CN101644792B - Polaroid sheet, manufacturing method thereof and liquid crystal display device - Google Patents

Polaroid sheet, manufacturing method thereof and liquid crystal display device Download PDF

Info

Publication number
CN101644792B
CN101644792B CN2009101590503A CN200910159050A CN101644792B CN 101644792 B CN101644792 B CN 101644792B CN 2009101590503 A CN2009101590503 A CN 2009101590503A CN 200910159050 A CN200910159050 A CN 200910159050A CN 101644792 B CN101644792 B CN 101644792B
Authority
CN
China
Prior art keywords
methyl
polaroid
compound
liquid crystal
protective seam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2009101590503A
Other languages
Chinese (zh)
Other versions
CN101644792A (en
Inventor
藤长将司
竹厚流
张柱烈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Corp
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN101644792A publication Critical patent/CN101644792A/en
Application granted granted Critical
Publication of CN101644792B publication Critical patent/CN101644792B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • 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
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Geometry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention relates to a polaroid sheet, a manufacturing method thereof and a liquid crystal display device using the polaroid sheet. The polaroid sheet is provided with a polarizing film (51) which has oriented dichroism pigment absorbed on a polyvinyl alcohol resin film, a first protective layer (52) which is stacked on one side of the polarizing film (51) and is made from condensate containing solidifying composition with active energy line, and a second protective layer (53) which is stacked on the other side of the polarizing film (51) by an adhesive layer (54) and is made from thermoplastic resin film.

Description

Polaroid and manufacture method thereof and liquid crystal indicator
Technical field
The liquid crystal indicator with the in-plane-switching mode action that the present invention relates to polaroid, especially in face, is fit to polaroid and the manufacture method of using thereof and has used this polaroid in the liquid crystal indicator of switching (IPS) pattern.
Background technology
In recent years, from low power consumption, low-work voltage, light weight, various advantages such as slim, liquid crystal indicator (LCD) as mobile phone, portable information terminal (personal digital assistant: PDA), information such as PC, TV with the purposes of display device in rapid increase.Be accompanied by the development of lcd technology, proposed the liquid crystal indicator of various patterns, eliminate the problem of the LCD of response speed, contrast, narrow field angle and so on gradually.
As one of countermeasure of field angle compensation, a kind of liquid crystal cells that can enlarge field angle has in itself been proposed.For example can enumerate and switch (In-Plane Switching:IPS) pattern etc. in optical compensation curved (Optically CompensatedBend:OCB) pattern, vertical orientated (Vertical Alignment:VA) pattern, the face.Wherein, the IPS pattern is the pattern that the state of orientation of liquid crystal molecule is changed by switching in the face that applies voltage in the direction parallel with real estate, with regard to the IPS pattern, do not applying under the state of voltage, the orientation of liquid crystal molecule is parallel with real estate, but whether as the TN pattern, twist, but roughly in same direction orientation.
Principle according to Fig. 1 and the IPS pattern of Fig. 2 is illustrated.Fig. 1 is the profile schema diagram of configuration example of the liquid crystal indicator of expression IPS pattern.Fig. 2 be for the principle that the IPS pattern is described to the schematic perspective view shown in the relevant normal black example, the state when (A) expression does not apply voltage, and (B) state when expression applies voltage.Need to prove, in Fig. 2, for the ease of understanding each interlayer separated and to illustrate.In addition, in Fig. 2 (B), only add reference symbol to being in the part of (A) different conditions, for the part of (A) equal state, for fear of not seeing accompanying drawing, omitted reference symbol.
Become the liquid crystal cells 10 at the liquid crystal indicator center of IPS pattern, by cell substrate 11 up and down, 12 and the liquid crystal layer 14 that is clamped between these cell substrates constitute.Constitute the liquid crystal molecule 15 of liquid crystal layer 14, be orientated with respect to each cell substrate 11,12 face almost parallel ground.And, about liquid crystal cells 10, dispose front face side polaroid 20, rear side polaroid 30 respectively, making in the light from the backlight 40 that is disposed at the outside, one side (rear side), only is that the rectilinearly polarized light parallel with the light transmission shaft of rear side polaroid 30 between liquid crystal cells 10 and backlight 40 is to liquid crystal cells 10 incidents.Polaroid generally includes light polarizing film and diaphragm etc.
Under the state that does not apply voltage shown in Fig. 2 (A), liquid crystal molecule 15 is parallel to the cell substrate face and is orientated in roughly the same direction.In this embodiment, liquid crystal molecule 15 is orientated in the direction with light transmission shaft 32 almost parallels of rear side polaroid 30.On a cell substrate (being the downside substrate in this example) 12, electrode 13,13 be arranged in parallel with the broach shape.In this state, seen through the rectilinearly polarized light 16 of rear side polaroid 30, not making under the state that polarized light state changes by liquid crystal layer 14 of former state, the state of identical rectilinearly polarized light 17 passes through the cell substrate 11 of upside during with incident with direction.If make thereon light transmission shaft 32 quadratures of light transmission shaft 22 and rear side polaroid 30 of the front face side polaroid 20 of configuration, then the rectilinearly polarized light 17 by upside cell substrate 11 can't pass through front face side polaroid 20, becomes demonstration and deceives state.
On the other hand, shown in Fig. 2 (B), when applying the electric field 18 that is represented by dotted lines between the electrode 13,13 of configured in parallel on cell substrate, can make the major axis of liquid crystal molecule 15 along electric field 18 orientations, depart from the light transmission shaft 32 of rear side polaroid 30.Its result, the rectilinearly polarized light 16 that has incided liquid crystal cells 10 polarized light state during by liquid crystal layer 14 changes, by becoming elliptically polarized light 17 ' behind the liquid crystal layer 14, generation can be passed through the composition of the light transmission shaft 22 of front face side polaroid 20, so just shows bright state.
In addition, in Fig. 2, the example that illustrates is to be configured to make the light transmission shaft 32 of rear side polaroid 30 and the major axis almost parallel of liquid crystal molecule 15, and be configured to make the light transmission shaft quadrature of front face side polaroid 20 and rear side polaroid 30, even if but be configured to make the light transmission shaft 22 of front face side polaroid 20 and the major axis almost parallel of liquid crystal molecule 15, and be configured to make the light transmission shaft quadrature of front face side polaroid 20 and rear side polaroid 30, also can obtain same result.Mainly be to be configured to make the light transmission shaft almost parallel of the major axis of liquid crystal molecule 15 and either party's polaroid to get final product.At this moment, the long axis direction of liquid crystal molecule 15 need not strictly parallel with the light transmission shaft of either party's polaroid, in order when applying electric field 18, to make liquid crystal molecule 15 towards certain orientation rotation, to depart from angle to a certain degree sometimes, for example with 10 ° with interior angle deviating.In addition, owing to be configured to make the light transmission shaft quadrature of front face side polaroid 20 and rear side polaroid 30, therefore when not applying voltage, show black state and show that when applying voltage the so-called normal black situation of bright state is in the majority, if and the light transmission shaft of configured in parallel front face side polaroid 20 and rear side polaroid 30 then becomes the so-called Chang Bai that shows bright state and show black state when not applying voltage when applying voltage.
So in the IPS pattern, because liquid crystal molecule is parallel with real estate and be orientated in same direction, so compare the field angle excellent with other patterns.Yet the tri acetyl cellulose membrane that all the time uses as the diaphragm in the polaroid is because the delay R in the face eBe roughly about 5nm the delay R of film thickness direction ThBe roughly 50nm, therefore in used as the liquid crystal indicator that is disposed at the diaphragm between liquid crystal cells and the light polarizing film, transmitted light produces birefringence, has the problem of light leak during black the demonstration.
In order to address this problem, for example in patent documentation 1 (spy opens the 2006-18245 communique), the delay R in the making face is disclosed eDelay R with film thickness direction ThLittle hyaline membrane and the technology of in polaroid, using as diaphragm.
On the other hand; in order to make the diaphragm attenuation of polaroid; for example disclosed technology is in patent documentation 2 (spy opens the 2004-245924 communique); to be adsorbed with the single face at least of the light polarizing film that dichromatism pigment and described dichromatism pigment be oriented at the polyvinyl alcohol resin film; after having applied uncured epoxy composite; said composition is solidified, form the technology of diaphragm thus.Yet; for the polaroid that the solidfied material that makes disclosed epoxy composite wherein forms diaphragm, permanance is insufficient, for example can't fully be suppressed at the contraction of the light polarizing film under the hot conditions; in size surpasses 15 inches polaroid, the problem that exists light polarizing film to break and so on.
Summary of the invention
The objective of the invention is to, a kind of delay R in the face of the protective seam that liquid crystal cell side disposes is provided eDelay R with film thickness direction ThThe polaroid of little polaroid and then slim light weight and endurance quality excellence, especially be adapted at switching in the face polaroid and the manufacture method of using in the liquid crystal indicator of (IPS) pattern thereof.In addition, other purposes of the present invention also are, the liquid crystal indicator that has used this polaroid, the liquid crystal indicator that especially moves with in-plane-switching mode are provided.
The invention provides a kind of polaroid, it possesses: second protective seam that forms on first protective seam that forms on the face that be adsorbed with light polarizing film that dichromatism pigment and described dichromatism pigment be oriented at the polyvinyl alcohol resin film, is layered in this light polarizing film and by the solidfied material of the solidification compound that contains the active energy ray-curable compound and another face that is layered in this light polarizing film by adhesive layer and by thermoplastic resin film.
In polaroid of the present invention; the solidification compound that uses in order to form first protective seam; preferably contain in molecule, have an epoxy radicals at least the epoxy based compound as the active energy ray-curable compound, more preferably this epoxy compound has an epoxy radicals that is bonded on the ester ring type ring at least.
Solidification compound can also contain the oxetanes based compound as the active energy ray-curable compound.In addition, solidification compound can also contain in molecule, have (methyl) acryloxy at least (methyl) acrylic acid series compound as the active energy ray-curable compound.
By first protective seam that the solidfied material of solidification compound forms, preferably its thickness is 0.1～10 μ m.
Second protective seam is preferably formed by the cellulose acetate resin film.In addition, adhesive layer is preferably formed by the solidfied material of the solidification compound that contains the active energy ray-curable compound.
Polaroid of the present invention can also further possess adhesive phase stacked on first protective seam and face described light polarizing film side opposition side.Polaroid of the present invention is adapted at using in the liquid crystal indicator with the in-plane-switching mode action.
In addition, liquid crystal indicator provided by the invention, it possesses liquid crystal cells and at a pair of polaroid of the two-sided configuration of this liquid crystal cells, at least one side in this a pair of polaroid is the polaroid of the present invention that possesses above-mentioned adhesive phase, and is fitted on the liquid crystal cells by this adhesive phase; The present invention also provides following liquid crystal indicator, namely possesses liquid crystal cells and at a pair of polaroid of the two-sided configuration of this liquid crystal cells, this a pair of polaroid all is the polaroids of the present invention that possess above-mentioned adhesive phase, is fitted on the described liquid crystal cells by this adhesive phase.
Liquid crystal cells in the liquid crystal indicator of the present invention preferably has two plate bases and is clamped between this substrate and at the liquid crystal layer that is not applying under the voltage status with substrate almost parallel ground orientation, and moves with in-plane-switching mode.
And then; according to the present invention; a kind of manufacture method of polaroid is provided; this polaroid possesses at the polyvinyl alcohol resin film and is adsorbed with the light polarizing film that dichromatism pigment and described dichromatism pigment are oriented; first protective seam that is layered on the face of light polarizing film and is constituted by the solidfied material of the solidification compound that contains the active energy ray-curable compound; and second protective seam that is layered in by adhesive layer on another face of light polarizing film and is formed by thermoplastic resin film; described manufacture method comprises following operation, and the coating layer that the coating layer of this solidification compound namely is set on the surface of base material forms operation; make the coating layer of the solidification compound that is arranged at substrate surface be fitted in coating layer bonding process on the face of light polarizing film; by the film bonding process of tackifier at another face applying second protective seam of light polarizing film; make the curing process of this coating layer and this adhesive solidification; and the base material that base material is removed removed operation.
Coating layer in curing process and the curing of tackifier are preferably by carrying out simultaneously from base material side irradiation active energy ray.
Polaroid of the present invention possesses the delay R in the face eDelay R with film thickness direction ThThe first little protective seam.Therefore, when the mode that this polaroid of the present invention is become liquid crystal cell side with its first protective seam is applied in the liquid crystal indicator, can prevent light leak effectively.In addition, constitute first protective seam by the solidfied material by solidification compound, compare with triacetyl cellulose (TAC) film etc. in the past, can reduce the thickness of protective seam, therefore can realize the slim lightweight of polaroid.
In addition, according to the manufacture method of polaroid of the present invention, under the situation that drying process is not set, the polaroid that relates among the present invention can be made, the simplification of manufacturing process can be realized.
Description of drawings
Fig. 1 is the profile schema diagram of configuration example of the liquid crystal display of expression IPS pattern.
Fig. 2 is to the schematic perspective view shown in the normal example of deceiving, the state when (A) expression does not apply voltage, the state when (B) expression applies voltage for IPS pattern principle is described.
Fig. 3 is the diagrammatic cross-section of a preferred example of the polaroid that relates among the present invention of expression.
Symbol description
The 10-liquid crystal cells; 11,12-cell substrate; the 13-electrode, 14-liquid crystal layer, 15-liquid crystal molecule; 16-is to the rectilinearly polarized light of liquid crystal cells incident; 17-is by the rectilinearly polarized light 17 ' behind the liquid crystal cells-by the elliptically polarized light behind the liquid crystal cells, 18-electric field, 20-front face side polaroid; the light transmission shaft of 22-front face side polaroid; 30-rear side polaroid, the light transmission shaft of 32-rear side polaroid, 40-backlight; the 50-polaroid; the 51-light polarizing film, 52-first protective seam, 53-second protective seam; the 54-adhesive layer, the 55-adhesive phase
Embodiment
＜polaroid 〉
Fig. 3 is the diagrammatic cross-section of a preferred example of the polaroid that relates among the present invention of expression.Polaroid 50 shown in Figure 3 possesses: light polarizing film 51, be layered on the face of light polarizing film 51 the first transparent protective seam 52 and on another face the stacked second transparent protective seam 53.First protective seam 52 is made of the solidfied material of the solidification compound that contains the active energy ray-curable compound.Second protective seam 53 is formed by thermoplastic resin film, fits on the light polarizing film 51 by adhesive layer 54.In addition, about polaroid 50, in the outside of first protective seam 52, namely on first protective seam 52 and faces light polarizing film 51 side opposition sides, have be used to the adhesive phase 55 that is fitted on liquid crystal cells etc.In addition, polaroid of the present invention also can not have adhesive phase.Below polaroid of the present invention is elaborated.
(light polarizing film)
Making it embody light polarizing film as the function of polaroid, is to be adsorbed with the light polarizing film that dichromatism pigment and described dichromatism pigment are oriented at the polyvinyl alcohol resin film.Constitute the polyvinyl alcohol resin of light polarizing film, by being that the resin saponification obtains with polyvinyl acetate.Be resin as polyvinyl acetate, except the polyvinyl acetate as the vinyl acetate homopolymer, can also the illustration vinyl acetate and can be with the multipolymer of other monomers of its copolymerization etc.As can with other monomers of vinyl acetate copolymerization, can enumerate for example unsaturated carboxylic acid class, unsaturated sulfonic acid class, olefines, vinyl ethers etc.The saponification degree of polyvinyl alcohol resin is normally about 85～100 moles of %, preferred 98～100 moles of %.Polyvinyl alcohol resin can also further be modified, for example also can use through the aldehydes modification and polyvinyl formal, polyvinyl acetal etc.In addition, the degree of polymerization of polyvinyl alcohol resin normally about 1,000～10,000, preferred about 1,500～10,000.
The film that this polyvinyl alcohol resin film processed is obtained can be used as the original membrane (former anti-Off イ Le system) of light polarizing film and uses.Method with polyvinyl alcohol resin film processed is not particularly limited, can be with known method film processed.Thickness to the original membrane made by polyvinyl alcohol resin is not particularly limited, but for example is about 10 μ m～150 μ m.
Light polarizing film is made via following operation usually, that is, to the original membrane of being made by aforesaid polyvinyl alcohol resin carry out the operation of uniaxial tension, with the operation that the polyvinyl alcohol resin film makes its operation of adsorbing this dichromatism pigment with the dichromatism pigment dyeing, the polyvinyl alcohol resin film that will be adsorbed with the dichromatism pigment is handled with boric acid aqueous solution and the operation of after handling through boric acid aqueous solution, washing.
Uniaxial tension can carry out before the dyeing that utilizes the dichromatism pigment, also can carry out simultaneously with this dyeing, can also carry out after this dyeing.When carrying out after uniaxial tension is utilizing the dyeing of dichromatism pigment, this uniaxial tension can carry out before boric acid is handled, and also can carry out in the boric acid processing procedure.In addition, also can carry out uniaxial tension in these a plurality of stages.When uniaxial tension, can between the different roller of peripheral speed, carry out uniaxial tension, can also use hot-rolling to carry out uniaxial tension.In addition, can be dry type stretching such as in atmosphere, stretch, can also be the wet type that stretches under the state of its swelling is stretched.Stretching ratio is normally about 4～8 times.
When the polyvinyl alcohol resin film is used the dichromatism pigment dyeing, for example, the polyvinyl alcohol resin film immersion is got final product in the aqueous solution that contains the dichromatism pigment.As the dichromatism pigment, can use iodine, dichroic dye etc.In addition, the polyvinyl alcohol resin film was preferably implemented the dip treating to water before dyeing is handled.
When using iodine as the dichromatism pigment, as colouring method, adopt the method for dipping polyvinyl alcohol resin film in the aqueous solution that contains iodine and potassium iodide usually.About the content of iodine in this aqueous solution, be about 0.01～0.5 weight portion with respect to water 100 weight portions usually, in addition, about the content of potassium iodide, be about 0.5～10 weight portion with respect to water 100 weight portions usually.Normally about 20～40 ℃, in addition, the dip time in this aqueous solution (dyeing time) is normally about 30～300 seconds for the temperature of the aqueous solution of using during dyeing.
On the other hand, when using dichroic dye as the dichromatism pigment, as colouring method, adopt the method for dipping polyvinyl alcohol resin film in containing the aqueous dye solutions of water-soluble dichroic dye usually.About the content of the dichroic dye in this aqueous dye solutions, be 1 * 10 with respect to water 100 weight portions usually -3～1 * 10 -2About weight portion.Aqueous dye solutions can also contain inorganic salts such as sodium sulphate as dyeing assistant.Normally about 20～80 ℃, in addition, the dip time in aqueous dye solutions (dyeing time) is normally about 30～300 seconds for the temperature of aqueous dye solutions.
Utilize the boric acid behind the dichromatism pigment dyeing to handle, carry out in the aqueous solution that contains boric acid by the polyvinyl alcohol resin film immersion that will be colored.About the boric acid content in containing the aqueous solution of boric acid, with respect to water 100 weight portions normally about 2～15 weight portions, about preferred 5～12 weight portions.When using iodine as the dichromatism pigment, the aqueous solution that contains boric acid preferably contains potassium iodide.About the content of the potassium iodide in containing the aqueous solution of boric acid, be about 2～20 weight portions with respect to water 100 weight portions normally, about preferred 5～15 weight portions.Dip time in containing the aqueous solution of boric acid is normally about 100～1,200 seconds, and preferred about 150～600 seconds, and then preferred about 200～400 seconds.Contain the temperature of aqueous solution of boric acid normally more than 50 ℃, preferred 50～85 ℃.
Polyvinyl alcohol resin film after boric acid is handled is implemented washing usually and handles.Washing is handled for example by carrying out in water through the polyvinyl alcohol resin film immersion that boric acid is handled.Normally about 5～40 ℃, dip time was about 2～120 seconds to the temperature of water when washing was handled.The dry processing implemented in the washing back, obtains light polarizing film.Dry processing can use air drier, far infra-red heater to carry out.Baking temperature is normally about 40～100 ℃.The dry time of handling is normally about 120～600 seconds.
As known from the above, can be produced on and on the polyvinyl alcohol resin film of uniaxial tension, be adsorbed with the light polarizing film that dichromatism pigment and described dichromatism pigment are oriented.The thickness of this light polarizing film can be made about 5～40 μ m.
(protective seam)
In the present invention, the solidfied material by the solidification compound that contains the active energy ray-curable compound is formed in first protective seam that arranges on the face of light polarizing film as implied above.In addition, second protective seam that arranges at another face of light polarizing film is formed by thermoplastic resin film, by adhesive layer this thermoplastic resin film is fitted on the described another side of light polarizing film.Below, describe according to the order of these first protective seams and second protective seam.In addition, solidification compound is also referred to as hardening resin composition.
(1) first protective seam
At first protective seam that a face of light polarizing film arranges, the solidfied material by the solidification compound that contains the active energy ray-curable compound constitutes as mentioned above.So-called active energy ray-curable compound refers to the compound that can solidify through the irradiation of active energy ray (for example ultraviolet ray, visible light, electron ray, X ray etc.).The active energy ray-curable compound can be the compound of cationically polymerizable, also can be free-radical polymerised compound.As the example of cationically polymerizable compound, can enumerate the epoxy based compound (following abbreviate as sometimes " epoxy based compound ") that in molecule, has an epoxy radicals at least, the oxetanes based compound (following abbreviate as sometimes " oxetanes based compound ") that in molecule, has an oxetanes ring at least etc.In addition, as the example of free-radical polymerised compound, can enumerate (methyl) acrylic acid series compound (following abbreviate as sometimes " (methyl) acrylic acid series compound ") that in molecule, has (methyl) acryloxy at least etc.In addition, so-called " (methyl) acryloxy " refers to methacryloxy or acryloxy.
To this solidfied material that contains the solidification compound irradiation active energy ray of active energy ray-curable compound and obtain, can be provided at the excellent and interior length of delay R of middle film (first protective seam) face that defines of following formula (1) in aspects such as the transparency, physical strength, thermal stability eLength of delay R with the film thickness direction of the film of definition in the following formula (2) ThBe roughly 0 protective seam.Here, what is called is roughly 0, refers to for R e, at 0≤R e≤ 20 scope, more preferably 0≤R e≤ 15, further preferred 0≤R e≤ 10.In addition, for R Th, what is called is roughly 0, refers to | R Th|≤25 scope, more preferably | R Th|≤23, further preferred | R Th|≤20.
R e＝(n x-n y)×d (1)
R th＝〔(n x+n y)/2-n z〕d (2)
Here, n x: the refractive index of slow-axis direction in the face of film
n y: the refractive index of quick shaft direction (with the direction of slow-axis direction quadrature) in the face of film
n z: the refractive index of the thickness direction of film
D: the thickness of film
By by the length of delay R in the face eLength of delay R with the film thickness direction of film ThThe solidfied material that is roughly 0 solidification compound constitutes first protective seam, when polaroid is fitted in liquid crystal cells by this first protective seam side, can prevent the light leak of liquid crystal indicator when black demonstration of gained effectively.In addition, owing to can reduce the thickness of protective seam, therefore can realize the slim lightweight of polaroid and liquid crystal indicator.
In addition, protective seam stacked on light polarizing film is preferably optically transparent, and therefore the haze value of first protective seam is preferably below 0.5%, and is more preferably below 0.3%, further preferred below 0.1%.Surpass at 0.5% o'clock at haze value, light generation scattering, so transmissivity reduces.
Above-mentioned solidification compound preferably contains the epoxy based compound at least as above-mentioned active energy ray-curable compound, thus, can obtain light polarizing film is demonstrated the protective seam of good adaptation.
As above-mentioned epoxy based compound, from viewpoints such as against weather, refractive index, cationically polymerizables, preferably use the epoxy based compound that in molecule, does not contain aromatic rings as principal ingredient.As this epoxy based compound that in molecule, does not contain aromatic rings, can illustration hydrogenation epoxy based compound, aliphatic epoxy based compound, ester ring type epoxy based compound etc.
Hydrogenation epoxy based compound can be by making the aromatic epoxies based compound optionally carry out hydrogenation to obtain in the presence of catalyzer, adding to depress.As the aromatic epoxies based compound, can enumerate the diglycidyl ether of bisphenol-A for example, the diglycidyl ether of Bisphenol F, the such bisphenol-type epoxy resin of diglycidyl ether of bisphenol S; The epoxy resin of the phenol aldehyde type that phenol novolac epoxy resins, cresol novolak epoxy, hydroxy benzaldehyde phenol novolac epoxy resins are such; Epoxy resin of the multifunctional type that the glycidol ether of tetrahydroxy diphenyl methane, the glycidol ether of tetrahydroxybenzophenone, epoxidation polyvinyl phenol are such etc.Wherein, as hydrogenation epoxy based compound, preferably use the glycidol ether of bisphenol-A hydride.
As the aliphatic epoxy based compound, can enumerate the polyglycidyl ether of aliphatic polyol or its alkylene oxide addition product.More specifically, can enumerate 1, the diglycidyl ether of 4-butylene glycol, the diglycidyl ether of 1,6-hexanediol, the triglycidyl ether of glycerine, the triglycidyl ether of trimethylolpropane, the diglycidyl ether of polyglycol, the diglycidyl ether of propylene glycol, on the such aliphatic polyol of ethylene glycol, propylene glycol, glycerine addition more than a kind or 2 kinds alkylidene epoxide (oxirane, epoxypropane) and polyglycidyl ether of the polyether glycol that obtains etc.
In addition, so-called ester ring type epoxy based compound refers to have at least an epoxy based compound that is bonded in the epoxy radicals on the ester ring type ring.So-called " being bonded in the epoxy radicals on the ester ring type ring " has the structure shown in the following formula, and in the formula, m is 2～5 integer.
Therefore, so-called ester ring type epoxy based compound is the compound that has a structure shown in the above-mentioned formula in molecule at least.More specifically, with (the CH in the above-mentioned formula 2) mIn one or more hydrogen remove and the group that obtains and other chemical constitution bondings and compound, can become ester ring type epoxy based compound.(CH 2) mIn one or more hydrogen, can also suitably replace with straight chain shape alkyl such as methyl, ethyls.
In above such epoxy based compound; preferred ester ring type epoxy based compound; namely; at least one of epoxy radicals is bonded in the compound on the ester ring type ring; especially, has the epoxy based compound of oxabicyclo hexane ring (m=3 in the above-mentioned formula), oxabicyclo heptane (m=4 in the above-mentioned formula), because the elastic modulus height of solidfied material; therefore the protective seam of the adaptation excellence of acquisition and light polarizing film more preferably uses easily.Below, particularly illustration the structure of the preferred ester ring type epoxy based compound that uses in the present invention, but be not limited to these compounds.
(a) the epoxycyclohexyl methyl epoxycyclohexane carboxylate class shown in the following formula (I):
Figure G2009101590503D00111
(in the formula, R 1And R 2The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)
(b) the epoxy radicals cyclohexane carboxylic-acid ester class of the alkanediol shown in the following formula (II):
Figure G2009101590503D00112
(in the formula, R 3And R 4Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, n represents 2～20 integer.)
(c) the epoxycyclohexyl methyl ester class of the dicarboxylic acid shown in the following formula (III):
Figure G2009101590503D00121
(in the formula, R 5And R 6Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, p represents 2～20 integer.)
(d) the epoxycyclohexyl methyl ethers of the polyglycol shown in the following formula (IV):
(in the formula, R 7And R 8Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, q represents 2～10 integer.)
(e) the epoxycyclohexyl methyl ethers of the alkane diol shown in the following formula (V):
(in the formula, R 9And R 10Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, r represents 0～18 integer.)
(f) bicyclic oxygen three spiro-compounds shown in the following formula (VI):
Figure G2009101590503D00124
(in the formula, R 11And R 12The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)
(g) the bicyclic oxygen list spiro-compound shown in the following formula (VII):
(in the formula, R 13And R 14The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)
(h) the vinyl cyclohexene diepoxide class shown in the following formula (VIII):
(in the formula, R 15The straight chain shape alkyl of expression hydrogen atom or carbon number 1～5.)
(i) the epoxide ring amyl group ethers shown in the following formula (IX):
Figure G2009101590503D00133
(in the formula, R 16And R 17The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)
(j) the bicyclic oxygen tristane shown in the following formula (X) (diepoxy tricyclodecane) class:
Figure G2009101590503D00141
(in the formula, R 18The straight chain shape alkyl of expression hydrogen atom or carbon number 1～5.)
In above-mentioned illustrative ester ring type epoxy based compound, for following ester ring type epoxy based compound, from having commercially available or its analog ratio is easier to reasons such as acquisition, the preferred use.
(A) carboxylate of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxa--two ring [4.1.0] heptan-3-yl) methyl alcohol [in above-mentioned formula (I), R 1=R 2The compound of=H]
(B) carboxylate of 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl-7-oxa--two ring [4.1.0] heptan-3-yl) methyl alcohol [in above-mentioned formula (I), R 1=4-CH 3, R 2=4-CH 3Compound]
(C) carboxylate of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethylene glycol [in above-mentioned formula (II), R 3=R 4The compound of=H, n=2]
(D) carboxylate of (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and hexane diacid [in above-mentioned formula (III), R 5=R 6The compound of=H, p=4]
(E) carboxylate of (4-methyl-7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and hexane diacid [in above-mentioned formula (III), R 5=4-CH 3, R 6=4-CH 3, p=4 compound]
(F) etherate of (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and 1,2-ethylene glycol [in above-mentioned formula (V), R 9=R 10The compound of=H, r=2]
In the present invention, the epoxy based compound can only use a kind ofly separately, and perhaps two or more kinds may be used.
About the solidification compound that uses in the formation of first protective seam, the epoxy based compound preferably all accounting for 30～100 weight % in the active energy ray-curable compound, more preferably accounts for 35～70 weight %, further preferably accounts for 40～60 weight %.At the content of epoxy based compound after a little while, the trend that exists the adaptation of light polarizing film and first protective seam to reduce.
In addition, about this solidification compound, except above-mentioned epoxy based compound, can also contain the oxetanes based compound as the active energy ray-curable compound.By adding the oxetanes based compound, can reduce the viscosity of solidification compound, accelerate curing rate.
The oxetanes based compound is the compound that has an oxetanes ring (quaternary cyclic ethers) in molecule at least, can enumerate for example 3-ethyl-3-hydroxymethyl oxetanes, 1, two [(3-ethyl-3-oxetanyl) methoxy] benzene of 4-, 3-ethyl-3-(phenoxymethyl) oxetanes, two [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes, phenol phenolic aldehyde oxetanes etc.These oxetanes based compounds, can easily obtain commercially available product, for example, all give an example with trade name, can enumerate " ARON OXETANE OXT-101 ", " ARON OXETANE OXT-121 ", " ARONOXETANE OXT-211 ", " ARON OXETANE OXT-221 ", " ARONOXETANE OXT-212 " (being East Asia synthetic (strain) system) etc.Use level to the oxetanes based compound is not particularly limited, but is below the 30 weight % in whole active energy ray-curable compounds usually, preferred 10～25 weight %.
The solidification compound that uses in the formation of first protective seam when containing cationically polymerizable compound such as epoxy based compound, oxetanes based compound, cooperates the cationic polymerization light trigger usually in this solidification compound.If use the cationic polymerization light trigger, then can form protective seam at normal temperatures, therefore can reduce consideration because of the thermotolerance of light polarizing film, necessity of the distortion that causes of expanding, can first protective seam be formed on the light polarizing film with good adaptation.In addition, the cationic polymerization light trigger is brought into play catalytic action because of light, even therefore be blended in the solidification compound, its storage stability, operability are also excellent.
About the cationic polymerization light trigger, it is the irradiation by luminous ray, ultraviolet ray, X ray, electron ray isoreactivity energy line, produce kation kind or lewis acid, the material that the polyreaction of epoxy based compound and/or oxetanes based compound is begun.In the present invention, the cationic polymerization light trigger of any kind be can use, if enumerate concrete example, the such salt of aromatic series diazo salt for example, aromatic series salt compounded of iodine, aromatic series sulfonium salt, fragrant luxuriant iron complex etc. then can be enumerated.
As the aromatic series diazo salt, can enumerate for example benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoro borate etc.
As the aromatic series salt compounded of iodine, can enumerate for example diphenyl iodonium four (pentafluorophenyl group) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoro antimonate, two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As the aromatic series sulfonium salt, can enumerate for example triphenylsulfonium hexafluorophosphate, the triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4, the two hexafluorophosphates of 4 '-two (diphenyl sulfonium) diphenyl sulfide, 4, the two hexafluoro antimonates of 4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium] diphenyl sulfide, the two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium] diphenyl sulfide, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone hexafluoro antimonate, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfide hexafluorophosphate, 4-(to the tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenyl sulfide hexafluoro antimonate, 4-(to the tert-butyl-phenyl carbonyl)-4 '-(p-methylphenyl) sulfonium-diphenyl sulfide four (pentafluorophenyl group) borate etc.
In addition, as the luxuriant iron complex of virtue, can enumerate for example dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, isopropyl benzene-cyclopentadienyl group iron (II) hexafluorophosphoric acid ester, dimethylbenzene-cyclopentadienyl group iron (II)-three (trifluoromethyl sulphonyl) methanides etc.
These cationic polymerization light triggers, can easily obtain commercially available product, for example, if name with trade name respectively, then can enumerate " Kayarad PCI-220 ", " Kayarad PCI-620 " (above by Nippon Kayaku K. K's system), " UVI-6990 " (associating carbonide (UnionCarbide) corporate system), " Adeka Optomer SP-150 ", " Adeka Optomer SP-170 " (above by (strain) ADEKA system), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (above by Tso Tat Co., Ltd., Japan's system), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (above by greening Co., Ltd. system), " PI-2074 " (Luo Diya (Rhodia) corporate system), " UVA CURE 1590 " (DAICEL-CYTEC (strain) system) etc.
These cationic polymerization light triggers can be distinguished separately and use, and also can mix more than 2 kinds and use.Wherein, aromatic series sulfonium salt especially, even if the wavelength region may more than 300nm also has the UVA characteristic, therefore curing property excellence, can provide have good mechanical strength and with the solidfied material of the good adaptation of light polarizing film, therefore preferred the use.
About the use level of cationic polymerization light trigger, with respect to total amount 100 weight portions of cationically polymerizable compounds such as epoxy based compound, oxetanes based compound, 0.5～20 weight portion normally, preferred 1～6 weight portion.When the use level of cationic polymerization light trigger is very few, solidify insufficient, the trend that exists the adaptation of physical strength, protective seam and diaphragm to reduce.On the other hand, when the use level of cationic polymerization light trigger was too much, ionic substance in the solidfied material increased, so the hydroscopicity of solidfied material improves, the possibility that exists the endurance quality of the polaroid of gained to reduce.
In addition, the solidification compound that uses in the formation of first protective seam preferably not only contains above-mentioned epoxy based compound, perhaps epoxy based compound and oxetanes based compound, but also contain free-radical polymerised (methyl) acrylic acid series compound.With (methyl) acrylic acid series compound, can obtain hardness height, physical strength excellence, the protective seam that endurance quality is higher by also.And then, can be more easily to the surface cure of the protective seam of the viscosity of solidification compound and curing rate and gained, adjust with the adaptation of light polarizing film etc.
As (methyl) acrylic acid series compound, can enumerate (methyl) acrylate monomer of in molecule, having 1 (methyl) acryloxy at least, make the functional compounds that contains more than 2 kinds react and obtain and (methyl) acrylate oligomer etc. of having 2 (methyl) acryloxies in molecule at least contains the compound of (methyl) acryloxy.These compounds can be distinguished use separately, and also two or more kinds may be used.And with more than 2 kinds the time, (methyl) acrylate monomer can be more than 2 kinds, (methyl) acrylate oligomer can be more than 2 kinds, certainly, also can and with in (methyl) acrylate monomer more than a kind and in (methyl) acrylate oligomer more than a kind.In addition, so-called " (methyl) acrylate " refers to acrylate or methacrylate.
As above-mentioned (methyl) acrylate monomer, can enumerate simple function (methyl) acrylate monomer that in molecule, has 1 (methyl) acryloxy, 2 officials energy (methyl) acrylate monomer that in molecule, has 2 (methyl) acryloxies and multifunctional (methyl) acrylate monomer that in molecule, has (methyl) acryloxy more than 3.
As the concrete example of simple function (methyl) acrylate monomer, can enumerate (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2 or 3-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid dihydro dicyclopentadiene (dicyclopentenyl) ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid dihydro bicyclic pentadiene oxygen base ethyl ester, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid ethyl carbitol ester, trimethylolpropane list (methyl) acrylate, single (methyl) acrylic acid pentaerythritol ester, phenoxy group polyglycol (methyl) acrylate etc.
In addition, as simple function (methyl) acrylate monomer, can also use (methyl) acrylate monomer that contains carboxyl.As the simple function that contains carboxyl (methyl) acrylate monomer, can enumerate 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, (methyl) acrylic acid carboxylic ethyl ester, 2-(methyl) acryloxy ethyl succinic acid, N-(methyl) acryloxy-N ', N '-two ethyloics-P-pHENYLENE dI AMINE, 4-(methyl) acryloxy ethyl trimellitic acid etc.
As 2 officials energy (methyl) acrylate monomer, aklylene glycol two (methyl) esters of acrylic acid is arranged typically, polyether polyols two (methyl) esters of acrylic acid, halo aklylene glycol two (methyl) esters of acrylic acid, two (methyl) esters of acrylic acid of aliphatic polyol, two (methyl) esters of acrylic acid of two (methyl) esters of acrylic acid diox glycol Huo diox dialkanol of hydrogenation bicyclopentadiene or tristane dialkanol, two (methyl) esters of acrylic acid of the alkylene oxide addition product of bisphenol-A or Bisphenol F, epoxy radicals two (methyl) esters of acrylic acid of bisphenol-A or Bisphenol F etc., but unqualified to them, can use various 2 officials energy (methyl) acrylate monomers.
If enumerate the example more specifically of 2 officials energy (methyl) acrylate monomer, ethylene glycol bisthioglycolate (methyl) acrylate is then arranged, 1,3-butylene glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite two (methyl) acrylate, two (trihydroxy methyl) propane two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, silicone two (methyl) acrylate, hydroxy new pentane acid ester neopentyl glycol two (methyl) acrylate, 2, two [4-(methyl) the acryloxy ethoxy ethoxy phenyl] propane of 2-, 2, two [4-(methyl) the acryloxy ethoxy ethoxy cyclohexyl] propane of 2-, hydrogenation dicyclopentadienyl two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, 1,3-diox-2,5-two base two (methyl) acrylate [another name: diox glycol two (methyl) acrylate], the acetal compound of hydroxy pivalin aldehyde and trimethylolpropane [chemical name: 2-(2-hydroxyl-1, the 1-dimethyl ethyl)-5-ethyl-5-methylol-1, the 3-diox] two (methyl) acrylate, three (hydroxyethyl) isocyanuric acid ester two (methyl) acrylate etc.
As above multifunctional (methyl) acrylate monomer of 3 officials energy, glycerine three (methyl) acrylate is arranged typically, trimethylolpropane tris (methyl) acrylate, two (trihydroxy methyl) propane three (methyl) acrylate, two (trihydroxy methyl) propane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, poly-(methyl) acrylate of the aliphatic polyol that 3 officials such as dipentaerythritol six (methyl) acrylate energy is above, in addition, can enumerate poly-(methyl) acrylate of the above halogenated polyol of 3 officials energy, three (methyl) acrylate of the alkylene oxide addition product of glycerine, three (methyl) acrylate of the alkylene oxide addition product of trimethylolpropane, 1,1,1-three [(methyl) acryloxy ethoxy ethoxy] propane, three (hydroxyethyl) isocyanuric acid ester three (methyl) esters of acrylic acid etc.
On the other hand, in (methyl) acrylate oligomer, carbamate (methyl) acrylate oligomer, polyester (methyl) acrylate oligomer, epoxy radicals (methyl) acrylate oligomer etc. are arranged.
So-called carbamate (methyl) acrylate oligomer is to have the carbamic acid key (NHCOO-) and the compound of at least 2 (methyl) acryloxies in molecule.Particularly, be in molecule, to have (methyl) acrylate monomer that contains hydroxyl of at least 1 (methyl) acryloxy and at least 1 hydroxyl and the urethane reaction product of polyisocyanate respectively; Polyalcohols and polyisocyanate are reacted and end contain the carbamate compounds of isocyano (isocyanato) base, with the urethane reaction product of (methyl) acrylate monomer that in molecule, has at least 1 (methyl) acryloxy and at least 1 hydroxyl respectively etc.
As (methyl) acrylate monomer that contains hydroxyl that in above-mentioned urethane reaction, uses, can enumerate (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, two (methyl) acrylic acid glyceride, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc.
As supplying with the polyisocyanate that reacts with this urethane that contains (methyl) acrylate monomer of hydroxyl, can enumerate hexamethylene diisocyanate, lysine (リ ジ Application) diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, toluene diisocyanate, Xylene Diisocyanate, diisocyanate (for example, the HTDI that aromatic isocyanate class in these diisocyanate is carried out hydrogenation and obtain, hydrogenated xylene diisocyanate etc.), triphenylmethane triisocyanate, dibenzyl benzene triisocyanate etc. two-or tri-isocyanate, and with above-mentioned diisocyanate multimerization and polyisocyanate etc.
In addition, as in order to be created on the polyalcohols that carbamate compounds that end contains isocyanate base uses by the reaction with polyisocyanate, except the polyvalent alcohol of aromatic series, aliphatics and ester ring type, can also use polyester polyol, polyether glycol etc.Polyvalent alcohol as aliphatics and ester ring type, can enumerate 1,4-butylene glycol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, two (trihydroxy methyl) propane, pentaerythrite, dipentaerythritol, dihydroxymethyl heptane, dihydromethyl propionic acid, dimethylolpropionic acid, glycerine, hydrogenated bisphenol A etc.
Polyester polyol can obtain by the dehydration condensation of above-mentioned polyalcohols and diversity carboxylic acid or its acid anhydrides.As polybasic carboxylic acid or its acid anhydrides, can enumerate succinic acid (acid anhydride), hexane diacid, maleic acid (acid anhydride), itaconic acid (acid anhydride), trimellitic acid (acid anhydride), pyromellitic acid (acid anhydride), phthalic acid (acid anhydride), m-phthalic acid, terephthalic acid (TPA), hexahydrophthalic acid (acid anhydride) etc.
About polyether glycol, except poly alkylene glycol, can also be polyoxy alkylidene modified polyalcohol of getting of the reaction by above-mentioned polyalcohols or dihydroxy benzenes class and alkylene oxide etc.
So-called polyester (methyl) acrylate oligomer is the compound that has ester bond and at least 2 (methyl) acryloxies in molecule.Particularly, can by (methyl) acrylic acid, polybasic carboxylic acid or its acid anhydrides, and the dehydration condensation of polyvalent alcohol obtain.As the polybasic carboxylic acid that in dehydration condensation, uses or its acid anhydrides, can enumerate succinic acid (acid anhydride), hexane diacid, maleic acid (acid anhydride), itaconic acid (acid anhydride), trimellitic acid (acid anhydride), pyromellitic acid (acid anhydride), hexahydrophthalic acid (acid anhydride), phthalic acid (acid anhydride), m-phthalic acid, terephthalic acid (TPA) etc.In addition, as the polyvalent alcohol that in dehydration condensation, uses, can enumerate 1,4-butylene glycol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, two (trihydroxy methyl) propane, pentaerythrite, dipentaerythritol, dihydroxymethyl heptane, dihydromethyl propionic acid, dimethylolpropionic acid, glycerine, hydrogenated bisphenol A etc.
Epoxy radicals (methyl) acrylate oligomer can obtain by polyglycidyl ether and (methyl) acrylic acid addition reaction, has 2 (methyl) acryloxies in molecule at least.As the polyglycidyl ether that in addition reaction, uses, can enumerate ethylene glycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether etc.
In above (methyl) acrylate based compound; have following formula (XI) or (XII) shown in the compound of structure; not only its solidfied material shows high elastic modulus; and when making up with cationically polymerizable compound, especially ester ring type epoxy based compound; can obtain the protective seam with the adaptation excellence of light polarizing film, therefore preferred.
Figure G2009101590503D00211
(in the formula, Q 1And Q 2Represent (methyl) acryloxy or (methyl) acryloxyalkyl independently of each other, here, the carbon number of alkyl is 1～10, Q 3Expression hydrogen or carbon number are 1～10 alkyl.)
In above-mentioned formula (XI) or (XII), work as Q 1Or Q 2During for (methyl) acryloxyalkyl, this alkyl can be that straight chain also can be side chain, can adopt 1～10 carbon number, but general carbon number is just enough about 1～6.In addition, in formula (XII), work as Q 3During for alkyl, can be that straight chain also can be side chain, alkyl typically.For the alkyl of this moment, general carbon number is just enough about 1～6.
Compound shown in the formula (XI), being two (methyl) acrylate derivative of hydrogenation bicyclopentadiene or tristane dialkanol, as its concrete example, is the material of previous example, can enumerate hydrogenation dicyclopentadienyl two (methyl) acrylate [in the formula (XI), Q 1=Q 2The compound of=(methyl) acryloxy], tristane dimethanol two (methyl) acrylate [in the formula (XI), Q 1=Q 2The compound of=(methyl) acryloyl-oxy ylmethyl] etc.
In addition, two (methyl) acrylate derivative of compound Shi diox glycol Huo diox dialkanol shown in the formula (XII), as its concrete example, be the material of previous example, can enumerate 1,3-diox-2,5-two base two (methyl) acrylate [another name: diox glycol two (methyl) acrylate, in formula (XII), Q 1=Q 2=(methyl) acryloxy, Q 3The compound of=H], two (methyl) acrylate of the acetal compound [chemical name: 2-(2-hydroxyl-1,1-dimethyl ethyl)-5-ethyl-5-methylol-1,3-diox] of hydroxy pivalin aldehyde and trimethylolpropane [in formula (XII), Q 1=(methyl) acryloyl-oxy ylmethyl, Q 2=2-(methyl) acryloxy-1,1-dimethyl ethyl, Q 3The compound of=ethyl] etc.
With regard to regard to the solidification compound that uses in the formation of first protective seam; (methyl) acrylic acid series compound is preferably all accounting for below the 70 weight % in the active energy ray-curable compound; more preferably account for 35～70 weight %, further preferably account for 40～60 weight %.When the content of (methyl) acrylic acid series compound surpasses 70 weight %, the trend that the adaptation of existence and light polarizing film reduces.
Contain at this solidification compound under the situation of free-radical polymerised compounds such as aforesaid (methyl) acrylic acid series compound, preferably cooperate the free radical polymerization light trigger.As the free radical polymerization light trigger, if can be by the irradiation of active energy ray, the material of the polymerization of the free-radical polymerised compound of beginning as (methyl) acrylic acid series compound gets final product, and can use known polymerization initiator in the past.If enumerate the concrete example of free radical polymerization light trigger, for example have with acetophenone, 3-methyl acetophenone, benzil dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, the 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl-2-morpholino propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone are the acetophenone series initiators of representative; With benzophenone, 4-chlorobenzophenone, 4,4 '-diaminobenzophenone is the benzophenone series initiators of representative; Be the benzoin ether series initiators of representative with benzoin propyl ether, benzoin ethyl ether; Be the thioxanthones series initiators of representative with the 4-isopropyl thioxanthone; In addition, xanthene ketone, Fluorenone, camphorquinone, benzaldehyde, anthraquinone etc. are arranged.
About the use level of free radical polymerization light trigger, with respect to free-radical polymerised compound 100 weight portions such as (methyl) acrylic acid series compounds, 0.5～20 weight portion normally, preferred 1～6 weight portion.If the use level of free radical polymerization light trigger is very few, then curing becomes insufficient, has the trend of the adaptation reduction of physical strength, protective seam and light polarizing film.In addition, when the use level of free radical polymerization light trigger is too much, has the possibility that the endurance quality of the polaroid of gained reduces.
Solidification compound can also contain photosensitizer as required.By using photosensitizer, the cationic polymerization of active energy ray-curable compound and/or the reactivity of free radical polymerization improve, and the adaptation of physical strength, protective seam and the light polarizing film of protective seam is improved.As photosensitizer, for example can enumerate carbonyls, organosulfur compound, persulfide, redox based compound, azo and diazo-compounds, halogenide, photo-reduction pigment etc.As concrete photosensitizer, for example can enumerate benzoin methylether, benzoin iso-propylether, α, the alpha, alpha-dimethyl oxygen base-α-such benzoin derivatives of phenyl acetophenone; Benzophenone, 2,4-dichloro benzophenone, o-benzoyl yl benzoic acid methyl esters, 4,4 '-two (dimethylamino) benzophenone, 4, the 4 '-such benzophenone derivates of two (lignocaine) benzophenone; 2-clopenthixal ketone, the such thioxanthone derivates of 2-isopropyl thioxanthone; 2-chloroanthraquinone, the such anthraquinone derivative of 2-methylanthraquinone; N-methylacridine ketone, the such acridone derivatives of N-butyl acridone; In addition, α, α-diethoxy acetophenone, benzil, Fluorenone, xanthene ketone, uranyl compound, halogenide etc.These can be used alone, but also also mix together respectively.Preferably with respect to active energy ray-curable compound 100 weight portions, contain photosensitizer with the scope of 0.1～20 weight portion.
In addition, solidification compound can also contain and is useful on the antistatic agent of polaroid being given antistatic performance.Antistatic agent is not particularly limited, can uses known antistatic agent.For example, can use the kation of acyl group (ア シ ロ イ Le) amido propyl dimethyl hydroxyethyl ammonium nitrate, acyl group amido propyl trimethyl ammonium sulfate, cetyl morpholine methyl sulfate and so on is surfactant; The negative ion of straight chained alkyl potassium phosphate, polyxyethylated potassium phosphate, alkane sulfonate and so on is surfactant; N, two (the hydroxyethyl)-N-alkyl amines of N-, its aliphatic ester derivatives, the such nonionic of polyol fat acid moieties ester class are surfactant etc.The match ratio of these antistatic agent suitably determines with the characteristic coupling of expecting, but with respect to active energy ray-curable compound 100 weight portions, normally about 0.1～20 weight portion.
In solidification compound, can also be added on normally used known polymeric additive in the macromolecular material.For example, can enumerate an antioxidant of phenol system, amine system and so on, the secondary antioxidant of sulphur system, hindered amine is light stabilizer (HALS), ultraviolet light absorbers such as benzophenone series, benzotriazole system, benzoic ether system etc.
In addition, can also in solidification compound, add silicon dioxide microparticle.By adding silicon dioxide microparticle, hardness and the physical strength of the protective seam of gained are further improved.
Silicon dioxide microparticle for example can cooperate with solidification compound with the liquid material of disperseing in organic solvent.
Silicon dioxide microparticle can also have hydroxyl, epoxy radicals, (methyl) acryloyl group, vinyl isoreactivity functional group on its surface.In addition, the particle diameter of silicon dioxide microparticle is normally below the 100nm, about preferred 5～50nm.When the particle diameter of particulate surpassed 100nm, existence can't obtain the trend of optically transparent protective seam.
When using the silicon dioxide microparticle that in organic solvent, disperses, this silica concentration is not particularly limited, can use can be as for example silicon dioxide about 20～40 weight % of commercially available product acquisition.
As the silicon dioxide microparticle that in organic solvent, disperses that can obtain with commercially available product, it for example can with an organic solvent be " methyl alcohol silicon dioxide gel " (daily output chemical industry (strain) system of methyl alcohol, silicon dioxide particle diameter 10～15nm, solid constituent 30 weight %), " MA-ST-M " (daily output chemical industry (strain) system, silicon dioxide particle diameter 20～25nm, solid constituent 40 weight %), " OSCAL 1132 " (catalyst changes into industry (strain) system, silicon dioxide particle diameter 10～20nm, solid constituent 30～31 weight %); Organic solvent is ethanol " OSCAL 1232 " (catalyst changes into industry (strain) system, silicon dioxide particle diameter 10～20nm, solid constituent 30～31 weight %); Organic solvent is n-propanol " OSCAL 1332 " (catalyst changes into industry (strain) system, silicon dioxide particle diameter 10～20nm, solid constituent 30～31 weight %); Organic solvent is isopropyl alcohol " IPA-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 30 weight %), " OSCAL 1432 " (catalyst changes into industry (strain) system, silicon dioxide particle diameter 10～20nm, solid constituent 30～31 weight %), organic solvent is normal butyl alcohol " NBA-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 20 weight %), " OSCAL1532 " (catalyst changes into industry (strain) system, silicon dioxide particle diameter 10～20nm, solid constituent 30～31 weight %), organic solvent is ethylene glycol " EG-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 20 weight %); Organic solvent is ethyl cellosolve " OSCAL 1632 " (catalyst changes into industry (strain) system, silicon dioxide particle diameter 10～20nm, solid constituent 30～31 weight %); Organic solvent is glycol monomethyl n-propyl ether " NPC-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 30 weight %); Organic solvent is dimethyl acetamide " DMAC-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 20 weight %), " DMAC-ST-ZL " (daily output chemical industry (strain) system, silicon dioxide particle diameter 70～100nm, solid constituent 20 weight %); Organic solvent is " XBA-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 30 weight %) of the potpourri of dimethylbenzene and normal butyl alcohol; Organic solvent is methyl isobutyl ketone " MIBK-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 30 weight %); Organic solvent is methyl ethyl ketone " MEK-ST " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～15nm, solid constituent 30 weight %), " SP-1120 " (little westernization industry (strain) system, silicon dioxide particle diameter 15～20nm, solid constituent 5～10 weight %), " SP-6120 " (little westernization industry (strain) system, silicon dioxide particle diameter 15～20nm, solid constituent 5～10 weight %) etc., can suitably use a kind of in these or more than 2 kinds.In addition, can use dispersion medium to be " Snotex 20 " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～20nm), " Snotex C " (daily output chemical industry (strain) system, silicon dioxide particle diameter 10～20nm) etc. of water.
Above-mentioned silicon dioxide microparticle, with respect to active energy ray-curable compound 100 weight portions contained in the solidification compound, preferred addition is 5～250 weight portions, more preferably 10～100 weight portions.When the addition of silicon dioxide microparticle is very few, the interpolation of the silicon dioxide microparticle sometimes and hardness of the protective seam that brings improves and is insufficient.On the other hand, when the addition of silicon dioxide microparticle was too much, the adaptation of light polarizing film and protective seam reduced sometimes.In addition, when the addition of silicon dioxide microparticle was too much, the dispersion stabilization of the particulate in the solidification compound reduced sometimes, and the excess stickiness of solidification compound raises sometimes.
And solidification compound can also contain solvent as required.Solvent can suitably be selected according to the dissolubility of the composition that constitutes solidification compound.As the solvent of common use, can enumerate normal hexane, the such fat hydrocarbon of cyclohexane; Such aromatic hydrocarbon based of toluene, dimethylbenzene; Methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the such alcohols of normal butyl alcohol; Acetone, methyl ethyl ketone, methyl isobutyl ketone, the such ketone of cyclohexanone; Methyl acetate, ethyl acetate, the such ester class of butyl acetate; Methyl cellosolve, ethyl cellosolve, the such cellosolve class of butyl cellosolve; Halogenated hydrocarbon that methylene chloride, chloroform are such etc.About the cooperation ratio of solvent, from considering the viewpoints of expecting such as solidification compound viscosity of processabilities such as film forming, suitably select.
In addition, solidification compound can contain levelling agent as required.When solidification compound being coated on light polarizing film, the base material, under the situation of the superficiality difference of the solidfied material of the situation that the wetting state on this light polarizing film, this base material is lacked, solidification compound, can improve by adding levelling agent.As levelling agent, can use all cpds such as silicone-based, fluorine system, polyethers system, acrylic acid copolymer system, titanate system.These levelling agents can be distinguished separately and use, and also can mix more than 2 kinds and use.
About above-mentioned levelling agent, active energy ray-curable compound 100 weight portions with respect to contained in the solidification compound preferably add 0.01～1 weight portion, more preferably 0.1～0.7 weight portion, further preferred 0.2～0.5 weight portion.When the addition of levelling agent is very few, there are wetting state, the inadequate situation of prima facie improvement.And when the addition of levelling agent is too much, have the situation of the adaptation reduction of light polarizing film and protective seam.
The thickness of first protective seam that is formed by the solidification compound that contains the active energy ray-curable compound discussed above, preferred 0.1～10 μ m, more preferably 1～5 μ m.Cross when thin at the thickness of first protective seam, it is insufficient that permanance becomes, and when blocked up, the slim light-weighted effect of polaroid reduces.Use method that solidification compound forms first protective seam as described later.
(2) second protective seams
Second protective seam that is formed by thermoplastic resin film is layered in by adhesive layer on the face of light polarizing film and the opposition side stacked above-mentioned first protective seam side.As second protective seam in the polaroid of the present invention; for example can use by following in the art always as the thermoplastic resin film that the widely used suitable material of material constitutes that forms of protective seam, described material is as being resin, polycarbonate-based resin, polyester based resin etc. for acetate fiber prime system resin, cyclic olefine resin, polyolefin-based resins, acrylic resin, polyimide with being not particularly limited.From the viewpoint of the property produced in batches, tackiness, in above-mentioned, preferably use cellulose acetate resin film or cyclic olefine resin molding as second protective seam.In addition, from easiness that surface-treated layer is set and the viewpoint of optical characteristics, more preferably use the cellulose acetate resin film as second protective seam.
Being adapted at the cyclic olefine resin that uses in second protective seam of the present invention, for example is the thermoplastic resin (being also referred to as thermoplasticity cyclic olefine resin) that has norborene, encircles the such monomeric unit that is made of cyclic olefin (cycloolefin) of norborneol alkene monomer more.The ring-opening polymerization polymer that this cyclic olefine resin can be above-mentioned cycloolefin, used the hydride of the ring-opening polymerization polymer of the cycloolefin more than 2 kinds, also can be cycloolefin and chain alkene, have an addition polymer of the aromatics etc. of vinyl etc.In addition, it also is effective importing polar group.
When the multipolymer that uses cycloolefin and chain alkene, have an aromatics of vinyl constitutes second protective seam; as chain alkene; can enumerate ethene, propylene etc.; and as the aromatics with vinyl, can enumerate styrene, α-Jia Jibenyixi, nuclear alkyl (nuclear ア Le キ Le) substituted phenylethylene etc.In this multipolymer, the monomeric unit that is made of cycloolefin can be 50 moles (preferred 15～50 moles of %) below the %.Especially when the terpolymer that uses cycloolefin, chain alkene and have an aromatics of vinyl constituted second protective seam, the monomeric unit that is made of cycloolefin can be fewer amount as mentioned above.In this terpolymer, the monomeric unit that is made of chain alkene is 5～80 moles of % normally, and the monomeric unit that is made of the aromatics with vinyl is 5～80 moles of % normally.
The cyclic olefine resin, can use suitable commercially available product, preferred " Topas " (Ticona corporate system), " ARTON " (JSR (strain) system), " ZEONOR " (Japanese ZEON (strain) system), " ZEONEX " (Japanese ZEON (strain) system), " APEL " (Mitsui Chemicals (strain) system) (more than be trade name) etc. for example used.When such cyclic olefine resin film processed is obtained film, can suitably use known method such as solvent cast method, extrusion by melting.In addition, can also be with for example " エ ス シ one Na " (ponding chemical industry (strain) system), " SCA40 " (ponding chemical industry (strain) system), " Zeonor Film " ((strain) オ プ テ ス system) etc. through the commercially available product of the cyclic olefine resin film processed of film processed in advance as second protective seam.
As the cyclic olefine resin molding of second protective seam, can also be through uniaxial tension or biaxial stretch-formed and film that obtain.Normally 1.1～5 times of the stretching ratios of this moment, preferably 1.1～3 times.
In addition, being suitable as the cellulose acetate resin film of second protective seam among the present invention, is the film that is made of cellulosic part or all of acid esterification thing, can enumerate for example tri acetyl cellulose membrane, diacetyl cellulose film etc.
As the acetate fiber prime system resin that constitutes this cellulose acetate resin film, can suitably use suitable commercially available product, for example " FUJITAC TD80 " (Fuji Photo-Film corporate system), " FUJITAC TD80UF " (Fuji Photo-Film corporate system), " FUJITACTD80UZ " (Fuji Photo-Film corporate system), " KC8UX2M " (KONICAMINOLTA OPTO (strain) system), " KC8UY " (KONICA MINOLTA OPTO (strain) system) etc. (more than be trade name) resinous film of acetate fiber prime system.
Second protective seam that in polaroid of the present invention, uses, preferably its thickness is little, if but thin excessively, have then that intensity reduces, the trend of poor in processability, and if blocked up, exist the transparency to reduce or trend that the weight of polaroid increases.From this point of view; thickness about second protective seam in the polaroid of the present invention; when being the protective seam that is constituted by the cyclic olefine resin; 5～200 μ m normally, preferred 10～150 μ m, more preferably 20～100 μ m; and when being the protective seam that is constituted by acetate fiber prime system resin; 20～200 μ m normally, preferred 30～150 μ m, more preferably 40～100 μ m.
Second protective seam in the polaroid of the present invention can also be the face to the face opposition side of pasting with light polarizing film, implements surface treatment such as anti-dazzle processing, hard conating processing, antistatic treatment, antireflection processing and the layer that obtains.In addition, can also on the face of the face opposition side of pasting with light polarizing film of second protective seam, form the coating that is constituted by liquid crystal compounds, its high-molecular weight compounds etc.
Light polarizing film and second protective seam (thermoplastic resin film) use tackifier as detailed below to paste.When using tackifier to carry out the stickup of these films; for tackiness is improved, can also be suitably implement surface treatments such as Cement Composite Treated by Plasma, corona treatment, ultraviolet treatment with irradiation, flame treatment, saponification processing to light polarizing film and/or with the gluing of surfaces of second protective seam of its applying.Handle as saponification, can enumerate the method that impregnated in the such aqueous alkali of NaOH, potassium hydroxide.Below, the tackifier that uses in the stickup of light polarizing film and second protective seam is described.
(adhesive layer)
The adhesive layer that polaroid of the present invention possesses is the layer that the tackifier (adhesive compound) that uses when being pasted by light polarizing film and second protective seam or its solidfied material constitute.This adhesive compound of the present invention is not particularly limited, but can enumerates the solidification compound that contains the active energy ray-curable compound, adhesive component is dissolved in the water and the material that obtains or adhesive component is scattered in the water and the water system tackifier that obtains.Wherein, never need the angle of drying process to set out, the preferred solidification compound that contains the active energy ray-curable compound that uses.
About the solidification compound as above-mentioned adhesive compound, can enumerate the composition same with the solidification compound that forms above-mentioned first protective seam.Form the solidification compound of first protective seam and wherein contained active energy ray-curable compound etc., with as the solidification compound of adhesive compound and contained active energy ray-curable compound etc. wherein; can be identical, also can be different.
In addition, as adhesive component being dissolved in the water and material or adhesive component is dispersed in the water and the water system tackifier that obtains, can enumerate and use polyvinyl alcohol resin, urethane resin as the adhesive compound of principal ingredient.
When using polyvinyl alcohol resin as the principal ingredient of water system adhesive compound; about this polyvinyl alcohol resin; except partly-hydrolysed polyvinyl alcohol (PVA), fully saponified polyvinyl alcohol (PVA), what also have carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, amino modified polyvinyl alcohol (PVA) etc. is resin through modified polyethylene alcohol.When using polyvinyl alcohol resin as adhesive component, this tackifier in most cases is that the aqueous solution with polyvinyl alcohol resin prepares.About the concentration of the polyvinyl alcohol resin in the tackifier, with respect to water 100 weight portions, normally about 1～10 weight portion, preferred 1～5 weight portion.
In containing the tackifier of polyvinyl alcohol resin as principal ingredient, improve in order to make tackiness, preferably add glyoxal, curing property composition or crosslinking chemical such as water-soluble epoxy resin.As water-soluble epoxy resin, can enumerate the polyamide epoxy polyamine resin that for example makes the reaction of chloropropylene oxide and following polyamide polyamines and obtain, described polyamide polyamines obtains by the reaction of the such dicarboxylic acid of the such polyalkylene polyamine of diethylene triamine, trien and hexane diacid.Commercially available product as this polyamide epoxy polyamine resin, " the Sumirez Resin 650 " and " Sumirez Resin 675 " that sold by Sumika Chemtex (strain) arranged, by " WS-525 " of Japanese PMC (strain) sale etc., can preferably use these commercially available products.About the addition of these curing property compositions or crosslinking chemical, with respect to polyvinyl alcohol resin 100 weight portions, 1～100 weight portion normally, preferred 1～50 weight portion.At its addition after a little while, tackiness improves effect and reduces, on the other hand, at its addition for a long time, the trend that exists adhesive layer to become fragile.
When using urethane resin as the principal ingredient of water system tackifier, as the example of suitable adhesive compound, can enumerate polyester is ionomer type polyurethane resin and the potpourri with compound of glycidoxypropyl.Here said polyester is ionomer type polyurethane resin, is the urethane resin with polyester backbone, and wherein importing has a spot of ionic composition (hydrophilic component).With regard to this ionomer type polyurethane resin, do not use directly emulsification and form emulsion in water of emulsifying agent, be preferred as the water system tackifier therefore.Polyester is that ionomer type polyurethane resin itself is known.For example open in the flat 7-97504 communique the spy, make phenol resin be dispersed in the example of the macromolecule dispersing agent of aqueous medium as being used for, having put down in writing polyester is ionomer type polyurethane resin, and open in 2005-070140 communique and the Te Kai 2005-181817 communique the spy, disclosed with polyester be ionomer type polyurethane resin and the potpourri of compound with glycidoxypropyl as tackifier, the cyclic olefine resin molding is bonded on the form on the light polarizing film that is constituted by polyvinyl alcohol resin.
The thickness of adhesive layer of the present invention is below the preferred 20 μ m, more preferably below the 10 μ m, further below the preferred 5 μ m.When the thin thickness of adhesive layer, the possibility of infringement polaroid outward appearance is little.
(adhesive phase)
In addition, polaroid of the present invention can have adhesive phase at the face with light polarizing film side opposition side of its first protective seam.This adhesive phase can use with the applying of for example liquid crystal cells the time.Using this adhesive phase; polaroid and liquid crystal cells are fitted when making liquid crystal indicator; be present in the protective seam between light polarizing film and the liquid crystal cells; become that solidfied material by solidification compound constitutes and face in and film thickness direction postpone to be roughly 0 first protective seam, the light leak situation in the time of therefore can preventing black the demonstration effectively.
Formation about adhesive phase, for example can carry out in the following way, namely, in organic solvents such as toluene, ethyl acetate, make the adhesive composition dissolving of the raw polymer that becomes adhesive ingredients etc. or disperse and prepare the solution of 10～40 weight %, it is directly coated first protective seam and form the mode of adhesive phase; Form adhesive phase at diaphragm in advance, it is transferred on first protective seam and form the mode etc. of adhesive phase.The thickness of adhesive phase decides according to its bonding force etc., but the scope of 1～50 μ m normally.
As raw polymer, can enumerate for example acrylic acid series polymeric compounds, silicone-based polymkeric substance, polyester, polyurethane, polyethers etc.Wherein, preferred select to use as with the bonding agent of acrylic acid series polymeric compounds as the acrylic adhesive of raw polymer; it is the optical transparence excellence; the wetting state, the cohesiveness that keep appropriateness; tackiness excellence with first protective seam, liquid crystal cells; and then have against weather, a thermotolerance etc., under the condition of heating, humidification, do not produce the bonding agent that the problem of peeling off such as floats, peels off.
As acrylic acid series raw polymer contained in the acrylic adhesive, the acrylic acid Arrcostab that can enumerate the alkyl of carbon number below 20 such as having methyl, ethyl, butyl contains the acrylic acid series copolymer of the acrylic monomer of functional group with (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate etc.The glass transition temperature of this acrylic acid series copolymer is preferably below 25 ℃, more preferably below 0 ℃.In addition, the weight-average molecular weight of this acrylic acid series copolymer is preferably more than 100,000.
Can also be as required in adhesive phase, cooperate the filling agent that constituted by inorganic powders such as glass fibre, beaded glass, resin bead, metal powder etc., pigment, colorant, antioxidant, ultraviolet light absorber etc.Salicylate based compound, benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex salt based compound etc. are arranged in the ultraviolet light absorber.
The manufacture method of＜polaroid 〉
Polaroid of the present invention can be made via following operation.Following operation (i) and order (ii) are not particularly limited, also can carry out simultaneously.
(i) face of light polarizing film form above-mentioned first protective seam operation and
(ii) by the operation of tackifier at above-mentioned second protective seam of another face applying of light polarizing film.
In above-mentioned operation (i), as the method that forms first protective seam, can enumerate following method.At first, the solidification compound that contains the active energy ray-curable compound at base material coating formation first protective seam carries out drying as required, and the coating layer (coating layer formation operation) of solidification compound is set at this substrate surface.Then, be that binding face is with light polarizing film and coating layer applying (coating layer bonding process) with this applicator surface.Then; to the duplexer that constituted by this light polarizing film/coating layer/base material (when operation is (ii) carried out prior to operation (i); this duplexer also contains adhesive layer and second protective seam); for example from base material side irradiation luminous ray, ultraviolet ray, X ray, electron ray isoreactivity energy line or heat, make the coating layer that is constituted by solidification compound be solidified to form first protective seam (curing process) thus.At last, the base material on first protective seam is removed (base material is removed operation).Here, as base material, for example can enumerate metal tape, glass plate, polyethylene terephthalate film, polycarbonate membrane, tri acetyl cellulose membrane, norborene film, polyester film, polystyrene film etc.Lift-off processing for example can also be implemented in the surface that is coated with solidification compound of base material.
In addition; additive method as above-mentioned operation (i); can also enumerate the solidification compound that contains the active energy ray-curable compound that will form first protective seam directly is coated on the light polarizing film; irradiation active energy ray or heating make the coating layer that is made of solidification compound be solidified to form the method for first protective seam thus.At this moment, can not need base material.
Above-mentioned operation (ii) in, as the method for second protective seam of fitting, can enumerate following method.At first, go up the adhesive coating composition at second protective seam (thermoplastic resin film), carry out drying as required.Then, be that binding face is with light polarizing film and second protective seam applying (film bonding process) with this applicator surface.Then; make by duplexer that this light polarizing film/tackifier/second protective seam constitutes (when operation (i) is (ii) carried out prior to operation; this duplexer also contains first protective seam (or coating layer of solidification compound) and base material) drying; perhaps to this duplexer irradiation luminous ray, ultraviolet ray, X ray, electron ray isoreactivity energy line or heat; adhesive compound is solidified; thereby make light polarizing film and second protective seam bonding, make its drying as required.The solidification compound that contains the active energy ray-curable compound in use is during as adhesive compound, owing to can omit drying process, the therefore raising that can realize making efficient.
In addition; can also enumerate following method; i.e. direct adhesive coating composition on light polarizing film; second protective seam of fitting is afterwards by making its dry or irradiation active energy ray or heating; adhesive compound is solidified; thereby make light polarizing film and second protective seam gluing, make its dry method as required.
First protective seam and second protective seam are formed simultaneously.For example; as tackifier; use to solidify property adhesive compound (contain the active energy ray-curable compound solidification compound, contain the water system tackifier of curing property composition or crosslinking chemical etc.); after making the duplexer that is constituted by second protective seam/tackifier/light polarizing film/coating layer/base material; by to this duplexer for example from base material side irradiation active energy ray or heat; tackifier and coating layer are solidified simultaneously, can obtain polaroid.According to this method, curing process is once finished, therefore the further raising that can realize making efficient.
In the present invention; the solidification compound that contains the active energy ray-curable compound that forms first protective seam and the coating method of adhesive compound are not particularly limited, for example can utilize various application pattern such as scraper, line rod, mould coating machine, comma coating machine, photogravure coating machine.In addition; in method as described below; material as roller can be used metal, rubber etc.; described method is after dripping the above-mentioned solidification compound or adhesive compound that contains the active energy ray-curable compound between light polarizing film and second protective seam or the base material, the method for spreading out equably with pressurization such as roller.In addition; in method as described below; those rollers can be identical materials; it also can be different materials; described method be make between light polarizing film and second protective seam or base material drip the above-mentioned solidification compound that contains the active energy ray-curable compound or adhesive compound and structure; between roller and roller, pressurization and the method for spreading out.
When the irradiation by active energy ray forms the curing of the solidification compound that contains the active energy ray-curable compound of first protective seam and/or adhesive compound; the light source that utilizes is not particularly limited, but can uses for example low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, the ultrahigh pressure mercury lamp, chemical with lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp etc. that below wavelength 400nm, has luminous distribution.
Intensity is penetrated in illumination to solidification compound, adhesive compound, can be according to each composition and different, and preferably the exposure intensity to the effective wavelength region may of activation of free radical polymerization light trigger and/or cationic polymerization light trigger is 10～2500mW/cm 2Undercapacity 10mW/cm is being penetrated in the illumination of solidification compound 2The time, the reaction time is long, is surpassing 2500mW/cm 2The time, because the heat release during from the polymerization of the heat of lamp radiation and solidification compound, adhesive compound exists to produce solidification compound, the xanthochromia of adhesive compound, the possibility of light polarizing film variation.The time is penetrated in illumination to solidification compound, adhesive compound, controls according to each composition, still is not particularly limited, and preferably setting into the represented accumulative total light quantity of the product of exposure intensity and irradiation time is 10～2500mJ/cm 2At the accumulative total deficiency in light quantity 10mJ/cm to solidification compound, adhesive compound 2The time, insufficient from the generation of the spike of polymerization initiator, there are the protective seam of gained, the inadequate possibility of curing of adhesive layer.And surpass 2500mJ/cm in the accumulative total light quantity 2The time, it is very long that irradiation time becomes, and improves in throughput rate to become unfavorable.In addition, the irradiation of active energy ray is preferably carried out in the scope that various performances such as the degree of polarization of light polarizing film, transmissivity do not reduce.
＜liquid crystal indicator 〉
Liquid crystal indicator of the present invention, the polaroid that possesses the invention described above, more specifically, be to possess liquid crystal cells and be the liquid crystal indicator of the polaroid of the invention described above at a pair of polaroid of the two-sided configuration of this liquid crystal cells and any one party or both sides' polaroid.Here, in liquid crystal indicator of the present invention, polaroid of the present invention, the mode that is liquid crystal cell side with its first protective seam is fitted on the liquid crystal cells.That is, when first protective seam arranges above-mentioned adhesive phase, be fitted on the liquid crystal cells by this adhesive phase.Liquid crystal indicator of the present invention with this structure, the light leak when not only preventing black the demonstration effectively, and realized slim lightweight.
The liquid crystal cells that uses in liquid crystal indicator of the present invention can be any pattern, when using the liquid crystal cells of the IPS pattern of moving with in-plane-switching mode, especially can access significant light leak of deceiving when showing and prevent effect.
Embodiment
Below, enumerate the present invention of embodiment and carry out more specific description, but the invention is not restricted to these examples.In the example, " part " and " % " of expression use amount or content if do not specify, is weight basis.
(Production Example 1: the making of light polarizing film)
99.9 moles of average degree of polymerization is about 2400, saponification degrees are more than the % and after the polyvinyl alcohol film of thickness 75 μ m impregnated in 30 ℃ pure water, flood in the weight ratio of iodine/potassium iodide/water is 0.02/2/100 aqueous solution under 30 ℃.Afterwards, in being 12/5/100 aqueous solution, the weight ratio of potassium iodide/boric acid/water floods under 56.5 ℃.Then, after the washing of 8 ℃ pure water, under 65 ℃, carry out drying, obtain being adsorbed with the light polarizing film that iodine and iodine are oriented at polyvinyl alcohol (PVA).Stretch and mainly carry out in the operation of iodine staining and boric acid processing, total stretching ratio is 5.3 times.
(Production Example 2: the preparation of solidification compound I)
At first, mix following each composition, obtain solidification compound I.
3,4-epoxy radicals cyclohexyl methyl-3,35 parts of 4-epoxy-cyclohexane carboxylates (Daicel chemistry (strain) system, Ceroxide 2021P)
15 parts in two (3-ethyl-3-oxetanes ylmethyl) ether (East Asia synthetic (strain) system, ARONOXETANE OXT-221)
The diacrylate of the acetal compound of hydroxy pivalin aldehyde and trimethylolpropane (Xin Zhong village chemical industry (strain) system, A-DOG) 50 parts
2.5 parts of 2-hydroxy-2-methyls-1-phenyl-propane-1-ketone (Ciba corporate system, DAROCURE1173, free radical polymerization light trigger)
2.5 parts of the two hexafluorophosphoric acid ester cation polymerization light initiating agents (DAICEL-CYTEC (strain) UVACURE 1590 processed) of 4,4 '-two [diphenyl sulfonium] diphenyl sulfide
Silicone-based levelling agent ((strain) Dow Corning Toray system, SH710) 0.2 part
In addition, above-mentioned A-DOG (diacrylate of the acetal compound of hydroxy pivalin aldehyde and trimethylolpropane) is the compound with following formula structure.
(Production Example 3: the preparation of solidification compound II)
Mix following each composition, obtain solidification compound II.
3,4-epoxy radicals cyclohexyl methyl-3,75 parts of 4-epoxy-cyclohexane carboxylates (Daicel chemistry (strain) system, Ceroxide 2021P)
25 parts in two (3-ethyl-3-oxetanes ylmethyl) ether (East Asia synthetic (strain) system, ARONOXETANE OXT-221)
5 parts of the two hexafluorophosphoric acid ester cation polymerization light initiating agents (DAICEL-CYTEC (strain) UVACURE 1590 processed) of 4,4 '-two [diphenyl sulfonium] diphenyl sulfide
Silicone-based levelling agent ((strain) Dow Corning Toray system, SH710) 0.2 part
(Production Example 4: the preparation of polyethenol series tackifier)
Mix following each composition, obtain the polyethenol series tackifier.
100 parts of pure water
Carboxy-modified polyvinyl alcohol (PVA) (" the Kuraray Poval KL 318 " of (strain) Kuraray system)
1.8 part
Water soluble polyamide epoxy resin (" the Sumirez Resin650 " of Sumika Chemtex (strain) system) (aqueous solution of solid component concentration 30%) 0.9 part
(Production Example 5: the making of polaroid A)
On the face of the light polarizing film of in Production Example 1, making; the polyethenol series tackifier that obtains in the coating Production Example 4; fit and to have implemented the protective seam (KONICA MINOLTA OPTO (strain) system, KC8UY, thickness 80 μ m) that triacetyl cellulose that saponification handles constitutes.It was descended dry 6 minutes at 60 ℃, be produced on the polaroid A that single face has protective seam.
＜embodiment 1 〉
Use coating machine (first physics and chemistry (strain) system, BAR COATER), on the single face of polyethylene terephthalate (PET) film ((strain) system, ESTER FILM E5100 spin in Japan), be coated in the solidification compound I that obtains in the Production Example 2.In addition, the single face of not implementing the protective seam (KONICA MINOLTA OPTO (strain) system, KC8UY, thickness 80 μ m) that tri acetyl cellulose membrane that saponification handles constitutes is implemented Corona discharge Treatment, coating curing composition I I similarly on this face.At this moment, the thickness of the coating layer when having applied solidification compound changes according to viscosity, therefore, by changing the excellent model (kind Line designation) that rod is coated with machine, thickness is regulated.Then; use adhering device (FUJIPLA (strain) system; LPA3301); become mode with the binding face of light polarizing film with separately coating layer side; the PET film that will have the coating layer of above-mentioned solidification compound I is fitted on the face of the light polarizing film of making in the Production Example 1, and the protective seam that will have the coating layer of above-mentioned solidification compound II is fitted on another face.
Utilize the D VALVE of Fusion UV Systems corporate system, from PET film side with accumulative total light quantity 1500mJ/cm 2, to this product irradiation ultraviolet radiation of fitting, the solidification compound I that makes in the two-sided configuration of light polarizing film and the coating layer curing of II.Then, peel off the PET film, be produced on the polaroid that the first transparent protective seam (solidfied material of solidification compound I) and another face are provided with transparent second protective seam (tri acetyl cellulose membrane) is set on the face of light polarizing film.In addition, ((strain) Nikon system, when ZC-101) measuring the thickness of this polaroid, the result is 116 μ m using the determining film thickness device.In addition, the thickness of first protective seam is 4 μ m.
＜embodiment 2 〉
Use coating machine (first physics and chemistry (strain) system, BAR COATER), on the single face of polyethylene terephthalate (PET) film ((strain) system, ESTER FILM E5100 spin in Japan), be coated in the solidification compound I that obtains in the Production Example 2.At this moment, the thickness of the coating layer when the coating curing composition changes according to viscosity, therefore, is coated with the excellent model of machine and thickness is regulated by changing rod.Then; use adhering device (FUJIPLA (strain) system; LPA3301) become mode with the binding face of light polarizing film with the coating layer side, will have the PET film of the coating layer of above-mentioned solidification compound I, fit on the opposition side of the face that is fitted with protective seam of the polaroid A of in Production Example 5, making.
Utilize the D VALVE of Fusion UV Systems corporate system, from PET film side with accumulative total light quantity 1500mJ/cm 2, to this product irradiation ultraviolet radiation of fitting, the coating layer of the solidification compound I that disposes in light polarizing film is solidified.Then, peel off the PET film, make polaroid.In addition, the thickness of this polaroid is 114 μ m.In addition, the thickness of first protective seam (solidfied material of solidification compound I) is 4 μ m.
＜comparative example 1 〉
The polaroid A that use is made in Production Example 5.The thickness of polaroid A is 110 μ m.
＜comparative example 2 〉
The light polarizing film of making is two-sided in Production Example 1; be coated on the polyethenol series tackifier that obtains in the Production Example 4; fit at face and to have implemented protective seam (KONICA MINOLTA OPTO (strain) system that triacetyl cellulose that saponification handles constitutes; KC8UY; thickness 80 μ m), another face fit constituted by triacetyl cellulose and face in delay R eDelay R with film thickness direction ThBe roughly 0 protective seam (KONICA MINOLTA OPTO (strain) system, KC4UEW, thickness 40 μ m).It was descended dry 6 minutes at 60 ℃, make polaroid.The thickness of this polaroid is 150 μ m.
＜evaluation test 〉
(1) bonding long duration test
Utilize following method, after the polaroid of above-described embodiment 1～2 and comparative example 1～2 arranges adhesive phase, according to following test method, estimate the permanance of polaroid.
[formation of adhesive phase]
The binder solution that will contain butyl acrylate and acrylic acid multipolymer, urethane acrylate oligomer, isocyanate-based crosslinking chemical and organic solvent; be coated on first protective seam of polaroid of embodiment 1 and 2, on the light polarizing film of the polaroid of comparative example 1 and on the protective seam (KC4UEW) that is constituted by triacetyl cellulose of the polaroid of comparative example 2; by making its drying, form adhesive phase at separately polaroid.
[test method]
With the above-mentioned polaroid that has an adhesive phase by its adhesive phase be fitted on glass after, carry out 300 hours heat resistant test of keeping under the drying condition of 80 ℃ of temperature, the polaroid after the visualization test.Show the result in table 1.Metewand is as follows.
Zero: almost can't see float, peel off, appearance change such as foaming.
△: float, peel off, appearance change such as foaming is obvious slightly.
*: obviously think have float, peel off, appearance change such as foaming.
(2) mensuration of the delay of protective seam
Measure the interior delay R of face of the protective seam (KC4UEW) that is constituted by triacetyl cellulose of the polaroid of first protective seam (solidfied material of solidification compound I) that uses in the polaroid of embodiment 1 and 2 and comparative example 2 in order to following method eDelay R with film thickness direction ThThe results are shown in table 1.In addition, the measurement result of the delay of first protective seam that uses in the polaroid about embodiment 1 and 2, be with above-mentioned the same the PET film form the solidfied material of solidification compound I and the PET film peeled off and the result of solidfied material film (thickness 4 μ m).
[the delay R in the face e]
Use the mensuration machine " KOBRA-21ADH " of prince's instrumentation machine (strain) system, with the monochromatic light utilization rotation analyzer method of wavelength 559nm, the delay R in the mensuration face e
[the delay R of film thickness direction Th]
Use " KOBRA-21ADH " same as described above, measure the delay R of film thickness direction with the monochromatic light of wavelength 559nm ThThis mensuration order of measuring machine is as follows.Utilize the delay R in the face e, the delay R that as sloping shaft its 40 degree that tilt measured with slow axis 40, the thickness d of film and the mean refractive index n of film 0, utilize numerical evaluation to obtain n by following formula (3)～(5) x, n yAnd n z, in the above-mentioned formula of their substitutions (2), calculate the delay R of film thickness direction Th
R e＝(n x-n y)×d (3)
R 40＝(n x-n y’)×d/cos(φ) (4)
(n x+n y+n z)/3＝n 0 (5)
Here,
φ＝sin -1〔sin(40°)/n 0〕
n y’＝n y×n 0/〔n y 2×sin 2(φ)+n z 2×cos 2(φ)〕 1/2
Table 1
Figure G2009101590503D00391
Should think this disclosed embodiment and embodiment, be illustration in all respects, is not limited to this.Scope of the present invention is not above-mentioned explanation, but is illustrated by the scope of protection of present invention, comprises the meaning that is equal to the scope of protection of present invention and all changes in scope.

Claims (13)

1. polaroid is characterized in that possessing:
Be adsorbed with the light polarizing film that dichromatism pigment and described dichromatism pigment are oriented at the polyvinyl alcohol resin film,
First protective seam that is layered on the face of described light polarizing film and is constituted by the solidfied material of hardening resin composition; wherein said hardening resin composition contain the epoxy based compound that in molecule, has an epoxy radicals at least and have following formula (XI) or (XII) shown in (methyl) acrylic acid series compound of structure as the active energy ray-curable compound, and
Second protective seam that is layered in by adhesive layer on another face of described light polarizing film and is formed by thermoplastic resin film,
Figure FSB00001062858400011
In the formula, Q 1And Q 2Represent (methyl) acryloxy or (methyl) acryloxyalkyl independently of each other, here, the carbon number of alkyl is 1～10, Q 3Expression hydrogen or carbon number are 1～10 alkyl.
2. polaroid according to claim 1 is characterized in that,
Described epoxy based compound has an epoxy radicals that is bonded on the ester ring type ring at least.
3. polaroid according to claim 1 and 2 is characterized in that,
Described solidification compound also contains the oxetanes based compound as described active energy ray-curable compound.
4. polaroid according to claim 1 and 2 is characterized in that,
The thickness of described first protective seam is 0.1～10 μ m.
5. polaroid according to claim 1 and 2 is characterized in that,
Described second protective seam is formed by the cellulose acetate resin film.
6. polaroid according to claim 1 and 2 is characterized in that,
Described adhesive layer is made of the solidfied material of the solidification compound that contains the active energy ray-curable compound.
7. polaroid according to claim 1 and 2 is characterized in that,
On described first protective seam and face described light polarizing film side opposition side, further be laminated with adhesive phase.
8. polaroid according to claim 1 and 2 is characterized in that,
In the liquid crystal indicator with the in-plane-switching mode action, use.
9. a liquid crystal indicator is characterized in that,
Possess liquid crystal cells and at a pair of polaroid of the two-sided configuration of described liquid crystal cells,
At least one side in the described a pair of polaroid is the described polaroid of claim 7, is fitted on the described liquid crystal cells by its adhesive phase.
10. a liquid crystal indicator is characterized in that,
Possess liquid crystal cells and at a pair of polaroid of the two-sided configuration of described liquid crystal cells,
Described a pair of polaroid all is the described polaroids of claim 7, is fitted on the described liquid crystal cells by its adhesive phase.
11. according to claim 9 or 10 described liquid crystal indicators, it is characterized in that,
Described liquid crystal cells has two plate bases and is clamped between the described substrate and at the liquid crystal layer that is not applying under the state of voltage with described substrate almost parallel ground orientation, and moves with in-plane-switching mode.
12. the manufacture method of a polaroid is characterized in that,
Described polaroid possesses: be adsorbed with the light polarizing film that dichromatism pigment and described dichromatism pigment are oriented at the polyvinyl alcohol resin film; First protective seam that is layered on the face of described light polarizing film and is constituted by the solidfied material of hardening resin composition, wherein said hardening resin composition contain the epoxy based compound that in molecule, has an epoxy radicals at least and have following formula (XI) or (XII) shown in (methyl) acrylic acid series compound of structure as the active energy ray-curable compound; And second protective seam that is layered in by adhesive layer on another face of described light polarizing film and is formed by thermoplastic resin film;
Figure FSB00001062858400021
In the formula, Q 1And Q 2Represent (methyl) acryloxy or (methyl) acryloxyalkyl independently of each other, here, the carbon number of alkyl is 1～10, Q 3Expression hydrogen or carbon number are 1～10 alkyl;
Described manufacture method comprises:
The coating layer that the coating layer of described solidification compound is set on the surface of base material form operation,
Make the coating layer of the solidification compound that is arranged at described substrate surface be fitted in coating layer bonding process on the face of described light polarizing film,
By tackifier another face of described light polarizing film fit described second protective seam the film bonding process,
Make described coating layer and described adhesive solidification curing process and
The base material that described base material is removed is removed operation.
13. the manufacture method of polaroid according to claim 12 is characterized in that,
In described curing process, the curing of described coating layer and described tackifier is by carrying out simultaneously from described base material side irradiation active energy ray.
CN2009101590503A 2008-08-06 2009-08-04 Polaroid sheet, manufacturing method thereof and liquid crystal display device Active CN101644792B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2008203419 2008-08-06
JP2008203419A JP5267920B2 (en) 2008-08-06 2008-08-06 Polarizing plate, method for manufacturing the same, and liquid crystal display device
JP2008-203419 2008-08-06

Publications (2)

Publication Number Publication Date
CN101644792A CN101644792A (en) 2010-02-10
CN101644792B true CN101644792B (en) 2013-08-07

Family

ID=41656753

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009101590503A Active CN101644792B (en) 2008-08-06 2009-08-04 Polaroid sheet, manufacturing method thereof and liquid crystal display device

Country Status (4)

Country Link
JP (1) JP5267920B2 (en)
KR (1) KR101722778B1 (en)
CN (1) CN101644792B (en)
TW (1) TWI483008B (en)

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5364943B2 (en) * 2009-03-26 2013-12-11 日東電工株式会社 Retardation film, method for producing the same, and image display device
CN102193131B (en) * 2010-03-10 2015-01-14 大赛璐-湛新株式会社 Polaroid and preparation method thereof
JP5450778B2 (en) 2012-06-08 2014-03-26 シャープ株式会社 Edge light type surface light source device and illumination device
US9244213B2 (en) 2012-07-04 2016-01-26 Sharp Kabushiki Kaisha Edge-light type planar light source device
TWI475321B (en) * 2013-03-06 2015-03-01 Chi Mei Corp Photosensitive resin composition and uses thereof
TWI628218B (en) * 2013-09-18 2018-07-01 東友精細化工有限公司 Colored curable resin composition
JP6477499B2 (en) * 2013-12-27 2019-03-06 日本ゼオン株式会社 Multilayer film, polarizing plate, and method for producing multilayer film
KR20150093591A (en) * 2014-02-07 2015-08-18 스미또모 가가꾸 가부시키가이샤 Process for producing long polarizing film
JP6249820B2 (en) * 2014-02-27 2017-12-20 住友化学株式会社 Manufacturing method of polarizing plate and polarizing plate
CN106415341B (en) * 2014-05-30 2020-03-17 住友化学株式会社 Adhesive-attached polarizing plate and liquid crystal display device
JP6603446B2 (en) 2014-06-18 2019-11-06 サムスン エスディアイ カンパニー，リミテッド Polarizing plate and display device using the same
JP6653990B2 (en) * 2014-10-27 2020-02-26 三星エスディアイ株式会社ＳＡＭＳＵＮＧ ＳＤＩ Ｃｏ．， ＬＴＤ． Polarizing plate and image display device having the same
KR102314512B1 (en) * 2014-11-10 2021-10-19 에스케이이노베이션 주식회사 Composition for making hard coating layer
KR102315118B1 (en) * 2014-11-13 2021-10-20 에스케이이노베이션 주식회사 Composition for making hard coating layer
JP6707807B2 (en) * 2014-12-24 2020-06-10 住友化学株式会社 Polarizing plate and liquid crystal display device
KR101780540B1 (en) 2015-02-16 2017-09-22 삼성에스디아이 주식회사 Polarizing plate and optical display apparatus comprising the same
JP6608150B2 (en) * 2015-03-03 2019-11-20 三星エスディアイ株式会社 Polarizing plate and image display device including the same
CN105137521B (en) * 2015-09-25 2018-07-06 武汉华星光电技术有限公司 A kind of polaroid and its building method
JP6388570B2 (en) 2015-09-29 2018-09-12 富士フイルム株式会社 Laminated film and method for producing the same, polarizing plate, liquid crystal panel, and liquid crystal display device
JP2016206684A (en) * 2016-08-16 2016-12-08 住友化学株式会社 Polarizer and optical member
JP2018072533A (en) * 2016-10-28 2018-05-10 住友化学株式会社 Polarizing plate set and liquid crystal panel
KR20180096051A (en) 2017-02-20 2018-08-29 동우 화인켐 주식회사 Polarizing plate and image display device
KR102008187B1 (en) * 2017-02-24 2019-08-07 삼성에스디아이 주식회사 Composition for barrier layer, polarizing plate comprising the same and optical display apparatus comprising the same
JP2018180407A (en) * 2017-04-19 2018-11-15 住友化学株式会社 Polarizing plate and liquid crystal panel
JP2018200413A (en) * 2017-05-29 2018-12-20 住友化学株式会社 Set of polarizing plates and liquid crystal panel
KR102092471B1 (en) * 2017-09-22 2020-03-23 주식회사 엘지화학 Polarizing plate and image display apparatus comprising the same
KR102244789B1 (en) * 2017-12-15 2021-04-26 주식회사 엘지화학 Polarzing plate, polarizing plate-carrier film laminate, the method for manufacturing the polarizing plate and the active energy beam-cured composition for protective layer of polarizer
KR102244791B1 (en) * 2017-12-15 2021-04-26 주식회사 엘지화학 Polarzing plate, polarizing plate-carrier film laminate, the method for manufacturing the polarizing plate and the active energy beam-cured composition for protective layer of polarizer
CN111373018B (en) * 2017-12-22 2023-08-08 株式会社Lg化学 Liquid crystal composition and use thereof
CN111565928B (en) 2018-01-02 2022-03-29 东友精细化工有限公司 Polarizing plate and image display device comprising same
WO2019225949A1 (en) * 2018-05-21 2019-11-28 주식회사 엘지화학 Polarizing plate, image display apparatus comprising same, and adhesive composition for polarizing plate
KR20200002427A (en) * 2018-06-29 2020-01-08 주식회사 엘지화학 Polarizing plate, liquid crystal panel, and display apparatus
CN111712742B (en) * 2018-06-29 2022-06-28 株式会社Lg化学 Polarizing plate, liquid crystal panel and display device
JP7185460B2 (en) * 2018-09-21 2022-12-07 住友化学株式会社 Polarizing film, polarizing plate containing the same, and display device
JP7082021B2 (en) * 2018-09-28 2022-06-07 住友化学株式会社 Polarizing film and its manufacturing method
TWI727371B (en) * 2019-07-16 2021-05-11 住華科技股份有限公司 Polarizer structure and manufacturing method thereof
CN114502995A (en) * 2019-09-30 2022-05-13 日东电工株式会社 Polarizing plate with phase difference layer and image display device using same
KR20230019666A (en) 2021-08-02 2023-02-09 동우 화인켐 주식회사 Polarizing plate and image display device including the same
KR20230019665A (en) 2021-08-02 2023-02-09 동우 화인켐 주식회사 Polarizing plate and image display device including the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1521523A (en) * 2003-02-12 2004-08-18 ס�ѻ�ѧ��ҵ��ʽ���� Polarizer and its manufacturing method ,optical element and liquid crystal display device

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4310957B2 (en) * 2001-12-21 2009-08-12 ソニーケミカル＆インフォメーションデバイス株式会社 Polarizer
JP2005092112A (en) * 2003-09-19 2005-04-07 Kuraray Co Ltd Polarizing plate and its manufacturing method
JP3938142B2 (en) * 2004-02-03 2007-06-27 住友化学株式会社 Liquid crystal display
JP2006163082A (en) * 2004-12-08 2006-06-22 Nippon Paper Chemicals Co Ltd Optical member, manufacturing method thereof and liquid crystal display device
JP2006178176A (en) * 2004-12-22 2006-07-06 Fuji Photo Film Co Ltd Polarizing plate and liquid crystal display device using the same
JP4785458B2 (en) * 2005-08-10 2011-10-05 株式会社巴川製紙所 Protective film for polarizing plate
JP2007316603A (en) * 2006-04-28 2007-12-06 Sumitomo Chemical Co Ltd Composite polarizing plate and liquid crystal display device using the same
JP4740184B2 (en) * 2006-05-16 2011-08-03 日東電工株式会社 Polarizing plate and image display device using the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1521523A (en) * 2003-02-12 2004-08-18 ס�ѻ�ѧ��ҵ��ʽ���� Polarizer and its manufacturing method ,optical element and liquid crystal display device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JP特开2006-163082A 2006.06.22
JP特开2007-47498A 2007.02.22

Also Published As

Publication number Publication date
KR20100018462A (en) 2010-02-17
TWI483008B (en) 2015-05-01
CN101644792A (en) 2010-02-10
JP5267920B2 (en) 2013-08-21
JP2010039299A (en) 2010-02-18
KR101722778B1 (en) 2017-04-05
TW201013240A (en) 2010-04-01

Similar Documents

Publication Publication Date Title
CN101644792B (en) Polaroid sheet, manufacturing method thereof and liquid crystal display device
CN101932960B (en) Polarizing plate, optical member, and liquid crystal display device
CN101672946B (en) Polarizer and manufacturing method thereof
JP6107991B2 (en) Manufacturing method of polarizing plate
TWI504711B (en) Photo-curable adhesive composition, polarizing adhesive and its manufacturing method, optical member and liquid crystal display device
JP2013160775A (en) Polarizer and optical member
JP5586174B2 (en) Optical laminate and method for producing the same
CN101813798B (en) Compound polarization plate and an IPS mode Liquid crystal display device
TWI570454B (en) Composite phase difference plate and composite polarizing plate using the same
JP2004245925A (en) Polarizing plate, its manufacturing method, optical member, and liquid crystal display device
KR20160078263A (en) Polarizing plate and liquid crystal display device
JP6119109B2 (en) Polarizing plate and liquid crystal display device
JP2009216874A (en) Polarizing plate and liquid crystal display
KR101875256B1 (en) Polarizing plate, high brightness polarizing plate, and ips mode liquid crystal display device
JP6707807B2 (en) Polarizing plate and liquid crystal display device
JP2016206684A (en) Polarizer and optical member
JP2010102311A (en) Composite polarizing plate and liquid crystal display device using the same
JP2012078621A (en) Optical laminate and method for producing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant