CN105143937A - Polarizing plate, method for producing same and liquid crystal display device - Google Patents

Polarizing plate, method for producing same and liquid crystal display device Download PDF

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Publication number
CN105143937A
CN105143937A CN201480022942.8A CN201480022942A CN105143937A CN 105143937 A CN105143937 A CN 105143937A CN 201480022942 A CN201480022942 A CN 201480022942A CN 105143937 A CN105143937 A CN 105143937A
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film
scope
formula
polarizer
polaroid
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铃木真一郎
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Konica Minolta Inc
Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The objective of the present invention is to provide a polarizing plate which uses an acrylic film and a cellulose ester film as protective films of a polarizer, and which is free from deterioration in adhesion to the polarizer such as waving and separation of a film and display unevenness of a liquid crystal panel even if temperature/humidity conditions in the environment of usage have changed in cases where the polarizing plate is provided in a liquid crystal display device. A polarizing plate of the present invention, in which a polarizer is sandwiched between a film A and a film B, respectively with an active ray-curable adhesive layer interposed therebetween, is characterized in that: the film A is an acrylic film that contains an acrylic resin, has a film thickness within the range of 20-60 [mu]m, and has a dimensional change characteristic within a specific range; and the film B is an cellulose acetate film which has a film thickness within the range of 20-60 [mu]m, contains a cellulose acetate having an average acetyl group substitution degree within the range of 2.0-2.5, and has a dimensional change characteristic within the above-described specific range.

Description

Polaroid, its manufacture method and liquid crystal indicator
Technical field
The present invention relates to polaroid, its manufacture method and liquid crystal indicator.More specifically; relate to a kind of acrylic film and cellulose acetate membrane of using as the polaroid of the diaphragm of the polarizer; and its manufacture method and possess the liquid crystal indicator of this polaroid; when possessing this polaroid in liquid crystal indicator, even if the display inequality of liquid crystal panel, the deterioration of polarizer adaptation are also can't see in the temperature humidity environmental change of environment for use.
Background technology
In recent years, require liquid crystal indicator maximize, lightening, the maximization of the polaroid possessed in liquid crystal indicator, lightening requirement are also improved.Specifically, for forming the polarizer of polaroid, the polaroid protective film expectation filming as diaphragm.But; if from the viewpoint of making the thinning and thinning cellulose ester membrane conventional as diaphragm of polaroid (such as; cellulose triacetate (TAC) film etc.); then there is the problem of film strength, planarity reduction and so on; particularly the film of less than 50 μm causes the reduction of film physical property, therefore becomes the obstacle of the filming realizing polaroid.
In order to improve the intensity of the polaroid with thin protective film as above, attempt increasing the protection film strength of polaroid, improving the cementability etc. of the polarizer and diaphragm.Such as, for the object of protection film strength increasing polaroid, propose and be used as the transparency, excellent in dimensional stability and the acrylic film (for example, referring to patent documentation 1) of the acryl resin of the resin of agent of low hygroscopicity.But such acrylic film has the character not easily presenting phase differential, be thus not suitable for VA mode LCD etc. to expand the phase retardation film for the purpose of field angle etc.
Therefore, such as the film of liquid crystal cell side being configured at above-mentioned VA mode LCD, consider from viewpoints such as easiness, throughput rate (operability, doing over again property etc.) and costs that phase differential presents, the existing phase retardation film containing cellulose ester resin of preferred use, as the formation of polaroid, preferred employing is followed successively by the such mode of the phase retardation film (the present invention, also referred to as cellulose ester membrane or cellulose acetate membrane) of acrylic film/polarizer/containing cellulose ester resin from visible side.
On the other hand, as the method for cementability improving the polarizer and diaphragm, such as, the method (for example, referring to patent documentation 2) of the polarizer and cellulose ester membrane being fitted via dynamic rays curing type bonding agent is disclosed.According to the method, even if can obtain waiting decolouring that the polarizer (polarizing coating) also not easily occurs under harsh environmental conditions and the polaroid high with the relevant permanance such as bonding hot and humid.
But, studying in great detail according to the present inventor, recognize if the liquid crystal indicator of the film polarizer of the formation possessed as the aforesaid propylene sorrel/polarizer/cellulose ester membrane to be shifted to from hot and humid environment under low temperature and low humidity environment and to observe display frame, then produce the distinctive display inequality of liquid crystal panel.And; the phenomenon of the expanded range of this display inequality when finding to use above-mentioned dynamic rays curing type bonding agent to carry out bonding; infer this is because when the temperature humidity environment of particularly environment for use sharply changes the change in size speed of above-mentioned 2 diaphragms different, thus produce optics inequality due to clamping 2 films of the polarizer and the strain of bonding agent part.
In addition, because this strain causes the adaptation between the polarizer and diaphragm to reduce, under environment harsh than ever during temperature humidity environmental change, the undulation, the film that also there is easily generation diaphragm peel off such problem.
Prior art document
Patent documentation
Patent documentation 1: JP 2012-237818 publication
Patent documentation 2: JP 2010-230806 publication
Summary of the invention
The present invention's situation and carrying out in view of the above problems; it solves problem and is to provide the polarizer to fit via dynamic rays curing type bond layer and diaphragm and uses acrylic film and cellulose acetate membrane as the polaroid of this diaphragm; when possessing this polaroid in liquid crystal indicator, even if the deterioration of the display inequality of liquid crystal panel and the polarizer adaptation such as undulation, film stripping of diaphragm is also can't see in the temperature humidity environmental change of environment for use.In addition, the liquid crystal indicator of the manufacture method that this polaroid is provided and the visuality excellence that possesses this polaroid.
The present inventor is in order to solve above-mentioned problem, in the process that the reason etc. of the problems referred to above is studied, even if find that the display inequality of liquid crystal panel is also can't see in the temperature humidity environmental change utilizing the polaroid with following feature can obtain environment for use, the polaroid of the deterioration of polarizer adaptation, thus complete the present invention, the feature of this polaroid is, the polarizer clamps via dynamic rays curing type bond layer tunicle A and film B, this film A is thin and change in size under specified conditions is the acrylic film in particular range, this film B is the cellulose acetate containing low degree of substitution, thin and above-mentioned change in size is similarly the cellulose acetate membrane in particular range.
That is, above-mentioned problem of the present invention is solved by following mode.
1. a polaroid, is characterized in that, the polarizer clamps via dynamic rays curing type bond layer tunicle A and film B,
In this film A to be thickness be scope of 20 ~ 60 μm, meet following formula (1) ~ (4) and acrylic film containing acryl resin,
Average substitution degree in this film B to be thickness be scope of 20 ~ 60 μm, containing acetyl group is cellulose acetate in the scope of 2.0 ~ 2.5 and meets the cellulose acetate membrane of following formula (1) ~ (4).
(1)0.03(％)≤L 1MD－L 5MD≤0.30(％)
(2)0.03(％)≤L 1TD－L 5TD≤0.30(％)
(3)0(％)≤L 5MD－L 30MD≤0.10(％)
(4)0(％)≤L 5TD－L 30TD≤0.10(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD represents the size changing rate of the film after 1 minute that utilizes following formula (a) ~ (f) to obtain, after 5 minutes and after 30 minutes.For following formula (a) ~ (f), with while the mode parallel with TD direction or MD direction gathers film A and the film B of rectangle, it is placed 24 hours under the temperature humidity condition of 23 DEG C of 55%RH, in the given size of MD direction and this film of TD direction detection, is set to L respectively 0mD and L 0tD.Be positioned over by this film in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, under being positioned over the temperature humidity environment of 23 DEG C of 55%RH, the size after MD direction and TD direction measure 1 minute respectively, the size after 5 minutes and the size after 30 minutes, be set to L respectively 1mD ', L 1tD ', L 5mD ', L 5tD ', L 30mD ' and L 30tD ', substitutes into following formula (a) ~ (f) and obtains above-mentioned size changing rate.
Size changing rate after 1 minute
(formula is L a) 1mD (%)=(L 1mD '-L 0mD)/L 0mD × 100
(formula b) L 1tD (%)=(L 1tD '-L 0tD)/L 0tD × 100
Size changing rate after 5 minutes
(formula c) L 5mD (%)=(L 5mD '-L 0mD)/L 0mD × 100
(formula d) L 5tD (%)=(L 5tD '-L 0tD)/L 0tD × 100
Size changing rate after 30 minutes
(formula e) L 30mD (%)=(L 30mD '-L 0mD)/L 0mD × 100
(formula f) L 30tD (%)=(L 30tD '-L 0tD)/L 0tD × 100
2. the polaroid according to above-mentioned 1st, is characterized in that, above-mentioned film A and above-mentioned film B meets following formula (5) ~ (8) respectively.
(5)0.05(％)≤L 1MD－L 5MD≤0.15(％)
(6)0.05(％)≤L 1TD－L 5TD≤0.15(％)
(7)0(％)≤L 5MD－L 30MD≤0.05(％)
(8)0(％)≤L 5TD－L 30TD≤0.05(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30the L of TD and the 1st 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD is equivalent in meaning.
3. the polaroid according to the 1st or the 2nd, is characterized in that, the L of above-mentioned film A and above-mentioned film B 30tD and L 30mD is respectively in the scope of-0.10 ~ 0.10%.
4. the polaroid according to any one of the 1st ~ the 3rd, is characterized in that, above-mentioned film A contains sugar ester or has the polycondensation ester of the structure that following general formula (1) represents.
General formula (1)
B 3－(G 2－A) n－G 2－B 4
(in above-mentioned general formula, B 3and B 4various places represent aliphatics or aromatic monocarboxylate's residue or hydroxyl independently.G 2represent that the aklylene glycol residue of carbon number 2 ~ 12, the aryl-diol residue of carbon number 6 ~ 12 or carbon number are the oxyalkylene diol residue of 4 ~ 12.A represents the alkylene dicarboxylic acids residue of carbon number 4 ~ 12 or aryl dicarboxylic acid's residue of carbon number 6 ~ 12.N represents the integer of more than 1.)
5. the polaroid according to any one of the 1st ~ the 4th, it is characterized in that, above-mentioned film A is the formation of corticated at least 3 layers of the both sides tool at sandwich layer, and this sandwich layer contains acryl resin, and this cortex contains cellulose esters.
6. the polaroid according to any one of the 1st ~ the 5th, is characterized in that, above-mentioned film A is be stretched in the scope of 1.05 ~ 1.5 times at the former width relative to TD direction.
7. the polaroid according to any one of the 1st ~ the 6th, it is characterized in that, in the face defined by following formula (i) and (ii) of above-mentioned film B, the length of delay Ro in direction is in the scope of 40 ~ 60nm, and the length of delay Rt of thickness direction is in the scope of 100 ~ 140nm.
Formula (i): Ro=(n x-n y) × d (nm)
Formula (ii): Rt={ (n x+ n y)/2-n z} × d (nm)
(in formula (i) and formula (ii), n xrepresent that in direction, refractive index reaches the refractive index of maximum direction x in the face of film.N yrepresent the refractive index of direction y orthogonal with above-mentioned direction x in direction in the face of film.N zrepresent the refractive index at the thickness direction z of film.D represents the thickness (nm) of film.Carry out with the mensuration wavelength of 590nm under being determined at the environment of 23 DEG C of 55%RH.〕
8. the polaroid according to any one of the 1st ~ the 7th, is characterized in that, the average substitution degree that above-mentioned film B contains acetyl group is the cellulose acetate in the scope of 2.1 ~ 2.4.
9. the polaroid according to any one of the 1st ~ the 8th, is characterized in that, above-mentioned film B contains sugar ester or has the polycondensation ester of the structure that following general formula (1) represents.
General formula (1)
B 3－(G 2－A) n－G 2－B 4
(in above-mentioned formula, B 3and B 4various places represent aliphatics or aromatic monocarboxylate's residue or hydroxyl independently.G 2represent that the aklylene glycol residue of carbon number 2 ~ 12, the aryl-diol residue of carbon number 6 ~ 12 or carbon number are the oxyalkylene diol residue of 4 ~ 12.A represents the alkylene dicarboxylic acids residue of carbon number 4 ~ 12 or aryl dicarboxylic acid's residue of carbon number 6 ~ 12.N represents the integer of more than 1.)
10. the polaroid according to any one of the 1st ~ the 9th; it is characterized in that; above-mentioned film B is the formation of corticated at least 3 layers of the both sides tool at sandwich layer; this sandwich layer contain degree of substitution with acetyl group be 2.0 ~ 2.45 scope in cellulose acetate, this cortex contain degree of substitution with acetyl group be 2.6 ~ 2.95 scope in cellulose acetate.
11. polaroids according to any one of the 1st ~ the 10th, it is characterized in that, the thickness of the above-mentioned polarizer is in the scope of 2 ~ 15 μm.
The manufacture method of 12. 1 kinds of polaroids, is characterized in that, is via the manufacture method of dynamic rays curing type bond layer at the two sides laminating film A of the polarizer and the polaroid of film B,
As this film A, thickness is used to be in the scope of 20 ~ 60 μm, to meet following formula (1) ~ (4) and acrylic film containing acryl resin,
This film B uses thickness to be average substitution degree in the scope of 20 ~ 60 μm, containing acetyl group to be the cellulose acetate in the scope of 2.0 ~ 2.5 and meets the cellulose acetate membrane of following formula (1) ~ (4).
(1)0.03(％)≤L 1MD－L 5MD≤0.30(％)
(2)0.03(％)≤L 1TD－L 5TD≤0.30(％)
(3)0(％)≤L 5MD－L 30MD≤0.10(％)
(4)0(％)≤L 5TD－L 30TD≤0.10(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD represents the size changing rate of the film after 1 minute that utilizes following formula (a) ~ (f) to obtain, after 5 minutes and after 30 minutes.For following formula (a) ~ (f), with while the mode parallel with TD direction or MD direction gathers film A and the film B of rectangle, it is placed 24 hours under the temperature humidity environment of 23 DEG C of 55%RH, in the given size of MD direction and TD direction detection film, is set to L respectively 0mD and L 0tD.This film is positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, then under the temperature humidity environment being positioned over 23 DEG C of 55%RH, the size after MD direction and TD direction measure 1 minute respectively, the size after 5 minutes and the size after 30 minutes, be set to L respectively 1mD ', L 1tD ', L 5mD ', L 5tD ', L 30mD ' and L 30tD ', substitutes into following formula (a) ~ (f) and obtains above-mentioned size changing rate.
Size changing rate after 1 minute
(formula is L a) 1mD (%)=(L 1mD '-L 0mD)/L 0mD × 100
(formula b) L 1tD (%)=(L 1tD '-L 0tD)/L 0tD × 100
Size changing rate after 5 minutes
(formula c) L 5mD (%)=(L 5mD '-L 0mD)/L 0mD × 100
(formula d) L 5tD (%)=(L 5tD '-L 0tD)/L 0tD × 100
Size changing rate after 30 minutes
(formula e) L 30mD (%)=(L 30mD '-L 0mD)/L 0mD × 100
(formula f) L 30tD (%)=(L 30tD '-L 0tD)/L 0tD × 100
The manufacture method of 13. polaroids according to the 12nd, is characterized in that, utilize following operation to form above-mentioned film A, that is,
Casting dope at least containing acryl resin and organic solvent is formed in metal support the operation of basement membrane (web),
The operation peeled off by the drying of the basement membrane of above-mentioned formation and from metal support,
By the operation that the basement membrane of above-mentioned stripping stretches,
By the basement membrane that the stretched operation in dry section drying, and
After above-mentioned basement membrane leaves this dry section, refrigerating work procedure basement membrane cooled with the speed in the scope of 50 ~ 100 DEG C/sec.
The manufacture method of 14. polaroids according to the 12nd or the 13rd, is characterized in that, utilize following operation to form above-mentioned film B, that is,
Casting dope at least containing cellulose acetate and organic solvent is formed in metal support the operation of basement membrane,
The operation peeled off by the drying of the basement membrane of above-mentioned formation and from metal support,
By the operation that the basement membrane of above-mentioned stripping stretches, and
By the operation of the above-mentioned basement membrane stretched in dry section drying,
When utilizing as above operation to form above-mentioned film B, above-mentioned basement membrane had bending operation in the operation of dry section drying, namely be maintained at the temperature within the scope of 130 ~ 150 DEG C and utilize transport roller with the A face of this basement membrane and relative B face alternately become inner side mode bend, this bending operation carries out as follows: when radius during this basement membrane of bending is set to a (mm), the value of 1/a is 0.035mm ﹣ 1~ 0.050mm ﹣ 1scope in, and repeat more than 50 times and lower than 120 times bend.
The manufacture method of 15. polaroids according to any one of the 12nd ~ the 14th, is characterized in that, utilizes following operation to form polarizability stacked film, that is,
Form polyvinyl alcohol resin layer in the one side of base material film rubber constituent being scattered in thermoplastic resin and obtain the operation of stacked film,
Above-mentioned stacked film is carried out uniaxial tension and obtains the operation of stretched film,
With dichromatism pigment, the above-mentioned polyvinyl alcohol resin layer dyeing of above-mentioned stretched film is obtained the operation of dyeing film,
The above-mentioned polyvinyl alcohol resin layer of above-mentioned dyeing film be impregnated in and form polarizer layer containing the solution of crosslinking chemical, obtain the operation of cross linking membrane, and
By the operation of above-mentioned cross linking membrane drying,
Utilize after as above operation forms polarizability stacked film, the above-mentioned polyvinyl alcohol resin layer of this polarizability stacked film is peeled off from base material film, uses this polyvinyl alcohol resin layer as the above-mentioned polarizer.
16. 1 kinds of liquid crystal indicators, is characterized in that, possess the polaroid according to any one of the 1st ~ the 11st.
17. liquid crystal indicators according to the 16th, it is characterized in that, above-mentioned liquid crystal indicator is VA mode LCD.
Utilize aforesaid way of the present invention; the polarizer can be provided to fit via dynamic rays curing type bond layer and diaphragm and use acrylic film and cellulose acetate membrane as the polaroid of this diaphragm; when liquid crystal indicator possesses this polaroid, even if the display inequality of liquid crystal panel and the deterioration of the polarizer adaptation such as undulation, film stripping are also can't see in the temperature humidity environmental change of environment for use.In addition, the manufacture method of this polaroid can be provided and possess the liquid crystal indicator of visuality excellence of this polaroid.
Effect of the present invention present mechanism or mechanism of action is still not clear, but infer as follows.
The polarizer is fitted via dynamic rays curing type bond layer and diaphragm and forms the film polarizer of the formation of the acrylic film/polarizer/cellulose acetate membrane there are the following problems: if to be shifted to from hot and humid environment by liquid crystal indicator under low temperature and low humidity environment and to observe display frame, then produce the distinctive display inequality of liquid crystal panel.Infer this is because when the temperature humidity environment of particularly environment sharply changes the change in size speed of above-mentioned 2 diaphragms different, thus produce strain between 2 diaphragms of the clamping polarizer and bonding agent part, produce optics uneven thereupon.
Even if the present inventor recognizes the change in size adjusting the film after placing the long periods such as one day night under particular circumstances as in the past in the process studied the change in size speed of diaphragm, the improvement effect of above-mentioned problem is also insufficient, in studying in great detail further, be conceived to from just sharply changing after the temperature humidity environment of environment to the change in size speed in the short period, result finds acrylic film and various cellulose ester membrane respective distinctive change in size course within this short time, infer the behavior difference by adjusting this change in size, problem of the present invention can be improved.
Fig. 1 is the schematic diagram of the size changing rate (%) in the MD direction that represents of above-mentioned formula (a) ~ (f) after representing after just environmental turbulence (the environment from 80 DEG C of 90%RH to 23 DEG C of 55%RH) 1 minute of acrylic film, after 5 minutes, after 30 minutes and after 60 minutes and TD direction.
Known acrylic film after 1 minute ~ 5 minute later stage between dimensional variations (contraction), take thereafter the stable behavior that size changes hardly.
Fig. 2 is the schematic diagram of the same change in size representing tri cellulose acetate membrane (TAC film).
Tri cellulose acetate membrane and acrylic film are different greatly, if from hot and humid shift to the environment of low temperature and low humidity, then film slightly expands, still take thereafter continue variation (contraction) behavior.
Fig. 3 is the schematic diagram of the same change in size representing cellulose-acetate propionate film (CAP film).
Cellulose-acetate propionate film is different from acrylic film, after 1 minute ~ 5 minute later stage between size significantly change (contraction), thereafter still continue variation (contraction).
Fig. 4 is the schematic diagram of the same change in size representing cellulose diacetate film (DAC film).
Find cellulose diacetate film after 1 minute ~ 5 minute later stage between see the dimensional variations (contraction) slightly larger than acrylic film, but take thereafter the stable behavior that size changes hardly in the same manner as acrylic film.
According to above result of study; if deducibility profit can adjust the change in size of the scope behind after environmental turbulence 1 minute ~ 5 minutes of cellulose diacetate film by some way; make it similar to the behavior of acrylic film; then become 2 diaphragms that the behavior of change in size is consistent, just should be able to reduce the strain between the polarizer and bonding agent part.
Therefore, deducibility adopt as the technical characteristic of polaroid of the present invention acrylic film and belong to cellulose acetate membrane containing the film of cellulose diacetate as 2 diaphragms, and adjust according to the mode that the change in size in their each leisure above-mentioned short time is controlled in specific scope, thus the strain at this diaphragm and bonding agent part can be suppressed, even if the temperature humidity environmental change obtaining environment for use also can reduce the display inequality that liquid crystal panel produces, even and if also can't see the polaroid with the adaptation deterioration of the polarizer under harsh environment.
Accompanying drawing explanation
Fig. 1 is the schematic diagram representing acrylic film change in size at short notice.
Fig. 2 is the schematic diagram representing tri cellulose acetate membrane change in size at short notice.
Fig. 3 is the schematic diagram representing cellulose-acetate propionate film change in size at short notice.
Fig. 4 is the schematic diagram representing cellulose diacetate film change in size at short notice.
Fig. 5 is the schematic diagram representing film B of the present invention (modified form cellulose diacetate film) change in size at short notice.
Fig. 6 is schematic diagram when representing the change in size measuring film.
Fig. 7 is the schematic diagram of an example of the coating preparation section of the preferred solution casting film-forming method representing cellulose ester membrane of the present invention, curtain coating operation and drying process.
Fig. 8 represents that common casting mold and curtain coating form the schematic diagram of the situation of sandwich construction basement membrane.
Fig. 9 is the schematic diagram representing the bending process device preferably adopted in the present invention.
Embodiment
The feature of polaroid of the present invention is that the polarizer clamps via dynamic rays curing type bond layer tunicle A and film B, this film A is thin and change in size is under given conditions the acrylic film in specific scope, this film B is cellulose acetate containing low degree of substitution, thin and above-mentioned change in size is similarly the cellulose acetate membrane in specific scope, even if the display providing in liquid crystal indicator the temperature humidity environmental change of environment for use when possessing this polaroid also to can't see liquid crystal panel is uneven, the polaroid of the deterioration of polarizer adaptation.This feature is the common technical characteristic of invention that the technical scheme of technical scheme 1 ~ technical scheme 17 relates to.
Should illustrate, in the present invention, MD is the abbreviation of longitudinally (MachineDirection), is commonly referred to as the direction of transport membrane of curtain coating direction, long side direction when MD direction is masking.TD is the abbreviation of laterally (TransverseDirection), and TD direction is commonly referred to as Width, the horizontal direction at a right angle with throughput direction.
In addition, in this instructions, sometimes by film A and film B referred to as diaphragm.
As embodiments of the present invention, from the viewpoint of presenting effect of the present invention, preferred above-mentioned film A and above-mentioned film B meets the polaroid of the scope of the change in size that above-mentioned formula (5) ~ (8) represent, even if when sharply changing from the temperature humidity environment of environment for use, also the generation of the display inequality of liquid crystal panel, further raising can be suppressed to consider for the viewpoint of the permanance of the adaptation deterioration with the polarizer, the L of above-mentioned film A and above-mentioned film B 30tD and L 30preferred mode in the scope that MD is respectively-0.10 ~ 0.10%.
In addition, the polycondensation ester that above-mentioned film A contains sugar ester or has a structure that above-mentioned general formula (1) represents reduces above-mentioned change in size and preferably from the viewpoint of utilizing its plasticization effect, further preferred above-mentioned film A is the formation of corticated at least 3 layers of the both sides tool at sandwich layer, this sandwich layer contains acryl resin, this cortex contains cellulose esters, so by overlapping different types of resin, more easily control to be adjusted in the scope of the change in size that above-mentioned formula (1) ~ (4) represent.Further preferred above-mentioned film A is stretched in the scope that the former width relative to TD direction is 1.05 ~ 1.5 times, so by improving the orientation of the strand of acryl resin, the change in size caused by discrepancy of moisture can be reduced, more easily present the display inequality of liquid crystal panel, the improvement effect of polarizer adaptation.
Make visual good from the viewpoint of the field angle expanding liquid crystal indicator, in the face defined by above-mentioned formula (i) and (ii) of preferred above-mentioned film B, the length of delay Ro in direction is in the scope of 40 ~ 60nm, and the length of delay Rt of thickness direction is in the scope of 100 ~ 140nm.In addition, in order to present above-mentioned length of delay, the average substitution degree preferably containing acetyl group is the cellulose acetate in the scope of 2.1 ~ 2.4.
In addition, stablize to make change in size, the polycondensation ester that above-mentioned film B contains sugar ester or has a structure that above-mentioned general formula (1) represents is owing to presenting its plasticization effect, thus preferred, further preferred above-mentioned film B is the formation of corticated at least 3 layers of the both sides tool at sandwich layer, this sandwich layer contains the cellulose acetate of degree of substitution with acetyl group in the scope of 2.0 ~ 2.45, this cortex contains the cellulose acetate of degree of substitution with acetyl group in the scope of 2.6 ~ 2.95, so by overlapping different types of resin, more easily can control the relation of the change in size that above-mentioned formula (1) ~ (4) represent, the impact of humidity variation on film of environment can be reduced.
From the viewpoint of making polaroid monolithic film membrane; the thickness of the preferred above-mentioned polarizer is in the scope of 2 ~ 15 μm; in addition because the flexibility of the polarizer increases; easily follow the change in size of diaphragm; therefore, it is possible to the adaptation of the polarizer improved further when using dynamic rays curing type bonding agent and diaphragm; and there is the effect reducing display inequality, thus preferably.
The polaroid of effect of the present invention is presented from the viewpoint of manufacturing, the manufacture method of preferred polaroid of the present invention is via the manufacture method of dynamic rays curing type bond layer at the two sides laminating film A of the polarizer and the polaroid of film B, and use the above-mentioned acrylic film containing acryl resin as this film A, use above-mentioned cellulose acetate membrane as this film B.
In the formation process of above-mentioned film A, at the basement membrane that will have stretched after the operation of dry section drying, formed by applying the refrigerating work procedure that cooled by basement membrane with the speed in the scope of 50 ~ 100 DEG C/sec, can make the state of the strand of film closely and adjust the amount of moisture that film can contain, effectively can control the shrinkage rates of the film containing moisture in addition, thus preferably.
In addition, above-mentioned film B is in its formation process, had by the operation of dry basement membrane and carry out the bending operation that bends being held in the dry section in specific temperature range the mode utilizing conveying roller alternately to become inner side with the A face of this basement membrane and relative B face, this bending operation makes radius during this basement membrane of bending be in specific scope, and in the scope of specific number of times repeated flex, thus can make the state of the strand of film closely and adjust the amount of moisture that film can contain, effectively can control the shrinkage rates of the film containing moisture thus, thus preferably.
In addition, as the above-mentioned polarizer, preferably form polyvinyl alcohol resin layer in the one side of base material film rubber constituent being scattered in thermoplastic resin, then after uniaxial tension, dyeing, crosslinked and dry operation form polarizability stacked film, the polyvinyl alcohol resin layer of this polarizability stacked film peeled off from base material film and is formed as this polarizer, so can obtain the thin and polaroid of high-quality.
Polaroid of the present invention is adapted to be possessed in liquid crystal indicator, is particularly suitable for VA mode LCD.
Below, to the present invention and inscape thereof be described in detail for implementing form mode of the present invention.Should illustrate, in the application, " ~ " uses to comprise the numerical value recorded before and after it as the implication of lower limit and higher limit.
" summary of polaroid of the present invention "
The feature of polaroid of the present invention is, the polarizer clamps via dynamic rays curing type bond layer tunicle A and film B,
In this film A to be thickness be scope of 20 ~ 60 μm, meet following formula (1) ~ (4) and acrylic film containing acryl resin,
Average substitution degree in this film B to be thickness be scope of 20 ~ 60 μm, containing acetyl group is cellulose acetate in the scope of 2.0 ~ 2.5 and meets the cellulose acetate membrane of following formula (1) ~ (4).
(1)0.03(％)≤L 1MD－L 5MD≤0.30(％)
(2)0.03(％)≤L 1TD－L 5TD≤0.30(％)
(3)0(％)≤L 5MD－L 30MD≤0.10(％)
(4)0(％)≤L 5TD－L 30TD≤0.10(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD represents the size changing rate of the film after 1 minute that utilizes following formula (a) ~ (f) to obtain, after 5 minutes and after 30 minutes.For following formula (a) ~ (f), with while the mode parallel with TD direction or MD direction gathers film A and the film B of rectangle, it is placed 24 hours under the temperature humidity environment of 23 DEG C of 55%RH, in the given size of MD direction and this film of TD direction detection, is set to L respectively 0mD and L 0tD.This film is positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, then under the temperature humidity environment being positioned over 23 DEG C of 55%RH, the size after MD direction and TD direction measure 1 minute respectively, the size after 5 minutes and the size after 30 minutes, be set to L respectively 1mD ', L 1tD ', L 5mD ', L 5tD ', L 30mD ' and L 30tD ', substitutes into following formula (a) ~ (f) and obtains above-mentioned size changing rate.
Size changing rate after 1 minute
(formula is L a) 1mD (%)=(L 1mD '-L 0mD)/L 0mD × 100
(formula b) L 1tD (%)=(L 1tD '-L 0tD)/L 0tD × 100
Size changing rate after 5 minutes
(formula c) L 5mD (%)=(L 5mD '-L 0mD)/L 0mD × 100
(formula d) L 5tD (%)=(L 5tD '-L 0tD)/L 0tD × 100
Size changing rate after 30 minutes
(formula e) L 30mD (%)=(L 30mD '-L 0mD)/L 0mD × 100
(formula f) L 30tD (%)=(L 30tD '-L 0tD)/L 0tD × 100
The intensity of polaroid when the present inventor is in order to improve polarizer film, have studied following formation: adopt in the one side of the polarizer and employ the transparency, excellent in dimensional stability, belong to the acrylic film of the acryl resin of agent of low hygroscopicity resin, and from the easiness that phase differential presents, throughput rate (operability, doing over again property etc.) and the viewpoint such as cost consider, adopt the existing phase retardation film containing cellulose ester resin as phase retardation film in the face of the opposition side of the polarizer, namely, the phase retardation film of acrylic film/polarizer/containing cellulose ester resin is followed successively by from visible side.
In addition, increase the intensity of polaroid in order to the cementability of the polarizer and diaphragm that improve film polarizer, have studied the method via the dynamic rays curing type bonding agent laminating polarizer and diaphragm simultaneously.
But, there are the following problems to find to be followed successively by the film polarizer of the formation of the aforesaid propylene sorrel/polarizer/cellulose ester membrane from the visible side of polaroid: if to be shifted to from hot and humid environment by liquid crystal indicator under low temperature and low humidity environment and to observe display frame, then produce the distinctive display inequality of liquid crystal panel.Infer this is because in short time particularly after just sharply changing the temperature humidity environment of environment the change in size speed of above-mentioned 2 diaphragms different, thus cause optics uneven because of clamping 2 diaphragms of the polarizer and the strain of bonding agent part.
Therefore; the present invention used the diaphragm change in size after placing the long periods such as one day night in certain circumstances being carried out adjusting as in the past; but use the speed of change in size of the short period of the temperature humidity environment of environment just sharply after change is adjusted to the diaphragm of certain films consistent in specific scope as film polarizer; even if the polaroid of the display inequality of liquid crystal panel, the deterioration of polarizer adaptation is also can't see in the temperature humidity environmental change obtaining environment for use thus, thus completes the present invention.
(mensuration of the size changing rate of film)
Film A of the present invention and film B, size changing rate in short period after the temperature humidity environment just sharply changing environment utilizes following method to measure.
(1) Fig. 6 represents the L that mensuration is concrete 0mD and L 0the schematic diagram of film during TD.
With while the mode parallel with TD direction or MD direction gathers each 2 of 10cm square film A and film B, be respectively used to the change in size measuring MD direction or TD direction.To be spaced apart the mode razor of 8cm to after this film mark signature, the constant temperature and humidity machine dropping into 23 DEG C of 55%RH places 24 hours.
The film of above-mentioned damping is positioned over microscopical objective table, puts glass plate and be fixed, in MD direction and TD direction microscope micrometric measurement given size (8cm), be set to L respectively 0mD and L 0tD.
Microscope uses NIKON NikonMEASURESCOPEMM-11, and (data determination machine uses NikonDP-302DATAPROCESSOR to be directly connected with microscope, and the data obtained are outputted to spreadsheet for eyepiece: × 10, object lens: × 3).
(2) this film to be positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, under moving to the temperature humidity environment of 23 DEG C of 55%RH again, size, the size after 5 minutes and the size after 30 minutes after MD direction and TD direction utilize above-mentioned microscope and data determination machine measures 1 minute respectively at once, be set to L respectively 1mD ', L 1tD ', L 5mD ', L 5tD ', L 30mD ' and L 30tD '.
Each size substitution of (3) (1) and (2) being tried to achieve is following, and (formula a) ~ (formula f), is obtained the size changing rate of the film after 1 minute, after 5 minutes and after 30 minutes, is set to L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD.
Size changing rate after 1 minute
(formula is L a) 1mD (%)=(L 1mD '-L 0mD)/L 0mD × 100
(formula b) L 1tD (%)=(L 1tD '-L 0tD)/L 0tD × 100
Size changing rate after 5 minutes
(formula c) L 5mD (%)=(L 5mD '-L 0mD)/L 0mD × 100
(formula d) L 5tD (%)=(L 5tD '-L 0tD)/L 0tD × 100
Size changing rate after 30 minutes
(formula e) L 30mD (%)=(L 30mD '-L 0mD)/L 0mD × 100
(formula f) L 30tD (%)=(L 30tD '-L 0tD)/L 0tD × 100
The feature of film A of the present invention and film B is, is the acrylic film and the cellulose acetate membrane that meet following (1) ~ (4).Namely; by meeting (1) and (2); (after 1 minute) after firm generation when sharply changing from the temperature humidity environment of environment is adjusted in following specific scope to the dimensional variations changing larger MD direction and TD direction after 5 minutes in this film A and film B; thus the strain of the diaphragm that can suppress different by both dimensional variations and cause and bonding agent part; by meet (3) and (4), make further through time effect stability.
(1)0.03(％)≤L 1MD－L 5MD≤0.30(％)
(2)0.03(％)≤L 1TD－L 5TD≤0.30(％)
(3)0(％)≤L 5MD－L 30MD≤0.10(％)
(4)0(％)≤L 5TD－L 30TD≤0.10(％)
In addition, preferred film A of the present invention and film B is for meeting acrylic film and the cellulose acetate membrane of following (5) ~ (8).
(5)0.05(％)≤L 1MD－L 5MD≤0.15(％)
(6)0.05(％)≤L 1TD－L 5TD≤0.15(％)
(7)0(％)≤L 5MD－L 30MD≤0.05(％)
(8)0(％)≤L 5TD－L 30TD≤0.05(％)
In addition, even if when sharply changing from the temperature humidity environment of environment, the viewpoint that also can improve the permanance of the adaptation deterioration of, diaphragm uneven for the display of liquid crystal panel and the polarizer is further considered, the L of above-mentioned film A and above-mentioned film B 30tD and L 30preferred mode in the scope that MD is respectively-0.10 ~ 0.10%.
The mode adjusted to by the initial size changing rate of film A of the present invention and film B in scope that above-mentioned (1) ~ (8) represent is not particularly limited, and can suitably adopt following mode to adjust.
As the mode size changing rate of film A of the present invention adjusted in scope that above-mentioned (1) ~ (8) represent, be not limited to under type, on the basis of the adjustment of the adjustment of the kind of acryl resin and the selection of weight-average molecular weight, the kind of plastifier and amount, draw direction and stretching ratio, thickness adjustment, preferably in the drying process of basement membrane, after above-mentioned basement membrane leaves this drying process (dry section), apply to be filmed with the refrigerating work procedure that basement membrane cools by the speed within the scope of 50 ~ 100 DEG C/sec, detailed content is aftermentioned.
In addition, preferably this film A is the film of stepped construction, be the formation of corticated at least 3 layers of the both sides tool at sandwich layer, this sandwich layer contains acryl resin, this cortex contains cellulose esters, so by overlapping different types of resin, in easier scope film A being controlled to the change in size that above-mentioned formula (1) ~ (8) represent.
In addition, also preferred by acryl resin and cellulose esters mixing and be used as thermoplastic resin, so can work in coordination with the characteristic playing different types of resin, in easier scope film A being controlled to the change in size that above-mentioned formula (1) ~ (8) represent.
As the mode size changing rate of film B of the present invention is adjusted in scope that above-mentioned (1) ~ (8) represent, be not limited to under type, in the degree of substitution with acetyl group of cellulose acetate and the selection of weight-average molecular weight, the kind of plastifier and the adjustment of amount, the adjustment of draw direction and stretching ratio, on the basis of thickness adjustment, preferably by the operation of basement membrane drying, there is bending operation, namely in the dry section within the scope of 130 ~ 150 DEG C, the mode utilizing conveying roller alternately to become inner side with the A face of this basement membrane and relative B face bends, this bending operation is when radius during this basement membrane of bending is set to a (mm), the value of 1/a is 0.035mm ﹣ 1~ 0.050mm ﹣ 1scope in and repeat more than 50 times and lower than 120 times bending masking, so make the state of the strand of film tight, adjust the amount of moisture that film can contain, thus effectively can control the shrinkage rates of the film containing moisture, detailed content is aftermentioned.
In addition; preferably this film B is the film of stepped construction; be the formation of corticated at least 3 layers of the both sides tool at sandwich layer; this sandwich layer contain degree of substitution with acetyl group be 2.0 ~ 2.45 scope in cellulose acetate; this cortex contain degree of substitution with acetyl group be 2.6 ~ 2.95 scope in cellulose acetate; so by overlapping different types of resin, be easily adjusted in the scope of the change in size that above-mentioned formula (1) ~ (4) represent.
Fig. 5 is the schematic diagram of the change in size representing film B of the present invention (modified form cellulose diacetate film).
By applying above-mentioned adjustment mode, the behavior of the change in size of cellulose diacetate film within the short time after just environmental turbulence can be made similar to the behavior of the change in size of the acrylic film that Fig. 1 represents.In addition, by known with the contrast of embodiment, be not the absolute value of change in size itself, but the behavior of the speed of change in size is the factor of impact display inequality.
Below, the constitution content of film A and film B, manufacture method are described successively.
" film A: acrylic film "
The feature of film A of the present invention is to be total film thickness to be acrylic film in the scope of 20 ~ 60 μm, by becoming the thickness within the scope of this, can be provided in the film polarizer possessing sufficient rigidity, operability excellence while presenting effect of the present invention.Be more preferably in the scope of 20 ~ 40 μm.
(acryl resin)
Film A of the present invention is the film containing acryl resin, and in the present invention, acryl resin refers to the polymkeric substance of acrylate or methacrylate, also comprises the multipolymer with other monomer.
Therefore, the acryl resin used in the present invention also comprises methacrylic resin.Be not particularly limited as resin, preferably by the resin that can form with other monomeric unit of methyl methacrylate units copolymerization in the scope of the methyl methacrylate units in the scope of 50 ~ 99 quality % and 1 ~ 50 quality %.
As other unit forming the acryl resin that copolymerization is formed, the carbon number can enumerating alkyl number is the alkyl methacrylate of 2 ~ 18, the carbon number of alkyl number is the alkyl acrylate of 1 ~ 18, isobornyl methacrylate, the hydroxyalkyl acrylates such as acrylic acid 2-hydroxy methacrylate, acrylic acid, the α such as methacrylic acid, beta-unsaturated acid, acryloyl morpholine, the acrylamides such as N hydroxyphenylmethyl acrylamide, NVP, maleic acid, fumaric acid, 2 yuan of carboxylic acids containing unsaturated group such as itaconic acid, styrene, the aromatic ethenyl compounds such as α-methyl styrene, vinyl cyanide, the α such as methacrylonitrile, alpha, beta-unsaturated nitriles, maleic anhydride, maleimide, N-substituted maleimide amine, glutarimide, glutaric anhydride etc.
As the unit formed in said units except glutarimide and glutaric anhydride can the monomer of copolymerization, the monomer corresponding with said units can be enumerated.Namely, the carbon number can enumerating alkyl number is the alkyl methacrylate of 2 ~ 18, the carbon number of alkyl number is the alkyl acrylate of 1 ~ 18, isobornyl methacrylate, the hydroxyalkyl acrylates such as acrylic acid 2-hydroxy methacrylate, acrylic acid, the α such as methacrylic acid, beta-unsaturated acid, acryloyl morpholine, the acrylamides such as N hydroxyphenylmethyl acrylamide, NVP, maleic acid, fumaric acid, 2 yuan of carboxylic acids containing unsaturated group such as itaconic acid, styrene, the aromatic ethenyl compounds such as α-methyl styrene, vinyl cyanide, the α such as methacrylonitrile, alpha, beta-unsaturated nitriles, maleic anhydride, maleimide, the monomers such as N-substituted maleimide amine.
In addition, glutarimide unit such as can be reacted by the midbody polymer and primary amine (acid imide agent) making to have (methyl) acrylic ester unit and carries out imidizate and formed (with reference to Japanese Unexamined Patent Publication 2011-26563 publication).
Glutaric anhydride unit such as can be formed by heating the midbody polymer with (methyl) acrylic ester unit (with reference to Japanese Patent No. 4961164 publication).
For the acryl resin that the present invention uses; in above-mentioned Component units; consider from mechanical property, particularly preferably containing isobornyl methacrylate, acryloyl morpholine, N-hydroxyphenylmethyl acrylamide, NVP, styrene, hydroxyethyl methacrylate, maleic anhydride, maleimide, N-substituted maleimide amine, glutaric anhydride or glutarimide.
In addition, as the acryl resin used in the present invention, consider from the viewpoint such as high-fire resistance, high transparent, preferably use the acryl resin in structure with lactonic ring structure.As the acryl resin with lactonic ring structure, such as, can enumerate (methyl) acrylic acid series copolymer with lactonic ring structure recorded in Japanese Unexamined Patent Publication 2000-230016 publication, Japanese Unexamined Patent Publication 2001-151814 publication, Japanese Unexamined Patent Publication 2002-120326 publication, Japanese Unexamined Patent Publication 2002-254544 publication, Japanese Unexamined Patent Publication 2005-146084 publication and Japanese Unexamined Patent Publication 2009-157352 publication etc.Specifically, R in the general formula (1) that can preferably use Japanese Unexamined Patent Publication 2009-157352 publication to record 1for hydrogen atom, R 2and R 3for (methyl) acrylic resin [mass ratio of comonomer: methyl methacrylate/2-(hydroxymethyl) methyl acrylate=8/2 with lactonic ring structure of methyl; Lactonic ring rate about 100%].
From the viewpoint of control relative to the change in size of the change of the temperature humidity environment of environment for use viewpoint and improve when film is produced from the drying property of the fissility of metal support, organic solvent, thermotolerance and mechanical property, the weight-average molecular weight (Mw) of the acryl resin used in film A of the present invention is preferably in the scope of 80,000 ~ 2,000,000, be more preferably in the scope of 90,000 ~ 1,000,000, be particularly preferably in the scope of 100,000 ~ 500,000.
If be more than 80,000, then thermotolerance and mechanical property excellence, if be less than 2,000,000, then from the fissility of metal support and the drying property excellence of organic solvent.If be more than 80,000, then thermotolerance and mechanical property more excellent, if be less than 500,000, then from the fissility of metal support and the drying property of organic solvent more excellent.
The weight-average molecular weight of the acryl resin used in the present invention can utilize gel permeation chromatography.Condition determination is as follows.
Solvent: methylene chloride
Post: ShodexK806, K805, K803G (Showa Denko K. K's system) 3 is connected and uses)
Column temperature: 25 DEG C
Sample solution concentration: 0.1 quality %
Detecting device: RIModel504 (GLScience Inc.)
Pump: L6000 (Hitachi Ltd.'s system)
Flow: 1.0ml/min
Typical curve: use the typical curve obtained by 13 samples in the scope of polystyrene standard STKstandardpolystyrene (TOSOH Co., Ltd. system) Mw=500 ~ 2800000.Preferably 13 samples are almost to use at equal intervals.
As the manufacture method of the acryl resin used in the present invention, be not particularly limited, the known methods such as suspension polymerization, emulsion polymerization, bulk polymerization or solution polymerization all can use.Here, as polymerization initiator, can use the polymerization initiator of common peroxidating system and azo system, in addition, also can be redox system.Polymerization temperature in the scope of 30 ~ 100 DEG C, can be implemented in suspension or emulsion polymerization in body or solution polymerization in the scope of 80 ~ 160 DEG C.In order to control the reduced viscosity of the multipolymer obtained, alkyl sulfhydryl etc. also can be used to implement polymerization as chain-transferring agent.
As the acryl resin used in the present invention, commercially available commodity can be used.Such as can enumerate Delpet60N, 80N, 980N, SR8200 (above is AsahiKaseiChemicals Co., Ltd. system), DianalBR52, BR80, BR83, BR85, BR88, EMB-143, EMB-159, EMB-160, EMB-161, EMB-218, EMB-229, EMB-270, EMB-273 (above is MitsubishiRayon Co., Ltd. system), KT75, TX400S, IPX012 (above is Deuki Kagaku Kogyo Co., Ltd's system) etc.Also the acryl resin that two or more kinds may be used.
Acryl resin is by the macromolecule of one or more monomer polymerizations containing acrylate monomer, from the viewpoint of optical characteristics, thermotolerance and mechanical property, and the multipolymer of preferred various of monomer.In addition, film A of the present invention can containing the adjuvant beyond acryl resin, from the viewpoint of optical characteristics, thermotolerance, mechanical property and cost, preferably with relative to film be 80 ~ 100 quality % scope in contain acryl resin.
As an example of adjuvant, in order to the adjustment of size changing rate and the physical strength of film, can containing the acrylic particles (D) recorded in No. 2010/001668th, International Publication.As the example of the commercially available product of so granular complex of sandwich construction acrylic acid series, such as can enumerate " MetablenW-341 " of MitsubishiRayon Inc., " Kaneace " of Kaneka Inc., " Paraloid " of Kureha Inc., " Acryloid " of RohmandHaas Inc., Ganz changes into " Stafyroid " of industrial group, ChemisnowMR-2G, " ParapetSA " of MS-300X (being Soken Chemical & Engineering Co., Ltd.'s system above) and Kuraray Inc. etc., they can be used alone or use two or more.
In addition, as other adjuvant, also preferably containing adjuvants such as plastifier described later, ultraviolet light absorber, antioxidant, anti-deterioration agent, stripping auxiliary agent, surfactant, dyestuff, particulates.
Particularly preferably containing following sugar ester or polycondensation ester.
(sugar ester)
From the viewpoint of the behavior of controlling dimension change, in the acrylic film as film A of the present invention, preferably contain the sugar ester beyond cellulose esters.
As sugar ester of the present invention, preferably there is the pyranose ring of 1 ~ 12 or at least a kind of furanose ring and whole or a part of esterified sugar esters of the OH base of its structure.
Sugar ester of the present invention refers to the compound of at least one containing furanose ring or pyranose ring, and can be monose, also can be the polysaccharide of 2 ~ 12 sugared anatomical connectivity.And, at least one the esterified compound of the OH base that preferred sugar ester has for sugared structure.In sugar ester of the present invention, average ester degree of substitution is preferably in the scope of 4.0 ~ 8.0, is more preferably in the scope of 5.0 ~ 7.5.
As sugar ester used in the present invention, be not particularly limited, the sugar ester that following general formula (A) represents can be enumerated.
General formula (A)
(HO) m－G－(O－C(＝O)－R 2) n
In above-mentioned general formula (A), G represents the residue of monosaccharide or disaccharides, R 2represent aliphatic group or aromatic group, m is the total with the number of the hydroxyl of the residue Direct Bonding of monosaccharide or disaccharides, n be with the residue Direct Bonding of monosaccharide or disaccharides-(O-C (=O)-R 2) total of number of base, 3≤m+n≤8, n ≠ 0.
The known sugar ester with the structure that general formula (A) represents is difficult to the number (m) of hydroxyl ,-(O-C (=O)-R 2) form of compound of the fixing single kind of the number (n) of base is separated, and become the compound of the different multiple mixing of composition of m, n in formula.Therefore, as number (m) ,-(O-C (=the O)-R of hydroxyl 2) performance of the respective potpourri of change of number (n) of base is important, for diaphragm of the present invention, preferred average ester degree of substitution is the sugar ester in the scope of 5.0 ~ 7.5.
In above-mentioned general formula (A), G represents the residue of monosaccharide or disaccharides.As the concrete example of monosaccharide, such as, can enumerate allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, wood sugar, lyxose etc.
Below, the concrete example with the compound of monosaccharide residue of the sugar ester that general formula (A) represents is shown, but the invention is not restricted to these illustrative compounds.
In addition, as the concrete example of disaccharides residue, such as, can enumerate trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, isotrehalose etc.
Below, the concrete example with the compound of disaccharides residue of the sugar ester that general formula (A) represents is shown, but the invention is not restricted to these illustrative compounds.
In general formula (A), R 2represent aliphatic group or aromatic group.Here, aliphatic group and aromatic group can have substituting group in various places independently.
In addition, in general formula (A), m is the total with the number of the hydroxyl of the residue Direct Bonding of monosaccharide or disaccharides, n be with the residue Direct Bonding of monosaccharide or disaccharides-(O-C (=O)-R 2) total of number of base.And needing is 3≤m+n≤8, be preferably 4≤m+n≤8.In addition, n ≠ 0.Should illustrate, when n is more than 2 ,-(O-C (=O)-R 2) base each other can be identical or different.
R 2definition in aliphatic group can be straight chain, can be side chain, can be also ring-type, preferred carbon number be 1 ~ 25, is more preferably 1 ~ 20, is particularly preferably 2 ~ 15.As the concrete example of aliphatic group, such as, can enumerate each group such as methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, bicyclooctyl, adamantyl, positive decyl, tertiary octyl group, dodecyl, cetyl, octadecyl, didecyl.
In addition, R 2definition in aromatic group can be aromatic hydrocarbyl, can be also aromatic heterocycle, be more preferably aromatic hydrocarbyl.As aromatic hydrocarbyl, preferred carbon number is 6 ~ 24, is more preferably 6 ~ 12.As the concrete example of aromatic hydrocarbyl, such as, can enumerate each rings such as benzene, naphthalene, anthracene, biphenyl, terphenyl.As aromatic hydrocarbyl, particularly preferably phenyl ring, naphthalene nucleus, cyclohexyl biphenyl.As aromatic heterocycle, preferably containing at least one ring in oxygen atom, nitrogen-atoms or sulphur atom.As the concrete example of heterocycle, such as can enumerate furans, pyrroles, thiophene, imidazoles, pyrazoles, pyridine, pyrazine, pyridazine, triazole, triazine, indoles, indazole, purine, thiazoline, thiadiazoles, azoles quinoline, azoles, diazole, quinoline, isoquinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, acridine, phenanthroline, azophenlyene, tetrazolium, benzimidazole, benzo each rings such as azoles, benzothiazole, benzotriazole, the purine (tetrazaindene).As aromatic heterocycle, particularly preferably pyridine ring, triazine ring, quinoline ring.
Next, the following preference that the sugar ester that general formula (A) represents is shown, but the invention is not restricted to these illustrative compounds.
Sugar ester can containing the different substituents of more than 2 in 1 molecule, aromatic substituents and aliphatic substitution can be contained in 1 molecule, containing the different aromatic substituents of more than 2 in 1 molecule, can contain the different aliphatic substitution of more than 2 in 1 molecule.
In addition, preferably mixing contains sugar ester of more than two kinds.Also preferably simultaneously containing there is the sugar ester of aromatic substituents and there is the sugar ester of aliphatic substitution.
< synthesis example: the synthesis example > of the sugar ester that general formula (A) represents
Below, an example of the synthesis being applicable to sugar ester of the present invention is shown.
In the four-hole boiling flask possessing stirring apparatus, reflux cooler, thermometer and nitrogen ingress pipe, add sucrose 34.2g (0.1 mole), benzoyl oxide 180.8g (0.8 mole) and pyridine 379.7g (4.8 moles) respectively, under agitation limit is blown into the intensification of nitrogen limit from nitrogen ingress pipe, carries out 5 hours esterifications at 70 DEG C.Next, 4 × 10 are decompressed to by flask 2below Pa, after heating up in a steamer excessive pyridine, is decompressed to 1.3 × below 10Pa by flask, is warming up to 120 DEG C at 60 DEG C, heats up in a steamer the benzoic major part of benzoyl oxide, generation.Then, then add the aqueous sodium carbonate 300g of toluene 1L, 0.5 quality %, after stirring 30 minutes at 50 DEG C, leave standstill, isolate toluene layer.Finally, add water 100g to isolated toluene layer, wash after 30 minutes at normal temperatures, isolate toluene layer, under reduced pressure (4 × 10 2below Pa), 60 DEG C heat up in a steamer toluene, obtain the potpourri of compd A-1, A-2, A-3, A-4 and A-5.Resolve the potpourri obtained with HPLC and LC-MASS, result A-1 is 7 quality %, A-2 be 58 quality %, A-3 be 23 quality %, A-4 be 9 quality %, A-5 is 3 quality %, and the average ester degree of substitution of sugar ester is 6.57.Should illustrate, utilize the part of silica gel column chromatography to the potpourri obtained to refine, obtain A-1, A-2, A-3, A-4 and A-5 of purity 100% respectively.
The addition of this sugar ester relative to acryl resin preferably to add in the scope of 0.1 ~ 20 quality %, more preferably to add in the scope of 1 ~ 15 quality %.
Preferred film A of the present invention contains following ester (polycondensation ester) in addition.
(polycondensation ester)
In film A of the present invention, as one of plastifier, preferably use the ester beyond sugar ester.
As the ester beyond sugar ester used in the present invention, be not particularly limited, preferably use the polycondensation ester with the structure that following general formula (1) represents.
This polycondensation ester is considered from its plasticization effect, in film A of the present invention, preferably to contain in the scope of 1 ~ 20 quality %, more preferably to contain in the scope of 2 ~ 15 quality %.
General formula (1)
B 3－(G 2－A) n－G 2－B 4
In above-mentioned general formula (1), B 3and B 4various places represent aliphatics or aromatic monocarboxylate's residue or hydroxyl independently.G 2represent that the aklylene glycol residue of carbon number 2 ~ 12, the aryl-diol residue of carbon number 6 ~ 12 or carbon number are the oxyalkylene diol residue of 4 ~ 12.A represents the alkylene dicarboxylic acids residue of carbon number 4 ~ 12 or aryl dicarboxylic acid's residue of carbon number 6 ~ 12.N represents the integer of more than 1.
In the present invention, polycondensation ester is the polycondensation ester containing the repetitive making dicarboxylic acid and glycol react and obtain, and A represents the carboxylic acid residues in polycondensation ester, G 2represent alcohol residue.
The dicarboxylic acid forming polycondensation ester is aromatic dicarboxylic acid, aliphatic dicarboxylic acid or ester ring type dicarboxylic acid, is preferably aromatic dicarboxylic acid.Dicarboxylic acid can be a kind, also can be potpourri of more than two kinds.Particularly preferably mixed aromatic, aliphatics.
The glycol forming polycondensation ester is aromatic diol, aliphatic diol or ester ring type glycol, is preferably aliphatic diol, is more preferably the glycol of carbon number 1 ~ 8.Glycol can be a kind, also can be potpourri of more than two kinds.
Wherein, preferably comprise and make at least containing the repetitive that the dicarboxylic acid of aromatic dicarboxylic acid and the glycol of carbon number 1 ~ 8 react and obtain, more preferably comprise the repetitive making to react containing aromatic dicarboxylic acid and the dicarboxylic acid of aliphatic dicarboxylic acid and the glycol of carbon number 1 ~ 8 and obtain.
Two ends of the molecule of polycondensation ester can by end-blocking, also can not by end-blocking.
As the concrete example of the alkylene dicarboxylic acids of the A of formation general formula (1), comprise by 1,2-ethane dicarboxylic acid (succinic acid), 1,3-propane dicarboxylic acid (glutaric acid), 1,4-butane dicarboxylic acid (hexane diacid), 1, the divalent group that 5-pentanedicarboxylic acid (heptandioic acid), 1,8-octane dicarboxylic acid (decanedioic acid) etc. are derivative.As the concrete example of the alkenylene dicarboxylic acids of formation A, maleic acid, fumaric acid etc. can be enumerated.As the concrete example of the aryl dicarboxylic acid of formation A, 1,2-phthalic acid (phthalic acid), 1,3-phthalic acid, Isosorbide-5-Nitrae-phthalic acid, 1,5-naphthalenedicarboxylic acid etc. can be enumerated.
A can be a kind, also can combine two or more.Wherein, the combination of the alkylene dicarboxylic acids of the preferred carbon number 4 ~ 12 of A and the aryl dicarboxylic acid of carbon number 8 ~ 12.
G in general formula (1) 2represent the divalent group that the divalent group derived by the aklylene glycol of carbon number 2 ~ 12, the divalent group derived by the aryl-diol of carbon number 6 ~ 12 or the oxyalkylene glycol by carbon number 4 ~ 12 derive.
G 2in the divalent group derived by the aklylene glycol of carbon number 2 ~ 12 example in comprise by ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 2-propylene glycol, 2-methyl isophthalic acid, ammediol, 1, 4-butylene glycol, 1, 5-pentanediol, 2, 2-dimethyl-1, ammediol (neopentyl glycol), 2, 2-diethyl-1, ammediol (3, 3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1, ammediol (3, 3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol, 1, 6-hexanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol and 1, the divalent group that 12-octacosanol etc. are derivative.
G 2in the divalent group derived by the aryl-diol of carbon number 6 ~ 12 example in comprise by 1,2-dihydroxy benzenes (catechol), 1, the divalent group that 3-dihydroxy benzenes (resorcinol), Isosorbide-5-Nitrae-dihydroxy benzenes (p-dihydroxy-benzene) etc. are derivative.The example of the divalent group that the oxyalkylene glycol being 4 ~ 12 by carbon number in G derives comprises by the derivative divalent group such as diethylene glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol.
G 2can be a kind, also can combine two or more.Wherein, G 2be preferably by the derivative divalent group of the aklylene glycol of carbon number 2 ~ 12, be more preferably 2 ~ 5, most preferably be 2 ~ 4.
B in general formula (1) 3and B 41 valency group or the hydroxyl derived by monocarboxylic acid or the aliphatic monocarboxylic acid containing aromatic rings respectively.
By the carboxylic acid that the monocarboxylic acid containing aromatic rings in the 1 valency group derived containing the monocarboxylic acid of aromatic rings is containing aromatic rings in molecule, not only comprise aromatic rings directly and the carboxylic acid of carboxylic-bond, also comprise aromatic rings via the carboxylic acid with carboxylic-bond such as alkylidene.The example of the 1 valency group derived by the monocarboxylic acid containing aromatic rings comprises by the 1 derivative valency group such as benzoic acid, p-tert-butyl benzoic acid, o-toluic acid, m-methyl benzoic acid, p-methylbenzoic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid, phenylacetic acid, 3-phenylpropionic acid.Wherein preferred benzoic acid, p-methylbenzoic acid.
The example of the 1 valency group derived by aliphatic monocarboxylic acid comprises by acetic acid, propionic acid, butyric acid, the 1 valency group that sad, caproic acid, capric acid, dodecylic acid, stearic acid, oleic acid etc. are derivative.Wherein, the 1 valency group that the alkyl monocarboxylate being preferably 1 ~ 3 by the carbon number of moieties derives, more preferably acetyl group (the 1 valency group derived by acetic acid).
The weight-average molecular weight of polycondensation ester of the present invention is preferably in the scope of 500 ~ 3000, is more preferably in the scope of 600 ~ 2000.Weight-average molecular weight can utilize above-mentioned gel permeation chromatography (GPC) to measure.
Below, the concrete example of the polycondensation ester with the structure that general formula (1) represents is shown, but is not limited thereto.
Below, the concrete synthesis example of the polycondensation ester of above-mentioned explanation is recorded.
< polycondensation ester P1 >
Using ethylene glycol 180g, phthalic anhydride 278g, hexane diacid 91g, benzoic acid 610g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 230 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted ethylene glycol decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P1 thus.Acid number is 0.20, and number-average molecular weight is 450.
< polycondensation ester P2 >
By 1,2-propylene glycol 251g, phthalic anhydride 244g, hexane diacid 103g, benzoic acid 610g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 230 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted 1,2-PD decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P2 thus.Acid number is 0.10, and number-average molecular weight is 450.
< polycondensation ester P3 >
By 1,4-butylene glycol 330g, phthalic anhydride 244g, hexane diacid 103g, benzoic acid 610g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 230 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted BDO decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P3 thus.Acid number is 0.50, and number-average molecular weight is 2000.
< polycondensation ester P4 >
By 1,2-propylene glycol 251g, terephthalic acid (TPA) 354g, benzoic acid 610g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 230 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted 1,2-PD decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P4 thus.Acid number is 0.10, and number-average molecular weight is 400.
< polycondensation ester P5 >
By 1,2-propylene glycol 251g, terephthalic acid (TPA) 354g, p-methylbenzoic acid 680g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 230 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted 1,2-PD decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P5 thus.Acid number is 0.30, and number-average molecular weight is 400.
< polycondensation ester P6 >
Using the hexane diacid of the 1,2-PD of 180g, 292g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 200 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted 1,2-PD decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P6 thus.Acid number is 0.10, and number-average molecular weight is 400.
< polycondensation ester P7 >
By 1 of 180g, 2-propylene glycol, phthalic anhydride 244g, hexane diacid 103g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 200 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted 1,2-PD decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P7 thus.Acid number is 0.10, and number-average molecular weight is 320.
< polycondensation ester P8 >
Using ethylene glycol 251g, phthalic anhydride 244g, succinic acid 120g, acetic acid 150g, drop into as the tetraisopropyl titanate 0.191g of esterification catalyst the four-hole boiling flask of 2L possessing thermometer, stirrer, pipe ball cooling tube, in nitrogen stream, be slowly warming up to 200 DEG C while stirring.Limit is observed degree of polymerization limit and is carried out dehydration condensation.At 200 DEG C, unreacted ethylene glycol decompression is heated up in a steamer after reaction terminates, obtain polycondensation ester P8 thus.Acid number is 0.50, and number-average molecular weight is 1200.
(film of stepped construction: (TAC/ acrylic acid/TAC) film)
Preferred film A of the present invention is the film of stepped construction, be the formation of corticated at least 3 layers of the both sides tool at sandwich layer, this sandwich layer contains acryl resin, this cortex contains cellulose esters, so by overlapping different types of resin, easily the size changing rate that above-mentioned formula (1) ~ (4) represent is controlled in desired scope.
In this instructions, " sandwich layer " refers to the layer that in the layer of film, thickness is the thickest, and " cortex " refers to that Film Thickness Ratio is somebody's turn to do " sandwich layer " thin layer.In addition, in the present invention, have further " cortex " in " sandwich layer " side of the film of the stepped construction of " sandwich layer " and " cortex ", the thickness in this case, being configured at " cortex " of the both sides of " sandwich layer " can be the same or different.
Acryl resin contained by sandwich layer can suitably use aforesaid propylene acid resin, adjuvant etc.
Cellulose esters contained by cortex is not particularly limited; as concrete cellulose esters; be preferably selected from (two; three) at least a kind in cellulose acetate, cellulose propionate, cellulose butyrate, cellulose-acetate propionate, cellulose acetate-butyrate, cellulose acetate phthalate and phthalate, cellulose; from the excellent adhesion with the polarizer; the viewpoint that the strain of the film that change reduced in size causes and bonding agent part produces is considered, particularly preferably the average substitution degree of acetyl group is the cellulose triacetate in the scope of 2.6 ~ 2.95.
In addition, preferably the adjuvants such as plastifier described later, ultraviolet light absorber, antioxidant, anti-deterioration agent, stripping auxiliary agent, surfactant, dyestuff, particulate are contained in sandwich layer and cortex.
As the method manufacturing film A of the present invention, preferred masking is multilayer casting film simultaneously, preferred curtain coating altogether described later.
For the situation of common curtain coating, be just not particularly limited as long as the above-mentioned sandwich layer of Film Thickness Ratio of the thickness cortex of each layer is thin, preferred cortex is 0.2 ~ 50% of the total thickness of film A, is more preferably the thickness of 2 ~ 30%.Total film thickness due to this film A is in the scope of 20 ~ 60 μm, so preferably adjust the thickness of sandwich layer and the thickness of cortex in above-mentioned scope.
(film of mixing acryl resin and cellulose esters)
Film A of the present invention can mix acryl resin and cellulose esters uses.During mixing, acryl resin is preferably acryl resin with the mixing quality ratio of cellulose esters: in the scope of cellulose esters=95:5 ~ 50:50, from the viewpoint of the behavior of the change in size controled environment caused by variation, more preferably in the scope of 90:10 ~ 70:30.
Acryl resin can from above-mentioned acryl resin suitably choice for use.As cellulose esters; also the resin that above-mentioned cortex contains can be used; more preferably in the scope using the average substitution degree of acetyl group to be cellulose triacetate in the scope of 2.6 ~ 2.95 or total total degree of substitution of acyl group to be 2.0 ~ 2.9 and the degree of substitution of acetyl group is 0.1 ~ 1.9 and the degree of substitution of propiono is the cellulose-acetate propionate of 1.1 ~ 2.8, this cellulose-acetate propionate is particularly preferably used.
" film B: cellulose acetate membrane "
The feature of film B of the present invention is, thickness is in the scope of 20 ~ 60 μm, and the average substitution degree containing acetyl group is the cellulose acetate in the scope of 2.0 ~ 2.5.Thickness is more preferably in the scope of 20 ~ 40 μm.If be within the scope of this, then possess sufficient rigidity, the characteristic of operability excellence can be obtained, easily make film polarizer.
(cellulose acetate)
The feature of film B of the present invention is to be formed for major component with the cellulose acetate of the average substitution degree of acetyl group in the scope of 2.0 ~ 2.5.The major component mentioned in the present invention refers in the cellulose acetate forming cellulose acetate membrane; ratio cellulose acetate shared by of average substitution degree in the scope of 2.0 ~ 2.5 of acetyl group is more than 60 quality %; be preferably more than 80 quality %, be more preferably more than 95 quality %.More preferably the average substitution degree of this acetyl group is in the scope of 2.1 ~ 2.4, and the behavior of so easily controlling dimension change, the presenting property of phase differential is also high in addition, can use as phase retardation film.
The average substitution degree of the acetyl group in cellulose acetate can measure based on ASTM-D817-96 and obtain.
In the present invention, as long as the average substitution degree of acetyl group of the cellulose acetate adopted is in above-mentioned scope, just can present effect of the present invention, and curtain coating adaptability when realizing masking is high, as the characteristic such as operability excellence of film.
In addition, the number-average molecular weight (Mn) of above-mentioned cellulose acetate is preferably in the scope of 80000 ~ 155000, is more preferably in the scope of 90000 ~ 152000.In addition, weight-average molecular weight (Mw) is preferably in the scope of 120000 ~ 310000.Weight-average molecular weight (Mw) is preferably in the scope of 1.4 ~ 2.5 with the ratio (Mw/Mn) of number-average molecular weight (Mn), is more preferably in the scope of 1.5 ~ 2.0.
The mean molecular weight (Mn, Mw) of above-mentioned cellulose acetate can utilize gel permeation chromatography respectively.Condition determination is described above.
Cellulose acetate of the present invention can with method manufactures such as customary way such as sulfuric acid catalysis method, Acetic, methylene chloride methods, starting material are not particularly limited, and can enumerate velveteen, wood pulp (derive from conifer, derive from broad leaf tree), mestha etc.The cellulose acetate obtained by them in addition separately can be used in combination in arbitrary ratio.In addition, cellulose acetate of the present invention can see, for example the method synthesis recorded in No. 10-45804, Japanese Unexamined Patent Publication, No. 2005-281645, Japanese Unexamined Patent Publication.
(sugar ester and the polycondensation ester with the structure that above-mentioned general formula (1) represents)
From the viewpoint of the speed of adjust size change, preferred film B of the present invention contains above-mentioned sugar ester or the above-mentioned polycondensation ester with the structure that general formula (1) represents in the same manner as film A.
This sugar ester and the content of this polycondensation ester in film B are preferably in the scope of 1 ~ 20 quality %, are more preferably in the scope of 2 ~ 15 quality %.
(other adjuvant)
Preferred film A of the present invention and film B contains the adjuvants such as plastifier, ultraviolet light absorber, antioxidant, anti-deterioration agent, stripping auxiliary agent, surfactant, dyestuff, particulate.Below, these adjuvant is described, in film A and film B, preferably suitably adjusts the kind of adjuvant, addition and using.Below, film A and film B is called diaphragm to be described.
(polyol ester)
Also contain the polyol ester that following general formula (2) represents in preferred diaphragm of the present invention.
General formula (2)
B 1－G－B 2
In above-mentioned general formula (2), B 1and B 2various places represent aliphatics or aromatic monocarboxylate's residue independently.G represents that carbon number is the aklylene glycol residue with straight chain or branched structure of 2 ~ 12.
In general formula (2), G represents by the derivative divalent group of the aklylene glycol with straight chain or branched structure of carbon number 2 ~ 12.
In the example of the divalent group derived by the aklylene glycol of carbon number 2 ~ 12 in G, can enumerate by ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 2-propylene glycol, 2-methyl isophthalic acid, ammediol, 1, 4-butylene glycol, 1, 5-pentanediol, 2, 2-dimethyl-1, ammediol (neopentyl glycol), 2, 2-diethyl-1, ammediol (3, 3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1, ammediol (3, 3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol, 1, 6-hexanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol and 1, the divalent group that 12-octacosanol etc. are derivative.Also preferably aklylene glycol mixes two or more use.
In general formula (2), B 1and B 2various places are the 1 valency group derived by monocarboxylic acid or the aliphatic monocarboxylic acid containing aromatic rings independently.
By the carboxylic acid that the monocarboxylic acid containing aromatic rings in the 1 valency group derived containing the monocarboxylic acid of aromatic rings is containing aromatic rings in molecule, not only comprise aromatic rings directly and the carboxylic acid of carboxylic-bond, also comprise aromatic rings via the carboxylic acid with carboxylic-bond such as alkylidene.The example of the 1 valency group derived by the monocarboxylic acid containing aromatic rings comprises by the 1 derivative valency group such as benzoic acid, p-tert-butyl benzoic acid, o-toluic acid, m-methyl benzoic acid, p-methylbenzoic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid, phenylacetic acid, 3-phenylpropionic acid.Wherein preferred benzoic acid, p-methylbenzoic acid.
The example of the 1 valency group derived by aliphatic monocarboxylic acid comprises by acetic acid, propionic acid, butyric acid, the 1 valency group that sad, caproic acid, capric acid, dodecylic acid, stearic acid, oleic acid etc. are derivative.Wherein, the 1 valency group that the alkyl monocarboxylate being preferably 1 ~ 10 by the carbon number of moieties derives, more preferably acetyl group (the 1 valency group derived by acetic acid).
Below, the concrete example of spendable polyol ester in the present invention is shown, but the invention is not restricted to these illustrative compounds.
The polyol ester with the structure that general formula (2) represents of the present invention relative to diaphragm preferably to contain in the scope of 0.5 ~ 5 quality %, more preferably to contain in the scope of 1 ~ 3 quality %, particularly preferably to contain in the scope of 1 ~ 2 quality %.
The polyol ester with the structure that general formula (2) represents of the present invention can synthesize according to known general synthetic method all the time.
(phosphate)
Diaphragm of the present invention can use phosphate.As phosphate, triaryl phosphate, diaryl phosphate, aryl phosphate, arylphosphonic acid compound, aryl oxidized phosphine compound, condensation aryl phosphate ester, halogenated alkyl phosphate, Halogen condensed phosphoric acid esters, Halogen condensation phosphonate ester, Halogen phosphite ester etc. can be enumerated.
As concrete phosphate, triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenyl-phosphonic acid, tricresyl phosphate (β-chloroethyl) ester, three (two chloropropyls) phosphate, three (tribromo neopentyl) phosphate etc. can be enumerated.
(the ester class of glycollic acid)
In addition, in the present invention, as a kind of polyol ester class, the ester class (ethyl glycolate compound) of glycollic acid can be used.
As ethyl glycolate compound spendable in the present invention, be not particularly limited, preferably can use alkyl phthalic acyl ethyl glycolate class.
As alkyl phthalic acyl ethyl glycolate class, such as, can enumerate methyl phthalyl ylmethyl ethyl glycolate, ethyl phthalyl, propyl group phthalyl propyl group ethyl glycolate, butyl phthalyl butyl alcohol acid esters, octyl phthalyl octyl ethyl glycolate, methyl phthalyl base ethyl hexanol acid esters, ethylphthalyl ethyl glycolate methyl ethanol acid esters, ethylphthalyl ethyl glycolate propyl group ethyl glycolate, methyl phthalyl base butyl alcohol acid esters, ethylphthalyl ethyl glycolate butyl alcohol acid esters, butyl phthalyl methyl ethanol acid esters, butyl phthalyl, propyl group phthalyl butyl alcohol acid esters, butyl phthalyl propyl group ethyl glycolate, methyl phthalyl Ji Xinji ethyl glycolate, ethylphthalyl ethyl glycolate octyl group ethyl glycolate, octyl phthalyl ylmethyl ethyl glycolate, octyl phthalyl base ethyl hexanol acid esters etc., preferred ethyl phthalyl.
(ultraviolet light absorber)
Consider from the sunproof viewpoint of raising, preferred diaphragm of the present invention contains ultraviolet light absorber.Ultraviolet light absorber object be by absorb below 400nm ultraviolet and improve photostability, be particularly preferably in the scope of 2 ~ 30% in the transmissivity of wavelength 370nm, be more preferably in the scope of 4 ~ 20%, more preferably 5 ~ 10% scope in.
The ultraviolet light absorber preferably used in the present invention is benzotriazole system ultraviolet light absorber, benzophenone series ultraviolet light absorber, triazine system ultraviolet light absorber, is particularly preferably benzotriazole system ultraviolet light absorber and benzophenone series ultraviolet light absorber.
Such as, there is the chloro-2-(3 of 5-, 5-di-sec-butyl-2-hydroxy phenyl)-2H-benzotriazole, (2-2H-benzotriazole-2-base)-6-(straight chain and side chain dodecyl)-4-methylphenol, 2-hydroxyl-4-behzyloxybenzophenone, 2,4-behzyloxybenzophenone etc., in addition, there are the Tinuvin classes such as Tinuvin109, Tinuvin171, Tinuvin234, Tinuvin326, Tinuvin327, Tinuvin328, Tinuvin928, these are the commercially available product of BASFJAPAN Inc., can preferably use.Wherein preferably halogen-free material.
In addition, also preferably use has the discoid compounds such as the compound of 1,3,5-triazines ring as ultraviolet light absorber.
Diaphragm of the present invention is preferably containing ultraviolet light absorber of more than two kinds.
In addition, as ultraviolet light absorber, also preferably use polymeric UV absorber, the ultraviolet light absorber of the polymer type particularly preferably using Japanese Unexamined Patent Publication 6-148430 publication to record.In addition, preferred ultraviolet light absorber does not have halogen group.
The adding method of ultraviolet light absorber adds in coating after ultraviolet light absorber can being dissolved in the organic solvent such as the alcohol such as methyl alcohol, ethanol, butanols or methylene chloride, methyl acetate, acetone, dioxolanes or their mixed solvent, or directly add in coating composition.
As inorganic particle, be insoluble to the material of organic solvent, stirring machine, sand mill can be used to add in coating after dispersion in organic solvent and cellulose esters (cellulose acetate).
The use amount of ultraviolet light absorber is according to the difference such as kind, service condition of ultraviolet light absorber; when the dry film thickness of diaphragm is in the scope of 15 ~ 50 μm; relative in the scope that diaphragm is preferably 0.5 ~ 10 quality %, be more preferably in the scope of 0.6 ~ 4 quality %.
(antioxidant)
Antioxidant is also referred to as anti-deterioration agent.When being placed with organic electro luminescent display device etc. under the state of high humidity high temperature, sometimes cause the deterioration of diaphragm.
Antioxidant owing to having the effect such as delayed or prevent because the halogen of the residual solvent amount in diaphragm, the phosphoric acid etc. of phosphoric acid system plastifier cause diaphragm to decompose, so preferably contain in diaphragm of the present invention.
As such antioxidant, the compound of preferred use hindered phenol system, such as can enumerate 2, 6-di-t-butyl-paracresol, pentaerythrite-four (3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester), triethylene glycol-bis-(3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester), 1, 6-hexanediol-bis-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester), 2, 4-pair-(n-octyl sulphur)-6-(4-hydroxyl-3, 5-di-tert-butyl amido)-1, 3, 5-triazine, 2, 2-sulphur-di ethylene bis (3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester), octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxy-hydrocineamide), 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester etc.
Particularly preferably 2,6-di-t-butyls-paracresol, pentaerythrite-four (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester), triethylene glycol-bis-(3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester).In addition, such as, can be used together N, the phosphorus system processing stabilizers such as metal passivator, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester of the hydrazine systems such as N '-bis-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hydrazine.
The addition of these compounds is preferably in the scope of 1ppm ~ 1.0% in mass ratio relative to diaphragm, is more preferably in the scope of 10 ~ 1000ppm.
(particulate (matting agent))
In order to improve smoothness of the surface, diaphragm can also contain particulate (matting agent) as required.
Particulate can be inorganic particles also can be organic fine particles.The example of inorganic particles comprises silicon dioxide (silicon dioxide), titania, aluminium oxide, zirconia, calcium carbonate, calcium carbonate, talcum, clay, fires porcelain earth, fires calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate etc.Wherein, preferred silicon dioxide, zirconia, in order to the mist degree reducing the film obtained increases, more preferably silicon dioxide.
The example of the particulate of silicon dioxide comprise AerosilR972, R972V, R974, R812,200,200V, 300, R202, OX50, TT600, NAX50 (above is Japanese Aerosil Co., Ltd. system), SeahostarKE-P10, KE-P30, KE-P50, KE-P100 (above is Nippon Shokubai Co., Ltd's system) etc.Wherein, because the turbidity of the film obtained can keep lower by AerosilR972V, NAX50, SeahostarKE-P30 etc., and friction factor can be reduced, so particularly preferably.
The primary particle size of particulate is preferably in the scope of 5 ~ 50nm, is more preferably in the scope of 7 ~ 20nm.Primary particle size is larger, and the effect improving the slickness of the film obtained is larger, but the transparency more easily reduces.Therefore, particulate also can contain with the form of the secondary aggregation body in the scope of particle diameter 0.05 ~ 0.3 μm.The size of the primary particle of particulate or its secondary aggregation body can by by transmission electron microscope to observe primary particle or secondary aggregation body in the scope of multiplying power 50 ~ 2,000,000 times, obtain the mean value of the particle diameter of 100 primary particles or secondary aggregation body.
The content of particulate is preferably in the scope of 0.05 ~ 1.0 quality % relative to the resin forming diaphragm, is more preferably in the scope of 0.1 ~ 0.8 quality %.
(film of stepped construction: (TAC/DAC/TAC) film)
Preferred film B of the present invention is also the film of stepped construction in the same manner as film A; be the formation of corticated at least 3 layers of the both sides tool at sandwich layer; this sandwich layer contain degree of substitution with acetyl group be 2.0 ~ 2.45 scope in cellulose diacetate (DAC); this cortex contain degree of substitution with acetyl group be 2.60 ~ 2.95 scope in cellulose triacetate (TAC); so by overlapping different types of resin, easily the size changing rate that above-mentioned formula (1) ~ (4) represent is controlled in desired scope.
If the average substitution degree of the acetyl group of the cellulose triacetate contained by cortex is more than 2.6, then with the excellent adhesion of the polarizer, the generation of the strain of the film caused by change reduced in size and bonding agent part, therefore considers from this viewpoint, particularly preferably.
In addition, suitably the adjuvants such as above-mentioned plastifier, ultraviolet light absorber, antioxidant, anti-deterioration agent, stripping auxiliary agent, surfactant, dyestuff, particulate are contained in preferred sandwich layer and cortex.
Just be not particularly limited as long as the above-mentioned sandwich layer of Film Thickness Ratio of cellulose acetate membrane cortex of the present invention is thin, preferred cortex is in the scope of 0.2 ~ 50% of the total thickness of film B, is more preferably the thickness in the scope of 2 ~ 30%.Total film thickness due to this film B is in the scope of 20 ~ 60 μm, so preferably adjust the thickness of sandwich layer and the thickness of cortex in above-mentioned scope.
" manufacture method of film A and film B "
As the manufacture method of the acrylic film belonging to film A of the present invention and the cellulose acetate membrane belonging to film B, the autofrettages such as common blow moulding, T-shaped die methods, rolling process, cutting method, the tape casting, emulsion method, pressure sintering can be used, from the viewpoint of suppressing painted, suppressing foreign matter shortcoming, suppressing the optical defects etc. such as die line, film-forming method can select solution casting masking method and melting casting film method, from the viewpoint of even and level and smooth surface can be obtained, particularly preferably solution casting masking method.
(solution casting masking method)
Below, the Production Example manufacturing diaphragm of the present invention with solution casting method is described.
As the manufacture method of diaphragm of the present invention; the autofrettages such as common blow moulding, T-die methods, rolling process, cutting method, the tape casting, emulsion method, pressure sintering can be used; but from the viewpoint of suppressing painted, suppressing foreign matter shortcoming, suppressing the optical defects etc. such as die line; film-forming method can select solution casting masking method and melting casting film method, particularly preferably solution casting method.
The manufacture of diaphragm of the present invention is carried out through following operation, and described operation the adjuvants such as acryl resin, cellulose esters and above-mentioned plastifier is dissolved in solvent and prepares the operation of coating; By the operation of coating curtain coating in the metal support of banded or drum type; Coating drying after curtain coating is made the operation of basement membrane; From the operation that metal support is peeled off; The operation stretched; The operation of further drying; And the operation reeled after cooling.Preferably to contain acryl resin or cellulose acetate in the scope of 60 ~ 95 quality % in the solid constituent of diaphragm of the present invention.
Here, be described for the film-forming method of the cellulose acetate membrane as film B, but be suitable for too as the manufacture method of the acrylic film of film A.In addition, particularly for the part of the manufacture method about acrylic film in following explanation, add as acrylic film and suitably illustrate.
(1) dissolution process
Dissolution process is in dissolution kettle, to dissolve this cellulose acetate, optionally and the sugar ester of the present invention used, polycondensation ester, polyol ester or other compound and form the operation of coating in the organic solvent that is good solvent for cellulose acetate while stirring, or in this cellulose acetate solution, mix sugar ester of the present invention, polycondensation ester, polyol ester or other compound solution and form the operation of the coating as main lysate.
When manufacturing cellulose acetate membrane of the present invention with solution casting method, as long as dissolve cellulose acetate for the formation of the organic solvent of coating and other compound just can unrestrictedly use simultaneously.
Such as, as chlorine-based organic solvent, can methylene chloride be enumerated, as chlorine-free organic solvent, methyl acetate, ethyl acetate, pentyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, Isosorbide-5-Nitrae-two can be enumerated alkane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanols, 2,2,3,3-hexafluoro-1-propyl alcohol, 1,3-bis-fluoro-2-propyl alcohol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol, 2,2,3, the fluoro-1-propyl alcohol of 3,3-five, nitroethane etc., can preferably use methylene chloride, methyl acetate, ethyl acetate, acetone.
In coating, except containing except above-mentioned organic solvent, also preferably containing the straight chain of carbon number 1 ~ 4 in the scope of 1 ~ 40 quality % or the aliphatic alcohol of branched.If the ratio height of the alcohol in coating, basement membrane gelation, easily peels off from metal support, in addition, also has the effect promoting that cellulose acetate and other compound dissolve in chlorine-free organic solvent system when the ratio of alcohol is few.In the masking of cellulose acetate membrane of the present invention, from the viewpoint of the planarity improving the cellulose acetate membrane obtained, the method using the coating of determining alcohol in the scope of 0.5 ~ 15.0 quality % to be filmed can be adopted.
Particularly preferably by coating composition that cellulose acetate and other compound obtain with the solvent be dissolved in the scope amounting to 15 ~ 45 quality % containing methylene chloride and the straight chain of carbon number 1 ~ 4 or the aliphatic alcohol of branched.
As the straight chain of carbon number 1 ~ 4 or the aliphatic alcohol of branched, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, the tert-butyl alcohol can be enumerated.Also better angularly consider from the stability of coating, boiling point also lower, drying property, particular methanol and ethanol in these.
The dissolving of cellulose acetate and sugar ester, polycondensation ester, polyol ester or other compound can be adopted with the following method: the method for carrying out at ambient pressure; The method of carrying out below the boiling point of main solvent; To pressurize more than the boiling point of main solvent the method for carrying out; By the method that the hot-cold lysis method recorded in Japanese Unexamined Patent Publication 9-95544 publication, Japanese Unexamined Patent Publication 9-95557 publication or Japanese Unexamined Patent Publication 9-95538 publication is carried out; The various dissolving methods such as the method for carrying out under the high pressure recorded in Japanese Unexamined Patent Publication 11-21379 publication, particularly preferably in the method for carrying out of more than boiling point of main solvent pressurizeing.
The concentration of the cellulose acetate in coating is preferably in the scope of 10 ~ 40 quality %.Add after compound makes it dissolve and disperse to the coating in dissolving or after dissolving, filter with filtering material, after deaeration, deliver to next operation with liquid-feeding pump.
Filter preferably use trapping particle diameter 0.5 ~ 5 μm scope in and filtering material in the scope of filtered water time 10 ~ 25sec/100ml.
In the method, by the condensation product remained during particle dispersion, add main coating time the condensation product that produces to use in the scope of trapping particle diameter 0.5 ~ 5 μm and filtering material in the scope of filtered water time 10 ~ 25sec/100ml only removes condensation product.Because in main coating, the concentration ratio annex solution of particle is much lower, so also can not occur when filtering that condensation product is glutinous each other causes filter pressure to rise sharp together.
Fig. 7 is the figure of the example schematically representing the coating preparation section of preferred solution casting film-forming method in the present invention, curtain coating operation and drying process.
Large condensation product is removed from feed chamber 41, to material stock still 42 liquor charging with filtrator 44.Thereafter, various annex solution is added from material stock still 42 to main coating dissolution kettle 1.
Thereafter, main coating is filtered by main filtrator 3, adds ultraviolet light absorber annex solution online wherein from 16.
Under most cases, main coating contains the material of doing over again of about 10 ~ 50 quality %.
The following material of materials'use of doing over again: by material broken for cellulose acetate membrane fine powder; Cut from two survey parts of film the material fallen by what produce during cellulose acetate membrane masking; Roll up (former anti-) beyond the cellulose acetate membrane of the setting of film because scratch waits.
In addition, as the raw material of the resin used in coating preparation, also can preferably use in advance by granular raw materials such as cellulose acetate and other compounds.
(2) curtain coating operation
(2-1) curtain coating of coating
Curtain coating operation is that coating is delivered to compression molding 30 by liquid-feeding pump (such as compression type quantitative gear pump), in the metal support 31 of the annular of unlimited transfer, such as, casting position in the metal support such as the metal drum of stainless steel band or rotation, from the operation of compression molding slit curtain coating coating.
The preferred effects on surface of metal support in curtain coating (casting) operation has carried out the metal support of mirror finish, as metal support, preferably uses the drum having carried out plating processing with stainless steel band or foundry goods effects on surface.The width of casting is in the scope of 1 ~ 4m, is preferably in the scope of 1.5 ~ 3m, is more preferably in the scope of 2 ~ 2.8m.The surface temperature of the metal support of curtain coating operation is set in ﹣ 50 DEG C ~ solvent and does not seethe with excitement in the scope of the temperature foamed, and is more preferably set in the scope of ﹣ 30 ~ 100 DEG C.The more high rate of drying more can accelerating basement membrane of temperature, thus preferably, if but too high, basement membrane foaming sometimes, or planarity deterioration.As preferred supporter temperature, suitably determine in the scope of 0 ~ 100 DEG C, more preferably in the scope of 5 ~ 30 DEG C.Or making basement membrane gelation peel off from drum under the state containing a large amount of residual solvent by cooling is also preferred method.The method controlling the temperature of metal support is not particularly limited, and has the method blowing warm air or cold wind; Make the method that the rear side of metal support contacts with warm water.Owing to using warm water more efficiently to carry out heat trnasfer, thus the temperature shortening metal support reaches the time of certain value, thus preferably.When using warm air, consider that the evaporation latent heat of solvent can cause the temperature of basement membrane to reduce, sometimes use the warm air of more than the boiling point of solvent, and use the wind of the temperature higher than target temperature while preventing from foaming.During stripping, change the temperature of supporter and the temperature of dry wind particularly preferably in from curtain coating, carry out drying efficiently.
Preferably can adjust the shape of slit of die bearing thus make thickness easily uniform compression molding.Compression molding has clothes hanger type mould (coathangerdie), T-shaped mould etc., all can preferably use.The surface of metal support becomes minute surface.In order to improve film speed, the compression molding of more than 2 can be set in metal support, split coating content and forming cladding.
(2-2) curtain coating is total to
The film of the stepped construction of (TAC/ acrylic acid/TAC) film of the invention described above and (TAC/DAC/TAC) film and so on can use the coating containing acryl resin and the coating containing cellulose esters respectively, is bringing or curtain coating multiple coating of more than two kinds and masking on drum as supporter level and smooth.
Can by coating of more than two kinds curtain coating on supporter simultaneously, also can curtain coating on supporter respectively.When distinguishing the successively the tape casting of curtain coating, first by supporting the casting dope on side, supporter is dried to a certain degree, thereon overlapping curtain coating.In addition, when using the coating of more than 3 kinds, also can suitably combine simultaneously curtain coating (also referred to as common curtain coating) and successively curtain coating to carry out curtain coating, the film of making layer stack structure.Different from the method be coated with on the film of drying by these methods of common curtain coating or successively casting film, the border with each layer of stepped construction is indefinite, sometimes cannot the such feature of clear resolution stepped construction in the observation in cross section, there is the effect of the adaptation improving each interlayer.
Manufacture method when film A of the present invention and film B being made the film of above-mentioned stepped construction is preferably carried out with being total to curtain coating from the viewpoint of throughput rate, can use known casting method altogether.Such as when film A, multiple curtain coating mouths that can arrange from the direct of travel along metal support every certain intervals respectively curtain coating contain the solution of acryl resin and the solution containing cellulose esters makes it stacked and makes film, such as, can adopt the method recorded in each publication of Japanese Laid-Open Patent Publication 61-158414 publication, Japanese Unexamined Patent Publication 1-122419 publication, Japanese Unexamined Patent Publication 11-198285 publication etc. etc.In addition, can the solution of acryl resin be contained from 2 curtain coating mouth curtain coatings and contain the solution of cellulose esters and make its membranization, such as, the method recorded in each publications such as Japanese Patent Publication 60-27562 publication, Japanese Laid-Open Patent Publication 61-94724 publication, Japanese Laid-Open Patent Publication 61-947245 publication, Japanese Laid-Open Patent Publication 61-104813 publication, Japanese Laid-Open Patent Publication 61-158413 publication, Japanese Unexamined Patent Publication 6-134933 publication can be adopted to implement.
Fig. 8 represents that common casting mold and curtain coating form the schematic diagram of the situation of sandwich construction basement membrane.
In figure, common casting mold 50 is shown respectively, die bearing 51, layer B, layer C slit 53,55, layer A slit 54, metal support 56, layer B, layer C coating 57,59, layer A coating 58, sandwich construction basement membrane 60, layer C61, layer A62, layer B63.
(3) solvent evaporization process
Solvent evaporization process is heated on curtain coating supporter by basement membrane (paint film formed by curtain coating coating on curtain coating supporter is called basement membrane), makes the operation that solvent evaporates.
During evaporating solvent, there are the method from basement membrane cross air blow or the back side from supporter to utilize the method for liquid thermal conductivity, utilize radiation heat from method etc. that is surperficial and back side heat conduction, but the drying efficiency of rear surface liquid heat-conducting method are high, thus preferably.In addition, the method they combined also preferably is used.Preferably that the basement membrane on the supporter after curtain coating is dry on supporter under the environment of 40 ~ 100 DEG C.In order to maintain 40 ~ 100 DEG C environment under, preferably to this temperature of basement membrane upper surface blown warm air or utilize the modes such as infrared ray to heat.
From the viewpoint of surface quality, moisture-penetrability, fissility, preferably within 30 ~ 120 seconds, this basement membrane is peeled off from supporter.
(4) stripping process
Stripping process is by the operation of vaporized for solvent basement membrane in the stripping of stripping position in metal support.The basement membrane be stripped is sent to next operation.
The temperature of the stripping position in metal support is preferably in the scope of 10 ~ 40 DEG C, is more preferably in the scope of 11 ~ 30 DEG C.
Should illustrate, during the stripping of basement membrane in the metal support peeling off the moment, residual solvent amount is preferably peeled off in the scope of 50 ~ 120 quality % according to the power of drying condition, the length of metal support etc., but when the residual solvent amount more moment peels off, if basement membrane is softness too, lesion level when peeling off, easily be peeling the adhesion (Star レ) caused by tension force, nicking, therefore mixed economy speed and quality decide residual solvent amount when peeling off.
The residual solvent amount of basement membrane is defined by following formula (Z).
Formula (Z)
Residual solvent amount (%)=(before the heating of basement membrane quality-basement membrane heating after quality)/(after the heating of basement membrane quality) × 100
Should illustrate, heating when measuring residual solvent amount represents the heating carried out at 115 DEG C 1 hour.
Stripping tension force when stripping metal supporter and film is generally in the scope of 196 ~ 245N/m, but when easily producing fold when peeling off, preferably peels off with the tension force of below 190N/m.
In the present invention, the temperature of the stripping position in this metal support is preferably in the scope of ﹣ 50 ~ 40 DEG C, is more preferably in the scope of 10 ~ 40 DEG C, most preferably is in the scope of 15 ~ 30 DEG C.
(5) dry and stretching process
Drying process also can be divided into preparation drying process, formal drying process carries out.
(preparation drying process)
By peeling off from metal support, the basement membrane obtained is dry.The drying of basement membrane can utilize the conveying basement membrane limit, multiple roller limit configured up and down dry, as drying tenter, also can fix conveying limit, limit, the both ends drying of basement membrane with fixture.
The means of basement membrane drying are not particularly limited, hot blast, infrared ray, warm-up mill, microwave etc. generally can be utilized to carry out, but from the viewpoint of convenience, preferably carry out with hot blast.
The thermal treatment that baking temperature in the drying process of basement membrane preferably carries out 10 minutes ~ 60 minutes in glass transition temperature-5 DEG C ~ 100 of film DEG C is effective.In the scope that baking temperature is 100 ~ 200 DEG C, in the scope being more preferably 110 ~ 160 DEG C, carry out drying.
(stretching process)
Preferably cellulose acetate membrane of the present invention is stretched in MD direction and/or TD direction, preferably utilize tentering stretching device at least to stretch in TD direction and manufacture.
This stretching can be uniaxial tension or biaxial stretch-formed, is also included in a direction and stretches in biaxial stretch-formed, relaxes the tension force of other direction and the mode of shrinking.
Preferred acrylic film of the present invention becomes mode in the scope of 20 ~ 60 μm or cellulose acetate membrane with the thickness after stretching and becomes mode in the scope of 20 ~ 60 μm in MD direction and/or TD direction, preferably in TD direction with the thickness after stretching, and when the glass transition temperature of film is set to Tg, stretch in the temperature range of (Tg+15) ~ (Tg+50) DEG C.If stretched within the scope of said temperature, then easily adjust delay, in addition owing to reducing drawing stress so mist degree step-down.In addition, can be inhibited fracture generation and the polaroid protective film of the coloring excellence of planarity, film self.Preferably carry out in the scope that draft temperature is (Tg+20) ~ (Tg+40) DEG C.
Should illustrate, the glass transition temperature Tg mentioned here uses commercially available Differential Scanning Calorimetry analyzer to measure and the intermediate point glass transition temperature (Tmg) obtained according to JISK7121 (1987) with programming rate 20 DEG C/min.
The assay method of the glass transition temperature Tg of concrete blooming according to JISK7121 (1987), and uses the differential scanning calorimeter DSC220 of SeikoInstruments Co., Ltd. to measure.
Acrylic film of the present invention preferably stretches in the scope that the former width relative to TD direction is 1.05 ~ 1.5 times.By stretching in above-mentioned scope, can planarity be improved, and by the Behavior-Based control of change in size in desired scope.
In addition, basement membrane is preferably at least stretched more than 1.1 times in TD direction by cellulose acetate membrane of the present invention.The scope stretched is preferably in the scope of 1.1 ~ 1.5 times relative to former width, is more preferably in the scope of 1.05 ~ 1.3 times.If be in above-mentioned scope, then the mobile of the molecule not only in film becomes large, can obtain desired phase difference value, can also by the Behavior-Based control of the change in size of film in desired scope.
In addition, for this stretching, preferably this film is started in MD direction when residual solvent amount is more than 40 quality % after masking to stretch, preferably stretch in TD direction lower than during 40 quality % in residual solvent amount.
In order to stretch in MD direction, preferably peel off to peel off tension force for more than 130N/m, being particularly preferably in the scope of 150 ~ 170N/m.Because the basement membrane after peeling off is high residue solvent state, so by maintaining the tension force same with peeling off tension force, can stretch to MD direction.Along with basement membrane is dry, residual solvent amount reduces, and the extensibility to MD direction reduces.
Should illustrate, the stretching ratio in MD direction can be calculated by the rotational speed of band supporter and stenter running speed.
When stretching in TD direction, such as, just like the method (being called tentering mode) of carrying out whole drying process or a part of drying process in the mode of the width edge drying at the cross direction two ends at Width fixture or pin limit maintenance basement membrane shown in Japanese Laid-Open Patent Publication 62-46625 publication, wherein, the tentering mode using fixture, the pin tentering mode using pin is preferably adopted.
Cellulose acetate membrane of the present invention must have delay by stretching, in face, the length of delay Rt of length of delay Ro and thickness direction can use automatic birefraction meter AxoScan (AxoScanMuellerMatrixPolarimeter:AxoMatrix Inc.), under the environment of 23 DEG C of 55%RH, carry out three-dimensional refractive index mensuration at the wavelength of 590nm, calculated by the refractive index nx obtained, ny, nz.
From the viewpoint of the visuality improving VA mode LCD, in the face defined by following formula (i) and (ii) of preferred cellulose acetate membrane of the present invention, the length of delay Ro in direction is in the scope of 40 ~ 60nm, and the length of delay Rt of thickness direction is in the scope of 100 ~ 140nm.By cellulose acetate membrane is at least stretched on adjustment stretching ratio limit, limit, above-mentioned TD direction, can adjust in the scope of above-mentioned length of delay.
Formula (i): Ro=(n x-n y) × d (nm)
Formula (ii): Rt={ (n x+ n y)/2-n z} × d (nm)
(in formula (i) and formula (ii), n xrepresent that in direction, refractive index reaches the refractive index of maximum direction x in the face of film.N yrepresent the refractive index of direction y orthogonal with above-mentioned direction x in direction in the face of film.N zrepresent the refractive index at the thickness direction z of film.D represents the thickness (nm) of film.〕
< bending operation >
For cellulose acetate membrane of the present invention, in order to the environment of the temperature humidity adjusting environment just change after the speed of change in size, preferably basement membrane is being stretched and next in the operation of dry section drying, there is bending operation, namely, this dry section is remained on the temperature in the scope of 130 ~ 150 DEG C, and the mode utilizing conveying roller alternately to become inner side with the A face of this basement membrane and opposed relative B face in dry section bends, this bending operation is that when radius during this basement membrane of bending is set to a (mm), the value of 1/a is 0.035mm -1~ 0.050mm -1scope in, and repeat more than 50 times and make it dry lower than 120 times bending.
Figure is utilized to be described the preferred above-mentioned bending process of the present invention.But, be not limited thereto.
Fig. 9 is the schematic diagram that can be preferred for bending process device of the present invention.
Be coated with feed liquid by from mould 101 curtain coating in metal support 102, via driven roller 103 in metal support by continuous drying, form basement membrane (the address mode of the following paint film of curtain coating in metal support is designated as basement membrane).Basement membrane is become the mode drying of desired value with residual solvent amount, after pick-up point 104 is in membranaceous stripping, implement preparation drying, stretch processing (not shown), be transported to buckled zone 106, the mode utilizing a large amount of conveying rollers 105 alternately to become the inner side of conveying roller 105 with A face (face that the face contacted with metal support with basement membrane is contrary), B face (face that basement membrane contacts with metal support) is carried thus repeated flex process continuously.This bending process is carried out in the buckled zone 106 with air entry 107 and exhausr port 108, adjusts in the mode that film is bent under desired environment temperature.
The diameter of conveying roller is preferably in the scope of 90 ~ 108mm, is preferably about 1800mm between each roller.0.035mm is become with the value of 1/a when radius during bending film being set to a (mm) -1~ 0.050mm -1scope in mode determine roller diameter.
At buckled zone 106, the hot blast that have adjusted temperature is imported from air entry 107, remains on certain environment temperature by buckled zone 106, and discharge from exhausr port 108.In order to adjust the environment temperature in buckled zone 106, can carry out with infrared ray, warm-up mill etc. in addition, but preferred hot blast carries out from the viewpoint of convenience.In addition, the environment in drying device is air, but also can carry out under the non-reactive gas ambient such as nitrogen, carbon dioxide, argon.
The environment temperature during bending process of cellulose acetate membrane of the present invention is preferably in the scope of 130 ~ 150 DEG C, from the viewpoint of obtaining effect of the present invention more preferably in the scope of 135 ~ 150 DEG C.
The number of bends of cellulose acetate membrane of the present invention preferably repeats more than 50 times and lower than 120 times, more preferably repeats 70 times ~ 100 times.The bending interval of film is preferably carried out in the scope of 1 second ~ 1 minute, more preferably carries out in the scope of 2 ~ 30 seconds.
Preferably carry out in the scope that the transporting velocity of cellulose acetate membrane of the present invention is 10 ~ 150m/ minute, from the viewpoint of throughput rate, more preferably the carrying out in the scope of 15 ~ 100m/ minute of fracture.
< refrigerating work procedure >
For acrylic film of the present invention, in order to the environment of the temperature humidity adjusting environment just change after the speed of change in size, preferably by basement membrane in the operation of dry section drying, after above-mentioned basement membrane leaves this dry section, formed further across refrigerating work procedure basement membrane cooled with the speed in the scope of 50 ~ 100 DEG C/sec.
At the basement membrane that will stretch after the operation of dry section drying, formed by applying the refrigerating work procedure that cooled by basement membrane with the speed in the scope of 50 ~ 100 DEG C/sec, the state of the strand of film can be made tight, the amount of moisture that adjustment film can contain, and effectively can control the shrinkage rates of the film containing moisture, thus preferably.Cooling velocity is more preferably the speed in the scope of 70 ~ 90 DEG C/sec.
During cooling basement membrane, preferably the cooling zone 109 in such as Fig. 9 is arranged on continuously after the buckled zone 106 of above-mentioned drying process.
The mode of cooling basement membrane is not particularly limited, and cold wind nozzle, chill roll etc. generally can be used to carry out, and from the viewpoint of convenience, preferably blows cold wind from cold wind nozzle to basement membrane on above-mentioned cooled region inner edge conveying basement membrane limit and carries out.Now blow cold wind to the two sides of basement membrane and can cool basement membrane accurately, thus preferably.
< annular knurl processing >
After the thermal treatment or cooling processing of regulation, cutting cutter is set before winding cuts end and can obtain good winding form, thus preferably.More preferably annular knurl processing is carried out at cross direction both ends.
Annular knurl processing can be formed by the knurling rolls that heat by pressing.Knurling rolls are formed thin concavo-convex, can be formed concavo-convex on film by pressing it, and improve end volume.
The height of the annular knurl at the cross direction both ends of phase retardation film of the present invention is preferably in the scope of 4 ~ 20 μm, and width is preferably in the scope of 5 ~ 20mm.
In addition, in the present invention, after the above-mentioned annular knurl processing drying be preferably arranged in the film making process of film terminates, before winding.
(6) rolling step
Rolling step is the operation that residual solvent amount in basement membrane becomes winding film forming after below 2 quality %, is that below 0.4 quality % can obtain the good film of dimensional stability by making residual solvent amount.
As long as method for winding adopts the general method used, the program tension control method etc. that persevering calibrated wrench method, identical tension method, taper tension method, internal stress are constant, these methods are all applicable.
(physical property of diaphragm)
(mist degree)
The mist degree of diaphragm of the present invention preferably lower than 1%, more preferably less than 0.5%.By making mist degree lower than 1%, there is the transparency of film higher, being more easily used as the such advantage of blooming.
(equilibrium moisture content)
Diaphragm of the present invention 25 DEG C, the equilibrium moisture content of relative humidity 60% is preferably less than 4%, is more preferably less than 3%.By making equilibrium moisture content be less than 4%, easily reply humidity change, optical characteristics, size more not easily change, thus preferably.
(film length and width degree)
Preferred diaphragm of the present invention is strip, specifically, is preferably the length of about 100 ~ 10000m, is wound into roll.In addition, the width of diaphragm of the present invention is preferably more than 1m, is more preferably more than 1.4m, is particularly preferably 1.4 ~ 4m.
" polaroid "
The feature of polaroid of the present invention is it is the polaroid that the polarizer is clamped by film A of the present invention and film B via dynamic rays curing type bond layer.
When polaroid of the present invention is used as the polaroid of visible side, preferably antiglare layer or transparent hard-coating layer, antireflection layer, antistatic backing, stain-proofing layer etc. are set in the visible side of film A.
(polarizer)
The polarizer as the main composition key element of polaroid of the present invention is the element only making the light of the plane of polarization of certain orientation pass through, and the now known representational polarizer is polyethenol series polarizing coating.Have in polyethenol series polarizing coating and iodine staining is made to polyvinyl alcohol mesentery and the polarizing coating that obtains and polarizing coating dichroic dye being dyeed and obtains.
As the polarizer, the following obtained polarizer can be used, by polyvinyl alcohol water solution masking, after carrying out uniaxial tension after uniaxial tension poststaining or dyeing are carried out to it, preferably carry out permanance process with boron compound and the polarizer that obtains.The thickness of the polarizer is preferably in the scope of 2 ~ 30 μm, is particularly preferably in the scope of 2 ~ 15 μm.
In addition, the ethylene modified polyvinyl alcohol (PVA) of the content 1 ~ 4 % by mole of the ethylene unit recorded in Japanese Unexamined Patent Publication 2003-248123 publication, Japanese Unexamined Patent Publication 2003-342322 publication etc., the degree of polymerization 2000 ~ 4000, saponification degree 99.0 ~ 99.99 % by mole can also preferably be used.Wherein, hot water is preferably used to cut off the ethylene modified polyvinyl alcohol film that temperature is 66 ~ 73 DEG C.Employ polarization property and the excellent durability of the polarizer of this ethylene modified polyvinyl alcohol film, and color spot is few, is particularly preferred for large-scale liquid crystal indicator.
(polarizer of stacked membranous type)
In addition, polaroid of the present invention is film, and from the viewpoint of intensity and the filming of the polaroid that gets both, particularly preferably the thickness of the polarizer is in the scope of 2 ~ 15 μm.
As the polarizer of such film, preferably make the polarizer of stacked membranous type by the method recorded in Japanese Unexamined Patent Publication 2011-100161 publication, Japanese Patent No. 4691205 publication, Japanese Patent No. 4751481 publications, Japanese Patent No. 4804589 publication.
As an example, use the polarizer (polarizability stacked film) of stacked membranous type of the film manufactured through following operation can improve the uneven and adaptation of display as effect of the present invention, thus particularly preferably.
(manufacture method of polarizability stacked film)
The manufacture method of polarizability stacked film of the present invention comprises following operation.
A () forms polyvinyl alcohol resin layer in the one side of base material film rubber constituent being scattered in thermoplastic resin and obtains the lamination process of stacked film,
B stacked film uniaxial tension is obtained the stretching process of stretched film by (),
C the polyvinyl alcohol resin layer dichromatism pigment dyeing of stretched film is obtained the dyeing process of dyeing film by (),
D the polyvinyl alcohol resin layer of dyeing film impregnated in the solution containing crosslinking chemical and forms polarizer layer by (), obtain the cross-linking process step of cross linking membrane, and
E () is by the drying process of cross linking membrane drying
Below, each operation is described,
(a) lamination process
In this operation, so that rubber constituent is disperseed (blended dispersion) in the film of thermoplastic resin for base material film, form polyvinyl alcohol resin layer in its one side and obtain stacked film.
(base material film)
Thermoplastic resin as the matrix of base material film is preferably the excellent thermoplastic resin such as the transparency, physical strength, thermal stability, stretchability.Enumerate the concrete example of such thermoplastic resin, such as, can enumerate chain polyolefin-based resins; Cyclic polyolefin hydrocarbon system resin; (methyl) acrylic resin; Polyester based resin; Cellulose esters system resin; Polycarbonate-based resin; Polyvinyl alcohol resin; Vinyl acetate system resin; Polyarylate system resin; Polystyrene resin; Polyethersulfone system resin; Polysulfones system resin; Polyamide series resin; Polyimide system resin; And their potpourri or multipolymer etc.
The rubber constituent being scattered in thermoplastic resin is the resinous principle with caoutchouc elasticity, is usually dispersed in thermoplastic resin with the form of rubber particles.By making rubber constituent mix dispersion, the tear strength of base material film or even stretched film can be improved.As long as the resin that rubber constituent has caoutchouc elasticity is just not particularly limited, from the viewpoint of the intermiscibility with thermoplastic resin, be preferably made up of the resin of the same race or similar with the thermoplastic resin used.
Such as, when thermoplastic resin is chain polyolefin-based resins, rubber constituent can for being selected from the multipolymer of the monomer of more than two kinds in ethene and alpha-olefin.In this case, the content (polymerization ratio) forming each monomer of this multipolymer preferably lower than 90 quality %, more preferably less than 80 quality %.
When thermoplastic resin is (methyl) acrylic resin, from the viewpoint of intermiscibility, preferably containing there is the acrylic acid series polymeric compounds of caoutchouc elasticity as rubber constituent.Acrylic acid series polymeric compounds is preferably polymkeric substance based on alkyl acrylate, can be the homopolymer of alkyl acrylate, also can be more than alkyl acrylate 50 quality % and the multipolymer of other below monomer 50 quality %.
The use level of rubber constituent is preferably 5 ~ 50 quality % of thermoplastic resin, is more preferably 10 ~ 45 quality %.If the use level of rubber constituent is very few, then has and be difficult to obtain the trend that sufficient tear strength improves effect, if the use level of rubber constituent is too much, then have the trend that the operability of base material film reduces.
The method that rubber constituent is disperseed in thermoplastic resin is not particularly limited, such as, can enumerate following method: by the thermoplastic resin made respectively and rubber constituent (rubber particles) with kneader (PLASTOMILL) etc. the mixing and method of dispersion; In identical reaction vessel, also prepare rubber constituent when preparing thermoplastic resin thus obtain being dispersed with the reactor blending method etc. of the thermoplastic resin of rubber constituent.Reactor blending method improve rubber constituent degree of scatter in favourable.
(polyvinyl alcohol resin layer)
As the polyvinyl alcohol resin forming polyvinyl alcohol resin layer, such as, can enumerate polyvinyl alcohol resin and derivant thereof.As the derivant of polyvinyl alcohol resin, except polyvinyl formal, beyond polyvinyl acetal etc., also can enumerate alkene such as polyvinyl alcohol resin ethene, propylene, the unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, the material of the modification such as Arrcostab, acrylamide of unsaturated carboxylic acid.Wherein, preferably polyvinyl alcohol resin is used.
Polyvinyl alcohol resin is preferably fully saponified product.In the scope ranging preferably from 80.0 ~ 100.0 % by mole of saponification degree, be more preferably in the scope of 90.0 ~ 99.5 % by mole, more preferably in the scope of 94.0 ~ 99.0 % by mole.
The adjuvant such as plastifier, surfactant can be added as required in above-mentioned polyvinyl alcohol resin.As plastifier, can polyvalent alcohol and condensation product etc. thereof be used, such as, can illustrate glycerine, diglycerol, triglycerin, ethylene glycol, propylene glycol, polyglycol etc.The use level of adjuvant is not particularly limited, and is preferably below the 20 quality % of polyvinyl alcohol resin.
As method polyvinyl alcohol resin solution is coated on base material film, from roller rubbing methods such as line rod rubbing method, reverse coating, intaglio plate coatings, suitably can select in the known methods such as spin-coating method, silk screen rubbing method, spray rubbing method, infusion process, spray-on process.Baking temperature is such as in the scope of 50 ~ 200 DEG C, is preferably in the scope of 60 ~ 150 DEG C.Drying time is such as in the scope of 2 ~ 20 minutes.
The thickness of the polyvinyl alcohol resin layer in stacked film is preferably 3 μm ~ 50 μm, is more preferably 5 μm ~ 45 μm.If be less than 3 μm, became the thin dyeability that makes after stretching and be obviously deteriorated, if more than 50 μm, then the polarizability stacked film obtained is thickening.
From the viewpoint of filming and intensity, flexibility as the polarizer, the thickness as the polyvinyl alcohol resin layer of the polarizer used in the present invention is preferably in the scope of 2 ~ 15 μm with the film thickness gauge after following stretch processing.
(b) stretching process
This operation is carried out uniaxial tension to the stacked film possessing base material film and polyvinyl alcohol resin layer and obtains the operation of stretched film.The stretching ratio of stacked film suitably can be selected according to desired polarization characteristic, but preferably relative to the raw footage of stacked film more than 5 times and be less than 17 times, more preferably above 5 times and be less than 8 times.
The longitudinal stretching stretched preferably is carried out in stretching along the long side direction (film throughput direction) of stacked film.As longitudinal stretching mode, the drawing process etc. of drawing process between roller, compression stretching method, use stenter can be enumerated.Should illustrate, uniaxial tension is not limited to longitudinal stretching process, also can for tilting to stretch.
(c) dyeing process
This operation is the operation polyvinyl alcohol resin layer dichromatism pigment dyeing of stretched film being obtained dyeing film.As dichromatism pigment, such as, iodine, organic dyestuff etc. can be enumerated.As organic dyestuff, such as RedBR can be used, RedLR, RedR, PinkLB, RubineBL, BordeauxGS, SkyBlueLG, LemonYellow, BlueBR, Blue2R, NavyRY, GreenLG, VioletLB, VioletB, BlackH, BlackB, BlackGSP, Yellow3G, YellowR, OrangeLR, Orange3R, ScarletGL, ScarletKGL, CongoRed, BrilliantVioletBK, SupraBlueG, SupraBlueGL, SupraOrangeGL, DirectSkyBlue, DirectFastOrangeS, FastBlack etc.These dichroic substance can be used alone or two or more kinds may be used.
When using iodine as dichromatism pigment, in order to staining efficiency can be improved further, preferably further iodide are added in the staining solution containing iodine.As these iodide, such as, can enumerate potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc.
(d) cross-linking process step
This operation is carried out crosslinking Treatment to the polyvinyl alcohol resin layer of the dyeing film obtained with dichromatism pigment dyeing and obtains with the operation of the polyvinyl alcohol resin layer cross linking membrane that is polarizer layer.Cross-linking process step such as can be undertaken by being impregnated into by dyeing film in the solution (crosslinker solution) containing crosslinking chemical.As crosslinking chemical, known material all the time can be used.Such as can enumerate the boron compound such as boric acid, borax, glyoxal, glutaraldehyde etc.These materials can be used alone a kind, and also two or more kinds may be used.
(e) drying process
After the cross linking membrane obtained cleans usually, dried.Obtain polarizability stacked film thus.Cleaning is undertaken by being impregnated in by cross linking membrane in the pure water such as ion exchange water, distilled water.Water cleaning temperature is generally in the scope of 3 ~ 50 DEG C, is preferably in the scope of 4 ~ 20 DEG C.Dip time is generally in the scope of 2 ~ 300 seconds, is preferably in the scope of 5 ~ 240 seconds.Cleaning can combine the cleaning treatment and water cleaning treatment that utilize iodide solution, also can the suitably collaboration solution of the liquid alcohols such as methyl alcohol, ethanol, isopropyl alcohol, butanols, propyl alcohol.
As drying means, method (such as, natural drying, air-supply drying, heat drying) suitable arbitrarily can be adopted.Such as, baking temperature during heat drying is generally in the scope of 20 ~ 95 DEG C, is generally about 1 ~ 15 minute drying time.
Polarizability stacked film is the polarizability stacked film possessing the polarizer layer be made up of the polyvinyl alcohol resin layer of dichromatism pigment gas absorption quantity, and itself can be used as polaroid.As preferred embodiment of the present invention, formed after polarizability stacked film through above-mentioned operation, the above-mentioned polyvinyl alcohol layer of this polarizability stacked film is peeled off from base material film, uses this polyvinyl alcohol layer as the polarizer of the present invention.According to method of the present invention, the thickness of polarizer layer can be made to be less than 15 μm, therefore, it is possible to obtain the slim polarizer.In addition, the polarization property of the polarizer used in the present invention and permanance are also excellent.
[dynamic rays curing type bonding agent]
The feature of polaroid of the present invention is, fits via dynamic rays curing type bonding agent as the acrylic film of the diaphragm of above-mentioned explanation and the polarizer and cellulose acetate membrane and the polarizer.
Dynamic rays curing type bonding agent preferably uses following ultraviolet hardening bonding agent in addition.
In the present invention, by by the laminating of ultraviolet hardening bonding agent for the protection of film and the polarizer, even if the thin intensity polaroid characteristic that also high, planarity is excellent can be obtained.
(composition of ultraviolet hardening bonding agent)
As the ultraviolet hardening adhesive composite of polaroid, there will be a known the optical free radical polymerizable composition utilizing optical free radical to be polymerized, the light cationic polymerization type composition utilizing light cationic polymerization and also use the hybrid composition of light free radical polymerization and light cationic polymerization.
As optical free radical polymerizable composition, there will be a known the composition comprising free-radical polymerised compound containing hydroxyl, carboxyl isopolarity group and the not free-radical polymerised compound of polar functionalities with special ratios recorded in Japanese Unexamined Patent Publication 2008-009329 publication) etc.Particularly preferably free-radical polymerised compound is the compound with the ethylenic unsaturated link that can carry out free radical polymerization.The preference with the compound of the ethylenic unsaturated link that can carry out free radical polymerization comprises the compound with (methyl) acryloyl group.The example with the compound of (methyl) acryloyl group comprises N and replaces (methyl) acrylamide based compound, (methyl) acrylate based compound etc.(methyl) acrylamide refers to acrylamide or Methacrylamide.
In addition, as light cationic polymerization type composition, the ultraviolet hardening adhesive composite that the light display contrasting the long wavelength of 380nm containing (α) cationically polymerizable compound, (β) light cationic polymerization initiators, (γ) disclosed in Japanese Unexamined Patent Publication 2011-028234 publication shows the photosensitizer of maximum absorption and each composition of (δ) naphthalene system photosensitizer additive can be enumerated.But also can use the ultraviolet hardening bonding agent beyond it.
(pretreatment procedure)
Pretreatment procedure is the operation of diaphragm and the bonding plane of the polarizer being carried out to easy bonding process.On the two sides of the polarizer respectively the bonding film A as diaphragm and film B time, with the bonding plane of the polarizer, easy bonding process is carried out respectively to each diaphragm.As easy bonding process, corona treatment, Cement Composite Treated by Plasma etc. can be enumerated.
(painting process of ultraviolet hardening bonding agent)
As the painting process of ultraviolet hardening bonding agent, in the bonding plane of the polarizer and diaphragm, at least one party is coated with above-mentioned ultraviolet hardening bonding agent.When the direct coated UV line curing type bonding agent in the surface of the polarizer or diaphragm, its coating process is not particularly limited.Such as, the various wet mode such as scraper, line rod, mould painting machine, comma coater, gravure coater can be utilized.In addition, also can utilize and make ultraviolet hardening bonding agent curtain coating to after between the polarizer and diaphragm, carrying out pressurizeing with roller etc. makes the method for its even expansion.
(bonding process)
After utilizing above-mentioned method coated UV line curing type bonding agent, use bonding process process.Such as, in this bonding process, in previous painting process when the surface coating ultraviolet curing type bonding agent of the polarizer, overlapping protection film thereon.In addition, first when the mode of the surface coating ultraviolet curing type bonding agent of diaphragm, the overlapping polarizer thereon.In addition, make ultraviolet hardening bonding agent curtain coating between the polarizer and diaphragm time, the overlapping polarizer and diaphragm in this condition.And, usually clamp with backer roll etc. from the diaphragm side on two sides and pressurize in this condition.The material of backer roll can use metal, rubber etc.The backer roll being configured at two sides can, for identical material, also can be different materials.
(curing process)
In curing process; to uncured ultraviolet hardening bonding agent irradiation ultraviolet radiation; make containing cationically polymerizable compound (such as; epoxy compound, oxetane compound), free-radical polymerised compound (such as; acrylate based compound, acrylamide based compound etc.) the solidification of ultraviolet hardening bond layer, be bonded together via the polarizer of ultraviolet hardening bonding agent overlap and diaphragm or the polarizer and phase retardation film.When the one side laminating diaphragm of the polarizer, active energy beam can irradiate from the either side polarizer side or diaphragm side.In addition; when the two sides of polarizer laminating diaphragm and phase retardation film; preferably to distinguish the state of overlapping protection film and phase retardation film via ultraviolet hardening bonding agent on the two sides of the polarizer, irradiation ultraviolet radiation, makes the ultraviolet hardening bonding agent on two sides solidify simultaneously.
As long as ultraviolet irradiation condition is the condition of the ultraviolet hardening bonding agent solidification that can make to use in the present invention, then can adopt condition suitable arbitrarily.Ultraviolet irradiation amount is preferably 50 ~ 1500mJ/cm with accumulative quantometer 2scope in, be more preferably 100 ~ 500mJ/cm 2scope in.
When carrying out the manufacturing process of polaroid with tinuous production, line speed was determined according to the set time of bonding agent, was preferably in the scope of 1 ~ 500m/min, was more preferably in the scope of 5 ~ 300m/min, in the scope of more preferably 10 ~ 100m/min.If line speed is more than 1m/min, then can guarantee throughput rate, or the damage to diaphragm A can be suppressed, the polaroid of excellent in te pins of durability can be made.In addition, if line speed is below 500m/min, then the solidification of ultraviolet hardening bonding agent is abundant, can be formed and possess aimed hardness and ultraviolet hardening bond layer excellent in adhesion.
" liquid crystal indicator "
By the polaroid being fitted with diaphragm of the invention described above is used for liquid crystal indicator, various visual excellent liquid crystal indicator of the present invention can be made.
Polaroid of the present invention can be used for the liquid crystal indicator of STN, TN, OCB, HAN, VA (MVA, PVA), the various type of drive such as IPS, OCB.Preferred VA (MVA, PVA) type liquid crystal indicator.
Usually use the polaroid of visible side and these 2 polaroids of polaroid of backlight side in liquid crystal indicator, also preferred polaroid polaroid of the present invention being used as both sides, is also preferably used as the polaroid of side.Particularly preferably polaroid of the present invention is used as the polaroid of the visible side directly contacted with external environment condition, now, preferred acrylic film of the present invention is configured at visible side, and cellulose acetate membrane of the present invention is configured at liquid crystal cell side as phase retardation film.
In addition, the polaroid of backlight side also can use the polaroid beyond the present invention, the two sides being now preferably used in the polarizer is fitted with such as commercially available cellulose ester membrane (such as, KonicaMinoltaTACKC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, it is more than Konica Minolta Opto Inc.'s system, FUJITACT40UZ, FUJITACT60UZ, FUJITACT80UZ, FUJITACTD80UL, FUJITACTD60UL, FUJITACTD40UL, FUJITACR02, FUJITACR06, be more than FujiFilm Co., Ltd. etc.) polaroid.
In addition, as the polaroid of backlight side, also preferably use following obtained polaroid, namely the liquid crystal cell side of the polarizer uses cellulose acetate membrane of the present invention, and the polaroid of fit on the face of opposition side above-mentioned commercially available cellulose ester membrane, polycarbonate membrane or cyclo-olefin-polymer films.
The polaroid of the application of the invention, even if particularly picture is the liquid crystal indicator of the large picture of more than 30 cun, also can obtain showing the visual excellent liquid crystal indicator such as inequality, front contrast.
In addition, polaroid of the present invention, except for except liquid crystal indicator, is also preferred for organic electroluminescence display device and method of manufacturing same.
Embodiment
Below, enumerate embodiment and the present invention is specifically described, but the invention is not restricted to these embodiments.Should illustrate, in embodiment, use the expression of " part " or " % " then to represent " mass parts " or " quality % " unless otherwise specified.
Embodiment 1
The making > of < film A and film B
(making of film A-101)
According to following method, make the film containing acryl resin, i.e. film A-101.
(preparation of microparticulate dilution)
With Aerosil972V (the Japanese Aerosil Inc. of stirring machine by 10 mass parts, mean grain size a: 16nm, apparent specific gravity 90g/L) and after the ethanol of 90 mass parts is uniformly mixed 30 minutes, use the Manton-Gaulin mill (MantonGolin) belonging to high pressure dispersing machine to disperse, prepare particle dispersion liquid.
In the particle dispersion liquid obtained, drop into the methylene chloride of 88 mass parts while stirring, be uniformly mixed 30 minutes with stirring machine and diluted.The solution AdvantecToyo Inc. PolypropyleneWoundCartridgeFiltersTCW-PPS-1N obtained is filtered, obtains microparticulate dilution.
(preparation of online annex solution)
In closed container, drop into the Tinuvin928 (BASFJAPAN Inc.) of 15 mass parts as ultraviolet light absorber and the methylene chloride of 100 mass parts, add after thermal agitation makes it dissolve completely, filter.The above-mentioned microparticulate dilution of 36 mass parts is added while stirring and Keep agitation after 30 minutes in the solution obtained, add the acryl resin of 6 mass parts while stirring: DianalBR85 ((MitsubishiRayon Inc., Mw:280000) Keep agitation 60 minutes.The solution Japan Jingxian Co., Ltd FinemetNF obtained is filtered, obtains online annex solution.Filtering material uses specified filtering accuracy to be the filtering material of 20 μm.
(preparation of coating 1)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 1.
The composition > of the main coating 1 of <
The online annex solution of main coating 1 and 2.5 mass parts of 100 mass parts online mixer (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) is fully obtained by mixing coating 1.
(film making process)
Band casting device is used to be the condition of the 40 μm coating 1 that obtains of curtain coating equably on stainless steel band supporter with the condition of the fluid temperature 35 DEG C of coating 1, width 1.7m, final thickness.On stainless steel band supporter, make the organic solvent evaporation in the paint film obtained until residual solvent amount is 100 quality % form basement membrane after, from stainless steel band supporter peel off basement membrane.By the basement membrane that obtains 110 DEG C of preparations after dry 10 minutes further, under the condition of 160 DEG C with stenter by the former width tension to 1.5 times of basement membrane relative to TD direction.The residual solvent amount of the basement membrane stretched when starting is 2.0 quality %.After stretching with stenter, after relaxing 5 minutes at 130 DEG C, utilize the dryer (buckled zone 106) shown in Fig. 9 130 DEG C of conveyings 15 minutes, be then cooled to 23 DEG C in cooling zone 109 with the speed of 30 DEG C/min.The film obtained is cut into 2.0m width, film two ends are implemented to the annular knurl processing of width 10mm, height 5 μm, be wound into internal diameter 15.24cm core with initial tension 220N/m, final tension force 110N/m, obtain the rectangular film A-101 containing acryl resin of length 4000m, thickness 40 μm.
(making of film A-102 ~ A-138)
In the making of above-mentioned film A-101, change the presence or absence of refrigerating work procedure, the cooling velocity of cooling zone and thickness, in addition, similarly obtain the rectangular film A-102 ~ A-138 containing acryl resin recorded in table 1 and table 2.
(making of film B-101)
(preparation of microparticulate dilution)
With AerosilR812 (the Japanese Aerosil Inc. of stirring machine by 10 mass parts, mean grain size a: 7nm, apparent specific gravity 50g/L) and after the ethanol of 90 mass parts is uniformly mixed 30 minutes, is used as the Manton-Gaulin mill of high pressure dispersing machine to disperse, prepares particle dispersion liquid.
In the particle dispersion liquid obtained, drop into the methylene chloride of 88 mass parts while stirring, and be uniformly mixed 30 minutes with stirring machine and diluted.The solution AdvantecToyo Inc. PolypropyleneWoundCartridgeFiltersTCW-PPS-1N obtained is filtered, obtains microparticulate dilution.
(preparation of online annex solution)
The microparticulate dilution of the above-mentioned making of 36 mass parts is added while stirring and Keep agitation after 30 minutes in the methylene chloride of 100 mass parts; add the cellulose diacetate (degree of substitution with acetyl group 2.3 of 6 mass parts while stirring; Mn=90000; Mw=152000, Mw/Mn=1.7) and Keep agitation 60 minutes.The solution Japan Jingxian Co., Ltd FinemetNF obtained is filtered, obtains online annex solution.Filtering material uses specified filtering accuracy to be the filtering material of 20 μm.
(preparation of coating 2)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 2.
The composition > of the main coating 2 of <
The online annex solution of main coating 1 and 2.5 mass parts of 100 mass parts online mixer (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) is fully mixed, obtains coating 2.
(film making process)
Band casting device is used to be the condition coating 2 that even curtain coating obtains on stainless steel band supporter of 40 μm with the condition of the fluid temperature 35 DEG C of coating 2, width 1.95m, final thickness.On stainless steel band supporter, make the organic solvent evaporation in the paint film obtained until residual solvent amount is 100 quality % form basement membrane after, from stainless steel band supporter peel off basement membrane.By the basement membrane that obtains 110 DEG C of preparations after dry 10 minutes further, under the condition of 160 DEG C with stenter by the former width tension to 1.2 times of basement membrane relative to TD direction.The residual solvent amount of the basement membrane stretched when starting is 2.0 quality %.After stretching with stenter, after relaxing 5 minutes at 130 DEG C, thereafter, the dryer shown in Fig. 9 (buckled zone 106) is utilized to remain on the temperature of 140 DEG C, and the mode utilizing conveying roller alternately to become inner side with the A face of this basement membrane and relative B face in dry section bends, when radius during bending is set to a (mm), become 0.040mm with the value of 1/a -1mode set diameter and the configuration of conveying roller, repeat 80 times bending, with the transporting velocity of 20m/ minute conveying basement membrane.
The film obtained is cut into 2.0m width, film two ends are implemented to the annular knurl processing of width 10mm, height 5 μm, be wound into internal diameter 15.24cm core with initial tension 220N/m, final tension force 110N/m, obtain the rectangular film B-101 containing cellulose diacetate of length 4000m, thickness 40 μm.
(making of film B-102 ~ B-138)
In the making of above-mentioned film B-101; change the degree of substitution with acetyl group (being designated as DAC degree of substitution in table) of cellulose diacetate, the value of the above-mentioned 1/a of buckled zone, number of bends and thickness; in addition, the rectangular film B-102 ~ B-132 recorded in table 1 and table 2 is similarly obtained.
Should illustrate, B-133 ~ B138 uses following main coating 3 ~ 8 respectively, makes in the same manner as the making of B-132.
The composition > of the main coating 3 of <
The composition > of the main coating 4 of <
The composition > of the main coating 5 of <
The composition > of the main coating 6 of <
The composition > of the main coating 7 of <
The composition > of the main coating 8 of <
The making > of < polaroid
(making of the polarizer 1)
Utilize following operation, in order to the film forming polarizer, make polarizability stacked film, and from this polarizability stacked film peeling base film, thus obtain the polarizer of film.
(1) making of base material film
Utilize reactor blending method, in identical reaction vessel, prepare thermoplastic resin and rubber constituent successively.Specifically, use Ziegler-natta catalyst, drop into propylene monomer in the gas phase as the first operation, manufacture the Noblen as thermoplastic resin.After stopping the charging of propylene monomer that reaction is stopped, vinyl monomer and propylene monomer is dropped in the gas phase as the second operation directly to this reaction vessel, manufacture as the ethylene-propylene copolymer of rubber constituent, obtain ethylene-propylene copolymer as rubber constituent with the Noblen of granular dispersion.Obtain ethylene unit content shared in the copolymer by material balance during polymerization, result is 35 quality %.In addition according to macromolecule handbook (nineteen ninety-five, Kinokuniya bookstore issues) the 616th page in the method recorded obtain ethylene unit content shared in resin entirety (total of thermoplastic resin and rubber constituent), ethylene-propylene copolymer content shared in resin entirety is calculated by this value, result is 29 quality % (that is, the content of ethylene-propylene copolymer is 40.8 quality % of thermoplastic resin).
After the hybrid resin obtained is carried out melting mixing at 250 DEG C, melt extrude by the temperature of T-shaped mould at 280 DEG C, obtain the base material film of thickness 100 μm.
(2) formation of undercoat
Pva powder (the Nippon Synthetic Chemical Industry Co., Ltd's system " Z-200 ", average degree of polymerization 1100, mean saponification degree 99.5 % by mole) is dissolved in the hot water of 95 DEG C, the polyvinyl alcohol water solution of preparation concentration 3 quality %.In the aqueous solution obtained, mixed phase is the crosslinking chemical (Sumitomo Chemical Co's system " SumirezResin650 ") of 5 mass parts for pva powder 6 mass parts.Use micro gravure coating machine to apply the mixed aqueous solution obtained on the corona treatment face of above-mentioned base material film of implementing corona treatment, 80 DEG C of dryings 10 minutes, form the undercoat of thickness 0.2 μm thus.
(3) formation of polyvinyl alcohol resin layer
Pva powder (Kuraray Co., Ltd. system " PVA124 ", average degree of polymerization 2400, mean saponification degree 98.0 ~ 99.0 % by mole) is dissolved in the hot water of 95 DEG C, the polyvinyl alcohol water solution of preparation concentration 8 quality %.Use nozzle coating machine (lipcoater) on above-mentioned undercoat, apply the aqueous solution obtained, 80 DEG C of dryings 2 minutes, in 70 DEG C of dryings 2 minutes, next drying under 60 DEG C of dryings condition of 4 minutes, be produced on stacked film base material film being laminated with polyvinyl alcohol resin layer via undercoat.The thickness of polyvinyl alcohol resin layer is 9.8 μm.
(4) making of stretched film
Above-mentioned stacked film is carried out the longitudinal uniaxial tension to 5.8 times of free end at the draft temperature of 160 DEG C, obtains stretched film.The thickness of the stretched film obtained is 28.5 μm, and the thickness of polyvinyl alcohol resin layer is 5.0 μm.
(5) making of polarizability stacked film
Above-mentioned stretched film to be impregnated in the temperature bath of 60 DEG C after 60 seconds, to impregnated in aqueous solution containing iodine and the potassium iodide i.e. staining solution of 30 DEG C about 150 seconds, carry out the dyeing of polyvinyl alcohol resin layer, next wash away unnecessary iodine liquid with the pure water of 10 DEG C.Next, impregnated in aqueous solution containing boric acid and the potassium iodide i.e. crosslinker solution 600 seconds of 76 DEG C.Thereafter, clean 4 seconds with the pure water of 10 DEG C, finally 50 DEG C of dryings 300 seconds, obtain polarizability stacked film thus.The polyvinyl alcohol resin layer of this polarizability stacked film is peeled off from base material film, uses polyvinyl alcohol resin layer as the polarizer.
(preparation of ultraviolet hardening bonding agent liquid 1)
After mixing following each composition, carry out deaeration, prepare ultraviolet hardening bonding agent liquid 1.Should illustrate, triaryl matte hexafluorophosphate is made into 50% polypropylene carbonate ester solution, the solid constituent amount of following expression triaryl matte hexafluorophosphate.
(making of polaroid 101)
According to following method, make polaroid 101.
First, use the film B-101 of above-mentioned making as phase retardation film, Corona discharge Treatment is implemented to its surface.Should illustrate, the condition of Corona discharge Treatment is set to corona output intensity 2.0kW, linear velocity 18m/ minute.Next, on the Corona discharge Treatment face of film B-101, apply the ultraviolet hardening bonding agent liquid 1 of above-mentioned preparation with excellent coating machine in the mode that the thickness after solidification becomes about 3 μm and form ultraviolet hardening bond layer.The ultraviolet hardening bond layer obtained to be fitted the polarizer (thickness 5 μm) side, thereafter the peeling base film of polarizability stacked film of above-mentioned making.
Next, use the film A-101 of above-mentioned making, implement Corona discharge Treatment.The condition of Corona discharge Treatment is set to corona output intensity 2.0kW, speed 18m/ minute.
Next, on the Corona discharge Treatment face of film A-101, apply the ultraviolet hardening bonding agent liquid 1 of above-mentioned preparation with excellent coating machine in the mode that the thickness after solidification becomes about 3 μm and form ultraviolet hardening bond layer.
Be fitted in the polarizer of the one side laminating of film B-101 at this ultraviolet hardening bond layer, obtain the duplexer being laminated with film A-101/ ultraviolet hardening bond layer/polarizer/ultraviolet hardening bond layer/film B-101.Now, fit in the mode that the absorption axle of the slow axis of film A-101 and film B-101 and the polarizer is mutually orthogonal.
The ultraviolet lamp (lamp uses the D bulb of FusionUVSystems Inc.) with travelling belt is used to count 750mJ/cm from the side, two sides of this duplexer with accumulative light quantity 2mode irradiation ultraviolet radiation, each ultraviolet hardening bond layer is solidified, and making total film thickness is the polaroid 101 of 91 μm.
(making of polaroid 102 ~ polaroid 138)
In the same manner as polaroid 101, use film A-102 ~ A-138 and film B-102 ~ B-138, respectively according to the formation of table 1 and table 2, make the polaroid 102 ~ polaroid 138 as film A/ ultraviolet hardening bond layer/polarizer/ultraviolet hardening bond layer/film B.
" evaluating 1 "
According to the method for above-mentioned " mensuration of the size changing rate of film ", respectively L is measured to film A-101 ~ film A-138 and film B-101 ~ film B-138 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD.(L is calculated respectively by measurement result 1mD-L 5mD), (L 1tD-L 5tD), (L 5mD-L 30and (L MD) 5tD-L 30tD) value (%).
" evaluating 2 "
(making of liquid crystal indicator)
Use commercially available VA type liquid crystal indicator (SONY system 40 cun of display KLV-40J3000), peel off the polaroid being fitted in the visible side of liquid crystal cells, and the mode polaroid 101 ~ 138 of above-mentioned making being configured at the face of liquid crystal cell side with film B is fitted, thus make liquid crystal indicator 101 ~ 138.The mode now becoming equidirectional with the absorption axle of the polaroid made and the absorption axle of the polaroid of to fit in advance is fitted and makes liquid crystal indicator, and uneven according to the display of following method evaluation.
(evaluation that display is uneven)
The liquid crystal indicator obtained to be positioned in the constant temperature and humidity cabinet of 50 DEG C of 90%RH after 1 hour, under being positioned over the temperature humidity environment of 23 DEG C of 55%RH again, at normal temperatures, liquid crystal indicator be shown as black state under, the difference (showing inequality) of the brightness near 4 summits of visualization display frame and the brightness near display frame central authorities.Uneven according to the display of following benchmark evaluation.In following evaluation, preferably zero or ◎.
◎: do not show inequality completely
Zero: find when very carefully observing to show inequality a little
Find in △: 4 summits that the display of 1 place is uneven
×: find that more than 3 places show inequality in 4 summits
(evaluation of polarizer adaptation)
The liquid crystal indicator obtained to be positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, be positioned over lower 1 hour of the temperature humidity environment of 23 DEG C of 55%RH again, it can be used as 1 circulation, repeatedly carry out 50 circulations, observe the undulation of panel surface, film is peeled off, the adaptation of evaluated for film A and film B and the polarizer.
◎: do not have the undulation of panel surface, film stripping completely
Zero: when very carefully observing, find that panel surface has a little undulation
△: be clear that panel surface has undulation, but do not have film to peel off
×: find that panel surface has undulation and film to peel off
The formation of the formation of film A and film B, polaroid, above-mentioned evaluation result are shown in table 1 and table 2 in the lump.
Table 1
Table 2
From table 1 and table 2: for film A, in the employings of plastifier such as the selection of the adjustment kind of acryl resin and weight-average molecular weight, sugar ester and polycondensation ester and the basis of thickness, by in the drying process of basement membrane, after above-mentioned basement membrane leaves this drying process (dry section), add following refrigerating work procedure to be filmed, can adjust in the scope of size changing rate of the present invention, this refrigerating work procedure is cooled by basement membrane with the speed in the scope of 50 ~ 100 DEG C/sec.
In addition; for film B; in the employings of plastifier such as the selection of the adjustment degree of substitution with acetyl group of cellulose acetate and weight-average molecular weight, sugar ester and polycondensation ester and the basis of thickness; by by the operation of basement membrane drying; in dry section in the scope of 130 ~ 150 DEG C; conveying roller is utilized alternately to become in the bending operation that bends of mode of inner side with the A face of this basement membrane and relative B face; repeat more than 50 times and bending lower than 120 times, can adjust in the scope of size changing rate of the present invention.
As shown in Table 1: even if the polaroid of the display inequality of liquid crystal panel and the deterioration of the polarizer adaptation such as undulation, film stripping is also can't see in the temperature humidity environmental change that the polaroid of the film A employed in the scope adjusting to size changing rate of the present invention and film B is environment for use.Even if particularly can obtain in the past non-existent under harsh temperature humidity condition loop test also can't see the polaroid of the deterioration of the polarizer adaptation such as undulation, film stripping.
In addition, employ and the coating of film B changed to not containing postponing the coating 7 of correctives with the polaroid of B-137 with B-138 of coating 8 compared with employing the polaroid of the B-132 ~ B-136 utilizing coating 2 ~ coating 6, no problem in practicality, but visual (contrast) is in a slight decrease.
Embodiment 2
In the film A-104 of embodiment 1 and the making of film B-104, in film A, change cooling velocity, baking temperature when changing bending in film B and number of times, make the L having and record in table 3 30mD, L 30film A-201 ~ film the A-204 of TD value and film B-201 ~ film B-204, makes polaroid similarly to Example 1, carries out showing evaluation that is uneven and polarizer adaptation.
Show the result in table 3.
Table 3
As shown in Table 3: if the L of film A and film B 30tD and L 30mD is respectively in the scope of ﹣ 0.10 ~ 0.10%, even if the more excellent polaroid of the display inequality of liquid crystal panel and the deterioration of the polarizer adaptation such as undulation, film stripping is also can't see in the temperature humidity environmental change then obtaining environment for use.
Embodiment 3
(film A-301:(TAC/ acryl resin 2/TAC) film and film A-302:(TAC/ acryl resin 3/TAC) making of film)
Use the common casting mold shown in Fig. 8, according to following step, utilize the film A-302 that 3 layers of film A-301 that the tape casting (altogether the tape casting) makes (TAC/ acryl resin 2/TAC) 3 layers formation are simultaneously formed with (TAC/ acryl resin 3/TAC) 3 layers.
(preparation of coating 9)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 9.
The composition > of the main coating 9 of <
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film A in the main coating 9 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 9.
(preparation of coating 10)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 10.
The composition > of the main coating 10 of <
Acryl resin 3: R in the general formula (1) that Japanese Unexamined Patent Publication 2009-157352 publication is recorded 1for hydrogen atom, R 2and R 3for (methyl) acrylic resin [mass ratio of comonomer: methyl methacrylate/2-(hydroxymethyl) methyl acrylate=8/2 with lactonic ring structure of methyl; Lactonic ring rate about 100%] potpourri of 90 mass parts and acrylonitrile-styrene (AS) resin (TOYOASAS20, ToyoStyrene Co., Ltd. system) 10 mass parts)
90 mass parts
Sugar ester: BzSc benzyl sucrose: the potpourri of compound a-1 ~ a-4 recorded in compound 3), average ester degree of substitution=5.510 mass parts
Methylene chloride 360 mass parts
Ethanol 15 mass parts
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film A in the main coating 10 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 10.
(preparation of coating 11)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 11.
The composition > of the main coating 11 of <
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film B in the main coating 11 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 11.
(film making process)
Use above-mentioned coating 9 and coating 11, from the side, 16, endless belt as curtain coating metal support shown in Fig. 8, simultaneously supply the coating 11 as cortex (B face), the coating 9 as sandwich layer, coating 11 as cortex (A face) to common casting mold 10, on endless belt 16, supplied the duplexer and casting films 20 that are made up of cortex (B face)/sandwich layer/cortex (A face) by tape casting operation once.The quantity delivered of each coating be controlled to final drying terminate after the thickness of each layer become the condition of cortex (B face)/sandwich layer/cortex (A face)=3 μm/30 μm/3 μm.
In curtain coating with on metal support supporter, make the organic solvent evaporation in the paint film obtained until residual solvent amount is 100 quality % form basement membrane after, from stainless steel band supporter peel off basement membrane.By the basement membrane that obtains 110 DEG C of preparations after dry 10 minutes further, with stenter with the condition of 160 DEG C by the former width tension to 1.3 times of basement membrane relative to TD direction.The residual solvent amount of the basement membrane stretched when starting is 2.0 quality %.After stretching with stenter, after relaxing 5 minutes at 130 DEG C, utilize the dryer (buckled zone 106) shown in Fig. 9 130 DEG C of conveyings 15 minutes, be next cooled to 23 DEG C in cooling zone 109 with the speed of 80 DEG C/min.The film obtained is cut into 2.0m width, film two ends are implemented to the annular knurl processing of width 10mm, height 5 μm, be wound into internal diameter 15.24cm core with initial tension 220N/m, final tension force 110N/m, obtain 3 layers of rectangular film A-301 formed of length 4000m, thickness 36 μm.Similarly, use coating 10 as sandwich layer, and use coating 11 as cortex, thus obtain 3 layers of film A-302 formed.
The making of (film A-303:(acryl resin 1/ cellulose esters) film)
(preparation of coating 12)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 12.
The preparation > of < acrylic particles (C1)
To internal volume 60 liters with dropping into ion exchange water 38.2 liters, dioctylis sulfosuccinas natricus 111.6g in the reactor of reflux cooler, stir with the rotating speed limit of 250rpm, while be warming up to 75 DEG C under nitrogen environment, on coming true, there is no the state of the impact of oxygen.Drop into ammonium persulfate (APS) 0.36g, stir the monomer mixture adding in the lump after 5 minutes and be made up of methyl methacrylate (MMA) 1657g, n-butyl acrylate (BA) 21.6g and allyl methacrylate (ALMA) 1.68g, continue maintenance 20 minutes after exothermal peak being detected to complete the polymerization of inner side hard layer.
Next, add APS3.48g, stir after 5 minutes, the monomer mixture be made up of BA8105g, polyethyleneglycol diacrylate (PEGDA: molecular weight 200) 31.9g and ALMA264.0g is added continuously with 120 minutes, add and terminate rear continuation maintenance 120 minutes, complete the polymerization of soft layer.
Next, drop into APS1.32g, stirs after 5 minutes, added with 20 minutes the monomer mixture be made up of MMA2106g, BA201.6g continuously, interpolation terminates rear continuation maintenance 20 minutes to complete the polymerization of outermost hard layer 1.
Next, drop into APS1.32g, after 5 minutes, added with 20 minutes the monomer mixture be made up of MMA3148g, BA201.6g and n-OM10.1g continuously, add and terminate rear continuation maintenance 20 minutes.Then be warming up to 95 DEG C and keep 60 minutes, completing the polymerization of outermost hard layer 2.
Gather the polymer latex so obtained on a small quantity, utilize absorbance method to obtain flat grain particle diameter, result is 0.10 μm.Dropped into by remaining latex in 3 quality % sodium sulphate warm water solution, carrying out saltouts solidifies, next, repeatedly dry after dehydration cleaning, obtains the acrylic particles (C1) of 3-tier architecture.
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film A in the main coating 12 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 12.
(film making process)
In the same manner as the making of the film A-101 of embodiment 1, using the coating 12 that obtains, and use band casting device with the condition of the fluid temperature 35 DEG C of coating 12, width 1.7m, take final thickness as the condition of 40 μm curtain coating equably on stainless steel band supporter.On stainless steel band supporter, make the organic solvent evaporation in the paint film obtained until residual solvent amount is 100 quality % form basement membrane after, from stainless steel band supporter peel off basement membrane.After the basement membrane obtained is prepared dry 10 minutes further at 110 DEG C, with the condition stenter of 160 DEG C by the former width tension to 1.5 times of basement membrane relative to TD direction.The residual solvent amount of the basement membrane stretched when starting is 2.0 quality %.After stretching with stenter, after relaxing 5 minutes at 130 DEG C, utilize the dryer (buckled zone 106) shown in Fig. 9 130 DEG C of conveyings 15 minutes, be next cooled to 23 DEG C in cooling zone 109 with the speed of 30 DEG C/min.The film obtained is cut into 2.0m width, film two ends are implemented to the annular knurl processing of width 10mm, height 5 μm, be wound into internal diameter 15.24cm core with initial tension 220N/m, final tension force 110N/m, obtain the rectangular film A-303 containing acryl resin of length 4000m, thickness 40 μm.
The film B opposed with the film A-301, film A-302 and A-303 that make uses film B-111 and is made into polaroid 301,302 and 303.
The polaroid 301,302 and 303 of use, becomes the appreciation condition of embodiment 1 into following appreciation condition and carrys out implementation evaluation.
(evaluation that display is uneven)
The liquid crystal indicator obtained to be positioned in the constant temperature and humidity cabinet of 50 DEG C of 90%RH after 1 hour, be positioned over lower 1 hour of the temperature humidity environment of 23 DEG C of 55%RH again, it can be used as 1 circulation, after repeating 10 circulations, at normal temperatures, liquid crystal indicator be shown as black state under, the difference (showing inequality) of the brightness near 4 summits of visualization display frame and the brightness near display frame central authorities.Uneven according to the display of following benchmark evaluation.In following evaluation, preferably zero or ◎.
◎: do not show inequality completely
Zero: find when very carefully observing to show inequality a little
Find in △: 4 summits that the display of 1 place is uneven
×: find that more than 3 places show inequality in 4 summits
(evaluation of polarizer adaptation)
The liquid crystal indicator obtained to be positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, be positioned over lower 1 hour of the temperature humidity environment of 23 DEG C of 55%RH again, it can be used as 1 circulation, after repeating 100 circulations, observe the undulation of panel surface, film is peeled off, the adaptation of evaluated for film A and film B and the polarizer.
◎: do not have the undulation of panel surface, film stripping completely
Zero: when very carefully observing, find that panel surface has a little undulation
△: be clear that panel surface has undulation, but do not have film to peel off
×: find that panel surface has undulation and film to peel off
Show the result in table 4.
Table 4
As shown in Table 4: become by making film A 3 layers of film formed that the such cortex of (TAC/ acryl resin/TAC) film uses TAC, even if thus the more excellent polaroid of the deterioration of the uneven and polarizer adaptation such as undulation, film stripping of the display of liquid crystal panel is also can't see in the temperature humidity environmental change obtaining environment for use under harsher condition.In addition, the liquid crystal panel employing the film that these 3 layers are formed further improves the warpage of panel.In addition, the film that the A-303 being mixed with acryl resin and cellulose esters is formed like this is also excellent in the display inequality and the polarizer adaptation such as undulation, film stripping of liquid crystal panel.
Embodiment 4
In the making of the film A-104 of embodiment 1, change the stretching ratio in TD direction by table 5, make film A-401 ~ film A-404, use film B-104 as opposed film B, make polaroid 401 ~ 404, carry out similarly to Example 1 showing evaluation that is uneven and polarizer adaptation.
Show the result in table 5.
Table 5
As shown in Table 5, by film A is stretched in the scope that the former width relative to TD direction is 1.05 ~ 1.5 times, even if the more excellent polaroid of the display inequality of liquid crystal panel and the deterioration of the polarizer adaptation such as undulation, film stripping is also can't see in the temperature humidity environmental change obtaining environment for use.
Embodiment 5
In the making of the film B-104 of embodiment 1, the stretching ratio in TD direction is changed in the scope of 1.05 ~ 1.4 times, make the film B-501 ~ film B-505 with the length of delay shown in table 6, use film A-104 as opposed film A, make polaroid 501 ~ 505, similarly to Example 1, carry out showing evaluation that is uneven and polarizer adaptation.Should illustrate, postpone to measure by above-mentioned method.
Show the result in table 6.
Table 6
As shown in Table 6: by film B is stretched in TD direction, even if the value that can obtain length of delay Ro and Rt is adjusted in the preferred scope of the present invention and the more excellent polaroid of the deterioration of the uneven and polarizer adaptation such as undulation, film stripping of the display of liquid crystal panel is also can't see in the temperature humidity environmental change of environment for use.
Embodiment 6
(film B-601:(TAC/DAC2/TAC) film and film B-602:(TAC/DAC3/TAC) making of film)
Use the common casting mold shown in Fig. 8, according to following step, utilize the film B-602 that 3 layers of film B-601 that the tape casting (altogether the tape casting) makes (TAC/DAC2/TAC) 3 layers formation are simultaneously formed with (TAC/DAC3/TAC) 3 layers.
(preparation of coating 13)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 13.
The composition > of the main coating 13 of <
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film B in the main coating 13 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 13.
(preparation of coating 14)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 14.
The composition > of the main coating 14 of <
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film B in the main coating 14 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 14.
(film making process)
Use the coating 11 made in above-mentioned coating 13 and embodiment 3, from the side, 16, endless belt as curtain coating metal support shown in Fig. 8, supply the coating 11 as cortex (B face) to common casting mold 10 simultaneously, as the coating 13 of sandwich layer, as the coating 11 in cortex (A face), by tape casting operation once, on endless belt 16, supply the duplexer and casting films 20 that are made up of cortex (B face)/sandwich layer/cortex (A face).The quantity delivered of each coating be controlled to final drying terminate after the thickness of each layer become the condition of cortex (B face)/sandwich layer/cortex (A face)=3 μm/30 μm/3 μm.
In curtain coating with on metal support supporter, make the organic solvent evaporation in the paint film obtained until residual solvent amount is 100 quality % form basement membrane after, from stainless steel band supporter peel off basement membrane.By the basement membrane that obtains 110 DEG C of preparations after dry 10 minutes further, with stenter with the condition of 160 DEG C by the former width tension to 1.3 times of basement membrane relative to TD direction.The residual solvent amount of the basement membrane stretched when starting is 2.0 quality %.After stretching with stenter, after relaxing 5 minutes at 130 DEG C, thereafter, the dryer shown in Fig. 9 (buckled zone 106) is utilized to remain on the temperature of 135 DEG C, and the mode utilizing conveying roller alternately to become inner side with the A face of this basement membrane and relative B face in dry section bends, when radius during bending is set to a (mm), become 0.040mm with the value of 1/a -1mode set diameter and the configuration of conveying roller, repeat 80 times bending, with the transporting velocity of 20m/ minute conveying basement membrane.
The film obtained is cut into 2.0m width, film two ends are implemented to the annular knurl processing of width 10mm, height 5 μm, be wound into internal diameter 15.24cm core with initial tension 220N/m, final tension force 110N/m, obtain 3 layers of rectangular film B-601 formed of length 4000m, thickness 40 μm.Similarly use coating 14 as sandwich layer, use coating 11 as cortex, obtain 3 layers of film B-602 formed.
In addition, use following coating 15, make the film B-603 of the individual layer containing cellulose diacetate in the same manner as the film B-116 of embodiment 1.
(preparation of coating 15)
Following compositions is dropped into closed container, heating and stir make it dissolve completely.The peace of the solution An Ji filter paper Co., Ltd. obtained is amassed filter paper No.24 filter, obtain main coating 15.
The composition > of the main coating 15 of <
The online mixer of online annex solution 2.5 mass parts (in TORAY silent oscillation pipe mixer Hi-Mixer, SWJ) made using as film B in the main coating 15 of 100 mass parts and embodiment 1 fully mixes, and obtains coating 15.
The film A opposed with the film B-601, the film B-602 that make and film B-603 uses film A-116 and is made into polaroid 601 ~ 603.
The polaroid 601 ~ 603 of use, according to the appreciation condition of embodiment 3, carries out showing evaluation that is uneven and polarizer adaptation.
Show the result in table 7.
Table 7
As shown in Table 7: become by making film B 3 layers of film formed that the such cortex of (TAC/DAC/TAC) film uses TAC, compared with the film of individual layer, even if the polaroid of the excellence of the display inequality of liquid crystal panel and the deterioration of the polarizer adaptation such as undulation, film stripping is also can't see in the temperature humidity environmental change obtaining environment for use under harsher condition.
Embodiment 7
In the making of the polarizability stacked film that embodiment 1 uses, change the thickness of the polarizer by table 7 and make the polarizer, making polaroid 701 ~ 705 with the formation of the polaroid 117 made in embodiment 1.
In order to observe the difference of the polarizer further, stretch processing being carried out to following shown existing polyvinyl alcohol (PVA) (PVA) film and makes the polarizer, similarly making polaroid 706.
(making of the polarizer 2)
By water-soluble swollen with 35 DEG C of polyvinyl alcohol (PVA) (PVA) film of thickness 45 μm.By the film immersion obtained in the aqueous solution be made up of iodine 0.075g, potassium iodide 5g and water 100g 60 seconds, then impregnated in by the aqueous solution of 45 DEG C that potassium iodide 3g, boric acid 7.5g and water 100g are formed.The film obtained is carried out uniaxial tension with the condition of draft temperature 55 DEG C, stretching ratio 5 times.After this monadic stretching membrane is washed, make it dry, obtain the polarizer of thickness 9 μm.
The polaroid 701 ~ 706 of use, according to the appreciation condition of embodiment 1, carries out showing evaluation that is uneven and polarizer adaptation.
Show the result in table 8.
Table 8
As shown in Table 8: by using the polarizer of polarizability stacked membranous type and thickness is the polarizer in the scope of 2 ~ 15 μm, even if the more excellent polaroid of the deterioration of the uneven and polarizer adaptation such as undulation, film stripping of the display of liquid crystal panel is also can't see in the temperature humidity environmental change obtaining environment for use.In addition, compared with the polarizer that obtains, the polaroid that display is uneven and the polarizer adaptation such as undulation, film stripping is more excellent of liquid crystal panel is obtained with being stretched by existing polyvinyl alcohol (PVA) (PVA) film.
Utilizability in industry
For polaroid of the present invention; when possessing the polaroid using acrylic film and cellulose ester membrane as the diaphragm of the polarizer in liquid crystal indicator; even if the display inequality of liquid crystal panel and the deterioration of the polarizer adaptation such as undulation, film stripping are also can't see in the temperature humidity environmental change of environment for use; therefore be suitable for liquid crystal display cells etc., be particularly suitable for VA mode LCD.
Symbol description
1 dissolution kettle
3,6,12,15 filtrators
4,13 material stock stills
5,14 liquid-feeding pumps
8,16 conduits
10 ultraviolet light absorber feed chambers
20 collecting fittings
21 mixers
30 compression moldings
31 metal tapes
32 basement membranes
33 peel off position
34 stenter stretching devices
35 drying devices
41 feed chambers
42 material stock stills
43 pumps
44 filtrators
50 are total to casting mold
51 die bearings
53,55 layers of B, layer C slit
54 layers of A slit
56 metal support
57,59 layers of B, layer C coating
58 layers of A coating
60 sandwich construction basement membranes
61 layers of C (cortex)
62 layers of A (sandwich layer)
63 layers of B (cortex)
100 moulds
102 metal support
103 driven rollers
104 pick-up points
105 conveying rollers
106 buckled zones
107 air entries
108 exhausr ports
109 cooling zones

Claims (17)

1. a polaroid, is characterized in that, the polarizer clamps via dynamic rays curing type bond layer tunicle A and film B,
In this film A to be thickness be scope of 20 ~ 60 μm, meet following formula (1) ~ (4) and acrylic film containing acryl resin,
Average substitution degree in this film B to be thickness be scope of 20 ~ 60 μm, containing acetyl group is cellulose acetate in the scope of 2.0 ~ 2.5 and meets the cellulose acetate membrane of following formula (1) ~ (4),
(1)0.03(％)≤L 1MD－L 5MD≤0.30(％)
(2)0.03(％)≤L 1TD－L 5TD≤0.30(％)
(3)0(％)≤L 5MD－L 30MD≤0.10(％)
(4)0(％)≤L 5TD－L 30TD≤0.10(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD represents the size changing rate of the film after 1 minute that utilizes following formula (a) ~ (f) to try to achieve, after 5 minutes and after 30 minutes, for following formula (a) ~ (f), with while the mode parallel with TD direction or MD direction gathers film A and the film B of rectangle, be positioned over lower 24 hours of the temperature humidity environment of 23 DEG C of 55%RH, in the given size of MD direction and this film of TD direction detection, be set to L respectively 0mD and L 0tD, this film to be positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, under being positioned over the temperature humidity environment of 23 DEG C of 55%RH again, the size after MD direction and TD direction measure 1 minute respectively, the size after 5 minutes and the size after 30 minutes, be set to L respectively 1mD ', L 1tD ', L 5mD ', L 5tD ', L 30mD ' and L 30tD ', substitutes into following formula (a) ~ (f) and obtains described size changing rate,
Size changing rate after 1 minute
(formula is L a) 1mD (%)=(L 1mD '-L 0mD)/L 0mD × 100
(formula b) L 1tD (%)=(L 1tD '-L 0tD)/L 0tD × 100
Size changing rate after 5 minutes
(formula c) L 5mD (%)=(L 5mD '-L 0mD)/L 0mD × 100
(formula d) L 5tD (%)=(L 5tD '-L 0tD)/L 0tD × 100
Size changing rate after 30 minutes
(formula e) L 30mD (%)=(L 30mD '-L 0mD)/L 0mD × 100
(formula f) L 30tD (%)=(L 30tD '-L 0tD)/L 0tD × 100.
2. polaroid according to claim 1, is characterized in that, described film A and described film B meets following formula (5) ~ (8) respectively,
(5)0.05(％)≤L 1MD－L 5MD≤0.15(％)
(6)0.05(％)≤L 1TD－L 5TD≤0.15(％)
(7)0(％)≤L 5MD－L 30MD≤0.05(％)
(8)0(％)≤L 5TD－L 30TD≤0.05(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30the L of TD and claim 1 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD is equivalent in meaning.
3. polaroid according to claim 1 and 2, is characterized in that, the L of described film A and described film B 30tD and L 30mD is respectively in the scope of-0.10 ~ 0.10%.
4. the polaroid according to any one of claims 1 to 3, is characterized in that, described film A contains sugar ester or has the polycondensation ester of the structure that following general formula (1) represents,
General formula (1)
B 3－(G 2－A) n－G 2－B 4
In described general formula, B 3and B 4various places represent aliphatics or aromatic monocarboxylate's residue or hydroxyl independently, G 2represent that the aklylene glycol residue of carbon number 2 ~ 12, the aryl-diol residue of carbon number 6 ~ 12 or carbon number are the oxyalkylene diol residue of 4 ~ 12, A represents the alkylene dicarboxylic acids residue of carbon number 4 ~ 12 or aryl dicarboxylic acid's residue of carbon number 6 ~ 12, and n represents the integer of more than 1.
5. the polaroid according to any one of Claims 1 to 4, is characterized in that, described film A is the formation of corticated at least 3 layers of the both sides tool at sandwich layer, and this sandwich layer contains acryl resin, and this cortex contains cellulose esters.
6. the polaroid according to any one of Claims 1 to 5, is characterized in that, described film A is be stretched in the scope of 1.05 ~ 1.5 times at the former width relative to TD direction.
7. the polaroid according to any one of claim 1 ~ 6, it is characterized in that, in the face defined by following formula (i) and (ii) of described film B, the length of delay Ro in direction is in the scope of 40 ~ 60nm, and the length of delay Rt of thickness direction is in the scope of 100 ~ 140nm
Formula (i): Ro=(n x-n y) × d (nm)
Formula (ii): Rt={ (n x+ n y)/2-n z} × d (nm)
In formula (i) and formula (ii), n xrepresent that in direction, refractive index reaches the refractive index of maximum direction x, n in the face of film yrepresent the refractive index of direction y orthogonal with described direction x in direction in the face of film, n zrepresent the refractive index at the thickness direction z of film, d represents the thickness of film, and thickness unit is nm, carries out under being determined at the environment of 23 DEG C of 55%RH with the mensuration wavelength of 590nm.
8. the polaroid according to any one of claim 1 ~ 7, is characterized in that, the average substitution degree that described film B contains acetyl group is the cellulose acetate in the scope of 2.1 ~ 2.4.
9. the polaroid according to any one of claim 1 ~ 8, is characterized in that, described film B contains sugar ester or has the polycondensation ester of the structure that following general formula (1) represents,
General formula (1)
B 3－(G 2－A) n－G 2－B 4
In described formula, B 3and B 4various places represent aliphatics or aromatic monocarboxylate's residue or hydroxyl independently, G 2represent that the aklylene glycol residue of carbon number 2 ~ 12, the aryl-diol residue of carbon number 6 ~ 12 or carbon number are the oxyalkylene diol residue of 4 ~ 12, A represents the alkylene dicarboxylic acids residue of carbon number 4 ~ 12 or aryl dicarboxylic acid's residue of carbon number 6 ~ 12, and n represents the integer of more than 1.
10. the polaroid according to any one of claim 1 ~ 9; it is characterized in that; described film B is the formation of corticated at least 3 layers of the both sides tool at sandwich layer; this sandwich layer contain acyl substitution be 2.0 ~ 2.45 scope in cellulose acetate, this cortex contain acyl substitution be 2.6 ~ 2.95 scope in cellulose acetate.
11. polaroids according to any one of claim 1 ~ 10, it is characterized in that, the thickness of the described polarizer is in the scope of 2 ~ 15 μm.
The manufacture method of 12. 1 kinds of polaroids, is characterized in that, is via the manufacture method of dynamic rays curing type bond layer at the two sides laminating film A of the polarizer and the polaroid of film B,
As this film A, thickness is used to be in the scope of 20 ~ 60 μm, to meet following formula (1) ~ (4) and acrylic film containing acryl resin,
This film B uses thickness to be average substitution degree in the scope of 20 ~ 60 μm, containing acetyl group to be the cellulose acetate in the scope of 2.0 ~ 2.5 and meets the cellulose acetate membrane of following formula (1) ~ (4),
(1)0.03(％)≤L 1MD－L 5MD≤0.30(％)
(2)0.03(％)≤L 1TD－L 5TD≤0.30(％)
(3)0(％)≤L 5MD－L 30MD≤0.10(％)
(4)0(％)≤L 5TD－L 30TD≤0.10(％)
In above formula, L 1mD, L 1tD, L 5mD, L 5tD, L 30mD and L 30tD represents the size changing rate of the film after 1 minute that utilizes following formula (a) ~ (f) to try to achieve, after 5 minutes and after 30 minutes, for following formula (a) ~ (f), with while the mode parallel with TD direction or MD direction gathers film A and the film B of rectangle, be positioned over lower 24 hours of the temperature humidity environment of 23 DEG C of 55%RH, in the given size of MD direction and this film of TD direction detection, be set to L respectively 0mD and L 0tD, this film to be positioned in the constant temperature and humidity cabinet of 80 DEG C of 90%RH after 1 hour, under being positioned over the temperature humidity environment of 23 DEG C of 55%RH again, the size after MD direction and TD direction measure 1 minute respectively, the size after 5 minutes and the size after 30 minutes, be set to L respectively 1mD ', L 1tD ', L 5mD ', L 5tD ', L 30mD ' and L 30tD ', substitutes into following formula (a) ~ (f) and obtains described size changing rate,
Size changing rate after 1 minute
(formula is L a) 1mD (%)=(L 1mD '-L 0mD)/L 0mD × 100
(formula b) L 1tD (%)=(L 1tD '-L 0tD)/L 0tD × 100
Size changing rate after 5 minutes
(formula c) L 5mD (%)=(L 5mD '-L 0mD)/L 0mD × 100
(formula d) L 5tD (%)=(L 5tD '-L 0tD)/L 0tD × 100
Size changing rate after 30 minutes
(formula e) L 30mD (%)=(L 30mD '-L 0mD)/L 0mD × 100
(formula f) L 30tD (%)=(L 30tD '-L 0tD)/L 0tD × 100.
13. the manufacture method of polaroid according to claim 12, is characterized in that, following operation is utilized to form described film A, that is,
Casting dope at least containing acryl resin and organic solvent is formed in metal support the operation of basement membrane,
The operation peeled off by the drying of the basement membrane of described formation and from metal support,
By the operation that the basement membrane of described stripping stretches,
By the operation of the described basement membrane stretched in dry section drying, and
After described basement membrane leaves this dry section, refrigerating work procedure basement membrane cooled with the speed in the scope of 50 ~ 100 DEG C/sec.
The manufacture method of 14. polaroids according to claim 12 or 13, is characterized in that, utilize following operation to form described film B, that is,
Casting dope at least containing cellulose acetate and organic solvent is formed in metal support the operation of basement membrane,
The operation peeled off by the drying of the basement membrane of described formation and from metal support,
By the operation that the basement membrane of described stripping stretches, and
By the operation of the described basement membrane stretched in dry section drying,
When utilizing as above operation to form described film B, described basement membrane had bending operation in the operation of dry section drying, namely be maintained at the temperature in the scope of 130 ~ 150 DEG C and utilize transport roller with the A face of this basement membrane and relative B face alternately become inner side mode bend, this bending operation carries out as follows: when radius during this basement membrane of bending is set to a, the value of 1/a is 0.035mm ﹣ 1~ 0.050mm ﹣ 1scope in, and repeat more than 50 times and lower than 120 times bend, wherein, the unit of a is mm.
The manufacture method of 15. polaroids according to any one of claim 12 ~ 14, is characterized in that, utilizes following operation to form polarizability stacked film, that is,
Form polyvinyl alcohol resin layer in the one side of base material film rubber constituent being scattered in thermoplastic resin and obtain the operation of stacked film,
Described stacked film is carried out uniaxial tension and obtains the operation of stretched film,
With dichromatism pigment, the described polyvinyl alcohol resin layer dyeing of described stretched film is obtained the operation of dyeing film,
The described polyvinyl alcohol resin layer of described dyeing film be impregnated in and form polarizer layer containing the solution of crosslinking chemical, obtain the operation of cross linking membrane, and
By the operation of described cross linking membrane drying,
Utilize after as above operation forms polarizability stacked film, the described polyvinyl alcohol resin layer of this polarizability stacked film is peeled off from base material film, uses this polyvinyl alcohol resin layer as the described polarizer.
16. 1 kinds of liquid crystal indicators, is characterized in that, possess the polaroid according to any one of claim 1 ~ 11.
17. liquid crystal indicators according to claim 16, is characterized in that, described liquid crystal indicator is VA mode LCD.
CN201480022942.8A 2013-04-26 2014-04-04 Polarizing plate, method for producing same and liquid crystal display device Pending CN105143937A (en)

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