CN106168693A - Duplexer and liquid crystal indicator - Google Patents
Duplexer and liquid crystal indicator Download PDFInfo
- Publication number
- CN106168693A CN106168693A CN201610339729.0A CN201610339729A CN106168693A CN 106168693 A CN106168693 A CN 106168693A CN 201610339729 A CN201610339729 A CN 201610339729A CN 106168693 A CN106168693 A CN 106168693A
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- China
- Prior art keywords
- duplexer
- methyl
- polarizer
- active energy
- protecting film
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
Abstract
The present invention relates to duplexer and liquid crystal indicator.The present invention provides the duplexer that solvent crackle does not occur on the protecting film constituting Polarizer, and then provides the visual excellent liquid crystal indicator being equipped with described duplexer.The duplexer of the present invention sequentially has substrate, active energy ray curable bond layer and Polarizer, and wherein, described Polarizer is to have polaroid and the Polarizer of annular ethylene series resin protecting film, and described duplexer meets following formula.S represents the dissolubility forming the polymerizable monomer comprised in the active energy ray curable adhesive composite of active energy ray curable bond layer in the water of 100g 25 DEG C.Phase difference value in the face of the annular ethylene series resin protecting film at Re (550) expression wavelength 550nm.δ represents SP value.Re (550) >=-38.37ln (S)-434.4 δ+8063.
Description
Technical field
The present invention relates to duplexer and liquid crystal indicator.
Background technology
Liquid crystal indicator has been mounted to the mobile devices such as mobile phone, PC, has been
To the plurality of devices such as large-scale tv machine.In the mobile devices such as mobile phone, in viewing side
Surface on configuration protection glass (cover glass) or with touch sensor (touch
Sensor) the protection glass (hereinafter referred to as touch panel (touch panel)) of assembly,
Between protection glass or touch panel and liquid crystal panel, optically transparent liquid adhesive is set
(Liquid Optically Clear Adhesives, hereinafter referred to as LOCA) also makes it solidify
Situation is more.By using LOCA, can suppress at liquid crystal panel and protection glass or touch
Engaging-in bubble between panel, and then the light loss caused because of reflection can be reduced.
But, when between protection glass or touch panel and liquid crystal panel, LOCA is set,
Sometimes the protection of Polarizer as one of the component of outmost surface constituting liquid crystal panel is had
The situation that the interarea of film contacts with LOCA, or occur to cause LOCA because LOCA is liquid
Liquid drops to the situation of Polarizer side.But also known have following situation: because of Polarizer
Interarea and side contact with LOCA, the bonding agent composition of LOCA cause constitute polarisation
On the protecting film on the surface of plate occur solvent crackle (solvent crack), display device can
Reduce depending on property.
Patent Document 1 discloses by forming sun on the two sides of the protecting film constituting Polarizer
The protecting film of photopolymerizable and in making the face of protecting film phase difference value Re be more than 50nm,
Thus improve the method that solvent resistant is anti-thread breakage.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2014-32270 publication
Summary of the invention
Invent problem to be solved
Yet suffer from solvent crackle, the visuality of liquid crystal indicator reduces such asking
Topic (according to the kind of the polymerizable monomer comprised in bonding agent and polymerizable monomer containing than
Example and constitute the difference of kind of protecting film of Polarizer and occur).Even protecting
In the case of the two sides of cuticula is formed with the protecting film of cationically polymerizable, also cannot avoid partially
Tabula rasa side contacts with bonding agent, solvent crackle still occurs so in the end of Polarizer
Problem not yet solve.
For solving the means of problem
The present invention includes following proposal.
[1] duplexer, described duplexer sequentially has substrate, active energy ray-curable
Type bond layer and Polarizer, wherein,
Described Polarizer is to have polaroid and the Polarizer of annular ethylene series resin protecting film,
Described duplexer meets following formula (1).
Re(550)≥-38.37ln(S)-434.4δ+8063 (1)
[in formula (1), S represents:
SkRepresent the active energy beam forming described active energy ray curable bond layer
The kth polymerizable monomer comprised in curing type adhesive composite is at 25 DEG C of 100g
Dissolubility in water, akRepresent the weight portion of described kth polymerizable monomer.
In Re (550) represents the face of the annular ethylene series resin protecting film at wavelength 550nm
Phase difference value.
δ represents by the calculated described annular ethylene series resin protecting film of Y-MB method
SP value.
Wherein, the unit of S be the unit that unit is nm, δ of g, Re (550) be (MPa)1/2。]
[2] duplexer described in item [1], wherein, active energy ray curable is bonding
Oxidant layer is to cover interarea and the layer of side of Polarizer.
[3] item [1] or the duplexer described in [2], wherein, active energy beam is solid
Change type adhesive composite comprises free-radical polymerised compound.
[4] item [1]～the duplexer according to any one of [3], wherein, ring-type alkene
The SP value of hydrocarbon system resin protection film is 17～19.
[5] item [1]～the duplexer according to any one of [4], wherein, duplexer
Be shaped as rectangle, a length of more than the 5cm on long limit, a length of more than the 3cm of minor face.
[6] liquid crystal indicator, it has according to any one of item [1]～[5]
Duplexer.
The effect of invention
Pass through the present invention, it is possible to provide on the protecting film constituting Polarizer, solvent crackle does not occur
Duplexer, and then the visual excellent liquid crystal display being equipped with described duplexer can be provided
Device.
Accompanying drawing explanation
[Fig. 1] is for representing the schematic diagram of an example of the Rotating fields of the duplexer of the present invention.
[Fig. 2] is for representing the schematic diagram of an example of the Rotating fields of the duplexer of the present invention.
[Fig. 3] for represent annular ethylene series resin protecting film in embodiment and comparative example with
The figure of relation between phase difference value Re (550) and dissolubility S in the face that SP value is corresponding.
Description of reference numerals
1 substrate
2 active energy ray curable bond layers
3 annular ethylene series resin protecting film
4 polaroids
5 other protecting film
6 binding agents
7 liquid crystal cells
Polarizer known to 8
10 Polarizers
11 with the Polarizer of binding agent
20 liquid crystal panels
100 duplexers
Detailed description of the invention
The duplexer of the present invention sequentially has substrate, active energy ray curable bond layer
And Polarizer, described Polarizer has polaroid and annular ethylene series resin protecting film.Hereinafter,
Each component of the duplexer constituting the present invention is illustrated.
[substrate]
The substrate used in the duplexer of the present invention is preferably optically transparent substrate.So-called light
Learn transparent, refer to the absorbance in the wave-length coverage of 460～720nm with 85%.Base
The thickness of plate is usually 0.5～5mm.It addition, the refractive index of substrate is preferably penetrated with active-energy
The refractive index of line curing type bond layer and liquid crystal panel is close, preferably 1.4～1.7.
Substrate can be glass substrate, it is also possible to for resin substrate.As forming glass substrate
Glass, borosilicic acid (borosilicic acid) type, soda lime type etc. can be enumerated.Concrete and
Speech, can enumerate EAGLE XG (registered trade mark) (Corning company) and JADE (note
Volume trade mark) (Corning company).As resin substrate, poly terephthalic acid second can be enumerated
The acrylic films such as the polyester films such as diol ester, polycarbonate membrane, polymethyl methacrylate film.
Substrate can also be touch panel.Touch panel can use existing known touch panel,
Generally, including the conductive layer being arranged between 2 transparent substrates.Transparent as 2
Substrate, can enumerate above-mentioned glass substrate, as conductive layer, can enumerate tin indium oxide.
[active energy ray curable bond layer]
Active energy ray curable bond layer is formed between substrate and Polarizer
Layer is the space (air gap) for clogging between substrate and Polarizer, by substrate and polarisation
The layer that plate is bonding.By filling space with active energy ray curable bond layer, can carry
High-impact, or reduce the light loss caused because of reflection.Active energy ray curable
Bond layer can be by irradiating active-energy to active energy ray curable adhesive composite
Ray, it is made to be solidified to form.Active energy ray curable bond layer is formed at aftermentioned
Polarizer on, but owing to can produce because adhesive composite is liquid and the liquid that causes
Body drips, so being generally also formed with active energy ray curable on the side of Polarizer
Bond layer.That is, active energy ray curable bond layer is usually inclined with covering described later
The mode on the surface of tabula rasa is set.
The thickness of active energy ray curable bond layer is usually 30～200 μm, preferably
It is 50～200 μm, more preferably 80～150 μm.Active energy ray curable bonding agent
Layer is preferably optical clear.So-called optical clear, refers in the range of 460～720nm
There is the absorbance of 85%.It addition, the refractive index of active energy ray curable bond layer
Preferably close with the refractive index of substrate and liquid crystal panel, preferably 1.4～1.7.
[active energy ray curable adhesive composite]
Active energy ray curable adhesive composite is liquid, comprises polymerizable monomer.
As polymerizable monomer, cationically polymerizable compound, free-radical polymerised chemical combination can be enumerated
Thing, preferably free-radical polymerised compound.As cationically polymerizable compound, can enumerate
There is the compound of at least 1 oxetanes ring (4 yuan of cyclic ethers) (below, in intramolecular
Be referred to as oxetane compound), in intramolecular, there is at least 1 oxirane ring (3
Unit cyclic ethers) compound (hereinafter referred to as epoxide) etc..As radical polymerization
Property compound, preferably has the chemical combination of at least 1 (methyl) acryloxy in intramolecular
Thing (hereinafter referred to as (methyl) acrylic compounds).It should be noted that this theory
In bright book, (methyl) acryloxy refers to, methacryloxy or acryloxy,
In other the term with (methyl) too.
As (methyl) acrylic compounds, can enumerate, in intramolecular, there is at least 1
(methyl) acrylate monomer of (methyl) acryloxy, have at least 2 in intramolecular
(methyl) acrylate oligomer etc. of individual (methyl) acryloxy.They can divide
It is not used alone, it is possible to and use two or more.And when using two or more, (methyl) third
Alkene acid ester monomer can be two or more, and (methyl) acrylate oligomer can be 2 kinds
Above, certainly, it is possible to and with (methyl) acrylate monomer of more than a kind and a kind with
On (methyl) acrylate oligomer.
As above-mentioned (methyl) acrylate monomer, can enumerate, in intramolecular, there is 1
Simple function (methyl) acrylate monomer of (methyl) acryloxy, have in intramolecular
There is two senses (methyl) acrylate monomer of 2 (methyl) acryloxies and dividing
There is in son multifunctional (methyl) acrylic acid of (methyl) acryloxy of more than 3
Ester monomer.
As simple function (methyl) acrylate monomer, (methyl) acrylic acid four can be enumerated
Hydrogen bran ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxyl third
Ester or (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl,
(methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-hydroxyl-3-benzene oxygen
Base propyl ester, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) third
Isopropyl gadoleate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (first
Base) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid
Monooctyl ester, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) propylene
Acid undecyl ester, (methyl) dodecylacrylate, (methyl) acrylate
Ester, 1,4-CHDM mono acrylic ester, (methyl) acrylic acid Bicvclopentyl ester
(dicyclopentanyl (meth) acrylate), (methyl) acrylic acid double cyclopentenyl ester
(dicyclopentenyl (meth) acrylate), (methyl) benzyl acrylate, (methyl)
Isobornyl acrylate, (methyl) acrylate, (methyl) acrylic acid are double
Cyclopentenyl epoxide ethyl ester (dicyclopentenyloxyethyl (meth) acrylate), (methyl)
Acrylate, ethyl carbitol (methyl) acrylate, trihydroxy methyl
Propane list (methyl) acrylate, tetramethylolmethane list (methyl) acrylate, phenoxy group
Polyethylene Glycol (methyl) acrylate (phenoxy polyethylene glycol
(meth) acrylate) etc..
As simple function (methyl) acrylate monomer, (methyl) containing carboxyl can be used
Acrylate monomer.As simple function (methyl) acrylate monomer containing carboxyl, can
Enumerate 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl
Epoxide ethyl hexahydrophthalic acid, (methyl) carboxyethyl acrylates, 2-(methyl)
Acryloyl-oxyethyl succinic acid, N-(methyl) acryloxy-N ', N '-dicarboxyl first
Base p-phenylenediamine, 4-(methyl) acryloyl-oxyethyl trimellitic acid etc..
As two senses (methyl) acrylate monomer, ethylene glycol bisthioglycolate (methyl) can be enumerated
Acrylate, 1,3 butylene glycol two (methyl) acrylate, BDO two (first
Base) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol
Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trihydroxy methyl third
Alkane two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, two or three hydroxyl first
Base propane two (methyl) acrylate, diethylene glycol two (methyl) acrylate, three second
Glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 3 the third two
Alcohol two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, polypropylene glycol
Two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate (polytetramethylene
Glycol di (meth) acrylate), polysiloxanes two (methyl) acrylate, hydroxyl spy penta
Acid two (methyl) acrylate of DOPCP, 2, double [4-(methyl) propylene of 2-
Oyloxyethoxy ethoxyl phenenyl] propane, 2, double [4-(methyl) acryloyl-oxy of 2-
Base oxethyl ethoxycyclohexyl] propane, hydrogenation dicyclopentadiene base two (methyl) third
Olefin(e) acid ester, Tricyclodecane Dimethanol two (methyl) acrylate, 1,3-dioxa hexamethylene
Alkane-2,5-diyl two (methyl) acrylate (another name: dioxane glycol two
(methyl) acrylate), the acetal chemical combination that formed of hydroxy pivalin aldehyde and trimethylolpropane
Thing (chemical name: 2-(2-hydroxyl-1,1-dimethyl ethyl)-5-ethyl-5-
Hydroxymethyl-1,3-dioxane) two (methyl) acrylate, three (hydroxyls
Base ethyl) isocyanuric acid ester two (methyl) acrylate etc..
As multifunctional (methyl) acrylate monomer more than trifunctional, glycerol can be enumerated
Three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two or three hydroxyls
Methylpropane three (methyl) acrylate, two trimethylolpropane four (methyl) acrylic acid
Ester, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate,
Dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate
And the aliphatic polybasic more than such trifunctional of dipentaerythritol six (methyl) acrylate
Many (methyl) acrylate of alcohol.Additionally, can enumerate more than trifunctional through halogen substiuted
Many (methyl) acrylate of polyhydric alcohol, three (methyl) of alkylene oxide addition product of glycerol
Acrylate, three (methyl) acrylate of alkylene oxide addition product of trimethylolpropane, 1,
1,1-tri-[(methyl) acryloyloxyethoxy ethyoxyl] propane, three (hydroxyl second
Base) isocyanuric acid ester three (methyl) esters of acrylic acid etc..
As (methyl) acrylate oligomer, carbamate (methyl) third can be enumerated
Olefin(e) acid ester (urethane (meth) acrylate) oligomer, polyester (methyl) acrylate are low
Polymers, epoxy (methyl) acrylate oligomer etc..
Carbamate (methyl) acrylate oligomer refers to have amino in intramolecular
Formic acid ester bond (-NHCOO-) and the compound of at least 2 (methyl) acryloxies.
Specifically, can enumerate, in intramolecular, there is at least 1 (methyl) acryloxy and extremely
(methyl) acrylate monomer containing hydroxyl of few 1 hydroxyl and the ammonia of polyisocyanates
The product of carbamateization reaction, makes polyhydric alcohol react with polyisocyanates and containing of obtaining
The carbamate compounds of terminal isocyanate group and be respectively provided with at least 1 in intramolecular
(methyl) acrylate monomer of individual (methyl) acryloxy and at least 1 hydroxyl
The product etc. of urethane reaction.
(methyl) acrylate containing hydroxyl used in reacting as urethane
Monomer, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxyl
Base propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 2-hydroxyl-
3-phenoxy-propyl, glycerol two (methyl) acrylate, trimethylolpropane two (methyl)
Acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl)
Acrylate etc..
As for the carbamic acid with above-mentioned (methyl) acrylate monomer containing hydroxyl
The polyisocyanates of esterification, can enumerate 1, and hexamethylene-diisocyanate, lysine two are different
Cyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, toluene two
Isocyanates, xylylene diisocyanate, aromatic by these diisocyanate
Isocyanates type hydrogenation and obtain diisocyanate (such as, hydrogenated tolylene diisocyanate,
Hydrogenation xylylene diisocyanate etc.), triphenylmethane triisocyanate, dibenzyl benzene
Triisocyanate etc. two-or tri-isocyanate and by above-mentioned diisocyanate multimerization
The polyisocyanates etc. obtained.
It addition, as in order to by making containing terminal isocyanate acid with the reaction of polyisocyanates
The carbamate compounds of ester group and the polyalcohols that uses, except aromatic series, aliphatic
And outside the polyhydric alcohol of ester ring type, also can enumerate PEPA, polyether polyol etc..Make
For aromatic polyhydric alcohol, can enumerate Isosorbide-5-Nitrae-benzene dimethanol, 1,3-benzene dimethanol, 1,
2-benzene dimethanol, 4,4 '-naphthalene dimethanol, 3,4 '-naphthalene dimethanol etc..As fat
Race and the polyhydric alcohol of ester ring type, can enumerate BDO, 1,6-hexanediol, second two
Alcohol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, three
Hydroxymethyl-propane, two trimethylolpropanes, tetramethylolmethane, dipentaerythritol, dihydroxymethyl
Heptane, dihydromethyl propionic acid, dimethylolpropionic acid, glycerol, hydrogenated bisphenol A etc..
PEPA is to be contracted by the dehydration of above-mentioned polyalcohols with polybasic carboxylic acid or its acid anhydride
The material closing reaction and obtain.As polybasic carboxylic acid or its acid anhydride, including succinic acid, succinic acid
Acid anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid,
Trimellitic anhydride, PMA, pyromellitic dianhydride, phthalic acid, phthalic anhydride,
M-phthalic acid, p-phthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride etc..
About polyether polyol, in addition to poly alkylene glycol, also can enumerate by above-mentioned
It is polyoxyalkylene-modified polynary that polyalcohols or dihydroxy benzenes class obtain with the reaction of alkylene oxide
Alcohol (polyoxyalkylene-modified polyol) etc..
Polyester (methyl) acrylate oligomer refers to have at least 2 esters in intramolecular
Key and the compound of at least 2 (methyl) acryloxies.Specifically, (first can be passed through
Base) acrylic acid, polybasic carboxylic acid or its acid anhydride and the dehydration condensation of polyhydric alcohol and obtain.
As the polybasic carboxylic acid used in dehydration condensation or its acid anhydride, succinic acid, succinum can be enumerated
Anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid,
Trimellitic anhydride, PMA, pyromellitic dianhydride, hexahydrophthalic acid, hexahydro neighbour's benzene
Dicarboxylic acid anhydride, phthalic acid, phthalic anhydride, M-phthalic acid, p-phthalic acid
Deng.It addition, as the polyhydric alcohol used in dehydration condensation, Isosorbide-5-Nitrae-fourth two can be enumerated
Alcohol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, new penta
Glycol, trimethylolethane, trimethylolpropane, two trimethylolpropanes, tetramethylolmethane,
Dipentaerythritol, dihydroxymethyl heptane, dihydromethyl propionic acid, dimethylolpropionic acid, glycerol,
Hydrogenated bisphenol A etc..
Epoxy (methyl) acrylate oligomer has at least 2 (methyl) in intramolecular
Acryloxy, can be by polyglycidyl ether and (methyl) acrylic acid additive reaction
Obtain.As the polyglycidyl ether used in additive reaction, ethylene glycol bisthioglycolate can be enumerated and shrink
Glycerin ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, 1,6-oneself
Hexanediol diglycidyl ether, bisphenol A diglycidyl ether etc..
Relative to 100 parts by weight of activated energy ray-curable adhesive composites, above-mentioned from
It is preferably 20～80 weight portions, more preferably 30～70 by the total amount of base polymerizable compound
Weight portion.
Active energy ray curable adhesive composite preferably comprises polymerization initiator.Comprise
When free-radical polymerised compound is as polymerizable monomer, preferably comprises radical polymerization and cause
Agent；When comprising cationically polymerizable compound as polymerizable monomer, preferably comprise cation
Polymerization initiator.As long as the irradiation that cationic polymerization initiators is by active energy beam,
Produce cation type (cationic species) or lewis acid, cause with epoxide
The material of polyreaction for the cationically polymerizable monomer of typical example.About free radical
Polymerization initiator, as long as by the irradiation of active energy beam, can cause (methyl) third
The material of the polymerization of the free-radical polymerised compounds such as olefin(e) acid based compound, can use
The radical polymerization initiator known.As radical polymerization initiator, can enumerate 1-Phenylethanone., 3
-methyl acetophenone, benzil dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxyl
Base-2-methylpropane-1-ketone, 2-methyl isophthalic acid-[4-(methylsulfany) phenyl-
2-morpholinopropane-1-ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone
Such 1-Phenylethanone. series initiators；Benzophenone, 4-chlorobenzophenone and 4,4 '-diamino
Base benzophenone such benzophenone series initiators；Benzoin propyl ether and benzoin ethyl
Ether such benzoin ether series initiators；ITX such thiaxanthone system causes
Agent；Other xanthone, Fluorenone, camphorquinone, benzaldehyde, anthraquinone etc..
For radical polymerization initiator, commercially available product can be readily available, such as, divide
Do not record with trade name, " the IRGACURE (registered trade mark) of BASF AG can be enumerated
184 ", " IRGACURE (registered trade mark) 907 ", " DAROCURE (registrar
Mark) 1173 ", " Lucirin (registered trade mark) TPO " etc..
For the content of radical polymerization initiator, relative to (methyl) acrylic acid series
Total amount 100 weight portion of the free-radical polymerised compounds such as compound, usually 0.5～20
Weight portion, preferably 1～6 weight portions.When the use level of radical polymerization initiator is few, Gu
Change and become insufficient, there is the closely sealed of active energy ray curable bond layer and Polarizer
Property reduce tendency.
For the content of cationic polymerization initiators, relative to the sun such as epoxide from
Total amount 100 weight portion of sub-polymerizable compound, usually 0.5～20 weight portion, it is preferably
1～6 weight portions.
When the use level of cationic polymerization initiators is few, solidification becomes insufficient, there is activity
The tendency that the adaptation of energy ray-curable bond layer and Polarizer reduces.
Active energy ray curable adhesive composite also can comprise plasticizer, photosensitizer,
Levelling agent (leveling agent), antioxidant, stabilizer, fire retardant, viscosity modifier,
Foam inhibitor, antistatic agent etc..
[Polarizer]
The Polarizer of the duplexer constituting the present invention has polaroid and annular ethylene series resin is protected
Cuticula.Annular ethylene series resin protecting film is arranged at least side of polaroid, it is possible to
It is arranged in both sides.Additionally, it is possible to form only one side at polaroid and there is the structure of protecting film,
And to make this protecting film be annular ethylene series resin protecting film.Annular ethylene series resin protecting film quilt
When being arranged in the both sides of polaroid, annular ethylene series resin protecting film can be by mutually the same
Resin formation, it is possible to by resin formation different from each other.Annular ethylene series resin protecting film is excellent
Choosing is laminated on polaroid.
The Polarizer of the duplexer constituting the present invention can be to have adhesive phase in its surface
The Polarizer with binding agent.The thickness of adhesive phase is usually 3～30 μm, is preferably
5～25 μm.By making Polarizer have adhesive phase, Polarizer can be attached at liquid crystal cell
(liquid crystal cell)。
Adhesive phase can be formed by adhesive composition, can by with (methyl) acrylic acid series,
Rubber series, carbamate system, ester system, polysiloxane series, polyvingl ether system are such
Resin is that the adhesive composition of main constituent is constituted.Wherein, with the transparency, against weather,
Polymer (base polymer) based on (methyl) acrylic resin that thermostability etc. are excellent
Adhesive composition be preferred.Adhesive composition can be active energy ray-curable
Type, thermohardening type.
Adhesive composition also can comprise cross-linking agent, polymerization initiator, sensitizer, for composing
Give light scattering microgranule, pearl (resin bead, bead etc.), glass fibre, cohesive
Imparting agent, filler (metal powder, other inorganic powders etc.), antioxidant, ultraviolet
Absorbent, dyestuff, pigment, coloring agent, defoamer, anticorrosive, Photoepolymerizationinitiater initiater
Deng additive.
[polaroid]
Polaroid preferably has absorption and has the linear polarization of the vibration plane parallel with optical axis
Light, make the blooming with the character of the linear polarization light transmission of vibration plane orthogonal with the optical axis,
Specifically, absorption dichromatic pigment (iodine or two in polyvinyl alcohol resin film can be enumerated
Color organic dyestuff) and make its polaroid being orientated.
The thickness of polaroid is usually below more than 2 μm 30 μm, below preferably 25 μm,
Below more preferably 15 μm, more preferably below 10 μm, particularly preferably 7 μm
Below.It should be noted that apply absorption dichromatic pigment in polyvinyl alcohol resin layer
And when making its polaroid being orientated as polaroid, can be individually to polyethenol series tree
Fat stretches；Also the solution of polyvinyl alcohol resin being coated base material etc. and can be made it
After drying, jointly stretch with base material, then remove base material.In the feelings jointly stretched with base material
Under condition, easily make the polaroid that thickness is below 7 μm.
As above-mentioned base material, polyethylene terephthalate film, Merlon can be enumerated
Film, tri acetyl cellulose membrane, norborene film, polyester film, polystyrene film etc..
As the polyvinyl alcohol resin of composition polyvinyl alcohol resin layer, can use poly-second
The resin saponification of vinyl acetate system and the resin that obtains.As polyvinyl acetate system resin, remove
Outside the homopolymer i.e. polyvinyl acetate of vinyl acetate, also can enumerate vinyl acetate
With can be with the copolymer of other monomers of its copolymerization.As can be with its of vinyl acetate copolymerization
His monomer, can enumerate unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, have
The acrylamide etc. of ammonium.
The saponification degree of polyvinyl alcohol resin is usually 80 moles of more than %, preferably 90～
99.5 moles of %, more preferably 94～99 moles %.When saponification degree is less than 80 moles of %,
The resistance to water of the Polarizer arrived and humidity resistance reduce.When saponification degree is more than 99.5 moles of %,
Sometimes dyeing kinetics is slack-off, and productivity ratio reduces, and can not get having sufficient polarizing properties
Polaroid.
Polyvinyl alcohol resin can be the modified polyvinylalcohol that a part is modified, such as,
Can use through olefin-modified polyvinyl alcohol based on ethylene and propylene etc.；Through based on third
The unsaturated carboxylic acid-modified polyvinyl alcohol of olefin(e) acid, methacrylic acid and .beta.-methylacrylic acid etc.；Utilize
The polyvinyl alcohol that the Arrcostab of unsaturated carboxylic acid, acrylamide etc. are modified and obtain.Poly-
The ratio of the modification of vinyl alcohol resin is preferred less than 30 moles of %, more preferably less than 10%.
When having carried out more than 30 moles of % modified, have that dichromatic pigment becomes to be difficult to adsorb inclines
To, sometimes can not get the polaroid with sufficient polarizing properties.
The average degree of polymerization of polyvinyl alcohol resin is preferably 100～about 10000, more preferably
It is 1500～8000, more preferably 2000～5000.
When average degree of polymerization is less than 100, exists and be difficult to obtain gratifying polarizing properties
, when average degree of polymerization is more than 10000, there is dissolubility in a solvent and be deteriorated in tendency, difficult
To form the tendency of polyvinyl alcohol resin layer.
As polyvinyl alcohol resin, suitable commercially available product can be used.As the most commercially available
Product, all record with trade name, can enumerate KURARAY CO., " PVA124 " of LTD.
And " PVA117 " (saponification degree is: 98～99 moles of %), " PVA624 " (soap
Change degree: 95～96 moles of %), " PVA617 " (saponification degree: 94.5～95.5 moles of %)；
" N-300 " and " NH-18 " (saponification degree of the Nippon Synthetic Chemical Industry Co., Ltd
Be: 98～99 moles of %), " AH-22 " (saponification degree: 97.5～98.5 moles of %),
" AH-26 " (saponification degree: 97～98.8 moles of %)；JAPAN VAM&POVAL
CO., LTD. " JC-33 " (saponification degree: 99 moles of more than %), " JF-17 ",
" JF-17L " and " JF-20 " (saponification degree is: 98～99 moles of %), " JM
-26 " (saponification degree: 95.5～97.5 moles of %), " JM-33 " (saponification degree: 93.5～
95.5 moles of %), " JP-45 " (saponification degree: 86.5～89.5 moles of %) etc..
About in polaroid containing the dichromatic pigment of (gas absorption quantity), iodine or two can be enumerated
Color organic dyestuff etc..As dichroic organic dye, red (red) BR, red can be enumerated
LR, red R, pink (pink) LB, rubine (rubine) BL, purplish red (bordeaux)
GS, sky blue (sky blue) LG, lemon yellow (lemon yellow), blue (blue) BR,
Blue 2R, dark blue (navy) RY, green (green) LG, purple (violet) LB, purple B,
Black (black) H, black B, black GSP, Huang (yellow) 3G, yellow R, orange (orange)
LR, orange 3R, scarlet (scarlet) GL, scarlet KGL, Congo red (Congo Red),
Brilliant violet (brilliant violet) BK, super indigo plant (Supra Blue) G, super blue GL,
Super orange (Supra Orange) GL, direct sky blue (direct sky blue), the most strong
Orange (direct fast orange) S, fast black (fast black).Dichromatic pigment can be the most single
Solely use a kind, it is possible to and use two or more.
[annular ethylene series resin protecting film]
The annular ethylene series resin protecting film that Polarizer is had can be by annular ethylene series resin shape
Become.As the monomer of composition annular ethylene series resin, norborene can be enumerated.As fall ice
The example of the substituent of sheet alkene, using the position of double bond of norborene as 1,2-position, including
3-substituent, 4-substituent, 4,5-is di-substituted, in addition, it is possible to by two polycyclics
Pentadiene, dimethano octahydro naphthalene (dimethanooctahydronaphthalene) etc. are as structure
The monomer of olefin-based resin circlewise.
Annular ethylene series resin with norborneol alkene monomer as construction unit can be at its main chain
On there is norbornane ring, it is possible to not there is norbornane ring.As being formed on main chain not
There is the norborneol alkene monomer of the annular ethylene series resin of norbornane ring, such as, can lift
Go out to be formed by open loop the norborneol alkene monomer of 5 rings, typically, fall can be enumerated
Bornylene, dicyclopentadiene, 1-or 4-methyinorbornene, 4-phenyl norbornene
Deng.When annular ethylene series resin is copolymer, the ordered state of its molecule is not particularly limited,
Can be random copolymer, it is also possible to for block copolymer, it is also possible to for graft copolymer.
As the more specifically example of annular ethylene series resin, including norborneol alkene monomer
The ring-opening copolymer of ring-opening polymerization polymer, norborneol alkene monomer and other monomers, for them
Carry out the polymer modification thing of maleic acid addition, cyclopentadiene addition etc., they have been hydrogenated
And the polymer obtained or copolymer, the addition polymer of norborneol alkene monomer, norborneol
Alkene monomer and the addition copolymer etc. of other monomers.In the case of forming copolymer
Other monomers, can enumerate alpha-olefines, cyclenes hydro carbons, non-conjugated diene class etc..In these,
Annular ethylene series resin is preferably to enter for the ring-opening polymerization polymer employing norborneol alkene monomer
Gone hydrogenation resin.
For annular ethylene series resin, except can to formed by it blank film (Japanese:
Former anti-Off ィ Le system) implement stretch processing and formed outside phase retardation film, it is possible to by not only
Carry out stretching but also the contractility film of the shrinkage factor with regulation of fitting and implement heating receive
Contracting processes, thus forms the phase retardation film that uniformity is high, have big phase difference value.
The annular ethylene series resin being polymerized as norborneol alkene monomer, including by Japan
" ZEONEX (registered trade mark) " and " ZEONOR that ZEON CORPORATION sells
(registered trade mark) ", " ARTON (registered trade mark) " sold by JSR Corp.
Deng.The film of these annular ethylene series resin, its stretched film also can obtain as commercially available product,
Such as, all record with trade name, including sold by Japan ZEON CORPORATION
" ZEONOR film (registered trade mark) ", " ARTON (note sold by JSR Corp.
Volume trade mark) film ", " ESCENA (registrar sold by Sekisui Chemical Co., Ltd
Mark) phase retardation film " etc..
It addition, be used as by comprising annular ethylene series resin of more than two kinds and olefin-based tree
Film that the hybrid resin of fat is formed, mixed by annular ethylene series resin and other thermoplastic resins
The film that resin is formed is as annular ethylene series resin protecting film.Such as, as comprising 2 kinds
Above annular ethylene series resin and the hybrid resin of olefin-based resin, can enumerate above-mentioned ring
Shape olefin-based resin and the mixture of chain fatty race olefin-based resin.Use cycloolefin
During the hybrid resin of resin and other thermoplastic resins, about other thermoplastic resins, according to
Purpose and select suitable thermoplastic resin.If enumerating concrete example, including polychlorostyrene second
Alkene system resin, cellulose-based resin, polystyrene resin, acrylonitrile/butadiene/styrene
Copolymer resins, acrylonitrile/styrene copolymerized resin, (methyl) acrylic resin, poly-second
Vinyl acetate system resin, polyvinylidene chloride resin, polyamide series resin, polyacetals system
Resin, polycarbonate-based resin, Noryl system resin, polybutylene terephthalate
Ester system resin, PET series resin, polyphenylene sulfide system resin, polysulfones
It is resin, polyether sulfone system resin, polyether-ether-ketone system resin, polyarylate system resin, liquid crystal liquid crystal property
Resin, polyamidoimide system resin, polyimides system resin, politef system resin
Deng.Thermoplastic resin can only be used alone a kind, it is possible to is applied in combination two or more.It addition,
For above-mentioned thermoplastic resin, carry out after the most suitable polymer modification can be carried out
Use.As the example of polymer modification, can enumerate copolymerization, crosslinking, molecular end modified,
Stereoregularity imparting etc..
When using the hybrid resin of annular ethylene series resin and other thermoplastic resins, for
For the content of other thermoplastic resins, generally, overall relative to resin, it is 50 weight %
Hereinafter, more preferably below 40 weight %.By making the content of other thermoplastic resins
Within the above range, the absolute value of available photoelastic coefficient is little, show that good wavelength divides
Dissipate characteristic and durability, mechanical strength and the phase retardation film of transparency excellence.
Annular ethylene series resin protecting film also can contain as desired residual solvent, stabilizer,
The compositions such as plasticizer, antioxidant, antistatic agent, UV absorbent, levelling agent.
The annular ethylene series resin protecting film used in the present invention preferably has phase contrast in face
Phase retardation film.Herein, the refractive index of slow-axis direction in the face of film is designated as nx, by face
The refractive index of quick shaft direction is designated as ny, and the refractive index of thickness direction is designated as nz, and by film
Thickness be designated as d, in face phase difference value Re by following formula (2) define.
Re=(nx-ny) × d (2)
Phase contrast also includes thickness direction phase difference value Rth, and it is defined by following formula (3).Separately
Outward, the Nz coefficient as the benchmark of the biaxiality of phase retardation film is defined by following formula (4).
Rth=((nx+ny)/2-nz) × d (3)
Nz coefficient=(nx-nz)/(nx-ny) (4)
When Nz coefficient is 1, the stretch orientation of phase retardation film becomes complete uniaxiality, by this
The effect that the solvent resistant of oolemma is anti-thread breakage is maximum.Along with the increase of Nz coefficient, become twin shaft
The orientation of property, is increasingly difficult to present the effect that the solvent resistant brought by the present invention is anti-thread breakage.
Therefore, for the annular ethylene series resin protecting film used in the present invention, preferably its Nz
Coefficient more than 1 in the scope of less than 3, the scope of more preferably less than more than 12.This
A little phase difference values and Nz coefficient can be the values at the wavelength of the immediate vicinity of visible ray, this theory
In bright book, unless otherwise specified, then for the value at wavelength 550nm.
Above-mentioned such annular ethylene series resin protecting film with refractive anisotrop, can
By utilizing free end longitudinal direction uniaxial tension, the horizontal uniaxial tension of stenter, simultaneously twin shaft to draw
Stretch, the most biaxial stretch-formed etc. suitable mode the film of annular ethylene series resin is stretched and
Obtain, by addition to suitably adjusting stretching ratio and draw speed, the most suitably select
Preheating temperature, draft temperature, heat fixation (heat set) temperature and cooling temperature during stretching
Various temperature and the respective changing patteries such as degree, can obtain giving desired refractive index
Anisotropic protecting film.
Annular ethylene series resin protecting film can be provided with in its surface protective layer by many
The structure that layer is formed, protective layer may be placed at the one side of protecting film, it is possible to is arranged at two
Face, from the standpoint of can improving productivity ratio, is preferably the protecting film at one side with protective layer
Or not there is the protecting film formed by monolayer of protective layer on surface.As protective layer, can lift
Go out hard conating, antiglare layer, anti-reflection layer, antistatic backing, stain-proofing layer.
[other protecting film]
The Polarizer of the duplexer constituting the present invention only has annular ethylene series resin in one side to be protected
During cuticula, can configure by the resin formation beyond annular ethylene series resin protecting film at opposite side
Protecting film (following, be sometimes referred to as other protecting film).In this case, it is also preferred that incite somebody to action
Other protecting film are laminated in polaroid.In this specification, sometimes annular ethylene series resin is protected
Cuticula and other protecting film are referred to as protecting film.
As other protecting film, can use by acetate fiber prime system resin, chain olefin system tree
Fat, acrylic resin, polyimides system resin, polycarbonate-based resin, Polyester tree
The material being in the past widely used as the forming material of protecting film in this areas such as fat is formed
Thermoplastic resin film.From the viewpoint of mass productivity and cementability, protecting film is preferred
For cellulose acetate resin film.
Cellulose acetate resin film is to be formed by the partially or completely acetas compound of cellulose
Film, tri acetyl cellulose membrane, diacetyl cellulose film etc. can be enumerated.
As cellulose acetate resin film, commercially available product can be used.As preferred commercially available product,
Can enumerate sold by Fujifilm Corporation " Fujitac (registered trade mark) TD80 ",
" Fujitac (registered trade mark) TD80UF ", " Fujitac (registered trade mark) TD80UZ "；
By Konica Minolta Opto Products Co., Ltd. sell " KC8UX2M ",
" KC8UY " (being trade name above) etc..
Chain olefin system resin is with ethylene, the such chain olefin of propylene as principal monomer
Polymer, can be homopolymer, it is also possible to for copolymer.Wherein, the homopolymerization of preferred propylene
Thing, in propylene the copolymer of the ethylene that copolymerization is a small amount of.
Acrylic resin is the polymer with methyl methacrylate as principal monomer, permissible
Homopolymer for methyl methacrylate, it is also possible to for methyl methacrylate and acrylic acid first
The copolymer of the such acrylate of ester.
Polyimides system resin is the polymer on main chain with imide bond, can enumerate
Tetracarboxylic dianhydride is made to be polymerized with diamidogen and form the polyamic acid of the precursor as polyimides
After (polyamic acid), utilize cyclodehydration (imidizate) reaction and obtain poly-
Imide series resin.
Polycarbonate-based resin is the polymer on main chain with carbonic acid ester bond, can enumerate logical
The polycarbonate-based resin crossing bisphenol-A and the condensation polymerization of phosgene and obtain.
Polyester based resin is by binary acid and being polymerized that the condensation polymerization of dihydroxylic alcohols obtains
Thing, can enumerate polyethylene terephthalate etc..
It addition, for other protecting film away from polaroid compared with the face in distally, anti-dazzle place can be implemented
The surface such as reason, hard painting process, antistatic process, antireflection process processes, it is possible to formed by
The coat that liquid crystal compounds, other high-molecular weight compounds etc. are formed.
When the thickness of protecting film is crossed thin, there is intensity reduction, the tendency of poor in processability；Thickness
Time blocked up, there is the tendency that the weight of transparency reduction or Polarizer increases.The present invention's
The thickness of the protecting film in Polarizer is usually 5～100 μm, preferably 10～80 μm, more
It is preferably below 50 μm, below particularly preferably 30 μm.
[bonding agent]
When by protecting film with polaroid stacking, bonding agent can be used to carry out protecting film and polarisation
The laminating of sheet.As bonding agent, can enumerate active energy ray curable adhesive composite,
Water system bonding agent.
As active energy ray curable adhesive composite, base can be arranged on above-mentioned
Active energy ray curable adhesive composite between plate with Polarizer is identical, it is also possible to
It is different from.
As water system bonding agent, can enumerate containing polyvinyl alcohol resin, carbamate tree
Fat is as the adhesive composite of main constituent.
The thickness of the bond layer being dried or obtaining after solidification is usually 0.01～5 μm, makes
During with water system bonding agent, it is usually formed as below 1 μm.On the other hand, activity energy is being used
In the case of amount ray curing bonding agent, also preferably forming is below 2 μm, more preferably shape
Become below 1 μm.When bond layer is crossed thin, bonding may become insufficient, bonding agent
When layer is blocked up, it is possible to the bad order of Polarizer occurs.
Present inventor has investigated active energy ray curable bonding agent group in the lump
Compound and annular ethylene series resin protecting film, it was found that by according to cycloolefin tree
The solubility parameter (hereinafter referred to as SP value) of fat protecting film, to meet following formula (1)
Polymerizable monomer that mode selects to comprise in active energy ray curable adhesive composite,
With phase difference value in the face of the annular ethylene series resin protecting film constituting Polarizer, thus can have
Effect prevents solvent crackle.Those skilled in the art can be according to the active energy beam as target
The bonding force of curing type bond layer, absorbance etc., suitably select in the way of meeting formula (1)
Select polymerizable monomer.
Re(550)≥-38.37ln(S)-434.4δ+8063 (1)
[in formula (1), S represents the dissolubility of polymerizable monomer, is expressed as following formula:
SkRepresent the active energy ray-curable forming active energy ray curable bond layer
Molten in the water of 100g 25 DEG C of the kth polymerizable monomer comprised in type adhesive composite
Xie Du, akRepresent that the kth comprised in active energy ray curable adhesive composite is gathered
The weight portion of conjunction property monomer.
In Re (550) represents the face of the annular ethylene series resin protecting film at wavelength 550nm
Phase difference value.
δ represents the SP by Y-MB method calculated annular ethylene series resin protecting film
Value.
It should be noted that about for determine substitute into various middle time the unit of numerical value, make S
Unit be g, the unit making Re (550) is nm, makes the unit of δ for (MPa)1/2。]
When at the both sides of polaroid configuration annular ethylene series resin protecting film, in above formula (1),
Re (550) is defined as: in the face of a pair annular ethylene series resin protecting film in phase difference value
Phase difference value in the face of the annular ethylene series resin protecting film that absolute value is little.
When at the both sides of polaroid configuration annular ethylene series resin protecting film, in above formula (1),
δ is defined as: absolute value in phase difference value in the face of a pair annular ethylene series resin protecting film
The δ of little annular ethylene series resin protecting film.Although also depending on cyclic olefin structure to be had
Functional group, but the SP value of annular ethylene series resin be preferably 17～19 (MPa)1/2。
In above formula (1), polymerizable monomer refers to may participate in irradiation based on active energy beam
The compound of polymerization, polymerizable monomer does not includes the antistatic agent being not involved in polyreaction
Deng additive.When using free-radical polymerised compound as polymerizable monomer, free radical
Polymerizable compound dissolubility in the water of 100g 25 DEG C is the most as shown in the table below.
From the standpoint of the protecting film that can use the widely annular ethylene series resin of kind, formula
(1) S in is preferably more than 10, and more preferably more than 50, can be more than 100.
It addition, S is usually less than 1500.
Table 1
| Free-radical polymerised compound | Dissolubility in the water of 25 DEG C of 100g |
| Isobornyl acrylate (IBOA) | 0.02g |
| Butyl acrylate (BA) | 1.4g |
| Ethyl acrylate (EA) | 15g |
| Acrylic acid methyl ester. (MA) | 52g |
| Acrylic acid 2-hydroxy methacrylate (2HEA) | 1000g |
For polymerizable monomer, even the active energy ray curable after Gu Hua glues
Connect oxidant layer, it is possible to add hot fluid, supercritical fluid etc. by use and solidfied material is resolved into list
Body unit, utilizes liquid chromatography, gas chromatography etc. to be analyzed and determine.
[manufacture method of duplexer]
The duplexer of the present invention can manufacture in the following manner: on Polarizer and/or on substrate
Coat activated energy ray-curable adhesive composite, by Polarizer and baseplate-laminating, makes
Active energy ray curable adhesive composite solidifies.Also Polarizer can be replaced to have
The liquid crystal panel of Polarizer and baseplate-laminating.
The shape of the duplexer of the present invention is not particularly limited, preferably rectangular.By making layer
Stack be shaped as rectangle, thus easily carry out active energy ray curable bonding agent combination
The setting of thing, the liquid crystal indicator that available visuality is more excellent.By common duplexer
When being assemblied in mobile phone, flat board (tablet) terminal such small-scale liquid crystal device,
Compared with when being assemblied in the such large-scale liquid crystal indicator of television set, relative to picture area
For the area of end relatively bigger, thus, there is solvent crackle in the end of Polarizer
Time, the visual part reduced easily is perceived by user.In the duplexer of the present invention,
Owing to there is not solvent crackle in the end of Polarizer, therefore, it is possible to be properly assembled in little
The liquid crystal indicator of type.For such stacking being assemblied in small-sized liquid crystal indicator
For the size of body, at duplexer when being shaped as rectangle, the length on its long limit is preferably 5cm
Above, can be more than 10cm, usually below 30cm.It addition, the length of minor face
It is preferably more than 3cm, can be more than 5cm, usually below 20cm.Need explanation
, end be the edge of span annular ethylene series resin protecting film be the district within 5mm
Territory.
As energy ray-curable bonding agent group coat activated on Polarizer and/or on substrate
The method of compound, can use die coating (die coating), scraper for coating (knife coating),
The known method such as curtain coating (curtain coating).
Active energy ray curable adhesive composite can be coated Polarizer and/or substrate
Whole interarea, it is also possible to remain not in a part for the interarea of Polarizer and/or substrate
The mode of coating part is coated.As the whole interarea coating Polarizer and/or substrate
Method, can enumerate so that the end of active energy ray curable adhesive composite and Polarizer
The method that the mode of portion and contacts side surfaces is coated.As with at Polarizer and/or substrate
Remain the method that the mode in uncoated portion is coated in a part for interarea, such as, can lift
Go out the method remaining uncoated portion in the end of Polarizer and/or the interarea of substrate.
Coat activated energy ray-curable adhesive composite on Polarizer and/or on substrate
After, by Polarizer and baseplate-laminating, obtain fitting body.Now, in order to adjust active-energy
The thickness of ray curing bond layer, available every rod and sept (spacer) etc., protect
Hold the distance between Polarizer and substrate.
By irradiating active energy beam to fitting body, thus active energy ray-curable can be made
Type adhesive composite solidifies, and forms active energy ray curable bond layer, obtains this
The duplexer of invention.
Penetrate as the active-energy irradiated to active energy ray curable adhesive composite
Line, can enumerate luminous ray, ultraviolet, X-ray, electron beam, wherein, preferably ultraviolet
Line.As the light source of active energy beam, low pressure mercury lamp, medium pressure mercury lamp, high pressure can be enumerated
Mercury lamp, ultrahigh pressure mercury lamp, xenon lamp, Halogen light, carbon arc (carbon arc) lamp, tungsten lamp,
Gallium lamp, excimer laser, send the light of wave-length coverage 380～440nm LED light source,
Chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp.
Active energy beam strong irradiated to active energy ray curable adhesive composite
Degree is usually 0.1～100mW/cm2.Active energy ray curable adhesive composite contains
During polymerization initiator, preferably make polymerization initiator is activated the work in effective wavelength region
The intensity of property energy-ray is 0.1～100mW/cm2.The intensity of active energy beam is above-mentioned
During scope, the response time can be shortened, and can suppress to cause because of radiant heat, reaction heat
The flavescence of active energy ray curable bond layer and annular ethylene series resin protecting film bad
Change.
Preferably make by the accumulated light of the intensity of active energy beam Yu the product representation of irradiation time
Become 10～5000mJ/cm2.When accumulated light is above-mentioned scope, enough polymerizations can be produced
The spike of initiator, and, the irradiation time of active energy beam can be shortened, can improve
Productivity ratio.
The Rotating fields of the duplexer of the present invention manufactured as described above is illustrated.Fig. 1
A () represents the two sides at polaroid 4 via active energy ray curable bond layer 2
On there is the Polarizer 10 of annular ethylene series resin protecting film 3 and substrate 1 stacking and obtain
Duplexer 100.Fig. 1 (b) represents will via active energy ray curable bond layer 2
The one side of polaroid 4 has annular ethylene series resin protecting film 3, has on another side
The Polarizer 10 of other protecting film 5 and substrate 1 stacking and the duplexer 100 that obtains.Fig. 1
In structure represented by (b), with interarea and the activity energy of annular ethylene series resin protecting film 3
The mode of the interarea contact of amount ray curing bond layer 2 is by its stacking.Fig. 1 (c) table
Showing will be at polarisation in the same manner as Fig. 1 (b) via active energy ray curable bond layer 2
There is in the one side of sheet 4 annular ethylene series resin protecting film 3, there is on another side other guarantors
The Polarizer 10 of cuticula 5 and substrate 1 stacking and the duplexer 100 that obtains.Fig. 1 (c) institute
In the structure represented, the interarea with other protecting film 5 is bonding with active energy ray curable
The mode of the interarea contact of oxidant layer 2 is by its stacking.
The duplexer of the present invention can also be by liquid via active energy ray curable bonding agent
Crystal panel and substrate stacking and the duplexer that obtains, described liquid crystal panel is will via binding agent
Liquid crystal cell fits in Polarizer and obtains.The stacking with the present invention that fitted at liquid crystal cell
The face of body is on the face of opposition side, generally can layered polarization plate.This Polarizer can be applied existing
Known Polarizer.Fig. 2 is by liquid crystal via active energy ray curable bond layer 2
Panel 20 and substrate 1 stacking and the duplexer that obtains.Liquid crystal panel 20 has a structure in which
Polarizer 11 with binding agent is fitted via binding agent 6 with liquid crystal cell 7, and then,
It is to paste on the face of opposition side in the face with the Polarizer 11 fitted with binding agent of liquid crystal cell
Conjunction has known Polarizer 8, in the described Polarizer 11 with binding agent, at polaroid 4
Two sides on there is annular ethylene series resin protecting film 3, and there is binding agent 6.
For the duplexer of the present invention, owing to inhibiting because adhesive composite contains
Polymerizable monomer and the generation of solvent crackle that causes, thus visual excellent, can be suitably
It is assembled in various liquid crystal indicator.
Embodiment
Hereinafter, enumerate embodiment so that the present invention to be described, but the present invention is not by these embodiments
Any restriction.
[computational methods of solubility parameter (SP value)]
Calculate annular ethylene series resin by the Y-MB method of the software of referred to as HSPiP to protect
The SP value of film.
[manufacture of active energy ray curable adhesive composite]
As described in table 2 below, by polymerizable monomer mix, obtain compositions 1～
12.By following formula, obtain the dissolubility S of the polymerizable monomer comprised in each compositions, merge
It is recorded in table 2.
SkRepresent the active energy ray-curable forming active energy ray curable bond layer
Molten in the water of 100g 25 DEG C of the kth polymerizable monomer comprised in type adhesive composite
Xie Du, akRepresent that the kth comprised in active energy ray curable adhesive composite is gathered
The weight portion of conjunction property monomer.
It should be noted that the abbreviation in table 2 represents following compound, 100g 25 DEG C
Water in dissolubility as shown in table 1.
IBOA: isobornyl acrylate
BA: butyl acrylate
EA: ethyl acrylate
MA: acrylic acid methyl ester.
2HEA: acrylic acid 2-hydroxy methacrylate
Table 2
[manufacture of Polarizer]
Utilize dry process by average degree of polymerization about 2400, saponification degree be 99.9 moles of more than %,
And the polyvinyl alcohol film uniaxial tension that thickness is 75 μm is to about 5 times, and then, keeping tight
It is impregnated in the case of the state that stretches tight in the pure water of 60 DEG C 1 minute, then at iodine/potassium iodide
The weight ratio of/water is in the aqueous solution of 0.05/5/100, impregnates 60 seconds in 28 DEG C.Then,
In the aqueous solution that weight ratio is 8.5/8.5/100 of potassium iodide/boric acid/water, in 72 DEG C of dippings
300 seconds.It follows that with the pure water 20 seconds of 26 DEG C, be then dried in 65 DEG C,
Obtain gas absorption quantity in polyvinyl alcohol and have the light polarizing film of iodine.
100 parts of water dissolves 3 parts of carboxy-modified polyvinyl alcohol (by KURARAY CO.,
LTD. " KL-318 " obtained), this aqueous solution adds 1.5 parts as water solublity ring
The Polyamide Epoxy system additive of epoxy resins (is obtained by Taoka Chemical Industries Co. Ltd.
Trade name " Sumirez Resin (registered trade mark) 650 (30) ", solid state component is dense
Degree is the aqueous solution of 30%), make water system bonding agent.
Use above-mentioned water system bonding agent, be 23 μm by the thickness that phase difference value in face is 0nm
Non-stretched annular ethylene series resin protecting film (Japan ZEON CORPORATION system,
ZEONOR film (registered trade mark), ZF14-023, SP value: 18.0 (MPa)1/2) patch
Together in the two sides of above-mentioned light polarizing film, obtain Polarizer 1.Before laminating, to cycloolefin
The binding face of resin protection film implements Corona discharge Treatment.After laminating, in 80 DEG C by Polarizer
1 is dried 5 minutes, and then in 40 DEG C of maintenances 168 hours.
It is the thickness of 90nm that annular ethylene series resin protecting film replaces to phase difference value in face
It is horizontal uniaxial tension annular ethylene series resin protecting film (the Japan ZEON of 25 μm
CORPORATION system, ZEONOR film (registered trade mark), ZT12-090079-
F1330, SP value: 18.0 (MPa)1/2), in addition, grasp in the same manner as Polarizer 1
Make, obtain Polarizer 2.
It is the thickness of 125nm that annular ethylene series resin protecting film replaces to phase difference value in face
It is annular ethylene series resin protecting film (the Japan ZEON of the horizontal uniaxial tension of 20 μm
CORPORATION system, SP value: 18.0 (MPa)1/2), in addition, with polarisation
Plate 1 similarly operates, and obtains Polarizer 3.
It is the thickness of 141nm that annular ethylene series resin protecting film replaces to phase difference value in face
It is oblique extension annular ethylene series resin protecting film (the Japan ZEON of 23 μm
CORPORATION system, ZEONOR film (registered trade mark), ZD12-141158-
A1330, SP value: 18.0 (MPa)1/2), in addition, grasp in the same manner as Polarizer 1
Make, obtain Polarizer 4.
It is the thickness of 90nm that annular ethylene series resin protecting film replaces to phase difference value in face
It is the oblique extension annular ethylene series resin protecting film (ARTON (registered trade mark) of 25 μm
Film, RJT1150, SP value: 17.8 (MPa)1/2), in addition, same with Polarizer 1
The operation of sample ground, obtains Polarizer 5.
[evaluation of the solvent resistant crack performance of Polarizer]
Glue with active energy ray curable for the Polarizer shown in table 3 below and table 4
Connect the combination of agent compositions, utilize method set forth below to evaluate solvent resistant crack performance.
Polarizer is cut into the square of 10cm × 10cm.(thick via pressure sensitive bonding agent sheet material
Degree is 25 μm, with butyl acrylate as main constituent, copolymerization have a small amount of acrylic acid 2-hydroxyl
Base ethyl ester and acrylic acid acrylic resin coordinate isocyanates system cross-linking agent and silane chemical combination
Thing forms), the Polarizer cut out is attached at the glass substrate that thickness is 0.4mm
(CORNING company system, EAGLE XG (registered trade mark)), makes sample for evaluation.
Then, in order to remove the bubble between glass substrate and sample for evaluation, utilize autoclave,
At 0.5MPa, carry out under conditions of 50 DEG C 20 minutes processing, in order to the deformation making film is very big
Change, carry out 30 minutes heat treatments in 105 DEG C.
Active energy ray curable adhesive composite is applied on the interarea of Polarizer,
Make thickness become 100 μm, place protection glass thereon.It should be noted that putting
Under the state having put protection glass, the side of Polarizer is bonding by active energy ray curable
Agent compositions covers.
Placing 24 hours in room temperature, then visualization is at the cycloolefin of sample for evaluation
Whether crackle is created on resin protection film.It should be noted that shown in table 3 and table 4
The determinating reference that solvent crackle is evaluated is as described below.
Zero: do not crack in annular ethylene series resin protecting film.
×: in annular ethylene series resin protecting film, create the crackle of more than 1.
Table 3
Table 4
As shown in table 3 and table 4, at experimental example (according to annular ethylene series resin protecting film
SP value, have selected active energy ray curable in the way of meeting formula (1) rightly and glues
Connect the kind of the polymerizable monomer comprised in agent compositions and mixing ratio and cycloolefin tree
Phase difference value in the face of fat protecting film) in, protect in the annular ethylene series resin constituting Polarizer
Solvent crackle is there is not on cuticula.Therefore, by the active energy beam that solvent crackle does not occurs
The duplexer that curing type adhesive composite obtains with the combination of Polarizer does not occur solvent to split
Stricture of vagina, available visual excellent liquid crystal indicator.
Industrial applicability
Pass through the present invention, it is possible to provide on the protecting film constituting Polarizer, solvent crackle does not occur
Duplexer, and the visual excellent liquid crystal display being equipped with described duplexer can be provided
Device, is therefore useful.
Claims (6)
1. duplexer, described duplexer sequentially has substrate, active energy ray curable glues
Connecing oxidant layer and Polarizer, wherein, described Polarizer is for having polaroid and cycloolefin tree
The Polarizer of fat protecting film, described duplexer meets following formula (1):
Re(550)≥-38.37ln(S)-434.4δ+8063 (1)
In formula (1), S represents:
SkRepresent the active energy beam forming described active energy ray curable bond layer
The kth polymerizable monomer comprised in curing type adhesive composite is at 25 DEG C of 100g
Dissolubility in water, akRepresent the weight portion of described kth polymerizable monomer；
In Re (550) represents the face of the annular ethylene series resin protecting film at wavelength 550nm
Phase difference value；
δ represents by the calculated described annular ethylene series resin protecting film of Y-MB method
SP value；
Wherein, the unit of S be the unit that unit is nm, δ of g, Re (550) be (MPa)
1/2。
2. duplexer as claimed in claim 1, wherein, active energy ray curable glues
Connecing oxidant layer is to cover interarea and the layer of side of Polarizer.
3. duplexer as claimed in claim 1 or 2, wherein, active energy ray-curable
Type adhesive composite comprises free-radical polymerised compound.
4. the duplexer as according to any one of claims 1 to 3, wherein, cyclic olefin
Be the SP value of resin protection film be 17～19.
5. the duplexer as according to any one of Claims 1 to 4, wherein, duplexer
It is shaped as rectangle, a length of more than the 5cm on long limit, a length of more than the 3cm of minor face.
6. liquid crystal indicator, it has the stacking according to any one of Claims 1 to 5
Body.
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| JP2015104249A JP2016218304A (en) | 2015-05-22 | 2015-05-22 | Laminate and liquid crystal display device |
| JP2015-104249 | 2015-05-22 |
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| JP (1) | JP2016218304A (en) |
| KR (1) | KR102519866B1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106393922A (en) * | 2015-07-30 | 2017-02-15 | 住友化学株式会社 | Optical layer laminated body and liquid crystal display device |
| CN112946949A (en) * | 2021-02-10 | 2021-06-11 | 惠州市华星光电技术有限公司 | Polarizing plate, display panel and preparation method thereof |
| CN113165308A (en) * | 2018-12-10 | 2021-07-23 | 住友化学株式会社 | Laminate and image display device using same |
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| KR102184392B1 (en) * | 2017-11-28 | 2020-11-30 | 주식회사 엘지화학 | Optical Device |
| KR102477378B1 (en) * | 2018-09-04 | 2022-12-14 | 주식회사 엘지화학 | Optical Device |
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| JP6119109B2 (en) * | 2012-04-27 | 2017-04-26 | 住友化学株式会社 | Polarizing plate and liquid crystal display device |
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| JP2014215560A (en) * | 2013-04-26 | 2014-11-17 | 日東電工株式会社 | Polarization film and manufacturing method thereof, optical film and image display unit |
| JP2014225015A (en) * | 2013-04-26 | 2014-12-04 | 富士フイルム株式会社 | Optical film, polarizing plate, and liquid crystal display device |
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| CN106393922B (en) * | 2015-07-30 | 2019-12-17 | 住友化学株式会社 | Optical laminate and liquid crystal display device |
| CN113165308A (en) * | 2018-12-10 | 2021-07-23 | 住友化学株式会社 | Laminate and image display device using same |
| CN112946949A (en) * | 2021-02-10 | 2021-06-11 | 惠州市华星光电技术有限公司 | Polarizing plate, display panel and preparation method thereof |
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| CN106168693B (en) | 2020-08-18 |
| TWI679459B (en) | 2019-12-11 |
| KR102519866B1 (en) | 2023-04-07 |
| KR20160137435A (en) | 2016-11-30 |
| JP2016218304A (en) | 2016-12-22 |
| TW201710717A (en) | 2017-03-16 |
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