CN103460090A - Polarizing plate - Google Patents

Polarizing plate Download PDF

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Publication number
CN103460090A
CN103460090A CN2012800159996A CN201280015999A CN103460090A CN 103460090 A CN103460090 A CN 103460090A CN 2012800159996 A CN2012800159996 A CN 2012800159996A CN 201280015999 A CN201280015999 A CN 201280015999A CN 103460090 A CN103460090 A CN 103460090A
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China
Prior art keywords
propylene resin
resin
transparent protective
propylene
film
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CN2012800159996A
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Chinese (zh)
Inventor
猪口雄平
高畑弘明
冈田知大
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of CN103460090A publication Critical patent/CN103460090A/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (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
    • 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
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • 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
    • 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
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/12—Biaxial compensators

Abstract

The invention provides a polarizing plate, wherein a transparent protective film formed from a propylene resin, a polarization film obtained by adsorption and orientation of a dichroic pigment on a polyvinyl alcohol film, and a biaxial phase difference film are laminated in succession; the propylene resin contains at least a UV absorber comprising a triazine compound represented by formula (I); the triazine compound content is less than 1 wt% of the propylene resin; and transmittance of light having a wavelength of 320 to 330 nm is 1% or less.

Description

Polaroid
Technical field
The present invention relates to the polaroid formed at the folded transparent protective film formed by the propylene resin film of at least one surface layer of the light polarizing film formed by polyvinyl alcohol resin.
Background technology
Polaroid is one of important composition parts that form the liquid crystal indicators such as LCD TV, LCD monitor, personal computer.Polaroid is usually following to be formed;; the single face of the light polarizing film formed at the polyvinyl alcohol resin that the bitintability pigment is arranged by absorption orientation or the two sides stacked transparent protective film that is situated between by bond layer, the transparent protective film of the acetate fiber prime system that the triacetyl cellulose of for example take is representative.Sometimes also at the single face of light polarizing film, be situated between by bond layer, the stacked phase retardation film formed by norbornene resin etc.
But; if use so hydrophilic transparent protective films such as tri acetyl cellulose membrane; under the condition of high temperature and humidity; the amount of moisture of understanding the light polarizing film to consisting of polyvinyl alcohol resin impacts; how many performances as polaroid can change; therefore; studied the polaroid formed that uses transparent protective film that the transparent protective film formed by hydrophobic resins such as propylene resins replaces consisting of hydrophilic resin also can do one's utmost to suppress environmental impact (for example, JP2009-258588-A etc.).
On the other hand, polaroid is also being born the effect that the liquid crystal cells of protecting in liquid crystal indicator is avoided influence of light, usually to middle ultraviolet light absorbers that adds such as the transparent protective films that is layered in light polarizing film, gives the following ultraviolet function of blocking-up 400nm.Yet, if add ultraviolet light absorber in this propylene resin film shown in above-mentioned JP2009-258588-A, ultraviolet light absorber oozes out and is detained at the interface with bond layer, the bonding strength of transparent protective film and light polarizing film may descend.
The object of the present invention is to provide a kind of polaroid, be that propylene resin film Jie who has been endowed ultraviolet blocking-up performance by adding ultraviolet light absorber is layered in by bond layer the polaroid formed on light polarizing film, can suppress ultraviolet light absorber and ooze out from this propylene resin film.
Summary of the invention
The present invention includes following content.
［ 1 ］ a kind of polaroid; the transparent protective film that will be formed by propylene resin, in polyvinyl alcohol resin, the absorption orientation has the light polarizing film of bitintability pigment and biaxiality phase retardation film to stack gradually to form; aforesaid propylene is that resin contains ultraviolet light absorber; above-mentioned ultraviolet light absorber at least contains the triazine based compound that following formula (I) means
Figure BDA0000389173660000021
(in formula, R 1the alkyl that means carbon number 1～12, R 2the alkyl that means hydrogen or carbon number 1～8), the content of above-mentioned triazine based compound is to be less than 1 % by weight in resin at aforesaid propylene, and wavelength is below 1% in the optical transmission rate between 320～330nm.
［ 2 ］ polaroid as described as ［ 1 ］, to be resin contain with the ratio of 0.5～0.8 % by weight the ultraviolet light absorber that the triazine based compound that only meaned by above-mentioned formula (I) forms to aforesaid propylene.
［ 3 ］ polaroid as described as ［ 1 ］, to be resin contain triazine based compound that above-mentioned formula (I) means and contain benzotriazole with the ratio of 0.1～0.7 % by weight with the ratio of 0.3～0.9 % by weight aforesaid propylene is the ultraviolet-absorbing compound, and wavelength is below 1% in the optical transmission rate between 310～350nm.
According to the present invention, be provided under hot environment or under hot and humid environment not from ultraviolet ray blocking-up excellent performance and the environment for use polaroid few on the impact of light polarizing film of the oozing out of the transparent protective film that formed by propylene resin, this film.Used the excellent in te pins of durability of liquid crystal indicator of the polaroid of the invention described above, and the excellent in stability of display performance.
Embodiment
(polaroid)
Polaroid of the present invention is the transparent protective film that will consist of propylene resin, in polyvinyl alcohol resin, the absorption orientation has the light polarizing film of bitintability pigment and biaxiality phase retardation film to stack gradually to form.The outside at the biaxiality phase retardation film further arranges adhesive phase usually.
(transparent protective film formed by propylene resin)
The transparent protective film used in polaroid of the present invention is that the propylene resin that will contain the structural unit consisted of propylene more than 90 % by weight is shaped to membranaceous and obtains.
Propylene resin can be the homopolymer of propylene, also can for propylene and can with the multipolymer of other monomers of its copolymerization.In addition, can be used together them.As can with other monomers of copolymerization of propylene, for example, can enumerate ethene, alpha-olefin.The carbon number of alpha-olefin is more than 4, preferably the alpha-olefin of carbon number 4～12.If enumerate the concrete example of the alpha-olefin of carbon number 4～12, for example, the straight chain shape monoene hydro carbons such as 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene; A chain mono-olefin class such as 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene; Vinyl cyclohexane etc.Propylene and can be random copolymers with the multipolymer of other monomers of its copolymerization can be also segmented copolymer.
When propylene resin consists of above-mentioned multipolymer, as the concrete example of its multipolymer, can enumerate propylene and the above-mentioned ethene such as propylene-ethylene random copolymers, propylene-1-butene random copolymer and propylene-ethylene-1-butene random copolymer and be selected from the binary of the one kind or two or more monomer in the alpha-olefin of carbon number 4～12 or terpolymer etc.
When propylene resin is above-mentioned multipolymer formation, from the structural unit of propylene, can select according to characteristics such as thermotolerances.While needing high-fire resistance, preferably containing in a large number the structural unit from propylene, is particularly more than 96 % by weight.Should illustrate, the containing ratio of the structural unit from these other monomers in multipolymer can be based on " macromolecule analysis handbook " (nineteen ninety-five, the distribution of Kinokuniya bookstore) in the 616th page, the method for record, try to achieve by carrying out infrared (IR) chromatographic determination.
The stereospecicity of aforesaid propylene homopolymer and propylene series copolymer can be isotactic, a rule, random in addition, but the viewpoint of balance excellence of the rigidity from being shaped to film, the transparency and so on, the preferably high acrylic polymer of isotactic.
In the present invention, propylene resin can, for polymkeric substance or the multipolymer that uses known catalyst for polymerization polymerization, as catalyst for polymerization, for example, can be enumerated following catalyzer.
(A) by take the Ti-Mg series catalysts that magnesium, titanium and halogen form as solid catalyst component that must composition,
(B) combine organo-aluminum compound and the sub-property of associating power supply compound grade in an imperial examination three compositions form as required catalyzer system take magnesium, titanium and halogen in must the solid catalyst component of composition,
(C) metallocene series catalysts etc.
As above-mentioned (A) solid catalyst component, for example, can enumerate the catalyzer system of record in JPS61-218606-A, JPS61-287904-A, JPH7-216017-A etc.In addition, preferred example as the organo-aluminum compound in above-mentioned (B) catalyzer system, can enumerate potpourri, tetraethyl two aikyiaiurnirsoxan beta (テ ト ラ エ チ Le ジ ア Le モ キ サ Application) of aluminium triethyl, triisobutyl aluminium, aluminium triethyl and diethyl aluminum chloride etc., as the preferred example of supplied for electronic compound, can enumerate cyclohexyl ethyl dimethoxy silane, tert-butyl group propyl group dimethoxy silane, tert-butyl group ethyl dimethoxy silane, dicyclopentyl dimethoxyl silane etc.In addition, as above-mentioned (C) metallocene series catalysts, for example, can enumerate the catalyzer system of record in JP2587251-B, JP2627669-B, JP2668732-B etc.
Propylene resin can utilize following method manufacture, for example, the solution polymerization process of the non-active solvent that hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, the such hydrocarbon compound of benzene,toluene,xylene be representative is take in use, use the mass polymerization of liquid monomer as solvent, make the gaseous polymerization etc. of the monomer direct polymerization of gas.Utilize the polymerization that these methods are carried out to carry out by batch (-type), also can continous way carry out.
The transparent protective film consisted of propylene resin used in the present invention is to be that resin utilizes extrusion by melting to extrude by aforesaid propylene; be shaped to membranaceous; now; for propylene resin; based on JIS K7210; the melt flow rate (MFR) of measuring under 230 ℃ of temperature, load 21.18N is preferably in the scope of 1～30g/10 minute, more preferably in the scope of 1～20g/10 minute, more preferably in the scope of 1.5～15g/10 minute.By using the propylene resin of MFR in this scope, thereby melt extrude in the film moulding of carrying out in utilization, reduce the load of extruder, and easily manufacture the film of even thickness.
In the present invention; the transparent protective film consisted of propylene resin that is fitted in the one side of light polarizing film as above illustrates; at least contain the triazine based compound of following formula (I) expression as ultraviolet light absorber, wavelength is below 1% in the optical transmission rate between 320～330nm.
Figure BDA0000389173660000051
If the content of above-mentioned triazine based compound is more than 1 % by weight in propylene resin, under hot and humid, the possibility of oozing out is arranged, therefore make this amount be less than 1 % by weight in propylene resin.The triazine based compound that only uses above-mentioned formula (I) to mean is during as ultraviolet light absorber, the scope that the amount that preferably makes this triazine based compound in propylene resin is 0.5～0.8 % by weight.Ultraviolet light absorber be only above-mentioned formula (I) mean the triazine based compound time, if its amount is less than 0.5 % by weight, the scarce capacity of ultraviolet blocking-up, being difficult to make wavelength is below 1% in the optical transmission rate between 320～330nm.On the other hand, if its amount is greater than 0.8 % by weight, sometimes inferior the causing of hot and humid degree condition, ooze out the infringement transparency.Due to this reason, the preferred use level of this triazine based compound during triazine based compound that ultraviolet light absorber only means for above-mentioned formula (I) is 0.5～0.8 % by weight.
In formula (I), R 1for the alkyl of carbon number 1～12, carbon number is 3 when above, can be straight or branched.If enumerate the example of abovementioned alkyl, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, tertiary octyl group, 2-ethylhexyl, 3-ethylhexyl, n-nonyl, different nonyl, positive decyl, n-undecane base, dodecyl etc. are arranged.
In addition, in formula (I), R 2for the alkyl of hydrogen or carbon number 1～8, if carbon number is the alkyl more than 3, can be also straight or branched.If enumerate the example of abovementioned alkyl, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, tertiary octyl group, 2-ethylhexyl etc. are arranged.
The preferred example of the triazine based compound meaned as above-mentioned formula (I), can enumerate following compound.
2,4,6-tri-(2-hydroxyl-4-octyl group oxygen base phenyl)-1,3,5-triazines (in formula (I), R 1=octyl group, R 2the compound of=H),
2,4,6-tri-(4-decyl oxygen base-2-hydroxy-3-methyl phenyl)-1,3,5-triazines (in formula (I), R 1=decyl, R 2the compound of=3-methyl), 2,4,6-tri-(4-hexyl oxygen base-2-hydroxy-3-methyl phenyl)-1,3,5-triazines (in formula (I), R 1=hexyl, R 2the compound of=3-methyl),
2,4,6-tri-(4-(3-ethylhexyl oxygen base)-2-hydroxy-3-methyl phenyl)-1,3,5-triazines (in formula (I), R 1=3-ethylhexyl, R 2the compound of=H) etc.
Together with the triazine based compound that also can mean with formula (I), also with other ultraviolet-absorbing compound, making wavelength is below 1% in the optical transmission rate between 320～330nm.As preferred ultraviolet-absorbing compound in the also use with the triazine based compound, can enumerate the benzotriazole based compound.By and with benzotriazole, be the ultraviolet-absorbing compound, can give the ultraviolet ability that blocking-up is positioned at the following short wavelength zone of 300nm, and can give the effect of oozing out that suppresses the ultraviolet light absorber that is engaged.Now preferred use level is with respect to propylene resin, and the triazine based compound that formula (I) means is 0.3～0.9 % by weight, and benzotriazole is the scope that the ultraviolet-absorbing compound is 0.1～0.7 % by weight.
Benzotriazole is that the ultraviolet-absorbing compound is to have the benzotriazole skeleton, preferably have a 2-(2-hydroxy phenyl)-2H-benzotriazole skeleton and there is the compound of UV absorbing properties.At benzotriazole, be in the ultraviolet-absorbing compound, the compound that preferred molecular weight is large, the compound that for example there is the molecular weight more than 350, particularly, can enumerate 2 of structure with following formula (II), 2 '-di-2-ethylhexylphosphine oxide (6-(2H-benzotriazole-2-yl)-4-(1, 1, 3, the 3-tetramethyl butyl) phenol), 2-(2-hydroxyl-3 with structure of following formula (III), two (the α of 5-, α-dimethylbenzyl) phenyl)-2H-benzotriazole, 2-(3 with structure of following formula (IV), 5-bis-tertiary pentyls-2-hydroxy phenyl)-2H-benzotriazole, there is the 2-(2H-benzotriazole of the structure of following formula (V)-2-yl)-4-methyl-6-(3, 4, 5, 6-tetrahydric phthalimide ylmethyl) phenol, there is the 6-(2H-benzotriazole of the structure of following formula (VI)-2-yl)-the tertiary octyl group-6 ' of the 4--tert-butyl group-4 '-methyl-2, 2 '-methylene bis-phenol etc.
Figure BDA0000389173660000072
Figure BDA0000389173660000073
Figure BDA0000389173660000074
Figure BDA0000389173660000075
Triazine based compound for the expression of adding type (I) in propylene resin; optionally add again other ultraviolet-absorbing compound; for example benzotriazole is that the ultraviolet-absorbing compound is manufactured the transparent protective film consisted of propylene resin, for example, can adopt following method.
(1) manufacture in advance the particle (being sometimes referred to as " ultraviolet light absorber masterbatch particle ") that the resin combination by the ultraviolet light absorber that contains 1～10 weight portion with respect to propylene resin 100 weight portions forms, it is mixed with the propylene resin particle fusion, the mode that becomes ormal weight with ultraviolet light absorber is manufactured the method for film forming
(2) manufacture in advance to coordinated the particle of the propylene resin composition of ultraviolet light absorber in propylene resin with ormal weight, this particle fusion is mixing, make the method for film,
(3) to coordinate the state melting mixing of the ultraviolet light absorber of ormal weight in propylene resin, manufacture the method for film forming.
In these; from the homogeneity of the transparent protective film formed by propylene resin that obtains and the viewpoint of manufacturing cost; most preferably as above-mentioned (1), manufacture in advance ultraviolet light absorber masterbatch particle, the method mixing with there is no the propylene resin particle fusion of combined with ultraviolet radiation absorbing agent by it.
The manufacture of ultraviolet light absorber masterbatch particle can be used the extruder of single shaft or twin shaft to carry out, but makes ultraviolet light absorber more be evenly dispersed in the viewpoint propylene resin from promoting shear rate, preferably uses biaxial extruder.While extruding, the temperature of the propylene resin of the mould of extruder part is preferably set in the mode of the scope at 180～260 ℃.If this temperature is greater than 260 ℃, worry the deteriorated of resin.In addition, when this temperature is greater than 210 ℃, from suppressing the deteriorated viewpoint of resin, preferably add phenol system, phosphorous antioxidant.By and with phenol, be antioxidant and phosphorous antioxidant, further improve the deteriorated effect that suppresses resin, so more preferably.While coordinating antioxidant, it is just much of that its amount reaches 1 weight portion left and right with respect to propylene resin 100 weight portions.
Can, in the scope that does not hinder effect of the present invention, coordinate known adjuvant in propylene resin.As adjuvant, for example, can enumerate triazine based compound that antioxidant, formula (I) mean and benzotriazole and be ultraviolet light absorber beyond the ultraviolet-absorbing compound, antistatic agent, lubricant, nucleator, antifoggant, anti blocking agent etc.As antioxidant, for example, can enumerate phenol and be antioxidant, phosphorous antioxidant, sulphur is that antioxidant, hindered amine are light stabilizer etc., in addition, also can use the compound antioxidant of the unit of the oxidation-resisting structure that there is the oxidation-resisting structure that for example simultaneously there is phenol system and phosphorus system in 1 molecule.The triazine based compound meaned as formula (I) and benzotriazole are the ultraviolet light absorber beyond the ultraviolet-absorbing compound, for example, can enumerate the ultraviolet-absorbing compound of 2-hydroxyl benzophenone derivant, benzoic ether system etc.Antistatic agent can be any in polymer-type, oligomeric, haplotype.As lubricant, can enumerate the senior fatty acid amides such as erucyl amide, oleamide, the senior fatty acid such as stearic acid and salt thereof etc.As anti blocking agent, the no matter inorganic system of the particulate of spherical or close with it shape, organic system all can be used.
In addition, can in the scope that does not hinder effect of the present invention, in propylene resin, add nucleator.While adding nucleator, can for inorganic be any in nucleator, organic system nucleator.As inorganic be nucleator, can enumerate talcum, clay, calcium carbonate etc.In addition, as the organic system nucleator, can enumerate the metallic salts such as the metallic salt of carboxylic acid, the metallic salt of aromatic phosphoric acid, trigalloyl amine, sorbose alcohols, high density polyethylene, poly--3-methyl butene-1, poly-cyclopentene, polyvinyl eyclohexane etc.Preferred organic core agent, further preferred above-mentioned carboxylic acid metal's salt, or trigalloyl amine, high density polyethylene of being tied to form in these.In addition, nucleator is preferably 0.01～3 % by weight with respect to the addition of propylene resin, more preferably 0.05～1.5 % by weight.Should illustrate, above-mentioned additive can be used together multiple.
It is membranaceous that the propylene resin used in the present invention preferably utilizes extrusion by melting to be shaped to, this extrusion by melting is the method for manufacturing as follows film,, by the propylene resin raw material supplying of powder shape or particle shape to the extruder that is heated to 180～300 ℃ of left and right, utilize the screw rod of extruder to carry out melting mixing, after the slit of T-shaped mould melt extrudes slabbing, make in various manners its with chill roll, contact carry out cooling.
The temperature of the propylene resin of the melting sheet be extruded is 180～300 ℃ of left and right.
If the temperature of melting sheet now is less than 180 ℃, there is ductility insufficient, the thickness of the film obtained becomes inhomogeneous, becomes the possibility of the film that has the phase differential inequality.In addition, if its temperature is greater than 300 ℃, easily cause deteriorated, the decomposition of resin, sometimes in sheet, produce bubble or contain carbonide.
Extruder can be single axle extruding machine or biaxial extruder.For example, while using single axle extruding machine, the screw rod of type etc. that can use perfect thread type, barrier type and have the mixing part of Maddock (Maddock) type, it is 24～36 left and right and as the spatial volume V of the thread groove in the resin supply unit that this screw rod meets L/D as the length L of screw rod and the ratio of diameter D 1spatial volume V with thread groove in resin metering section 2ratio (V 1/ V 2) ratio of compression be 1.5～4 left and right.From suppress propylene resin deteriorated, decompose, carry out the viewpoint of even melting mixing and so on and set out, preferably using L/D is 28～36 and ratio of compression V 1/ V 2it is 2～3 screw rod.In addition, for suppress propylene resin deteriorated, decompose, preferably carry out nitrogen purging etc. and drive the oxygen in extruder out of.And, go back the aperture that diameter 1～5mm φ preferably is set at the front end of extruder, improve the resin pressure of extruder fore-end.The resin pressure that arranges to improve the extruder fore-end by throttle orifice refers to the back pressure improved at this fore-end, sometimes can improve thus the homogeneity of melting mixing and then the stability that raising is extruded.The diameter of the aperture used is 2～4mm φ more preferably.
The T-shaped mould of extruding middle use is preferably used the T-shaped mould of design in the following manner, that is, stream is clothes hanger (coat hanger) shape, at the Width of T-shaped mould slit portion, melting propylene be the flow velocity, pressure of resin etc. as far as possible evenly and balance.In addition, preferably the flow path surfaces at resin does not have small difference in height, scar, its die lip part can be the hard chrome plating, but containing being soaked with this fluorine-containing system of fluorine based material, silicon based material, the plating of silicon based material etc. and melting propylene, is preferably plating that the friction factor of resin is little or with hard material spraying platings such as tungsten carbides.And that die lip part preferably has is polished, with surfaceness, count extremely flat, the concavo-convex few surface below 0.1S, and further preferably the die lip front end is the edge shape that grinds to form the following point of 0.3mm φ.The T-shaped mould that has die lip as above by use, can suppress the generation of gum (order ヤ ニ), suppresses die line (ダ イ ラ イ Application) simultaneously, easily obtains the resin molding of the excellent in uniformity of outward appearance.
Should illustrate, from suppressing the viewpoint of extruding change of propylene resin, preferably, between extruder and T-shaped mould, be situated between by contact maker mounting teeth wheel pump, make pressure stability supply with resin to T-shaped mould.Pressure now, be preferably in 0.1MPa as the change value.In order to realize this change value, gear-type pump is preferably Direct Action Type, and most preferably to use the number of gears be 2 to 3, for transmitting gear-type pump resin, that eliminate phase type.
In order to remove the foreign matter existed in propylene resin, the leaf disc filter preferably is installed in addition.The sheet number of leaf disc filter and the filter area of every a slice can be that the viscosity of resin and the thermotolerance of extrusion capacity (flow) and resin are selected arbitrarily according to melting propylene.About filtering accuracy, in the situation of the propylene resin film used in the present invention, the capture rate of using foreign matter is more than 98% and foreign matter size is that the following filtrator of 10 μ m can reduce the foreign matter amount in film, improves the quality as film, so preferably.With same reason filtering accuracy, more preferably below 5 μ m, further most preferably be below 3 μ m.In addition, from realizing stable foreign matter, remove such viewpoint, the setting position of leaf disc filter is preferably pressed the order setting of extruder, gear-type pump, leaf disc filter, T-shaped mould.
And then the propylene resin of the melting sheet of extruding from T-shaped mould contacts with metal chill roll (also referred to as chilled roll or water Casting Roller), by being cooled with chill roll is closely sealed.Now, influential to the transparency to the adhesion method of chill roll.To the closely sealed of chill roll, can implement by known method, for example, a) give static to the propylene resin of melting sheet, make the closely sealed and cooling method of chill roll that itself and surface state are minute surface, between the metallic roll (also referred to as touch roll) or metal tape of the elastically deformable that the chill roll that is b) minute surface by the propylene resin cramping of melting sheet in surface state and surface state are minute surface, make the closely sealed and cooling method of itself and chill roll, while c) propylene resin of melting sheet being contacted with chill roll, the air that utilization is discharged from air chamber makes the closely sealed and cooling method of itself and chill roll etc.
A) mode is the method that is called as static anchoring (electrostatic pinning) mode, at the melting propylene of extruding from T-shaped mould, to be only the both ends (being sometimes referred to as ear) of the membranoid substance of resin or the Width front face of above-mentioned membranoid substance, core shape, wire or banded power supply are set, using high frequency electric source is that resin is given high voltage to melting propylene, make its static electrification, then contact with chill roll, carry out the method for cooling curing.In this mode, be difficult for being created in from the die lip of T-shaped mould and assign to the deviation that melting propylene is the film of resin and the chill roll part (being called air gap) of joining, in addition, due to the length that can shorten unsettled air gap, easily guarantee the homogenieity of film, institute thinks preferred mode.
For the chill roll used in a) mode, owing to there being the chill roll surface to be transferred to the trend on film surface, so the surface of roller is preferably counted below 0.5S with surfaceness.Its Facing material is used the conductive material of the spraying plating etc. of hard chrome plating, tungsten carbide etc. in addition, is preferably the spraying plating surface of cold chromium oxide etc.
B) mode is the mode that is called as the touch roll moulding, that melting propylene by extruding from T-shaped mould is that the membranoid substance cramping of resin makes itself and chill roll closely sealed between the metallic roll of chill roll and elastically deformable or metal tape, make the film cooling curing, obtain the mode of the film that the transparency is excellent.The metallic roll of elastically deformable refer to have thickness be the following roller surface of 5mm, and chill roll between cramping melting propylene while being resin, can not form resin and accumulate the metallic roll of cramping (sometimes also referred to as heap (bank)), metal tape is the following endless metal belt of thickness 1mm, by rubber rollers, metallic roll, supported, rotation, and between chill roll, the cramping melting propylene is the membranoid substance of resin.In the situation of this mode, according to cooling condition, when using transparent impaired crystalline resin etc., easily making the shaping speed high speed, is preferred mode from such a viewpoint.
For b) for the chill roll simultaneously used in mode and the metallic roll or metal tape of elastically deformable, because their surface all directly is transferred to the film surface, so preferably the surface of roller is counted below 0.3S with surfaceness.In addition, due to powerful cramping, so melting propylene is that the membranoid substance of resin is optionally excessively closely sealed and make roller break away from variation with the metallic roll of chill roll or elastically deformable or surfaces of metallic strip sometimes, from preventing the viewpoint of this situation, sealing of hole as the minute crack on the surface of embedding hard chrome plating is processed, use silicon based material, fluorine based material, in addition, also be preferably formed spraying plating surface or its sealing of hole treatment surface of chromium oxide, tungsten carbide etc.
C) mode is the mode that is called as " air chamber mode ", the melting propylene that makes to extrude from T-shaped mould is that the membranoid substance of resin is while contacting with chill roll, utilizing air chamber from a side contrary with this chill roll is the membranoid substance blow air of resin to melting propylene, thus, making melting propylene is that membranoid substance and the chill roll of resin is closely sealed.Air chamber can be used commercially available applicable product without particular limitation, for the air blowed, for example, preferably with fan blower etc., be situated between by high efficiency particle air filter (HEPA filtrator: High Efficiency Particulate Air Filter) suck the air in manufacturing environment space, make in air chamber to become the pressurized state of 50～300Pa.If the pressure in air chamber is this scope, because above-mentioned air is suitable to the pressure of film, so distance (being called air gap) contacted with chill roll to the resin of melting sheet at the die lip from T-shaped mould, can not cause deviation, can carry out stable masking, certainly, the stability of thickness and precision of film etc. also improves.From this reason, consider, the pressure in air chamber is 100～200Pa more preferably.
C) chill roll in mode for example preferably is adjusted into the scope of 0～60 ℃ by surface temperature.If the surface temperature of chill roll is greater than 60 ℃, due to the cooling curing spended time of the propylene resin of melting sheet, the crystallised component growth in propylene resin, the transparency of the film obtained is poor.On the other hand, if the surface temperature of chill roll is less than 0 ℃, the surface sweating of chill roll is arranged and adhere to water droplet, making the trend of the appearance degradation of the film that obtains.
C) chill roll in mode has its surface state to be transferred to the trend of propylene resin film, but unlike above-mentioned a) mode or b) mode, in addition, if using the chill roll of mirror status not being included in melting propylene is the membranoid substance of resin and the Free up Memory of the air between chill roll, the difficulty so moulding uniformly becomes.So c), in the situation of mode, chill roll is used the chill roll of the surfaceness of 0.6～4S left and right.From improving the inhomogeneity viewpoint on film surface, preferably about 0.8～2S.
Preferably by a)～c) temperature of chill roll in mode for example surface temperature be adjusted into the scope of 0～60 ℃.If the surface temperature of chill roll is greater than 60 ℃, due to the cooling curing spended time of the propylene resin of melting sheet, thus the growth of the crystallised component in propylene resin, the transparent variation of the film obtained.On the other hand, if the surface temperature of chill roll is less than 0 ℃, the surface sweating of chill roll is arranged and adhere to water droplet, making the trend of the appearance degradation of the film that obtains.
Process velocity during transparent protective film that manufacture consists of propylene resin depends on the time that the propylene resin cooling curing of melting sheet is required.If it is large that the diameter of the chill roll used becomes, the distance that the propylene resin of melting sheet contacts with this chill roll is elongated, therefore can carry out manufacture more at a high speed.Particularly, while using the cooling roller of metal-made of 600mm φ to manufacture haze value to be the transparent propylene resin film below 1.0, process velocity was to the maximum about 50m/ minute.
The transparent protective film consisted of propylene resin of using in polaroid of the present invention can be by being that the resin masking obtains by aforesaid propylene.The above-mentioned transparent protective film preferably clear excellence consisted of propylene resin, particularly, total haze value of measuring based on JIS K7136 is preferably below 10%, more preferably below 7%.
The thickness of the transparent protective film consisted of propylene resin in polaroid of the present invention is preferably 5～200 μ m left and right.More preferably more than 10 μ m, in addition, more preferably below 150 μ m.
In the scope that does not hinder effect of the present invention, also can implement to the transparent protective film formed by propylene resin in polaroid of the present invention the surface treatments such as corona treatment, Cement Composite Treated by Plasma.In addition, can anti-reflection layer, hard conating etc. be set on surface by methods such as coatings.
During when the transparent protective film consisted of propylene resin in polaroid of the present invention is manufactured with extrusion by melting or by mixing manufacture of high concentration masterbatch particle fusion of above-mentioned adjuvant etc.; prevent the viewpoint of oxidative degradation from the protection propylene resin, preferably near the hopper of single shaft or biaxial extruder or mould outlet, carry out the nitrogen sealing.In addition, will melt extrude, the material of melting mixing takes care of respectively under the nitrogen environment below oxygen concentration 1vol% before being supplied to extruder usually, also the degradation inhibiting to resin is effective the oxygen molecule contained in material to be replaced as to the inactive gas such as nitrogen molecular, also preferably uses in the present invention.
(the biaxiality phase retardation film formed by norbornene resin)
Polaroid of the present invention is fitted with the biaxiality phase retardation film at the face of a side contrary with being fitted with transparent protective film one side that consists of propylene resin of above-mentioned light polarizing film.As such biaxiality phase retardation film, the phase retardation film formed by norbornene resin in the phase differential in preferred face, each comfortable particular range of phase differential of thickness direction.As the film formed by norbornene resin used in polaroid of the present invention, have by norborene such as serving as reasons, encircle the film that the thermoplastic resin of the unit of the monomer that the cyclic olefin (cycloolefin) such as norborneol alkene monomer forms forms more.Norbornene resin can be for the ring-opening polymerization polymer of above-mentioned cycloolefin, use the hydride of the ring opening copolymer thing of cycloolefin of more than two kinds, in addition also can or have the addition copolymer of the aromatics etc. of vinyl for cycloolefin and cyclic olefin.In addition, the norbornene resin that has imported polar group is also effective.
When using cycloolefin and chain alkene or thering is the multipolymer of aromatics of vinyl, as chain alkene, ethene, propylene etc. can be enumerated, as the aromatics with vinyl, styrene, α-methyl styrene, core alkyl-substituted styrene etc. can be enumerated in addition.In such multipolymer, the unit of the monomer consisted of cycloolefin can be for (being preferably 15～50 % by mole) below 50 % by mole.In particular for cycloolefin, chain alkene with while having the terpolymer of aromatics of vinyl, the unit of the monomer consisted of cycloolefin can be small amount as mentioned above.In above-mentioned terpolymer, the unit of the monomer consisted of chain alkene is generally 5～80 % by mole, and the unit of the monomer consisted of the aromatics with vinyl is generally 5～80 % by mole.
The cyclic olefine resin can preferably be used applicable commercially available product, such as Topas(TopasAdvanced Polymers GmbH company system), ARTON(JSR Co., Ltd. system), ZEONOR(ZEON Co., Ltd. system), ZEONEX(ZEON Co., Ltd. system), APEL(Mitsui Chemicals, Inc system) etc.During by such cyclic olefine resin film forming, suitably use the known methods such as solvent cast method, extrusion by melting.In addition, can use the system such as ESCENA(Sekisui Chemical Co., Ltd), SCA40(Sekisui Chemical Co., Ltd system), ZEONOR film (ZEON Co., Ltd. system), ARTON film (JSR Corp.'s system) etc. by the commercially available product of the resinous film of cyclic olefine of masking in advance as transparent protective film.
The film consisted of norbornene resin, at least in unilateral stretching, can carry out the optical compensation of liquid crystal thus, contributes to the visual angle of liquid crystal indicator to enlarge.For the biaxiality phase retardation film consisted of norbornene resin used in the present invention, in the face by stretched film, the refractive index of slow-axis direction is made as n x, in face, with the refractive index of the direction (quick shaft direction) of its quadrature, be made as n y, and the refractive index of thickness direction is made as n z, when the thickness of film is made as d, phase difference value R in the face of the film meaned by following formula respectively 0with thickness direction phase difference value R thphase difference value R in face 0be that 40～300nm(is preferably 40～120nm) scope in, and thickness direction phase difference value R thbe that 80～300nm(is preferably 100～250nm) scope in.
R 0＝（n x－n y）×d
R th＝〔（n x＋n y）/2－n z〕×d
Phase difference value R in face 0while being less than 40nm or while being greater than 300nm, the viewing angle compensation of panel can reduce.In addition, thickness direction phase difference value R thwhile being less than 80nm or while being greater than 300nm, the viewing angle compensation of panel can also can reduce.Phase difference value R in above-mentioned face should be described 0with thickness direction phase difference value R thfor example can use prince's KOBRA21ADH(instrumentation machine Co., Ltd. system) measure.
In order to obtain having the biaxiality phase retardation film formed by norbornene resin of refractive index characteristic as above, except suitably adjusting draw ratio and draw speed, the various temperature such as the preheat temperature in the time of can suitably selecting to stretch, draft temperature, well heater design temperature, chilling temperature with and pattern.By being stretched under slower condition, obtain above-mentioned refractive index characteristic, for example stretching ratio is preferably the scope of 1.05～1.6 times, further is preferably 1.1～1.5 times.When biaxial stretch-formed, the stretching ratio that makes the maximum tension direction is that above-mentioned scope gets final product.
Its thickness of biaxiality phase retardation film consisted of norbornene resin be stretched used in the present invention is not particularly limited, and is preferably in the scope of 20～80 μ m, more preferably in the scope of 40～80 μ m.When the thickness of the biaxiality phase retardation film consisted of norbornene resin is less than 20 μ m, the operation difficulty of film, the trend that the phase difference value that is difficult to present regulation is arranged in addition, on the other hand, when the thickness of norbornene resin film is greater than 80 μ m, the processability variation, in addition, the transparency may reduce, or the weight of the polaroid obtained may become large etc.
(bonding agent)
Polaroid of the present invention for example is situated between on the two sides of above-mentioned light polarizing film, by bonding agent fit the respectively transparent protective film that consists of polypropylene-based resin, the above-mentioned biaxiality phase retardation film consisted of norbornene resin.For polaroid of the present invention, can use bonding agent of the same race on the two sides of light polarizing film, in addition, also can use different types of bonding agent separately.As from making the preferred bonding agent of viewpoint that bond layer is thin, can enumerate the bonding agent of water system, that is, and make the bonding agent composition water-soluble and material or be scattered in water and material.In addition, as the preferred bonding agent of the viewpoint from bonding strength, can enumerate itself Photocurable adhesive agent because of photocuring.
As Photocurable adhesive agent, such as the potpourri that can enumerate photo-curable photoreactive epoxy resin cationic polymerization initiators etc.From the angle of bonding strength, most preferably this bonding agent with added the combination of the propylene resin film of specific ultraviolet light absorber.This Photocurable adhesive agent solidifies Photocurable adhesive agent by irradiating activation-energy-ray.The light source of activation-energy-ray is not particularly limited, preferably below wavelength 400nm, have and send out activation-energy-ray photodistributed, particularly, preferred lower pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp etc.
Method as the above-mentioned transparent protective film of laminating, biaxiality phase retardation film on light polarizing film; it can be generally well-known method; for example; can enumerate following method;; utilize Meyer rod painting method, intaglio plate rubbing method, comma coating machine method, scrape the skill in using a kitchen knife in cookery, mould is coated with method, dip coating, spray-on process etc. in light polarizing film and/or is fitted in the bonding plane coating adhesive of the film on light polarizing film, and both are overlapped.In above-mentioned coating process, from the viewpoints such as size of the thickness and precision of coated film, coating thickness, equipment, consider, preferably intaglio plate rubbing method, mould are coated with method, from the same viewpoint, more preferably intaglio plate rubbing method.The intaglio plate rubbing method is the rubbing method that uses the gravure roll of considering that coating weight is selected,, in the position that surrounds gravure roll, chamber is set, the method be coated with in the mode of feed fluid in chamber, the direction rotation that described gravure roll is contrary to the flow direction of the film with coating.After coating adhesive, utilize the clamping light polarizing film and the film engaged such as niproll, make their laminatings.
In addition; in order to improve cementability, can suitably implement to the bonding agent coated face of light polarizing film, transparent protective film and/or biaxiality phase retardation film the surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, flame (frame) processing, saponification processing.Process as saponification, can enumerate the method in the aqueous solution that is immersed in the such alkali of NaOH, potassium hydroxide.
After the two sides of light polarizing film is situated between respectively by bond layer stacked transparent protective film, biaxiality phase retardation film, while using the water system bonding agent, implements heat treated and make its drying.Heat treated is undertaken by for example blowing hot blast, and its temperature is generally in the scope of 40～100 ℃, is preferably in the scope of 60～100 ℃.In addition, be generally 20～1200 seconds drying time.
On the other hand, while using Photocurable adhesive agent, the thickness of bond layer is generally 0.5～5 μ m, is preferably 1～4 μ m, more preferably 1.5～4 μ m.When the thickness of bond layer is less than 0.5 μ m, bonding possibility is insufficient, in addition, if the thickness of bond layer is greater than 5 μ m, may produce the bad order of polaroid.
(bonding agent)
In polaroid of the present invention, on the surface of biaxiality phase retardation film, adhesive phase is set usually.When polaroid is used for to liquid crystal indicator, this adhesive phase goes for the laminating to liquid crystal cells.As the bonding agent used in adhesive phase, can use known applicable bonding agent in the past without particular restriction ground, such as enumerating acrylic adhesive, polyurethane series bonding agent, silicon-type bonding agent etc.Wherein, from viewpoints such as the transparency, bounding force, reliability, doing over again property, consider, preferably use acrylic adhesive.Adhesive phase can will contain the solution coat of bonding agent on the norbornene resin film by utilizing mould coating machine, intaglio plate coating machine etc., its dry method is arranged, in addition also can utilize the method that will be transferred on the norbornene resin film at the upper adhesive phase formed of plastic foil (being called diffusion barrier) of having implemented demoulding processing to arrange.The thickness of adhesive phase generally is preferably in the scope of 2～40 μ m.
(liquid crystal indicator)
Polaroid of the present invention is applicable to liquid crystal indicator.In liquid crystal indicator, polaroid of the present invention is situated between and is configured in the rear side of liquid crystal panel by adhesive phase.Now, the propylene resin film that polaroid of the present invention contains ultraviolet light absorber with it becomes from the mode of the side away from liquid crystal cells and configures, to configure with the opposed mode of backlight.Above-mentioned liquid crystal indicator is owing to having used polaroid of the present invention, excellent in te pins of durability, and the excellent in stability of display performance.In liquid crystal indicator, for the part beyond above-mentioned feature, can adopt the applicable formation of known liquid crystal indicator in the past, can suitably possess the component parts (light diffusing sheet, backlight etc.) that liquid crystal indicator usually possesses except liquid crystal panel.Should illustrate, " rear side " of liquid crystal panel refers to the source backlight when liquid crystal panel is equipped on to liquid crystal indicator, and on the other hand, " front face side " of liquid crystal panel refers to viewable side when liquid crystal panel is equipped on to liquid crystal indicator.
Embodiment
Below enumerate embodiment, the present invention is described in more detail, but the invention is not restricted to these embodiment.Carry out the mensuration of mist degree, the mensuration of transmittance, the durable evaluation (oozing out) of polaroid by method as follows.
［ mensuration of mist degree ］
Use the mist degree instrument HM150 of color technical institute system in (strain) village, based on JISK7136, measure mist degree.
［ mensuration of transmittance ］
Use the ultra-violet and visible spectrophotometer UV-2450 of (strain) Shimadzu Seisakusho Ltd. system, after being determined at the optical transmission rate of the every 1nm of wavelength coverage of 220～700nm, in the transmissivity that to get wavelength be each wavelength between 320～330nm, mxm. is the transmittance between 320～330nm as wavelength.Equally, in the transmissivity that to get wavelength be each wavelength between 310～350nm, mxm. is the transmittance between 310～350nm as wavelength, by following benchmark, is classified.These values are less, mean the light that blocks each wavelength coverage, to be that performance is blocked in ultraviolet ray more excellent.
Zero: the optical transmission rate is below 1%,
△: the optical transmission rate is greater than 1% and be less than 2%,
*: the optical transmission rate is more than 2%.
［ durability evaluation of polaroid ］
Polaroid is cut into to 40mm * 40mm, be situated between and be fitted on soda-lime glass by bonding agent, the baking oven of putting into 80 ℃ of drying regimes keeps, after 1500 hours, being confirmed whether to produce exudate from the propylene resin film.In addition, put into the baking oven maintenance of temperature 60 C, relative humidity 90% after 1500 hours, be confirmed whether to produce exudate from the propylene resin film.For whether producing exudate, use the mist degree instrument HM150 of color technical institute system in (strain) village, the mist degree before and after determination test, judge with its rate of change.
Zero: the variable quantity of the mist degree that % means is in 1,
The variable quantity of the mist degree that △: % means is greater than 1 and be less than 2 points,
*: the variable quantity of the mist degree that % means is more than 2.
<embodiment 1>
To ethylene contents be 0.4% and the MFR propylene-ethylene copolymers that is 9g/10 minute in coordinate as 2 of triazine based compound, 4, 6-tri-(4-hexyl oxygen base-2-hydroxy-3-methyl phenyl)-1, 3, 5-triazine (molecular weight: 700, from (strain) ADEKA, obtain, as " triazine 1 ") 0.3 % by weight and be 2-(2-hydroxyl-3 of ultraviolet-absorbing compound as benzotriazole, two (the α of 5-, α-dimethylbenzyl) phenyl)-2H-benzotriazole (molecular weight: 447, from BASF Japan Co., Ltd., obtain, as " benzotriazole 1 ") 0.7 % by weight, carry out melting mixing with the extruder that is heated to the 50mm φ of 275 ℃, then with molten condition, from the T-shaped mould of 600mm width, extrude, cooling with the chill roll of adjustment to 20 ℃, make the film of thickness 75 μ m.The mist degree of the transparent protective film consisted of propylene resin obtained is 1.2%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.7%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.8%.Should illustrate, the chemical constitution of triazine 1, benzotriazole 1 is as follows respectively.
Figure BDA0000389173660000191
Figure BDA0000389173660000192
Next, after the single face of the transparent protective film consisted of propylene resin of above-mentioned making is implemented to corona treatment, at the corona treatment face, with thickness 4 μ m, apply the Photocurable adhesive agent that contains photo-curable photoreactive epoxy resin cationic polymerization initiators.On the other hand, to biaxial stretch-formed, thickness, be phase difference value R in 50 μ m, face 0for 55nm, thickness direction phase difference value R thfor after the single face of the biaxiality phase retardation film consisted of norbornene resin of 124nm implements corona treatment, at its corona treatment face, with thickness 4 μ m, apply photo-curable bonding agent same as described above.Then; bond layer at the above-mentioned transparent protective film formed by propylene resin of the one side of light polarizing film laminating; while is at the bond layer of the above-mentioned biaxiality phase retardation film consisted of norbornene resin of another side laminating, with the niproll cramping of a pair of 100mm φ.From the transparent protective film side irradiation ultraviolet radiation that by norbornene resin formed, make the adhesive phase on two sides solidify making polaroid thereafter.The permanance of the polaroid obtained like this with the method evaluation shown in above-mentioned, result is through 1500 hours under 80 ℃ of drying conditions, the variable quantity of mist degree is 0.0 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.3 point.
<embodiment 2>
The use level that makes triazine 1 is 0.4 % by weight, and the use level of benzotriazole 1 is 0.6 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 1.0%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.4%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.5%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.1 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.4 point.
<embodiment 3>
The use level that makes triazine 1 is 0.5 % by weight, and the use level of benzotriazole 1 is 0.5 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.8%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.2%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.3%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.1 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.7 point.
<embodiment 4>
The use level that makes triazine 1 is 0.6 % by weight, and the use level of benzotriazole 1 is 0.4 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.6%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.1%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.2%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.3 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.3 point.
<embodiment 5>
The use level that makes triazine 1 is 0.7 % by weight, and the use level of benzotriazole 1 is 0.3 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.7%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.1%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.1%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.2 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.3 point.
<embodiment 6>
The use level that makes triazine 1 is 0.8 % by weight, and the use level of benzotriazole 1 is 0.2 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.6%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.0%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.1%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.4 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.6 point.
<embodiment 7>
The use level that makes triazine 1 is 0.9 % by weight, and the use level of benzotriazole 1 is 0.1 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.6%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.0%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.1%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.1 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.9 point.
<embodiment 8>
Making the use level of triazine 1 is 0.5 % by weight, and mismatching benzotriazole is the ultraviolet-absorbing compound, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.1%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.9%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 2.0%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.0 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.2 point.
<embodiment 9>
Making the use level of triazine 1 is 0.6 % by weight, and mismatching benzotriazole is the ultraviolet-absorbing compound, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.1%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.1%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.4%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.1 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.4 point.
<comparative example 1>
The use level that makes triazine 1 is 0.1 % by weight, and the use level of benzotriazole 1 is 0.9 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 1.2%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 38.2%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 42.2%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result be under 80 ℃ of drying conditions through 1500 hours; the variable quantity of mist degree is 0.1 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.7 point.For this polaroid, the maximal value of the optical transmission rate that wavelength is 320～330nm is 38.2%, because the orientation of the liquid crystal cells that makes the light orientating type is at random, so can't use.
<comparative example 2>
The use level that makes triazine 1 is 0.2 % by weight, and the use level of benzotriazole 1 is 0.8 % by weight, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 1.0%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 1.4%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 1.4%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.0 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.3 point.For this polaroid, the maximal value of the optical transmission rate that wavelength is 320～330nm is 1.4%, because the orientation of the liquid crystal cells that makes the light orientating type is at random, so can't use.
<comparative example 3>
Making the use level of triazine 1 is 0.35 % by weight, and mismatching benzotriazole is the ultraviolet-absorbing compound, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.1%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 5.1%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.7%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.2 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 0.4 point.For this polaroid, the maximal value of the optical transmission rate that wavelength is 320～330nm is 5.1%, because the orientation of the liquid crystal cells that makes the light orientating type is at random, so can't use.
<comparative example 4>
Making the use level of triazine 1 is 1.00 % by weight, and mismatching benzotriazole is the ultraviolet-absorbing compound, in addition, similarly to Example 1, makes the transparent protective film consisted of propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 0.1%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.0%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.1%.Use the propylene resin film obtained herein, in addition, make similarly to Example 1 polaroid, permanance is estimated, result is through 1500 hours under 80 ℃ of drying conditions, the variable quantity of mist degree is 0.2 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 2.8 points.For this polaroid, owing to oozing out through 1500 hours at 60 ℃, 90%, so can't use.
<comparative example 5>
Coordinate following chemical constitution to mean 2; 2 '-di-2-ethylhexylphosphine oxide (6-(2H-benzotriazole-2-yl)-4-(1; 1,3,3-tetramethyl butyl) phenol) (molecular weight: 664; from (strain) ADEKA, obtain; as " benzotriazole 2 ") 0.30 % by weight is ultraviolet light absorber as benzotriazole, mismatches the triazine based compound, in addition; similarly to Example 1, make the transparent protective film formed by propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 2.1%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 15.5%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 15.5%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 1.1 points, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 1.1 points.For this polaroid, the maximal value of the optical transmission rate that wavelength is 320～330nm is 15.5%, because the orientation of the liquid crystal cells that makes the light orientating type is at random, so can't use.
Figure BDA0000389173660000241
<comparative example 6>
The use level that makes benzotriazole 2 is 1.00 % by weight, in addition, with comparative example 5 similarly, make the transparent protective film formed by propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 1.1%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 0.5%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 0.5%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 21.5 points, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 13.5 points.For this polaroid, due under 80 ℃ of drying conditions through 1500 hours, at 60 ℃, 90%, through 1500 hours, ooze out, so can't use.
<comparative example 7>
The 2-(2-hydroxyl that coordinates following chemical constitution to mean-4-octyl group oxygen base phenyl)-4; 6-two (2; the 4-3,5-dimethylphenyl)-1,3,5-triazines (molecular weight: 509; from CYTEC INDUSTRIES INC., obtain; as " triazine 2 ") 1.00 % by weight are ultraviolet light absorber as triazine, mismatching benzotriazole is the ultraviolet-absorbing compound, in addition; similarly to Example 1, make the transparent protective film formed by propylene resin.The mist degree of the transparent protective film that should consist of propylene resin is 1.0%, and the maximal value of the optical transmission rate that wavelength is 320～330nm is 1.2%, and the maximal value of the optical transmission rate that wavelength is 310～350nm is 1.2%.Use the transparent protective film formed by propylene resin obtained herein; in addition; make similarly to Example 1 polaroid; permanance is estimated; result is through 1500 hours under 80 ℃ of drying conditions; the variable quantity of mist degree is 0.2 point, and under the condition of temperature 60 C, relative humidity 90%, through 1500 hours, the variable quantity of mist degree was 8.0 points.For this polaroid, so owing at 60 ℃, 90%, through 1500 hours, oozing out and can't use.
Figure BDA0000389173660000251
Composition and the evaluation result of embodiment 1～9, comparative example 1～7 are shown in to table 1.
Table 1
Figure BDA0000389173660000261

Claims (3)

1. a polaroid is the transparent protective film that will consist of propylene resin, in polyvinyl alcohol resin, the absorption orientation has the light polarizing film of bitintability pigment and biaxiality phase retardation film to stack gradually to form,
Described propylene resin contains ultraviolet light absorber, and described ultraviolet light absorber at least contains the triazine based compound that following formula (I) means,
Figure FDA0000389173650000011
In formula (I), R 1the alkyl that means carbon number 1～12, R 2the alkyl that means hydrogen or carbon number 1～8,
The content of described triazine based compound is less than 1 % by weight in described propylene resin,
Wavelength is below 1% in the optical transmission rate between 320～330nm.
2. polaroid according to claim 1, wherein, described propylene resin contains with the ratio of 0.5～0.8 % by weight the ultraviolet light absorber that the triazine based compound that only meaned by described formula (I) forms.
3. polaroid according to claim 1, wherein, described propylene resin contains triazine based compound that described formula (I) means and contains benzotriazole with the ratio of 0.1～0.7 % by weight with the ratio of 0.3～0.9 % by weight is the ultraviolet-absorbing compound, and wavelength is below 1% in the optical transmission rate between 310～350nm.
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