having the one-piece type touch panel module of the polarization plates of transparency conducting layer in the identification side of VA mode-type liquid crystal cells; it is characterized in that; the one-piece type touch panel module of polarization plates with above-mentioned transparency conducting layer has in optical compensation films of at least one side with transparency conducting layer, polarizer and diaphragm successively from above-mentioned VA mode-types liquid crystal cells to identification side, and the glass transition temperature Tg of above-mentioned optical compensation films is in the range of 155~250 DEG C.

Description

Liquid crystal disply device and its preparation method with contact panel

Technical field

The present invention relates to the Liquid crystal disply device and its preparation method with contact panel.More specifically, it is related to front The excellent Liquid crystal disply device and its preparation method with contact panel of contrast.

Background technology

In recent years, the popularization for carrying the liquid crystal display device of contact panel continues to develop, it is contemplated that also may proceed to increase from now on.

For example, the capacitance type touch panel module used in contact panel is formed on transparent substrate using transparent The X electrode pattern in X-direction extension of conductive layer (also referred to as transparency electrode), and formed using other transparency conducting layers in Y The Y electrode pattern of direction extension.By using the surface of finger contact contact panel, X electrode pattern and Y electrode pattern contacts, profit Go out the change of the electrostatic capacitance of the position with the X and Y electrode pattern detection.

As the composition for combining this transparency conducting layer with 2 electrodes with polarization plates and liquid crystal cells, such as have Outer hung type touch panel module etc..

Fig. 1 represents one of the conventional liquid crystal display device with contact panel for possessing outer hung type touch panel module The schematic diagram of example.

Illustrate after detailed content, it is adjacent with liquid crystal cells and configure the polarization formed with 2 diaphragms clamping polarizers Plate, be arranged on thereon via adhesive linkage on transparent base material film formed with the transparency electrode containing ITO (tin indium oxide) etc. and The film sensors (also referred to as touch panel module) of the protective layer of the transparency electrode are protected, and then, via adhesive linkage and such as glass Or front panel as acrylic board is bonded.

In the case of this composition, because polarization plates and film sensors are each independent, turn into thickness to a certain degree Contact panel.

From now on, it is also further to the contact panel requirement as main member in the development of display device slimming Slimming.

Formed as the contact panel for tackling slim requirement, it is integrated with polarization plates to have attempted film sensors, phase For outer hung type, there is the touch panel module for being referred to as so-called Mid-cell types or interior insert-type (for example, referring to patent text Offer 1 and patent document 2).These polarization plates integration type touch panel modules are by being used as the inscape of polarization plates Above-mentioned transparency electrode is formed on optical compensation films, diaphragm so as to tackle the module of component slimming.

On the other hand, 1 of main member as liquid crystal display device, can enumerate liquid crystal cells.

Although multiple types according to the liquid crystal molecule used be present in liquid crystal cells, current VA (it is vertical orientated, Vertical alignment) pattern and IPS (plane conversion, in-plane switching) pattern turn into main flow.It is general and Speech, it is believed that VA patterns front contrast compared with IPS patterns is excellent.Because VA mode liquid crystals molecule is when electric field is closed Liquid crystal molecule is vertically oriented, therefore can further be suppressed the backlight light in black display and be revealed to identification side.

The present inventor by the one-piece type touch panel module of polarization plates of above-mentioned so-called Mid-cell types or interior insert-type with VA mode-types liquid crystal display combines, as a result, can not obtain relative to pre- using institute during IPS mode-type liquid crystal displays The improvement for the front contrast thought.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-81810 publications

Patent document 2：Japanese Unexamined Patent Publication 2013-104847 publications

The content of the invention

The present invention in view of the above problems situation and complete, it solves problem, and to be to provide a kind of front contrast excellent The Liquid crystal disply device and its preparation method with contact panel for possessing VA mode-type liquid crystal cells.

The present inventor has found to solve above-mentioned problem during studying the reason for above mentioned problem etc.：Tool It is standby that there is carrying for the one-piece type touch panel module of the polarization plates of transparency conducting layer to touch in the identification side of VA mode-type liquid crystal cells The liquid crystal display device of panel is controlled, the above-mentioned one-piece type touch panel module of polarization plates is from above-mentioned VA mode-types liquid crystal cells to identification Side is successively with optical compensation films of at least one side with transparency conducting layer, polarizer and diaphragm, above-mentioned optical compensation films Glass transition temperature Tg for the specific value above when, can solve the problem of the present invention.

That is, above-mentioned problem involved in the present invention can solve by the following method.

1. a kind of liquid crystal display device with contact panel, it is to possess to have in the identification side of VA mode-type liquid crystal cells The liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates of transparency conducting layer,

The one-piece type touch panel module of polarization plates with above-mentioned transparency conducting layer from above-mentioned VA mode-types liquid crystal cells to Side is identified successively with optical compensation films of at least one side with transparency conducting layer, polarizer and diaphragm, and

In the range of the glass transition temperature Tg of above-mentioned optical compensation films is 155~250 DEG C.

2. according to the liquid crystal display device with contact panel described in the 1st, it is characterised in that above-mentioned optical compensation films Contain any of cyclic olefine resin, polyimides system resins or polyarylate system resin.

3. according to the liquid crystal display device with contact panel described in the 1st or the 2nd, it is characterised in that above-mentioned light Learn the compensation film scope that the phase difference value Ro in direction variation is ± 3.0% in the face when having carried out heat treatment in 1 hour for 150 DEG C It is interior, in the range of the phase difference value Rt of thickness direction variation is ± 4.0%.

4. according to the liquid crystal display device with contact panel any one of the 1st~the 3rd, its feature exists In the range of the thickness of, above-mentioned optical compensation films is 10~40 μm.

5. according to the liquid crystal display device with contact panel any one of the 1st~the 4th, its feature exists In above-mentioned optical compensation films contain the nitrogen-containing heterocycle compound with the structure represented by following formulas (3) as on phase difference Rise agent.

Formula (3)

(in formula, A represents pyrazole ring.Ar₁And Ar₂Aromatic series hydrocarbon ring or heteroaromatic are represented respectively, there can be substitution Base.R₁Represent hydrogen atom, alkyl, acyl group, sulfonyl, alkoxy carbonyl or aryloxycarbonyl.Q represents 1 or 2.The respective tables of n and m Show 1~3 integer.)

6. a kind of manufacture method of the liquid crystal display device with contact panel, it is manufacture the 1st~any one of the 5th The manufacture method of the liquid crystal display device with contact panel of the described liquid crystal display device with contact panel, its feature It is possess following process：

After at least one side of above-mentioned optical compensation films forms above-mentioned transparency conducting layer, it is heat-treated more than 150 DEG C Process；

It is bonded, is made in a manner of the optical compensation films formed with above-mentioned transparency conducting layer and diaphragm clamping polarizer Make the process of the one-piece type touch panel module of polarization plates；And

The above-mentioned optical compensation films side of the one-piece type touch panel module of above-mentioned polarization plates is fitted in into above-mentioned VA mode-types liquid The process of brilliant unit.

By the above method of the present invention, it can provide front contrast the excellent band for possessing VA mode-type liquid crystal cells There is the Liquid crystal disply device and its preparation method of contact panel.

It is still not clear, but is presumed as follows for the expression mechanism or mechanism of action of the effect of the present invention.

In general, in the case of IPS mode-type liquid crystal cells, preferably do not have phase difference using optical compensation films, i.e., The film that the phase difference value Ro in direction and the phase difference value Rt of thickness direction are zero or so in face.On the other hand, VA mode-types liquid crystal In the case of unit, preferably using film high above-mentioned phase difference value Ro and Rt, such as Ro be 20~70nm scope and Rt be 70 The phase retardation film of~200nm scope is as optical compensation films.

The high film of this phase difference value is generally carried out stretch processing in the fabrication process, by the polymer point for forming film Son is highly orientated, so as to obtain the phase difference value.

In order to manufacture the above-mentioned one-piece type contact panel of polarization plates for being referred to as so-called Mid-cell types or interior insert-type Module, when setting transparency conducting layer on above-mentioned optical compensation films, after the transparency conducting layer is formed, for the low electricity of conductive layer Resistance is, it is necessary to be heat-treated and (also referred to as make annealing treatment).For example, specifically, at the heating that 150 DEG C carry out 30 minutes or so Reason, thus it is speculated that thus, the orientation disorder of the polymer molecule in above-mentioned optical compensation films, as a result, required optical compensation performance Become insufficient, front contrast declines.

According to the composition of the present invention, in order to tackle above-mentioned phenomenon, the tool that glass transition temperature Tg is more than 155 DEG C is used There are the optical compensation films of heat resistance, change, may achieve as VA patterns so as to suppress the phase difference value caused by above-mentioned heat treatment The excellent front contrast of type liquid crystal inherent feature.

In addition, as described above, in order that contact panel is thinned, optical compensation films are also required below 40 μm of thickness sometimes Slimming.Now, with thickness there is opposite relation in phase difference value, therefore, during filming below 40 μm, be added in film By addition and can to lift the additive of phase difference value (in this application be also referred to as phase difference rise agent) be effective.This hair A person of good sense is found that the phase difference with specific structure of available more excellent effect in the research for rising agent to various phase differences Rise agent.Speculate by adding the additive, in above-mentioned heat treatment, phase difference rises the orientation disorder of agent itself, causes and Change from the phase difference of the compound, changed so as to offset the phase difference from the polymer molecule for forming film, even Film can also realize that excellent phase difference value and heat treatment change patience.

Brief description of the drawings

Fig. 1 is an example of the composition for representing the conventional liquid crystal display device with outer hung type touch panel module Schematic diagram.

Fig. 2 is the liquid crystal display with contact panel for possessing the one-piece type touch panel module of polarization plates for representing the present invention The schematic diagram of one example of the composition of device.

Fig. 3 is the liquid crystal display with contact panel for possessing the one-piece type touch panel module of polarization plates for representing the present invention The schematic diagram of another example of the composition of device.

Fig. 4 is the liquid crystal display with contact panel for possessing the one-piece type touch panel module of polarization plates for representing the present invention The schematic diagram of another example of the composition of device.

Fig. 5 is the liquid crystal display with contact panel for possessing the one-piece type touch panel module of polarization plates for representing the present invention The schematic diagram of another example of the composition of device.

Fig. 6 is the liquid crystal display with contact panel for possessing the one-piece type touch panel module of polarization plates for representing the present invention The schematic diagram of another example of the composition of device.

Embodiment

The liquid crystal display device with contact panel of the present invention is that possess in the identification side of VA mode-type liquid crystal cells tool There is the liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates of transparency conducting layer, its feature exists In the one-piece type touch panel module of polarization plates with above-mentioned transparency conducting layer is from above-mentioned VA mode-types liquid crystal cells to identification side Successively with optical compensation films of at least one side with transparency conducting layer, polarizer and diaphragm, and above-mentioned optical compensation films Glass transition temperature Tg be 155~250 DEG C in the range of.This feature is the common skill of the invention involved by each claim Art feature.

As embodiments of the present invention, from the viewpoint of the effect for embodying the present invention, above-mentioned optical compensation films contain Any of cyclic olefine resin, polyimides system resins or polyarylate system resin, from the glass for meeting above-mentioned optical compensation films It is preferred from the viewpoint of glass transition temperature Tg.

In addition, the phase difference value Ro in above-mentioned optical compensation films direction in the face when having carried out heat treatment in 1 hour for 150 DEG C Change in the range of ± 3.0% and the phase difference value Rt of thickness direction variation be ± 4.0% in the range of, this is from abundant body Show optical compensation function and suppress when the phase difference caused by heat treatment changes, may achieve using VA mode-type liquid crystal cells It is preferable performance from the viewpoint of excellent front contrast.

In addition, the thickness of above-mentioned optical compensation films be 10~40 μm in the range of be that slimming to contact panel is preferable Thickness, in this case, required from imparting containing the nitrogen-containing heterocycle compound with the structure represented by above-mentioned formula (3) Phase difference value and further suppression are preferred from the viewpoint of being changed relative to the phase difference of heat treatment.

The manufacture method of the liquid crystal display device with contact panel of the present invention is preferably provided with following process：In above-mentioned light Learn compensation film at least one side form above-mentioned transparency conducting layer after, the process that is heat-treated more than 150 DEG C；With formed with upper The mode of the optical compensation films and diaphragm clamping polarizer of stating transparency conducting layer is bonded and makes the one-piece type touch surface of polarization plates The process of plate module；And the above-mentioned optical compensation films side of the one-piece type touch panel module of above-mentioned polarization plates is fitted in into above-mentioned VA The process of mode-type liquid crystal cells.

Hereinafter, the present invention and its inscape and the form mode for implementing the present invention are said in detail It is bright.It should illustrate, in this application, "~" is to be used as lower limit and the meaning of higher limit comprising its front and rear described numerical value Come what is used.

《The summary of the liquid crystal display device with contact panel of the present invention》

The liquid crystal display device with contact panel of the present invention is that possess in the identification side of VA mode-type liquid crystal cells tool There is the liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates of transparency conducting layer, its feature exists In,

As described above, the liquid crystal display device with contact panel of the present invention is characterised by possessing VA mode-type liquid crystal Display unit, by using the VA mode-type liquid crystal displays, with the conventional band using IPS mode-type liquid crystal displays The liquid crystal display device for having contact panel is compared, and improves front contrast.

From the viewpoint of the effect for changing, improving above-mentioned contrast from phase difference value when suppressing to be heat-treated, above-mentioned optics The glass transition temperature Tg of compensation film is needed for more than 155 DEG C.If less than 155 DEG C, the heat after transparency conducting layer is formed The variation of the phase difference value caused by the disorder of the polymer molecule of optical compensation films can be produced in processing, under optical compensation function Drop, can not obtain the excellent front contrast as VA mode-type liquid crystal inherent features.

In addition, from the viewpoint of optical and physics sexual function is improved, various add is added in above-mentioned optical compensation films Add agent, but, it is necessary to meet the scope of above-mentioned glass transition temperature in the state of containing them.If for example, addition plasticizer Deng then glass transition temperature declines also according to its species and addition sometimes, needs to pay attention in design.

Above-mentioned glass transition temperature Tg can use such as Seiko Instruments strains formula according to JIS K-7121 The differential scanning calorimetry (DSC) DSC220 of commercial firm is measured and obtained.As specific method, by 10mg or so sample film Be fixed on container, under conditions of nitrogen flow 50ml/min, with 20 DEG C/min from room temperature to 250 DEG C and keep 10 minutes (the 1st scanning), then it is cooled to 30 DEG C with 20 DEG C/min speed and keeps 10 minutes (the 2nd scanning), and then, with 20 DEG C/min is warming up to 250 DEG C (the 3rd times scanning), DSC curve is made, vitrifying is obtained by the DSC curve of the 3rd scanning of gained Transition temperature Tg.

And then as described above, by it is further suppress heat treatment when phase difference value change for the purpose of, it is involved in the present invention Optical compensation films preferably comprise the phase difference with the structure represented by above-mentioned formula (3) and rise agent.

During present invention research, various researchs are carried out to general resin film, as a result, cellulose diacetate film Dimensional variations caused by humidity are big, if forming transparency conducting layer on the film, are produced in preservation and shrink, extend and produce Rupture of electrode etc., it is difficult to use.In addition, the phase difference of PET film is excessive and is difficult to as VA mode-type liquid crystal display devices Optical compensation films use.Similarly, the photoelastic coefficient of makrolon (PC) film is big, is similarly not suitable as VA mode-type liquid The optical compensation films of crystal device.And then the glass transition temperature Tg of acrylic resin film is low, is not suitable as the present invention Optical compensation films.

The composition ＞ of the liquid crystal display device with contact panel of the ＜ present invention

The liquid crystal display device with contact panel of the present invention is that possess in the identification side of VA mode-type liquid crystal cells tool There is the liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates of transparency conducting layer, its feature exists In the one-piece type touch panel module of polarization plates with above-mentioned transparency conducting layer is from above-mentioned VA mode-types liquid crystal cells to identification side Successively with optical compensation films of at least one side with transparency conducting layer, polarizer and diaphragm, and above-mentioned optical compensation films Glass transition temperature Tg be 155~250 DEG C in the range of, it is sub- that above-mentioned optical compensation films contain cyclic olefine resin, polyamides Any of amine system resin or polyarylate system resin, this is preferred from the viewpoint of control heat resistance and phase difference value.

Illustrate the composition of the liquid crystal display device with contact panel and the composition of comparative example of the present invention together with accompanying drawing.

Fig. 1 is the structure for representing the conventional liquid crystal display device with contact panel for possessing outer hung type touch panel module Into an example schematic diagram.

The liquid crystal display device 10 with contact panel as comparative example has with diaphragm in the one side of liquid crystal cells 1 The polarization plates P1 that T1 and optical compensation films T2 clamping polarizers 2 form, will have thereon on the two sides of conductive layer base material film 4 The touch panel module T of transparency conducting layer 5 and protective layer 6 is Nian Jie with above-mentioned polarization plates P1 via adhesive linkage 3, and then, in touch-control On panel module T front panel 7 is bonded via adhesive linkage 3.The another side of above-mentioned liquid crystal cells 1 has with optical compensation films T3 and guarantor The polarization plates P2 that cuticula T4 clamping polarizers 2 form.Polarization plates P1 sides are identification side, and polarization plates P2 sides are backlight side.Here, In general, above-mentioned liquid crystal cells 1 are IPS mode-types.

The liquid crystal display device 20 with contact panel of the present invention possesses with so-called Mid-cell types or embedded The one-piece type touch panel module of polarization plates of type structure, i.e. have in the one side of liquid crystal cells 1 with diaphragm T1 and optical compensation The polarization plates P1 that film T2 clamping polarizers 2 form, optical compensation films T2 is in its two surface side formed with transparency conducting layer 5.Pass through This composition is set to, compared with outer hung type the liquid crystal display device with contact panel can be thinned.Each film or interlayer Bonding be preferably suitably formed adhesive linkage 3 and carry out.

Similarly have with optical compensation films T3 and diaphragm T4 clamping polarizers 2 in the another side of above-mentioned liquid crystal cells 1 The polarization plates P2 formed.Here, above-mentioned liquid crystal cells 1 are VA mode-types.

In addition, above-mentioned formed to be minimum, can be arranged as required between each component functional layer (hard conating, intermediate layer, Antistatic backing, smooth layer, UV-absorbing layer, bending prevent layer etc.), hard conating is formed as the protective layer of film or is formed anti-quiet Electric layer is preferred embodiment.

The overall thickness of the one-piece type touch panel module of polarization plates involved in the present invention is not particularly limited, curved from preventing The viewpoints such as bent, good resistance value, treatability are set out, in the range of preferably 7~80 μm, more preferably 10~60 μm of scope It is interior.

Fig. 3 composition is to form transparency conducting layer 5 respectively as diaphragm T1 and the composition on optical compensation films T2 upper strata.

Fig. 4 composition is to form transparency conducting layer 5 respectively as diaphragm T1 upper strata and optical compensation films T2 lower floor Composition.

Fig. 5 composition is to form transparency conducting layer 5 as one layer and be configured at the composition of optical compensation films T2 lower floor.This The transparency conducting layer of kind situation is preferably to have the composition of X electrode pattern and Y electrode pattern across insulating barrier in layer.

Fig. 6 composition is to form transparency conducting layer 5 as one layer and be configured at the composition on optical compensation films T2 upper strata.Together Sample, transparency conducting layer now is that have the composition of X electrode pattern and Y electrode pattern across insulating barrier in layer.

Hereinafter, each key element of the one-piece type touch panel module of polarization plates to forming the present invention is described in detail.

(1) optical compensation films

In the range of the glass transition temperature Tg of optical compensation films involved in the present invention is 155~250 DEG C, as Tg Lower limit, it is necessary to for more than 155 DEG C.Optical compensation films usually contain resin, plasticizer, various additives and delustering agent etc., this In invention using the glass transition temperature Tg of the film completed be more than 155 DEG C as feature.

From the viewpoint of the phase difference of heat treatment when suppressing to be formed transparency conducting layer relative to film changes, above-mentioned glass Changing transition temperature Tg needs for more than 155 DEG C, is less than 250 DEG C as the upper limit of glass transition temperature Tg.If Tg is more than 250 DEG C, then cause adaptation, resistance to anti-thread breakage decline with the rising of internal stress sometimes.Therefore, in the present invention, will Glass transition temperature Tg be 250 DEG C untill optical compensation films as object.

For the preferred resin used in optical compensation films involved in the present invention, the glass transition as resin simple substance Temperature Tg is preferably more than 155 DEG C, and then, if the embodiment of phase difference, stability are considered, wherein preferably comprising cellulose esters It is any of resin, cyclic olefine resin, polyimides system resins or polyarylate system resin, further preferably cyclenes Any of hydrocarbon system resin, polyimides system resins or polyarylate system resin, particularly preferably contain cyclic olefine resin.

(1.1) cellulose esters system resin

When being contained in optical compensation films, the cellulose ester resin that glass transition temperature Tg is more than 155 DEG C is (following to be also referred to as For cellulose esters) be preferably cellulose low-grade fatty acid ester.Wherein from easily there is phase difference, size relative to the steady of humidity From the viewpoint of qualitative, preferably using mixed aliphatic esters such as cellulose-acetate propionate, cellulose acetate-butyrates.

Among above-mentioned, the low-grade fatty acid ester of the cellulose particularly preferably used is cellulose-acetate propionate (in the application Also referred to as CAP).

Cellulose-acetate propionate and cellulose acetate-butyrate have the acyl group of carbon number 2~4 as substituent, with second The substitution value of acyl group is X, using the substitution value of propiono or bytyry as Y when, preferably meet following formula (I)s and (II) simultaneously.

It is preferred that：

Formula (I) 2.0≤X+Y≤3.0,

Formula (II) 1.0≤X≤2.0 and 0.1≤Y≤1.0.

The assay method of the substitution value of above-mentioned acyl group can be measured according to ASTM-D817-96.

As cellulose-acetate propionate and the molecular weight of cellulose acetate-butyrate, preferably：Number-average molecular weight (Mn) is 100000 less than 180000, Mw be 200000 less than the scope that 360000, Mw/Mn is 1.8~2.0.

The number-average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose esters can be surveyed using high performance liquid chromatography It is fixed.Condition determination is as follows.

Solvent：Dichloromethane

Post：Shodex K806、K805、K803G

(connect the post of 3 Showa Denko K. K and use)

Column temperature：25℃

Sample solution concentration：0.1 mass %

Detector：RI Model 504 (GLScience company systems)

Pump：L6000 (Hitachi Ltd.'s system)

Flow：1.0ml/min

Calibration curve：Use utilization polystyrene standard STKstandard polystyrene (Tosoh Co. Ltd. systems) Mw= The calibration curve that 13 samples untill 500~1000000 obtain.13 samples preferably almost to use at equal intervals.

(1.2) cyclic olefine resin

As cyclic olefine resin, the polymer of various cycloolefin monomers can be used, preferably use there will be ENB Polymer obtained from the cycloolefin monomers homopolymerization or copolymerization of skeleton.

Hereinafter, the explanation of cycloolefin monomers used in the present invention is carried out.

Cyclic olefine resin involved in the present invention is preferably the cyclenes by being represented with following formulas (A-1) and (A-2) Hydrocarbon monomer carries out polymer obtained from homopolymerization or copolymerization.

Cycloolefin monomers with the structure represented by formula (A-1) are illustrated.

Formula (A-1)

(in formula (A-1), R¹~R⁴Hydrogen atom or halogen atom are represented independently of one another.Or expression can have contain Oxygen atom, nitrogen-atoms, sulphur atom or silicon atom linking group substituted or unsubstituted carbon number 1~30 alkyl, Or polar group.P represents 0~2 natural number.)

Above-mentioned polar group refers to the functional group that polarization is produced using the high atom of the electronegativity such as oxygen, sulphur, nitrogen, halogen.Make For above-mentioned polar group, it is former that carboxyl, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, amide groups, cyano group, halogen can be enumerated Son etc., these polar groups can also be bonded via linking groups such as methylene.In addition, can have containing oxygen atom, nitrogen-atoms, The alkyl of the substituted or unsubstituted carbon number 1~30 of the linking group of sulphur atom or silicon atom, such as carbonyl, ether, first Silylation ether, thioether group, imino group etc. have the carbon number that the organic group of the divalent of polarity turns into linking group and is bonded 1~30 alkyl etc. can also be enumerated as polar group.Among these, preferably carboxyl, hydroxyl, alkoxy carbonyl or aryloxy group Carbonyl, particularly preferably alkoxy carbonyl or aryloxycarbonyl, it is thought of as from deliquescent viewpoint when ensuring solution film-forming excellent Choosing.

Then, the cycloolefin monomers represented by formula (A-2) are illustrated.

Formula (A-2)

(in formula (A-2), R⁵Independently represent hydrogen atom, carbon number 1~5 alkyl or with carbon number 1~ The aIkylsilyl groups of 5 alkyl.R⁶Represent carboxyl, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, amide groups, cyano group, Fluorine atom, chlorine atom, bromine atoms or iodine atom.P represents 0~2 integer.)

In the present invention, by using substituent R as being represented such as formula (A-2)⁵And R⁶It is substituted in the ring of unilateral carbon Olefinic monomer, the symmetry of molecule are lost, or, with the resin and the mutual diffusion motion of additive when promoting solvent to volatilize And promote additive to be moved to the film surface of film, it is partially preferred from the viewpoint of from additive therefore.

R⁵The preferably alkyl of carbon number 1~3, R⁶Preferably carboxyl, hydroxyl, alkoxy carbonyl or aryloxycarbonyl, it is special Not You Xuanwei alkoxy carbonyl or aryloxycarbonyl, be also preferred from the viewpoint of dissolubility when ensuring solution film-forming.

Hereinafter, the formula (A-1) and the structure of (A-2) being specifically illustrated in the application, but be not limited in detail below Example.

It is by with there is being represented by above-mentioned formula (A-1) and (A-2) for ENB skeleton as cyclic olefine resin Structure cycloolefin monomers carry out homopolymerization or copolymerization obtained from polymer, such as following polymer can be enumerated.

(1) ring-opening polymerization polymer of cycloolefin monomers

(2) ring-opening copolymer of cycloolefin monomers and co-polymerized monomer

(3) the hydrogenation (co) polymer of the open loop (co) polymer of above-mentioned (1) or (2)

(4) the open loop (co) polymer of above-mentioned (1) or (2) is cyclized by Knut Fridell-Kerafyrm thatch reaction Afterwards, the (co) polymer that hydrogenation forms is carried out

(5) cycloolefin monomers and the saturated polymer of the compound containing unsaturated double-bond

(6) the add-on type (co) polymer of cyclic olefine monomer and its hydrogenation (co) polymer

(7) cyclic olefine monomer and methacrylate or the alternate copolymer with acrylate

The polymer of above-mentioned (1)~(7) can pass through any known method, such as Japanese Unexamined Patent Publication 2008-107534 Method described in publication, Japanese Unexamined Patent Publication 2005-227606 publications obtains.For example, used in the ring opening copolymer of above-mentioned (2) Catalyst or solvent urging described in the 0019th~0024 section of Japanese Unexamined Patent Publication 2008-107534 publications for example can be used Agent or solvent.Japanese Unexamined Patent Publication 2008-107534 public affairs for example can be used in the catalyst used in the hydrogenation of above-mentioned (3) and (6) Catalyst described in the 0025th~0028 section of report.The acidity used in the Knut Fridell of above-mentioned (4)-Kerafyrm thatch reaction The acid compound described in the 0029th section of Japanese Unexamined Patent Publication 2008-107534 publications for example can be used in compound.It is above-mentioned (5) catalyst used in the addition polymerization of~(7) for example can be used the 0058th of Japanese Unexamined Patent Publication 2005-227606 publications Catalyst described in~0063 section.The alternating copolymerization of above-mentioned (7) for example can be No. 2005-227606 by Japanese Unexamined Patent Publication Method described in the 0071st and 0072 section of publication is carried out.

Wherein, the polymer of preferably above-mentioned (1)~(3) and (5), the polymer of more preferably above-mentioned (3) and (5).

As preferred cyclic olefin polymer involved in the present invention, can enumerate with by following formulas (B-1) and formula (B-2) polymer of the construction unit represented.This cyclic olefine resin can only contain the knot represented by formula (B-1) Structure unit, only contain the construction unit represented by formula (B-2), each structure containing formula (B-1) and formula (B-2) The copolymer of unit.

The preferably only structure containing formula (B-2) or containing formula (B-1) and formula (B-2) both sides The resin of the copolymer of construction unit.It is high from the glass transition temperature height and transmissivity of the cyclic olefine resin as gained It is preferred from the aspect of excellent resin.

Formula (B-1)

(in formula (B-1), X is by-CH=CH- the groups represented or by formula：- CH₂CH₂- the group represented.R¹ ~R⁴Hydrogen atom is represented independently of one another；Halogen atom；There can be the substitution or not of the linking group comprising oxygen, nitrogen, sulphur or silicon The alkyl of substituted carbon number 1~30；Or polar group.P represents 0~2 natural number.)

Formula (B-2)

(in formula (B-2), X is by-CH=CH- the groups represented or by formula：- CH₂CH₂- the group represented.R⁵ The alkylsilyl groups of hydrogen atom, the alkyl of carbon number 1~5 or the alkyl with carbon number 1~5 are represented independently of one another Base.R⁶Represent that carboxyl, hydroxyl, alkoxy carbonyl, aryloxycarbonyl, amino, amide groups, cyano group, fluorine atom, chlorine atom, bromine are former Son or iodine atom.P represents 0~2 integer.)

In this specification, for manufacture method of the cyclic olefine resin involved by the application etc., Japanese Unexamined Patent Publication has been quoted The record of 2008-107534 publications, the description thereof will be omitted.

Cyclic olefine resin can be used alone or and use two or more.

For the preferred molecular weight of cyclic olefine resin involved in the present invention, preferably with above-mentioned gel permeation chromatography (GPC) number-average molecular weight (Mn) of the polystyrene conversion of measure for 8000~100000, more preferably 10000~ 80000, particularly preferably 12000~50000, weight average molecular weight (Mw) are 20000~300000, more preferably 30000 ~250000, particularly preferably 40000~200000 scope.

It is usually more than 110 DEG C, excellent as the glass transition temperature (Tg) of cyclic olefine resin involved in the present invention Elect 110~350 DEG C, more preferably 120~250 DEG C, particularly preferably 120~220 DEG C as.It it is more than 110 DEG C in Tg In the case of, due to being not easy to cause deformation because of the secondary operation such as use under the high temperature conditions or coating, printing, therefore it is excellent Choosing.

On the other hand, by the way that Tg is set into less than 350 DEG C, processing and forming can be avoided to become difficult situation, suppress due into Hot and resin deterioration possibility when type is processed.

In the range of the effect of the present invention is not damaged, such as Japanese Unexamined Patent Publication can be coordinated in cyclic olefine resin Specific hydrocarbon system resin or known thermoplastic described in 9-221577 publications, Japanese Unexamined Patent Publication 10-287732 publications Property resin, thermoplastic elastomer (TPE), rubber polymer, organic fine particles, inorganic particles etc., can also contain specific wavelength dispersion The additives such as agent, plasticizer, antioxidant, stripping accelerator, rubber particles, ultra-violet absorber.

In addition, cyclic olefine resin can preferably use commercially available product, as the example of commercially available product, by JSR Corp. with ARTON(ARTON：Registration mark) G, ARTON F, trade name as ARTONR and ARTON RX sell, they can be used.

(1.3) polyimides system resins

Polyimides system resins involved in the present invention carry out chemical imidization preferably by by polyimide precursor Obtained from by following formula (P1) represent polyimides system resins.

Formula (P1)

[polymerization of polyimide precursor]

The manufacture method of the polyimide precursor with the structure represented by formula (P1) used in the present invention described below An example.

First, in aggregation container using as the 2 of diamines, 2 '-bis- (trifluoromethyl) -4,4 '-benzidine (TFMB) it is dissolved in polymer solvent.Double (3,4- dicarboxyphenyis) the hexafluoro propionic acid two of 2,2- are gently added to the diamine solution The powder of acid anhydride (6FDA), using mechanical agitator -20~100 DEG C scope, preferably 20~60 DEG C scope stirring 1~ 72 hours.By using TFMB, 6FDA, it is seen that transmittance, the dissolubility of light improve.The molal quantity of diamines and tetracarboxylic dianhydride's Molal quantity is substantially added with equimolar.In addition, total monomer concentration during polymerization is 5~40 mass %, preferably 10~30 matter Measure %.By being polymerize in the monomer concentration scope, uniform and high polymerization degree polyimide precursor solution can obtain.If with Concentration less than above-mentioned monomer concentration scope is polymerize, it is likely that and the degree of polymerization of polyimide precursor will not be uprised fully, The polyimides system resins film finally given becomes crisp, not preferably.

As polymer solvent, it is not particularly limited, usable DMA, N, N- diethyl acetamides, N,N-dimethylformamide, METHYLPYRROLIDONE, hexamethyl phosphoramide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, 1, 3- dimethyl -2- imidazolidinones, 1,2- dimethoxy-ethanes-bis- (2- methoxy ethyls) ether, tetrahydrofuran, 1,4- TwoThe non-protonic solvents such as alkane, picoline, pyridine, acetone, chloroform, toluene, dimethylbenzene and phenol, orthoresol, The protonic solvents such as cresols, paracresol, orthomonochlorphenol, m-Chlorophenol, parachlorphenol.In addition, these solvents can be used alone, can also It is mixed with two or more.

[manufacture methods of polyimides system resins]

The polyimides system resins represented by formula (P1) can be by the de- of the polyimide precursor that method described above obtains Water ring-closure reaction (imidization reaction) is manufactured.Polyimides system resins obtained by imidization reaction use show more excellent The chemical imidization of different dimensional stability.Chemical imidization can use to be made up of the acid anhydrides and trimethylamine of organic acid Cyclodehydration agent (chemical imidization agent) carry out.For example, directly using polyimide precursor varnish or with solvent appropriateness After dilution, cyclodehydration reagent is put into wherein, is stirred 0.5~48 hour at 0~100 DEG C, preferably 20~60 DEG C, so as to Easily carry out imidizate.

As the acid anhydrides of the organic acid now used, be not particularly limited, can be used acetic anhydride, propionic andydride, maleic anhydride, Phthalic anhydride etc., from the viewpoint of cost and the easiness of post processing, preferably using acetic anhydride.In addition, as organic Tertiary amine, it is not particularly limited, pyridine, 1,5- lutidines, beta-picoline, γ-picoline, dimethyl can be used Pyridine, isoquinolin, triethylamine, N, accelerine etc..

When chemical imidization reacts, the usage amount of the acid anhydrides in cyclodehydration reagent is preferably the reason of polyimide precursor By 1~10 times mole of scope of dehydrating amount, the usage amount of the base catalyst in cyclodehydration reagent is preferred relative to acid anhydrides For 0.1~2 times mole of scope.If chemical imidization is carried out outside these scopes, it is likely that imidization reaction is endless Into, or separate out the unfinished polyimides system resins of imidizate in reaction solution and imidizate is still insufficient.

After imidizate terminates, reaction solution can be directly used in coating, or reaction solution can be added dropwise to largely Poor solvent in or poor solvent made an addition into reaction solution, by polyimides system resins separate out cleaning and except dereaction is molten Agent after the excessive chemical imidization agent of removing, is dried under reduced pressure in chemical imidization and obtains polyimides system tree The powder of fat.As workable poor solvent, as long as insoluble polyimides system resins, are not particularly limited, from Reaction dissolvent, chemical imidization agent compatibility and using dry easily remove from the viewpoint of, preferably using water, methanol, Ethanol, normal propyl alcohol, isopropanol etc..

The weight average molecular weight of polyimides system resins is not particularly limited, and preferably 5000~2000000, further preferably For 10000~1000000, more preferably 50000~500000.If weight average molecular weight is more than 5000, when film is made Sufficient intensity is can obtain, additionally, there are the trend that dimensional stability improves, therefore can obtain sufficient dimensional stability.Separately On the one hand, if less than 2000000, then solution viscosity will not become too high, be easily processed.It should illustrate, above-mentioned Weight-average molecular Amount refers to the value to be converted using the polyethylene glycol of SEC (SEC).

(1.3) polyarylate system resin

Polyarylate system resin involved in the present invention is preferably the poly- virtue containing bisphenol residue and aromatic dicarboxylic acid residue Ester system resin.

Bisphenol residue has the structure represented by formula (P2).

Formula (P2)

In formula (P2), it is the divalent group containing fluorine atom that X, which needs,.By the way that the X in formula (P2) is set to containing fluorine The divalent group of atom, can obtain heat resistance and visible ray regions and the wavelength region shorter than visible ray regions is (ultraviolet Line region) transmitance it is excellent, and with excellent anti-flammability than ever, and suppress the poly- of the xanthochromia caused by ultraviolet Aromatic ester resin.If X is the divalent group without fluorine atom, anti-flammability declines, and xanthochromia, light occur due to ultraviolet irradiation Line transmissivity declines.

Divalent group containing fluorine atom is for example represented by formula (P2a).

Formula (P2a)

In formula (P2a), R^1aAnd R^2aIt independently is trifluoromethyl (CF₃Base), difluoromethyl (CF₂H yls), single methyl fluoride (CH₂F yls) or fluorine atom.Among these, R^1aAnd R^2aPreferably trifluoromethyl.

R¹And R²Represent the substituent being bonded with the phenyl ring in formula (P2).

From it is industrial be readily available or be readily synthesized give the bis-phenol of the structure represented by formula (P2), formula (P2) In, R¹And R²It independently is alkyl, haloalkyl or the halogen atom that carbon number is 1~6.Among these, preferably chlorine is former Son, bromine atoms, methyl, ethyl, phenyl, cyclohexyl, more preferably bromine atoms, methyl.

P and q represents the substituent R being bonded with phenyl ring respectively¹And R²Quantity, independently be 0~4 integer.For example, p and When q is 0, represent all hydrogen atoms being bonded with phenyl ring in formula (P2) not by R¹And R²Substitution.When p is 2~4, multiple R¹ Can be the substituent or different substituents being mutually identical.When q is 2~4, multiple R²It can be mutually identical Substituent or different substituents.From the industrial knot for being readily available or being readily synthesized and give and represented by formula (P2) The bis-phenol of structure sets out, and p and q are preferably 0.

As the bis-phenol for giving the structure by formula (P2) expression, such as double (4- hydroxy phenyls) hexafluoros of 2,2- can be enumerated Double (3,5- dimethyl -4- hydroxy phenyls) HFC-236fas of propane (BisAF), 2,2-, the double (tetramethyl -4- hydroxyls of 2,2- Phenyl) HFC-236fa.From industrial be readily available, among these, preferably BisAF.During using BisAF, formula (P2) In, p=0, q=0, X=-C (CF₃)₂-.

In the present invention, bisphenol residue can also contain to remove in the range of the effect of the present invention is not damaged gives formula (P2) Structure bis-phenol beyond other bis-phenols residue.As the bis-phenol for giving this residue, for example, it is double to enumerate 2,2- Double (the 3- first of (4- hydroxy phenyls) propane (BisA), 2,2-bis(3-methyl-4-hydroxyphenyl) propane (BisC), 9,9- Base -4- hydroxy phenyls) fluorenes (BCF), double (3,5- dimethyl -4- hydroxy phenyls) propane of 2,2-, double (the 4- hydroxyls of 1,1- Phenyl) -1- diphenylphosphino ethanes, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 1,1- double (4- hydroxy phenyls) ethane, 1,1- Double (3,5- dimethyl -4- hydroxy phenyls) ethane, 1,1- double (3- methyl -4- hydroxy phenyls) ethane, double (4- hydroxyls Phenyl) methane, double (3,5- dimethyl -4- hydroxy phenyls) methane, double (3- methyl -4- hydroxy phenyls) methane, 1,1- Double (3,5- dimethyl -4- hydroxy phenyls) hexanes of double (4- hydroxy phenyls) hexanes, 1,1-.

In order to assign high flame retardant to polyarylate resin and further suppress the xanthochromia caused by ultraviolet, polyarylate resin Present in bisphenol residue entirety, be preferably 50~100 moles of % as the ratio shared by the bisphenol residue that formula (P2) represents, More preferably 80~100 moles of %, more preferably 100 moles of %.

Aromatic dicarboxylic acid residue preferably has the structure represented by formula (P3).By with being represented by formula (P2) Structure and the structure represented by formula (P3), can realize excellent heat resistance, anti-flammability and visible ray regions simultaneously With the suppression of the transmitance and the xanthochromia caused by ultraviolet of the wavelength region (ultraviolet range) shorter than visible ray regions. When aromatic dicarboxylic acid residue does not have the structure of formula (P2), the transmitance of short wavelength region (ultraviolet range) declines, Or the easy xanthochromia due to ultraviolet.For example, aromatic dicarboxylic acid be used only give formula (P3) not shown structure to benzene During dioctyl phthalate, the transmitance in the short wavelength region (ultraviolet range) of polyarylate resin declines, easily the xanthochromia because of ultraviolet.

Formula (P3)

In formula (P3), R³And R⁴Represent the substituent being bonded with the phenyl ring in formula (P3).

From it is industrial be readily available or be readily synthesized give the aromatic dicarboxylic acid of the structure represented by formula (P3), R³And R⁴It independently is alkyl, haloalkyl or the halogen atom that carbon number is 1~6.Among these, preferably chlorine, bromine, first Base, ethyl, phenyl, cyclohexyl, more preferably bromine, methyl.

R and s represents the quantity for the substituent being bonded with phenyl ring, independently is 0~4 integer.For example, when r and s is 0, table Show all hydrogen atoms being bonded with phenyl ring in formula (P2) not by R³And R⁴Substitution.When r is 2~4, multiple R³Can be mutual Phase identical substituent or different substituents.When s is 2~4, multiple R⁴Can be the substituent being mutually identical, Can be different substituents.

As the aromatic dicarboxylic acid for giving the structure by formula (P3) expression, such as diphenyl ether -2 can be enumerated, 2 ' - Dicarboxylic acids, diphenyl ether -2,3 '-dicarboxylic acids, diphenyl ether -2,4 '-dicarboxylic acids, diphenyl ether -3,3 '-dicarboxylic acids, Diphenyl ether -3,4 '-dicarboxylic acids, diphenyl ether -4,4 '-dicarboxylic acids.From industrial be readily available, among these, Preferably diphenyl ether -4,4 '-dicarboxylic acids.Diphenyl ether -4 are being used, during 4 '-dicarboxylic acids, in formula (P3), r=0, s =0.

In the present invention, aromatic dicarboxylic acid residue can also contain logical except giving in the range of effect of the present invention is not damaged The residue of other aromatic dicarboxylic acids beyond the aromatic dicarboxylic acid of the structure of formula (P3).As the fragrance for giving this residue Race's dicarboxylic acids, for example, terephthalic acid (TPA), M-phthalic acid, phthalic acid can be enumerated, wherein, preferably M-phthalic acid.It is logical Cross and use M-phthalic acid, the xanthochromia caused by ultraviolet can be suppressed.

In order to further suppress the xanthochromia caused by ultraviolet, aromatic dicarboxylic acid residue present in polyarylate resin is whole In body, aromatic dicarboxylic acid residue with the structure represented by formula (P3) (be during containing isophthalic acid residues with by The aromatic dicarboxylic acid residue of the structure that formula (P3) represents and isophthalic acid residues it is total) shared by ratio be preferably 35 ~100 moles of %, more preferably 50~100 moles of %, more preferably 80~100 moles of %, most preferably 100 rub You are %.

From the viewpoint of the tension fracture elongation rate of polyarylate resin, aromatic dicarboxylic acid present in polyarylate resin In residue entirety, it is preferably 35~100 to have the ratio shared by the aromatic dicarboxylic acid residue of the structure represented as formula (P3) Mole %, more preferably 100 moles of %.

Polyarylate resin involved in the present invention is preferably comprised for by the terminal groups of the end-capped of the molecule.If it will divide The acid number reduction of the end-capped of son, then polyarylate resin, it is difficult to decomposed by light.From the aspect of it can reduce acid number, Terminal groups are preferably monohydric phenol residue, unitary acyl chlorides residue, monohydric alcohol residue and/or monocarboxylic acid residue, more preferably unitary Phenol residue and monohydric alcohol residue.

In the present invention, in the range of the effect of the present invention is not damaged, aliphatic two can be contained in polyarylate resin The residue of alcohol, the residue of alicyclic diol, the residue of aliphatic dicarboxylic acid, the residue of alicyclic dicarboxylic acid.As aliphatic two Alcohol, for example, ethylene glycol, propane diols can be enumerated.As alicyclic diol, for example, Isosorbide-5-Nitrae-cyclohexane diol, 1 can be enumerated, 3- cyclohexane diols, 1,2- cyclohexane diols.As aliphatic dicarboxylic acid, for example, adipic acid, decanedioic acid can be enumerated.Make For alicyclic dicarboxylic acid, for example, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 1,3- cyclohexane cyclohexanedimethanodibasics, 1,2- hexamethylenes two can be enumerated Formic acid.

As the manufacture method of polyarylate resin involved in the present invention, interfacial polymerization, solution polymerization process can be enumerated The method reacted Deng the method reacted in organic solvent, or melt polymerization etc. with molten condition.From polymerism, obtained resin Outward appearance in terms of set out, be preferably used in organic solvent react, the interfacial polymerization that can especially react at low temperature.

From high tension fracture elongation rate is obtained, the weight average molecular weight of polyarylate system resin is preferably set to more than 12000, More preferably it is set to more than 50000.

(2) phase difference rises agent

Described phase difference rises the compound that agent refers to have following function in the application：Relative in optical compensation films The mass parts of resin 100 used contain the phase difference value Rt of the thickness direction of the optical compensation films of the mass parts of compound 3 (23 Determined under DEG C 55%RH, wavelength 590nm) more than 1.1 times are shown compared with the optical compensation films for being not added with the compound Value.

Phase difference involved in the present invention rises agent and is not particularly limited, such as previously known Japanese Unexamined Patent Publication can be used Described in 2006-113239 publications (0143)~(0179) section with aromatic ring discoid compound (1,3, 5- triazine based compounds etc.), the bar-shaped chemical combination recorded of Japanese Unexamined Patent Publication 2006-113239 publications (0106)~(0112) section Pyrimidine compound, the Japanese Unexamined Patent Publication of thing, Japanese Unexamined Patent Publication 2012-214682 publications (0118)~(0133) section record Epoxy ester compounds that 2011-140637 publications (0022)~(0028) section is recorded etc., International Publication 2012/014571 Petchem that number (0044)~(0058) section is recorded etc..

Rise the characteristic needed for agent as phase difference involved in the present invention, excellent in compatibility, general with resin can be enumerated During film filming phase difference expression power it is excellent and it is resistance to separate out property excellent, high humility under with the discrepancy of moisture phase difference value It is excellent etc. to change patience, rises agent by adding the phase difference, in above-mentioned heat treatment, the orientation that phase difference rises agent itself is disorderly Disorderly, the phase difference from the compound is caused to change, so as to offset the phase difference variable from the polymer molecule for forming film It is dynamic, it is preferred.

From this point of view, following nitrogen-containing heterocycle compounds are preferably used to rise agent as phase difference.

(nitrogen-containing heterocycle compound)

It is preferably the nitrogen heterocyclic ring with the structure represented by following formulas (1) that phase difference involved in the present invention, which rises agent, Compound.

Nitrogen-containing heterocycle compound involved in the present invention is especially with the nitrogenous of the structure represented by following formulas (1) In heterocyclic compound, from the oriented tapes of molecular resin when rising function and heat treatment to phase difference come the sight that preferably interacts Point sets out, it is however preferred to have pyrrole ring, pyrazole ring, the nitrogen-containing heterocycle compound of triazole ring or imidazole ring.

＜ has the compound ＞ of the structure represented by formula (1)

Formula (1)

In above-mentioned formula (1), A₁、A₂Represent alkyl (methyl, ethyl, n-propyl, isopropyl, tertiary fourth independently of one another with B Base, n-octyl, 2- ethylhexyls etc.), cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane butylcyclohexyls etc.), aromatic hydrocarbon Ring or heteroaromatic.Wherein, preferably aromatic series hydrocarbon ring or heteroaromatic, particularly preferably 5 yuan or 6 yuan of aromatic series Hydrocarbon ring or heteroaromatic.

Be not limited to 5 yuan or 6 yuan of aromatic series hydrocarbon ring or the structure of heteroaromatic, for example, can enumerate phenyl ring, pyrrole ring, Pyrazole ring, imidazole ring, 1,2,3- triazole rings, 1,2,4- triazole rings, tetrazole ring, furan nucleus,It is azoles ring, differentAzoles ring, It is diazole ring, differentDiazole ring, thiphene ring, thiazole ring, isothiazole ring, Thiadiazole, different Thiadiazole etc..

By A₁、A₂There can be substituent with B 5 yuan or 6 yuan of the aromatic series hydrocarbon rings or heteroaromatic represented, as The substituent, such as halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), alkyl (methyl, ethyl, just can be enumerated Propyl group, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyls etc.), cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane basic rings Hexyl etc.), alkenyl (vinyl, acrylic etc.), cycloalkenyl group (2- cyclopentene -1- bases, the dilute -1- bases of 2- hexamethylenes etc.), alkynes Base (acetenyl, propargyl etc.), aromatic cyclic hydrocarbon group (phenyl, p-methylphenyl, naphthyl etc.), aromatic heterocycle (2- pyrroles Base, 2- furyls, 2- thienyls, pyrrole radicals, imidazole radicals,Oxazolyl, thiazolyl, benzimidazolyl, benzoOxazolyl, 2- Benzothiazolyl, pyrazoline ketone group, pyridine radicals, pyriconyl, 2- pyrimidine radicals, triazine radical, pyrazolyl, 1,2,3- triazolyls, 1,2,4- triazolyls,It is oxazolyl, differentOxazolyl, 1,2,4-Di azoly, 1,3,4-Di azoly, thiazolyl, different thiophene Oxazolyl, 1,2,4- thiadiazolyl groups, 1,3,4- thiadiazolyl groups etc.), cyano group, hydroxyl, nitro, carboxyl, alkoxy (methoxyl group, second Epoxide, isopropoxy, tert-butoxy, n-octyloxy, 2- methoxy ethoxies etc.), aryloxy group (phenoxy group, 2- methylenedioxy phenoxies Base, 4- tert-butyl benzenes epoxide, 3- nitro-phenoxies, 2- Tetradecanoylamino phenoxy groups etc.), acyloxy (formyloxy, Acetoxyl group, new pentane acyloxy, stearoyl-oxy, benzoyloxy, p-methoxyphenyl carbonyloxy group etc.), amino (amino, first Base amino, dimethylamino, anilino-, N- metlyl-phenylamines base, diphenyl amino etc.), acyl amino (Formylamino, second Acyl amino, valeryl amino, lauroyl amino, benzoyl-amido etc.), alkyl and arlysulfonylamino (methyl Sulfuryl amino, butyl sulfuryl amino, phenyl sulfonyl amino, 2,3,5- trichlorophenyls sulfuryl amino, p-methylphenyl Sulfuryl amino etc.), sulfydryl, alkyl sulfenyl (methyl mercapto, ethylmercapto group, n-hexadecyl sulfenyl etc.), artyl sulfo (phenyl sulphur Base, rubigan sulfenyl, m-methoxyphenyl sulfenyl etc.), sulfamoyl (N- ethylsulfamovls, N- (3- dodecyls Epoxide propyl group) sulfamoyl, N, N- DimethylsuIfamoyls, N- acetylsulfamoyls, N- benzoyls sulfamoyl, N- (N '-phenylcarbamoyl) sulfamoyl etc.), sulfo group, acyl group (acetyl group, valeryl benzoyl etc.), amino Formoxyl (carbamoyl, N- methylcarbamoyls, N, N- formyl-dimethylaminos, N, N- bis--n-octyl amino Formoxyl, N- (methyl sulphonyl) carbamoyl etc.) etc. each group.

In above-mentioned formula (1), A₁、A₂Phenyl ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- triazole rings or 1 are represented with B, During 2,4- triazole ring, can obtain optical characteristics changes excellent effect and the optical compensation films of excellent in te pins of durability, therefore is excellent Choosing.

In above-mentioned formula (1), T₁And T₂Independently of one another represent pyrrole ring, pyrazole ring, imidazole ring, 1,2,3- triazole rings or 1,2,4- triazole rings.Among these, the variation of phase difference when can obtain being heat-treated when being pyrazole ring, triazole ring or imidazole ring Inhibition is especially excellent and resin combination of excellent in te pins of durability, therefore is preferred, particularly preferably pyrazole ring.By T₁And T₂ The pyrazole ring of expression, 1,2,3- triazole rings or 1,2,4- triazole rings, imidazole ring can also be dynamic isomers.Pyrrole described below Cough up the concrete structure of ring, pyrazole ring, imidazole ring, 1,2,3- triazole rings or 1,2,4- triazole rings.

In formula, ※ is represented and the L in formula (1)₁、L₂、L₃Or L₄The position of bonding.R⁵Represent that hydrogen atom or non-aromatic take Dai Ji.As by R⁵The non-aromatic substituent of expression, it can enumerate and the A in above-mentioned formula (1)₁In the substituent that can have The same group of non-aromatic substituent.By R⁵When the substituent of expression is the substituent with aromatic group, A₁With T₁Or B With T₁Become easily to distort, A₁, B and T₁The interaction with resin can not be formed, therefore, it is difficult to suppress the variation of optical characteristics. In order to improve the variation inhibition of optical characteristics, R⁵Preferably hydrogen atom, the alkyl of carbon number 1~5 or carbon number 1~ 5 acyl group, particularly preferably hydrogen atom.

In above-mentioned formula (1), T₁And T₂Can have substituent, as the substituent, can enumerate with above-mentioned formula (1) A₁And A₂The same group of the substituent that can have.

In above-mentioned formula (1), L₁、L₂、L₃And L₄Represent the linking group of singly-bound or divalent independently of one another, via 2 with Under atom connect 5 yuan or 6 yuan of aromatic series hydrocarbon ring or heteroaromatic.Refer to form connection via the atoms of less than 2 In the atom of group between the substituent of connection existing minimum atomicity.The divalent for being less than 2 as connection atomicity Linking group, it is not particularly limited, is 2 in alkylidene, alkenylene, alkynylene, O, (C=O), NR, S, (O=S=O) The linking group of valency, or represent they combining 2 linking groups formed.R represents hydrogen atom or substituent.Represented by R Substituent example include alkyl (methyl, ethyl, n-propyl, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyls etc.), Cycloalkyl (cyclohexyl, cyclopenta, 4- n-dodecane butylcyclohexyls etc.), aromatic cyclic hydrocarbon group (phenyl, p-methylphenyl, naphthyl Deng), aromatic heterocycle (2- furyls, 2- thienyls, 2- pyrimidine radicals, 2-[4-morpholinodithio base, 2- pyridine radicals etc.), cyanogen Base etc..By L₁、L₂、L₃And L₄The linking group of the divalent of expression can have substituent, as substituent, be not particularly limited, For example, it can enumerate and the A in above-mentioned formula (1)₁And A₂The same group of the substituent that can have.

Uprised by the flatness of the compound with the structure represented by above-mentioned formula (1), the interaction with resin Becoming strong, the variation of optical characteristics is suppressed, therefore, the L in above-mentioned formula (1)₁、L₂、L₃And L₄Preferably singly-bound or O, (C= O)-O, O- (C=O), (C=O)-NR or NR- (C=O), more preferably singly-bound.

In above-mentioned formula (1), n represents 0~5 integer.It is multiple in above-mentioned formula (1) when n represents more than 2 integer A₂、T₂、L₃、L₄It can be the same or different.N is bigger, has the compound and resin of the structure represented by above-mentioned formula (1) Interaction it is stronger, therefore the variation inhibition of optical characteristics is excellent, and n is smaller, more excellent with the compatibility of resin.Cause This, n is preferably 1~3 integer, more preferably 1 or 2 integer.

＜ has the compound ＞ of the structure represented by formula (2)

Compound with the structure represented by formula (1) is preferably the compound with the structure represented by formula (2).

Formula (2)

(in formula, A₁、A₂、T₁、T₂、L₁、L₂、L₃And L₄Each with the A in above-mentioned formula (1)₁、A₂、T₁、T₂、L₁、L₂、L₃With L₄It is synonymous.A₃And T₃Each represent and the A in formula (1)₁And T₁Same group.L₅And L₆Represent and the L in above-mentioned formula (1)₁ Same group.The integer of m tables 0~4.)

M is smaller, more excellent with the compatibility of resin, therefore m is preferably 0~2 integer, more preferably 0~1 integer.

＜ has the compound ＞ of the structure represented by formula (1.1)

Compound with the structure represented by formula (1) is preferably with the structure represented by following formulas (1.1) Triazole compounds.

Formula (1.1)

(in formula, A₁、B、L₁And L₂Represent and the A in above-mentioned formula (1)₁、B、L₁And L₂Same group.K represents 1~4 Integer.T₁Represent 1,2,4- triazole rings.)

And then the triazole compounds with the structure represented by above-mentioned formula (1.1) are preferably with by following formulas (1.2) triazole compounds of the structure represented.

Formula (1.2)

(in formula, Z represents the structure of following formulas (1.2a).Q represents 2~3 integer.At least two Z are relative to being replaced in At least one Z of phenyl ring is bonded to ortho position or meta.)

Formula (1.2a)

(in formula, R¹⁰Represent hydrogen atom, alkyl or alkoxy.P represents 1~5 integer.* the position being bonded with phenyl ring is represented Put.T₁Represent 1,2,4- triazole rings.)

Compound with the structure represented by above-mentioned formula (1), (2), (1.1) or (1.2) can also be formed hydrate, Solvate or salt.In addition, in the present invention, hydrate can contain organic solvent, in addition, solvate can contain water. That is, " hydrate " and " solvate " include the mixed solvent compound that water and organic solvent all contain.As salt, comprising with inorganic Or the acid-addition salts that organic acid is formed.As the example of inorganic acid, halogen acids (hydrochloric acid, hydrobromic acid etc.), sulfuric acid, phosphoric acid are included Deng in addition, being not limited to them.In addition, the example of organic acid can enumerate acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, lemon Acid, benzoic acid, alkyl sulfonic acid (Loprazolam etc.), allyl sulphonic acid (benzene sulfonic acid, 4- toluenesulfonic acids, 1,5- naphthalenedisulfonic acids etc.) Deng in addition, being not limited to them.Among these, preferably hydrochloride, acetate, propionate, butyrate.

As the example of salt, can enumerate acidic moiety present in parent compound by metal ion (such as alkali metal salt, Such as sodium or sylvite, alkali salt, such as calcium or magnesium salts, ammonium salt alkali metal ion, alkaline-earth metal ions or aluminium ion etc.) Substitution, or the salt formed during organic base (monoethanolamine, diethanol amine, triethanolamine, morpholine, piperidines etc.) is adjusted to, in addition, unlimited Due to them.Among these, preferably sodium salt, sylvite.

The example for the solvent that solvate contains includes any one of in general organic solvent.Specifically, can enumerate Alcohol (such as methanol, ethanol, 2- propyl alcohol, n-butyl alcohol, 1- methoxy-2-propanols, tert-butyl alcohol), ester (such as ethyl acetate), Hydrocarbon (such as toluene, hexane, heptane), ether (such as tetrahydrofuran), nitrile (such as acetonitrile), ketone (acetone) etc..Preferably alcohol (such as Methanol, ethanol, 2- propyl alcohol, n-butyl alcohol, 1- methoxy-2-propanols, the tert-butyl alcohol) solvate.These solvents can be The solvent that partial crystallization after the reaction dissolvent used during the synthesis of above-claimed cpd or synthesis uses when refined, Huo Zheye It can be their mixing.

Furthermore, it is possible to the form containing solvent of more than two kinds or comprising water and solvent is (for example, water and alcohol simultaneously (for example, methanol, ethanol, tert-butyl alcohol etc.) etc.).

Furthermore it is possible to will have by above-mentioned formula (1), (2), (1.1) or (1.2) represent structure compound with without Water or solvent, the form addition of salt, can also form hydrate, solvate or salt in the optical compensation films of the present invention.

The molecular weight of compound with the structure represented by above-mentioned formula (1), (2), (1.1) or (1.2) is not special Limitation, it is smaller, it is more excellent with the compatibility of resin, it is bigger, relative to the variation inhibition of the optical value of ambient humidity change It is higher, thus preferably 150~2000 scope, more preferably 200~1500, more preferably 300~1000 scope.

And then nitrogen-containing heterocycle compound involved in the present invention is particularly preferably with the knot represented by following formulas (3) The compound of structure.

Formula (3)

By Ar₁And Ar₂The aromatic series hydrocarbon ring or heteroaromatic of expression be respectively preferably enumerated in formula (1) 5 yuan or The aromatic series hydrocarbon ring or heteroaromatic of 6 yuan of person.In addition, as Ar₁And Ar₂Substituent, can enumerate with by above-mentioned formula (1) the same substituent of the substituent that shows in the compound of the structure represented.

As R₁Concrete example, halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), alkyl (first can be enumerated Base, ethyl, n-propyl, isopropyl, the tert-butyl group, n-octyl, 2- ethylhexyls etc.), acyl group (acetyl group, valeryl benzoyl Base etc.), sulfonyl (such as methyl sulphonyl, ethylsulfonyl etc.), alkoxy carbonyl (such as methoxycarbonyl), aryloxy group carbonyl Base (such as phenyloxycarbonyl etc.) etc..

Q represents 1 or 2, n and the integer of m expressions 1~3.

The compound with 5 yuan or 6 yuan of aromatic series hydrocarbon ring or heteroaromatic used in the present invention is preferably it In have by above-mentioned formula (1), (2), (1.1), (1.2) represent structure compound, more preferably further have by leading to The compound for the structure that formula (3) represents.The workable aromatic series hydrocarbon ring or fragrance with above-mentioned 5 yuan or 6 yuan in the present invention The compound of race's heterocycle can enumerate the compound described in [0140]~[0214] section of International Publication No. 2014/109350 As concrete example.It should illustrate, the present invention is not by any restriction of the concrete example.In addition, concrete example can be tautomerism Body, hydrate, solvate or salt can also be formed.

The synthetic method for the compound enumerated in above-mentioned concrete example similarly can refer to International Publication No. 2014/109350 [0215]~[0239] section.

Application method ＞s of the ＜ on the compound with the structure represented by formula (1)~(3)

The compound with the structure represented by above-mentioned formula (1)~(3) involved in the present invention can be adjusted to appropriate Measure and be contained in optical compensation films, as addition, in optical compensation films, preferably comprise 0.1~10 mass %, particularly preferably Containing 1~5 mass %, particularly preferably containing 2~5 mass %.Addition according to the species of resin, the species of the compound without Together, but the addition of required phase difference value can be shown according to the optical compensation films of the present invention to determine optimum value.If In the range of being somebody's turn to do, then the mechanical strength of the optical compensation films of the present invention will not be damaged, phase difference variable can be also reduced in heat treatment It is dynamic.

In addition, the adding method as the compound with the structure represented by above-mentioned formula (1)~(3), can be in shape Added into the resin of optical compensation films with powder, the tree to form optical compensation films can also be made an addition to after solvent is dissolved in In fat.

(3) other additives

In optical compensation films involved in the present invention, in addition to above-mentioned additive, plasticizer, anti-oxidant can also be contained Agent, delustering agent, light stabilizer, optical anisotropy controlling agent, antistatic agent, remover etc..Main additive is recorded below Detailed content.

[plasticizer]

In general, plasticizer refers to the additive having the effect that：Generally by being added in macromolecule to improve Fragility declines melt viscosity or assigns flexibility, but makes the glass transition of optical compensation films due to addition sometimes Temperature Tg declines, therefore preferably makes by the scope of the glass transition temperature Tg control of optical compensation films within the scope of the present invention With.

In the present invention, as plasticizer, known phthalic acid ester system, fatty acid ester system, trimellitate can be used The plasticizer such as system, phosphate system, Polyester, sugar ester system, acrylic acid series polymeric compounds.

In the range of the addition of plasticizer is preferably 0.1~10 mass % relative to resin, more preferably 0.5~ In the range of 5 mass %.

[ultra-violet absorber]

Optical compensation films involved in the present invention can contain ultra-violet absorber.

As ultra-violet absorber, such as dihydroxy benaophenonel based compound, BTA based compound, bigcatkin willow can be enumerated Acid esters based compound, benzophenone based compound, cyanoacrylate based compound, nickel complex salt based compound etc., it is preferably The few BTA based compound of color.In addition, it is also preferred that use Japanese Unexamined Patent Publication 10-182621 publications, Japanese Unexamined Patent Publication Macromolecule described in ultra-violet absorber, Japanese Unexamined Patent Publication 6-148430 publications described in 8-337574 publications is purple Ultraviolet absorbers.

As the ultra-violet absorber used in the present invention, go out from the viewpoint of polarizer, liquid crystal display deterioration is prevented Hair, the absorbability from below wavelength 370nm ultraviolet is excellent and the display of liquid crystal display from the viewpoint of, preferably Possesses the few characteristic of the absorption of visible ray more than wavelength 400nm.

In the range of the addition of ultra-violet absorber is 0.1~5 mass % preferably with respect to resin, more preferably In the range of 0.5~5 mass %.

As enumerate BTA system ultra-violet absorber useful in the present invention, for example, can enumerate 2- (2 '-hydroxyl -5 ' - Aminomethyl phenyl) BTA, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl phenyl) BTA, 2- (2 '-hydroxyl - 3 '-tert-butyl group -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyl -3 ', 5 '-di-t-butyl phenyl) -5- chlorine BTA, 2- [2 '-hydroxyls -3 '-(3 ", 4 ", 5 ", 6 "-tetrahydric phthalimide methyl) -5 '-methylbenzene Base] BTA, 2,2- di-2-ethylhexylphosphine oxides [4- (1,1,3,3- tetramethyl butyls) -6- (2H- BTA -2- bases) Phenol], 2- (2 '-hydroxyl -3 '-tert-butyl group -5 '-aminomethyl phenyl) -5- chlorobenzotriazoles, 2- (2H- benzos three Azoles -2- bases) -6- (straight chain and side chain dodecyl) -4- methylphenols, 3- [3- tertiary butyl-4-hydroxies -5- (chloro- 2H- BTAs -2- bases) phenyl] [(5- is chloro- by 3- tertiary butyl-4-hydroxies -5- with 3- for octyl propionate 2H- BTA -2- bases) phenyl] propionic acid 2- ethylhexyls mixture etc., but be not limited to them.

In addition, as commercially available product, preferably use " TINUVIN 928 ", " TINUVIN 171 ", " TINUVIN 326 ", " TINUVIN 328 " (being above trade name, BASF Japan company systems).

[antioxidant]

Antioxidant is such as with using the halogen of residual solvent in optical compensation films, the phosphoric acid of phosphate plasticizer The effect for postponing or preventing optical compensation films from decomposing, therefore preferably contain in film.

As this antioxidant, preferably using the compound of hindered phenol series, such as 2,6- di-t-butyl -s can be enumerated Paracresol, pentaerythrite base-four (3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester), triethylene glycol-bis- (3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester), 1,6-HD-bis- (3- (bis--uncles of 3,5- Butyl -4- hydroxy phenyls) propionic ester), 2,4- it is double-(just pungent sulfenyl) -6- (4- hydroxyl -3,5- di-t-butyl benzene Amido) -1,3,5- triazines, double (3- (the 3,5- di-t-butyl -4- hydroxy phenyls) propionic acid of 2,2- thiodiethylenes Ester), octadecyl -3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester, N, N '-hexamethylene bis (3,5- Di-t-butyl -4- hydroxy-hydrocineamides), (the 3,5- di-t-butyl -s of 1,3,5- trimethyls -2,4,6- three 4- hydroxybenzyls) benzene, three-(3,5- di-t-butyl -4- hydroxybenzyls)-isocyanuric acid esters etc..

Particularly preferred 2,6- di-t-butyl -s paracresol, (3- (the 3,5- di-t-butyl -s of pentaerythrite base-four 4- hydroxy phenyls) propionic ester), triethylene glycol-bis- (3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester). In addition it is also possible to and with the hydrazine system such as such as N, N '-bis- (3- (3,5- di-t-butyl -4- hydroxy phenyls) propiono) hydrazine Matal deactivator, the phosphorus system processing stabilizers such as three (2,4- di-t-butyls phenyl) phosphite esters.

In the range of the addition of antioxidant is preferably 0.1~5 mass % relative to resin, more preferably 0.5 In the range of~3 mass %.

[delustering agent]

In order to prevent that made film from scratching in processing or transporting is deteriorated, it is also preferred that in optics involved in the present invention Compensate and particulate is added in film as delustering agent.

As particulate, particulate, the particulate of resin of inorganic compound can be enumerated.Example as the particulate of inorganic compound Son, can enumerate silica, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talcum, clay, calcined kaolin, Baked calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate etc..Particulate contains silicon It is preferred that particularly preferably silica.

The average grain diameter of the primary particle of particulate is preferably more preferably 10~300nm in the range of 5~400nm In the range of.They mainly can be contained in the form of 2 agglomerates in the μ m of particle diameter 0.05~0.3, as long as it is average Particle in the range of 80~400nm of particle diameter, then it is also preferred that not condensing and being contained in the form of primary particle.

The content of these particulates in film is preferably particularly preferably 0.05~0.5 matter in the range of 0.01~1 mass % In the range of amount %.

For example, the particulate of silica can use such as AEROSIL R972, R972V, R974, R812,200,200V, 300th, R202, OX50, TT600 (being above Japanese AEROSIL Co. Ltd. systems) trade name are commercially available and use.

The particulate of zirconium oxide can use such as AEROSIL R976 and R811 (being above Japanese AEROSIL Co. Ltd. systems) Trade name it is commercially available and use.

As the example of the particulate of resin, organic siliconresin, fluororesin and acrylic resin can be enumerated.It is preferred that organosilicon tree Fat, particularly preferably have tridimensional network particulate, such as can use TOSPEARL103, TOSPEARL105, TOSPEARL108, TOSPEARL120, TOSPEARL145, TOSPEARL 3120 and TOSPEARL240 are (organic for Toshiba above Silicon Co. Ltd. system) trade name it is commercially available and use.

Among these, AEROSIL 812, AEROSIL R972V rub due to being reduced while the mist degree of film is kept as into low It is big to wipe the effect of coefficient, therefore particularly preferably uses.

In the range of the coefficient of kinetic friction of optical compensation films involved in the present invention preferably at least one side is 0.2~1.0.

(4) manufacture method of optical compensation films

As the manufacture method of optical compensation films involved in the present invention, to be said using the example of cyclic olefine resin It is bright.

(4.1) solution curtain coating film method

The manufacture method of the optical compensation films of the present invention is preferably film-made method (hereinafter also referred to solution curtain coating with solution curtain coating Method) carry out, can be suitably using known method.

As the solvent used in solution casting method, such as the chlorine series solvent such as chloroform, dichloromethane can be enumerated；Toluene, two The fragrant family solvents such as toluene, benzene and their mixed solvent；The alcohol systems such as methanol, ethanol, isopropanol, n-butanol, 2- butanol are molten Agent；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide (DMSO), twoAlkane, cyclohexanone, four Hydrogen furans, acetone, methyl ethyl ketone (MEK), ethyl acetate, Anaesthetie Ether etc..These solvents can be used only a kind, can also And use two or more.

The solvent used in the present invention is preferably the mixed solvent of good solvent and poor solvent, for the good solvent, for example, As chlorine-based organic solvent, dichloromethane can be enumerated, as chlorine-free organic solvent, methyl acetate, ethyl acetate, second can be enumerated Sour pentyl ester, acetone, methyl ethyl ketone, tetrahydrofuran, 1,3- dioxolanes, 1,4- bis-Alkane, cyclohexanone, Ethyl formate, 2, 2,2- trifluoroethanols, 2,2,3,3- hexafluoro -1- propyl alcohol, the fluoro- 2- propyl alcohol of 1,3- bis-, 1,1,1,3,3,3- hexafluoros - 2- methyl-2-propanols, 1,1,1,3,3,3- hexafluoro -2- propyl alcohol, the fluoro- 1- propyl alcohol of 2,2,3,3,3- five, nitro second Alkane, methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol etc., wherein, preferably dichloromethane.

Poor solvent is preferably alcohol series solvent, and the alcohol series solvent is selected from methanol, ethanol and butanol, this from improve fissility and It is preferred that can carry out from the viewpoint of high speed curtain coating.

In the present invention, if mixed solvent, then it is the upper of more than 55 mass % preferably to use relative to solvent entire amount Good solvent is stated, more preferably using more than 70 mass %, further preferably uses more than 80 mass %.

When manufacturing optical compensation films with solution casting method, such as prepare containing with above-mentioned cyclic olefine resin and by formula (3) compound of structure and the rubber cement of solvent represented, the rubber cement is cast on supporter.

That is, preferably with following process：At least make cyclic olefine resin and the chemical combination with the structure represented by formula (3) The process that thing dissolves and prepares rubber cement；Rubber cement is cast the process in banding or the metal support of drum type；By the glue of curtain coating Starch the process dried in the form of tablet (ウェ Block)；The process peeled off from metal support；Stretching or the process for keeping width； The process being further dried；The process that the film roll of completion is taken.

In solution casting method, for the concentration of the cyclic olefine resin in rubber cement, concentration is higher, can more reduce be cast in Drying load after metal support and be preferred, if but cyclic olefine resin excessive concentration, load increase during filtering, Filtering accuracy is deteriorated.As the concentration for having the two effects concurrently, preferably 10~35 mass %, more preferably 15~25 Quality %.The metal support preferred pair surface being cast in (casting) process carries out minute surface finishing, excellent as metal support Choosing is used stainless steel band or has been carried out the drum that coating polishes to surface with casting.

The width of casting can be set to 1~4m.The surface temperature for being cast the metal support of process is appropriate at 0~100 DEG C Determine, more preferably 5~30 DEG C, below the temperature for being set as solvent not boiling and foaming.Temperature is higher, can more accelerate The rate of drying of tablet, therefore be preferred, but tablet can foam sometimes if residue is too high or flatness deteriorates.

In addition, tablet gelation is made by cooling to be also preferred side containing being peeled off in the state of a large amount of residual solvents from drum Method.Control the method for the temperature of metal support to be not particularly limited, have and blow the method for warm wind or cold wind, make warm water and metal branch The method of the backside contact of support body.Can efficiently it be conducted heat using warm water, therefore the temperature arrival of metal support is constant Time it is short, be preferred.

During using warm wind, it is contemplated that the Wen Duxiajiang of the tablet caused by the evaporation latent heat of solvent, sometimes using solvent Warm wind more than boiling point, and foaming is prevented while the temperature in use wind higher than target temperature.

Particularly preferably from be cast to peel off during change supporter temperature and dry wind temperature, efficiently enter Row drying.

In order that optical compensation films show good flatness, residual solvent amount when peeling off tablet from metal support Preferably 10~150 mass %, more preferably 20~40 mass % or 60~130 mass %, particularly preferably 20~30 Quality % or 70~120 mass %.

Residual solvent amount is defined by following formula.

Residual solvent amount (quality %)={ (M-N)/N } × 100

Should illustrate, M be in the mill or manufacture after any time extraction tablet or film obtained by sample quality, N It is the quality after M is heated 1 hour at 115 DEG C.

In addition, in the drying process of optical film, preferably tablet is peeled off from metal support, is further dried, makes residual Quantity of solvent is below 1 mass %, more preferably below 0.1 mass %, particularly preferably below 0~0.01 mass %.

In film drying process, typically using roller drying mode (tablet is alternately passed through in the multiple rollers configured up and down and Make its dry mode), while convey tablet in a manner of stenter on one side make its drying in the way of.

From the viewpoint of flatness, progress adjusting offset from film, optical compensation films involved in the present invention preferably enter Row stretching.

In the manufacture method of optical film involved in the present invention, preferably in long side direction and/or broadside or inclination Direction is stretched.

Stretched operation is segmented into the multistage and implemented.In addition, carry out it is biaxial stretch-formed when can carry out simultaneously twin shaft drawing Stretch, can also periodically implement.In this case, it is interim to refer to for example carry out the different drawing of draw direction successively Stretch, unidirectional stretching can also be divided into the multistage, and apply the stretching of different directions in either phase.

That is, for example, it is also possible to carry out following stretching step：

Stretch → → stretched in broadside stretching in long side direction → in long side direction and stretched in long side direction

Stretch → → stretched in broadside stretching in long side direction → in broadside and stretched in long side direction

In addition, simultaneously biaxial drawing is also contained in a direction stretching and the feelings that another direction is relaxed into tension force and shunk Condition.

In the range of residual solvent amount when stretching starts is preferably 2~50 mass %.

If the residual solvent amount is more than 2 mass %, thickness deviation diminishes, be from the viewpoint of flatness it is preferred, Within 50 mass %, then the concavo-convex reduction on surface, flatness improves, and is preferred.

In the manufacture method of optical compensation films involved in the present invention, required scope can also be turned into the thickness after stretching Mode in long side direction and/or broadside, preferably stretched in broadside.Although according to the species of resin without Together, when minimum Tg is set to TgL, highest Tg is set into TgH but in the glass transition temperature Tg by film, preferably exist The temperature range of (TgL-200 DEG C)~(TgH+50 DEG C) is stretched.If being stretched in said temperature scope, can drop Low tensile stress, therefore mist degree step-down.In addition, can obtain suppressing the generation of fracture, and the coloring of flatness, film itself is excellent The optical compensation films containing cyclic olefine resin.Draft temperature is more preferably in the scope of (TgL-150 DEG C)~(TgH+40 DEG C) Carry out.

, can be by having what is peeled off from supporter from branch in the manufacture method of optical compensation films involved in the present invention The film of support property is so that draw roll limits gait of march and is stretched in long side direction.The stretching ratio of long side direction is at 30~250 DEG C Temperature range is preferably 1.03~2.00 times, more preferably 1.10~1.80 times, more preferably 1.20~1.60 times.

When broadside is stretched, for example, it is preferable to using as described in Japanese Unexamined Patent Application 62-46625 publications It is such the width both ends of film is kept width with cloth gripper or needle plate in width whole drying process or part processing While make its dry method (being referred to as stenter mode), wherein it is preferred that using using cloth gripper stenter mode.

Width both ends are preferably being held in cloth gripper by the film or non-stretched film stretched in long side direction In the state of be directed into stenter, advanced together with stenter cloth gripper and meanwhile to width stretch.The drawing of width Stretch multiplying power to be not particularly limited, be preferably 1.03~2.00 times, more preferably 1.10~1.80 in 30~300 DEG C of temperature ranges Times, more preferably 1.20~1.60 times.

When being stretched to broadside, from the viewpoint of the flatness for improving film, preferably film broadside with 50~ 1000%/min draw speed is stretched.

If draw speed is more than 50%/min, flatness improves, furthermore it is possible to high speed processing film, therefore from life It is preferred from the viewpoint of production adaptability, within 1000%/min, then can be handled in the case where film is not broken, To be preferred.

In the range of preferred draw speed is 100~500%/min.Draw speed is defined by following formula.

Draw speed (%/min)=[(d₁/d₂) -1] × 100 (%)/t

(in above-mentioned formula, d₁Be stretching after resin film above-mentioned draw direction width dimensions, d₂It is the resin before stretching The width dimensions of the above-mentioned draw direction of film, t are the stretching required time (min).)

In stretching process, holding mitigation is generally carried out after the stretch.That is, this process preferably is entered to be about to film stretching successively Draw stage, by film keep in a stretched state keep the stage and by film stretching direction relax the mitigation stage.Keep In stage, the stretching under the stretching ratio that will reach in draw stage is kept with the draft temperature of draw stage.In the mitigation stage, After being stretching in draw stage is kept in the holding stage, the tension force for stretching is released, so as to relax stretching.The mitigation stage As long as carried out below the draft temperature of draw stage.

In addition, when incline direction stretches, Japanese Unexamined Patent Publication 2005-321543 publications and Japanese Unexamined Patent Publication can refer to 2013-120208 publications.

Next, the film after stretching is heated and makes its drying.When using hot blast etc., film is heated, it is also preferred that using setting The nozzle that used hot blast (wrap solvent-laden air, be mixed into the air of moisture) can be vented, prevents used hot blast Mixed method.Hot blast temperature is more preferably 40~350 DEG C of scope.In addition, drying time is preferably 5 seconds~30 minutes left sides The right side, more preferably 10 seconds~15 minutes.

In addition, heating and drying method is not limited to hot blast, for example, infrared ray, heating roller, microwave etc. can be used.From simplicity From the viewpoint of, preferably while to be configured to staggered roller transport membrane, while being dried with hot blast etc..It is molten in view of remaining Expansion and contraction in dosage, conveying etc., drying temperature is more preferably 40~350 DEG C of scope.

It is below 0.5 mass % preferably by film drying to residual solvent amount in drying process.

Coiling process is the process batched the film of gained and be cooled to room temperature.As long as the usually used coiling machine of coiling machine , for example, the constant program tension control method of constant tension method, constant-torque method, taper tension method, internal stress can be used Batched Deng method for coiling.

The thickness of optical compensation films involved in the present invention is different according to application target, usually 5~500 μm of model Enclose, preferably 10~150 μm of scope, for being preferably 10~80 μm during liquid crystal display device, it is contemplated that nearest slimming When be particularly preferably 10~40 μm of scope.

When the optical compensation films is formed less than 40 μm of film, it is however generally that, in order to maintain the performance of phase retardation film, it is necessary to Increase the content that phase difference rises the additives such as agent, although additive is oozed out as problem, involved in the present invention has The compound of the structure represented by formula (3) it is resistance to exudative excellent, therefore being capable of filming.

As long as the preparation of film thickness adjusts solid component concentration contained in rubber cement, die head in a manner of as required thickness The slit gap of nozzle, the extrusion pressure from die head, metal support speed etc..What is obtained in the above described manner is transparent The width of resin film is preferably 0.5~4m scope, more preferably 0.6~3m scope, more preferably 0.8~2.5m. Length is preferably batched in each 100~10000m of roller scope, more preferably 500~9000m scope, more preferably 1000~8000m scope.

Optical compensation films involved in the present invention can pass through the species of the polymer architecture used in suitably adjusting, additive Evaporated into residual when addition, stretching ratio, stripping and grade process conditions to realize required optical characteristics.

Optical compensation films involved in the present invention are by carrying out stretch processing or preferably by rising agent simultaneously containing phase difference Carry out stretch processing and there is required phase difference value.The phase difference value Rt of phase difference value Ro and thickness direction can be used in face Automatic birefringence meter Axo Scan (Axo Scan Mueller Matrix Polarimeter：Axo Metrix company systems), Wavelength in 590nm in the environment of 23 DEG C of 55%RH carries out three-dimensional refractive index measure, by the refractive index n of gained_x、n_y、n_zCalculate Go out.

When optical compensation films involved in the present invention are contained in VA type liquid crystal display devices, from the raising angle of visual field, contrast From the viewpoint of the identities such as degree, the phase difference in direction in faces preferably represented by following formula (i) and (ii), optical compensation films In the range of value Ro is 40~60nm, the phase difference value Rt of film thickness direction is in the range of 110~140nm.Optical compensation films can At least to adjust extensibility while being stretched to be adjusted to the scope of above-mentioned phase difference value in above-mentioned broadside by one side It is interior.

Formula (i)：Ro=(n_x- n_y)×d(nm)

Formula (ii)：Rt={ (n_x+n_y)/2-n_z}×d(nm)

(in formula (i) and formula (ii), n_xRepresent the refractive index of the direction x that direction refractive index is maximum in the face of film.n_yRepresent Refractive index of the direction in the direction y orthogonal with above-mentioned direction x in the face of film.n_zRepresent the refractive index in the thickness direction z of film. D represents the thickness (nm) of film.〕

In addition, in the face preferably when having carried out heat treatment in 1 hour for 150 DEG C direction for optical compensation films involved in the present invention Phase difference value Ro variation be ± 3.0% in the range of, the phase difference value Rt of thickness direction variation is ± 4.0% scope It is interior.

The heat treatment can be obtained by following formula places film sample 1 hour in the thermostats such as baking box at 150 DEG C The variation of front and rear phase difference value.

Phase difference value Ro or Rt variation=(the Ro values or Rt values before Ro values or Rt values-heat treatment after heat treatment)/ (Ro values or Rt values before heat treatment) } × 100 (%)

In order to which the variation of the variation of the Ro values caused by above-mentioned heat treatment of optical compensation films and Rt values is controlled above-mentioned In the range of, the addition (species, addition) that selection and above-mentioned phase difference by resin involved in the present invention rise agent carries out group Conjunction is effective method, can be by appropriately combined and could be adjusted to reach.

(4.2) casting film method is melted

The manufacture method of the optical compensation films of the present invention can also (hereinafter also referred to melting be flowed by melting casting film method Prolong method) carry out.

The situation that optical compensation films involved in the present invention are manufactured by melting the tape casting is illustrated.

[melt granules manufacturing process]

The composition containing resin used in melting extrusion is generally preferably kneaded and granulated in advance.

Granulating use known to method, for example, can by dry resin and additive with feeding machine supply to Extruder, using uniaxially or biaxially extruder be kneaded, be extruded as from die head it is linear, carry out water cooling or air cooling, cut.

For raw material, it is important to be pre-dried before extrusion in terms of raw material decomposition is prevented.Especially Sometimes the easy moisture absorption of resin, therefore preferably dried 3 hours at 70~140 DEG C with dehumidifying air drier, vacuum drier in advance More than, it is below 200ppm to make moisture rate, and then, it is below 100ppm.

Additive can be supplied to extruder with reference to extruder, can also be supplied respectively with different feeding machines.It is anti-oxidant A small amount of additive such as agent is preferably pre-mixed in advance in order to equably mix.

The mixing of antioxidant can be mixed with solid matter, as needed can also be dissolved in antioxidant in advance molten Agent, it is set to be impregnated in thermoplastic resin and mix, or, it can also be sprayed and be mixed.

Vacuum nauta mixer etc. can be dried and mix simultaneously, therefore be preferred.In addition, with from feeding machine Portion, die head outlet etc. air contact when, be preferably set to dehumidified air, the N through dehumidifying₂Under the environment such as gas.

Extruder preferably can with suppress shearing force and do not make resin deterioration (molecular weight and molecular weight, coloring, gel generation etc.) Mode granulates, and processes at low temperature as far as possible.For example, in the case of biaxial extruder, preferably using the screw rod of deep channel type, edge Equidirectional rotates.From the uniformity of mixing, preferably engagement type.

Film manufacture is carried out using the particle obtained in the above described manner.Can also be without granulating and by the powder of raw material Directly supplied with feeding machine to extruder, directly carry out film manufacture.

[process for extruding molten mixture from die head to chill roll]

First, melting temperature Tm when extruding made particle using the extruder of uniaxially or biaxially type is set to 200 ~300 DEG C or so, after removing foreign matter with the filtering such as filter of leaf dish type, go out from T-shaped mould coextrusion head to be membranaceous, in chill roll Upper solidification, while carrying out extruding while being cast with Elastic Contact roller.

When being imported from feed hopper to extruder, preferably under vacuo or decompression under, anti-block under non-reactive gas ambient Change decomposition etc..It should illustrate, Tm is the temperature of the die exit portion of extruder.

If adhering to the foreign matters such as the coagulation of scar, plasticizer on die head, sometimes the defects of generation tendon shape.Also will be this Defect is referred to as moulding mark, the defects of in order to reduce the surfaces such as moulding mark, is preferably set in the pipe arrangement from extruder to die head subtract as far as possible The structure in the delay portion of few resin.It is preferably used in the inside of die head, lip is tried one's best the structure of no scratch etc..

The inner face that extruder, die head etc. contact with molten resin preferably reduces surface roughness or using the low material of surface energy Matter etc. is implemented to be not easy the Surface Machining for adhering to molten resin.Specifically, by carried out hard chrome plating, ceramic spraying plating surface with Surface roughness is the surface that below 0.2S mode is ground.

Chill roll is not particularly limited, and is the metallic roll of high rigidity and possesses the thermal medium for internally flowing temperature controllable Or the roller of the structure of cold medium, size do not limit, as long as it is enough the size for cooling down the film through melting extrusion, generally A diameter of 100mm to 1m of chill roll or so.

The Facing material of chill roll can enumerate carbon steel, stainless steel, aluminium, titanium etc..In order to further improve the hardness on surface, or Improvement and the fissility of resin, it is preferable to carry out the surface treatments such as hard chrome plating or nickel plating, plating Amorphous Chromium etc. or ceramic spraying plating.

Cooling roller surface surface roughness less than 0.1 μm is preferably set in terms of Ra, be further preferably set to 0.05 μm with Under.Because roller surface is more smooth, the surface of the film of gained can also be more smooth.Certain preferably surface through Surface Machining is entered One step is ground and above-mentioned surface roughness is made.

As Elastic Contact roller, Japanese Unexamined Patent Publication 03-124425 publications, Japanese Unexamined Patent Publication 08-224772 can be used Number publication, Japanese Unexamined Patent Publication 07-100960 publications, Japanese Unexamined Patent Publication 10-272676 publications, No. WO97/028950, day This Unexamined Patent 11-235747 publications, Japanese Unexamined Patent Publication 2002-36332 publications, Japanese Unexamined Patent Publication 2005-172940 publications Or the silicon rubber that surface is coated to film metal sleeve and formed as described in Japanese Unexamined Patent Publication 2005-280217 publications Roller.

From chill roll stripping film when, preferably control tension force and prevent the deformation of film.

The later process of above-mentioned stripping is identical with above-mentioned solution casting method.

(5) touch panel module

Touch panel module involved in the present invention is characterised by, is formed on optical compensation films involved in the present invention Transparency conducting layer, as long as the shape of transparent electrode pattern as touch panel module (for example, electrostatic capacitance mode contact panel Module) pattern that operates well is not particularly limited, such as can enumerate Japanese Unexamined Patent Application Publication 2011-511357 publications, Japan JP 2010-164938 publications, Japanese Unexamined Patent Publication 2008-310550 publications, Japanese Unexamined Patent Application Publication 2003-511799 publications, Pattern described in Japanese Unexamined Patent Application Publication 2010-541109 publications.

Touch panel module involved in the present invention can substantially make in the following way：It will be formed in optical compensation films On the transparency conducting layer patterned in X-axis or Y-axis, be formed on the optical compensation films or other diaphragms in Y-axis or X The transparency conducting layer overlapping of axle patterning, is suitably laminated polarizer, diaphragm etc., as needed in most surface using adhesive linkage Protective glass is set.And then by the way that above-mentioned contact panel is combined with VA mode-type liquid crystal display devices, it can make the present invention's Liquid crystal display device with contact panel.

(5.1) transparency conducting layer

For transparency conducting layer involved in the present invention, as the square resistance of transparency conducting layer, preferably 0.01~ In the range of 150 Ω/.In the range of more preferably the resistance value of transparency conducting layer is 0.1~100 Ω/.If transparency conducting layer Resistance value be 0.01 Ω/more than, then durability is can obtain to environmental turbulences such as high temperature, high humiditys, resistance value is 150 Ω/ Then it is preferred from the viewpoint of it can suppress curling when following.

[transparent conductive material]

As long as transparency conducting layer involved in the present invention meets that then material is not particularly limited for above-mentioned resistance value, preferably make With the transparent conductive material such as ITO (tin indium oxide) or IZO (indium zinc oxide), especially from the viewpoint of electric conductivity, the transparency, It is preferred that use ITO.Rubbing method, ink-jet method, cladding process, infusion process etc., which can be enumerated, using ITO transparency conducting layer uses wet type work The method or vapour deposition method (resistance heating, EB methods etc.) of skill, sputtering method, CVD etc. are preferably logical using method of dry process etc. Cross vapour deposition method and formed.

After forming transparency conducting layer, in order to reduce the resistance value of the transparency conducting layer, preferably it is heat-treated and (is also referred to as moved back Fire).Heating-up temperature is 150~250 DEG C of scope, and the heat time is the scope of 1~60 minute.As long as according to support electrically conducting transparent Composition, the characteristic of base material of layer makes constrained optimization, in the substrate using cyclic olefine resin when, preferably heating-up temperature is 150~180 DEG C of scope, the scope that the heat time is 5~30 minutes.

[metal nanometer line]

In addition, it is also preferred that use the transparency conducting layer being made up of metal fine (metal nanometer line, wire netting).

Metal nanometer line refers to that material is metal, is shaped as the conductive materials of needle-like or thread, a diameter of nano-scale.Gold It can be linear or curve-like to belong to nano wire.If use the transparency conducting layer being made up of metal nanometer line, metal Nano wire turns into mesh-shape, even so as to which a small amount of metal nanometer line can also form good conductive path, can obtain electricity Hinder small transparency conducting layer.And then mesh-shape is turned into by metal nanometer line, form opening portion in the gap of mesh and can obtain The high nesa coating of light transmission.

The rugosity d and length L of above-mentioned metal nanometer line ratio (aspect ratio：L/d) it is preferably in the range of 10~100000, In the range of more preferably 50~100000, in the range of particularly preferably 100~10000.It is if so big using aspect ratio Metal nanometer line, then metal nanometer line intersect well, high electric conductivity can be presented using a small amount of metal nanometer line.It is tied Fruit, it can obtain the high nesa coating of light transmission.

In addition, in this specification, " rugosity of metal nanometer line " refers to that its is straight when the section of metal nanometer line is circular Footpath, to refer to its short diameter during ellipse, to refer to the diagonal most grown during polygon.The rugosity and length of metal nanometer line Degree can be confirmed by scanning electron microscope or transmission electron microscope.

The rugosity of above-mentioned metal nanometer line is preferably smaller than 500nm, more preferably less than 200nm, particularly preferably 10~100nm In the range of, in the range of most preferably 10~50nm.If this scope, then the high electrically conducting transparent of light transmission can be formed Layer.

The length of above-mentioned metal nanometer line is preferably more preferably 10~500 μm of scope in the range of 2.5~1000 μm It is interior, in the range of particularly preferably 20~100 μm.If this scope, then the high transparency conducting layer of electric conductivity is can obtain.

As the metal for forming above-mentioned metal nanometer line, as long as the metal that electric conductivity is high, then it is arbitrary appropriate to can be used Metal.As the metal for forming above-mentioned metal nanometer line, for example, silver, gold, copper, nickel etc. can be enumerated.In addition it is also possible to use These metals are carried out with the material of plating (for example, gold-plated processing).Wherein, it is preferably silver from the viewpoint of electric conductivity Or copper.

As the manufacture method of above-mentioned metal nanometer line, arbitrary appropriate method can be used.Such as it can enumerate in solution The method of middle reduction silver nitrate；Make applied voltage or the function of current in precursor surface from the top ends of probe, in probe distal end portion Draw metal nanometer line, the method for being continuously formed above-mentioned metal nanometer line etc..In the method for reducing silver nitrate in the solution, In the presence of the polyalcohols such as ethylene glycol and PVP, by carrying out the liquid-phase reduction of the silver salt such as silver nitrate, it can close Into nano silver wire.

The nano silver wire of uniform-dimension for example can be according to Xia, Y.etal., Chem.Mater. (2002), 14,4736- 4745th, the method described in Xia, Y.etal., Nano letters (2003) 3 (7), 955-960 largely produces.

Above-mentioned transparency conducting layer can be by being coated with containing upper on optical compensation films or diaphragm involved in the present invention State the transparency conducting layer formation composition of metal nanometer line and formed.More specifically, above-mentioned gold will can in a solvent be made The scattered dispersion liquid (transparency conducting layer is formed with composition) formed of category nano wire is coated on above-mentioned optical compensation films or diaphragm After upper, make coating layer dry and form transparency conducting layer.

As above-mentioned solvent, it is molten that water, alcohol series solvent, ketone series solvent, ether series solvent, hydrocarbon system solvent, fragrant family can be enumerated Agent etc..From the viewpoint of carrying capacity of environment is reduced, preferably using water.

The dispersion concentration of metal nanometer line in transparency conducting layer formation composition comprising above-mentioned metal nanometer line is excellent In the range of electing 0.1~1 mass % as.If this scope, then it can form electric conductivity and excellent transparent of transmitance is led Electric layer.

Transparency conducting layer formation composition comprising above-mentioned metal nanometer line can be according to purpose further containing arbitrary Appropriate additive.As above-mentioned additive, for example, the anticorrosion material for preventing metal nanometer line from corroding can be enumerated, prevent gold Belong to surfactant of nano wire cohesion etc..Species, number and the amount of the additive used can suitably be set according to purpose.This Outside, then can be as needed containing arbitrary suitable as long as above-mentioned transparency conducting layer formation composition can obtain the effect of the present invention When adhesive resin.

As the coating method of the transparency conducting layer formation composition comprising above-mentioned metal nanometer line, can use arbitrary Appropriate method.As coating method, for example, spraying process, stick coating method, rolling method, die coating method, ink-jet application method, silk can be enumerated Net rubbing method, Dipcoat method, toppan printing, woodburytype, gravure processes etc..

As the drying means of coating layer, arbitrary appropriate drying means can be used (for example, spontaneously drying, air-supply is done Dry, heat drying).For example, in heat drying, it is drying time in the range of 100~200 DEG C that drying temperature is representational Representational is in the range of 1~10 minute.

After drying, similarly in order to reduce the resistance value of transparency conducting layer, preferably it is heat-treated and (is also referred to as annealed).Add Hot temperature is 150~250 DEG C of scope, and the heat time is the scope of 1~60 minute.As long as according to the base of support transparency conducting layer Composition, the characteristic of material make constrained optimization, in the substrate using cyclic olefine resin when, preferably heating-up temperature be 150~ 180 DEG C of scope, the scope that the heat time is 5~30 minutes.

When above-mentioned transparency conducting layer includes metal nanometer line, the thickness of above-mentioned transparency conducting layer is preferably 0.01~10 μm In the range of, in the range of more preferably 0.05~3 μm, in the range of particularly preferably 0.1~1 μm.If this scope, then may be used Obtain electric conductivity and the excellent transparency conducting layer of transmitance.

When above-mentioned transparency conducting layer includes metal nanometer line, the total light transmittance of above-mentioned transparency conducting layer is preferably 85% More than, more preferably more than 90%, more preferably more than 95%.

[wire netting]

Transparency conducting layer comprising wire netting is that metal fine forms the pattern of clathrate on above-mentioned transparent base and formed 's.As the metal for forming above-mentioned wire netting, as long as arbitrary appropriate metal then can be used in the high metal of electric conductivity.As The metal of above-mentioned wire netting is formed, for example, silver, gold, copper, nickel etc. can be enumerated.In addition it is also possible to plated using to these metals Cover the material of processing (for example, gold-plated processing).Wherein, preferably copper, from being difficult to transport phenomena occurs, broken string during button is suppressed From the viewpoint of be also preferred.

Transparency conducting layer comprising wire netting can be formed by arbitrary appropriate method.Above-mentioned transparency conducting layer is for example Can be by the way that the photosensitive composite (transparency conducting layer is formed with composition) comprising silver salt be coated on above-mentioned layered product, its Afterwards, processing and development treatment are exposed, metal fine is formed as into defined pattern and obtained.In addition, above-mentioned electrically conducting transparent Thickener (transparency conducting layer is formed with composition) comprising metal particle can also be printed as defined pattern and obtained by layer.

The detailed content of this transparency conducting layer and forming method thereof is for example recorded in Japanese Unexamined Patent Publication 2012-18634 public affairs Report, it is recorded quotes in this specification as reference.In addition, as transparency conducting layer being made up of wire netting and forming method thereof Another example, transparency conducting layer described in Japanese Unexamined Patent Publication 2003-331654 publications and forming method thereof can be enumerated.

When above-mentioned transparency conducting layer includes wire netting, the thickness of above-mentioned transparency conducting layer is preferably 0.1~30 μm of scope It is interior, in the range of more preferably 0.1~9 μm.

When above-mentioned transparency conducting layer includes wire netting, the transmissivity of above-mentioned transparency conducting layer is preferably more than 80%, more excellent Elect more than 85%, more preferably more than 90% as.

(5.2) adhesive linkage

The adhesive linkage used in the present invention is preferably to contain adhesive, and the adhesive contains thermosetting resin, ultraviolet (UV) curable resin or chemically curable resin and optically transparent, and show the viscoplasticity of appropriateness, adhesion properties Layer.

As specific adhesive, acrylic acid series copolymer, epoxy system resin, polyurethane, silicon-type polymerization can be enumerated Bonding agent or the adhesives such as thing, polyethers, butyral system resin, polyamide series resin, polyvinyl alcohol resin, synthetic rubber Deng.In the present invention, film is formed preferably by thermal curing method, photocuring processes, chemical reaction etc., the adhesive for solidifying it, its In, acrylic acid series copolymer, epoxy system resin are easiest to control bonding physical property, and the transparency, weatherability, durability etc. are excellent, Can preferably it use.

Above-mentioned adhesive can be one-pack-type, the type that can also mix more than 2 liquid to use before use.On in addition, It can be using organic solvent as the emulsion-type of the solvent system of medium or medium using water as principal component, colloid to state adhesive The water systems such as dispersion liquid type, aqueous solution type or no-solvent type.As long as the concentration of above-mentioned adhesive liquid is according to the film after bonding Thickness, coating machine, application conditions etc. are next suitably to be determined, usually 0.1~50 mass %.

The thickness of adhesive linkage can be suitably formed in 0.1~100 μm of scope, preferably 0.5~50 μm, particularly preferably 0.5~30 μm.When being coated, viscosity of the adhesive at 25 DEG C is generally 1000~6000mPa/sec, preferably 2000 ~4000mPa/sec, such as 3000~4000mPa/sec.Here, viscosity is for example using Tokimec (Tokyo gauge) company Brookfield viscometer BH II, make after standing rotor rotate 30 seconds and read value.The poplar of adhesive resin after being fully cured Family name's modulus (E) is preferably 1~100MPa, such as 5~20MPa.

As acrylic adhesive, can enumerate makes (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third Olefin(e) acid N-butyl, (methyl) isobutyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid 2- ethyls butyl ester, (first Base) acrylic acid of carbon number 1~20 such as 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate The one or two or more kinds of Arrcostab and (methyl) acrylic acid, itaconic acid, Malaysia that can be copolymerized with aforesaid propylene acid alkyl ester The copolymerization of the monomers such as acid, maleic anhydride, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls The crosslinking agent such as thing and isocyanates base system crosslinking agent, epoxy crosslinking agent, aziridine system crosslinking agent, metallo-chelate system crosslinking agent React the adhesive formed.

As epoxy system resin adhesive, can enumerate the epoxy resin of ultraviolet photo-curing with organosilicone elastic structural reform Property, and resin combination of the precipitated silica as inorganic filling material is added, for example, can be used Edmund Optics public " NORLAND optical cements NOA68 ", " the Photoelasticity tree of Sony Chemical＆InformationDevice companies of department Fat (Super View Resin) ".

In order to promote the photocuring of above-mentioned adhesive, preferably further contain Photoepolymerizationinitiater initiater.Trigger as photopolymerization The use level of agent, preferably by quality ratio with Photoepolymerizationinitiater initiater：Adhesive=20：100~0.01：100 contain.

As Photoepolymerizationinitiater initiater, specifically, alkyl phenyl ketone system, acetophenone, benzophenone, hydroxyl hexichol can be enumerated Ketone, Michler's keton, α-amyl group oxime ester, thioxanthones etc. and their derivative, but be not particularly limited in them.They can be with Using commercially available Photoepolymerizationinitiater initiater, for example, Irgacure 184, the Irgacure of BASF Japan Co. Ltd. systems can be enumerated 907th, Irgacure 651 etc. illustrates as preferred.

As the method for setting adhesive linkage, preferably set by being coated with the composition containing above-mentioned adhesive, for example, can Enumerate stick coating method, scraper for coating method, rolling method, scraper plate rubbing method, die coating method, gravure coating process, curtain coating processes, ink-jet method etc. Known method.

In the case of heat cure, apply more than 80 DEG C of heating preferably in drying machine, the heat time can suitably set.

As the light source of UV curing process, as long as producing the light source of ultraviolet can then use without limitation.For example, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp can be used Deng.

Irradiation condition is different according to each lamp, and the exposure of dynamic rays is usually 50~1000mJ/cm², it is preferably 50~300mJ/cm².In addition, the heat treatment temperature after solidifying as UV, preferably more than 80 DEG C.

In addition, after adhesive linkage is set, untill being bonded with other components during, be preferably laminated stripping film on surface.

Various stripping films can be used in stripping film, and representational is by having the substrate sheets of fissility to form on surface.Make For substrate sheets, can enumerate the films such as polyester resin, polyvinyl resin, acrylic resin, polystyrene resin, polycarbonate resin, Or coordinate film or synthetic paper that the filler such as filler forms etc. in these films.In addition, can enumerate glassine paper, clay coated paper, The paper base materials such as good quality paper.

(6) polarization plates

Polarization plates involved in the present invention from VA mode-types liquid crystal cells to identification side successively with least one side with Optical compensation films, polarizer and the diaphragm of above-mentioned transparency conducting layer.

(6.1) polarizer

Polarizer is the element of the light of the plane of polarization only by certain orientation, and its example includes polyethenol series polarizing coating.

Polyethenol series polarizing coating has the film for forming iodine staining in polyvinyl alcohol mesentery and dyes dichroic dye The film formed.

Polyvinyl alcohol film can be carried out uniaxial tension poststaining or carry out single shaft after polyvinyl alcohol film is dyed by polarizer Stretching, preferably so that boron compound further carries out durability processing and obtains.

The thickness of polarizer is preferably in the range of 5~30 μm, in the range of more preferably 5~15 μm.

As polyvinyl alcohol film, preferably using Japanese Unexamined Patent Publication 2003-248123 publications, Japanese Unexamined Patent Publication 2003- The content of ethylene units described in No. 342322 publications etc. is 1~4 mole of %, the degree of polymerization is 2000~4000, saponification degree For 99.0~99.99 moles of % ethylene modified polyvinyl alcohol.Furthermore it is preferred that pass through Japanese Unexamined Patent Publication 2011-100161 public affairs Method described in report, No. 4804589 No. 4691205 publications of Japanese Patent No., Japanese Patent No. publications makes polarizer, makes it It is bonded with the base material film of the present invention and makes polarization plates.

(6.2) diaphragm

The face with being fitted with optical compensation films for being configured at polarizer is that the film of opposite side is preferably the guarantor as polarizer Cuticula plays the film of function.

As this diaphragm, above-mentioned optical compensation films can be used, such as can preferably use commercially available cellulose ester membrane (for example, Konica Minolta Tac KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, the above are Konica Minolta Opto Inc.'s system, FUJITAC T40UZ, FUJITAC T60UZ, FUJITACT80UZ、FUJITAC TD80UL、FUJITAC TD60UL、FUJITAC TD40UL、FUJITAC R02、FUJITAC R06, the above are FUJI FILM Co. Ltd. systems).

In addition, can enumerate the resin films such as polyethylene terephthalate, PEN, makrolon, The resin films such as polyarylate, polyether sulfone, polysulfones, fluorenes ring modified polycarbonate, alicyclic modified makrolon, acryloyl compounds.This In a little resin base materials, from the aspect of cost, the easiness obtained, preferably using polyethylene terephthalate (referred to as： PET), polybutylene terephthalate (PBT), PEN (abbreviation：PEN), makrolon (abbreviation：The film such as PC) Resin base material as flexibility.

The thickness of diaphragm is not particularly limited, and can be set in the range of 10~200 μm or so, preferably 10~100 μm, In the range of more preferably 10~70 μm.

(6.3) preparation method of polarization plates

The making of polarization plates is preferably sent out this using fully saponified type polyvinyl alcohol water solution (water paste) or above-mentioned adhesive Bright involved optical compensation films and diaphragm are bonded with polarizer.Optical compensation films involved in the present invention are preferably in liquid crystal The liquid crystal cell side of polarizer is arranged in showing device.

Pretreatment procedure during as fitting, the bonding plane progress with polarizer of preferred pair optical compensation films, diaphragm Easy bonding processing, handles as the easy bonding, can enumerate saponification process, sided corona treatment and corona treatment etc..

(7) other layers

The one-piece type touch panel module of polarization plates involved in the present invention can arbitrarily possess other layers as needed.Make For above-mentioned other layers, for example, hard conating, antistatic backing, antiglare layer, anti-reflection layer, color-filter layer etc. can be enumerated.

Hard conating can also be in order that the protective layer of identification side improves scratch resistance and formed, or conduct forms electrically conducting transparent Layer when protective layer and be formed at optical compensation film surface.The hard conating preferably comprises ultraviolet hardening urethane acrylate It is that resin, ultraviolet hardening polyester acrylate system resin, ultraviolet hardening epoxy acrylate system resin, ultraviolet are solid Change type polyalcohol acrylate system's resin or ultraviolet hardening epoxy resin etc., wherein, preferably comprise ultraviolet hardening third Olefin(e) acid ester system resin.

Antistatic backing is to contain square resistance can be made to be 1 × 10 when forming antistatic backing¹¹Ω/below, preferably For 1 × 10¹⁰Ω/below, more preferably 1 × 10⁹The layer of Ω/below material.As antistatic agent, gold can be enumerated Category oxide, surfactant type antistatic agent, silicon-type antistatic agent, organic boronic system antistatic agent, macromolecular are prevented Electrostatic agent, antistatic polymeric material etc., known conjugation based polymer, ionic polymers and electric conductive polymer can be used Deng.

(8) liquid crystal display device

The liquid crystal display device with contact panel of the present invention is characterised by, uses VA patterns (MVA, PVA) type liquid Crystalline substance, the advantages of VA patterns can the be provided i.e. excellent liquid crystal display device with contact panel of front contrast.For VA moulds Formula type liquid crystal, can be without limitation using known liquid crystal.

In liquid crystal display device, generally by identify side polarization plates and this 2 polarization plates of the polarization plates of backlight side via Adhesive linkage is bonded and used with liquid crystal cells, but the polarization plates for possessing optical compensation films involved in the present invention are configured at identification Side, function is played as the one-piece type touch panel module of polarization plates.

On the other hand, the polarization plates of backlight side are preferably to be sequentially laminated with optical compensation films, polarization from liquid crystal cell side The polarization plates of piece and diaphragm, as optical compensation films, the preferably optical compensation films using the present invention or other optical compensation films. As other optical compensation films, can be selected from above-mentioned commercially available cellulose ester membrane and it is preferred that using.In addition, diaphragm Can equally be selected from above-mentioned commercially available cellulose ester membrane and it is preferred that use, and then, can be used polyester film, acrylic film or Polycarbonate membrane etc..

Embodiment

Hereinafter, enumerate embodiment and specifically describe the present invention, but the present invention is not limited to them.It should illustrate, embodiment The middle expression for having used " part " or " % ", " mass parts " or " quality % " are then represented unless otherwise specified.

Embodiment 1

As used in embodiment cellulose esters system resin, cyclic olefine resin, polyimides system resins, polyarylate system Resin and acrylic resin, use following resins enumerated.

[resin]

Cyclic olefine resin (COP)：ARTON G7810, JSR Corp.'s system

Cellulose-acetate propionate (CAP)：Degree of substitution with acetyl group 1.5, propiono substitution value 1.0, total acyl substitution 2.5, Weight average molecular weight 25 is ten thousand)

Polyimides system resins (PI)：With following method synthesis of polyimides system resins.

＜ polyimide resins A：Polyimides ＞ with the structure represented by formula (P1)

(polymerization of polyimide precursor)

Using possess stainless steel detachable flask as reaction vessel, to possess 2 paddle wings detachable as this Agitating device in flask, the device for possessing the cooling capacity with 20.9kJ/min manufacture as the reaction unit of cooling device Polyamic acid.In the polymerization in order to prevent being mixed into for moisture, by by the nitrogen that is dehydrated in silica gel with 0.05L/ Min flows and carries out polymerisation.

Load DMF (DMF) 223.5g in above-mentioned detachable flask as polymer solvent, at it Middle dissolving trifluoromethylbenzene (TFMB) 40.0g (0.125 mole).1,1,1,3,3,3- hexafluoros -2,2- is added in the solution Two (3,4- dicarboxyphenyis) propane dianhydride (6FDA) 55.5g (0.125 mole) and being stirred is completely dissolved it.Completely After dissolving, being stirred makes polymeric viscosity rise to 80Pas.The viscosity of polyamic acid solution be be incubated it is water-soluble in 23 DEG C 1 hour is incubated in liquid, what rotor No.7 was measured with rotating speed 4rpm is made with Brookfield viscometer to viscosity now.It should illustrate, The addition concentration of aromatic diamine compound and aromatic tetracarboxylic acid's dianhydride in the reaction solution is relative to total overall reaction liquid 30 mass %.

(to the chemical imidization of polyimide resin)

DMF is added in above-mentioned solution makes solid component concentration be 15 mass %, addition pyridine (pkBH+；5.17)60g (mol ratio=3 of amide groups in imidizate accelerator/polyamic acid) are used as imidizate accelerator, are completely dispersed it. With the 1g per minute speed addition acetic anhydride 30.6g (mol ratio of amide groups in dehydrating agent/polyamic acid in scattered solution =1.2), further stir 30 minutes.Internal temperature is risen to 100 DEG C after stirring and carry out crossing thermal agitation in 5 hours.

(extraction of polyimide resin)

The solution of polyimide resin is put into the funnel that the diameter in hole is about 5mm, is added drop-wise in 5L methanol and carries out Extraction.During extraction, while methanol is stirred while being extracted at high speed with the stirring vane for rotating to be more than 1500 turns.On one side Adjusted in a manner of the diameter of the polyimide solution of dropwise addition is below 1mm near Methanol Interface funnel and methanol liquid level it Between height while be added drop-wise in a manner of as threadiness polyimide resin in methanol solution, solution sometimes also into For threadiness, but by continuing to stir, the polyimide resin for once turning into threadiness in solution is decomposed and is broken in the solution For below 5mm fiber.

In the resin solid content solution of fracture, the methanol for further adding 5L fully extracts solid constituent and taken Go out, after solid constituent is cleaned using isopropanol with Soxhlet extraction device, heated with Minton dryer at 100 DEG C Dry, taken out in the form of polyimide resin.Weight average molecular weight is 100,000.

Polyarylate system resin (PA)：With following methods synthesis polyarylate system resin.

In possessing the reaction vessel of agitating device, make as double (4- hydroxy phenyls) hexafluoros third of 2,2- of bisphenol component 100 mass parts of alkane (BisAF), 1.34 mass parts of p-t-butyl phenol (PTBP) as end-capping reagent, the hydrogen-oxygen as alkali Change sodium (NaOH) 25.4 mass parts, as polymerization catalyst three-normal-butyl benzyl ammonium chloride (TBBAC) 50 mass % The mass parts of the aqueous solution 1.28,0.5 mass parts as the sodium dithionite of antioxidant are dissolved in the mass parts (water of water 1750 Phase).

In addition, additionally, make diphenyl ether -4 as aromatic dicarboxylic acid composition, 4 '-diacid chloride (DEDC) 89.1 mass parts are dissolved in the mass parts of dichloromethane 1200 (organic phase).

Stirring aqueous phase in advance, organic phase is made an addition in aqueous phase with vigorous stirring, its interface polymerization reaction 2 is made at 15 DEG C Hour.Mol ratio is set to BisAF：DEDC：PTBP：TBBAC：NaOH=98.5：100.0：3.0：0.68：210.

Thereafter, stop stirring, aqueous phase and organic phase are decanted and separated.After removing aqueous phase, by the mass of dichloromethane 500 Part, the mass parts of pure water 2000 and the mass parts of acetic acid 2 make an addition to organic phase and stop reaction, are stirred 30 minutes at 15 DEG C.Thereafter, will Organic phase is cleaned 10 times with pure water, and organic phase, which is made an addition in methanol, precipitates polymer.The polymer of precipitation is filtered, It is dried, obtains the polyarylate resin that weight average molecular weight is 110,000.

Cellulose triacetate (TAC)：Degree of substitution with acetyl group 2.85, weight average molecular weight 25 is ten thousand)

Acrylic resin (Ac)：DIANAL BR85 (Mitsubishi Rayon Co., Ltd's system, weight average molecular weight：28 ten thousand)

[additive]

As additive, phase difference rises immunomodulator compounds A1~compound A-45, polyester plasticizer B1 and acrylic acid series tree Fat B2 uses following compounds.

Polyester plasticizer B1：With following step synthesizing polyester system plasticizer.

Using ethylene glycol 180g, phthalic anhydride 278g, adipic acid 91g, benzoic acid 610g, the titanium as esterification catalyst Four isopropyl ester 0.191g of acid be fitted into possess thermometer, agitator, emergency cooling tube 2L four-hole boiling flask in, while in nitrogen stream Middle stirring is slowly warming up to 230 DEG C on one side.It is set to carry out dehydration condensation while observing the degree of polymerization.Reaction terminate after 200 DEG C of decompressions evaporate unreacted ethylene glycol, so as to obtain polyester plasticizer B1.Acid number is 0.20, and number-average molecular weight is 450。

Acrylic resin B2：With following step acrylic acid synthesizing system resin.

24 liters of deionized water is put into the SUS polymerizing reactors for 40 liters of internal volume for possessing mixer, adds and makees Stirred for anion system high-molecular compound aqueous solution 30g, the sodium sulphate 36g as stably dispersing auxiliary agent of dispersion stabilizer Mixing makes its dissolving.In addition, possesses the container of mixer other, by methyl methacrylate (MMA) and acryloyl morpholine (ACMO) by MMA be (using the addition mol ratio of total as MMA/ACMO=in a manner of 73.1 mass %, ACMO are 22.4 mass % 70/30 mode) input, 2 as polymerization initiator, 2 '-azodiisobutyronitrile 12g, conduct are added in monomer mixture The n octylmercaptan 24g of chain-transferring agent, the stearyl alcohol 24g as releasing agent is stirred makes its dissolving.It will obtain by this way To monomer mixture dissolved with polymerization initiator, chain-transferring agent and releasing agent put into the above-mentioned internal volume 40 for possessing mixer In the SUS polymerizing reactors (housing deionized water, dispersion stabilizer and stably dispersing auxiliary agent) risen, while carrying out nitrogen displacement While stirred 15 minutes with 175rpm.Thereafter, being heated to 80 DEG C starts polymerization, after polymerization exotherm peak terminates, in 115 DEG C of progress The heat treatment of 10 minutes, terminate polymerization.By bead polymer filtering, the washing of gained, in 80 DEG C of dry 24hr, divided equally again The methyl methacrylate (MMA) of son amount 60,000 and the acrylic resin B2 of acryloyl morpholine (ACMO).

Embodiment 1

The making ＞ of ＜ optical compensation films 101

(preparation of particulate annex solution)

Particulate (AEROSILR812：Japanese AEROSIL Co. Ltd. systems, an average grain diameter：7nm, apparent specific gravity 50g/L)

4 mass parts

The mass parts of dichloromethane 48

The mass parts of ethanol 48

After above composition is stirred into 50 minutes with dissolvers, disperseed with Manton Gaulin.

And then disperseed in a manner of the particle diameter of offspring turns into prescribed level with grater.By it with Japanese essence The FINEMET NF of line Co. Ltd. system are filtered, and prepare particulate annex solution.

Next, prepare the main rubber cement 1 of following compositions.First, added in dissolved under pressure tank with 400kg/min flow Dichloromethane and ethanol is added with 20kg/min flow.After addition solvent is started 3 minutes, in above-mentioned dissolved under pressure tank Stir the flow input cyclic olefine resin (COP) while with 200kg/min.Next, 5 points after input solvent is started Zhong Hou, particulate annex solution is put into, while being heated to 80 DEG C and stirring, fully dissolved on one side.Heating-up temperature be with 5 DEG C/ Min after dissolving in 30 minutes, is cooled from room temperature with 3 DEG C/min.

Cement viscosity is 10000CP, moisture content 0.50%.It is accumulated into filter paper using the peace of peace product filter paper Co. Ltd. system No.244 (filtering accuracy 0.005mm) is with filtering traffic 300L/m²H, filtering pressure 1.0 × 10⁶Pa is filtered, and prepares main rubber cement 1。

The composition ＞ of the main rubber cements 1 of ＜

Cyclic olefine resin (COP)：ARTON G7810, the mass parts of JSR Corp.'s system 100

The mass parts of dichloromethane 200

The mass parts of ethanol 10

The mass parts of particulate annex solution 3

Next, using endless belt casting device, above-mentioned rubber cement is cast for 33 DEG C in temperature with 1500mm even widths To stainless steel band supporter.The temperature control of stainless steel band is 30 DEG C.

On stainless steel band supporter, it is 75% to make the residual solvent amount that solvent is evaporated in the film of curtain coating (casting), is connect Get off, peeled off with peeling off tension force 130N/m from stainless steel band supporter.

While 160 DEG C of heat is applied while being carried out using stenter in broadside to the cyclic olefine resin film of stripping 20% stretching.Residual solvent when stretching starts is 15%.Next, while dry section is conveyed while making to dry knot with multiple rollers Beam.Drying temperature is 130 DEG C, conveyance tension 100N/m.After drying, 1.5m width is cut into, implements width at film both ends 10mm, 10 μm of height annular knurl processing, coil into web-like, obtain the optical compensation films 101 of 45 μm of dry film thickness.

The making ＞ of ＜ optical compensation films 102

In the making of optical compensation films 101, prepare following main rubber cements 2 and use, thickness is set to 10 μm, in addition, Similarly make optical compensation films 102.

The composition ＞ of the main rubber cements 2 of ＜

It should illustrate, stretching ratio is adjusted in a manner of the phase difference value described in optical compensation films turn into table 1.

The making ＞ of ＜ base material films A103~108

In the making of optical compensation films 102, make the record of the species, addition, Thickness Variation Cheng Rubiao 1 of additive, remove Beyond this, optical compensation films 103~108 are similarly made.

The making ＞ of ＜ optical compensation films 109

In the making of optical compensation films 101, prepare following main rubber cements 3 and use, in addition, similarly make optics and mend Repay film 109.

The composition ＞ of the main rubber cements 3 of ＜

The making ＞ of ＜ optical compensation films 110

In the making of optical compensation films 109, the additive A 2 of 5 mass parts is added, by stretching ratio with as described in table 1 The mode of phase difference value be adjusted, thickness is produced change, in addition, similarly make optical compensation films 110.

The making ＞ of ＜ optical compensation films 111

In the making of optical compensation films 101, prepare following main rubber cements 4 and use, in addition, similarly make optics and mend Repay film 110.

The composition ＞ of the main rubber cements 4 of ＜

The making ＞ of ＜ optical compensation films 112

In the making of optical compensation films 111, add 2 mass parts additive A 2, by stretching ratio with optical compensation films into Mode for the phase difference value described in table 1 is adjusted, and thickness is produced change, in addition, is similarly made optics and is mended Repay film 112.

The making ＞ of ＜ optical compensation films 113

In the making of optical compensation films 101, prepare following main rubber cements 5 and use, in addition, similarly make optics and mend Repay film 113.

The composition ＞ of the main rubber cements 5 of ＜

The making ＞ of ＜ optical compensation films 114

In the making of optical compensation films 113, add 2 mass parts additive A 2, by stretching ratio with optical compensation films into Mode for the phase difference value described in table 1 is adjusted, and thickness is produced change, in addition, is similarly made optics and is mended Repay film 114.

The making ＞ of ＜ optical compensation films 115

In the making of optical compensation films 102, prepare following main rubber cements 6 and use, thickness is set to 45 μm, in addition, Similarly make optical compensation films 115.

The composition ＞ of the main rubber cements 6 of ＜

It should illustrate, stretching ratio is adjusted in a manner of as the phase difference value described in table 1.

The making ＞ of ＜ optical compensation films 116

In the making of optical compensation films 110, prepare following main rubber cements 7 and use, thickness is set to 45 μm, in addition, Similarly make optical compensation films 116.

The composition ＞ of the main rubber cements 7 of ＜

The making ＞ of ＜ optical compensation films 117

In the making of optical compensation films 101, in long side direction and broadside respectively stretching 5%, thickness is set to 45 μm, removed Beyond this, optical compensation films 117 are similarly made.

The making ＞ of ＜ optical compensation films 118

In the making of optical compensation films 116, prepare following main rubber cements 8 and use, respectively drawn in long side direction and broadside 5% is stretched, thickness is set to 45 μm, in addition, similarly makes optical compensation films 118.

The composition ＞ of the main rubber cements 8 of ＜

The making ＞ of ＜ optical compensation films 119

In the making of optical compensation films 116, prepare following main rubber cements 9 and use, thickness is set to 45 μm, in addition, Similarly make optical compensation films 118.

The composition ＞ of the main rubber cements 9 of ＜

Acrylic resin (Ac)：DIANAL BR85 (Mitsubishi Rayon Co., Ltd's system) 100 mass parts

The mass parts of dichloromethane 200

The mass parts of ethanol 10

The mass parts of particulate annex solution 3

The making ＞ of ＜ transparency conducting layers

The nano silver wire used is in Y.Sun, B.Gates, B.Mayers , ＆Y.Xia, " Crystalline silver Nanowires by soft solution processing ", Nanoletters, (2002), described in 2 (2) 165~168 The method using polyalcohol after, in the presence of PVP (PVP), silver sulfate is dissolved in ethylene glycol, will It is reduced, so as to the nano silver wire of synthesis.That is, used in the present invention and pass through CambriosTechnologies Corporation The polyxol method of amendment described in U.S. Provisional Application No. 60/815627 and the nano wire synthesized.

By the short shaft diameter about 70~80nm synthesized by the above method containing 0.5wt%/v in an aqueous medium, in length and breadth Nano silver wire aqueous dispersion composition of the nano silver wire as the metal nanometer line for forming transparency conducting layer than more than 100 (ClearOhmTM, Ink-AAQ of Cambrios Technologies Corporation company systems) is coated with using slot die Machine, after being coated in the one side of optical compensation films 101~119 and dry in a manner of thickness after drying being 1.5 μm, with pressure 2000kN/m²Pressurized treatments are carried out, form transparency conducting layer.

Next, transparency conducting layer is also formed as described above on the another side of optical compensation films, thereafter, in order to low Resistance value, the heat treatment (annealing) of 30 minutes is carried out at 150 DEG C.

The making of ＜ polarization plates and the one-piece type touch panel module of polarization plates：The ＞ of reference picture 2

80 μm of rolled polyvinyl alcohol film of thickness is continuously stretched as 5 times in iodine aqueous solution, is dried and obtains The polarizer that 20 μm of thickness.

Next, the polarizer of above-mentioned making is provided with transparent lead with the optical compensation films 101~119 of above-mentioned making The side of electric layer and Konica Minolta TacKC4UA (Konica Minolta Opto Inc.'s system) clampings as diaphragm, It is bonded via following ultraviolet hardening bonding agent liquid, makes the one-piece type touch panel module 101~119 of polarization plates.

(preparation of ultraviolet hardening bonding agent liquid 1)

After following each compositions are mixed, deaeration is carried out, prepares ultraviolet hardening bonding agent liquid 1.It should illustrate, triaryl Sulfonium hexafluorophosphate is coordinated in the form of 50% polypropylene carbonate ester solution, the solid of triaryl matte hexafluorophosphate described below Component amount.

In addition, the making of polarization plates is with corona output intensity 2.0kW, linear speed on the surface of optical compensation films and diaphragm Degree 18m/ minutes implement Corona discharge Treatment, are applied in Corona discharge Treatment face in a manner of the thickness after solidifying is about 3 μm with rod Machine is coated with the ultraviolet hardening bonding agent liquid 1 of above-mentioned preparation and forms ultraviolet hardening bond layer.

Above-mentioned polarization plates are that using the ultraviolet lamp with conveyer belt, (lamp uses Fusion UV from diaphragm side The D bulbs of Systems company systems) using integrating light quantity as 750mJ/cm²Mode irradiate ultraviolet, be bonded ultraviolet hardening Oxidant layer solidifies.

＜ possesses the making of the liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates：Reference Fig. 2 ＞

The one-piece type touch panel module of polarization plates of the optical compensation films 101~116 of above-mentioned making be will be provided with polarization plates Optical compensation films side fit in homemade VA mode-types liquid crystal cells, make the liquid crystal display device 101 with contact panel ~116.

In addition, the one-piece type touch panel module of polarization plates for possessing the optical compensation films 117~119 of above-mentioned making is from city Touch panel module is carefully peeled off in the IPS mode-type liquid crystal display devices with contact panel sold, by the light of polarization plates Learn compensation film side and fit in IPS mode-type liquid crystal cells, make the liquid crystal display device 117~119 with contact panel.

By optical compensation films (Konica Minolta Tac KC8UCR3)/polarizer/diaphragm (Konica Minolta Tac KC4UA, be Konica Minolta Opto Inc.'s system) the polarization plates of composition liquid crystal cells are turned into optical compensation films side The mode of side is fitted on the face of opposite side of above-mentioned liquid crystal cells via adhesive phase.

《Evaluation》

(1) phase difference value of optical compensation films

The phase difference value Rt of phase difference value Ro and thickness direction is to use automatic birefringence meter in the face of optical compensation films Axo Scan(Axo Scan Mueller Matrix Polarimeter：AxoMetrix company systems) 23 DEG C of 55%RH's Three-dimensional refractive index measure is carried out under environment in 590nm optical wavelength, the refractive index according to following formula (i) with (ii) by gained n_x、n_y、n_zCalculate.

Formula (i)：Ro=(n_x- n_y)×d(nm)

Formula (ii)：Rt={ (n_x+n_y)/2-n_z}×d(nm)

(in formula (i) and formula (ii), n_xRepresent that direction is in the maximum direction x of refractive index refractive index in the face of film.n_yTable Show that direction is in the direction y orthogonal with above-mentioned direction x refractive index in the face of film.n_zRepresent the refraction in the thickness direction z of film Rate.D represents the thickness (nm) of film.〕

(2) phase difference value of optical compensation films changes

Above-mentioned optical compensation films sample is placed 1 hour in baking box with 150 DEG C and is heat-treated, is asked by following formula The variation of the phase difference value gone out before and after it.

(3) glass transition temperature of optical compensation films

Glass transition temperature Tg uses such as Seiko Instruments Co. Ltd. systems according to JIS K-7121 Differential scanning calorimetry (DSC) DSC220 is measured and obtained.Fixed 10mg or so optical compensation films sample, in nitrogen flow 50ml/ 10 minutes (the 1st time scanning) from room temperature to 250 DEG C and is kept with 20 DEG C/min under conditions of min, then, with 20 DEG C/min Speed be cooled to 30 DEG C and keep 10 minutes (the 2nd time scanning), and then, be warming up to 250 DEG C with 20 DEG C/min and (sweep for the 3rd time Retouch), DSC curve is made, glass transition temperature Tg is obtained by the DSC curve of the 3rd scanning of gained.

(4) front contrast

For the made liquid crystal display device 101~119 with contact panel, respective front contrast is determined. The measure of front contrast is carried out using the front contrast measure device (EZ-contrast) of ELDIM company systems, dialogue Light quantity during display and during black display is measured, and obtains its ratio.

More than, the constitution content of optical compensation films and above-mentioned evaluation result are shown in table 1 below.

As shown in Table 1, using the VA patterns with contact panel of optical compensation films 101~114 involved in the present invention For type liquid crystal display device compared with IPS mode-types liquid crystal display device 117~119, front contrast is excellent.

In addition, optical compensation films 115 and 116 of the glass transition temperature Tg of optical compensation films less than 155 DEG C are due to phase Potential difference value changes greatly, and front contrast is also inferior, therefore contrast is low compared with IPS mode-type liquid crystal display devices.

Embodiment 2

The making ＞ of ＜ touch panel modules

The one side of the optical compensation films 104,110,112 and 114 involved in the present invention made in embodiment 1 is by splashing Penetrate method using thickness for 20nm in a manner of form ito film as transparency conducting layer, the 1st electrode pattern of X-direction is formed by etching.

Then, will in a manner of thickness is 200nm using sputtering method as the insulating barrier being configured between electrode pattern SiO₂Film forming, ito film is formed in a manner of thickness is 20nm sputtering thereon, the 2nd electrode is formed in the Y direction by etching Pattern.And then using sputtering method in a manner of thickness is 200nm by SiO thereon₂Film forming is as insulating barrier.Next, in order to Low resistance value, the heat treatment (annealing) of 30 minutes is carried out at 150 DEG C, make correspond respectively to optical compensation films 104, 110th, 112 and 114 optical compensation films 201~204 for possessing transparency conducting layer.

The making of ＜ polarization plates and the one-piece type touch panel module of polarization plates：The ＞ of reference picture 6

By the polarizer made in embodiment 1 be provided with transparency conducting layer the one of above-mentioned optical compensation films 201~204 Side and Konica Minolta Tac KC4UA (Konica Minolta Opto Inc.'s system) clampings as diaphragm, via implementation The ultraviolet hardening bonding agent liquid 1 of example 1 is bonded, and makes the one-piece type touch panel module 201~204 of polarization plates.

＜ possesses the making of the liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates：Reference Fig. 6 ＞

It will be provided with the one-piece type touch panel module 201~204 of polarization plates of the optical compensation films 201~204 of above-mentioned making Homemade VA mode-types liquid crystal cells are fitted in not form the optical compensation films side of transparency conducting layer, making carries contact panel Liquid crystal display device 201~204.

By optical compensation films (Konica Minolta Tac KC8UCR3)/polarizer/diaphragm (Konica Minolta Tac KC4UA, be Konica Minolta Opto Inc.'s system) the polarization plates of composition liquid crystal cells are turned into optical compensation films side The mode of side fits in the face of the opposite side of liquid crystal cells via adhesive phase.

What measure was made similarly to Example 1 the possess one-piece type touch panel module of polarization plates carries contact panel Liquid crystal display device 201~204 front contrast, its result understand, contrast ratio is 7500：1, it can obtain again real Apply example 1 and there is liquid crystal display device of the VA mode-types with contact panel of excellent contrast.

Industrial applicability

The liquid crystal display device with contact panel of the present invention by having at least one side involved in the present invention successively Optical compensation films, polarizer and diaphragm with transparency conducting layer, film can be provided and front contrast is excellent, possesses The liquid crystal display device with contact panel of VA mode-type liquid crystal cells.

Symbol description

1 liquid crystal cells

2 polarizers

T1 diaphragms

T2 optical compensation films

P1 polarization plates (identification side)

3 adhesive linkages

4 conductive layer base material films

5 transparency conducting layers

6 protective layers

7 front panels

T touch panel modules

T3 optical compensation films

T4 diaphragms

P2 polarization plates (backlight side)

The liquid crystal display device with contact panel of 10 comparative examples

The liquid crystal display device with contact panel of 20 present invention

Claims

1. a kind of liquid crystal display device with contact panel, be possess have in the identification side of VA mode-type liquid crystal cells it is transparent The liquid crystal display device with contact panel of the one-piece type touch panel module of polarization plates of conductive layer, it is characterised in that

The one-piece type touch panel module of polarization plates with the transparency conducting layer is from the VA mode-types liquid crystal cells to identification Side successively with optical compensation films of at least one side with transparency conducting layer, polarizer and diaphragm, and

In the range of the glass transition temperature Tg of the optical compensation films is 155~250 DEG C.

2. the liquid crystal display device according to claim 1 with contact panel, it is characterised in that the optical compensation films Contain any of cyclic olefine resin, polyimides system resins or polyarylate system resin.

3. the liquid crystal display device according to claim 1 or 2 with contact panel, it is characterised in that the optics is mended Repay film 150 DEG C carried out 1 hour heat treatment when face in direction phase difference value Ro variation be ± 3.0% in the range of, In the range of the phase difference value Rt of thickness direction variation is ± 4.0%.

4. according to the liquid crystal display device according to any one of claims 1 to 3 with contact panel, it is characterised in that institute In the range of the thickness for stating optical compensation films is 10~40 μm.

5. according to the liquid crystal display device according to any one of claims 1 to 4 with contact panel, it is characterised in that institute State optical compensation films contain with by following formulas (3) represent structure nitrogen-containing heterocycle compound as phase difference rising agent,

Formula (3)

In formula, A represents pyrazole ring, Ar₁And Ar₂Aromatic series hydrocarbon ring or heteroaromatic are represented respectively, can have substituent, R₁ Hydrogen atom, alkyl, acyl group, sulfonyl, alkoxy carbonyl or aryloxycarbonyl are represented, q expressions 1 or 2, n and m each represent 1~3 Integer.

6. a kind of manufacture method of the liquid crystal display device with contact panel, is any one of manufacturing claims 1~5 The liquid crystal display device with contact panel the liquid crystal display device with contact panel manufacture method, its feature exists In possessing following process：

After at least one side of the optical compensation films forms the transparency conducting layer, the work that is heat-treated more than 150 DEG C Sequence；

It is bonded, is made inclined in a manner of the optical compensation films formed with the transparency conducting layer and diaphragm clamping polarizer The process of the one-piece type touch panel module of vibration plate；And

The optical compensation films side of the one-piece type touch panel module of the polarization plates is fitted in into the VA mode-types liquid crystal list The process of member.