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CN104245851B - Blooming, polaroid and liquid crystal indicator - Google Patents

Blooming, polaroid and liquid crystal indicator Download PDF

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Publication number
CN104245851B
CN104245851B CN201380010749.8A CN201380010749A CN104245851B CN 104245851 B CN104245851 B CN 104245851B CN 201380010749 A CN201380010749 A CN 201380010749A CN 104245851 B CN104245851 B CN 104245851B
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Prior art keywords
blooming
formula
acid
represent
present
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CN104245851A (en
Inventor
中原成
中原一成
木内宏佳
福坂洁
铃木隆嗣
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C08J2301/12—Cellulose acetate
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The problem to be solved in the present invention is, it is provided that a kind of has high latency expression power, can suppress to ooze out and internal haze is low, fragility is excellent, light resistance, blooming that humidity resistance is high in addition.The blooming of the present invention is the blooming containing thermoplastic resin, and it contains the compound shown in following formula (1).(in formula (1), X1Represent oxygen atom or sulphur atom, Y1Represent oxygen atom, sulphur atom, nitrogen-atoms or NR41, Z1Represent oxygen atom, nitrogen-atoms or sulphur atom.R11、R21And R31Represent substituent group.R41Represent hydrogen atom or substituent group.K1 represents the integer of 1～5.M1 represents the integer of 0～4.N1 represents the integer of 0～4.Dotted portion represents singly-bound or double bond.)

Description

Blooming, polaroid and liquid crystal indicator
Technical field
The present invention relates to a kind of blooming, polaroid and liquid crystal indicator.More specifically, relate to one and comprise thermoplastic The property blooming of resin, the polaroid possessing this blooming and liquid crystal indicator.
Background technology
At present, the thermoplastic resin film such as cellulose esters, Merlon, polyolefin, for blooming, is mainly used in liquid crystal Showing device optical compensation films.Wherein, the blooming (cellulose ester membrane) containing cellulose esters is to the polyethylene as polarizer The stickiness of alcohol film is excellent, thus is widely used.Cellulose ester membrane itself, the birefringence required for optical compensation films Aspect is insufficient, therefore, carries out giving cellulose ester membrane the various researchs of birefringence.
In recent years, the TV of slim light weight notebook computer and slim big picture develops development, with this development, liquid crystal Display device optical compensation films to filming, maximization, high performance requirement more and more stronger.Cellulose ester membrane wet Degree durability depends on the film thickness of film, can be improved by the film thickness of thinning film.Opposite to that, if the thickness of film Spend thinning, then length of delay diminishes.Therefore, seek a kind of delay and rise the high additive of energy (postponing performance agent).
As postponing the high compound of ascending ability, such as propose to have a kind of 1,3,5-triazines compounds (referring for example to Patent documentation 1.).But, even if using this compound, postpone expression power the most insufficient.And then specify that, use containing this change The polaroid of the optical compensation film production of the filming of compound and employ the liquid crystal indicator of described polaroid and exist fast light The inferior such problem of durability such as property and humidity resistance.And then, in the case of placing under high temperature, the high humidity, it has been found that just Face contrast is uneven and the problem such as visible angle deterioration.If it addition, add this compound, then the fragility deterioration of film, thus cutting Cut characteristic aspect existing problems.
On the other hand, disclose and a kind of in cellulose esters, add the benzo as UV absorbentOxazinone compound Technology (referring for example to patent documentation 2, patent documentation 3 and patent documentation 4.).But, even if adding this change in cellulose esters Compound makes blooming, postpones expression power the lowest.It addition, this compound and the poor compatibility of cellulose esters, therefore, easily ooze Going out, the haze value after internal haze and stretching is big, is therefore the film that contrast is low.
The delay expression power of the most existing known delay performance agent is the most insufficient, there are above-mentioned durability and visibility etc. Problem, expects further to improve.
It addition, benzoThe compound of piperazine ketone skeleton as UV absorbent it is known that but as postpone performance agent the most not Know.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-188718 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-185217 publication
Patent documentation 3: Japanese Unexamined Patent Application Publication 2005-504047 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2009-20399 publication
Summary of the invention
Invent problem to be solved
The present invention in view of the above problems/situation and carry out, it is solved the problem in that, it is provided that one has Gao Yan Late expression power, can suppress to ooze out and internal haze is low, fragility is excellent, light resistance, blooming that humidity resistance is high in addition.
And then, the problem to be solved in the present invention is, it is provided that a kind of possess described blooming, there is good light resistance And the polaroid of humidity resistance, it is provided that a kind of through time the liquid crystal display that front contrast is uneven and the deterioration of visible angle is excellent Device.
The method of solution problem
The present inventor etc., in order to solve the problems referred to above, find during studying the reason etc. of the problems referred to above, Thermoplastic resin with the addition of the benzo with ad hoc structureThe film of oxazinone compound has high latency expression power and for low interior Portion's mist degree.Specifically, find benzoPiperazine ketone skeleton, carries out substituted phenyl using-OCO-as even at ad-hoc location Connect group and import substituent group, thus improve the interaction with cellulose esters, improve the compatibility, raising orientation, thus optics Film shows high latency.And then, find that this with the addition of the benzo with ad hoc structureOozing out of the blooming of oxazinone compound Characteristic, internal haze, fragility, light resistance and humidity resistance are good.Have been found that this blooming of use, then can obtain that there is height The polaroid that the front contrast of light resistance and humidity resistance, suppression liquid crystal indicator is uneven, make visible angle improve.
That is, the problem above-mentioned to be solved that the present invention relates to can solve by the following method.
1. a blooming, it contains the compound shown in thermoplastic resin and following formula (1).
[chemical formula 1]
Formula (1)
(in formula (1), X1Represent oxygen atom or sulphur atom, Y1Represent oxygen atom, sulphur atom, nitrogen-atoms or NR41, Z1Represent Oxygen atom, nitrogen-atoms or sulphur atom.R11、R21And R31Represent substituent group.As with R11The substituent group represented, represents alkyl, ring Alkyl, alkoxyl, aryl, aryloxy group, amino, alkyl amino, arylamino, alkylthio group, arylthio or heterocyclic radical.As with R21And R31The substituent group represented, represents alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, acyl group, alkoxy carbonyl, virtue respectively Epoxide carbonyl, carbamoyl, acyl amino, sulfonyl, sulfonyloxy, amino, alkylthio group or halogen atom.R41Represent hydrogen Atom or substituent group.As R41Shown substituent group, represents alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, acyl group, alcoxyl Base carbonyl, aryloxycarbonyl, amino, alkylthio group or halogen atom.K1 represents the integer of 1～5.M1 represents the integer of 0～4.n1 Represent the integer of 0～4.Dotted portion represents singly-bound or double bond.)
2. according to the blooming described in above-mentioned 1, wherein, the compound shown in described formula (1) is shown in following formula (2) Compound.
[chemical formula 2]
Formula (2)
(in formula (2), X2Represent oxygen atom or sulphur atom, Y2Represent oxygen atom, sulphur atom, nitrogen-atoms or NR42, Z2Represent Oxygen atom, nitrogen-atoms or sulphur atom.R12And R22Represent substituent group.R42Represent hydrogen atom or substituent group.Substituent R12、R22And R42Respectively with the R in formula (1)11、R21And R41Same meaning.M2 represents the integer of 0～4.N2 represents the integer of 0～4.Dotted line Part represents singly-bound or double bond.)
3. according to the blooming described in above-mentioned 2, wherein, the compound shown in described formula (2) is shown in following formula (3) Compound.
[chemical formula 3]
Formula (3)
(in formula (3), R13And R23Represent substituent group.Substituent R13And R23Respectively with the R in formula (1)11And R21Meaning Identical.K3 represents the integer of 1～5.M3 represents the integer of 0～4.).
[chemical formula 4]
Formula (4)
(in formula (4), R14Represent substituent group.Substituent R14With the R in formula (1)11Same meaning.K4 represents 1～5 Integer.)
4. according to the blooming described in above-mentioned 3, wherein, the compound shown in described formula (3) is shown in following formula (4) Compound,
[chemical formula 4]
Formula (4)
(in formula (4), R14Represent substituent group；Substituent R14With the R in formula (1)11Same meaning；K4 represents 1～5 Integer.)
5. according to the blooming described in above-mentioned 1, wherein, described thermoplastic resin comprises cellulose esters.
6., according to the blooming described in above-mentioned 5, wherein, described cellulose esters meets any one of following formula (a) and (b).
Formula (a) 1.5≤X+Y≤2.5
Formula (b) 0≤Y≤1.5
(in formula, X represents the substitution value of acetyl group.Y represents propiono or the substitution value of bytyry or its replacement amounted to Degree.)
7. according to the blooming described in above-mentioned 1, wherein, the film thickness of described blooming is in the range of 20～60 μm.
8. according to the blooming described in above-mentioned 1, wherein, 23 DEG C, in the environment of 55%RH, when measuring wavelength 590nm, In face shown in following formula, the length of delay Ro in direction is in the range of 20～150nm, the length of delay Rth of thickness direction 70～ In the range of 350nm.
Formula (I) Ro=(nx-ny)×d
Formula (II) Rth={ (nx+ny)/2-nz}×d
(nxRepresent that in direction, refractive index is the refractive index of maximum direction x in the face of blooming；nyRepresent the folding of direction y Penetrating rate, described direction y direction in the face of blooming is vertical with described direction x；nzRepresent the refraction of the thickness direction z of blooming Rate；D (nm) represents the thickness of blooming.)
9. a polaroid, wherein, at least one side at polarizer possesses the blooming according to any one of above-mentioned 1～8.
10. a liquid crystal indicator, wherein, at least one side at liquid crystal cell possesses the polaroid described in above-mentioned 9.
Invention effect
Said method according to the present invention, it is possible to provide one has high latency expression power, can suppress to ooze out and internal haze Low, fragility is excellent, light resistance, blooming that humidity resistance is high in addition.And then, the polaroid possessing this blooming can have good Good light resistance and humidity resistance, by using this polaroid, it is possible to provide through time front contrast uneven and visible angle is bad Change excellent liquid crystal indicator.
The expression mechanism of effect or mechanism of action about the present invention are clear and definite, but are presumed as follows.
The compound shown in formula (1) of the present invention by ad-hoc location carry out substituted phenyl using-OCO-as Linking group imports substituent group, forms hydrogen bond with thermoplastic resin and is orientated, thus to the optics containing thermoplastic resin Film gives high phase contrast.And then, above-claimed cpd is high due to the compatibility with thermoplastic resin, therefore, can suppress internal haze Deterioration and ooze out, fragility is excellent, improves light resistance, humidity resistance in addition.
Accompanying drawing explanation
Fig. 1 represents the schematic diagram of the state having dripped glycerol on microscope slide；
Fig. 2 represents the schematic diagram of the state that placed sample film on glycerol；
Fig. 3 represents the schematic diagram of the state having dripped glycerol in sample film；
Fig. 4 represents the schematic diagram of the state that placed coverslip on glycerol.
Detailed description of the invention
The blooming of the present invention is the blooming containing thermoplastic resin, and it contains the compound shown in above-mentioned formula (1).
Here, so-called " thermoplastic resin " refer to by be heated to vitrification point or fusing point can deliquescing, thus be configured to The resin of target shape.
This feature is the technical characteristic that the invention in 1 with the present invention～10 is common.
As embodiments of the present invention, from the viewpoint of the effect of the present invention is expressed, the change shown in above-mentioned formula (1) Compound is preferably the compound shown in above-mentioned formula (2).It addition, the compound shown in above-mentioned formula (2) is preferably by above-mentioned formula (3) represent, and then, from can provide have high latency expression power, can suppress to ooze out, to reduce internal haze, fragility excellent and fast light Property, from the standpoint of the high blooming of humidity resistance, the compound shown in above-mentioned formula (3) is preferably shown in above-mentioned formula (4) Compound.
It addition, from above-mentioned formula (1), above-mentioned formula (2), above-mentioned formula (3) and the compound shown in above-mentioned formula (4) Excellent compatibility, obtain having the blooming that high latency expression power and light resistance, humidity resistance are high from the standpoint of, thermoplasticity Resin is preferably cellulose esters.
It addition, from above-mentioned formula (1), above-mentioned formula (2), above-mentioned formula (3) and the compound shown in above-mentioned formula (4) Excellent compatibility, obtain having high latency expression power, can suppress to ooze out, internal haze reduce and fragility is excellent and light resistance, From the standpoint of the blooming that humidity resistance is high, above-mentioned cellulose esters preferably has and meets the specific of above-mentioned formula (a) and (b) The cellulose esters of acyl substitution.
It addition, from can suppress to ooze out, from the viewpoint of fragility excellence, the film thickness of above-mentioned blooming is preferably in 20～60 μm In the range of.
And then, from the standpoint of the blooming providing visibility good, blooming is preferably at 23 DEG C, the ring of 55%RH Border, and when mensuration wavelength is 590nm, in the face shown in following formula, the length of delay Ro in direction is in the range of 20～150nm, thickness The length of delay Rth in direction is in the range of 70～350nm.
The blooming of the present invention is preferably provided with in polaroid and liquid crystal indicator, it is possible to provide a kind of have good resistance to Photosensitiveness and the polaroid of humidity resistance and the liquid crystal display dress that front contrast is uneven and the Humidity Dependence at visible angle reduces Put.
Hereinafter, to the present invention and its element and be used for implementing embodiments of the present invention and be described in detail.Need It is noted that in this application, "～" make as the implication of lower limit and higher limit comprising resin described before and after it With.
<blooming of the present invention>
The blooming of the present invention contains the compound shown in thermoplastic resin, formula (1) and other any composition.
<thermoplastic resin>
Thermoplastic resin can be cellulose esters resin, polycarbonate resin, polystyrene resins, polysulfones tree Fat, polyester resin, polyarylate resinoid, (methyl) acrylic resin, olefine kind resin (such as norborneol alkenes Resin, cyclic olefin resinoid, cyclic conjugated diene resinoid, alicyclic vinyl ring type hydrocarbon resins) etc..Wherein, preferred fiber Element esters resin, (methyl) acrylic resin, polycarbonate resin, cyclic olefin resinoid, most preferably cellulose esters Resin.
<cellulose esters>
Cellulose esters contained in the blooming of the present invention is not particularly limited, preferably carbon number 2～about 22 The carboxylate of straight or branched.The carboxylic acid constituting ester can form ring, it is also possible to for aromatic carboxylic acid.The carboxylic acid constituting ester also may be used To have substituent group.The carboxylic acid particularly preferably carbon number constituting ester is the lower fatty acid of less than 6.
For the concrete example of preferred cellulose esters, cellulose ethanoate, cellulose acetate propionate, fiber can be enumerated Element acetate butyrate, cellulose acetate propionate butyrate is such is also bonded with propanoic acid ester group or fourth in addition to acetyl group The mixed aliphatic ester of the cellulose of perester radical.
Cellulose esters meets following formula (a) and (b) the most simultaneously.In formula, X be the substitution value of acetyl group, Y be propiono Or the substitution value of bytyry or the substitution value of its mixture.The substitution value of acyl group can be measured according to ASTM-D817-96.
Formula (a) 1.5≤X+Y≤2.5
Formula (b) 0≤Y≤1.5
The further preferred cellulose ethanoate of cellulose esters (Y=0) and cellulose acetate propionate (Y；Propiono, Y > 0).Cellulose acetate propionate is preferably 1.0≤X≤2.4,0.1≤Y≤1.5,2.0≤X+Y≤2.5.As cellulose second Acid esters, preferably 1.5≤X≤2.5, the cellulose ethanoate of further preferred 2.0≤X≤2.5.Can cellulose most preferably with Acetas is the cellulose diacetate (DAC) of 2.0≤X≤2.5.
By using above-mentioned cellulose ethanoate or cellulose acetate propionate, can obtain postponing excellence, machinery by force The blooming that degree, environmental turbulence are excellent.
In order to obtain desired optical characteristics, it is also possible to be used in mixed way the cellulose ethanoate that substitution value is different.Different The mixing ratio of cellulose ethanoate is not particularly limited, can be in the range of 10:90～90:10 (mass ratio).
The number-average molecular weight of cellulose esters is preferably 6 × 104～3 × 105Scope, more preferably 7 × 104～2 × 105Scope.This is because the mechanical strength of the film obtained is improved.Weight average molecular weight Mw of cellulose esters, the equal molecule of number Amount Mn can use gel permeation chromatography (GPC) to be measured.One example of condition determination is as described below, but is not limited to This, it is possible to use equal assay method.
Solvent: dichloromethane
Post: Shodex K806, K805, K803G (connect the post that 3 Showa electricians (strain) make to use)
Column temperature: 25 DEG C
Sample solution concentration: 0.1 mass %
Detector: RI Model 504 (GLScience company system)
Pump: L6000 (Hitachi (strain) makes)
Flow: 1.0ml/min
Calibration trace: use by polystyrene standard STK standard polystyrene (east Cao (strain) system) Mw= The calibration trace that 13 samples of 1000000～500 obtain.13 samples use the most at equal intervals.
The raw cellulose of cellulose esters is not particularly limited, and can enumerate: cotton linter, wood pulp, mestha etc..It addition, by The cellulose esters that they obtain can be used in mixed way with arbitrary ratio respectively.
The cellulose esters such as cellulose ethanoate, cellulose acetate propionate can be manufactured by known method.Specifically For, the method described in Japanese Unexamined Patent Publication 10-45804 that is referred to synthesizes.
<compound shown in formula (1)>
The blooming of the present invention contains the compound shown in formula (1).Compound shown in formula (1) can be formula (2), formula (3) and the compound shown in formula (4).
[chemical formula 5]
In above-mentioned formula (1), R11Represent substituent group.Alternatively base, from dissolubility and and the fiber of this compound From the viewpoint of the interaction (compatibility and phase contrast expression power) of element, following substituent group.
As with R11The substituent group represented.Can enumerate: alkyl (such as methyl, ethyl, propyl group, isopropyl, the tert-butyl group, Amyl group, hexyl, octyl group, dodecyl, trifluoromethyl etc.), cycloalkyl (such as cyclopropyl, cyclopenta, cyclohexyl, adamantyl Deng), aryl (such as phenyl, naphthyl etc.), alkoxyl (such as alkoxyl, tert-butoxy etc.), aryloxy group (such as phenoxy group, naphthalene Epoxide etc.), alkyl amino (such as ethylamino etc.), arylamino (such as phenyl amino etc.), alkylthio group (such as methyl mercapto, 2-ethyl hexyl sulfenyl etc.), arylthio (such as thiophenyl etc.), heterocyclic radical (such as pyridine radicals, pyrimidine radicals, oxazolyl, thiazolyl, Di azoly, thiadiazolyl group, miaow di azoly etc.), amino (such as amino, ethylamino, dimethylamino, butylamino, ring penta Base amino, 2-ethylhexylamino, dodecylamino etc.).
R11Shown substituent group can be replaced by following multiple groups further, and adjacent substituent group can also bond together And form ring: alkyl (such as methyl, ethyl, propyl group, isopropyl, the tert-butyl group, amyl group, hexyl, octyl group, dodecyl, fluoroform Base etc.), cycloalkyl (such as cyclopropyl, cyclopenta, cyclohexyl, adamantyl etc.), aryl (such as phenyl, naphthyl etc.), heterocycle Base (such as pyridine radicals, pyrimidine radicals, oxazolyl, thiazolyl, di azoly, thiadiazolyl group, miaow di azoly etc.), acyl amino (example Such as acetyl-amino, benzoyl-amido etc.), alkylthio group (such as methyl mercapto, ethylmercapto group etc.), arylthio (such as thiophenyl, naphthalene Sulfenyl etc.), alkenyl (such as vinyl, 2-acrylic, 3-cyclobutenyl, 1-methyl-3-acrylic, 3-pentenyl, 1-methyl- 3-cyclobutenyl, 4-hexenyl, cyclohexenyl group, styryl etc.), (such as fluorine atom, chlorine atom, bromine atoms, iodine are former for halogen atom Son etc.), alkynyl (such as propargyl etc.), alkyl sulphonyl (such as methyl sulphonyl, ethylsulfonyl etc.), aryl sulfonyl (such as phenyl sulfonyl, Naphthylsulfonyl etc.), alkyl sulphinyl (such as methylsulfinyl etc.), aryl sulfonyl kia (such as phenylsufinyl etc.), phosphono, acyl group (such as acetyl group, pivaloyl group, benzoyl etc.), carbamyl Base (such as amino carbonyl, methylaminocarbonyl, Dimethylaminocarbonyl, butylamino carbonyl, cyclohexylaminocarbonyl, phenyl Amino carbonyl etc.), sulfamoyl (such as amino-sulfonyl, methylaminosulfonyl, dimethylamino-sulfonyl, butylamino Sulfonyl, hexylamino sulfonyl, Cyclohexylamino sulfonyl, octyl amino sulfonyl, dodecylamino sulfonyl, phenyl Amino-sulfonyl, naphthyl-amino sulfonyl, 2-pyridinylamino sulfonyl etc.), sulfamoyl (such as sulfonyl methane amido, benzene Sulfoamido etc.), cyano group, alkoxyl (such as methoxyl group, ethyoxyl, propoxyl group etc.), aryloxy group (such as phenoxy group, naphthoxy Deng), siloxy, acyloxy (such as acetoxyl group, benzoyloxy etc.), sulfonic group or its salt, amino carbonyloxy group, amino (example Such as amino, ethylamino, dimethylamino, butylamino, clopentylamino, 2-ethylhexylamino, dodecylamino Deng), anilino-(such as phenyl amino, chlorphenylamino, toluene amido, anisidino, naphthyl-amino, 2-pyridinylamino Deng), imide, urea groups (such as methyl urea groups, ethyl urea groups, amyl group urea groups, cyclohexylureido, octyl group urea groups, dodecyl Urea groups, phenyl urea groups, naphthyl urea groups, 2-pyridinylamino urea groups etc.), alkoxycarbonyl amino (such as methyloxycarbonylamino, Phenoxycarbonylamino etc.), alkoxy carbonyl (such as methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl etc.), aryloxy group carbonyl Base (such as phenyloxycarbonyl etc.), carbamate groups (such as methyl carbamate base, carbanilate base), alcoxyl Base phenyl (such as methoxyphenyl etc.), phenyl (such as acetoxyl group phenyl etc.), ghiourea group, carboxyl, the salt of carboxylic acid, Hydroxyl, sulfydryl, nitro etc..
As R11Preference, preferably alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, amino, alkyl amino, aryl Amino, alkylthio group；Preferably alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, alkylthio group；Further preferably alkyl, alkoxyl, Aryl, aryloxy group；Particularly preferably alkyl, alkoxyl, most preferably alkyl.At R11In the case of alkyl, preferably carbon number is 1 ～the alkyl of 8.Further preferably carbon number is the alkyl of 1～4.By by R11It is set to these substituent groups, becomes compound Intermiscibility improves, internal haze reduces, the blooming of high latency.
In above-mentioned formula (1), R21And R31Represent substituent group.As R21And R31Shown substituent group, can enumerate: alkane Base (such as methyl, ethyl, propyl group, isopropyl, the tert-butyl group, amyl group, hexyl, octyl group, dodecyl, trifluoromethyl etc.), cycloalkanes Base (such as cyclopropyl, cyclopenta, cyclohexyl, adamantyl etc.), aryl (such as phenyl, naphthyl etc.), heterocyclic radical (such as pyridine Base, pyrimidine radicals, oxazolyl, thiazolyl, di azoly, thiadiazolyl group, miaow di azoly etc.), acyl amino (such as acetyl group ammonia Base, benzoyl-amido etc.), alkylthio group (such as methyl mercapto, ethylmercapto group etc.), arylthio (such as thiophenyl, naphthalene sulfenyl etc.), halogen Element atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), sulfonyl (alkyl sulphonyl (such as methyl sulphonyl, second Base sulfonyl etc.), aryl sulfonyl (such as phenyl sulfonyl, Naphthylsulfonyl etc.)), acyl group (such as acetyl group, trimethyl second Acyl group, benzoyl etc.), carbamoyl (such as amino carbonyl, methylaminocarbonyl, Dimethylaminocarbonyl, butylamino Carbonyl, cyclohexylaminocarbonyl, phenyl amino carbonyl etc.), alkoxyl (such as methoxyl group, ethyoxyl, propoxyl group etc.), aryloxy group (such as phenoxy group, naphthoxy etc.), amino (such as amino, ethylamino, dimethylamino, butylamino, clopentylamino, 2-ethylhexylamino, dodecylamino etc.), alkoxy carbonyl (such as methoxycarbonyl, ethoxy carbonyl, phenoxy group carbonyl Base etc.), aryloxycarbonyl (such as phenyloxycarbonyl etc.), alkylthio group (such as methyl mercapto, 2-ethyl hexyl sulfenyl etc.).
R in formula (1)21And R31The substituent group represented can replace further with multiple same groups, adjacent Substituent group can also bond together and form ring.
As R21Preference, preferably alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, acyl group, alkoxy carbonyl, virtue Epoxide carbonyl, amino, alkylthio group, halogen atom；Further preferably alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, acyl group, Alkoxy carbonyl, aryloxycarbonyl, halogen atom；Particularly preferably alkyl, alkoxyl, acyl group, alkoxy carbonyl.By by R21If For these substituent groups, become the intermiscibility raising of compound, internal haze reduction, inhibit blooming that ooze out, high latency.
As R31Preferred example, preferably alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, acyl group, acyloxy, alkane Epoxide carbonyl, aryloxycarbonyl, amino, alkylthio group, halogen atom；Preferably alkyl, cycloalkyl, alkoxyl, aryl, aryloxy group, Acyl group, acyloxy, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio group, halogen atom；Particularly preferably alkyl, alkoxyl, virtue Base, aryloxy group, acyl group, acyloxy, alkoxy carbonyl, aryloxycarbonyl.By by R31It is set to these substituent groups, becomes compound Intermiscibility improve, internal haze reduce, inhibit blooming that ooze out, high latency.
R41Represent hydrogen atom or substituent group, as R41Shown substituent group, can enumerate: alkyl, cycloalkyl, alkoxyl, Aryl, aryloxy group, acyl group, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio group, halogen atom.
As R41Preference, preferably hydrogen atom, alkyl, cycloalkyl, aryl, acyl group, alkoxy carbonyl, aryloxy group carbonyl Base；Further preferably hydrogen atom, alkyl, cycloalkyl, aryl, acyl group, particularly preferred alkyl, aryl, acyl group.By importing so Group, become the compatibility raising of compound, internal haze reduce, inhibit blooming that ooze out, high latency.
As the integer shown in the k1 in formula (1), from the viewpoint of phase contrast expression power and the compatibility, preferably 1～4 Scope, the scope of further preferred 1～3, particularly preferred 1.
In formula (1), as the substituted the position of substitution of-OCO-, the position that is bonded with benzoxazinone skeleton is set to 1 Time, preferably replace at 3,4,5, further preferably replace at 4.By replacing in these positions, Show high latency.
As the integer shown in the m1 in formula (1), from the viewpoint of phase contrast expression power, the scope of preferably 0～4, The scope of further preferred 0～3, particularly preferred 0.
As the integer shown in the n1 in formula (1), from the viewpoint of the compatibility, the scope of preferably 0～4, further The scope of preferably 0～3, particularly preferred 0.
X in formula (1)1From the viewpoint of light resistance, preferably oxygen atom.
Y1 in formula (1) from the viewpoint of light resistance, preferably oxygen atom or nitrogen-atoms or NR41, further preferred oxygen Atom or nitrogen-atoms, particularly preferred oxygen atom.
Z in formula (1)1From the viewpoint of light resistance, preferably oxygen atom or nitrogen-atoms, particularly preferred nitrogen-atoms.
X in formula (2)2、Y2、Z2、R12、R22、R42, k2 and m2 respectively with the X in formula (1)1、Y1、Z1、R11、R21、 R41, k1 and m1 same meaning.
R in formula (3)13、R23, k3 and m3 respectively with the R in formula (1)11、R21, k1 and m1 same meaning.
R in formula (4)14, and k4 respectively with the R in formula (1)11, k1 same meaning.
Hereinafter enumerate above-mentioned formula (1), above-mentioned formula (2), above-mentioned formula (3) and the compound shown in above-mentioned formula (4) Concrete example, but the present invention is not by any restriction of following concrete example.
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
The blooming of the present invention comprises the compound shown in thermoplastic resin and formula (1), but in order to obtain desired prolonging Late, preferably the compound shown in formula (1) is made an addition in thermoplastic resin.What is called is added with and refers to be dissolved or dispersed in thermoplastic In property resin.Only by being only coated the compound shown in formula (1) on the surface of blooming, it is impossible to obtain desired prolonging Late.
The blooming of the present invention in order to obtain desired delay, preferably with respect to thermoplastic resin 100 mass parts 0.1～ The compound shown in formula (1) is comprised in the range of 20 mass parts, in the range of preferably 1～15 mass parts, further preferred 1.5 ～10 in the range of mass parts, in the range of particularly preferred 2～6 mass parts.If above-mentioned should in the range of, then the light to the present invention Learn film to give and sufficiently postponing, and internal haze, the compatibility, ooze out that characteristic becomes good.
The thickness direction phase difference value Rth of blooming550nm(phase difference value of the thickness direction recorded at 550 nm) with not The thermoplastic resin film added is compared, preferably more than 1.1 times, more preferably 1.2 times～the scope of 10 times, particularly preferably Being 1.3 times～the scope of 4 times, described blooming contains 3 mass parts formula ofs of the present invention relative to thermoplastic resin 100 mass parts (1) compound shown in.By adding the compound of above-mentioned scope, it is possible to provide the blooming that the expression power of delay is excellent.
As long as the blooming of the present invention comprises the compound shown in the above-mentioned formula of more than at least one (1), it is also possible to group Close and use the compound beyond above-mentioned formula (1) to give delay.
<synthesis of the compound shown in formula (1)>
Compound shown in formula (1) can be synthesized by general method.The synthesis example of exemplary compounds set forth below.
(synthesis of exemplary compounds A-022)
[chemical formula 21]
In the eggplant-shape bottle of 2L add 4-HBA 56g, 1N NaOH aqueous solution 800ml, at 40 DEG C stir, molten Solve, drip acetic anhydride 50g.After stirring 1 hour, carry out water cooling, add acetic acid 30ml.After stirring 1 hour, carry out filtering, water Wash, be dried, thus obtain 54.5g intermediate A.
In the eggplant-shape bottle of 100ml, add intermediate A 5.0g, thionyl chloride 3.0ml, DMF0.1ml, add at 80 DEG C Heat 3 hours.Remove solvent and thionyl chloride under reduced pressure, thus obtain intermediate B 5.6g.
In the eggplant-shape bottle of 200ml, add pyridine 50ml, isatoic anhydride 4.5g, after being heated to 50 DEG C, drip intermediate B5.6g.After completion of dropwise addition, outer temperature is warming up to 120 DEG C.After 2 hours, it is cooled to room temperature, adds water 100ml and stir 1 hour.? Carry out filtering, methanol is dried after cleaning, and thus obtains coarse-fine thing 6.4g processed.Column chromatography is utilized (to launch molten coarse-fine thing processed Agent: toluene) refine, thus obtain exemplary compounds A-022 of 3.8g.Exemplary compounds A-022 obtained by NMR and Mass spectrum is identified.
(synthesis of exemplary compounds A-073)
[chemical formula 22]
In 500ml eggplant-shape bottle, add salicylamide 42.0g, dimethylbenzene 100ml, pyridine 5ml, heat at 150 DEG C, return Stream.Intermediate B 66.9g was dripped through 1 hour in this reactant liquor.After completion of dropwise addition, it is heated to reflux 7 hours, is subsequently cooled to Room temperature, decompression is distilled off solvent.Remainder utilize column chromatography (developing solvent: toluene/acetone=5/1) refine, Thus obtain exemplary compounds A-073 of 8.7g.Exemplary compounds A-073 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-115)
[chemical formula 23]
Methyl 2-aminobenzoate 10g and pyridine 30ml is dissolved and carries out frozen water cooling.This solution drips in 14g Mesosome B.In reactant liquor, add water 200ml and stir 2 hours.Filter, wash the solid separated out, thus obtain in the middle of 13.2g Body C.
Add 10.4g intermediate C, 5 phosphoric sulfide 18g and dry pyridine 150ml, be heated to 140 DEG C and to be heated to reflux 18 little Time.After heating terminates, reactant liquor injected in frozen water and stir.After filtering the solid separated out, it is dissolved in dichloromethane.Use nothing Water magnesium sulfate is dried.Decompression is distilled off dichloromethane, dichloromethane/ethanol carry out recrystallization, thus obtain 6.9g Exemplary compounds A-115.Exemplary compounds A-115 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-124)
[chemical formula 24]
In the eggplant-shape bottle of 200ml, add 4-cyanophenol 5.6g, 1N NaOH aqueous solution 80ml and stir at 40 DEG C, Dropping acetic anhydride 5.5g.After stirring 1 hour, carry out water cooling, add acetic acid 3ml.Carry out after stirring 1 hour filtering, wash, dry Dry, obtain 4.7g intermediate D.
Intermediate D4.7g, thio-methyl salicylate 9.8g, triethylamine 6.5g, toluene 30ml is added in 200ml eggplant-shape bottle And nitrogenize, it is heated to reflux 25 hours.After heating terminates, decompression is distilled off solvent.Utilize column chromatography (developing solvent: own Alkane/ethyl acetate=5/1) refine, thus obtain exemplary compounds A-124 of 3.2g.Exemplary compounds A-124 obtained Identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-133)
[chemical formula 25]
In 300ml eggplant-shape bottle, add intermediate C6.2g, Lawesson's reagent 40g, toluene 100ml and be heated to reflux 10 hours.Filter solid, concentrating under reduced pressure filtrate is crossed after being cooled to room temperature.Remainder is utilized column chromatography (developing solvent: heptane/ Ethyl acetate=9/1) refine, thus obtain 4.3g intermediate E.
In 200ml eggplant-shape bottle, add intermediate E 4.3g, acetone 50ml, acetic anhydride 10g and be heated to reflux 4 hours.Cooling Rear addition methanol 50ml also stirs 1 hour.Filter the solid separated out, methanol cleans, and thus obtains 3.2g and illustrates chemical combination Thing A-133.Exemplary compounds A-133 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-146)
[chemical formula 26]
In 1L eggplant-shape bottle, add ortho-aminobenzoic acid 40g, triethylamine 32.0g, acetone 100ml and stir under water cooling Mix.This reactant liquor stirred 3 hours after dropping intermediate B 58.0g through 1 hour.After reactant liquor concentrating under reduced pressure, add 2 Ethylhexylamine 51.8g, acetonitrile 1ml are also stirred at room temperature.PCl is added in this reactant liquor355g, is warming up to 50 DEG C and stirs 20 hours.Heating is cooled to room temperature after terminating, add ethyl acetate 500ml.According to 1N hydrochloric acid, 5%NaHCO3Aqueous solution, pure water Order carry out separatory, concentrating under reduced pressure organic layer.Remainder is utilized column chromatography (developing solvent: toluene/ethyl acetate=5/ 1) refine, thus obtain exemplary compounds A-146 of 12.5g.Exemplary compounds A-146 obtained passes through NMR and mass spectrum Identify.
Other the compound shown in formula (1) can also be with reference to the disclosure of description of the invention and known technology Synthesize.
Beyond compound shown in the blooming heat extraction plastic resin of the present invention and formula (1), it is also possible to containing other Arbitrarily composition.Arbitrarily the example of composition comprise wavelength dispersion controlling agent, sugar ester, plasticizer, UV absorbent, antioxidant, And microgranule etc..
<wavelength dispersion controlling agent>
The blooming of the present invention can also contain wavelength dispersion controlling agent.So-called " wavelength dispersion controlling agent " refers to regulate light Learn the compound of the wavelength dependency that film postpones.The preference of wavelength dispersion controlling agent comprises Japanese Unexamined Patent Publication 2001-166144 Discoid compound described in publication and Japanese Unexamined Patent Publication 2003-344655 publication and Japanese Unexamined Patent Publication 2010-163482 public affairs Compound described in report.
Wavelength dispersion controlling agent is preferably at wave-length coverage or the wave-length coverage tool of 270nm～380nm of 250nm～400nm There is absorption maximum.
Wavelength dispersion controlling agent can be used alone or is mixed with two or more.The addition of wavelength dispersion controlling agent Preferably with respect to thermoplastic resin 100 mass parts in the range of 1.0～20 mass %, further preferably in 1.5～15 matter In the range of amount %, most preferably in the range of 2.0～10 mass %.The adding method of wavelength dispersion controlling agent can at alcohol or Dichloromethane, dioxolane organic solvent in dissolve after wavelength decentralised control agent and add to thermoplastic resin solution's (glue Slurry), or can also directly be added on to rubber cement composition.
Wavelength dispersion controlling agent can add in advance to the mixed solution of thermoplastic resin, it is also possible to is making thermoplasticity The rubber cement of resin is added to arbitrary operation of curtain coating.In the latter case, wavelength dispersion controlling agent and a small amount of is made The solution that thermoplastic resin dissolves adds online to thermoplastic resin and is dissolved in the rubber cement of solvent.This mixing Preferably with such as static mixer (Toray Engineering system), SWJ (blender Hi-Mixer in eastern beautiful silent oscillation pipe) etc. Online mixer is carried out.
Delustering agent can be together added, it is also possible to interpolation delay controlling agent, plasticizer, deterioration are prevented with wavelength dispersion controlling agent The additives such as only agent, stripping accelerator.
In the case of using online mixer, the most under high pressure concentrate dissolving；As long as pressurizing vessel can tolerate regulation Pressure and can heat under elevated pressure, stir.Pressurizing vessel suitably arranges the instrument class such as piezometer, thermometer.Pressurization can By being pressed into the method for the noble gases such as nitrogen or carrying out by adding the rising of thermally-induced solvent vapour pressure.
Heating is preferably carried out from external container, the such as easy control of temperature of jacketing heat device, therefore preferably.Add solvent The temperature of the scope that heating-up temperature is preferably used more than the boiling point of solvent and this solvent will not seethe with excitement, is set as such as 30～150 DEG C scope.At a set temperature, adjusting pressure makes solvent to seethe with excitement.Cool down after dissolving while from container take out or Extract out from container with pump etc., use the coolings such as heat exchanger, provide it to masking.Chilling temperature now can also cool down To room temperature, but it is cooled to the temperature of low 5～10 DEG C than boiling point and carries out casting at temperature and can reduce cement viscosity, therefore preferably.
<sugar ester>
The blooming of the present invention preferably comprises the sugar ester beyond cellulose esters.This sugar ester so-called refers to containing furanose structure Or at least any of compound of pyranose structure.Sugar ester can be monosaccharide, it is also possible to form for connecting 2～12 sugared structures Polysaccharide.And, at least one of the OH base that sugar structure is preferably had by sugar ester carries out the compound being esterified.Sugar ester Esterification yield is preferably present in more than 70% of the OH base in pyranose structure or furanose structure.
The example of the sugar constituting sugar ester comprises glucose, galactose, mannose, fructose, xylose or arabinose, breast Sugar, sucrose, C24H42 O21,1F-Fructofuranosyl nystose, stachyose, maltose alcohol, lactose, lactulose, cellobiose, maltose, fibre Dimension trisaccharide, maltotriose, Raffinose or ketose.And then, the example of the sugar constituting sugar ester also comprises gentiobiose, Radix Gentianae Trisaccharide, Radix Gentianae tetrose, xylotriose, galactosyl sucrose etc..Certainly, sugar is not limited to these sugar.Constitute the sugared structure of sugar ester Particularly preferably containing pyranose structure and furanose structure.
The preference of the sugar constituting sugar ester is sucrose, ketose, C24H42 O21,1F-Fructofuranosyl nystose, stachyose etc., enters One step is preferably sucrose.
In sugar ester, the whole OH bases in pyranose structure or furanose structure or one are carried out a point esterification.For The monocarboxylic acid of esterification is not particularly limited, it is possible to use known aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate Deng.The carboxylic acid used can be a kind, it is also possible to for mixing of more than two kinds.
Constitute sugar ester ester, the example of preferred aliphatic monocarboxylic acid comprise acetic acid, propanoic acid, butanoic acid, isopropylformic acid., penta Acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, 2-ethyl-hexanecarboxylic acid, hendecanoic acid, lauric acid, tridecanoic acid, Semen Myristicae Acid, pentadecanoic acid, Palmic acid, heptadecanoic acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, cerinic acid, two Satisfied fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, the Asias such as heptadecanoic acid, montanic acid, melissic acid, lacceroic acid The unsaturated fatty acids etc. such as fiber crops acid, arachidonic acid, octenoic acid.
Constitute sugar ester ester, that the example of preferred cycloaliphatic monocarboxylic comprises Cyclopentane carboxylic acid, cyclohexane-carboxylic acid, ring is pungent Alkane carboxylic acid or their derivant.
Constitute sugar ester ester, the example of preferred aromatic monocarboxylate comprise benzoic acid, toluic acid etc. at benzoic acid Phenyl ring in imported alkyl, the aromatic monocarboxylate of alkoxyl, cinnamic acid, diphenylglycollic acid, biphenyl carboxylic acids, naphthalene-carboxylic acid, four Hydrogenated naphthalene carboxylic acid etc. has aromatic monocarboxylate or their derivant of more than 2 phenyl ring.More specifically, diformazan is comprised Benzoic acid, mellic acid, 3,5-mesitylenic acid, 2,3,4-trimethylbenzene formic acid, γ-different acid, durylic acid, 2,4,6-trimethylbenzene Formic acid, α-different acid, cumic acid, α-toluic acid, hydratropic acid, atropic acid, hydrocinnamic acid, salicylic acid, o-anisic acid, Between anisic acid, paraanisic acid, Mixture of the isomeric cresotic acids., ortho-homosalicylic acid (o-ホ モ サ リ チ Le acid homosalicylic acid), Cresotic acid (m-ホ モ サ リ チ Le acid homosalicylic acid), paracresotic acid (m-ホ モ サ リ チ Le acid Homosalicylic acid), pyrocatechuic acid, β-resorcylic acid, vanillic acid, isovanillic acid, veratric acid, adjacent veratric acid, no food Son acid, asarylic acid, mandelic acid, to methoxybenzene glycolic, 4-hydroxy-3-methoxy-.alpha.-toluic acid., homoveratric acid, adjacent homoveratric acid, neighbour's carboxyl styrene ketone Acid, P-coumaric acid；Particularly preferably benzoic acid.
The ester of oligosaccharide can be used as the sugar ester in the present invention.Oligosaccharide makes amylase etc. act on enzyme to make with starch, sucrose etc. Making, the example of preferred oligosaccharide comprises Fructus Hordei Germinatus oligose, isomalto Oligosaccharide, fruit oligose, galactooligosaccharicomposition, xylooligosaccharide.
Sugar ester is for condensation more than 1 and 12 with the pyranose structure shown in following formula (A) or furanose structure extremely The compound of few a kind.R in formula (A)11～R15、R21～R25Represent acyl group or hydrogen atom that carbon number is 2～22, M and n is respectively the integer of 0～12, and m+n is the integer of 1～12.
[chemical formula 27]
Formula (A)
R11～R15、R21～R25It is preferably benzoyl, hydrogen atom.Benzoyl can also have substituent R26(p is 0 ～5), can enumerate such as alkyl, alkenyl, alkoxyl, phenyl and then, these alkyl, thiazolinyl, phenyl can also have and take Dai Ji.The ester of oligosaccharide also can be by the method manufacture as other sugar ester.
As the concrete example of the sugar ester used in the present invention, can enumerate: Japanese Unexamined Patent Publication 2012-230154 publication section Fall [0130]～[0137] and compound described in Japanese Unexamined Patent Publication 2012-230282 publication paragraph [0077]～[0078], But the present invention is not limited to this.
The blooming of the present invention, in order to suppress variation and the stabilisation display grade of phase difference value, preferably comprises above-mentioned sugar Ester is 0.5～30 mass % of blooming, particularly preferably containing 5～30 mass %.
<plasticizer>
The blooming of the present invention can contain plasticizer.Plasticizer is not particularly limited, but preferably increases from polybasic carboxylic acid esters Mould agent, glycolic ester plasticizer, phthalic ester plasticizer, fatty acid ester plasticiser, polyalcohol ester plasticizer, Polyesters plasticizer, Acrylic Plasticizer etc. select.The situation of two or more plasticizer is contained in the blooming of the present invention Under, preferably at least a kind is preferably polyalcohol ester plasticizer.
(polyalcohol ester plasticizer)
Polyalcohol ester plasticizer is the plasticizer that the ester of the aliphatic polyol by more than 2 yuan and monocarboxylic acid is constituted, excellent It is selected in intramolecular and there is aromatic rings or cycloalkyl ring.It is preferably the aliphatic polybasic alcohol ester of 2～20 yuan.
Come from different backgrounds and possess different abilities alkoxide plasticizer polyhydric alcohol by below general formula (a) represent.
Formula (a) Ra-(OH)n
Here, Ra represents the organic group of n valency, n represents the positive integer of more than 2, OH basis representation alcohol or the hydroxyl of phenol.
Come from different backgrounds and possess different abilities alkoxide plasticizer, the example of preferred polyhydric alcohol comprise ribitol, 1,2,3,4,5-pentanepentol, second two Alcohol, diethylene glycol, triethylene glycol, TEG, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-fourth Glycol, 1,3 butylene glycol, 1,4-butanediol, dibutylene glycol, 1,2,4-butantriol, 1,5-pentanediol, 1,6-HD, oneself three Alcohol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, Sorbitol, trimethylolpropane, three hydroxyls Methyl ethane, xylitol etc., but be not particularly limited.Particularly preferably triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, Sorbitol, trimethylolpropane, xylitol.
The example of monocarboxylic acid of alkoxide plasticizer of coming from different backgrounds and possess different abilities is not particularly limited, it is possible to use known aliphatic list Carboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate etc..If using cycloaliphatic monocarboxylic, aromatic monocarboxylate, then from improving thoroughly From the standpoint of moist, retention, preferably.
As the example of preferred monocarboxylic acid, following monocarboxylic acid can be enumerated, but be not limited to this.
The example of aliphatic monocarboxylic acid comprises straight chain or the fatty acid of side chain with carbon number 1～32.Carbon number More preferably 1～20, particularly preferably 1～10.If containing acetic acid, then the compatibility with cellulose increases, therefore preferably. It is also preferred that carry out mixing using by acetic acid and other monocarboxylic acid.
As preferred aliphatic monocarboxylic acid, can enumerate: acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, nonyl Acid, capric acid, the acid of 2-ethyl-hexan, hendecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, Palmic acid, 17 Alkanoic acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, cerinic acid, carboceric acid, montanic acid, melissic acid, The insatiable hungers such as the satisfied fatty acid of lacceroic acid etc., undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid With fatty acid etc..
Preferably the example of cycloaliphatic monocarboxylic comprise Cyclopentane carboxylic acid, cyclohexane-carboxylic acid, cyclooctanecarboxylic acid or they Derivant.
The example of preferred aromatic monocarboxylate comprises benzoic acid, toluic acid etc. and has imported 1 in benzoic phenyl ring ～the carboxylic acid of alkoxyl, biphenyl carboxylic acids, naphthalene-carboxylic acid, the tetralincarboxylic acid etc. such as 3 alkyl, methoxyl group or ethyoxyl have 2 The aromatic monocarboxylate of individual above phenyl ring or their derivant.Particularly preferably benzoic acid.
The carboxylic acid of ester of alkoxide plasticizer of coming from different backgrounds and possess different abilities can be a kind, it is also possible to for combination of more than two kinds.It addition, it is many OH base in unit's alcohol can all be esterified, it is also possible to a part is retained with the state of OH base.
The molecular weight of polyalcohol ester plasticizer is not particularly limited, but the scope of preferably 300～1500, the most excellent Elect the scope of 350～750 as.The big aspect of molecular weight is due to the most volatile, therefore preferably, from poisture-penetrability and thermoplastic resin From the standpoint of the compatibility, a least side.
(glycolic ester plasticizer)
Glycolic ester plasticizer is not particularly limited, but preferably uses alkyl phthalic acyl group alkyl glycolate ester Class.The example of alkyl phthalic acyl glycolic esters comprises methyl phthalyl acid methyl ester, ethyl neighbour Phenyl-diformyl base ethyl glycolate, propyl group phthalyl propyl propionate, butyl phthalyl acid butyl ester, pungent The misery ester of base phthalyl, methyl phthalyl acetoacetic ester, ethyl phthalyl acid first Ester, ethyl phthalyl propyl propionate, methyl phthalyl acid butyl ester, ethyl phthalyl Acid butyl ester, butyl phthalyl acid methyl ester, butyl phthalyethyl glycolate, propyl group phthalyl Butyl glycolate, butyl phthalyl propyl propionate, the misery ester of methyl phthalyl, ethyl O-phthalic Acyl group glycolic monooctyl ester, octyl phthalyl base methyl glycollate, octyl phthalyl base ethyl glycolate etc..
(phthalic ester plasticizer)
The example of phthalic ester plasticizer comprises diethyl phthalate, phthalic acid dimethoxy second Ester, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, phthalic acid two-2-ethyl hexyl Ester, dioctyl phthalate, dicyclohexyl phthalate, p-phthalic acid dicyclohexyl maleate etc..
(citric acid ester plasticizer)
The example of citric acid ester plasticizer comprises citric acid acetyl three methyl ester, acetyl triethyl citrate, Fructus Citri Limoniae Acid acetyl etc..
(fatty acid ester plasticiser)
The example of fatty acid ester plasticiser comprises butyl oleate, methylacetyl acetyl group ester, dibutyl sebacate Deng
(phosphate plasticizer)
The example of phosphate plasticizer comprises triphenyl phosphate, tricresyl phosphate, tricresyl phosphate base diphenyl ester, phosphoric acid Octyl group diphenyl ester, diphenyl phosphate Biphenyl Ester, tricresyl phosphate octyl group ester, tributyl phosphate etc..
(polybasic carboxylic acid esters plasticizer)
Polybasic carboxylic acid esters plasticizer is more than 2 yuan, preferably 2 yuan～the polybasic carboxylic acid of 20 yuan and the carboxylate of alcohol.It addition, Aliphatic polycarboxylic acid is preferably 2～20 yuan, in the case of aromatic polycarboxylic acid, ester ring type polybasic carboxylic acid, and preferably 3 yuan ～20 yuan.
Polybasic carboxylic acid is represented by below general formula (b).
Formula (b) Rb (COOH)m(OH)n
(wherein, Rb represents the organic group of (m+n) valency, and m represents the positive integer of more than 2, and n represents the integer of more than 0, COOH basis representation carboxyl, OH basis representation alcohol or phenolic hydroxyl group.)
The preferably example of polybasic carboxylic acid comprises as more than the trivalent of trimellitic acid, trimesic acid, Pyromellitic Acid etc Aromatic polycarboxylic acid or derivatives thereof, as succinic acid, adipic acid, Azelaic Acid, decanedioic acid, oxalic acid, fumaric acid, maleic acid, The aliphatic polycarboxylic acid of tetrahydrophthalic acid etc, such as the hydroxyl of tartaric acid, hydroxymalonic acid, malic acid, citric acid etc Polybasic carboxylic acid etc., but it is not limited to these.Especially with hydroxyl polycarboxylic acid, then the retention of plasticizer (will not be from light Learn film volatilization) improve, therefore preferably.
The alcohol of ester of carboxylic acid esters plasticizer of coming from different backgrounds and possess different abilities can also be not particularly limited for known alcohol, phenols.Such as For having the straight chain of carbon number 1～32 or the aliphatic saturated alcohols of side chain or aliphatic unsaturated alcohol.More preferably carbon Atomic number 1～20, particularly preferably carbon number 1～10.Additionally, it also may be preferable for use the alicyclic alcohol such as cyclopentanol, Hexalin The aromatic alcohols or derivatives thereofs etc. such as or derivatives thereof, benzylalcohol, cinnamyl alcohol.
The alcohols of ester of carboxylic acid esters plasticizer of coming from different backgrounds and possess different abilities can be a kind, it is also possible to for mixing of more than two kinds.
In the case of using hydroxyl polycarboxylic acid as polybasic carboxylic acid, it is possible to use monocarboxylic acid is by hydroxyl polycarboxylic acid's Alcohol hydroxyl group or phenolic hydroxyl group esterification.Monocarboxylic acid is preferably aliphatic monocarboxylic acid, but is not limited to this.
Aliphatic monocarboxylic acid preferably has straight chain or the fatty acid of side chain of carbon number 1～32.More preferably carbon Atomic number 1～20, particularly preferably carbon number 1～10.As preferred aliphatic monocarboxylic acid, can enumerate: acetic acid, third Acid, butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, 2-ethyl-hexanecarboxylic acid, hendecanoic acid, lauric acid, tridecane Acid, myristic acid, pentadecanoic acid, Palmic acid, heptadecanoic acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignocerane The satisfied fatty acid such as acid, cerinic acid, carboceric acid, montanic acid, melissic acid, lacceroic acid, undecylenic acid, oleic acid, sorbic acid, The unsaturated fatty acids etc. such as linoleic acid, linolenic acid, arachidonic acid.
The preferably example of cycloaliphatic monocarboxylic can be enumerated: Cyclopentane carboxylic acid, cyclohexane-carboxylic acid, cyclooctanecarboxylic acid or Their derivant.
The preferably example of aromatic monocarboxylate can be enumerated: benzoic acid, toluic acid etc. are led in benzoic phenyl ring Entered the monocarboxylic acid of alkyl, biphenyl carboxylic acids, naphthalene-carboxylic acid, tetralincarboxylic acid etc. have more than 2 phenyl ring aromatic monocarboxylate, Or their derivant.
The carboxylic acid that alcohol hydroxyl group or the phenolic hydroxyl group of hydroxyl polycarboxylic acid carry out being esterified is particularly preferably acetic acid, propanoic acid, Benzoic acid.
The molecular weight of polybasic carboxylic acid esters plasticizer is not particularly limited, but the scope of preferably molecular weight 300～1000, The more preferably scope of 350～750.From the standpoint of the retention of plasticizer improves, a biggest side；From moisture-inhibiting From the standpoint of the compatibility of property and cellulose esters, a least side.
The acid number of polybasic carboxylic acid esters plasticizer is preferably below 1mgKOH/g, more preferably 0.2mgKOH/g with Under.By making acid number be above-mentioned scope, the environmental turbulence of delay is also inhibited, therefore preferably.Acid number refers to neutralize sample The milligram number of the potassium hydroxide required for acid (carboxyl being present in sample) contained in 1g.Acid number enters according to JIS K0070 Row measures.
The more preferred example of polybasic carboxylic acid esters plasticizer can be enumerated: triethyl citrate, tributyl citrate, Acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), citric acid benzoyl tributyl, citric acid second Acyl group triphenylmethyl methacrylate, citric acid acetyl three benzyl ester, dibutyl tartrate, tartaric acid diacetyl dibutyl ester, tri trimellitate fourth Ester, Pyromellitic Acid four butyl ester etc., but it is not limited to these.
(polyesters plasticizer)
Polyesters plasticizer for example, has the polyesters plasticizer of aromatic rings or cycloalkyl ring in intramolecular.Polyesters increases Mould the aromatic series end ester plasticizer shown in the most following formula (c) of agent.
Formula (c) B-(G-A)n-G-B
(in formula, B represents benzene monocarboxylic acid residue, and G represents aklylene glycol residue or the carbon number 6 of carbon number 2～12 ～the aryl-diol residue of 12 or oxyalkylene diol residue that carbon number is 4～12, A represents the Asia of carbon number 4～12 Alkyl dicarboxylic aid's residue or aryl dicarboxylic acid's residue of carbon number 6～12, it addition, n represents the integer of more than 1.)
The polyesters plasticizer of formula (c) is sub-by the aklylene glycol residue shown in the benzene monocarboxylic acid residue shown in B, G, oxygen Alkyl diol residue or the alkylene dicarboxylic acids residue shown in aryl-diol residue, A or aryl dicarboxylic acid's residue are constituted.Polyesters Plasticizer is obtained by the reaction as common polyesters plasticizer.
The example of the benzene monocarboxylic acid composition of polyesters plasticizer comprise benzoic acid, p-tert-butyl benzoic acid, ortho-toluic acid, Meta-toluic acid, paratolunitrile, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, amino benzoic Acid, acetyl oxygen Yl benzoic acid, can be these one kind or two or more combination.
The example of the aklylene glycol composition of the carbon number 2～12 of polyesters plasticizer comprises ethylene glycol, 1,2-the third two Alcohol, 1,3-propylene glycol, 1,2-butanediol, 1,3 butylene glycol, 1,2-propylene glycol, 2-methyl 1,3-propylene glycol, 1,4-butanediol, 1, 5-pentanediol, 2,2-dimethyl-1,3-propylene glycol (neopentyl glycol), 2,2-diethyl-1,3-propylene glycol (3,3-dihydroxymethyl penta Alkane), 2-normal-butyl-2-ethyl-1,3 propylene glycol (3,3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol, 1,6-HD, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-ethohexadiol, 1,9-nonanediol, 1,10-last of the ten Heavenly stems two Alcohol, 1,12-octacosanol.These glycol can use with the form of one kind or two or more mixture.Particularly carbon atom The aklylene glycol of several 2～12 and the excellent compatibility of cellulose esters, therefore particularly preferably.
As the oxyalkylene diol component of the carbon number 4～12 of polyesters plasticizer, such as, there are diethylene glycol, three second Glycol, TEG, dipropylene glycol, tripropylene glycol etc., these glycol can make with the form of one kind or two or more mixture With.
The example of the alkylene dicarboxylic acids composition of the carbon number 4～12 of polyesters plasticizer comprise succinic acid, maleic acid, Fumaric acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid, decanedioic acid, dodecanedicarboxylic acid etc..These dicarboxylic acids can be respectively with a kind or 2 The form planting above mixture uses.As the arlydene dicarboxylic acid component of carbon number 6～12, there is phthalic acid, right Phthalic acid, M-phthalic acid, 1,5-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids etc..
The number-average molecular weight of polyesters plasticizer is preferably the scope of 300～1500, the model of more preferably 400～1000 Enclose.It addition, its acid number is below 0.5mgKOH/g, hydroxyl value is below 25mgKOH/g, more preferably acid number be 0.3mgKOH/g with Under, hydroxyl value be below 15mgKOH/g.
(Acrylic Plasticizer)
As (methyl) acrylic polymer of Acrylic Plasticizer can be weight average molecular weight more than 3000 and The polymer X of less than 30000, it by not having the ethylene unsaturated monomer Xa of aromatic rings and hydroxyl to major general in intramolecular There is the ethylene unsaturated monomer Xb of hydroxyl and carry out copolymerization with not there is aromatic rings in intramolecular and and obtain.
Or, as (methyl) acrylic polymer of Acrylic Plasticizer can be weight average molecular weight more than 500 and The polymer Y of less than 3000, it obtains by being polymerized the ethylene unsaturated monomer Ya without aromatic rings.
Preferred polymers X is represented by following logical formula (X), and polymer Y is represented by following formula (Y).
Logical formula (X) :-[CH2-C(-Rc)(-CO2Rd)]m-[CH2-C(-Re)(-CO2Rf-OH)-]n-[Xc]p-
Formula (Y): Ry-[CH2-C(-Rg)(-CO2Rh-OH)-]k-[Yb]q-
In formula (X) or formula (Y), Rc, Re, Rg represent H or methyl.Rd represents alkyl or the cycloalkanes of carbon number 1～12 Base.Rf, Rh represent-CH2-、-C2H4-or C3H6-.Ry represents the alkyl within hydroxyl, H or carbon number 3.Xc represent can with Xa, The monomeric unit of Xb polymerization.Yb represent can with Ya copolymerization and monomeric unit.M, n, k, p and q represent molar composition ratio.Wherein, m ≠ 0, n ≠ 0, k ≠ 0, m+n+p=100, k+q=100.
As the addition of these plasticizers, it is being preferably in the range of 0.5～30 mass % relative to thermoplastic resin Contain, particularly preferably contain in the range of 5～20 mass %.
[other resin]
Containing thermoplastic resin in the blooming of the present invention but it also may comprise beyond the thermoplastic resin mainly contained Other resin.The example of other resin comprise cellulose ether resinoid, polycarbonate resin, polystyrene resins, Polysulfones resin, polyester resin, polyarylate resinoid, acrylic resin, olefine kind resin (norborneol alkenes tree Fat, cyclic olefin resinoid, cyclic conjugated diene resinoid, alicyclic vinyl ring type hydrocarbon resins etc.) etc..Other resin excellent The example of choosing comprises cellulose esters resinoid, polycarbonate resin, acrylic resin, cyclic olefin resinoid.Using In the case of other resin, in the range of 5～70 mass % of the preferred blooming of its content.
[UV absorbent]
The blooming of the present invention can contain UV absorbent, it is also possible to containing two or more UV absorbent.Ultraviolet The purpose of light absorbers is, improves durability by absorbing the ultraviolet of below 400nm, particularly optimal wavelength 370nm Under transmitance be less than 10%, more preferably less than 5%, more preferably less than 2%.
UV absorbent is not particularly limited, such as, can enumerate: epoxide benzophenone compound, benzotriazole Compound, salicylate compounds, benzophenone compound, cyanoacrylate compound, compound in triazine class, nickel Complex salts compounds, inorganic particle etc..
The concrete example of UV absorbent have the chloro-2-of 5-(3,5-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 benzyloxy hexichol first Ketone, 2,4-behzyloxybenzophenone etc., it addition, have Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, the Tinuvin class such as Tinuvin 327, Tinuvin 328, Tinuvin 928, these are the city of BASF Japanese firm Sell product, preferably use.
UV absorbent is Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbent, triazines purple Ultraviolet absorbers, particularly preferably Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbent.Additionally, have The discoid compounds such as the compound of 1,3,5-triazine ring are also preferably as UV absorbent.
UV absorbent can be polymeric UV absorber；Particularly preferably Japanese Unexamined Patent Publication 6-148430 record The UV absorbent of polymer-type.
The interpolation of UV absorbent can the alcohol such as methanol, ethanol, butanol or dichloromethane, methyl acetate, acetone, two Make an addition to rubber cement or be directly added on glue after the organic solvents such as alkane or their mixed solvent dissolve UV absorbent In slurry component.It addition, the dispersions such as substance migration dissolvers or the sand mill of organic solvent will not be dissolved in as inorganic particle Machine is added in rubber cement after disperseing in the solution of organic solvent and cellulose esters.
The content of the UV absorbent in blooming is in the case of the dry film thickness of blooming is 30～200 μm, excellent Select the scope of 0.5～10 mass %, the scope of further preferred 0.6～4 mass %.But, according to the kind of UV absorbent Class, use condition etc. to be adjusted.
[antioxidant]
Antioxidant is also referred to as deterioration preventing agent.In the state that liquid crystal image display device etc. is placed on high humidity high temperature In the case of Xia, sometimes cause the deterioration of blooming.Antioxidant such as postpones or suppresses blooming to decompose, and it is due to blooming In the halogen of residual solvent amount or the phosphoric acid etc. of phosphoric acid class plasticizer and produce.
Antioxidant such as preferably hindered phenol compound.The example of hindered phenol compound can be enumerated: 2,6-bis--uncle Butyl-paracresol, tetramethylolmethane-four [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(3- The tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1,6-HD-bis-[3-(3,5-di-t-butyl-4-hydroxy phenyl) third Acid esters], 2,4-double-(the most pungent sulfenyl)-6-(4-hydroxyl-3,5-di-t-butyl anilino-)-1,3,5-triazine, 2,2-sulfur generation-two Ethylenebis [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyl Phenyl) propionic ester, N, N '-hexa-methylene double (3,5-di-t-butyl-4-hydroxy-hydrocineamide), 1,3,5-trimethyl- 2,4,6-tri-(3,5-di-t-butyl-4-hydroxybenzyl) benzene, three-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanuric acid esters Deng.Particularly preferably 2,6-di-t-butyl-paracresol, tetramethylolmethane-four [3-(3,5-di-t-butyl-4-hydroxy phenyl) propanoic acid Ester], triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester].
As antioxidant, it is also possible to be applied in combination N, N '-bis-[3-(3,5-di-t-butyl-4-hydroxy phenyl) propionyl Base] the Phosphorus processing stabilizers such as the matal deactivator of the hydrazine such as hydrazine or three (2,4-di-t-butyl phenyl) phosphite ester
The addition of the antioxidant in the blooming of the present invention is by preferred based on the mass ratio of thermoplastic resin The scope of 1ppm～1.0%, further preferred 10～the scope of 1000ppm.
[microgranule]
The blooming of the present invention can be used for making sliding good containing microgranule.The dynamic of the one side of the blooming of the present invention rubs Wipe coefficient and be preferably the scope of 0.2～1.0.
Microgranule can be mineral particulates, it is also possible to for Organic substance microgranule.The example of mineral particulates comprise silicon dioxide, Titanium dioxide, aluminium oxide, zirconium oxide, calcium carbonate, calcium carbonate, Talcum, clay, burn till Kaolin, burn till calcium silicates, silicate hydrate Calcium, aluminium silicate, magnesium silicate and calcium phosphate.The example of Organic substance microgranule comprises politef, cellulose ethanoate, polyphenyl second Alkene, polymethyl methacrylate, polypropylmethacryla,es, polymethyl acrylate, polyethylencarbonate, styrene class Resin, silicone resin, polycarbonate resin, benzoguanamine resinoid, tripolycyanamide resinoid, TPO powder, polyester The organic high molecular compounds such as resinoid, polyamide-based resin, polyimide based resin or polyvinyl fluoride resinoid, starch Crushing and classification thing etc..And then, the macromolecular compound that synthesized by suspension polymerization, by spray drying method or dispersion method It also is used as microgranule etc. the macromolecular compound or inorganic compound being formed as ball-type.Wherein, microgranule preferably comprises the micro-of silicon Grain, particularly preferred silicon dioxide.This is the turbidity in order to reduce blooming.
The mean diameter of the primary particle of microgranule preferably 5～the scope of 400nm, more preferably 10～the scope of 300nm.Optics In film, microgranule mainly contains with the form of the secondary aggregation body of particle diameter 0.05～0.3 μm.If the primary particle of microgranule is average Particle diameter is the scope of 100～400nm, then it is also preferred that be not condensed and contain in blooming with the form of primary particle.
The content of the microgranule in blooming is preferably the scope of 0.01～1 mass %, particularly preferred 0.05～0.5 mass % Scope.In the case of the blooming utilizing the multiple structure that the tape casting is formed altogether, preferably at this addition of film surface configuration Microgranule.
The microgranule of silicon dioxide such as with Aerosil R972, R972V, R974, R812,200,200V, 300, R202, The trade name of OX50, TT600 (above Japan Aerosil (strain) system) carries out commercially available.Zirconic microgranule is such as with Aerosil The trade name of R976 and R811 (above Japan Aerosil (strain) system) carries out commercially available.
The example of Organic substance microgranule comprises silicone resin, fluororesin and acrylic resin etc..Preferably silicone resin, the most excellent Choosing has a material of tridimensional network, such as with Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120 and Tospearl 240 (be that Toshiba's silicone (strain) is made above) Trade name is commercially available.
Wherein, Aerosil 200V, Aerosil R972V make the turbidity that blooming holding is relatively low, reduce friction system simultaneously The effect of number is obvious, therefore, can particularly preferably use.
The solution containing the thermoplastic resin i.e. glue that arbitrary composition (various additive) can be added batch-wise to masking In slurry, it is also possible to prepare additive lysate separately and add online.Especially for reducing microgranule, filtering material is born Lotus, a preferably online interpolation part or total amount.
In the case of additive lysate is added online, for the Combination with rubber cement, preferably at additive Lysate adds a small amount of thermoplastic resin.The amount of the thermoplastic resin in additive lysate is preferably with respect to solvent 100 Mass parts is the scope of 1～10 mass parts, the scope of more preferably 3～5 mass parts.
Online interpolation and mixing are preferably used such as static mixer (Toray Engineering system), SWJ, and (east is beautiful quiet Only blender Hi-Mixer in type pipe) etc. online mixer etc. carry out.
<manufacture method of blooming>
The manufacture method of the blooming of the present invention is illustrated.The blooming of the present invention can pass through solution casting method system Make, it is also possible to made by melted curtain coating legal system.
The manufacture of the blooming of the present invention can be carried out by following operation: makes thermoplastic resin and additive be dissolved in solvent And prepare the operation of rubber cement；By rubber cement curtain coating operation on the annular metal supporting mass persistently moved；Rubber cement system by curtain coating Reticulate thing the operation being dried；The operation peeled off from metal support；Carry out the operation stretched or width keeps；Enter The operation that one step is dried；The operation that the film completed is wound.
(rubber cement preparation section)
The operation preparing rubber cement is illustrated.If the concentration of the thermoplastic resin in rubber cement is high, then at metal support Drying load after being cast on body reduces, therefore preferably.On the other hand, if the concentration mistake of the thermoplastic resin in rubber cement Height, then load when filtering increases, and filtering accuracy is deteriorated.Therefore, the concentration of the thermoplastic resin in rubber cement preferably 10～35 matter The scope of amount %, the more preferably scope of 15～25 mass %.
The solvent of rubber cement is mixed solvent independent or of more than two kinds, but if the good solvent of thermoplastic resin and bad The mixed solvent of solvent, then from the standpoint of becoming to produce efficiency, preferably.From thermoplastic resin deliquescent from the standpoint of, excellent Select good solvent many.The preferred scope of the blending ratio of good solvent and poor solvent be good solvent be the model of 70～98 mass % Enclosing, poor solvent is the scope of 2～30 mass %.The solvent dissolving the thermoplastic resin used individually is defined as good molten Agent, is poor solvent by the most swelling Material Definitions that maybe will not dissolve used thermoplastic resin.At thermoplastic resin In the case of cellulose esters, the kind of good solvent and poor solvent becomes according to averagely degree of acetifying (degree of substitution with acetyl group) Change.Such as acetone is good solvent for the acetas (degree of substitution with acetyl group 2.4), cellulose acetate propionate of cellulose, It is poor solvent for the acetas (degree of substitution with acetyl group 2.8) of cellulose.
The example of good solvent can be enumerated: the organic halogen compounds such as dichloromethane and dioxolane, acetone, acetic acid first Ester, methyl acetoacetate etc., be not particularly limited.Can particularly preferably enumerate dichloromethane or methyl acetate.
The example of poor solvent can be enumerated: methanol, ethanol, n-butyl alcohol, hexamethylene, Ketohexamethylene etc., is not particularly limited. It addition, the content of the water in rubber cement is preferably the scope of 0.01～2 mass %.
By being dried the solvent removing and reclaiming rubber cement from film in film making process.Recycling design can be recycled.Return In receipts solvent, trace contains additive, such as plasticizer, UV absorbent, polymer, monomer component etc., even if containing the most sometimes These are had the most preferably to recycle, it is also possible to carry out refined recycling as required.
The dissolving of the thermoplastic resin in the preparation of rubber cement can use general method.If pressurizeed while adding Heat, then can be heated to the temperature of more than the boiling point under normal pressure.If at ambient pressure more than the boiling point of solvent and the most molten Stirring and dissolving solution at a temperature of the scope that agent will not be seethed with excitement, then be possible to prevent to be referred to as the undissolved thing of bulk of gel or powder ball Generation.It addition, it is also preferred that after thermoplastic resin is mixed with poor solvent making it moistening or swelling, add good molten further Agent is dissolved.
Pressurization can be by the method for the noble gases such as press-in nitrogen or the method for the vapour pressure being produced solvent by heating Carry out.Heating is preferably carried out from outside, on the other hand, the such as pressurization of jacketing heat device be easily controlled temperature, therefore preferably.
The thermoplastic resin that heating-up temperature is high, its dissolubility improves, therefore preferably.On the other hand, if heating-up temperature is too high, Then reaction pressure uprises, and productivity ratio reduces.Preferably heating-up temperature is the scope of 45～120 DEG C, the model of more preferably 60～110 DEG C Enclose, further preferred 70 DEG C～the scope of 105 DEG C.Make solvent will not seethe with excitement at a set temperature it addition, adjust pressure.
The preparation of rubber cement the most preferably uses hot-cold lysis method.Thermoplastic resin can be made to be dissolved in second by hot-cold lysis method Acid methyl ester equal solvent.
Then, thermoplastic resin solution use the suitable filtering materials such as filter paper filter.In order to remove insoluble matter Deng, the filtering precision of filtering material is the least.But, if filtering precision is too small, the most easily produce filter material The blocking of material.It is therefore preferable that the filter material of below filtering precision 0.008mm, the scope of more preferably 0.001～0.008mm Filter material, the filter material of the scope of further preferred 0.003～0.006mm.
The material of filtering material is not particularly limited, it is possible to use common filtering material.Polypropylene, polytetrafluoroethylene (registration Trade mark) etc. the metal filtering material such as plastic filter material and rustless steel there is no coming off of fiber, therefore preferably.Preferably pass through It is filtered to remove and reduces impurity contained in the cellulose esters of raw material, particularly bright spot foreign body.
So-called bright spot foreign body refers to configure 2 polaroids with orthogonal polarization state, places blooming etc. betwixt, from partially Light is irradiated in the shake side of sheet, and when the opposite side of polaroid is observed, light spills and visible point (foreign body) from opposition side, has The bright spot number of the diameter of more than 0.01mm is preferably 200/cm2Below.More preferably 100/cm2Hereinafter, more preferably 50/m2Hereinafter, more preferably 0～10/cm2.Additionally, it is preferred that the bright spot of below 0.01mm is also few.
The filtration of thermoplastic resin solution can be carried out by usual way.If more than the boiling point of solvent at ambient pressure And filter at a temperature of the scope that solvent will not seethe with excitement under elevated pressure, then the difference (referred to as differential pressure) of the filter pressure produced before and after filtering Little.Preferably temperature is the scope of 45～120 DEG C, the scope of more preferably 45～70 DEG C, the more preferably model of 45～55 DEG C Enclose.The pressure preferably filtering environment is little, preferably below 1.6MPa, more preferably below 1.2MPa, more preferably 1.0MPa below.
(curtain coating of rubber cement, dry, stripping process)
Then, curtain coating rubber cement.The surface of the metal support in curtain coating (casting) operation preferably carries out minute surface polish.Gold Belong to the preferred stainless steel band of supporting mass or or surface carry out electroplating the drum of polish with foundry goods.The width of casting can be The scope of 1～4m.
The surface temperature of the metal support of curtain coating operation can-50 DEG C～set less than the temperature of boiling point of solvent Fixed.The curtain coating that the surface temperature of metal support is high, the rate of drying of net can accelerate, therefore preferably.On the other hand, if The surface temperature of metal support is too high, produces foaming or flatness deterioration the most sometimes.Preferably supporting mass temperature is 0～40 DEG C scope, the scope of further preferred 5～30 DEG C.It addition, it is also preferred that make net gel by cooling metal support Change and peel off from drum more to contain the state of residual solvent.
The method of temperature controlling metal support is not particularly limited, have blow warm braw or cold wind method and make warm water with The method of the rear-face contact of metal support.The method of controls temperature using warm water can carry out hot transmission effectively, therefore, The time that the temperature of metal support reaches constant is short, preferably.In the case of using warm braw, sometimes use temperature than target temperature Spend high wind.
In order to improve the flatness of blooming, the residual solvent amount in net when peeling off from metal support is preferred 10～150 mass %, the more preferably scope of 20～40 mass % or the scope of 60～130 mass %, particularly preferably The scope of 20～30 mass % or the scope of 70～120 mass %.
In the present invention, residual solvent amount following formula defines.In following formula, after " M " is in the mill or manufactures The net of any time collection or the quality of film." N " is the quality after this net or film being heated 1 hour at 115 DEG C.
Residual solvent amount (quality %)={ (M-N)/N} × 100
(stretching process)
The net peeled off from metal support preferably stretches.Specifically, preferably to hold net with fixture etc. The stenter mode at the two ends etc. of shape thing (laterally) stretches in the width direction.Peel off tension force and be preferably set to below 300N/m.
The net preferably peeled off from metal support by stretching carries out refractive index control (control of delay).
Stretching such as can be along the length direction (masking direction) of film or direction (the i.e. width side vertical in face with it To) uniaxial tension or gradually or simultaneously carry out biaxial stretch-formed along two directions.The most biaxial stretch-formed also comprise along one direction stretching right The opposing party's tension force that relaxes makes it shrink.
The stretching ratio of mutually perpendicular biaxially oriented is the most finally set to the model of 0.8～1.5 times in curtain coating direction Enclose, be set at width the scope of 1.1～2.5 times；Preferably it is set to the scope of 0.9～1.0 times, in width side in curtain coating direction To the scope being set to 1.2～2.0 times.
Draft temperature preferably 120 DEG C～the scope of 200 DEG C, more preferably 140 DEG C～the scope of 180 DEG C.During stretching Residual solvent in film preferably 20～the scope of 0%, more preferably 15～the scope of 0%.
The method of stretching net is not particularly limited.Such as can enumerate: multiple rollers are given week speed difference betwixt Utilize roller week speed difference along longitudinally carrying out the method stretched, the two ends fixing net with fixture or pin, by fixture or the interval of pin The method that is longitudinally stretched along travel direction extension, the most transversely extension and the method that transversely stretches or along vertical Horizontal stroke extends and the method etc. of edge two directions stretchings in length and breadth simultaneously.These methods can also be combined.It addition, at so-called tenter frame process In the case of, if driving fixture to part by rear wheel drive mode, then can carry out the stretching smoothed, it is possible to reduce the danger such as fracture Property.
These width of film making process keep or horizontal stretching is preferably carried out by stenter, pin stenter or cloth Pincers stenter.Furthermore it is possible to stretch conveying direction and width simultaneously, it is also possible to gradually stretch.
(film drying process)
Preferably being dried further by the film stretched, making residual solvent amount is below 1 mass %, more preferably Below 0.1 mass %, below particularly preferably 0～0.01 mass %.In film drying process, generally use by the roller side of being dried Formula (mode that net is alternately dried by the multiple rollers vertically configured) or by stenter mode transmission net on one side Shape thing while be dried mode.
The method being dried stretched film is not particularly limited, it is however generally that can use hot blast, infrared ray, heating roller, microwave etc. Carry out, but from the standpoint of simplicity, preferably carry out with hot blast.Baking temperature in the drying process of net is preferably 40 ～the scope next stage property ground of 200 DEG C improves.
It addition, here, solution casting film method is described, but do not hinder and make film by melted casting film legal system.
<characteristic of blooming>
The film thickness of the blooming of the present invention is not particularly limited, the scope of preferably 10～200 μm, more preferably 10～ The scope of 100 μm, the more preferably scope of 20～60 μm.If in this scope, then the film thickness depending on film can be had both The improvement of moisture permeability and the expression power of delay, therefore preferably.It addition, the cutting characteristic of the blooming of the thickness of this scope is the best Good.
The width of the blooming of the present invention preferably 1～the scope of 4m, more preferably 1.4～the scope of 4m, particularly preferably 1.6 ～the scope of 3m.If it exceeds 4m, then it is difficult to carry.
The moisture permeability of the blooming of the present invention preferably 40 DEG C, be 10～1200g/m under 90%RH2The scope of 24h.Thoroughly Humidity can be measured according to the method described in JIS Z 0208:1976.
The elongation at break of the blooming of the present invention is preferably the scope of 10～80%.Elongation at break can pass through foundation JIS-K7127-1999 is measured and tries to achieve.
The visible light transmissivity of the blooming of the present invention is preferably more than 90%, and more preferably more than 93%.Use The U-4000 self-recording spectrophotometer foundation of company of Hitachi, is measured 380 according to JIS Z 8722 assay method ～the visible light transmissivity (Tv) under 780nm.
The mist degree of the blooming of the present invention is preferably shorter than 1%, particularly preferably 0～the scope of 0.1%.Use haze meter (1001DP type, Japan's electricity color industry (strain) system) is measured.
The change in size that the humidity resistance of the blooming of the present invention can produce by changing relative to humidity is evaluated. Carried out by following method relative to the evaluation of the change in size of damp and hot change.The curtain coating direction of the blooming made is added Labelling (cross) at 2.It is processed 1000 hours under temperature 60 C, relative humidity 90%RH.Use at light microscope determining Labelling (cross) before reason and after process distance each other.Size changing rate (%) is calculated by following formula.
Size changing rate (%)=[(a1-a2)/a1] × 100
A1: the distance before humid heat treatment
A2: the distance after humid heat treatment
If the protective film for polarizing plate of liquid crystal indicator makes size change because of moisture absorption, then produce uneven or phase The change of potential difference value, the reduction producing contrast or the such problem of irregular colour.The particularly liquid crystal display dress of outdoor application Polaroid protective film used in putting significantly produces this problem.Therefore, the blooming of the present invention is being used as liquid crystal In the case of the protective film for polarizing plate of showing device, size changing rate (%) preferably shorter than 0.5%, more preferably less than 0.3%.As Fruit is such size changing rate, then can be evaluated as showing the blooming of sufficient agent of low hygroscopicity.
Formation liquid crystal layer or resin bed can also be coated with on the blooming of the present invention and further it is stretched.By This stacked film obtained can have the phase difference value of broad range further.
<purposes of blooming>
The blooming of the present invention is preferably the various displays such as liquid crystal display, plasma scope, organic el display Functional membrane used in device.Specifically, the blooming of the present invention can be the polaroid protection of liquid crystal indicator Film, phase retardation film, antireflection film, brightness improve the optical compensation films such as film, hard coat film, antiglare film, electrostatic prevention film, the amplification of visible angle Deng.For typical case, the blooming of the present invention is polaroid protective film, phase retardation film, optical compensation films.The blooming of the present invention can To double as phase retardation film and polaroid protective film
(optical compensation films)
Liquid crystal display uses has anisotropic liquid crystal material or polaroid, though available time therefore in terms of front Good display, there is also the problem that display performance when oblique seeing reduces such visible angle.Therefore, in order to improve liquid crystal Show the performance of device, need visible angle compensation plate.The index distribution of average liquid crystal cell is big, in face at the thickness direction of unit Direction is less.Thus, it can be seen that angle compensation plate must offset this anisotropy.I.e., it is seen that angle compensation plate has the folding of film thickness direction Penetrate the little refractive index in direction in rate specific surface, to have so-called negative uniaxiality structure the most effective.The blooming of the present invention can also For having the optical compensation films of such function.
In the case of the liquid crystal cell that the blooming of the present invention is used for VA pattern, can respectively use 1 in the both sides of unit The blooming (2 types) that opening and closing meter is 2, it is also possible to the only upper and lower either side at unit uses blooming (1 type).
In the face shown in the preferred following formula of blooming of the present invention length of delay Ro in direction 23 DEG C, in the environment of 55%RH And measure when wavelength is 590nm in the range of 40～150nm, in the range of further preferred 50nm～130nm.Thickness direction Length of delay Rth preferably 23 DEG C, in the environment of 55%RH and measure when wavelength is 590nm in the range of 70～350nm, enter In the range of one preferred 170nm～270nm of step.
These length of delays can use automatic birefringence meter KOBRA-WPR (prince measures machine) to be measured.
Formula (I) Ro=(nx-ny)×d
Formula (II) Rth={ (nx+ny)/2-nz}×d
(nxRepresent that in direction, refractive index is the refractive index of maximum direction x in the face of blooming；nyRepresent the folding of direction y Penetrating rate, described direction y direction in the face of blooming is vertical with described direction x；nzRepresent the refraction of the thickness direction z of blooming Rate；D (nm) represents the thickness of blooming.)
The blooming of the present invention has slow axis or fast axle in face, angle formed by the axle in slow axis or fast axle and masking direction Degree " θ 1 " is preferably more than-1 ° and less than+1 °, more preferably more than-0.5 ° and less than+0.5 °.θ 1 can be carried out as the angle of orientation Definition, the mensuration of θ 1 can use automatic birefringence meter KOBRA-WPR (prince measures machine) to carry out.Above-mentioned relation is met containing θ 1 Blooming liquid crystal indicator, its display image brightness be improved, suppress or prevent light leak, Color Liquid Crystal Display fill Verily reproduction color in putting.
<polaroid>
The blooming of the present invention can be used for polaroid and possesses its liquid crystal indicator.The blooming of the present invention is preferably adopted With the film doubling as polaroid protective film and phase retardation film.Now, it is not necessary to prepare to be different from the phase retardation film of polaroid protective film. Therefore, it can the thickness of reducer crystal device, manufacturing process can be simplified.
Polaroid has polarizer, and is pasted onto the polaroid protective film of the one or both sides of polarizer.
So-called polarizer refers to only pass through the element of the light of the plane of polarization of certain orientation, and the polarizer representing type is polyethylene Alcohols polarizing coating, its polarizing coating that polyvinyl alcohol film is carried out dyeing iodine and the polarizing coating of dyeing dichroic dye.
Polarizer obtains as follows: by polyvinyl alcohol water solution masking, it is carried out uniaxial tension and dyes or after dyeing Carry out uniaxial tension, then, preferably carry out durability process with boron compound.The model of the film thickness of polarizer preferably 5～30 μm Enclose, the scope of particularly preferably 10～20 μm.
The polaroid of the present invention can make by general method.To, be attached at the blooming of the present invention of polarizer Surface carries out saponification process.In at least one side of the polarizer impregnating stretching in iodine solution and make, use fully saponified The blooming of the type polyvinyl alcohol water solution laminating present invention.Can fit at the another side of polarizer other existing polaroid Protecting film.
The example of existing polaroid protective film comprises commercially available cellulose ester membrane (such as Konica Minolta TAC KC8UX、KC5UX、KC8UCR3、KC8UCR4、KC8UCR5、KC8UY、KC6UY、KC4UY、KC4UE、KC8UE、KC8UY-HA、 KC8UX-RHA, KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, above it is KONICA MINOLTA ADVANCED LAYERS (strain) makes) etc..
<liquid crystal indicator>
The liquid crystal indicator of the present invention possesses the polaroid of the blooming containing the present invention.Specifically, at liquid crystal cell At least one side on blooming containing the present invention in the polaroid that configured；The film of the liquid crystal cell side of this polaroid is the present invention Blooming.
In the liquid crystal indicator of the present invention, preferably polaroid fits in the one side or two of liquid crystal cell via adhesive layer Face.
The polaroid protective film that the face side of the liquid crystal indicator of the present invention is used removes antiglare layer or transparent hard painting Beyond Ceng, preferably there is anti-reflection layer, antistatic backing, stain-proofing layer, back coating.
It is various that the blooming of the present invention or polaroid can be used for STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB etc. The liquid crystal indicator of type of drive.Particularly preferred for VA (MVA, PVA) type liquid crystal indicator.The most i.e. it is used in 30 The liquid crystal indicator of big picture more than type, it is possible to coloring during the black display that reduction light leak causes, can improve front contrast The visibilitys such as degree.As it has been described above, the various visibilitys of the liquid crystal indicator of the present invention are excellent.
Embodiment
Hereinafter, enumerate embodiment and the present invention is specifically illustrated, but invention is not limited to these.It addition, in reality Execute use " part " or the expression of " % " in example, unless otherwise specified, then it represents that " mass parts " or " quality % ".
Embodiment 1
The details of the cellulose esters used in embodiment 1 is shown.
The cellulose diacetate of the number-average molecular weight 70000 of cellulose esters A: degree of substitution with acetyl group 2.40 (in table, is designated as DAC)
Cellulose esters B: degree of substitution with acetyl group 1.58, propiono substitution value 0.9, the equal molecule of number of total acyl substitution 2.48 The cellulose acetate propionate (being designated as CAP in table) of amount 70000
The cellulosic triacetate of the number-average molecular weight 70000 of cellulose esters C: degree of substitution with acetyl group 2.85 (in table, is designated as TAC)
<making of blooming 101>
<preparation of particle dispersion liquid>
The microgranule (Aerosil R972V Japan Aerosil (strain) system) of 11.3 mass parts and the ethanol of 84 mass parts are used After dissolvers stirring mixing 50 minutes, disperse with refiner (Manton-Gaulin).
<preparation of microgranule annex solution 1>
Well-beaten dichloromethane (100 mass parts) in dissolving tank is slowly added the microgranule dispersion of 5 mass parts Liquid.And then, the particle diameter carrying out disperseing to make offspring with grater becomes the size of regulation.Japan's essence line (strain) is used to make Fine Met NF filters, and prepares microgranule annex solution.
<preparation of main rubber cement>
The main rubber cement of preparation following compositions.First, dissolved under pressure tank adds dichloromethane and ethanol.Putting into solvent Dissolved under pressure tank in general stirring input cellulose esters A on one side, be heated, stir and make it be completely dissolved.
<composition of main rubber cement>
[chemical formula 28]
And then, above-mentioned additive component is put into hermetic container, stirs and dissolve, used the long-pending filter paper of peace The peace that (strain) makes is amassed filter paper No.244 and is filtered, and prepares main rubber cement.Then, use endless belt casting device by rubber cement in temperature It is cast equably on stainless steel band supporting mass with 1500mm width at 31 DEG C.It is 28 DEG C that the temperature of stainless steel band controls.
On stainless steel band supporting mass, until to curtain coating (casting) film in residual solvent amount be 75% carry out molten Agent is evaporated.Then, peel off from stainless steel band supporting mass peeling off tension force 128N/m.By the film peeled off while applying 142 DEG C Heat is while using stenter to stretch 24% in the width direction.Residual solvent when stretching starts is 17%.
Then, conveying is carried out while terminating to be dried in arid region with multiple rollers.Baking temperature is 120 DEG C, conveying Tension force is 122N/m.As above the blooming 101 that desciccator diaphragm thickness is 40 μm is obtained.
<making of blooming 102～141>
In the making of blooming 101, only using the kind of cellulose esters with as shown in the formula (1) postponing performance agent The kind of the exemplary compounds of compound and amount (mass parts) change as table 1 and table 2, in addition, similarly make The blooming 102～131 making the present invention and the blooming 132～141 compared.Instead of using the fiber of cellulose esters A (DAC) The addition of element ester is set to the mass parts identical with cellulose esters A (DAC).
The structure of delay performance agent (C-001～C-005) used in the manufacture of the blooming 132～138 compared is shown.
[chemical formula 29]
" evaluation of blooming "
The blooming 101～141 made is carried out following evaluation.Evaluation result is shown in table 1 and table 2.
(delay)
Abbe refractomecer (4T) is used to measure the mean refractive index of blooming.It addition, use commercially available micrometer to measure The thickness of blooming.
Use birefringence meter KOBRA-WPR (prince measure machine (strain) system), to 23 DEG C, place in the environment of 55%RH The blooming of 24 hours under equivalent environment, carry out the mensuration of the delay of blooming under wavelength 590nm.By mean refractive index and film Thick input following formula, tries to achieve the value of the length of delay Rth of the length of delay Ro in direction in face, thickness direction.Measure slow axis the most simultaneously Direction.In following formula, nxRepresent the largest refractive index in face, nyRepresent and nxThe refractive index of vertical direction, nzRepresent thickness The refractive index in degree direction, d represents the thickness (nm) of film.
Formula (I) Ro=(nx-ny)×d
Formula (II) Rth={ (nx+ny)/2-nz}×d
(internal haze value)
By the cellulose ethanoate film that makes in the environment of 23 DEG C of 55%RH after damping more than 5 hours, by following side Method evaluates internal haze value.
<internal haze determinator>
Use haze meter (scopometer) (model: NDH 2000, Japan's electricity color industry (strain) system)
Light source uses 5V9W halogen lamp, and light receiver uses silicon photocell (equipped with luminosity coefficient optical filter).
The solvent of the refractive index of film refractive index ± 0.05 is being dripped by the cellulose ethanoate film of the present invention with this device During the mist degree of film time on film measures, its value is preferably less than 0.05.Condition determination is measured according to JISK-7136.
Internal haze is determined as follows and carries out.Illustrate with Fig. 1～Fig. 4.
First, the blank mist degree 1 of the measuring instrument beyond mensuration film.
1. on clean microscope slide, drip a glycerol (0.05ml).Now, note drop can not enter bubble.Glass Even if glass surface seem cleaning, the most also can be contaminated, therefore, it is necessary to use abluent be carried out after glass. (with reference to Fig. 1.).
Load coverslip the most thereon.Even if not pressing coverslip, glycerol also can extend.
3. it is configured on haze meter, measures blank mist degree 1.
Then, the mist degree 2 comprising sample is measured by below step.
4. on microscope slide, drip glycerol 0.05ml (with reference to Fig. 1.).
Load the sample film of mensuration the most thereon and bubble can not be entered (with reference to Fig. 2.).
6. in sample film, drip glycerol 0.05ml (with reference to Fig. 3.).
Load coverslip the most thereon (with reference to Fig. 4.).
8. the duplexer (starting from above as upper coverslip/glycerol/sample film/glycerol/microscope slide) as above made is set Put mensuration mist degree 2 on haze meter.
9. calculate (mist degree 2)-(mist degree 1)=(internal haze of the cellulose ethanoate film of the present invention).
The survey of above-mentioned mist degree is all carried out under 23 DEG C of 55%RH.
It addition, the microscope slide, the glycerol that use in said determination are as described below.
Glass: MICRO SLIDE GLASS S9213 MATSUNAMI
Glycerol: Northeast chemistry deer superfine (purity > 99.0%) refractive index 1.47
(oozing out patience)
By the patience of oozing out of following description, durability is evaluated.By blooming 80 DEG C, 90%RH hot and humid Placing after 1000 hours under atmosphere, visualization oozes out (crystallization) with or without blooming surface.Result according to the observation, foundation Following benchmark is evaluated.Evaluate A and B and be judged as level no problem in practicality.
A: the most unconfirmed to the generation oozed out on surface
B: somewhat confirm oozing out of part on surface
C: somewhat confirm on surface throughout whole ooze out
D: confirm clear and definite the oozing out throughout whole on surface
(humidity resistance: relative to the change in size of damp and hot change)
Add in the curtain coating direction of the blooming Zhi Zuoing labelling at 2 (cross) and 60 DEG C, to process 1000 under 90%RH little Time, by the distance of light microscope determining labelling (cross) before and after treatment.According to measurement result, comment with following benchmark Valency change in size, thus, as the durability evaluation humidity resistance of blooming.
Size changing rate (%)=[(a1-a2)/a1] × 100 (a1 represent humid heat treatment before distance, a2 represent damp and hot place Distance after reason)
A: less than 0.3%
B:0.3%～less than 0.5%
C:0.5%～less than 0.7%
More than D:0.7%
(Compatibility Evaluation)
Make the film before the stretching in the manufacture of blooming be dried 15 minutes at 120 DEG C, the mist degree of this film is used mist degree Meter (1001DP type, Japan's electricity color industry (strain) system) is measured.According to measurement result, it is evaluated according to following benchmark.Comment Valency A and B is evaluated as level no problem in practicality.
A: mist degree is less than 0.5%
B: mist degree is less than 0.5～1.0%
C: mist degree is less than 1.0～1.5%
D: mist degree is more than 1.5%
E: compound separates out
(mist degree after stretching)
Haze meter (1001DP type, Japan's electricity color industry (strain) system) is used to measure the mist degree of the blooming made.According to survey Determine result, be evaluated according to following benchmark.Evaluate A and B and be judged as level no problem in practicality.
A: mist degree is less than 0.5%
B: mist degree is 0.5～less than 1.0%
C: mist degree is 1.0～less than 1.5%
D: mist degree is more than 1.5%
E: compound separates out
As shown in table 1 and table 2, it is known that the blooming 101～131 of embodiment and the blooming 132～141 of comparative example Comparing, the expression power of delay is excellent, and internal haze, the compatibility (mist degree) and durability (oozing out patience) are good, are in practicality Excellent blooming.
Can by the comparison with the result of the blooming 132～135 employing comparative compound C-001, C-002, C-004 Know, if as postponing the compound of performance agent has specific substituent group, then a value step-down of internal haze, the compatibility and prolonging Expression power improves late.It addition, the poor compatibility of C-003 and C-005, compound separates out in film, therefore, it is impossible to carry out length of delay Mensuration and the mensuration of internal haze.
From blooming 101～131, particularly 124～the result of 129, the delay table containing the present invention of embodiment The blooming of existing agent shows bigger phase contrast, even if increasing the addition postponing performance agent, also mixes with cellulose esters, because of This, be the excellent blooming that internal haze is low, length of delay is high.
On the other hand, use TAC little, no as cellulose esters and the length of delay without the blooming 141 postponing performance agent There is the function as optical compensation films.
Embodiment 2
Use the main rubber cement used in the making of the blooming 104 of embodiment 1, the flow of rubber cement during change curtain coating, system The blooming 201～206 of the thickness shown in tabulation 3.In addition to the flow of the rubber cement when curtain coating, make similarly to Example 1. Blooming 201～206 is evaluated similarly to Example 1.Now, blooming 132 conduct made in embodiment 1 is added Comparative example.
It addition, fragility is evaluated with following evaluation methodology.
(cutting adaptive)
The cutting adaptive of fragility following description is evaluated.Oil pressure type bench press is installed 60 ° pass through wear away Upper cutter and the lower cutter of 90 ° so that it is be spaced 30 μm.Then, blooming is placed between two cutting knifes, with the decline of upper cutter Speed 6m/ minute cuts out 100 width 90cm, the sample of length 100cm size continuously.Optical microscope is used to carry out with 50 times Observe the plane of disruption of each sample after cutting.Cutting situation is compared.Statistics create burr, split, cannot cut off, The sheet number of the film of some unfavorable condition such as cutting swarf, calculates fraction defective, carries out cutting the evaluation of adaptive according to following benchmark.Comment Valency A and B is judged as level no problem in practicality.
A: fraction defective is less than 2%
B: fraction defective is less than 2～5%
C: fraction defective is less than 5～10%
D: fraction defective is less than more than 10%
[table 3]
By table 3 clearly, the delay expression power of the blooming 201～206 of embodiment is excellent, and fragility (cutting adaptive) and resistance to Property (oozing out patience) is excellent for a long time.And then, it is known that, thickness is special in the effect above of the blooming 202～205 of the scope of 20～60 μm The highest.
The thickness of the blooming 132 of comparative example is 40 μm, but fragility (cutting adaptive) and durability (oozing out patience) inequality.
Embodiment 3
<making of polaroid and evaluation>
The polyvinyl alcohol film of thickness 120 μm is carried out uniaxial tension (temperature 110 DEG C, stretching ratio 5 times).By drawing of obtaining Stretch film to impregnate 52 seconds in the aqueous solution being made up of iodine 0.069g, potassium iodide 4.5g, water 100g, then, be immersed in by potassium iodide In the aqueous solution of 60 DEG C of 6.5g, boric acid 7.0g, water 100g composition.Carried out washing, being dried as becoming polarizer.
Then, according to following operation 1～5 the one side of polarizer fit blooming 101～141 and blooming 201～ 206；And at another side laminating Konica Minolta TAC KC4UY (the KONICA MINOLTA ADVANCED of polarizer LAYERS (strain) cellulose ester membrane processed), make polaroid 101～141 and polaroid 201～206.
Operation 1: by blooming 101～141, blooming 201～206 in the sodium hydroxide solution of the 2 moles/L of 60 DEG C Impregnate 95 seconds, then, wash and be dried, obtain to have carried out the blooming of saponification with polarizer laminating side.
Operation 2: polarizer is impregnated in the polyvinyl alcohol bonding agent groove of solid constituent 2 mass % 1～2 second, then, gently Lightly wipe the too much bonding agent being attached to polarizer.
Operation 3: the polarizer obtained in operation 2 is arranged in operation 1 on the blooming processed.
Operation 4: by the blooming of duplexer obtained in operation 3 and polarizer with pressure 20～30N/cm2, transporting velocity Within about 2m/ minute, fit.
Operation 5: by the polarizer of duplexer made in operation 4 and Konica Minolta in the drying machine of 80 DEG C TAC KC4UY fits and is dried 2 minutes, makes polaroid 101～141 and polaroid 201～206.
The durability of the polaroid of making is evaluated as follows.Show the result in table 4.
(light resistance)
Measure parallel transmitance (H0) and the vertical transmitance (H90) forcing deterioration untreated samples.By measured value foundation Following formula calculates degree of polarization P0.Then, by each polaroid in sunshine weather meter, do not have under conditions of UV light filter to implement Force degradation treatment 500 hours.Then, parallel transmitance (H0 ') and vertical transmitance (H90 ') are again measured, by measured value root The degree of polarization P500 after forcing degradation treatment is calculated according to following formula.
Degree of polarization P0=[(H0-H90)/(H0+H90)]1/2×100
Degree of polarization P500=[(H0 '-H90 ')/(H0 '+H90 ')]1/2×100
Degree of polarization variable quantity is calculated according to following formula by the degree of polarization P0 calculated and degree of polarization P500.
Degree of polarization variable quantity=P0-P500
For the degree of polarization variable quantity tried to achieve, carry out sunproof evaluation with following benchmark.Evaluate A and B and be judged as reality Use no problem level.
A: degree of polarization variable quantity is less than 2%
B: degree of polarization variable quantity is 2% less than 10%
C: degree of polarization variable quantity is 10% less than 25%
D: degree of polarization variable quantity is more than 25%
(humidity resistance)
Prepare the polaroid of 3 500mm × 500mm.Carry out respectively humid heat treatment (condition: 70 DEG C, place under 90%RH 100 hours).2 polaroids are carried out stacking in the way of becoming vertical Niccol (crossed nicols) state.Measure from When the one side of polaroid irradiates light, the length of the blank parts that the edge portions at another side produces.Sky as evaluation object Gutter the longest in multiple blank parts that each immediate vicinity of 4 edge portions that white part is set to polaroid produces Point.The blank that edge portions produces refers to that the edge portions being not through the polaroid of light under vertical Niccol state is through light State, becomes the edge portions at polaroid and does not show the failure cause of image.
Calculate the length of blank parts of mensuration relative to the ratio of the length (500mm) on one side of polaroid.By when being somebody's turn to do Ratio is judged as level no problem in practicality based on following benchmark evaluation humidity resistance, evaluation A and B.
The blank at A: edge was less than for 5% (as the level that polaroid is no problem)
The blank at B: edge is 5% less than 10% (as the level that polaroid is no problem)
The blank at C: edge is 10% less than 20% (level used reluctantly as polaroid)
The blank at D: edge is more than 20% (as the in-problem level of polaroid)
[table 4]
Polaroid No. Blooming No. Light resistance Humidity resistance Remarks
101 101 B B The present invention
102 102 B B The present invention
103 103 B B The present invention
104 104 A A The present invention
105 105 A A The present invention
106 106 A A The present invention
107 107 A A The present invention
108 108 A A The present invention
109 109 A A The present invention
110 110 A A The present invention
111 111 A A The present invention
112 112 A A The present invention
113 113 A A The present invention
114 114 A A The present invention
115 115 A A The present invention
116 116 A A The present invention
117 117 A A The present invention
118 118 B A The present invention
119 119 B A The present invention
120 120 B A The present invention
121 121 B A The present invention
122 122 B A The present invention
123 123 A A The present invention
124 124 A A The present invention
125 125 A A The present invention
126 126 A A The present invention
127 127 A A The present invention
128 128 A A The present invention
129 129 A A The present invention
130 130 A A The present invention
131 131 A A The present invention
132 132 C C Comparative example
133 133 C C Comparative example
134 134 C C Comparative example
135 135 C C Comparative example
136 136 C C Comparative example
137 137 C C Comparative example
138 138 C C Comparative example
139 139 C C Comparative example
140 140 C C Comparative example
141 141 C C Comparative example
201 201 B A The present invention
202 202 B A The present invention
203 203 A A The present invention
204 204 A A The present invention
205 205 A A The present invention
206 206 A B The present invention
By table 4 clearly, the polaroid 101 of embodiment～131 and polaroid 201～206 and the polaroid 132 compared～ 141 compare, for polaroid excellent in the practicality that light resistance, humidity resistance are good.By with employ comparative compound C-001, The comparison of the result of the polaroid 132～138 of C-002, C-003, C-004, C-005 understands, and the compound postponing performance agent leads to Cross and there is specific structure and substituent group, problem to be solved by this invention can be realized.
According to the result of polaroid 101～131, particularly polaroid 124～129, the delay performance agent containing the present invention The phase contrast of blooming big, even if increasing the addition postponing performance agent, postpone performance agent also compatible with cellulose esters.Cause This, the polaroid of the present invention is polaroid excellent in practicality.
Embodiment 4
<making of liquid crystal indicator and evaluation>
Be carried out as follows making liquid crystal panel to measure visible angle, evaluate liquid crystal indicator characteristic.To SONY system 40 type The polaroid on the two sides fitting in liquid crystal cell in display KLV-40J3000 is peeled off.Polarization by the making of replacement Sheet 101～141 and polaroid 201～206 fit in the two sides of glass surface of liquid crystal cell respectively.The laminating carrying out polaroid makes The blooming of embodiment and comparative example is liquid crystal cell side, and the direction absorbing axle of the polaroid of laminating is inclined with fitted in advance Shake sheet absorb axle direction identical.Make the most respectively liquid crystal indicator 101～141 and liquid crystal indicator 201～ 206。
As above the liquid crystal indicator made is carried out evaluation set forth below.The results are shown in table 6 and table 7.
(front contrast is uneven)
The backlight of each liquid crystal indicator is lighted 1 week by environment at 23 DEG C of 55%RH continuously.Then, from display picture The normal direction in face measures white display and the brightness of black display of liquid crystal indicator.Measure and use ELDIM company EZ- Contrast160D.The ratio of the brightness recorded is set to front contrast.Front contrast is with formula (the normal side from display device Brightness to the black display of the brightness of the white display recorded/measure from the normal direction of display device) it is defined.
The front contrast of any 5 of the display picture of mensuration liquid crystal indicator, is evaluated with following benchmark. Evaluate A and B and be judged as level no problem in practicality.
A: front contrast is 0～is less than the distribution of 5%, uneven little
B: front contrast is 5%～is less than the distribution of 10%, somewhat has inequality
C: front contrast is the distribution of more than 10%, uneven big
(deterioration of visible angle)
The liquid crystal indicator placed 5 hours in the environment of 25 DEG C of 50%RH is carried out visible angle mensuration.Then, should Liquid crystal indicator is placed 5 hours in the environment of 25 DEG C of 20%RH, carries out visible angle mensuration.Then, this liquid crystal display is filled Put and place 5 hours in the environment of 23 DEG C of 80%RH, measure the visible angle of liquid crystal indicator.Finally, this liquid crystal display is filled Put and again place 5 hours in the environment of 25 DEG C of 55%RH, measure the visible angle of liquid crystal indicator, when confirming said determination Be changed to reversible variation.These are determined as the mensuration carried out after this environment is placed 5 hours by liquid crystal indicator.It addition, For visible angle measures, show and the display picture of black display at liquid crystal indicator midpoint brilliant white, use ELDIM company system EZ-Contrast160D, is set to visible angle by the angle that can maintain contrast 10:1.
According to these measurement results, deteriorate with angle seen from following benchmark evaluation.Evaluate A and B to be judged as in practicality not asking The level of topic.
A: unconfirmed to visible angular variable
B: somewhat confirm visible angular variable
C: confirm visible angular variable
[table 5]
Liquid crystal indicator No. Polaroid No. Front contrast Visible angle deteriorates Remarks
101 101 B A The present invention
102 102 A B The present invention
103 103 A B The present invention
104 104 A A The present invention
105 105 A A The present invention
106 106 A A The present invention
107 107 A A The present invention
108 108 A A The present invention
109 109 A A The present invention
110 110 A A The present invention
111 111 A A The present invention
112 112 A A The present invention
113 113 A A The present invention
114 114 A A The present invention
115 115 A A The present invention
116 116 A A The present invention
117 117 A A The present invention
118 118 B A The present invention
119 119 B A The present invention
120 120 A B The present invention
121 121 A B The present invention
122 122 B A The present invention
123 123 A A The present invention
124 124 A A The present invention
125 125 A A The present invention
126 126 A A The present invention
127 127 A A The present invention
128 128 B A The present invention
129 129 B A The present invention
130 130 A A The present invention
131 131 A A The present invention
132 132 C B Comparative example
133 133 C C Comparative example
134 134 C C Comparative example
135 135 C C Comparative example
136 136 C C Comparative example
137 137 C C Comparative example
138 138 C C Comparative example
139 139 C C Comparative example
140 140 C C Comparative example
141 141 C C Comparative example
201 201 B A The present invention
202 202 B A The present invention
203 203 A A The present invention
204 204 A A The present invention
205 205 A A The present invention
206 206 A B The present invention
By table 5 clearly, possesses the polaroid 101 of the present invention～131 and the liquid crystal indicator of polaroid 201～206 101～131 and the liquid crystal indicator of liquid crystal indicator 201～206 and the polaroid 132～141 employing comparative example 132～141 compare, and front contrast is not well, even if under conditions of humidity changes, it is seen that angular variable is also few.As above Understand as stabilizer pole and the liquid crystal indicator of excellent in te pins of durability.
By the knot with the polaroid 132～138 employing comparative compound C-001, C-002, C-003, C-004, C-005 Fruit compares and understands, and has specific structure and substituent group by postponing performance agent, can realize to be solved by this invention asking Topic.
Industrial utilizability
The blooming of the present invention for having high latency expression power, can suppress to ooze out and internal haze is low, fragility is excellent, in addition The blooming that light resistance, humidity resistance are high, therefore, can particularly preferably be used as liquid crystal indicator blooming, especially as The polaroid protective film with optical compensation function uses.Thus, the front contrast of liquid crystal indicator can be suppressed not All, visible angle is improved.
Symbol description
GL microscope slide
Gr glycerol
F sample film

Claims (10)

1. a blooming, it contains thermoplastic resin and the following formula (1) being dissolved or dispersed in described thermoplastic resin Shown compound,
[chemical formula 1]
Formula (1)
In formula (1), X1Represent oxygen atom or sulphur atom；Y1Represent oxygen atom, sulphur atom or nitrogen-atoms；Z1Represent oxygen atom, nitrogen Atom or sulphur atom；R11、R21And R31Represent substituent group, as with R11The substituent group represented, represents alkyl, cycloalkyl, alcoxyl Base, aryl, alkyl amino or alkylthio group；As with R21The substituent group represented, represents hydrogen atom or alkyl；As R31Represent Substituent group, represents alkyl, alkoxyl or acyloxy；K1 represents the integer of 1～5；M1 represents the integer of 0～4；N1 represents 0～4 Integer；Dotted portion represents singly-bound or double bond.
Blooming the most according to claim 1, wherein, the compound shown in described formula (1) is shown in following formula (2) Compound,
[chemical formula 2]
Formula (2)
In formula (2), X2Represent oxygen atom or sulphur atom；Y2Represent oxygen atom, sulphur atom or nitrogen-atoms；Z2Represent oxygen atom, nitrogen Atom or sulphur atom；R12And R22Represent substituent group；Substituent R12And R22Respectively with the R in formula (1)11And R21Same meaning； M2 represents the integer of 0～4；K2 represents the integer of 1～5；Dotted portion represents singly-bound or double bond.
Blooming the most according to claim 2, wherein, the compound shown in described formula (2) is shown in following formula (3) Compound,
[chemical formula 3]
Formula (3)
In formula (3), R13And R23Represent substituent group, substituent R13And R23Respectively with the R in formula (1)11And R21Same meaning； K3 represents the integer of 1～5；M3 represents the integer of 0～4.
Blooming the most according to claim 3, wherein, the compound shown in described formula (3) is shown in following formula (4) Compound,
[chemical formula 4]
Formula (4)
In formula (4), R14Represent substituent group；Substituent R14With the R in formula (1)11Same meaning；K4 represents the integer of 1～5.
Blooming the most according to claim 1, wherein, described thermoplastic resin comprises cellulose esters.
Blooming the most according to claim 5, wherein,
Described cellulose esters meets any one of following formula (a) and (b),
Formula (a) 1.5≤X+Y≤2.5
Formula (b) 0≤Y≤1.5
In formula, X represents the substitution value of acetyl group；Y represents propiono or the substitution value of bytyry or its substitution value amounted to.
Blooming the most according to claim 1, wherein, the film thickness of described blooming is in the range of 20～60 μm.
Blooming the most according to claim 1, wherein, 23 DEG C, in the environment of 55%RH, be 590nm measuring wavelength Time, in the face shown in following formula, the length of delay Ro in direction is in the range of 20～150nm, and the length of delay Rth of thickness direction is 70 ～in the range of 350nm,
Formula (I) Ro=(nx-ny)×d
Formula (II) Rth={ (nx+ny)/2-nz}×d
nxRepresent that in direction, refractive index is the refractive index of maximum direction x in the face of blooming；nyRepresent the refractive index of direction y, Described direction y direction in the face of blooming is vertical with described direction x；nzRepresent the refractive index of the thickness direction z of blooming；d (nm) thickness of blooming is represented.
9. a polaroid, it possesses the blooming according to any one of claim 1～8 at least one side of polarizer.
10. a liquid crystal indicator, it possesses the polaroid described in claim 9 at least one side of liquid crystal cell.
CN201380010749.8A 2012-02-22 2013-02-14 Blooming, polaroid and liquid crystal indicator Expired - Fee Related CN104245851B (en)

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