CN110361805A - Polarization plates and display device - Google Patents

Polarization plates and display device Download PDF

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Publication number
CN110361805A
CN110361805A CN201910283668.4A CN201910283668A CN110361805A CN 110361805 A CN110361805 A CN 110361805A CN 201910283668 A CN201910283668 A CN 201910283668A CN 110361805 A CN110361805 A CN 110361805A
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CN
China
Prior art keywords
film
phase difference
layer
polarizing plate
circularly polarizing
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Granted
Application number
CN201910283668.4A
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Chinese (zh)
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CN110361805B (en
Inventor
神野亨
住吉铃鹿
柳智熙
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2018220022A external-priority patent/JP6866339B2/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Abstract

A kind of circularly polarizing plate, it is the circularly polarizing plate with polarization plates and phase difference film, above-mentioned phase difference film includes phase separation layer, the puncture elasticity modulus of above-mentioned phase difference film be 15gf/mm or more, it is φ 1mm that above-mentioned puncture elasticity modulus, which is by using point diameter, the needle of 0.5R and pierce through speed be 0.33cm/ second test measure elasticity modulus.

Description

Polarization plates and display device
Technical field
The present invention relates to polarization plates and display devices.
Background technique
In recent years, using organic electroluminescent (hereinafter also referred to organic EL) display device as the image display device of representative just In rapid proliferation.Equipped with the circularly polarizing plate for having polarizing film and phase difference film (plate of λ/4) in organic EL display device.By matching Circularly polarizing plate is set, the reflection of outer light can be prevented and improves the identification of picture.
It is more strong to the expectation of the slimming of image display device due to the rise of organic EL display device, with this phase Circularly polarizing plate is also required to be thinned with ground.It is studying and energy is changed to by the previous phase difference film for being molded with resin film The phase difference film formed using liquid-crystal compounds as material being enough thinned (referring for example to patent document 1).Polymerism liquid is used The phase difference film of brilliant compound is that polymerizable liquid crystal compound is coated on substrate to and is made its orientation, carries out illumination as needed Penetrate and fixed orientation state and manufacture.If will have the circularly polarizing plate of the phase difference film formed by polymerizable liquid crystal compound It is placed under hot environment, then there is a problem of that the form and aspect of circularly polarizing plate become blue or red from A-stage.Specifically, working as When circularly polarizing plate is rectangle, the form and aspect of the reflected light near 4 edge of circularly polarizing plate become blue or red respectively sometimes.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2017-54093 bulletin
Summary of the invention
Problems to be solved by the invention
It is an object of the invention to solve the above subject.The object of the present invention is to provide a kind of circularly polarizing plates, to have The circularly polarizing plate of phase difference film, before placing under high temperature environment and after placing, the form and aspect variation of reflected light is small.
The means used to solve the problem
[1] a kind of circularly polarizing plate is the circularly polarizing plate with polarization plates and phase difference film,
Above-mentioned phase difference film includes phase separation layer,
The puncture elasticity modulus of above-mentioned phase difference film is 15gf/mm or more,
It is φ 1mm that above-mentioned puncture elasticity modulus, which is by using point diameter, the needle of 0.5R and puncture speed are 0.33cm/ The elasticity modulus of the test measurement of second.
[2] circularly polarizing plate according to [1], wherein above-mentioned circularly polarizing plate has adhesive phase on its surface,
Above-mentioned polarization plates have polarizing film,
Above-mentioned phase separation layer includes layer made of polymerizable liquid crystal compound solidification,
Above-mentioned phase difference film configuration is between above-mentioned polarization plates and above-mentioned adhesive phase.
[3] circularly polarizing plate according to [2], wherein layer made of above-mentioned polarizing film is solidified as liquid-crystal compounds is formed.
[4] circularly polarizing plate according to [2] or [3], wherein the shape of above-mentioned circularly polarizing plate is essentially rectangle,
In above-mentioned polarization plates, it is laminated with protective film on the face with phase difference film side opposite side of above-mentioned polarizing film,
Said protection film is stretched film,
The draw direction of said protection film and the short side direction of circularly polarizing plate are substantial parallel.
[5] circularly polarizing plate according to any one of [1]~[4], wherein above-mentioned phase difference film includes two layers of phase difference Layer.
[6] a kind of circularly polarizing plate of subsidiary front panel, wherein [1] circularly polarizing plate described in~[5] and front panel are via viscous Layer is connect to be laminated.
[7] a kind of display device, wherein [2] circularly polarizing plate described in any one of~[4] via above-mentioned adhesive phase and It is laminated in display element.
The effect of invention
According to the present invention it is possible to provide it is a kind of have phase difference film, under high temperature environment place before and place after it is anti- The form and aspect for penetrating light change small circularly polarizing plate.
Detailed description of the invention
Fig. 1 is an example for showing the schematic sectional view of layer composition of circularly polarizing plate.
Fig. 2 is an example for showing the schematic sectional view of layer composition of organic EL display device.
Fig. 3 is the top view of sample for evaluation.
Description of symbols
1 polarization plates
2 phase difference films
3 organic EL display elements
4 front panels
5 points
10 polarizing films
11,12 protective film
13,14,16 adhesive phase
15 adhesive layers
20, layer made of the solidification of 21 polymerizable liquid crystal compounds
100,101,102,103 circularly polarizing plate
104,105,106 organic EL display device
Specific embodiment
<circularly polarizing plate>
Circularly polarizing plate of the invention has polarization plates and phase difference film.Polarization plates for example can be via bonding with phase difference film Layer and be laminated.As adhesive layer, it can be mentioned, for example aftermentioned adhesive phases, adhesive layer.In the present invention, polarization plates refer to: packet Laminated body containing polarizing film He the protective film for the one or two sides for being fitted in polarizing film.
Hereinafter, referring to Fig.1 come illustrate circularly polarizing plate of the invention layer constitute an example.It should be noted that in Fig. 1 not Adhesive layer for polarizing film 10 to be bonded respectively with protective film 11,12 is shown.The tool of circularly polarizing plate 100 shown in (a) of Fig. 1 The phase difference film 2 of layer 20 made of having polarization plates 1 and solidifying comprising polymerizable liquid crystal compound is laminated via adhesive phase 13 Layer constitute, wherein the polarization plates 1 are laminated with the first protective film 11 polarizing film 10 on one side, and in the another of polarizing film 10 It is laminated with the second protective film 12 on one side.In addition, circularly polarizing plate 100 is on the face with 1 side opposite side of polarization plates of phase difference film 2 With adhesive phase 14.Adhesive phase 14 can be the adhesive phase for being bonded to organic EL display element etc..
There is circularly polarizing plate 101 shown in (b) of Fig. 1 polarization plates 1 and phase difference film 2 to be laminated via adhesive phase 13 Layer is constituted, wherein the polarization plates 1 are laminated with the first protective film 11 polarizing film 10 on one side, and in the another of polarizing film 10 Surface layer is laminated with the second protective film 12.In circularly polarizing plate 101, phase difference film 2 has made of polymerizable liquid crystal compound solidification The layer that layer 21 made of layer 20 solidifies with polymerizable liquid crystal compound is laminated via adhesive layer 15 is constituted.In addition, circularly polarizing plate 101 have adhesive phase 14 on the face with 1 side opposite side of polarization plates of phase difference film 2.Adhesive phase 14, which can be, to be used for The adhesive phase that organic EL display element etc. is bonded.
There is circularly polarizing plate 103 shown in (c) of Fig. 1 polarization plates 1 and phase difference film 2 to be laminated via adhesive phase 13 Layer is constituted, wherein the polarization plates 1 are laminated with the first protective film 11 polarizing film 10 on one side.In circularly polarizing plate 103, partially Vibration plate 1 is that only have the polarization plates of protective film in the one side of polarizing film 10.In circularly polarizing plate 103, phase difference film 2 has polymerization Property liquid-crystal compounds solidification made of layer 20 and polymerizable liquid crystal compound solidification made of layer 21 be laminated via adhesive layer 15 Layer constitute.In addition, circularly polarizing plate 103 has adhesive phase on the face with 1 side opposite side of polarization plates of phase difference film 2 14.Adhesive phase 14 can be the adhesive phase for being bonded to organic EL display element etc..
As shown in Figure 1, phase difference film can have one layer of phase separation layer, it is possible to have two layers.In addition, phase difference film can With with alignment films, the alignment films are for being orientated polymerizable liquid crystal compound in the fabrication stage of phase difference film.Such as Fig. 1 institute Show, polarization plates only can be laminated with protective film in polarizing film on one side, can also be laminated with protective film on two sides.
Circularly polarizing plate can have the layer other than layer shown in FIG. 1.It, can as the layer that circularly polarizing plate can further have Enumerate front panel, light-shielding pattern etc..Front panel can be configured at the opposite side of the side for being laminated with phase difference film of polarization plates.
Light-shielding pattern can be formed on the face of polarization plates side of front panel.Light-shielding pattern can be formed in image display dress The frame (non-display area) set, so that user be made to can't see the wiring of image display device.
The interarea shape of circularly polarizing plate can be essentially rectangle.Interarea refers to: corresponding with display surface to have largest face Long-pending face.It is essentially that rectangle refers to: can be and cut off in such a way that at least one corner among 4 angles (corner) becomes obtuse angle Obtained by shape, the shape equipped with radian；Or it can have the direction recess into face perpendicular to a part of the end face of interarea Obtained by recess portion (notch)；Or a part in interarea can have and be dug into round, ellipse, polygon and their group The aperture portion of the shapes such as conjunction.
The size of circularly polarizing plate is not particularly limited.When circularly polarizing plate is essentially rectangle, the length of long side is preferably 6cm or more and 35cm hereinafter, more preferably 10cm or more and 30cm hereinafter, the length of short side be preferably 5cm or more and 30cm with Under, more preferably 6cm or more and 25cm or less.
<polarization plates>
In the present invention, polarization plates refer to the stacking of the protective film comprising polarizing film He the one or two sides for being fitted in polarizing film Body.The protective film that polarization plates have can have the surface-treated layers such as aftermentioned hard conating, anti-reflection layer, antistatic layer.Partially Vibration piece can for example be laminated with protective film via adhesive layer, adhesive phase.Illustrate the component that polarization plates have below.
(1) polarizing film
The polarizing film that polarization plates have can be the polarizing film for the absorption-type having the following properties, and the property is will have There is the linear polarization light absorption of the vibration plane parallel with its absorption axis and makes with orthogonal with absorption axiss (parallel with the axis of homology ) the linear polarization light transmission of vibration plane.As polarizing film possessed by first layer, can properly use makes through being uniaxially stretched Polyvinyl alcohol resin film absorption dichroism pigment and be orientated obtained by polarizing film.Polarizing film for example can use comprising following The method of process manufactures, the process are as follows: the process being uniaxially stretched to polyvinyl alcohol resin film；By polyethenol series The process that resin film dichroism pigment dyed and made its absorption dichroism pigment；The polyvinyl alcohol of dichroism pigment will be adsorbed with The process of the crosslinked fluids such as resin film boric acid aqueous solution processing；And the process washed after being handled with crosslinked fluid.
As polyvinyl alcohol resin, used after polyvinyl acetate system resin being saponified.As polyvinyl acetate Ester system resin, in addition to the homopolymer of vinyl acetate can be enumerated, i.e. other than polyvinyl acetate, can also enumerate vinyl acetate with The copolymer etc. that the other monomers that can be copolymerized are formed.It can include: not with the example of other monomers of vinyl acetate copolymerization Saturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and (methyl) acrylic amide with ammonium etc..
In this specification, " (methyl) acrylic compounds " refer at least one in acrylic compounds and methacrylic Person." (methyl) acryloyl group ", " (methyl) acrylate " etc. are also the same.
The saponification degree of polyvinyl alcohol resin is usually 85~100mol%, preferably 98mol% or more.Polyethenol series Resin can be by being modified, for example, it is also possible to using through the modified polyvinyl formal of aldehydes or polyvinyl acetal etc.. The average degree of polymerization of polyvinyl alcohol resin is usually 1000~10000, and preferably 1500~5000.Polyvinyl alcohol resin Average degree of polymerization can be found out based on JIS K 6726.
By this polyvinyl alcohol resin film obtained by film can be used as polarizing film former material film come using.To polyvinyl alcohol It is that the method that resin is filmed is not particularly limited, well known method can be used.The thickness of polyethenol series former material film does not have It is particularly limited to, in order to the thickness of polarizing film is set as 15 μm or less and it is preferable to use 5~35 μm of former material films.More preferably 20 μm or less.
Polyvinyl alcohol resin film be uniaxially stretched can before the dyeing of dichroism pigment, dyeing while or dye it After carry out.In the case where being uniaxially stretched after dyeing, this is uniaxially stretched can be before crosslinking Treatment or crosslinking Treatment Middle progress.Alternatively, it is also possible to be uniaxially stretched in their more than two stages.
When being uniaxially stretched, it can be stretched between the different roller of peripheral speed along an axis, heat also can be used Roller is stretched along an axis.It can be the dry type stretching stretched in an atmosphere in addition, being uniaxially stretched, be also possible to make The wet tensile stretched in the state of making polyvinyl alcohol resin membrane swelling with solvent, water.Stretching ratio is usually 3~8 Times.
As the method for dyeing polyvinyl alcohol resin film with dichroism pigment, such as can be used the film immersion in containing There is the method for the aqueous solution of dichroism pigment.As dichroism pigment, iodine, dichroic organic dye are used.It should be noted that For polyvinyl alcohol resin film, preferably implement impregnation in water in advance before dyeing processing.
As the crosslinking Treatment after being dyed with dichroism pigment, generally use the polyvinyl alcohol resin film leaching after dyeing Stain is in the method for the aqueous solution containing boric acid.It, should the aqueous solution containing boric acid in the case where using iodine as dichroism pigment Preferably comprise potassium iodide.
The thickness of polarizing film be usually 30 μm hereinafter, preferably 15 μm hereinafter, more preferably 13 μm hereinafter, further preferably For 10 μm hereinafter, particularly preferably 8 μm or less.The thickness of polarizing film is usually 2 μm or more, and preferably 3 μm or more.According to this hair The research of bright people etc. knows that the reason of form and aspect of circularly polarizing plate change is the variation of the phase difference value of phase difference film.Also know phase The reason of variation of the phase difference value of potential difference film is: dimensional contraction occurs for polarization plates in the circularly polarizing plate being placed under hot environment When stress.Therefore, from the viewpoint of influencing caused by the contraction for reducing polarizing film, the thickness of polarizing film is set as 15 μm It is effective below for preventing form and aspect from changing.
As polarizing film, such as can be consolidated as being recorded Japanese Unexamined Patent Publication 2016-170368 bulletin by liquid-crystal compounds Layer made of change is formed, and is taken in the cured film that liquid-crystal compounds is polymerized specifically, dichroism pigment can be used The polarizing film made of.As dichroism pigment, can be used has two colors absorbed in the range of 380~800nm of wavelength Property pigment.As dichroism pigment, it is preferable to use organic dyestuff.As dichroism pigment, it can be mentioned, for example azo-compounds.Liquid Brilliant compound is the liquid-crystal compounds that can be polymerize with the state of orientation, can have polymerizable group in the molecule.It should The polarizing film of type obtains as follows: the composition comprising liquid-crystal compounds and dichroism pigment is coated in alignment films, according to It needs to irradiate ultraviolet light or heating, thus fixes liquid-crystal compounds and dichroism pigment and obtain.Alternatively, it is also possible to such as WO2011/024891, the record of Japanese Unexamined Patent Publication 2018-120229 bulletin are formed partially by the dichroism pigment with liquid crystal liquid crystal property like that Shake piece.Layer made of so being solidified as liquid-crystal compounds forms polarizing film and can contribute to reduce the polarizing film under hot environment Change in size, for preventing form and aspect variation effective.
When the polarizing film of the layer made of solidifying comprising liquid-crystal compounds is as polarizing film, the thickness of polarizing film can be with It is set as 500nm or more, can be set to 3 μm or less.
(2) protective film
In circularly polarizing plate of the invention, preferably there is protective film in at least one side of polarizing film, preferably polarizing film with There is protective film on the face of phase difference film side opposite side.In circularly polarizing plate be essentially rectangle and protective film is stretched film In the case of, the preferably draw direction of protective film and the short side direction of circularly polarizing plate is substantial parallel.It is essentially in circularly polarizing plate In the case that rectangle and protective film are unstretching film, the maximum direction of tensile modulus of elasticity and circle preferably in protection film surface are inclined The short side direction of vibration plate is substantial parallel.If draw direction (or the maximum direction of tensile modulus of elasticity) has with short side direction This relationship, no matter then how the form and aspect of circularly polarizing plate change the tendency all reduced to the slow-axis direction of presence phase difference film.It is protecting In the case that the draw direction (or the maximum direction of tensile modulus of elasticity) of cuticula is parallel to short side, the polarizing film under hot environment And the draw direction for being less than protective film to the convergent force of draw direction of the caused protective film of stretching relaxation of protective film (or is drawn Stretch the maximum direction of elasticity modulus) the case where being parallel to long side, it is believed that form and aspect become smaller.It should be noted that stretching Elasticity modulus uses value of the tensile modulus of elasticity at 80 DEG C, such as utilizes AUTOGRAPH (registered trademark) (Co., Ltd. island Saliva makes made, model: AG-IS) it measures.
The draw direction of the protective film and short side direction of circularly polarizing plate is substantial parallel refers to: not only comprising both it is stringent flat Capable situation also includes the case where the two angulation is 0 ± 10 °.The draw direction of protective film and the short side of circularly polarizing plate Direction angulation is preferably 0 ± 5 °.Unstretching film is also comprising stretching ratio other than comprising unstretched film 1.1 times of substantially unstretched films below.
It can be in the protective film that the two sides of polarizing film is laminated comprising (preferably optically transparent) thermoplastic with translucency Property resin, such as chain polyolefin-based resins (polypropylene-based resin), cyclic polyolefin hydrocarbon system resin (norbornene resin Deng) etc polyolefin-based resins；The cellulose-based resin of triacetyl cellulose, diacetyl cellulose etc；Poly- terephthaldehyde The polyester based resin of sour glycol ester, polybutylene terephthalate (PBT) etc；Polycarbonate-based resin；Methyl methacrylate It is (methyl) acrylic resin of resin etc；Polystyrene resin；Polyvinyl chloride resin；Acrylonitrile butadiene Phenylethylene resin series；Acrylonitrile styrene system resin；Polyvinyl acetate system resin；Polyvinylidene chloride resin；Polyamides Amine system resin；Polyacetals system resin；Noryl system resin；Polysulfones system resin；Polyether sulfone system resin；Polyarylate system resin； Polyamidoimide system resin；The film of polyimides system resins etc..
As chain polyolefin-based resins, can enumerate: polyvinyl resin (polyvinyl resin of the homopolymer as ethylene, Copolymer based on ethylene), acrylic resin is (as the acrylic resin of the homopolymer of propylene, based on propylene Copolymer) etc chain olefin homopolymer and the copolymer that is formed by chain olefin of more than two kinds.
Cyclic polyolefin hydrocarbon system resin is the general name of resin obtained by being polymerize using cyclic olefin as polymerized unit, it can be mentioned, for example In Japanese Unexamined Patent Publication 1-240517 bulletin, Japanese Unexamined Patent Publication 3-14882 bulletin, Japanese Unexamined Patent Publication 3-122137 bulletin etc. The resin of record.It is open loop (co) polymer, the ring-type of cyclic olefin if enumerating the specific example of cyclic polyolefin hydrocarbon system resin (representative be nothing to the copolymer that the chain olefin of addition polymer, cyclic olefin and the ethylene of alkene or propylene etc is formed Advise copolymer) and by they with unsaturated carboxylic acid or derivatives thereof it is modified obtained by graft polymers and their hydrogenation Object.Wherein, as cyclic olefin, it is preferable to use: the norbornene of norbornene, polycyclic orbornene-based monomer etc is utilized It is the norbornene resin of monomer.
Polyester based resin is the resin with ester bond other than following cellulose esters systems resin, generally comprises polynary carboxylic The condensation polymer that acid or derivatives thereof is formed with polyalcohol.As polybasic carboxylic acid or derivatives thereof, can be used 2 yuan dicarboxylic acids or Its derivative, it can be mentioned, for example terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl esters.As 2 yuan of glycol can be used in polyalcohol, and it can be mentioned, for example ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexamethylene diformazans Alcohol.As the representative example of polyester based resin, the poly- terephthaldehyde as the condensation polymer of terephthalic acid (TPA) and ethylene glycol can be enumerated Sour glycol ester.
(methyl) acrylic resin is using the compound with (methyl) acryloyl group as the resin of main composition monomer. The specific example of (methyl) acrylic resin includes for example: poly- (methyl) acrylate of polymethyl methacrylate etc； Methyl methacrylate-(methyl) acrylic copolymer；Methyl methacrylate-(methyl) acrylate copolymer；Methyl-prop E pioic acid methyl ester-acrylate-(methyl) acrylic copolymer；(methyl) acrylate-styrene copolymer (MS resin etc.)； Copolymer (such as methyl methacrylate-methacrylic acid of methyl methacrylate and the compound with alicyclic alkyl Hexamethylene ester copolymer, methyl methacrylate-(methyl) acrylic acid norbornyl ester copolymer etc.).It is preferable to use with poly- (methyl) Poly- (methyl) the acrylic acid C of methyl acrylate etc1-6Arrcostab polymer as main component, more preferable use is with methyl-prop E pioic acid methyl ester is the methyl methacrylate system resin of main component (50~100 weight %, preferably 70~100 weight %).
Cellulose esters system resin is the ester of cellulose and fatty acid.The specific example of cellulose esters system resin includes cellulose Triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate.In addition, their copolymerization can be enumerated A part cellulose esters system resin made of the modification of other substituent groups of object, hydroxyl.Among these, particularly preferred cellulose iii Acetic acid esters (triacetyl cellulose).
Polycarbonate-based resin is the engineering plastics for the polymer being bonded comprising monomeric unit by carbonate group.
It is also useful for the phase difference value of protective film being controlled to be suitable for the value of the image display devices such as liquid crystal display device 's.For example, it is preferable to use the film that phase difference value is essentially zero is made in the liquid crystal display device of plane conversion (IPS) mode For protective film.Phase difference value is essentially zero to refer to: phase difference value Re (550) is 10nm hereinafter, wave in face when wavelength 550nm The absolute value of thickness direction phase difference value Rth when long 550nm is 10nm or less.Thickness direction phase when 480~750nm of wavelength The absolute value of potential difference value Rth is preferably 15nm or less.In addition, in order to improve picture identification whens user wears polariscope etc. Property, phase difference value Re (550) is set as 70~140nm in face when can be by wavelength 550nm.
For example, it is also possible to protective film is stretched according to the mode of liquid crystal display device and/or shrinks processing etc., by This assigns suitable phase difference.For example, can for compensation field angle purpose and use the film of single or multi-layer structure as Protective film.
The thickness of protective film is usually 1~100 μm, more excellent from the viewpoints such as intensity, treatability, preferably 5~60 μm It is selected as 10~55 μm, further preferably 15~40 μm.
It can be made of thermoplastic resin of the same race in the protective film that the one or two sides of polarizing film is bonded, it can also be by not Thermoplastic resin of the same race is constituted.In addition, thickness can be the same or different.It is possible to further phase having the same Poor characteristic, it is possible to have different phase difference characteristics.
As described above, at least either in protective film can have in its outer surface (face with polarizing film side opposite side) The surface-treated layer of standby hard conating, antiglare layer, optical diffusion layer, anti-reflection layer, low-index layer, antistatic layer or stain-proofing layer etc (coating).It should be noted that the thickness of protective film includes the thickness of surface-treated layer.
Protective film for example can fit in polarizing film via adhesive layer or adhesive phase.As formation adhesive layer Water system bonding agent, active energy ray-curable bonding agent or Thermocurable bonding agent, preferably water system can be used in bonding agent Bonding agent or active energy ray-curable bonding agent.As adhesive phase, aftermentioned adhesive phase can be used.
As water system bonding agent, the bonding agent comprising polyvinyl alcohol resin aqueous solution, water system two-component-type ammonia can be enumerated Carbamate system emulsion adhesive etc..Wherein, it is preferable to use the water system bonding agent comprising polyvinyl alcohol resin aqueous solution.As Polyvinyl acetate as the homopolymer of vinyl acetate is carried out saponification process in addition to can be used by polyvinyl alcohol resin Obtained from other than alcotex, can also use by vinyl acetate with can be formed with other monomers of its copolymerization Copolymer carry out polyvinyl alcohol based copolymer obtained from saponification process or by their hydroxyl carry out it is partially modified obtained by Modified polyvinylalcohol based polymer etc..Water system bonding agent may include aldehyde compound (glyoxal etc.), epoxide, melamine The crosslinking agents such as amine compound, methylol compound, isocyanate compound, amine compounds, multivalent metal salt.
In the case where using water system bonding agent, after being bonded polarizing film with protective film, it is preferably implemented for removing water system The drying process of water contained in bonding agent.After drying process, can be set such as 20~45 DEG C at a temperature of conserve support Nurse's sequence.
Above-mentioned active energy ray-curable bonding agent refers to: containing by irradiating ultraviolet light, visible light, electron beam or X The active energy beam of ray etc and the bonding agent of cured curability compound, preferably ultra-violet solidified bonding agent.
Above-mentioned curability compound can be the curability compound of cationically polymerizable, free-radical polymerised curability Compound.As the curability compound of cationically polymerizable, it can be mentioned, for example: epoxy compound (intramolecular have 1 or The compound of 2 or more epoxy groups), oxetanes based compound (intramolecular have 1 or 2 or more oxetanes ring Compound) or their combination.As free-radical polymerised curability compound, it can be mentioned, for example: (methyl) acrylic acid Based compound (compound of the intramolecular with 1 or 2 or more (methyl) acryloxy) has free-radical polymerised double bond Other vinyl compounds or their combination.It can also be by the curability compound and radical polymerization of cationically polymerizable The curability compound of conjunction property is applied in combination.Active energy ray-curable bonding agent is usually also comprising for causing above-mentioned solidification The cationic polymerization initiators and/or radical polymerization initiator of the curing reaction of property compound.
It, to improve cementability can be at least any among them when polarizing film to be bonded with protective film The binding face of person implements surface activation process.It as surface activation process, can enumerate: sided corona treatment, corona treatment, electric discharge Processing (glow discharge process etc.), flame treatment, ozone treatment, UV ozone treatment and ionization activity Irradiation are (at ultraviolet light Reason, electron beam treatment etc.) etc dry process；Water, the ultrasonication of acetone equal solvent, saponification process and anchor has been used to apply The wet processed of processing etc.These surface activation process can be carried out individually, can also be combined two or more.
In the case where the two sides of polarizing film is bonded protective film, the bonding agent for being bonded these protective films be can be together The bonding agent of kind, is also possible to bonding agent not of the same race.
As the alternative solution of protective film, protective layer can also be formed in at least one side of polarizing film.Protective layer can not Polarizing film is formed in via adhesive layer, adhesive phase.That is, protective layer can contact polarizing film and be formed.Protective layer can be with It is layer, the layer comprising aqueous resin comprising (methyl) acrylic resin.
Layer comprising (methyl) acrylic resin can be formed: will include the combination of (methyl) acrylic resin Object is coated on polarizing film, heating or irradiation active energy beam；Alternatively, coating includes (methyl) acrylic acid series tree on base material film The composition of rouge, heating or irradiation active energy beam.In the latter case, (methyl) acrylic acid series tree can also included Polarizing film is formed on the layer of rouge.
(methyl) acrylic resin refers to: among the monomer of composition (methyl) acrylic resin, having (methyl) The monomer of acryloyl group polymer as main component.Here, main component refers to: constituting the list of (methyl) acrylic resin The most monomer of content (quality %) among body ingredient.By using (methyl) acrylic resin as the material for forming protective layer Material, can also inhibit the optical characteristics of circularly polarizing plate to decline under hygrothermal environment.
As (methyl) acrylic resin, (methyl) acrylic acid series tree obtained by preferably polymerizeing photopolymerization monomer Rouge, for example, can be by with (methyl) acryloyl group monofunctional monomer or polyfunctional monomer be polymerized alone or mix 2 kinds with (methyl) acrylic resin obtained by upper polymerization.It can polymerize to have in (methyl) acrylic resin and there is (methyl) acryloyl Monomer other than the monomer of base, such as can polymerize and have the monomer with vinyl.
It as the monomer with (methyl) acryloyl group, is not particularly limited, can enumerate has 1 or 2 in the molecule The compound of (methyl) acryloyl group above, these can be used alone or mix two or more and use.Specifically, can arrange It lifts: dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) propylene Acid esters, double trimethylolpropane four (methyl) acrylate, the ethylene oxide of above-mentioned (methyl) acrylate or propylene oxide add At compound；In the molecule with oligoester (methyl) acrylate, oligo-ether (methyl) of 4 or more (methyl) acryloyl groups Acrylate, oligomeric carbamate (methyl) acrylate, oligomeric epoxy (methyl) acrylate, oligomeric melamine (first Base) acrylate, the polyfunctional acrylic ester with dendrimer, dendritic polymer structure etc..
The thickness of layer comprising (methyl) acrylic resin is usually 0.1 μm or more, preferably 0.3 μm or more, more excellent Be selected as 0.5 μm or more, in addition, usually 20.0 μm hereinafter, preferably 15 μm hereinafter, more preferably 10 μm or less.By making to wrap The thickness of layer containing (methyl) acrylic resin within the above range, is easy to get flexible circularly polarizing plate.
Layer comprising aqueous resin can be formed: the composition comprising aqueous resin is coated on polarizing film, heating Or irradiation active energy beam；Coating includes the composition of (methyl) acrylic resin on base material film, and heating or irradiation are lived Property energy-ray.In the latter case, polarizing film can also be formed on the layer comprising aqueous resin.
As aqueous resin, polyvinyl alcohol, vinyl-vinyl acetate copolymer, polyvinylpyrrolidone, shallow lake can be enumerated Water-soluble polymers such as powder class, methylcellulose, carboxymethyl cellulose, mosanom etc., wherein it is preferred that polyvinyl alcohol.
The thickness of layer comprising aqueous resin is preferably 0.1 μm or more, and more preferably 0.3 μm or more；Additionally, it is preferred that being 3 μ M hereinafter, more preferably 1.5 μm hereinafter, further preferably 1 μm or less.By making the thickness of the layer comprising aqueous resin upper It states in range, is thus easy to get flexible circularly polarizing plate.
Protective layer can be single layer, can also be formed by more than two layers.Protection is formed as by more than two layers The form of layer, can enumerate protective layer by the laminated body structure of the layer comprising (methyl) acrylic resin and the layer comprising aqueous resin At form.
<phase difference film>
Circularly polarizing plate of the invention has phase difference film.The puncture elasticity modulus of phase difference film is 15gf/mm or more, preferably For 20gf/mm or more, more preferably 25gf/mm or more, further preferably 30gf/mm or more.The puncture elasticity of phase difference film The upper limit value of modulus is not particularly limited, and can be set to such as 200gf/mm or less, or 50gf/mm or less.With this The phase difference film of the puncture elasticity modulus of kind range has the tendency for being not easy to produce phase difference value variation under high temperature environment.Thorn Wear that elasticity modulus is bigger, then relative to the dimensional contraction because of polarization plates due to the stress that generates, phase difference value is more difficult to change.
When phase difference film includes 1 layer of phase separation layer, the puncture elasticity modulus of phase difference film is 15gf/mm or more, preferably For 20gf/mm or more, more preferably 25gf/mm or more, further preferably 30gf/mm or more.The puncture elasticity of phase difference film The upper limit value of modulus is not particularly limited, and can be set to such as 200gf/mm hereinafter, can be 90gf/mm or less, or 50gf/mm or less.
When phase difference film includes 2 layers of phase separation layer, the puncture elasticity modulus of phase difference film is preferably 30gf/mm or more, More preferably 40gf/mm or more, further preferably 50gf/mm or more, particularly preferably 70gf/mm or more.Phase difference film The upper limit value for piercing through elasticity modulus is not particularly limited, can be set to such as 200gf/mm hereinafter, can for 150gf/mm hereinafter, It may be 100gf/mm or less.
Elasticity modulus is pierced through to refer to: when puncturing needle (piercing through tool) vertically relative to the interarea of phase difference film, phase Potential difference film will be broken the power (gf) before (or cracking) divided by value obtained by deformation (mm) at this time.As needle, can be used Point diameter is the needle of φ 1mm, 0.5R.The puncture speed of needle can be set to 0.33cm/ seconds.The measurement for piercing through elasticity modulus passes through Phase difference film is sandwiched and is provided between 2 plates that needle may pass through, diameter 15mm round hole below and carries out.Pierce through springform The measurement of amount can carry out in the environment of 23 DEG C of temperature.For example, elasticity modulus can be pierced through to 5 phase difference film measurements, and Using its average value as the puncture elasticity modulus of phase difference film.Piercing through in the measurement of elasticity modulus can use commercially available device. As commercially available device, can enumerate KATOTECH corporation portable compact testing machine " KES-G5 needle penetrates through power measurement specification ", Small desk testing machine " EZ Test " of Shimadzu Scisakusho Ltd etc..
The puncture elasticity modulus of phase difference film for example can be by adjusting used polymerizable liquid crystal compound, alignment films Type, the curing degree of polymerizable liquid crystal compound, phase difference film thickness etc. control.
Phase difference film has phase separation layer.Phase separation layer preferably has by the composition structure comprising polymerizable liquid crystal compound At layer.Polymerizable liquid crystal compound is specifically referred to by the layer that the composition comprising polymerizable liquid crystal compound is constituted to solidify Layer.In this specification, sometimes by the layer for providing the phase difference of λ/2, the layer (A layers positive) for the phase difference for providing λ/4 and just C layers etc. Collectively referred to as phase separation layer.Further, phase difference film may include aftermentioned alignment films.
As the layer for the phase difference for providing λ/2, preferably refer in the face in wavelength 550nm phase difference value be 200~ The layer of 280nm more preferably refers to the layer that phase difference value is 215~265nm in face.As the layer for the phase difference for providing λ/4, preferably Refer to that phase difference value in the face in wavelength 550nm is the layer of 100~160nm, more preferably refer in face phase difference value be 110~ The layer of 150nm.Positive C layers can be the relational layer that refractive index shows nx ≈ ny < nz.The phase of positive C layers of thickness direction Difference can be -50nm~-150nm in wavelength 550nm, can be -70nm~-120nm.
Layer made of polymerizable liquid crystal compound solidifies for example is formed in the alignment films for being set to substrate.Above-mentioned substrate can To be to have the function of supporting alignment films and be formed as the substrate of strip.The substrate can be used as the support with release property Body works, and can support transferred phase separation layer.Further, surface preferably has the bonding of this peelable degree Power.As above-mentioned base material, the resin film that the above-mentioned material as protective film can be enumerated and exemplified.
It as the thickness of substrate, is not particularly limited, is preferably set to such as 20 μm or more and 200 μm of ranges below.Base Material with a thickness of 20 μm or more when, intensity can be assigned.When on the other hand, with a thickness of 200 μm or less, add carrying out severing to substrate Work and when single substrate is made, the increase of processing bit, the abrasion of cutting edge can be inhibited.
It should be noted that various Anti-adhesives have can be implemented in substrate.As Anti-adhesive, it can be mentioned, for example: Processing, the embossing processing (indentation processing) etc. of easy bonding processing, incorporation filler etc..By implementing this place that prevents adhesion to substrate Reason, can be effectively prevented substrate when batching substrate be bonded each other, i.e. so-called adhesion, can manufacture optics to high production rate Film.
Layer made of polymerizable liquid crystal compound solidification is formed on substrate via alignment films.That is, according to substrate, orientation The sequence of film is laminated, and layer stackup made of polymerizable liquid crystal compound solidification is in above-mentioned alignment films.
It should be noted that alignment films are not limited to vertical alignment layer, it is also possible to make the molecule of polymerizable liquid crystal compound The alignment films that axis is horizontally oriented can also be the orientation for making the molecular axis of polymerizable liquid crystal compound carry out tilted alignment Film.As alignment films, preferably there is solvent resistance, i.e. not because applying aftermentioned composition comprising polymerizable liquid crystal compound etc. And dissolve, additionally, it is preferred that having tolerance for removing the heat resistance of solvent, the heat treatment for being orientated liquid-crystal compounds.As Alignment films can enumerate the alignment films comprising orientation polymer, optical alignment film and surface and be formed with relief pattern or two or more Groove and make its be orientated groove orientation film.The thickness of alignment films is usually the range of 10nm~10000nm, preferably 10nm The range of~1000nm, more preferably 500nm are hereinafter, the further preferably range of 10nm~200nm.Phase difference film, which has, to be taken In the case where film, if increasing the thickness of alignment films, being easy, which makes to pierce through elasticity modulus, becomes larger.
Alignment films comprising orientation polymer are generally as follows to obtain: will be dissolved with the group of orientation polymer in a solvent Object is closed to be coated on substrate and remove solvent or be coated on substrate and remove solvent for orientation polymer composition, into Row rubs (rubbing manipulation) and obtains.As orientation polymer, it can be mentioned, for example: in the molecule the polyamide with amido bond or Gelatin class, the in the molecule polyimides with imide bond and polyamic acid, polyvinyl alcohol, alkyl as its hydrolysate change Property polyvinyl alcohol, polyacrylamide, poly- oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and Polyacrylate.Wherein, preferred polyvinyl alcohol.Orientation polymer can be used alone or two or more is applied in combination.
Optical alignment film is generally as follows to obtain: by the combination of polymer or monomer comprising solvent and with photoreactive group Object is coated on substrate, irradiates polarised light (preferably polarization UV) after removing solvent, thus obtains.Optical alignment film is passing through selection institute The polarization direction of the polarised light of irradiation and the direction this respect that can arbitrarily control orientation control force is also advantageous.
Photoreactive group refers to: the group of liquid crystal aligning ability is generated by carrying out light irradiation.Specific enumerable ginseng With the group of light reaction, wherein the light reaction refers to that the orientation induction of the molecule generated by light irradiation or isomerization are anti- Answer, dimerization, photo-crosslinking or photolysis reactions etc. become liquid crystal aligning ability origin reaction.Wherein, from taking The excellent angle of tropism is set out, and the group of dimerization or photo-crosslinking is preferably engaged in.As photoreactive group, preferably Group with unsaturated bond, particularly double bond particularly preferably has and is selected from carbon-to-carbon double bond (C=C key), carbon-to-nitrogen double bond (C= N key), the group of at least one of nitrogen-nitrogen double bond (N=N key) and carbon-oxygen double bond (C=O key).
As the photoreactive group with C=C key, vinyl, polyene-based, Stilbene base, Stilbene oxazolyl can be enumerated (stilbazole), Stilbene oxazolyl (stilbazolium), chalcone base and cinnamoyl etc..It is anti-as the light with C=N key Answering property group can be enumerated with aromatic series schiff bases, the isostructural group of aromatic series hydrazone.As the photoreactivity with N=N key Group can be enumerated with azobenzene, azo naphthalene, heteroaromatic azo group, bisazo base, formazan base and azoxybenzene The group etc. of structure.As the photoreactive group with C=O key, can enumerate benzophenone base, cumarin base, anthraquinonyl and Dimaleoyl imino etc..These groups can have alkyl, alkoxy, aryl, allyloxy, cyano, alkoxy carbonyl group, hydroxyl, The substituent groups such as sulfonic group, halogenated alkyl.
Wherein, preferably engage in photodimerizationization reaction photoreactive group, from light orientation needed for polarizing light irradiation amount compared with It less and is easy to get from the viewpoint of thermal stability and the excellent optical alignment film of ageing stability, preferably cinnamoyl and looks into That ketone group.As the polymer with photoreactive group, the terminal part of the particularly preferred polymer lateral chain forms cinnamic acid knot The polymer with cinnamoyl of structure.
It about the type of polymerizable liquid crystal compound used in present embodiment, is not particularly limited, according to its shape Shape can be divided into rodlike type (Rod-like liquid crystal compound) and discoid type (disc-like liquid crystal compound, disc-like liquid crystal chemical combination Object).In addition, being respectively present low molecule type and polymer type.It should be noted that macromolecule typically refers to the degree of polymerization is (Polymer Physics phase translocation shifting ダ イ Na ミ Network ス (Polymer Physics-transition kinetics), Tu Jing are just male for 100 or more substance It writes, page 2, Yan Bo bookstore, 1992).
In the present embodiment, any polymerizable liquid crystal compound also can be used.Alternatively, it is also possible to use two or more Rod-like liquid crystal compound, disc-like liquid crystal compound of more than two kinds or Rod-like liquid crystal compound and disc-like liquid crystal chemical combination The mixture of object.
It should be noted that can be suitable for using such as Japanese Kohyo 11-513019 as Rod-like liquid crystal compound The rodlike liquid recorded in the claim 1 of bulletin or paragraph [0026]~[0098] of Japanese Unexamined Patent Publication 2005-289980 bulletin Brilliant compound.It can be suitable for the paragraph using such as Japanese Unexamined Patent Publication 2007-108732 bulletin as disc-like liquid crystal compound [0020] rod shaped liquid crystal recorded in~[0067] or paragraph [0013]~[0108] of Japanese Unexamined Patent Publication 2010-244038 bulletin Compound.
Polymerizable liquid crystal compound can also be used in combination of two or more.In this case, at least one kind of to have in the molecule There are 2 or more polymerizable groups.That is, layer made of above-mentioned polymerizable liquid crystal compound solidification preferably has polymerizable group Liquid-crystal compounds pass through the layer that polymerization is fixed, is formed.In this case, it no longer needs to show liquid crystal liquid crystal property after forming the layers.
Polymerizable liquid crystal compound has the polymerizable group that may be polymerized reaction.As polymerizable group, preference The functional group that such as polymerism ethylenically unsaturated group, cyclopolymerization group are able to carry out polyaddition reaction.More specifically, As polymerizable group, it can be mentioned, for example (methyl) acryloyl group, vinyl, styryl, allyls etc..Wherein preferred (first Base) acryloyl group.It should be noted that (methyl) acryloyl group is comprising the general of both methylacryloyl and acryloyl group It reads.
As described later, layer made of polymerizable liquid crystal compound solidifies can be by that will include polymerizable liquid crystal compound Composition is coated in such as alignment films and irradiates active energy beam and formed.It may include above-mentioned polymerization in above-mentioned composition Ingredient other than property liquid-crystal compounds.For example, preferably comprising polymerization initiator in above-mentioned composition.Used polymerization initiator Such as thermal polymerization, Photoepolymerizationinitiater initiater can be selected according to the form of polymerization reaction.For example, causing as photopolymerization Agent can enumerate alpha-carbonyl compound, asioinether, α-hydrocarbon substituted aromatic acyloin com, multicore naphtoquinone compounds, triarylimidazoles The combination etc. of dimer and p-aminophenyl ketone.The usage amount of polymerization initiator is relative to total solid state component in above-mentioned coating liquid Preferably 0.01~20 mass %, more preferably 0.5~5 mass %.
In addition, may include polymerism list in above-mentioned composition from the uniformity of coated film and the angle of film-strength Body.As polymerizable monomer, free-radical polymerised or cationically polymerizable compound can be enumerated.Wherein preferably it is multi-functional from By base polymerizable monomer.
It should be noted that can be preferably copolymerized with above-mentioned polymerizable liquid crystal compound as polymerizable monomer Polymerizable monomer.The usage amount of polymerizable monomer is preferably 1~50 mass % relative to the gross mass of polymerizable liquid crystal compound, More preferably 2~30 mass %.
In addition, may include surfactant from the uniformity of coated film and the angle of film-strength, above-mentioned composition. As surfactant, conventionally known compound can be enumerated.Wherein, particularly preferred fluorine system compound.
In addition, may include solvent in above-mentioned composition, it is preferable to use organic solvent.As organic solvent, example can be enumerated Such as amide (such as n,N-Dimethylformamide), sulfoxide (such as dimethyl sulfoxide), heterocyclic compound (such as pyridine), hydrocarbon (example Such as benzene, hexane), alkyl halide (such as chloroform, methylene chloride), ester (such as methyl acetate, ethyl acetate, butyl acetate), Ketone (such as acetone, methyl ethyl ketone), ether (such as tetrahydrofuran, 1,2- dimethoxy-ethane).Wherein optimizing alkyl halide, ketone. Furthermore it is possible to which two or more organic solvent combinations is used.
In addition, may include polarizing film interface side vertical-tropism agent, Air Interface side vertical-tropism agent in above-mentioned composition Promote Deng the horizontal alignments such as vertically oriented promotor and the agent of polarizing film interface side horizontal alignment, the horizontal alignment agent of Air Interface side Into the various alignment agents of agent etc.In addition, in addition to the above ingredients can also include closely sealed modifying agent, increasing in above-mentioned composition Mould agent, polymer etc..
Above-mentioned active energy beam includes ultraviolet light, visible light, electron beam, X-ray, preferably ultraviolet light.As above-mentioned The light source of active energy beam, it can be mentioned, for example: low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, halogen It is lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, the LED light source of light for issuing 380~440nm of wave-length coverage, chemical lamp, black Light lamp, microwave-excited mercury lamp, metal halide lamp etc..
Ultraviolet irradiation intensity is usually 100mW/cm2~3,000mW/cm2.Ultraviolet irradiation intensity is preferably to work Change the intensity in cationic polymerization initiators or the effective wavelength region of radical polymerization initiator.The time for irradiating ultraviolet light is logical It is often 0.1 second~10 minutes, preferably 0.1 second~5 minutes, more preferably 0.1 second~3 minutes, further preferably 0.1 second~ 1 minute.
Ultraviolet light can irradiate 1 time or be divided into and repeatedly irradiate.It is preferred that carrying out multiple ultraviolet light irradiation.If liquid-crystal compounds Aggregate rate improve, then pierce through elasticity modulus and be easy to be increased in the scope of the present invention.Although also depending on used polymerization Initiator, but the accumulated light at wavelength 365nm is preferably set to 700mJ/cm2More than, more preferably it is set as 1,100mJ/cm2More than, Further preferably it is set as 1,300mJ/cm2More than.It is set as the polymerism liquid that above-mentioned accumulated light constitutes phase difference film for improving The aggregate rate of brilliant compound is advantageous the puncture elasticity modulus increase of phase difference film.Accumulated light at wavelength 365nm is excellent Choosing is set as 2,000mJ/cm2Hereinafter, being more preferably set as 1,800mJ/cm2Below.It is set as above-mentioned accumulated light and has to lead to phase difference film The worry of coloring.
In addition, the orientation of liquid-crystal compounds is upset because just irradiating the heat after ultraviolet light in order to prevent, preferably in ultraviolet light Cooling process is set after irradiation.By the way that cooling process is arranged after uv irradiation, the heat because generating after just irradiation can be inhibited The orientation of caused liquid-crystal compounds is upset.As a result, the degree of orientation of liquid-crystal compounds improves, it is available with higher The film of rigidity.Cooling temperature can be set to such as 20 DEG C hereinafter, can be set to 10 DEG C or less.Cooling time for example can be set to 10 Second or more, it can be set to 20 seconds or more.
In present embodiment, the thickness of phase separation layer is preferably 0.5 μm or more.In addition, the thickness of above-mentioned phase separation layer is excellent 10 μm are selected as hereinafter, more preferably 5 μm or less.It should be noted that above-mentioned upper limit value and lower limit value can be in any combination.Such as Fruit phase separation layer with a thickness of above-mentioned lower limit value more than, then sufficient durability can be obtained.If phase separation layer with a thickness of upper Upper limit value is stated hereinafter, then facilitating the thin layer of circularly polarizing plate.The adjustable thickness of phase separation layer is that can be provided λ/4 Phase difference layer, provide λ/2 phase difference layer or positive C layers of desired face in the phase of phase difference value and thickness direction The thickness of difference.
Phase difference film may include layer made of layers of polymer liquid-crystal compounds solidification, also may include two layers or more Layer made of polymerizable liquid crystal compound solidification.When phase difference film includes layer made of two layers of polymerizable liquid crystal compound solidification, Two layers is preferably to provide the layer and the layer of positive C layers of combination or the phase difference for providing λ/4 and offer λ/2 of the phase difference of λ/4 The combination of the layer of phase difference.It, can be by taking when phase difference film includes layer made of two layers of polymerizable liquid crystal compound solidification Made respectively on film layer made of polymerizable liquid crystal compound solidification and by the two via adhesive layer or adhesive layer by layer It folds to manufacture phase difference film, polymerizable liquid crystal can also be further formed on the layer made of polymerizable liquid crystal compound solidification Close layer made of object solidification.After the two is laminated, substrate and alignment films can be removed.The thickness of phase difference film is preferably 3 ~30 μm, more preferably 5~25 μm.
<adhesive phase>
Adhesive phase can be by with (methyl) acrylic acid series, rubber series, carbamate system, ester system, organic silicon-type, poly- second The resin of alkene ether system etc adhesive composition as main component is constituted.Wherein, preferably clear, weatherability, heat resistance Etc. it is excellent with (methyl) acrylic resin be basic polymer adhesive composition.Adhesive composition can be activity Energy ray-curable, thermohardening type.The thickness of adhesive phase is usually 3~30 μm, and preferably 3~25 μm.
It can be suitable for using as (methyl) acrylic resin (base polymer) used in adhesive composition Such as with (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid 2- ethyl One kind or two or more polymer or copolymer for monomer in (methyl) acrylate of own ester etc.It is preferred that making polar monomer It is copolymerized with base polymer.As polar monomer, it can be mentioned, for example (methyl) acrylic acid, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) hydroxy-ethyl acrylate, (methyl) acrylamide, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid The monomer with carboxyl, hydroxyl, amide groups, amino, epoxy group etc. of ethylene oxidic ester etc.
Adhesive composition can only include above-mentioned base polymer, but usually also contain crosslinking agent.It, can as crosslinking agent It illustrates: forming the metal ion of the divalent of carboxylic metallic salt or more between carboxyl；The polyaminated of amido bond is formed between carboxyl Close object；Polyepoxy compound, the polyalcohol of ester bond are formed between carboxyl；The polyisocyanates of amido bond is formed between carboxyl Compound.Wherein preferred polyisocyanate compound.
<front panel>
The present invention includes a kind of circularly polarizing plate of subsidiary front panel, wherein circularly polarizing plate and front panel via adhesive layer and It is laminated.Front panel is configured in the identification side of polarization plates.Front panel can be laminated in polarization plates via adhesive layer.As Adhesive layer, it can be mentioned, for example above-mentioned adhesive phases, adhesive layer.As shown in (a), (b), (c) of Fig. 2, front panel 4 can be through It is layered on the protective film 11 of polarization plates 1 by adhesive phase 16.
As front panel, at least one side that can be enumerated in glass, resin film includes front panel etc. made of hard conating.As Such as high transmission glass, strengthened glass can be used in glass.When especially with thin transparent facestock, chemistry was preferably implemented The glass of reinforcing.The thickness of glass can be set to such as 100 μm~5mm.
At least one side of resin film include front panel made of hard conating can unlike existing glass it is hard directly, and It is with soft characteristic.The thickness of hard conating is not particularly limited, and can be such as 5~100 μm.
As resin film, the film formed by macromolecule can be, the macromolecule is with comprising norbornene or polycyclic Cyclic olefine derivative, cellulose (diacetyl cellulose, three of the unit of the monomer of the cycloolefin of orbornene-based monomer etc Acetylcellulose, acetylcellulose butyrate, isobutyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl fiber Element) vinyl-vinyl acetate copolymer, polycyclic alkene, polyester, polystyrene, polyamide, polyetherimide, polyacrylic, Polyimides, polyether sulfone, polysulfones, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, gathers inclined dichloro at polyamidoimide Ethylene, polyvinyl alcohol, poly- second contracting acetal, polyether-ketone, polyether-ether-ketone, polyether sulfone, polymethyl methacrylate, poly terephthalic acid Glycol ester, polybutylene terephthalate (PBT), polyethylene naphthalate, polycarbonate, polyurethane, epoxy resin etc.. Unstretching film, monadic stretching membrane or biaxially-stretched film can be used in resin film.These macromolecules can respectively be used alone or by 2 Kind or more be used in mixed way.As resin film, the polyamidoimide film or polyimide film of preferably clear and excellent heat resistance, The polyester film, the transparency and the excellent heat resistance that are stretched uniaxially or biaxially and the cyclic olefine for the enlargement that can cope with film spreads out Biomembrane, polymethyl methacrylate film and the transparency and optics aspect do not have anisotropic triacetyl cellulose and different Butyl ester cellulose membrane.The thickness of resin film can be 5~200 μm, preferably 20~100 μm.
Above-mentioned hard conating can be formed by the solidification of hard coating combination, the hard coating combination include irradiation luminous energy or Thermal energy and the reactive explosive for forming cross-linked structure.Above-mentioned hard conating can be by including light-cured type (methyl) acrylic acid simultaneously The solidification of the hard coating combination of ester monomer or oligomer and light-cured type epoxy monomer or oligomer is formed.Above-mentioned photocuring Type (methyl) acrylate monomer may include selected from epoxy (methyl) acrylate, carbamate (methyl) acrylate and One or more of polyester (methyl) acrylate.Above-mentioned epoxy (methyl) acrylate can make have (methyl) acryloyl group Carboxylic acid react and obtain relative to epoxide.
Hard coating combination can be also comprising more than one of solvent, photoinitiator and additive.Additive can be with Comprising being selected from one of inorganic nano-particle, levelling agent and stabilizer or more, in addition to this, as usual in the technical field Each ingredient used, can be also including, for example, antioxidant, UV absorbent, surfactant, lubricant, anti-fouling agent etc..
<light-shielding pattern>
Light-shielding pattern can be used as the framework of the display device of front panel or application front panel or at least part of shell And it provides.Light-shielding pattern can be formed in the display element side of front panel.Light-shielding pattern can block each wiring of display device, To make user can't see each wiring.The color and/or material of light-shielding pattern are not particularly limited, can with black, The resinous substances of the multiple colors such as white, gold is formed.In one embodiment, the thickness of light-shielding pattern can be 2 μm~ 50 μm, it can be preferably 4 μm~30 μm, 6 μm~15 μm of range can be more preferably.In addition, in order to inhibit by light-shielding pattern Bubble caused by difference in height between display unit is mixed into and sees boundary portion, can assign shape to light-shielding pattern.
<manufacturing method of circularly polarizing plate>
Illustrate the manufacturing method of circularly polarizing plate for the circularly polarizing plate 100 shown in (a) of Fig. 1.Circularly polarizing plate 100 can be with It is manufactured and polarization plates 1 and phase difference film 2 are laminated via adhesive phase 13.
Polarization plates 1 polarizing film 10 can be laminated via adhesive layer respectively with protective film 11,12 to manufacture.Polarization Plate can by prepare the component of strip and in a manner of roll-to-roll by after the fitting of each component, be cut into regulation shape and manufacture, It can also be bonded again after each component is cut into regulation shape.After being bonded protective film 11,12 on polarizing film 10, Ke Yishe Set heating process, damping process.
Phase difference film 2 can for example manufacture as follows.Alignment films are formed on substrate, coating includes polymerism in alignment films The coating liquid of liquid-crystal compounds.Active energy beam is irradiated in the state of being orientated polymerizable liquid crystal compound, thus Solidify polymerizable liquid crystal compound.Stacking is formed in viscous on stripping film on layer made of solidifying in polymerizable liquid crystal compound Mixture layer 14.Then peeling base and/or alignment films.Then the adhesive phase being formed on stripping film is laminated on protective film 12 13.Phase difference film 2 can by prepare strip component and in a manner of roll-to-roll by each component fitting after, be cut into regulation shape Shape manufactures, and each component can also be cut into after regulation shape and is bonded again.
Then, the removing film stripping that will be laminated on adhesive phase 13 by phase difference film 2 and is polarized via adhesive phase 13 Plate 1 is bonded, it is possible thereby to make circularly polarizing plate 100.
After cognizable color difference can be by making heat resistant test in circular polarization plate face after heat resistant test on reflecting plate Reflection form and aspect in circular polarization plate face homogenize to reduce.As for making the reflected colour in the circular polarization plate face after heat resistant test Element necessary to mutually homogenizing, reflection form and aspect in circular polarization plate face before can enumerating heat resistant test are uniformly and resistance to heat examination The reflected colour phase change for testing front and back is small.
The form and aspect of reflected light before the heat resistant test of circularly polarizing plate uniform this point in face, after reducing heat resistant test Circular polarization plate face in reflected light hue difference for be preferred.Specifically, the center in interarea before heat resistant test Excentral part in the form and aspect and interarea of the reflected light of (can be center of gravity, be also possible to the point 5 in center shown in Fig. 3) (such as can be it is shown in Fig. 3 it is centrally located other than point 5 at reflected light form and aspect) reflected light form and aspect difference it is big Small preferably 1.0 hereinafter, more preferably 0.8 hereinafter, further preferably 0.6 or less.The reflected light of central portion and other parts Hue difference can for example be calculated by the following formula.
Δ a*b*=((Δ a*)2+(Δb*)2〕1/2
In formula, Δ a* is the difference of the a* of central portion and the a* of excentral part, and Δ b* is the difference of b* correspondingly. When the uniformity of the form and aspect of the reflected light in circular polarization plate face before heat resistant test is low, even if the form and aspect of the reflected light of heat-resisting front and back Change small, the improvement of identification also becomes smaller sometimes.Heat resistant test for example can be by being set as temperature 80 for circularly polarizing plate DEG C drying machine in take care of 168 hours and carry out.
<purposes>
Circularly polarizing plate can be used in various display devices.Display device refers to the device with display element, comprising making For the light-emitting component or light emitting device of light emitting source.As display device, it can be mentioned, for example: liquid crystal display device, organic EL are shown Device, inorganic EL (hereinafter also referred to inorganic EL) display device, electron emission display (such as Field emission displays Device (also referred to as FED), surface field emission display (also referred to as SED)), Electronic Paper (used electronic ink, electrophoresis element Display device, plasm display device, projection type image display apparatus (such as grating light valve (also referred to as GLV) display device, tool Have the display device of DMD Digital Micromirror Device (also referred to as DMD)) and piezoelectric ceramics display etc..Liquid crystal display device further includes transmission Any one of type liquid crystal display device, transflective liquid crystal display device etc..These display devices can be 2 dimension image of display Display device, be also possible to show 3 d image 3 d display device.Circularly polarizing plate can be particularly useful for being especially In organic EL display device or inorganic EL display device.
In (a), (b) of Fig. 2, organic EL display device 104,105 has via being laminated on phase difference film 20 Adhesive phase 14 constitutes the layer that circularly polarizing plate is laminated in organic EL display element 3.
Embodiment
(1) measuring method of film thickness
It is measured using the digital micrometer MH-15M of Nikon Corporation.
(2) measuring method of phase difference value
It is measured using measuring difference of phases device KOBRA-WPR (prince measures machine Co. Ltd. system).
[production of phase difference film 1]
By 5 parts of the light orientation materials of following structures (weight average molecular weight: 30,000) mixing with 95 parts of cyclopentanone (solvent), Obtained mixture is stirred 1 hour at 80 DEG C, thus obtains composition for forming alignment film.
Relative to by polymerizable liquid crystal compound A and polymerizable liquid crystal compound B as shown below according to 90: 10 quality Than 100 parts of mixture be obtained by mixing, levelling agent (F-556 is added；Dainippon Ink Chemicals's system) 1.0 parts and as polymerization initiator 2- dimethylamino -2- benzyl -1- (4- morphlinophenyl) butane -1- ketone (" IRGACURE 369 (Irg369) ", BASF JAPAN Co. Ltd. system) 6 parts.
N-methyl-2-pyrrolidone (NMP) is added again so that solid component concentration reaches 13%, is stirred 1 hour at 80 DEG C, To obtain liquid crystal cured film formation composition.
Polymerizable liquid crystal compound A is manufactured by the method that Japanese Unexamined Patent Publication 2010-31223 bulletin is recorded.In addition, poly- Conjunction property liquid-crystal compounds B is manufactured based on the method that Japanese Unexamined Patent Publication 2009-173893 bulletin is recorded.Respective point described below Minor structure.
(polymerizable liquid crystal compound A)
(polymerizable liquid crystal compound B)
(manufacture of the laminated body of layer made of solidifying comprising substrate, alignment films, polymerizable liquid crystal compound)
In the cyclic olefine resin film (trade name " ZF-14- of Zeon Corp of 50 μ m-thicks as substrate 50 ") implement sided corona treatment on.On the face for implementing sided corona treatment, composition for forming alignment film is coated with bar coater.It will apply Cloth film is 1 minute dry at 80 DEG C.For the coated film after drying, using polarized UV radiation device (USHIO Electric Co., Ltd Trade name " SPOT CURE SP-9 "), UV is polarized along the 45 ° of irradiations of shaft angle degree, obtains alignment films.Polarization UV irradiation carry out to The accumulated light of wavelength 313nm reaches 100mJ/cm2。
Then, with bar coater in alignment films coating of liquid crystalline cured film formation composition.By coated film in 120 DEG C of dryings 1 minute.For the coated film after drying, with the high-pressure sodium lamp (trade name of USHIO Electric Co., Ltd: " Unicure VB- 15201BY-A ") irradiation ultraviolet light.Ultraviolet irradiation process carries out in a nitrogen atmosphere to the accumulated light of wavelength 365nm reaching To 250mJ/cm2.After rigid irradiation, as cooling process, cured film investment is set as in 5 DEG C of baking oven 20 seconds.From baking oven After taking-up, be again carried out above-mentioned ultraviolet light irradiation process and above-mentioned cooling process immediately, thus obtain comprising substrate, alignment films, And polymerizable liquid crystal compound solidify made of layer laminated body.
(measurement of phase difference value)
Adhesive phase is laminated on the layer made of the polymerizable liquid crystal compound solidification of laminated body.It will via the adhesive phase Laminated body fits in glass.Then, the substrate that removing laminated body has, obtains the sample for evaluating phase difference value.It is tied Fruit is, as the phase difference value Re (λ) under each wavelength, layer made of polymerizable liquid crystal compound solidification have Re (450)= 121nm, Re (550)=142nm, Re (650)=146nm.As a result Re (450)/Re (550)=0.85, Re is calculated (650)/Re (550)=1.03.Layer made of polymerizable liquid crystal compound solidifies is to provide the layer of the phase difference of λ/4.
(measurement for piercing through elasticity modulus)
The measurement for piercing through elasticity modulus carries out as follows.To the portable compact testing machine " KES- of KATOTECH Co. Ltd. system G5 needle penetrates through power and measures specification " installation needle.Make needle relative to it is between 2 plates for being fixed on the round hole for being provided with diameter 11mm, The interarea of the laminated body of peeling base vertically pierces through, calculates the power (gf) before will being broken divided by deformation (mm) at this time Obtained by be worth.The operation is carried out respectively relative to 5 phase difference films (puncture test sample), using its average value as phase difference The puncture elasticity modulus of film.As needle, having used point diameter is the needle of φ 1mm, 0.5R.The speed for piercing through needle is set as 0.33cm/ seconds.The puncture elasticity modulus of phase difference film 1 is shown in table 1.
[production of phase difference film 2]
According to every 1 accumulation of the ultraviolet light irradiated when solidifying the coated film of liquid crystal cured film formation composition Light quantity reaches 400mJ/cm at wavelength 365nm2(that is, total accumulated light of ultraviolet light irradiation twice is 800mJ/cm2) side Formula is operated, and in addition to this, is equally carried out with [production of phase difference film 1], production includes the laminated body of phase difference film 2.With The above-mentioned puncture elasticity modulus for similarly measuring phase difference film 2.The puncture elasticity modulus of phase difference film 2 is shown in table 1.
[production of phase difference film 3]
According to every 1 accumulation of the ultraviolet light irradiated when solidifying the coated film of liquid crystal cured film formation composition Light quantity reaches 600mJ/cm at wavelength 365nm2(that is, total accumulated light of ultraviolet light irradiation twice is 1200mJ/cm2) Mode is operated, and in addition to this, is equally carried out with [production of phase difference film 1], thus production includes the stacking of phase difference film 3 Body.The puncture elasticity modulus of phase difference film 3 is measured as described above.The puncture elasticity modulus of phase difference film 3 is shown in table 1.
[production of phase difference film 4]
According to every 1 accumulation of the ultraviolet light irradiated when solidifying the coated film of liquid crystal cured film formation composition Light quantity reaches 800mJ/cm at wavelength 365nm2(that is, total accumulated light of ultraviolet light irradiation twice is 1600mJ/cm2) Mode is operated, and in addition to this, is equally carried out with [production of phase difference film 1], thus production includes the stacking of phase difference film 4 Body.The puncture elasticity modulus of phase difference film 4 is measured as described above.The puncture elasticity modulus of phase difference film 4 is shown in table 1.
[production of phase difference film 5]
It will be as the commercially available orientation polymer Sun Ever SE-610 of vertical alignment layer formation composition (daily output Chemical industry Co. Ltd. system) 5 parts by weight mix with 95 parts by weight of methyl ethyl ketone (solvent), and it obtains vertical alignment layer and is formed with combination Object.
By the optical polymerism nematic liquid crystal compound (Merck & Co., Inc. as vertically oriented phase separation layer formation composition RMM28B processed) 20 parts by weight and 1 parts by weight of IRGACURE 907 (BASF AG Irg-907) as Photoepolymerizationinitiater initiater it is molten Thus solution prepares vertically oriented phase separation layer formation coating liquid in 80 parts by weight of propylene glycol monomethyl ether.
In the cyclic olefine resin film (trade name " ZF-14- of Zeon Corp of 50 μ m-thicks as substrate 50 ") implement sided corona treatment on.Vertical alignment layer formation composition is coated on the face for implemented sided corona treatment with bar coater. By coated film with 100 DEG C are heated 120 seconds and make its solidification, vertical alignment layer is consequently formed.
Vertically oriented phase separation layer formation coating liquid is coated on the vertical alignment layer obtained before this, by coated film with temperature 80 DEG C are spent to heat 60 seconds.Then, carrying out accumulated light is 220mJ/cm2Ultraviolet light (UVB) irradiation, make vertically oriented phase difference Layer formation is polymerize with composition, is solidified, and 0.7 μm of thickness of vertically oriented phase separation layer is formed on vertical alignment layer.Measurement institute Phase difference value of the obtained vertically oriented phase separation layer at wavelength 550nm, result be Re (550)=1nm, Rth (550)=- 75nm.That is, vertically oriented phase separation layer is positive C layers for meeting nx ≈ ny < nz this relationship.It should be noted that as substrate Phase difference value of the cyclic olefine resin film at wavelength 550nm be almost 0, therefore do not influence the light of vertically oriented phase separation layer Learn characteristic.
Then, it is formed on obtained vertically oriented phase separation layer in the same manner as [production of phase difference film 2] and λ/4 is provided Phase difference layer, thus production include phase difference film 5 laminated body.Thus it has made and has been sequentially laminated with substrate, vertical orientation Film, C layers positive, alignment films, provide λ/4 phase difference layer the laminated body comprising phase difference film 5.Phase is measured as described above The puncture elasticity modulus of potential difference film 5.The puncture elasticity modulus of phase difference film 5 is shown in table 1.
[table 1]
Pierce through elasticity modulus/gf/mm
Phase difference film 1 12.1
Phase difference film 2 18.1
Phase difference film 3 29.0
Phase difference film 4 36.4
Phase difference film 5 90.1
[preparation of adhesive phase]
Adhesive A: thick 5 μm of sheet adhesive (" NCF#L2 " of Lintec Co. Ltd. system)
Adhesive B: thick 25 μm of sheet adhesive (" P-3132 " of Lintec Co. Ltd. system)
[preparation of protective film]
Protective film A: the film of thick 3 μm of hard conating is formed in thick 25 μm of the stretched film comprising norbornene resin (the trade name " COP25ST-HC " of Jujo Paper Co., Ltd
Protective film B: thick 20 μm of tri acetyl cellulose membrane (trade name " ZRG20SL " of Fuji Photo Film Co., Ltd.)
Protective film C: thick 25 μm of the unstretching film comprising triacetyl cellulose
[production of front panel]
Prepare the front panel that there is hard conating on the two sides of base material film.Base material film is thick 50 μm of polyimide film, hard to apply Layer with a thickness of 10 μm.
[embodiment 1]
[production of polarization plates]
Thick 20 μm of polyvinyl alcohol film (99.9 moles of average degree of polymerization about 2400, saponification degree % or more) is drawn by dry type It stretches and is uniaxially stretched to about 4 times, then after being impregnated 40 seconds in 40 DEG C of pure water with keeping tensioning state, in iodine/potassium iodide/water weight It is impregnated 30 seconds at 28 DEG C in the aqueous solution that amount ratio is 0.052/5.7/100 and carries out dyeing processing.Then, in potassium iodide/boron Acid/water weight ratio is to impregnate 120 seconds in the aqueous solution of 11.0/6.2/100 at 70 DEG C.Then, with pure water 15 seconds of 8 DEG C Afterwards, 50 seconds dry, then 20 seconds dry with 75 DEG C with 60 DEG C in the state of the tension holding with 300N, it obtains making polyvinyl alcohol Film gas absorption quantity has 7 μm of thickness of polarizing film of iodine.
In the coated on one side water system bonding agent of polarizing film, it is bonded protective film A.At this point, according to the draw direction phase of protective film A The mode that absorption axiss for polarizing film are 45 degree is bonded.It is coated with water system bonding agent in the another side of polarizing film, fitting is protected Cuticula B.Then it makes it dry, obtains polarization plates.Above-mentioned water system bonding agent is relative to 100 parts of water dissolved with carboxy-modified poly- second Enol (trade name " KL-318 " obtained by Kuraray Co., Ltd.) 3 parts and added with gathering as water-soluble epoxy resin Amide epoxy system additive (trade name " Sumirez Resin 650 (30) " of Taoka Chemical Industries Co. Ltd., solid-state at The aqueous solution that point concentration is 30%) bonding agent obtained by 1.5 parts.
The layer upper layer made of the polymerizable liquid crystal compound solidification of made laminated body in [production of phase difference film 2] Folded adhesive A.Then, from laminated body peeling base, laminating adhesive B on the face exposed after removing.Thus production is comprising viscous The phase difference film of the two-sided subsidiary adhesive of layer made of mixture A, polymerizable liquid crystal compound solidify, alignment films and adhesive B 2。
[production of circularly polarizing plate]
It is bonded double on the protective film B of above-mentioned polarization plates via the adhesive A of the phase difference film 2 of two-sided subsidiary adhesive Face is attached to the phase difference film 2 of adhesive.Absorption of the slow axis of layer made of polymerizable liquid crystal compound solidifies relative to polarizing film Axis is 45 degree, and the draw direction relative to protective film A is 90 degree.Thus production includes protective film A, water system adhesive layer, polarization Layer, alignment films and adhesive B made of piece, water system adhesive layer, protective film B, adhesive A, polymerizable liquid crystal compound solidification Circularly polarizing plate.
Circularly polarizing plate is cut in such a way that the slow axis of layer made of polymerizable liquid crystal compound solidifies is parallel to long side At the rectangle of 140mm × 70mm size.At this point, the draw direction of protective film A is parallel to short side direction.Circle obtained by cutting Glass plate (the Corning Incorporated's system, product number: EAGLE XG (registrar that polarization plates are fitted to via adhesive B with a thickness of 0.4mm Mark)).Thus the sample of evaluation is made.
[embodiment 2]
In embodiment 1, the laminated body made in [production of phase difference film 3] is used to replace [production of phase difference film 2] The laminated body of middle production makes circularly polarizing plate in addition to this similarly to Example 1, makes the sample of evaluation.
[embodiment 3]
In embodiment 1, the laminated body made in [production of phase difference film 4] is used to replace [production of phase difference film 2] The laminated body of middle production makes circularly polarizing plate in addition to this similarly to Example 1, makes the sample of evaluation.
[embodiment 4]
In example 2, absorption of the slow axis of layer made of solidifying according to polymerizable liquid crystal compound relative to polarizing film Protective film A is fitted in polarizing film by the mode that axis is 45 degree and the draw direction relative to protective film A is 0 degree, in addition to this, Circularly polarizing plate is made similarly to Example 2, makes the sample of evaluation.At this point, the draw direction of protective film A is parallel to long side side To.
[embodiment 5]
In embodiment 1, the laminated body made in [production of phase difference film 5] is used to replace [production of phase difference film 2] The laminated body of middle production makes circularly polarizing plate in addition to this similarly to Example 1, makes the sample of evaluation.
[embodiment 6]
Protective film B is not laminated in the production of polarization plates, in addition to this, makes circularly polarizing plate similarly to Example 1.Again Adhesive phase B is layered on protective film A.Above-mentioned front panel is bonded with circularly polarizing plate via adhesive phase B.Thus it makes It is solid to contain front panel, adhesive phase B, protective film A, water system adhesive layer, polarizing film, adhesive A, polymerizable liquid crystal compound The circularly polarizing plate of layer, alignment films made of change and adhesive B.Make the sample of evaluation similarly to Example 1 again.
[embodiment 7]
[surface-treated layer, which is formed, uses composition]
Following compositions are mixed and prepare surface-treated layer formation composition.
The dendrimer, dendritic polymer acrylate (Miramer SP1106, Miwon company) 2.0 with acryloyl group of 18 functions Mass parts,
The urethane acrylate (Miramer PU-620D, Miwon company) with acryloyl group of 6 functions 10.0 mass parts,
Acrylate monomer (M340, Miwon company) 8.0 mass parts with acryloyl group of 3 functions,
Photoepolymerizationinitiater initiater (Irgacure-184, BASF AG) 2 mass parts,
Levelling agent (BYK-3530, BYK company) 0.1 mass parts,
77.9 mass parts of methyl ethyl ketone (MEK)
[polarizing film, which is formed, uses composition]
(polymerizable liquid crystal compound)
Polymerizable liquid crystal compound has used polymerizable liquid crystal compound [hereinafter also referred to compound shown in formula (1-6) (1-6)] and formula (1-7) shown in polymerizable liquid crystal compound [hereinafter also referred to compound (1-7)].
Compound (1-6) and compound (1-7) according to Lub et al.Recl.Trav.Chim.Pays-Bas, 115, 321-328 (1996) record method and synthesize.
(dichroism pigment)
Dichroism pigment used following formula (2-1a), (2-1b), Japanese Unexamined Patent Publication 2013-101328 shown in (2-3a) The azopigment recorded in the embodiment of bulletin.
Polarization layer formation uses composition to prepare as follows: by 75 parts of compound (1-6), 25 parts of compound (1-7), as two colors The above-mentioned formula (2-1a) of property dyestuff, (2-1b), azopigment shown in (2-3a) be 2.5 parts each, 2- bis- as polymerization initiator Methylamino -2- benzyl -1- (4- morphlinophenyl) butane -1- ketone (Irgacure369, BASF JAPAN corporation) 6 weight Part and 1.2 parts of the polyacrylic acid ester compounds (BYK-361N, BYK-Chemie corporation) as levelling agent are mixed into as molten In 400 parts of toluene of agent, obtained mixture is stirred 1 hour at 80 DEG C, is thus prepared.
Above-mentioned surface-treated layer formation composition is coated on protective film A.Film is 5 minutes dry at 80 DEG C, then Ultraviolet light is irradiated with UV irradiation unit, so that light exposure is 500mJ/cm2(365nm benchmark), thus makes curing of coating.UV irradiation Device has used SPOT CURE SP-7, USHIO Electric Co., Ltd system.Surface-treated layer with a thickness of 10.0 μm.
Alignment films shape used in the production of phase difference film 1 is coated on the surface-treated layer of protective film A by stick coating method At with composition.Film is 1 minute dry at 80 DEG C.Then, film is irradiated using above-mentioned UV irradiation unit and wiregrating and is polarized UV, to assign orientation characteristic to film.Light exposure is 100mJ/cm2(365nm benchmark).Wiregrating has used UIS-27132## (USHIO Electric Co., Ltd system).Alignment films are consequently formed.Alignment films with a thickness of 100nm.
Above-mentioned polarizing film formation composition is coated on being formed by alignment films by stick coating method.By film with 100 DEG C After heat drying 2 minutes, it is cooled to room temperature.Using above-mentioned UV irradiation unit, with accumulated light 1200mJ/cm2(365nm benchmark) Ultraviolet light is irradiated to film, polarizing film is consequently formed.Obtained polarizing film with a thickness of 3 μm.Coating is comprising poly- on polarizing film The composition of ethylene alcohol and water so that after dry with a thickness of 0.5 μm, protective layer is formed with the drying 3 minutes of 80 DEG C of temperature.By This production includes protective film A, surface-treated layer, alignment films, the polarization plates of polarizing film, protective layer.
Using above-mentioned polarization plates, in addition to this, circularly polarizing plate is made similarly to Example 6, make the sample of evaluation. Sample for evaluation successively has front panel, adhesive phase B, protective film A, surface-treated layer, alignment films, polarizing film, protective layer, glues Layer, alignment films and adhesive B made of mixture A, polymerizable liquid crystal compound solidification.
[embodiment 8]
The laminated body of protective film A and surface-treated layer is replaced to make similarly to Example 7 in addition to this using protective film C Make circularly polarizing plate, makes the sample of evaluation.Sample for evaluation successively has front panel, adhesive phase B, protective film C, orientation Layer, alignment films and adhesive B made of film, polarizing film, protective layer, adhesive A, polymerizable liquid crystal compound solidification.
[embodiment 9]
Front panel is not laminated, in addition to this, makes circularly polarizing plate similarly to Example 8, makes sample for evaluation.Evaluation Successively have made of protective film C, alignment films, polarizing film, protective layer, adhesive A, polymerizable liquid crystal compound solidification with sample Layer, alignment films and adhesive B.
[comparative example 1]
In embodiment 1, the laminated body made in [production of phase difference film 1] is used to replace [production of phase difference film 2] The laminated body of middle production makes circularly polarizing plate in addition to this similarly to Example 1, makes the sample of evaluation.
[the form and aspect evaluation before and after heat resistant test]
As reflecting plate, prepare the MIRO (5011GP) of ALANOD corporation.The reflecting plate is that have by the way that shape is deposited At reflecting surface mirror reflective plate.
Above-mentioned sample for evaluation is placed in said reflection plate.Use spectral photometric colour measuring meter (Konica Minolta Japanese strain Formula commercial firm trade name: CM-2600d) implement reflected light form and aspect (a*, b*) measurement.The form and aspect of reflected light be light source be D65 when Value, (include positive reflection light) is measured in a manner of SCI.
Specifically, being measuring point with point 5 shown in Fig. 3.9 points 5 shown in Fig. 3 are that the end apart from circularly polarizing plate is The point in the region on the inside of 5mm exists in a manner of being separated by about 30mm on short side direction, be separated by about 65mm in longitudinal direction.
For the sample for evaluation made in above-described embodiment 1~9 and comparative example 1, the drying machine at 80 DEG C of temperature is measured The form and aspect of the reflected light of 168 hours front and backs of middle keeping.Calculate the absolute value of the form and aspect changes delta a*b* of each point.With form and aspect variation The form and aspect changing value that each point is calculated based on direction sets the difference of the maxima and minima of the form and aspect changing value of each evaluation sample For Δ a*b* (MAX-MIN).Show the result in table 2 and table 3.
Δ a*=a* (after heat resistant test)-a* (before heat resistant test)
Δ b*=b* (after heat resistant test)-b* (before heat resistant test)
Δ a*b*=((Δ a*)2+(Δb*)2〕1/2
It should be noted that form and aspect changing value is set as Δ a*b* when Δ a* is 0 or more, and when Δ a* is less than 0, form and aspect Changing value is set as Δ a*b* × -1.
[table 2]
[table 3]
Industrial availability
According to the present invention it is possible to provide a kind of color having phase difference film, being placed after preceding and placement under high temperature environment The small circularly polarizing plate of the variation of phase, thus it is useful.

Claims (7)

1. a kind of circularly polarizing plate is the circularly polarizing plate with polarization plates and phase difference film,
The phase difference film includes phase separation layer,
The puncture elasticity modulus of the phase difference film is 15gf/mm or more,
It is φ 1mm that the puncture elasticity modulus, which is by using point diameter, the needle of 0.5R and puncture speed are 0.33cm/ seconds Test the elasticity modulus of measurement.
2. circularly polarizing plate according to claim 1, wherein the circularly polarizing plate has adhesive phase on its surface,
The polarization plates have polarizing film,
The phase separation layer includes layer made of polymerizable liquid crystal compound solidification,
The phase difference film configuration is between the polarization plates and described adhesive layer.
3. circularly polarizing plate according to claim 2, wherein layer shape made of the polarizing film is solidified as liquid-crystal compounds At.
4. circularly polarizing plate according to claim 2 or 3, wherein the shape of the circularly polarizing plate is essentially rectangle,
In the polarization plates, it is laminated with protective film on the face with phase difference film side opposite side of the polarizing film,
The protective film is stretched film,
The draw direction of the protective film and the short side direction of circularly polarizing plate are substantial parallel.
5. circularly polarizing plate according to any one of claims 1 to 4, wherein the phase difference film includes two layers of phase difference Layer.
6. a kind of circularly polarizing plate of subsidiary front panel, wherein circularly polarizing plate described in Claims 1 to 5 and front panel are via viscous Layer is connect to be laminated.
7. a kind of display device, wherein circularly polarizing plate described in any one of claim 2~4 via described adhesive layer and It is laminated in display element.
CN201910283668.4A 2018-04-11 2019-04-09 Polarizing plate and display device Active CN110361805B (en)

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CN114786940A (en) * 2019-12-10 2022-07-22 住友化学株式会社 Laminate and optical laminate

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