CN103443236B - Light curable adhesive, polaroid and laminated optical component - Google Patents

Light curable adhesive, polaroid and laminated optical component Download PDF

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Publication number
CN103443236B
CN103443236B CN201280015670.XA CN201280015670A CN103443236B CN 103443236 B CN103443236 B CN 103443236B CN 201280015670 A CN201280015670 A CN 201280015670A CN 103443236 B CN103443236 B CN 103443236B
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polariser
light
polaroid
protecting film
curable adhesive
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CN103443236A (en
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久米悅夫
岩田智
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Adeka Corp
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
Asahi Denka Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising 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

Abstract

The present invention provides light curable adhesive; this light curable adhesive is for the protecting film being made up of transparent resin of fitting on the polariser being made up of polyvinyl alcohol resin film; it contains 100 weight portions light cation-curable composition (A) and 1-10 weight portion light cationic polymerization initiators (B); light cation-curable composition (A) its total amount is benchmark, containing following (A1)-(A3) of following amounts.Ester ring type di-epoxy compounds (A1) shown in 60-75 weight % following formula (I)；Diglycidyl compounds (A2) shown in 5-35 weight % following formula (II)；And the monofunctional epoxy compound (A3) shown in 2-15 weight % following formula (III).

Description

Light curable adhesive, polaroid and laminated optical component
Technical field
The present invention relates to the light curable adhesive of the polariser for being made by the polyvinyl alcohol resin film being adsorbed and orientation and the protecting film laminating being made up of transparent resin by dichroic dye；This light curable adhesive is used to fit on the polarizer the polaroid of protecting film；And on this polaroid the laminated optical component of other optical layers such as stacking phase retardation film.
Background technology
Polaroid can be used as one of optics constituting liquid crystal indicator.Generally, polaroid has the structure of the two sides stacked guard film at polariser, is assembled in liquid crystal indicator.It is known that the polaroid that protecting film is only set at the one side of polariser, but also fitting at another side under most circumstances is not singly protecting film, but also serve as the layer of the optical function with other of protecting film.It addition, the manufacture method of polariser is widely used, and the uniaxial tension polyvinyl alcohol resin film dyeed with dichroic dye is carried out boric acid process, method dry after washing.
Usually at above-mentioned washing and protecting film of fitting on the polarizer immediately after drying.This is because, the physical strength of dried polariser is weak, once it is curling, occur easily along machine direction problems of crack.Therefore, it is common that polariser after the drying is coated with the aqueous solution of the polyvinyl alcohol resin as aqueous adhesive immediately, via this binding agent, protecting film of simultaneously fitting on the two sides of polariser.Usual protecting film uses the tri acetyl cellulose membrane of thickness 30-100 μm.
The advantage that triacetyl cellulose has excellence as protecting film: the transparency is excellent; easily form various surface-treated layers or optical functional layer; additionally moisture permeability is also high; drying after using the laminating on the polarizer of above-mentioned aqueous adhesive can be smoothed out; but there is problems in that on the contrary owing to moisture permeability is high, made polaroid that protecting film laminating obtains under damp and hot, under such as temperature 70 C, the such condition of relative humidity 90% easily caused by deterioration etc..Therefore, it is also known that by lower than the moisture permeability of triacetyl cellulose, such as using amorphous polyolefins system resin that norbornene resin is typical example as protecting film.
When the protecting film being made up of the resin that moisture permeability is low is fitted on polyethenol series polariser; if using the aqueous solution of in the past conventional in polyethenol series polariser with tri acetyl cellulose membrane laminating polyvinyl alcohol resin as binding agent; then there is bonding strength deficiency or the problem of the bad order of gained polaroid.This is because, the low resin molding of moisture permeability is generally hydrophobicity, or owing to moisture permeability is low, it is impossible to using fully dry etc. as the water of solvent.It is known that different types of protecting film of can fitting on the two sides of polariser on the other hand.The scheme such as having proposes: the protecting film being made up of the resin that the moisture permeability of amorphous polyolefins system resin etc. is low of fitting in a face of polariser, the protecting film being made up of the resin that the moisture permeability of the cellulose-based resin etc. being representative with triacetyl cellulose is high of fitting in another face of polariser.
Therefore; as to giving high adhesion between the protecting film being made up of the resin that moisture permeability is low and polyethenol series polariser, simultaneously to the binding agent also giving high adhesion between high resin and the polyethenol series polariser of the moisture permeabilitys such as cellulose-based resin, can attempt using light curable adhesive.The binding agent such as, disclosed in Japanese Unexamined Patent Publication 2004-245925 publication (patent documentation 1) being main constituent with the epoxide not containing aromatic ring; propose: by the irradiation of active energy beam, utilize the cationic polymerization that ultraviolet irradiation carries out specifically; make this binding agent solidify, make polariser and protecting film bonding.Additionally; a kind of light curable adhesive is used for disclosed in Japanese Unexamined Patent Publication 2008-257199 publication (patent documentation 2) technology of polariser and the bonding of protecting film, and this light curable adhesive is to be combined with the epoxide without ester ring type epoxy radicals, coordinate light cationic polymerization initiators further by cycloaliphatic epoxy.
Patent documentation 1: Japanese Unexamined Patent Publication 2004-245925 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-257199 publication.
Summary of the invention
The problem that invention to solve
But, patent documentation 1 or in patent documentation 2 viscosity of the binding agent of concrete disclosed composition not of a sufficiently low, coat on polariser or the protecting film fitted with it, form uniform adhesive phase in the form of a film again and be also not easy to.Additionally, these binding agents solidify after adhesive phase do not show enough storage moduluss as a result, when gained polaroid stands violent temperature history, such as, when standing to be repeatedly performed the cold shock testing kept under low temperature and keep under high temperature, polariser is it may happen that break.
And; although polariser is bonded with protecting film by these known light curable adhesive with the bonding force of appropriateness; but its bonding force is also insufficient to; such as use this light curable adhesive that polariser is bonded the polaroid of gained when in order to cutting becomes given size suitable in liquid crystal indicator with protecting film; if polishing its end, then protecting film is likely to from polariser to peel off in its end.
When the problem of the present invention is to fit protecting film on the polarizer; a kind of light curable adhesive is provided; it has the of a sufficiently low viscosity that can be at room temperature coated with; show sufficient storage modulus after solidification, be also difficult to produce to break and bonding force between polariser/protecting film also obtains the polaroid that improves even if the polariser when standing violent temperature history can be obtained.Another problem of the present invention is in that to provide a kind of polaroid, and this polaroid is to use this light curable adhesive by polariser and protecting film laminating, and both bonding forces are excellent, even if simultaneously when standing violent temperature history, polariser is also difficult to break.Another problem of the present invention is in that to provide a kind of laminated optical component, and this laminated optical component is other optical layers of stacking phase retardation film etc. on this polaroid, is suitable for liquid crystal indicator.
The present inventor conducts in-depth research for solving described problem, and result completes the present invention.Specifically, it is found that for the light curable adhesive coordinating light cationic polymerization initiators in light cation-curable composition with ormal weight, using following compositions is effective as light cation-curable composition, said composition is based on specific ester ring type di-epoxy compounds, wherein coordinate in molecule the diglycidyl compounds that there are 2 epoxy radicals do not closed with ester ring type loops, not there is aromatic ring, coordinate in molecule the monofunctional epoxy compound with 1 epoxy radicals do not closed with ester ring type loops simultaneously further on a small quantity.Namely it is found that the light curable adhesive of described specific composition at room temperature shows low viscosity, give the good coating suitability, after solidifying, show high storage modulus simultaneously, by polariser and protecting film good bond.The present invention comprises herein below.
[1] light curable adhesive; this light curable adhesive is for the protecting film being made up of transparent resin of fitting at least one face of the polariser being made up of the adsorbed also polyvinyl alcohol resin film that orientation of dichroic dye; it contains 100 weight portions light cation-curable composition (A) and 1-10 weight portion light cationic polymerization initiators (B); above-mentioned smooth cation-curable composition (A) is with its total amount for benchmark, containing following (A1), (A2) and (A3) of following amounts:
Ester ring type di-epoxy compounds (A1) shown in 60-75 weight % following formula (I):
In formula, R1And R2Each independent, represent the alkyl of hydrogen atom or carbon number 1-6, when the carbon number of alkyl is more than 3, can having alicyclic structure, X represents the divalent group shown in any one of oxygen atom, alkane two base of carbon number 1-6 or following formula (1a)-(1d):
Here, Y1-Y4Representing alkane two base of carbon number 1-20 respectively, when carbon number is more than 3, can have alicyclic structure, a and b represents the integer of 0-20 respectively；
Diglycidyl compounds (A2) shown in 5-35 weight % following formula (II):
In formula, Z represents the alkylene base of carbon number 1-9, the alkylidene radical of carbon number 3 or 4, divalent ester ring type alkyl or formula-CmH2m-Z1-CnH2n-shown divalent group, here ,-Z1-represent-O-,-CO-O-,-O-CO-,-SO2-,-SO-or-CO-, m and n each independent, represent the integer of more than 1, both add up to less than 9；
Monofunctional epoxy compound (A3) shown in 2-15 weight % following formula (III):
In formula, R3Represent the alkyl of carbon number 1-15.
[2] light curable adhesive of [1], wherein, in the formula (III) representing monofunctional epoxy compound (A3), R3Alkyl for carbon number 6-10.
[3] light curable adhesive of [1] or [2], wherein, the viscosity at 25 DEG C is the 100mPa second below.
[4] light curable adhesive any one of [1]-[3], wherein, its solidfied material shows 1 at 80 DEG C, the storage modulus of more than 000mPa.
[5] polaroid; this polaroid is made up of polariser and protecting film; described polariser is made up of the adsorbed also polyvinyl alcohol resin film that orientation of dichroic dye; described protecting film is fitted at least one face of this polariser via binding agent; being made up of transparent resin, this binding agent is the solidfied material of the light curable adhesive any one of [1]-[4].
[6] polaroid of [5], wherein, fit in protecting film at least one face of polariser from the acetyl fibre prime system resin-made of UV absorbent become.
[7] polaroid of [5], wherein, the protecting film fitted at least one face of polariser is made up of the transparent resin selected from amorphous polyolefins system resin, polyester based resin and chain polyolefin-based resins.
[8] polaroid any one of [5]-[7], wherein, the bonding strength that 180 degree of disbonded tests between polariser and protecting film obtain is more than 0.6N/25mm.
[9] laminated optical component, this laminated optical component includes the duplexer of the polaroid any one of [5]-[8] and other optical layers.
[10] laminated optical component of [9], wherein, above-mentioned optical layers contains phase retardation film.
Invention effect
The light curable adhesive of the present invention is to coordinate ester ring type di-epoxy compounds (A1), diglycidyl compounds (A2) and monofunctional epoxy compound (A3) as light cation-curable composition (A) using ormal weight respectively; thus reach low viscosity; and make the storage modulus of the adhesive phase after solidification improve, the bonding strength between polariser and protecting film can be improved simultaneously.Therefore, via this binding agent, even if the polaroid that the protecting film being made up of transparent resin of fitting at least one face of polariser obtains stands violent temperature history as such in cold shock testing, polariser is also difficult to break, and resistance to sudden heating is excellent.The laminated optical component that other optical layers of stacking obtains on this polaroid also can fully show the function of polaroid, and resistance to sudden heating is excellent simultaneously.
Detailed description of the invention
Embodiment of the present invention described further below.The present invention is provided to bond the light curable adhesive of the protecting film being made up of transparent resin on the polariser being made up of polyvinyl alcohol resin film.The present invention also provides for using this light curable adhesive, fits the protecting film being made up of transparent resin and the polaroid obtained on above-mentioned polariser, it is further provided on this polaroid stacking other optical layers and the laminated optical component that obtains.These light curable adhesive, polaroid and laminated optical component are sequentially carried out explanation.
[light curable adhesive]
In the present invention, the light curable adhesive for bonding the protecting film being made up of transparent resin on the polariser being made up of polyvinyl alcohol resin film contains following (A) and (B) two kinds of compositions.
(A) light cation-curable composition and
(B) light cationic polymerization initiators.
(light cation-curable composition)
It is the main constituent of light curable adhesive, is given light cation-curable composition (A) of bonding force by polymerizing curable containing following three kinds of compounds.
(A1) the ester ring type di-epoxy compounds shown in above formula (I),
(A2) diglycidyl compounds shown in above formula (II) and
(A3) monofunctional epoxy compound shown in above formula (III).
The amount of the ester ring type di-epoxy compounds (A1) in light cation-curable composition (A) is with the total amount of light cation-curable composition (A) for benchmark, for 60-75 weight %.By containing the ester ring type di-epoxy compounds (A1) of more than 60 weight % in light cation-curable composition (A); the storage modulus after solidifying containing its light curable adhesive can be made to improve; such as can make the storage modulus at 80 DEG C is 1; more than 000MPa; even if the polaroid of polariser with protecting film laminating being subject to violent temperature history via this binding agent, it is also possible to prevent breaking of polariser.And if this amount is more than 75 weight %; then the diglycidyl compounds (A2) of the following stated is relative with the amount of monofunctional epoxy compound (A3) reduces, it is difficult to realizes the closing force between low viscosity and the polariser/protecting film of the desired light curable adhesive of the present invention simultaneously and improves.More preferably with the total amount of light cation-curable composition (A) for benchmark, ester ring type di-epoxy compounds (A1) is containing more than 70 weight %.
The amount of the diglycidyl compounds (A2) in light cation-curable composition (A) is 5-35 weight %.By coordinating the diglycidyl compounds (A2) of more than 5 weight % in light cation-curable composition (A); the storage modulus after solidifying containing its light curable adhesive can be made to keep high level, the closing force between polariser and protecting film can be improved simultaneously.And if this amount is more than 35 weight %, then the closing force between polariser and protecting film is not enough, meanwhile, light curable adhesive solidify after storage modulus also have reduction tendency.Be preferred value to make the closing force between polariser and protecting film or the storage modulus after light curable adhesive solidification, then the amount being more highly preferred to the diglycidyl compounds (A2) made in light cation-curable composition (A) is below 25 weight %.
Further, the amount of the monofunctional epoxy compound (A3) in light cation-curable composition (A) is 2-15 weight %.By coordinating the monofunctional epoxy compound (A3) of more than 2 weight % in light cation-curable composition (A); the decrease in viscosity of light curable adhesive can be made; show good coating, show the effect of the closing force improved between polariser and protecting film simultaneously.And if this amount is more than 15 weight %, then the storage modulus after light curable adhesive solidification does not fully improve, and easily produces to break by polaroid polariser when being subject to dramatic temperature course that polariser and protecting film laminating obtain via this binding agent.
Represent in the above formula (I) of ester ring type di-epoxy compounds (A1), R1And R2Each independent, for the alkyl of hydrogen atom or carbon number 1-6, when the carbon number of alkyl is more than 3, it is possible to there is alicyclic structure.The position of the cyclohexane ring being combined with X in formula (I) is 1-position (thus, the position of the epoxy radicals in two cyclohexane rings is 3,4-positions), then this alkyl can combine in the optional position of 1-position～6-position.This alkyl is it is of course possible to be straight chain, when carbon number is more than 3, it is possible to be side chain.As it has been described above, when carbon number is more than 3, it is possible to there is alicyclic structure.The exemplary with the alkyl of alicyclic structure is cyclopenta or cyclohexyl.
Same in formula (I), connect the X of two 3,4-epoxy-cyclohexane rings to be oxygen atom, carbon number be any one shown divalent group in alkane two base of 1-6 or above formula (Ia)-(Id).Here, alkane two base is the concept comprising alkylene base or alkylidene radical, and alkylene base can be straight chain, when carbon number is more than 3, it is possible to be side chain.
When X is any one shown divalent group in above formula (Ia)-(Id), the linking group Y in various1、Y2、Y3And Y4Respectively carbon number 1-20 alkane two base, when the carbon number of this alkane two base is more than 3, it is possible to have alicyclic structure.These alkane two bases are it is of course possible to be straight chain, when carbon number is more than 3, it is possible to be side chain.As it has been described above, can have alicyclic structure when carbon number is more than 3.The exemplary of alkane two base with alicyclic structure is cyclopentylene or cyclohexylidene.
Ester ring type di-epoxy compounds (A1) shown in formula (I) is illustrated, X in formula (I) is the divalent group shown in above formula (Ia), a in this formula is the compound of 0 is 3, the carboxylate of 4-expoxycyclohexyl methanol (can in conjunction with the alkyl of carbon number 1-6 on this cyclohexane ring) and 3,4-epoxy-cyclohexane formic acid (can in conjunction with the alkyl of carbon number 1-6 on this cyclohexane ring).Enumerate its object lesson, be 3,4-epoxy-cyclohexane formic acid 3,4-expoxycyclohexyl methyl ester [in formula (I) the divalent group shown in formula (Ia) of a=0 (X be), R1=R2The compound of=H], 3,4-epoxy radicals-6-cyclohexanecarboxylic acid 3,4-epoxy radicals-6-methylcyclohexyl methyl ester [have in the formula (I) of X same as described above, R1=6-methyl, R2The compound of=6-methyl], 3,4-epoxy radicals-1-cyclohexanecarboxylic acid 3,4-epoxy radicals-1-methylcyclohexyl methyl ester [have in the formula (I) of X same as described above, R1=1-methyl, R2The compound of=1-methyl], 3,4-epoxy radicals-3-cyclohexanecarboxylic acid 3,4-epoxy radicals-3-methylcyclohexyl methyl ester [have in the formula (I) of X same as described above, R1=3-methyl, R2The compound of=3-methyl] etc..
X in formula (I) is the compound of the divalent group shown in formula (Ib) is the carboxylate of alkylene base glycols and 3,4-epoxy-cyclohexane formic acid (can in conjunction with the alkyl of carbon number 1-6 on its cyclohexane ring).X in formula (I) is the compound of the divalent group shown in formula (Ic) is the carboxylate of aliphatic dicarboxylic acid class and 3,4-expoxycyclohexyl methanol (can in conjunction with the alkyl of carbon number 1-6 on its cyclohexane ring).The compound that X in formula (I) is the divalent group shown in formula (Id) is 3, the ether body (during b=0) of 4-expoxycyclohexyl methanol (can in conjunction with the alkyl of carbon number 1-6 on its cyclohexane ring), or the etherate (during b > 0) of alkylene base glycols or poly-alkylene base glycols and 3,4-expoxycyclohexyl methanol (can in conjunction with the alkyl of carbon number 1-6 on its cyclohexane ring).
Represent that in the above formula (II) of diglycidyl compounds (A2), Z is the alkylene base of carbon number 1-9, the alkylidene radical of carbon number 3 or 4, divalent ester ring type alkyl or formula-CmH2m-Z1-CnH2n-shown divalent group, here ,-Z1-it is-O-,-CO-O-,-O-CO-,-SO2-,-SO-or-CO-, m and n each independent, be the integer of more than 1, both add up to less than 9.The exemplary of divalent ester ring type alkyl is cyclopentylene or cyclohexylidene.
In formula (II), Z is the compound of alkylene base is the diglycidyl ether of alkylene base glycol.Provide its object lesson, be then ethylene glycol diglycidyl base ether, 1,3-propane diol diglycidyl ether, Isosorbide-5-Nitrae-butanediol diglycidyl ether, 1,6-hexane diol diglycidyl ether etc..
In formula (II), Z is formula-CmH2m-Z1-CnH2nThe situation of-shown divalent group is equivalent to: Z is the alkylene base of carbon number more than 2, and the C-C key of this alkylene base is by-O-,-CO-O-,-O-CO-,-SO2-,-SO-or-CO-cut off.
Represent in the above formula (III) of monofunctional epoxy compound, R3Alkyl for carbon number 1-15.This alkyl is it is of course possible to be straight chain, when carbon number is more than 3, it is also possible to be side chain.The carbon number of this alkyl is relatively more, for instance be preferably more than 6, it is preferred that in the scope of carbon number 6-10.The wherein alkyl of preferred side chain.The exemplary of the monofunctional epoxy compound shown in formula (III) can enumerate 2-ethylhexyl glycidyl ether.
Light cation-curable composition (A) constituting light curable adhesive contains ester ring type diepoxide (A1) described above, diglycidyl compounds (A2) and monofunctional epoxy compound (A3) according to ratio discussed above respectively.In order to more effectively realize the raising of closing force between raising and polariser and the protecting film of the storage modulus of the lowering viscousity of light curable adhesive before solidifying, its solidfied material; with the total amount of light curable adhesive for benchmark, it is preferable that the total amount of diglycidyl compounds (A2) and monofunctional epoxy compound (A3) is more than 25 weight %.
Ester ring type di-epoxy compounds (A1), diglycidyl compounds (A2) and monofunctional epoxy compound (A3) are when the scope of amount discussed above, and light cation-curable composition (A) can contain other cationically polymerizable compound.
(light cationic polymerization initiators)
In the present invention, the cationic polymerization undertaken by the irradiation of active energy beam makes above-mentioned smooth cation-curable composition solidify, and forms adhesive phase, therefore to coordinate light cationic polymerization initiators (B) in Photocurable adhesive composition.The irradiation that light cationic polymerization initiators is the active energy beam by such as visible ray, ultraviolet, X ray or electron ray produces cation or lewis acid, causes the material of the polyreaction of light cation-curable composition (A).Light cationic polymerization initiators is to play catalytic action by light, and therefore, even if mixing with light cation-curable composition (A), its storage stability, operability are also excellent.Produce cation by the irradiation of active energy beam or lewis acidic compound such as can be enumerated: aryl diazonium salt；Salt such as aromatic iodonium salts or aromatics sulfonium salt etc；Iron-arene complex etc..
Aryl diazonium salt such as can enumerate following compound.
Hexafluoro-antimonic acid diazobenzene,
Hexafluorophosphoric acid diazobenzene,
Hexafluoro boric acid diazobenzene etc..
Aromatic iodonium salts such as can enumerate following compound.
Diphenyl iodine four (pentafluorophenyl group) borate,
Diphenyl iodine hexafluorophosphate,
Diphenyl iodine hexafluoro antimonate,
Two (4-nonyl phenyl) iodine hexafluorophosphate etc..
Aromatics sulfonium salt such as can enumerate following compound.
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
The double; two hexafluorophosphate of 4,4 '-bis-[diphenyl sulfonium] diphenyl sulfides,
The double; two hexafluoro antimonate of 4,4 '-bis-[two (beta-hydroxy ethyoxyl) phenyl sulfonium] diphenyl sulfides,
The double; two hexafluorophosphate of 4,4 '-bis-[two (beta-hydroxy ethyoxyl) phenyl sulfonium] diphenyl sulfides,
7-[two (p-methylphenyl) sulfonium]-ITX hexafluoro antimonate,
7-[two (p-methylphenyl) sulfonium]-ITX four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfide hexafluorophosphate,
4-(to tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenyl sulfide hexafluoro antimonate,
4-(to tert-butyl-phenyl carbonyl)-4 '-two (p-methylphenyl) sulfonium-diphenyl sulfide four (pentafluorophenyl group) borate etc..
Iron-arene complex such as can enumerate following compound.
Dimethylbenzene-cyclopentadienyl group ferrum (II) hexafluoro antimonate,
Cumene-cyclopentadienyl group ferrum (II) hexafluorophosphate,
Imines etc. between dimethylbenzene-cyclopentadienyl group ferrum (II) three (trifluoromethyl sulfonyl).
These light cationic polymerization initiators can individually use, it is also possible to two or more mixing is used.Wherein, particularly aromatics sulfonium salt wavelength region near 300nm also has Ultraviolet Light, therefore can obtain curable excellence, have the solidfied material of good mechanical strength and bonding strength, it is thus preferred to use.
The use level of light cationic polymerization initiators (B) is all relative to 100 weight portions light cation-curable composition (A), for 1-10 weight portion.Every 100 weight portions light cation-curable composition (A) coordinate the light cationic polymerization initiators of more than 1 weight portion, light cation-curable composition (A) thus can be made fully to solidify, make gained polaroid have high mechanical properties and bonding strength.On the other hand, if its amount increases, then the ionic substance in solidfied material increases, thus, the hygroscopicity of solidfied material improves, the endurance quality being likely to make polaroid reduces, and therefore, the amount of light cationic polymerization initiators (B) is to be below 10 weight portions relative to every 100 weight portions light cation-curable composition (A).The use level of light cationic polymerization initiators (B) is more than 2 weight portions preferably with respect to every 100 weight portions light cation-curable composition (A), it is also preferred that be below 6 weight portions.
(other composition in light curable adhesive can be matched with)
The light curable adhesive of the present invention is except above-described light cation-curable composition (A) containing epoxide and light cationic polymerization initiators (B), it is also possible to containing known other composition being matched with in conventional light-cured resin or binding agent.The example being suitable for of other composition can enumerate photosensitizer and photosensitizer additive.Photosensitizer is the compound of the polymerization initiation reaction produced in the display absorption maximum in wavelength place more longer than the maximum absorption wavelength shown by light cationic polymerization initiators (B), promotion light cationic polymerization initiators (B).Photosensitizer additive is the compound of the effect promoting photosensitizer further.The preferably kind according to protecting film, coordinates such photosensitizer, coordinates photosensitizer additive further.
Photosensitizer is preferably the compound of the light display absorption maximum of the wavelength contrasting 380nm length.The wavelength place display absorption maximum that above-mentioned smooth cationic polymerization initiators (B) is short near 300nm or than it, sense the light of its neighbouring wavelength, generate cation or lewis acid, cause the cationic polymerization of light cation-curable composition (A), if but coordinated above-mentioned photosensitizer, then also could sense the light of the wavelength more longer than it, particularly longer than 380nm wavelength.Described photosensitizer can effectively utilize anthracene based compound.The object lesson of anthracene system photosensitizer such as following compound.
9,10-dimethoxy anthracene,
9,10-diethoxy anthracene,
9,10-dipropoxy anthracene,
9,10-diisopropoxy anthracene,
9,10-dibutoxy anthracene,
9,10-bis-amoxy anthracene,
9,10-bis-hexyloxy anthracene,
9,10-bis-(2-methoxy ethoxy) anthracene,
9,10-bis-(2-ethoxy ethoxy) anthracene,
9,10-bis-(2-Butoxyethoxy) anthracene,
9,10-bis-(3-butoxy propoxy) anthracene,
2-methyl-or 2-ethyl-9,10-dimethoxy anthracene,
2-methyl-or 2-ethyl-9,10-diethoxy anthracene,
2-methyl-or 2-ethyl-9,10-dipropoxy anthracene,
2-methyl-or 2-ethyl-9,10-diisopropoxy anthracene,
2-methyl-or 2-ethyl-9,10-dibutoxy anthracene,
2-methyl-or 2-ethyl-9,10-two amoxy anthracene,
2-methyl-or 2-ethyl-9,10-two hexyloxy anthracene etc..
By coordinating above-mentioned photosensitizer in light curable adhesive, compared with ill-matched situation, the curable of binding agent improves.Relative to 100 weight portions light cation-curable composition (A), by coordinating the photosensitizer of more than 0.1 weight portion, then can show the effect above.On the other hand, if the use level of photosensitizer increases, then the problem that precipitation etc. occurs when there is low temperature keeping, therefore its amount is preferably with respect to 100 weight portions light cation-curable composition (A), is below 2 weight portions.From the viewpoint of keep the neutral gray of polaroid; keep in the scope of appropriateness at the bonding force of polariser with protecting film; reduce the use level of photosensitizer advantageously; such as; relative to 100 weight portions light cation-curable composition (A); the amount that can make photosensitizer is 0.1-0.5 weight portion, it is preferred that the scope of 0.1-0.3 weight portion.
Below photosensitizer additive is illustrated.Photosensitizer additive also has various, can effectively utilize naphthalene series compound.The object lesson of naphthalene system photosensitizer additive has the following stated compound.
4-methoxyl group-1-naphthols,
4-ethyoxyl-1-naphthols,
4-propoxyl group-1-naphthols,
4-butoxy-1-naphthols,
4-hexyloxy-1-naphthols,
1,4-dimethoxy-naphthalene,
1-ethyoxyl-4-methoxynaphthalene,
1,4-diethoxy naphthalene,
1,4-dipropoxy naphthalene,
1,4-dibutoxy naphthalene etc..
By coordinating naphthalene system photosensitizer additive in light curable adhesive, compared with ill-matched situation, the curable of binding agent improves.Relative to 100 weight portions light cation-curable composition (A), by coordinating 0.1 weight portion above naphthalene system photosensitizer additive, the effect above thus can be showed.On the other hand, if the use level of naphthalene system photosensitizer additive increases, then when there is low temperature keeping, the problems such as precipitation occurring, therefore its amount is preferably with respect to 100 weight portions light cation-curable composition (A), it is below 5 weight portions, further preferably below 3 weight portions.
(physical property of light curable adhesive)
The light curable adhesive of the present invention as described above, for protecting film being fitted in the polariser being made up of polyvinyl alcohol resin film.At least one binding face in these polarisers and protecting film is coated with this binding agent, then makes both overlap via this adhesive phase, make binding agent solidify.In order to improve the coating suitability to polariser and/or protecting film, it is preferable that the viscosity of this binding agent is low.In the present invention, by specify that ratio coordinates specific 3 kinds of compounds of described above as light cation-curable composition (A), the decrease in viscosity of light curable adhesive, the coating suitability improves.Specifically, this light curable adhesive viscosity at 25 DEG C can be the 100MPa second below.
It addition, in the adaptation improved between polariser and protecting film, this binding agent is made to solidify the storage modulus of the adhesive phase obtained more high more preferred.In the present invention, remain the specific 3 kinds of compounds by coordinating described above using regulation ratio as light cation-curable composition (A), as it has been described above, make the viscosity before solidification keep lower value, keep the coating suitability, the storage modulus of solidfied material can be improved simultaneously.Specifically, the solidfied material of this light curable adhesive can show 1 at 80 DEG C, the storage modulus of more than 000MPa.
[polaroid]
In the present invention, via light curable adhesive described above, the protecting film being made up of transparent resin of fitting at least one face of the polariser being made up of polyvinyl alcohol resin film, make this light curable adhesive solidify, make polaroid.As set forth above, it is possible to improve the storage modulus of the adhesive phase of the solidfied material as light curable adhesive in the present invention, improve the adaptation between polariser and protecting film.Therefore, 180 degree of disbonded tests between polariser and protecting film obtain bonding strength can be more than 0.6N/25mm.Here, 180 degree of disbonded tests carry out according to JISK6854-2:1999 " binding agent-peel adhesion strength test method-2: 180 degree stripping ".
Polariser and protecting film to the polaroid of the composition present invention illustrate below, further the manufacture method of polaroid are briefly described.
(polariser)
Polariser is made up of the polyvinyl alcohol resin film having adsorbed dichroic dye orientation.Constitute the polyvinyl alcohol resin of polariser by making the resin saponification of polyvinyl acetate base ester system obtain.Polyvinyl acetate base ester system resin is except the homopolymer polyvinyl acetate base ester of vinyl-acetic ester, it is also possible to be vinyl-acetic ester and can with the copolymer of other monomer of its copolymerization.Such as can enumerate with other monomer of vinyl-acetic ester copolymerization: unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc..The saponification degree of polyvinyl alcohol resin is generally the scope of 85-100 mole of %, preferred 98-100 mole of %.Polyvinyl alcohol resin can be modified further, for instance can use the polyvinyl formal modified with aldehydes or Pioloform, polyvinyl acetal etc..The degree of polymerization of polyvinyl alcohol resin is generally 1,000-10, and 000, it is preferable that 1,500-5, the scope of 000.
Polariser manufactures via following operation: by the operation of above-mentioned polyvinyl alcohol resin film uniaxial tension；Polyvinyl alcohol resin film dichroic dye is dyeed, makes the operation that this dichroic dye adsorbs；The operation that the polyvinyl alcohol resin film boric acid aqueous solution having adsorbed dichroic dye is processed.
Uniaxial tension can carry out before utilizing dichroic dye dyeing, it is also possible to carry out with utilizing dichroic dye dyeing, it is also possible to carry out after utilizing dichroic dye dyeing simultaneously.When carrying out uniaxial tension after utilizing dichroic dye dyeing, this uniaxial tension can carry out before boric acid processes, it is also possible to carries out during boric acid processes.It is of course also possible to carry out uniaxial tension in these multiple stages.For uniaxial tension, it is possible to be along uniaxial tension between the roller that peripheral speed is different, it is possible to use hot-rolling is along uniaxial tension.Can also is that the dry type stretching carrying out stretching in an atmosphere, it is also possible to be that the wet type carrying out stretching when with solvent swell stretches.Stretching ratio is generally about 4-8 times.
In order to polyvinyl alcohol resin film dichroic dye is dyeed, for instance can polyvinyl alcohol resin film is soaked in the aqueous solution containing dichroic dye.Dichroic dye specifically can use iodine or dichroic organic dye.
When using iodine as dichroic dye, it is typically employed in the aqueous solution containing iodine and potassium iodide and soaks the method that polyvinyl alcohol resin film carries out dyeing.In this aqueous solution, the content of iodine is usually relative to 100 weight parts waters is about 0.01-0.5 weight portion, and it is about 0.5-10 weight portion that the content of potassium iodide is usually relative to 100 weight parts waters.The temperature of this aqueous solution is generally about 20-40 DEG C, it addition, the soak time (dyeing time) in this aqueous solution was generally about the 30-300 second.
And when using dichroic organic dye as dichroic dye, generally adopt the method being soaked in the aqueous solution containing water miscible dichroic organic dye by polyvinyl alcohol resin film to carry out dyeing.It is 1 × 10 that the content of the dichroic organic dye in this aqueous solution is usually relative to 100 weight parts waters-3-1×10-2About weight portion.This aqueous solution can contain the inorganic salt of sodium sulfate etc..The temperature of this aqueous solution is generally about 20-80 DEG C, it addition, the soak time (dyeing time) in this aqueous solution was generally about the 30-300 second.
Utilizing the boric acid after dichroic dye dyeing to process is undertaken by being soaked in boric acid aqueous solution by the polyvinyl alcohol resin dyeed film.It is about 2-15 weight portion that the content of the boric acid in boric acid aqueous solution is usually relative to 100 weight parts waters, it is preferable that about 5-12 weight portion.When using iodine as dichroic dye, it is preferable that this boric acid aqueous solution contains potassium iodide.It is about 2-20 weight portion that the content of the potassium iodide in boric acid aqueous solution is usually relative to 100 weight parts waters, it is preferable that 5-15 weight portion.Soak time in boric acid aqueous solution is generally 100-1, about 200 seconds, it is preferable that about the 150-600 second, it is preferred that about the 200-400 second.The temperature of boric acid aqueous solution is generally more than 50 DEG C, it is preferable that 50-85 DEG C.
Polyvinyl alcohol resin film after boric acid process generally carries out washing process.Washing processes such as can be passed through the polyvinyl alcohol resin film after by boric acid process and be soaked in water to carry out.Implement dried after washing, obtain polariser.The temperature of water when washing processes is generally about 5-40 DEG C, and soak time was generally about the 2-120 second.The dried carried out afterwards generally uses air drier or far infra-red heater to carry out.Baking temperature is generally 40-100 DEG C.The time of dried was generally about the 120-600 second.
The thickness of the polariser being made up of polyvinyl alcohol resin film obtained above can be about 10-50 μm.
(protecting film)
Via the light curable adhesive illustrated before, protecting film of fitting on the polariser being made up of polyvinyl alcohol resin film described above, make light curable adhesive solidify, make polaroid.Protecting film can by be representative currently as the most widely used triacetyl cellulose of the protecting film of polaroid acetylcellulose resin film or the resin molding lower than triacetyl cellulose moisture permeability constituted.The moisture permeability of triacetyl cellulose is approximately 400g/m2/ 24 hours.
In a preferred scheme, the protecting film fitted with at least one face of polariser is made up of acetyl fibre prime system resin.Particularly can be made up of the acetyl fibre prime system resin being combined with UV absorbent with the protecting film of a face laminating of polariser.In another preferred embodiment, the protecting film fitted with at least one face of polariser is 300g/m by the low resin molding of the moisture permeability than triacetyl cellulose, such as moisture permeability2The resin molding of less than/24 hours is constituted.The resin constituting the low resin molding of above-mentioned moisture permeability can be enumerated: amorphous polyolefins system resin, polyester based resin, acrylic resin, polycarbonate-based resin, chain polyolefin-based resins etc..Wherein, it is preferred to use amorphous polyolefins system resin, polyester based resin and chain polyolefin-based resins.It is preferred that a scheme in; via the protecting film that above-mentioned adhesive phase is become by acetyl fibre prime system resin-made in the laminating of face of polariser; similarly, fit the protecting film be made up of the transparent resin that above-mentioned moisture permeability is low at the another side of polariser via above-mentioned adhesive phase.
Acetyl fibre prime system resin is at least some of resin obtained by acid esterification of the hydroxyl in cellulose, it is possible to be make a part by acid esterification, another part by other Esterification mixed ester.The object lesson of acetyl fibre prime system resin can be enumerated: triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc..
Amorphous polyolefins system resin is to have such as norborene or tetracyclododecane (another name dimethyl bridge octahydro naphthalene) or be combined with on them that the compound of substituent group is such, the polymer of the polymerized unit of cyclic olefin, it is possible to be the copolymer making chain olefin and/or aromatic vinyl compound and cyclic olefin copolymerization obtain.During for the copolymer of the homopolymer of cyclic olefin or two or more cyclic olefin, remain double bond due to ring-opening polymerisation, therefore, the product of its hydrogenation is typically used as amorphous polyolefins system resin.Wherein representational for thermoplastic norbornene system resin.
Polyester based resin is the polymer obtained by the polycondensation of binary acid Yu dihydroxylic alcohols, representational for polyethylene terephthalate.The polymer that acrylic resin is is principal monomer with methyl methacrylate, except the homopolymer of methyl methacrylate, it is also possible to be the copolymer of methyl methacrylate and acrylate as such in acrylic acid methyl ester. or aromatic vinyl compound etc..Polycarbonate-based resin is the polymer that main chain has carbonic acid ester bond (-O-CO-O-), its representational resin being bisphenol-A and obtaining with phosgene polycondensation.The polymer that chain polyolefin-based resins is is principal monomer with the chain olefin of such as ethylene or propylene, it is possible to be homopolymer or copolymer.Wherein, representational it is the homopolymer of propylene or copolymer that copolymerization is a small amount of in propylene ethylene obtains.
Said protection film can have various surface-treated layer as such in hard coat, anti-reflection layer, antiglare layer or antistatic layer on the opposite face in the face fitted with polariser.Protecting film comprises the situation defining such surface-treated layer, and its thickness can be about 5-150 μm.Its thickness preferably more than 10 μm, it is also preferred that less than 120 μm, it is preferred that less than 100 μm.
(manufacture method of polaroid)
When polaroid manufactures; the coating layer of the light curable adhesive of described above is formed at a side or two sides of the binding face of polariser and protecting film; via this coating layer; by polariser and protecting film laminating; the coating layer being made so uncured light curable adhesive of formation by the irradiation of active energy beam is solidified, and makes protecting film secure fit on polariser.The coating layer of light curable adhesive can be formed on the binding face of polariser, it is also possible to is formed on the binding face of protecting film.The formation of coating layer such as available paint chipping chisel, wire bar applicator, die coating machine, the unfilled corner wheel various coating method such as coating machine, gravure coater.Can also adopt and polariser and protecting film are supplied continuously with the form that both binding face is inner side, make the mode of binding agent curtain coating in-between simultaneously.Each coating method all has each best range of viscosities, and therefore, using solvent to carry out viscosity adjustment is also effective technology.For this, solvent to adopt the optical property that will not make polariser to reduce, can the solvent of excellent dissolution light curable adhesive, its kind is not particularly limited, for instance can use with toluene be representative hydro carbons, be representative with ethyl acetate the organic solvent such as esters.The thickness of adhesive phase is generally less than 20 μm, it is preferable that less than 10 μm, it is preferred that less than 5 μm.If adhesive phase is thickening, then the response rate of binding agent reduces, and the humidity resistance of polaroid has the tendency of variation.
When by polariser with protecting film bonding; before forming the coating layer of binding agent, it is possible to a side or two sides to both binding face implement such as Corona discharge Treatment, Cement Composite Treated by Plasma, flame treatment, prime treatment or the anchoring coating such easy adhesion process of process.
As long as the light source that the coating layer of light curable adhesive irradiates active energy beam produces the light source of ultraviolet, electron ray, X ray etc..Be particularly well suited for use in below wavelength 400nm have send out photodistributed, such as low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halid lamp etc..The exposure rate of light curable adhesive is determined by active energy beam according to every kind of objective composition, it does not have be particularly limited to, it is preferable that the exposure rate activating effective wavelength region to light cationic polymerization initiators is 0.1-100mW/cm2.If the photo-irradiation intensity of light curable adhesive is too small, then the response time is long, and if this photo-irradiation intensity is excessive, then the heating during polymerization of the light and heat curing adhesive that radiated by lamp may result in the xanthochromia of light curable adhesive or the deterioration of polariser.To the control by every kind of compositions to solidify of the light irradiation time of light curable adhesive, also it is not particularly limited, it is preferable that be set as: with the accumulated light of exposure rate and the product representation of irradiation time for 10-5,000mJ/cm2.If the accumulated light of light curable adhesive is too small, then not enough from the generation of the spike of light cationic polymerization initiators, the solidification of gained adhesive phase is likely to insufficient, and if increase its accumulated light, then irradiation time is very long, and productivity raising aspect is unfavorable.
When the two sides of polariser laminating protecting film; the irradiation of active energy beam can be undertaken by arbitrary protecting film side; such as; when protecting film in side contains UV absorbent, the protecting film of opposite side does not contain UV absorbent; active energy beam is irradiated by the protecting film side not containing UV absorbent; this can effectively utilize the active energy beam irradiated, and improves curing rate, it is preferable that.
[laminated optical component]
The polaroid of the present invention can the optical layers with optical function beyond laminated polarizing sheet, make laminated optical component.Typically via binding agent or adhesive; stacking laminating optical layers on the protecting film of polaroid; thus make laminated optical component; in addition; such as can via light curable adhesive; laminating protecting film on a face of polariser, via binding agent or adhesive, stacking laminating optical layers on the another side of polariser.When the latter, if for the polariser binding agent use light curable adhesive given to this invention with optical layers of fitting, then this optical layers also becomes protecting film given to this invention simultaneously.
The example of the optical layers being laminated on polaroid can be enumerated: relative to the polaroid being configured at liquid crystal cell reverse side, is laminated in the reflecting layer of the side contrary with towards liquid crystal cell side of this polaroid, Transflective layer, light diffusion layer, light collecting plate, raising brightness film etc..And for being configured at the polaroid of side before liquid crystal cell and being configured at the random polarization sheet of polaroid of liquid crystal cell reverse side, also have and be laminated in this polaroid and be intended for the phase retardation film etc. of liquid crystal cell side.
Reflecting layer, Transflective layer or light diffusion layer are set to make the polaroid of reflection-type (optical component), the polaroid (optical component) of Transflective or the polaroid (optical component) of diffused respectively.The polaroid of reflection-type is for the liquid crystal indicator by reflecting the type considering oneself as the incident illumination recognizing side and display, it is convenient to omit the light sources such as backlight, therefore easily makes liquid crystal indicator slimming.And the polaroid of Semitransmissive at bright place as reflection-type, the liquid crystal indicator of type that in the dark displays by light from a backlight.Optical component as reflection type polarizer can be such as set up the paper tinsel formed by metals such as aluminum or evaporation film on the protecting film of polariser, forms reflecting layer.As the optical component of Semitransmissive polaroid, be that above-mentioned reflecting layer is made half-mirror, or by containing pearlescent pigment, show that semi-transmissive reflecting plate and polaroid-bindnig are formed.On the other hand, as the optical component of diffused polaroid, for instance be adopt the protecting film on polaroid is implemented the method that delustring processes；The method of the coating resin containing microgranule；The various methods such as the method for the bonding film containing microgranule, form minute concave-convex structure on surface.
Also can form the optical component playing the effect that dual-purpose polaroid is spread in reflection further, in this case, for instance the method that the reflecting layer etc. reflecting this concaveconvex structure is set on the minute concave-convex structure face of diffused polaroid can be adopted.The reflecting layer of minute concave-convex structure has the advantage making incident illumination diffusion by scattering, preventing directivity or dazzle, light and shade can be suppressed unequal.It addition, spread when layer containing microgranule of incident illumination and reflection light transmission thereof containing fine-grained resin bed or film, it may have the advantage that light and shade is unequal can be suppressed.The reflectance layer of reflection surface minute concave-convex structure is such as by vacuum evaporation, ion plating or as sputtered the method such as such evaporation or coating, the surface that metal is directly located at minute concave-convex structure is formed.The microgranule coordinated to form surface minute concave-convex structure can be such as such as the inorganic system microgranule of silicon dioxide that mean diameter is 0.1-30 μm, aluminium oxide, titanium oxide, zirconium oxide, stannum oxide, Indium sesquioxide., Aska-Rid., stibium oxide etc., such as the organic system microgranule etc. of crosslinking or noncrosslinking polymer.
Light collecting plate is for the purpose of light path control etc. and uses, and therefore can make the form of the plate etc. of prism array sheet or lens array plate or attachment point.
The purpose improving brightness film is the raising of the brightness for liquid crystal indicator, and therefore its example can be enumerated: be designed to film multi-disc stacking mutually different for the anisotropy of refractive index, the anisotropic reflective polarizing light separating sheet producing reflectance；Film base material supports the alignment films of cholesteric liquid crystal polymer or the circularly polarizing separation sheet etc. of this aligned liquid-crystal layer.
On the other hand, the purpose of the above-mentioned phase retardation film playing optical layers effect is the phase difference compensation etc. for liquid crystal cell.Its example can be enumerated: the film of the birefringence film that formed by the stretched film etc. of various plastics, orientation fixing discotic mesogenic or nematic liquid crystal, defines the material etc. of above-mentioned liquid crystal layer on film base material.When film base material forms liquid crystal layer, it is preferred to use the cellulose-based resin molding such as triacetyl cellulose is as film base material.
The plastics of form dielectric grid film such as can be enumerated: as amorphous polyolefins system resin, polycarbonate-based resin, acrylic resin, polypropylene chain polyolefin-based resins, polyvinyl alcohol, polystyrene, polyarylate, polyamide etc..Should illustrating, stretched film can be processed by the suitable mode such as uniaxially or biaxially and obtain.The purpose of phase retardation film is by the control of the optical characteristics such as broadband, it is possible to 2 combination of the above used.
In laminated optical component, containing phase retardation film as the optical layers beyond polaroid, this can be effectively taking place optics guarantee when being applied to liquid crystal indicator, it is thus preferred to uses.The phase difference value of phase retardation film (in face and thickness direction) can select optimum according to the liquid crystal cell applied.
Laminated optical component can be by polaroid and according to 1 layer or 2 layers of combination of the above that application target selects from above-mentioned various optical layers, makes 2 layers or 3 layers of layer above stack.In this case, the various optical layers forming laminated optical component use binding agent or adhesive, form one with polaroid, as long as the binding agent used for this or adhesive can well form adhesive phase or adhesive layer, it does not have be particularly limited to.Consider from the simplicity of bonding operation or the generation preventing optical aberration etc., it is preferred to use adhesive (also referred to as contact adhesive).Adhesive can use the material using acrylic acid series polymeric compounds or silicon-type polymer, polyester, polyurethane, polyethers etc. as raw polymer.Wherein, such as acrylic pressure-sensitive adhesive, it is preferable that select that optical transparence is excellent, keep the cohesive of the wellability of appropriateness or aggregation force and base material also excellent and there is weatherability or thermostability etc., not occurring when heating or humidification to tilt or the stripping problem such as peeling and use.In acrylic pressure-sensitive adhesive, acrylic acid series copolymer can be used as raw polymer, this acrylic acid series copolymer has coordinated (methyl) acrylic acid Arrcostab with methyl or alkyl that the carbon number such as ethyl or butyl is less than 20 and the acrylic monomer containing functional group being made up of (methyl) acrylic acid or (methyl) Hydroxyethyl Acrylate etc., its glass transition temperature is preferably less than 25 DEG C, it is preferred that less than 0 DEG C, weight average molecular weight is more than 100,000.
Polaroid forms adhesive phase, for instance can carry out in the following manner: dissolve or dispersion agent adhesive composition in the organic solvent such as toluene or ethyl acetate, prepare the solution of 10-40 weight %, be directly coated at the mode on polaroid；Or on protecting film, form adhesive layer in advance, by the mode etc. in its transfer lamination to polaroid.The thickness of adhesive layer determines according to its bonding force etc., and the scope of about 1-50 μm is comparatively suitable.
Also as required, adhesive layer can coordinate the filler being made up of glass fibre or bead, resin bead, metal powder or other inorganic powder etc., pigment or coloring agent, antioxidant, UV absorbent etc..UV absorbent has: salicylate based compound or benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex salt based compound etc..
Laminated optical component is configurable on the one or both sides of liquid crystal cell.The liquid crystal cell used is arbitrary, for instance for be representative with film transistor type active matrix drive-type, with super-twist nematic be representative simple matrix driving etc., can use various liquid crystal cell formed liquid crystal indicator.The bonding of laminated optical component and liquid crystal cell generally uses adhesive similar to the above.
Embodiment
Embodiments given below, is further elaborated with the present invention, but the present invention is not by the restriction of these embodiments.In example, as being not particularly limited, represent content and make the % of consumption and part be weight basis.The light cation-curable composition and the light cationic polymerization initiators that use in example below are as follows, represent with following symbol respectively.
(A) light cation-curable composition
(a1) 3,4-epoxy-cyclohexane formic acid 3,4-expoxycyclohexyl methyl ester [in above formula (I), R1=R2=H、X=-COOCH2-compound]
(a2) Isosorbide-5-Nitrae-butanediol diglycidyl ether [in above formula (II), Z=-(CH2)4-compound]
(a3) 2-ethylhexyl glycidyl ether [in above formula (III), R3=CH3(CH2)3-CH(CH2CH3)-CH2-compound].
(B) light cationic polymerization initiators (referred to as " initiator " in table)
(b1) triaryl matte hexafluorophosphate.
[embodiment 1 and 2 and comparative example 1-9]
(1) preparation of light curable adhesive
Shown in table 1, each composition is mixed, then deaeration by proportioning (unit is part), prepares light curable adhesive liquid.Should illustrating, light cationic polymerization initiators (b1) coordinates with the form of 50% polypropylene carbonate ester solution, and table 1 is with its solid matter quantity representation.
[table 1]
(2) binding agent liquid viscosimetric analysis at 25 DEG C
For each binding agent liquid of above-mentioned preparation, use the rotary determination of viscoelasticity device " PhysicaMCR301 " that AntonPaar society manufactures, measure the viscosity at temperature 25 DEG C.Result is as shown in table 2.
(3) mensuration of solidfied material storage modulus at 80 DEG C
Use coating machine [metering bar coater, first physics and chemistry (strain) manufactures], in polyethylene terephthalate film [trade name " エ ス テ Le Off ィ Le system E7002E7002 spins in Japan ", Japan's weaving (strain) manufactures] a face on be coated with in above-mentioned (1) each binding agent liquid of preparation, make the thickness after solidification be about 30 μm.Then, " the D バ Le Block " irradiation ultraviolet radiation manufactured with Off ュ ジ ョ Application UV シ ス テ system ズ society, accumulated light is 3,000mJ/cm2, make binding agent solidify.Its cutting is become 5mm × 30mm size, peels off polyethylene terephthalate film, obtain the cured film of binding agent.ア イ テ ィ measurement is used to control the Measurement of Dynamic Viscoelasticity device " DVA-220 " that (strain) manufactures, this cured film is clamped with grip separation 2cm, making its long limit is draw direction, the frequency stretched and shrink is 1Hz, will heat up speed and be set as 3 DEG C/min, obtain the storage modulus at temperature 80 DEG C.Result is as shown in table 2.
(4) manufacture of polaroid
Tri acetyl cellulose membrane [trade name " U ニ カ タ ッ Network KC8UX2MV " to the thickness containing UV absorbent 80 μm, U ニ カ ミ ノ Le タ オ プ ト (strain) manufacture] surface implement Corona discharge Treatment, use wire rod coating machine, this Corona discharge Treatment face is coated with each binding agent liquid of above-mentioned preparation, makes the thickness after solidification about 2 μm.The polyvinyl alcohol of coating thickness 28 μm-iodine system polariser on this adhesive phase.Also phase retardation film [the trade name " N-TACKC4FR-1 " to the thickness 40 μm become by acetyl fibre prime system resin-made, U ニ カ ミ ノ Le タ オ プ ト (strain) manufacture] surface implement Corona discharge Treatment, use metering bar coater, coating adhesive liquid on this Corona discharge Treatment face as described above, makes the thickness after solidification about 2 μm.The tri acetyl cellulose membrane of above-mentioned preparation the fitted polariser side of polariser on one face is fitted on this adhesive phase, makes sandwich.Using the ultraviolet lamp with conveyer belt (lamp uses " the D バ Le Block " that Off ュ ジ ョ Application UV シ ス テ system ズ society manufactures), by the acetyl fibre prime system phase retardation film side irradiation ultraviolet radiation of this sandwich, accumulated light is 250mJ/cm2, make binding agent solidify.So, the polaroid of protecting film of having fitted on polariser two sides has been made.
(5) 180 degree of disbonded tests
By the size of the polaroid cutting growth 200mm × wide 25mm of making in above-mentioned (4).The adhesive layer of acrylic acid series is set in acetyl fibre prime system phase retardation film side, as being used for measuring the test film of the peel strength between this acetyl fibre prime system phase retardation film and polariser, with this phase independence, the adhesive layer of acrylic acid series is set in the tri acetyl cellulose membrane side of thickness 80 μm, as being used for measuring the test film of the peel strength between tri acetyl cellulose membrane and the polariser of thickness 80 μm.The adhesive layer of each test film is pasted on glass plate; the blade of cut-off knife is inserted between the protecting film (tri acetyl cellulose membrane of acetyl fibre prime system phase retardation film or thickness 80 μm) of polariser and adhesive side; by end strip off 30mm along its length, the clamp portion of the part testing machine of this strip off is clamped.By the test film of this state in the atmosphere of temperature 23 DEG C and relative humidity 55%, according to JISK6854-2:1999 " binding agent-peel adhesion strength test method-2: 180 degree stripping ", within translational speed 300mm/ minute, carry out 180 degree of disbonded tests with fixture, obtain the Average peel force of 170mm length outside the 30mm removing clamp portion.Result is as shown in table 2.In 180 degree of peel strength items of table 2, " N-TAC/PVA " string represents the peel strength between above-mentioned acetyl fibre prime system phase retardation film and polyvinyl alcohol-iodine system polariser, and " TAC/PVA " string represents the peel strength between the tri acetyl cellulose membrane of above-mentioned thickness 80 μm and polyvinyl alcohol-iodine system polariser.
(6) durability of polaroid is evaluated by cold shock testing
The polaroid cutting made in above-mentioned (4) is become the size of 170mm × 110mm, the adhesive layer of acrylic acid series is set in acetyl fibre prime system phase retardation film side, this adhesive layer is pasted on glass plate, carries out cold shock testing (thermal shock test).Cold shock testing is to be kept 1 hour at-35 DEG C by the polaroid sample fitted on above-mentioned glass plate, is then warming up to 70 DEG C, keeps 1 hour, using this operation as 1 cycle, is repeatedly performed 300 cycles of total.Respectively each 6 polaroid samples are carried out this test, to observe after test that polariser has the number broken to be evaluated relative to the ratio of all sample numbers (6).Result is as shown in table 2.
[table 2]
From table 1 and table 2; in the comparative example 1-2 of the binary system that light cation-curable composition (A) is (a1) and (a2); for the peel strength between protecting film and polariser, all less than 0.6N/25mm between N-TAC/PVA and between TAC/PVA.In comparative example 3, the elastic modelling quantity of binding agent solidfied material is low, and in cold shock testing, polariser has and breaks.In the comparative example 4 and 5 of the binary system that light cation-curable composition (A) is (a1) and (a3), the elastic modelling quantity of binding agent solidfied material is low, and in cold shock testing, polariser breaks.When the ternary system that light cation-curable composition (A) is (a1) and (a2) and (a3), having coordinated the comparative example 8 and 9 of 20 parts [being 20% in light cation-curable composition (A)] (a3) is also that the elastic modelling quantity of binding agent solidfied material is low, and therefore in cold shock testing, polariser breaks.And in the comparative example 6 and 7 that the use level of (a1) is more than 80 parts [being more than 80% in light cation-curable composition (A)], the peel strength between protecting film and PVA is not up to more than 0.6N/25mm.On the other hand, such as embodiment 1 and 2, to specify that ratio coordinates the binding agent of (a1) and (a2) and (a3) to be low viscous, this solidfied material has high elastic modulus, therefore polariser is difficult to break, and can obtain the polaroid that adaptation is high.

Claims (10)

1. light curable adhesive; this light curable adhesive is for the protecting film being made up of transparent resin of fitting at least one face of the polariser being made up of the adsorbed also polyvinyl alcohol resin film that orientation of dichroic dye; it contains 100 weight portions light cation-curable composition (A) and 1-10 weight portion light cationic polymerization initiators (B); above-mentioned smooth cation-curable composition (A) is with its total amount for benchmark, containing following (A1), (A2) and (A3) of following amounts:
Ester ring type di-epoxy compounds (A1) shown in 60-75 weight % following formula (I):
In formula, R1And R2Each independent, represent the alkyl of hydrogen atom or carbon number 1-6, when the carbon number of alkyl is more than 3, can have alicyclic structure,
X represents the divalent group shown in any one of oxygen atom, alkane two base of carbon number 1-6 or following formula (1a)-(1d):
Wherein, Y1-Y4Represent alkane two base that carbon number is 1-20 respectively, when carbon number is more than 3, can have alicyclic structure,
A and b represents the integer of 0-20 respectively；
Diglycidyl compounds (A2) shown in 5-35 weight % following formula (II):
In formula, Z represents the alkylene base of carbon number 1-9, the alkylidene radical of carbon number 3 or 4, divalent ester ring type alkyl or formula-CmH2m-Z1-CnH2n-shown divalent group, here ,-Z1-represent-O-,-CO-O-,-O-CO-,-SO2-,-SO-or-CO-, m and n each independent, represent the integer of more than 1, both add up to less than 9；And
Monofunctional epoxy compound (A3) shown in 2-15 weight % following formula (III):
In formula, R3Represent the branched alkyl of carbon number 3-15.
2. the light curable adhesive of claim 1, wherein, in the formula (III) representing monofunctional epoxy compound (A3), R3Branched alkyl for carbon number 6-10.
3. the light curable adhesive of claim 1, wherein, the viscosity at 25 DEG C is the 100mPa second below.
4. the light curable adhesive of claim 1, wherein, its solidfied material shows 1 at 80 DEG C, the storage modulus of more than 000MPa.
5. polaroid; this polaroid is made up of polariser and protecting film; described polariser is made up of the adsorbed also polyvinyl alcohol resin film that orientation of dichroic dye; described protecting film is fitted at least one face of this polariser via binding agent; being made up of transparent resin, above-mentioned binding agent is the solidfied material of the light curable adhesive of claim 1.
6. the polaroid of claim 5, wherein, fit in protecting film at least one face of polariser from the acetyl fibre prime system resin-made of UV absorbent become.
7. the polaroid of claim 5, wherein, the protecting film fitted at least one face of polariser is made up of the transparent resin selected from amorphous polyolefins system resin, polyester based resin and chain polyolefin-based resins.
8. the polaroid of claim 5, wherein, the bonding strength that 180 degree of disbonded tests between polariser and protecting film obtain is more than 0.6N/25mm.
9. laminated optical component, this laminated optical component includes the polaroid of claim 5 and the duplexer of other optical layers.
10. the laminated optical component of claim 9, wherein, above-mentioned optical layers contains phase retardation film.
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