CN104245851A - Optical film, polarizer and liquid crystal display device - Google Patents
Optical film, polarizer and liquid crystal display device Download PDFInfo
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- CN104245851A CN104245851A CN201380010749.8A CN201380010749A CN104245851A CN 104245851 A CN104245851 A CN 104245851A CN 201380010749 A CN201380010749 A CN 201380010749A CN 104245851 A CN104245851 A CN 104245851A
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- 0 CC[C@](C)(C(C)=CC=C(CCNC1=CCC=CC=C1C(C1C=C1)=*)C=C)OC(C1C#C1)=O Chemical compound CC[C@](C)(C(C)=CC=C(CCNC1=CCC=CC=C1C(C1C=C1)=*)C=C)OC(C1C#C1)=O 0.000 description 2
- UAMINMIPVMYMCV-UHFFFAOYSA-N C=NC(c1ccccc1O)O Chemical compound C=NC(c1ccccc1O)O UAMINMIPVMYMCV-UHFFFAOYSA-N 0.000 description 1
- SBVZREVJIJZZFC-UHFFFAOYSA-N CC(O)Oc(cc1)ccc1C(C1NC1C1=CCCC=C1C(OC)=O)=O Chemical compound CC(O)Oc(cc1)ccc1C(C1NC1C1=CCCC=C1C(OC)=O)=O SBVZREVJIJZZFC-UHFFFAOYSA-N 0.000 description 1
- UGCDCYWXFWBIAO-UHFFFAOYSA-N CC(Oc1ccc(C(O)Cl)cc1)=O Chemical compound CC(Oc1ccc(C(O)Cl)cc1)=O UGCDCYWXFWBIAO-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
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- 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
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- 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
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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
- 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 Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention addresses the problem of providing an optical film in which bleed out is inhibited, and which has low internal haze, and exhibits excellent brittleness, high retardation development properties, light resistance, and wet heat resistance. This optical film contains a thermoplastic resin, and a compound represented by general formula (1). (In general formula (1), X1 represents an oxygen atom or a sulfur atom; Y1represents an oxygen atom, a sulfur atom, a nitrogen atom, or NR41; Z1 represents an oxygen atom, a nitrogen atom, or a sulfur atom; R11, R21 and R31 represent a substituent; R41 represents a hydrogen atom or a substituent; k1 represents an integer between 1 and 5; m1 represents an integer between 0 and 4; n1 represents an integer between 0 and 4; and the dash line represents a single bond or a double bond.)
Description
Technical field
The present invention relates to a kind of blooming, polaroid and liquid crystal indicator.More specifically, relate to and a kind ofly comprise the blooming of thermoplastic resin, the polaroid possessing this blooming and liquid crystal indicator.
Background technology
At present, the thermoplastic resin films such as cellulose ester, polycarbonate, polyolefine are used for blooming, are mainly used in liquid crystal display optical compensate film.Wherein, the stickiness of the blooming (cellulose ester membrane) containing cellulose ester to the polyvinyl alcohol film being used as polarizer is excellent, is thus widely used.Cellulose ester membrane itself, insufficient in the birefringence required for optical compensation films, therefore, carry out the various researchs of cellulose ester membrane being given to birefringence.
In recent years, the TV of slim light weight notebook computer and slim large picture develops development, and with this development, the requirement of liquid crystal display optical compensate film to filming, maximization, high performance is also more and more stronger.The humidity weather resistance of cellulose ester membrane depends on the film thickness of film, and the film thickness by thinning film improves.Contrary with it, if the film thickness of film is thinning, then length of delay diminishes.Therefore, a kind of additive (postponing performance agent) postponing rising can be high is sought.
As postponing the high compound of ascending ability, such as, propose there is a kind of 1,3,5-triazines compounds (such as with reference to patent documentation 1.)。But even if use this compound, delay expression power is also insufficient.And then specify that, there is the inferior such problem of the weather resistance such as photostabilization and humidity resistance in the polaroid using the optical compensation film production of the filming containing this compound and the liquid crystal indicator employing described polaroid.And then, when placing under high temperature, high humidity, have also discovered the problem such as front contrast inequality and the deterioration of visible angle.In addition, if add this compound, then the fragility deterioration of film, thus have problems in cutting characteristic.
On the other hand, a kind of benzo added in cellulose ester as UV light absorber is disclosed
the technology of oxazinone compound is (such as with reference to patent documentation 2, patent documentation 3 and patent documentation 4.)。But even if add this compound to make blooming in cellulose ester, delay expression power is also low.In addition, the poor compatibility of this compound and cellulose ester, therefore, easily oozes out, and internal haze and the haze value after stretching greatly, are therefore the films that contrast gradient is low.
As above the delay expression power of existing known delay performance agent is also insufficient, there is the problems such as above-mentioned weather resistance and visibility meter, expects further to improve.
In addition, benzo
the compound of piperazine ketone skeleton is known as UV light absorber, but also unknown as postponing performance agent.
Prior art document
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 carrying out, its problem solved is, provides a kind of and has high latency expression power, can suppress to ooze out and internal haze is low, fragility is excellent, photostabilization, blooming that humidity resistance is high in addition.
And then the problem to be solved in the present invention is, provide a kind of possess described blooming, there is good photostabilization and the polaroid of humidity resistance, provide a kind of through time the liquid crystal indicator that front contrast is uneven and the deterioration of visible angle is excellent.
The method of dealing with problems
The present inventor etc., in order to solve the problem, find in the process study, with the addition of the benzo with ad hoc structure in thermoplastic resin to the reasons etc. of the problems referred to above
the film of oxazinone compound has high latency expression power and is low internal haze.Specifically, find benzo
piperazine ketone skeleton, imports substituting group using-OCO-as linking group to the phenyl carrying out replacing at specific position, improve with the interaction of cellulose ester thus, improve consistency, improve orientation, thus blooming shows high latency.And then, find that this with the addition of the benzo with ad hoc structure
the blooming of oxazinone compound to ooze out characteristic, internal haze, fragility, photostabilization and humidity resistance good.If find to use this blooming, then can obtain having uneven, the polaroid that visible angle is improved of front contrast of high-light-fastness and humidity resistance, suppression liquid crystal indicator.
That is, the above-mentioned problem that will solve that the present invention relates to solves by following methods.
1. a blooming, it contains the compound shown in thermoplastic resin and following general formula (1).
[chemical formula 1]
General formula (1)
(in general formula (1), X
1represent Sauerstoffatom or sulphur atom, Y
1represent Sauerstoffatom, sulphur atom, nitrogen-atoms or NR
41, Z
1represent Sauerstoffatom, nitrogen-atoms or sulphur atom.R
11, R
21and R
31represent substituting group.As with R
11the substituting group represented, represents alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, amino, alkylamino, arylamino, alkylthio, arylthio or heterocyclic radical.As with R
21and R
31the substituting group represented, represents alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, acyl amino, alkylsulfonyl, sulfonyloxy, amino, alkylthio or halogen atom respectively.R
41represent hydrogen atom or substituting group.As R
41shown substituting group, represents alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio or halogen atom.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.)
2. the blooming according to above-mentioned 1, wherein, the compound shown in described general formula (1) is the compound shown in following general formula (2).
[chemical formula 2]
General formula (2)
(in general formula (2), X
2represent Sauerstoffatom or sulphur atom, Y
2represent Sauerstoffatom, sulphur atom, nitrogen-atoms or NR
42, Z
2represent Sauerstoffatom, nitrogen-atoms or sulphur atom.R
12and R
22represent substituting group.R
42represent hydrogen atom or substituting group.Substituent R
12, R
22and R
42respectively with the R in general formula (1)
11, R
21and R
41same meaning.M2 represents the integer of 0 ~ 4.N2 represents the integer of 0 ~ 4.Dotted portion represents singly-bound or double bond.)
3. the blooming according to above-mentioned 2, wherein, the compound shown in described general formula (2) is the compound shown in following general formula (3).
[chemical formula 3]
General formula (3)
(in general formula (3), R
13and R
23represent substituting group.Substituent R
13and R
23respectively with the R in general formula (1)
11and R
21same meaning.K3 represents the integer of 1 ~ 5.M3 represents the integer of 0 ~ 4.)。
[chemical formula 4]
General formula (4)
(in general formula (4), R
14represent substituting group.Substituent R
14with the R in general formula (1)
11same meaning.K4 represents the integer of 1 ~ 5.)
5. the blooming according to any one of above-mentioned 1 ~ 4, wherein, described thermoplastic resin comprises cellulose ester.
6. the blooming according to above-mentioned 5, wherein, described cellulose ester 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 ethanoyl.Y represents substitution value or its substitution value amounted to of propionyl or butyryl radicals.)
7. the blooming according to any one of above-mentioned 1 ~ 6, wherein, the film thickness of described blooming is in the scope of 20 ~ 60 μm.
8. the blooming according to any one of above-mentioned 1 ~ 7, wherein, 23 DEG C, under 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 scope of 20 ~ 150nm, and the length of delay Rth of thickness direction is in the scope of 70 ~ 350nm.
Formula (I) Ro=(n
x-n
y) × d
Formula (II) Rth={ (n
x+ n
y)/2-n
z} × d
(n
xrepresent that in direction, specific refractory power is the specific refractory power of maximum direction x in the face of blooming; n
yrepresent the specific refractory power of direction y, described direction y direction in the face of blooming is vertical with described direction x; n
zrepresent the specific refractory power of the thickness direction z of blooming; D (nm) represents the thickness of blooming.)
9. a polaroid, wherein, possesses the blooming according to any one of above-mentioned 1 ~ 8 at least one face of polarizer.
10. a liquid crystal indicator, wherein, possesses the polaroid described in above-mentioned 9 at least one face of liquid crystal cell.
Invention effect
According to aforesaid method of the present invention, can provide a kind of there is high latency expression power, can suppress to ooze out and internal haze is low, fragility is excellent, photostabilization, blooming that humidity resistance is high in addition.And then the polaroid possessing this blooming can have good photostabilization and humidity resistance, by using this polaroid, can provide through time the liquid crystal indicator that front contrast is uneven and the deterioration of visible angle is excellent.
About the expression mechanism of effect of the present invention or mechanism of action clear and definite, but to be presumed as follows.
Compound shown in general formula of the present invention (1) is by importing substituting group using-OCO-as linking group to the phenyl carrying out replacing at specific position, form hydrogen bond with thermoplastic resin and carry out orientation, giving high phase differential to the blooming containing thermoplastic resin thus.And then above-claimed cpd, due to high with the consistency of thermoplastic resin, therefore, can suppress the deterioration of internal haze and ooze out, fragility is excellent, improves photostabilization, humidity resistance in addition.
Accompanying drawing explanation
Fig. 1 represents the schematic diagram of the state having dripped glycerine on slide glass;
Fig. 2 represents the schematic diagram of the state that placed sample film on glycerine;
Fig. 3 represents the schematic diagram of the state having dripped glycerine in sample film;
Fig. 4 represents the schematic diagram of the state that placed cover glass on glycerine.
Embodiment
Blooming of the present invention is the blooming containing thermoplastic resin, and it contains the compound shown in above-mentioned general formula (1).
At this, so-called " thermoplastic resin " refers to can deliquescing by being heated to second-order transition temperature or fusing point, thus is configured as the resin of target shape.
This be characterized as with of the present invention 1 ~ 10 in the common technical characteristic of invention.
As embodiments of the present invention, express from the viewpoint of effect of the present invention, the compound shown in above-mentioned general formula (1) is preferably the compound shown in above-mentioned general formula (2).In addition, compound shown in above-mentioned general formula (2) is preferably represented by above-mentioned general formula (3), and then, have high latency expression power from the viewpoint of providing, can suppress to ooze out, reduce internal haze, the fragility excellent and blooming that photostabilization, humidity resistance are high, the compound shown in above-mentioned general formula (3) is the compound shown in above-mentioned general formula (4) preferably.
In addition, from the viewpoint of with the excellent compatibility of the compound shown in above-mentioned general formula (1), above-mentioned general formula (2), above-mentioned general formula (3) and above-mentioned general formula (4), obtain there is high latency expression power and photostabilization, humidity resistance high blooming, thermoplastic resin is preferably cellulose ester.
In addition; from the excellent compatibility with the compound shown in above-mentioned general formula (1), above-mentioned general formula (2), above-mentioned general formula (3) and above-mentioned general formula (4); obtain having high latency expression power, can suppress to ooze out, internal haze reduces and the excellent and aspect that the is blooming that photostabilization, humidity resistance are high of fragility is considered, above-mentioned cellulose ester preferably has the cellulose ester of the specific acyl substitution meeting above-mentioned formula (a) and (b).
In addition, from the viewpoint of can suppress to ooze out, fragility excellence, the film thickness of above-mentioned blooming is preferably in the scope of 20 ~ 60 μm.
And then, from the viewpoint of the blooming providing good visibility, blooming is preferably at 23 DEG C, the environment of 55%RH, and measure wavelength when being 590nm, in face shown in following formula, the length of delay Ro in direction is in the scope of 20 ~ 150nm, and the length of delay Rth of thickness direction is in the scope of 70 ~ 350nm.
Blooming of the present invention preferably possesses in polaroid and liquid crystal indicator, can provide the liquid crystal indicator that a kind of Humidity Dependence of the polaroid and the uneven and visible angle of front contrast with good photostabilization and humidity resistance reduces.
Below, to the present invention and its integrant and be described in detail for implementing embodiments of the present invention.It should be noted that, in this application, " ~ " uses to comprise before and after it described resin as the implication of lower value and higher limit.
< blooming > of the present invention
Blooming of the present invention contains thermoplastic resin, the compound shown in general formula (1) and other any composition.
< thermoplastic resin >
Thermoplastic resin can be cellulose esters resin, polycarbonate resin, polystyrene resins, polysulfones resin, polyester resin, polyarylate resinoid, (methyl) acrylic resin, olefine kind resin (such as norbornene resin, cyclic olefin resinoid, cyclic conjugated diene resinoid, alicyclic vinyl ring type hydrocarbon resin) etc.Wherein, preferred cellulose esters resin, (methyl) acrylic resin, polycarbonate resin, cyclic olefin resinoid, most preferably cellulose ester resinoid.
< cellulose ester >
Cellulose ester contained in blooming of the present invention is not particularly limited, and is preferably the carboxylicesters of the straight or branched of carbonatoms about 2 ~ 22.The carboxylic acid forming ester can form ring, also can be aromatic carboxylic acid.The carboxylic acid forming ester also can have substituting group.The carboxylic acid forming ester is particularly preferably the lower fatty acid that carbonatoms is less than 6.
For the concrete example of preferred cellulose ester, the cellulosic mixed aliphatic ester being also bonded with propionic acid ester group or butyric acid ester group except ethanoyl that cellulose ethanoate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyric ester are such can be enumerated.
Cellulose ester more preferably meets following formula (a) and (b) simultaneously.In formula, X is the substitution value of ethanoyl, Y is the substitution value of propionyl or butyryl radicals or the substitution value of its mixture.The substitution value of acyl group can measure according to ASTM-D817-96.
Formula (a) 1.5≤X+Y≤2.5
Formula (b) 0≤Y≤1.5
The further preferred cellulose acetic ester (Y=0) of cellulose ester and cellulose acetate propionate (Y; Propionyl, 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 ethanoate, preferably 1.5≤X≤2.5, the further cellulose ethanoate of preferred 2.0≤X≤2.5.The cellulose ethanoate that can most preferably use is the cellulose diacetate (DAC) of 2.0≤X≤2.5.
By using above-mentioned cellulose ethanoate or cellulose acetate propionate, the blooming postponing excellence, physical strength, environmental turbulence excellence can be obtained.
In order to obtain the optical characteristics expected, also can the different cellulose ethanoate of substitution value used in combination.The ratio of mixture of different cellulose ethanoates is not particularly limited, can in the scope of 10:90 ~ 90:10 (mass ratio).
The number-average molecular weight of cellulose ester is preferably 6 × 10
4~ 3 × 10
5scope, more preferably 7 × 10
4~ 2 × 10
5scope.This is because the physical strength of the film obtained is improved.Weight-average molecular weight Mw, the number-average molecular weight Mn of cellulose ester can use gel permeation chromatography (GPC) to measure.An example of condition determination is as described below, but is not limited thereto, and also can use equal measuring method.
Solvent: methylene dichloride
Post: Shodex K806, K805, K803G (connecting the post that 3 Showa electricians (strain) make to use)
Column temperature: 25 DEG C
Sample solution concentration: 0.1 quality %
Detector: RI Model 504 (GLScience Inc.)
Pump: L6000 (Hitachi (strain) makes)
Flow: 1.0ml/min
Calibration curve: use the calibration curve obtained by 13 samples of polystyrene standard STK standard polystyrene (eastern Cao (strain) system) Mw=1000000 ~ 500.13 samples use roughly at equal intervals.
The raw cellulose of cellulose ester is not particularly limited, and can enumerate: linters, wood pulp, mestha etc.In addition, the cellulose ester obtained by them can be used in combination with arbitrary ratio respectively.
The cellulose ester such as cellulose ethanoate, cellulose acetate propionate can be manufactured by known method.Specifically, can synthesize with reference to the method recorded in No. 10-45804, Japanese Unexamined Patent Publication.
Compound > shown in < general formula (1)
Blooming of the present invention contains the compound shown in general formula (1).Compound shown in general formula (1) can be the compound shown in general formula (2), general formula (3) and general formula (4).
[chemical formula 5]
In above-mentioned general formula (1), R
11represent substituting group.Alternatively base, from the view point of the solvability of this compound and with cellulosic interaction (consistency and phase differential expression power), be preferably following substituting group.
As with R
11the substituting group represented.Can enumerate: alkyl (such as methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, amyl group, hexyl, octyl group, dodecyl, trifluoromethyl etc.), cycloalkyl (such as cyclopropyl, cyclopentyl, cyclohexyl, adamantyl etc.), aryl (such as phenyl, naphthyl etc.), alkoxyl group (such as alkoxyl group, tert.-butoxy etc.), aryloxy (such as phenoxy group, naphthyloxy etc.), alkylamino (such as ethylamino etc.), arylamino (such as phenyl amino etc.), alkylthio (such as methylthio group, 2-ethyl hexyl sulfenyl etc.), arylthio (such as thiophenyl etc.), heterocyclic radical (such as pyridyl, pyrimidyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl group, miaow di azoly etc.), amino (such as amino, ethylamino, dimethylamino, butyl is amino, clopentylamino, 2-ethylhexylamino, dodecylamino etc.).
R
11shown substituting group can be replaced by following multiple group further, and adjacent substituting group also can bond together and form ring: alkyl (such as methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, amyl group, hexyl, octyl group, dodecyl, trifluoromethyl etc.), cycloalkyl (such as cyclopropyl, cyclopentyl, cyclohexyl, adamantyl etc.), aryl (such as phenyl, naphthyl etc.), heterocyclic radical (such as pyridyl, pyrimidyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl group, miaow di azoly etc.), acyl amino (such as acetylamino, benzoyl-amido etc.), alkylthio (such as methylthio group, ethylmercapto group etc.), arylthio (such as thiophenyl, naphthalene sulfenyl etc.), alkenyl (such as vinyl, 2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, 4-hexenyl, cyclohexenyl, styryl etc.), halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine 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 ethanoyl, pivaloyl, benzoyl etc.), formamyl (such as aminocarboxyl, methylaminocarbonyl, Dimethylaminocarbonyl, butyl aminocarboxyl, cyclohexylaminocarbonyl, phenyl amino carbonyl etc.), sulfamyl (such as amino-sulfonyl, methylaminosulfonyl, dimethylamino-sulfonyl, butyl amino-sulfonyl, hexylamino alkylsulfonyl, Cyclohexylamino alkylsulfonyl, octyl amino alkylsulfonyl, dodecylamino alkylsulfonyl, phenylaminosulfonyl group, naphthyl-amino alkylsulfonyl, 2-pyridinylamino alkylsulfonyl etc.), sulfamyl (such as sulfonyl methane amido, benzene sulfonamido etc.), cyano group, alkoxyl group (such as methoxyl group, oxyethyl group, propoxy-etc.), aryloxy (such as phenoxy group, naphthyloxy etc.), siloxy, acyloxy (such as acetoxyl group, benzoyloxy etc.), sulfonic group or its salt, amino carbonyl oxygen base, amino (such as amino, ethylamino, dimethylamino, butyl is amino, clopentylamino, 2-ethylhexylamino, dodecylamino etc.), anilino (such as phenyl amino, chlorphenylamino, toluene amido, anisidino, naphthyl-amino, 2-pyridinylamino etc.), 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.), aryloxycarbonyl (such as phenyloxycarbonyl etc.), carbamate groups (such as methyl carbamate base, phenylcarbamate base), alkoxyl phenyl (such as p-methoxy-phenyl etc.), phenyl (such as acetoxyl group phenyl etc.), thioureido, carboxyl, the salt of carboxylic acid, hydroxyl, sulfydryl, nitro etc.
As R
11preference, preferred alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, amino, alkylamino, arylamino, alkylthio; Preferred alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, alkylthio; Further preferred alkyl, alkoxyl group, aryl, aryloxy; Particularly preferably alkyl, alkoxyl group, most preferably alkyl.At R
11when for alkyl, preferred carbonatoms is the alkyl of 1 ~ 8.Preferably carbonatoms is the alkyl of 1 ~ 4 further.By by R
11be set to these substituting groups, become the blooming of the intermiscibility raising of compound, internal haze reduction, high latency.
In above-mentioned general formula (1), R
21and R
31represent substituting group.As R
21and R
31shown substituting group, can enumerate: alkyl (such as methyl, ethyl, propyl group, sec.-propyl, the tertiary butyl, amyl group, hexyl, octyl group, dodecyl, trifluoromethyl etc.), cycloalkyl (such as cyclopropyl, cyclopentyl, cyclohexyl, adamantyl etc.), aryl (such as phenyl, naphthyl etc.), heterocyclic radical (such as pyridyl, pyrimidyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl group, miaow di azoly etc.), acyl amino (such as acetylamino, benzoyl-amido etc.), alkylthio (such as methylthio group, ethylmercapto group etc.), arylthio (such as thiophenyl, naphthalene sulfenyl etc.), halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), alkylsulfonyl (alkyl sulphonyl (such as methyl sulphonyl, ethylsulfonyl etc.), aryl sulfonyl (such as phenyl sulfonyl, Naphthylsulfonyl etc.)), acyl group (such as ethanoyl, pivaloyl, benzoyl etc.), formamyl (such as aminocarboxyl, methylaminocarbonyl, Dimethylaminocarbonyl, butyl aminocarboxyl, cyclohexylaminocarbonyl, phenyl amino carbonyl etc.), alkoxyl group (such as methoxyl group, oxyethyl group, propoxy-etc.), aryloxy (such as phenoxy group, naphthyloxy etc.), amino (such as amino, ethylamino, dimethylamino, butyl is amino, clopentylamino, 2-ethylhexylamino, dodecylamino etc.), alkoxy carbonyl (such as methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl etc.), aryloxycarbonyl (such as phenyloxycarbonyl etc.), alkylthio (such as methylthio group, 2-ethyl hexyl sulfenyl etc.).
R in general formula (1)
21and R
31the substituting group represented can replace further with multiple same group, and adjacent substituting group also can bond together and form ring.
As R
21preference, preferred alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio, halogen atom; Further preferred alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, halogen atom; Particularly preferably alkyl, alkoxyl group, acyl group, alkoxy carbonyl.By by R
21be set to these substituting groups, the intermiscibility raising, the internal haze that become compound reduce, inhibit blooming that ooze out, high latency.
As R
31preferred example, preferred alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, acyloxy, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio, halogen atom; Preferred alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, acyloxy, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio, halogen atom; Particularly preferably alkyl, alkoxyl group, aryl, aryloxy, acyl group, acyloxy, alkoxy carbonyl, aryloxycarbonyl.By by R
31be set to these substituting groups, the intermiscibility raising, the internal haze that become compound reduce, inhibit blooming that ooze out, high latency.
R
41represent hydrogen atom or substituting group, as R
41shown substituting group, can enumerate: alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio, halogen atom.
As R
41preference, preferred hydrogen atom, alkyl, cycloalkyl, aryl, acyl group, alkoxy carbonyl, aryloxycarbonyl; Preferred hydrogen atom, alkyl, cycloalkyl, aryl, acyl group, particularly preferably alkyl, aryl, acyl group further.By importing such group, the consistency becoming compound improves, internal haze reduces, inhibits blooming that ooze out, high latency.
As the integer shown in the k1 in general formula (1), from the viewpoint of phase differential expression power and consistency, the preferably scope of 1 ~ 4, further preferably 1 ~ 3 scope, particularly preferably 1.
In general formula (1), as the position of substitution that-OCO-replaces, when the bonding position with benzoxazinone skeleton is set to 1, preferably replace at 3,4,5, preferably further to replace at 4.By replacing in these positions, show high latency.
As the integer shown in the m1 in general formula (1), from the viewpoint of phase differential expression power, the preferably scope of 0 ~ 4, further preferably 0 ~ 3 scope, particularly preferably 0.
As the integer shown in the n1 in general formula (1), from the viewpoint of consistency, the preferably scope of 0 ~ 4, further preferably 0 ~ 3 scope, particularly preferably 0.
X in general formula (1)
1consider from sunproof viewpoint, preferred Sauerstoffatom.
Y1 in general formula (1) considers from sunproof viewpoint, preferred Sauerstoffatom or nitrogen-atoms or NR
41, preferred Sauerstoffatom or nitrogen-atoms, particularly preferably Sauerstoffatom further.
Z in general formula (1)
1consider from sunproof viewpoint, preferred Sauerstoffatom or nitrogen-atoms, particularly preferably nitrogen-atoms.
X in general formula (2)
2, Y
2, Z
2, R
12, R
22, R
42, k2 and m2 respectively with the X in general formula (1)
1, Y
1, Z
1, R
11, R
21, R
41, k1 and m1 same meaning.
R in general formula (3)
13, R
23, k3 and m3 respectively with the R in general formula (1)
11, R
21, k1 and m1 same meaning.
R in general formula (4)
14, and k4 respectively with the R in general formula (1)
11, k1 same meaning.
Below enumerate the concrete example of above-mentioned general formula (1), above-mentioned general formula (2), above-mentioned general formula (3) and the compound shown in above-mentioned general formula (4), 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]
Blooming of the present invention comprises the compound shown in thermoplastic resin and general formula (1), but in order to obtain the delay expected, is preferably made an addition in thermoplastic resin by the compound shown in general formula (1).What is called is added with and refers to and be dissolved or dispersed in thermoplastic resin.By means of only only carrying out being coated with the compound shown in general formula (1) on the surface of blooming, desired delay cannot be obtained.
Blooming of the present invention is in order to obtain the delay expected, preferably in the scope of 0.1 ~ 20 mass parts, comprise the compound shown in general formula (1) relative to thermoplastic resin 100 mass parts, in the scope of preferred 1 ~ 15 mass parts, in the scope of preferred 1.5 ~ 10 mass parts further, in the scope of particularly preferably 2 ~ 6 mass parts.If above-mentioned within the scope of this, then blooming of the present invention given and postponing fully, and internal haze, consistency, ooze out that characteristic becomes good.
The thickness direction phase difference value Rth of blooming
550nm(phase difference value of the thickness direction recorded at 550 nm) is compared with un-added thermoplastic resin film, be preferably more than 1.1 times, the scope of more preferably 1.2 times ~ 10 times, be particularly preferably the scope of 1.3 times ~ 4 times, described blooming contains the compound shown in 3 mass parts formula of of the present invention (1) relative to thermoplastic resin 100 mass parts.By adding the compound of above-mentioned scope, the blooming of the expression power excellence of delay can be provided.
As long as blooming of the present invention comprises the compound shown in more than at least a kind above-mentioned general formula (1), compound beyond above-mentioned general formula (1) also can be combinationally used to give delay.
The synthesis > of the compound shown in < general formula (1)
Compound shown in general formula (1) synthesizes by general method.Below record the synthesis example of exemplary compounds.
(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, stir at 40 DEG C, dissolve, drip diacetyl oxide 50g.Stir after 1 hour, carry out water cooling, add acetic acid 30ml.Stir after 1 hour, carry out filtering, wash, dry, obtain 54.5g intermediate A thus.
In the eggplant-shape bottle of 100ml, add intermediate A 5.0g, thionyl chloride 3.0ml, DMF0.1ml, heat 3 hours at 80 DEG C.Remove desolventizing and thionyl chloride under reduced pressure, obtain intermediate B 5.6g thus.
In the eggplant-shape bottle of 200ml, add pyridine 50ml, isatoic anhydride 4.5g, after being heated to 50 DEG C, drip intermediate B 5.6g.After dropping terminates, outer temperature is warming up to 120 DEG C.After 2 hours, be cooled to room temperature, add water 100ml and stir 1 hour.Carry out drying carrying out filtering, after washed with methanol, slightly refined thing 6.4g thus.Utilizing column chromatography (developing solvent: toluene) to refine by slightly refining thing, obtaining the exemplary compounds A-022 of 3.8g thus.The exemplary compounds A-022 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-073)
[chemical formula 22]
In 500ml eggplant-shape bottle, add salicylic amide 42.0g, dimethylbenzene 100ml, pyridine 5ml, heat at 150 DEG C, reflux.Intermediate B 66.9g was dripped through 1 hour in this reaction solution.After dropping terminates, reflux 7 hours, is then cooled to room temperature, and underpressure distillation is except desolventizing.Utilized by remainder column chromatography (developing solvent: toluene/acetone=5/1) to refine, obtain the exemplary compounds A-073 of 8.7g thus.The exemplary compounds A-073 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-115)
[chemical formula 23]
Methyl o-aminobenzoate 10g and pyridine 30ml is dissolved and carries out frozen water cooling.14g intermediate B is dripped in this solution.In reaction solution, add water 200ml and stir 2 hours.Filter, wash the solid of separating out, obtain 13.2g intermediate C thus.
Add 10.4g intermediate C, 5 phosphoric sulfide 18g and dry pyridine 150ml, be heated to 140 DEG C and reflux 18 hours.After heating terminates, reaction solution is injected frozen water and stirs.After filtering the solid of separating out, be dissolved in methylene dichloride.Anhydrous magnesium sulfate is used to carry out drying.Underpressure distillation removing methylene dichloride, carries out recrystallization by methylene dichloride/ethanol, obtains 6.9g exemplary compounds A-115 thus.The 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, dripping diacetyl oxide 5.5g.Stir after 1 hour, carry out water cooling, add acetic acid 3ml.Stir to carry out after 1 hour filtering, wash, dry, obtain 4.7g intermediate D.
Intermediate D4.7g, thio-methyl salicylate 9.8g, triethylamine 6.5g, toluene 30ml carry out nitrogenize, reflux 25 hours is added in 200ml eggplant-shape bottle.After heating terminates, underpressure distillation is except desolventizing.Utilize column chromatography (developing solvent: hexane/ethyl acetate=5/1) to refine, obtain the exemplary compounds A-124 of 3.2g thus.The exemplary compounds A-124 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-133)
[chemical formula 25]
Intermediate C6.2g, Lawesson's reagent 40g, toluene 100ml is added and reflux 10 hours in 300ml eggplant-shape bottle.Be cooled to filtering solids after room temperature, concentrating under reduced pressure filtrate.Utilized by remainder column chromatography (developing solvent: heptane/ethyl acetate=9/1) to refine, obtain 4.3g intermediate E thus.
Intermediate E 4.3g, acetone 50ml, diacetyl oxide 10g reflux 4 hours is added in 200ml eggplant-shape bottle.Add methyl alcohol 50ml after cooling and stir 1 hour.To separate out solid filter, washed with methanol, obtain 3.2g exemplary compounds A-133 thus.The exemplary compounds A-133 obtained is identified by NMR and mass spectrum.
(synthesis of exemplary compounds A-146)
[chemical formula 26]
Anthranilic acid 40g, triethylamine 32.0g, acetone 100ml stirring under water cooling is added in 1L eggplant-shape bottle.Stir 3 hours after 1 hour drips intermediate B 58.0g in this reaction solution.After reaction solution concentrating under reduced pressure, add 2 ethylhexylamine 51.8g, acetonitrile 1ml and at room temperature stir.PCl is added in this reaction solution
355g, is warming up to 50 DEG C and stirs 20 hours.Be cooled to room temperature after heating terminates, add ethyl acetate 500ml.According to 1N hydrochloric acid, 5%NaHCO
3the order of the aqueous solution, pure water carries out separatory, concentrating under reduced pressure organic layer.Utilize column chromatography (developing solvent: toluene/ethyl acetate=5/1) to refine to remainder, obtain the exemplary compounds A-146 of 12.5g thus.The exemplary compounds A-146 obtained is identified by NMR and mass spectrum.
Other the compound shown in general formula (1) also can synthesize with reference to the disclosure of specification sheets of the present invention and known technology.
Blooming of the present invention, can also containing other any composition except the compound shown in thermoplastic resin and general formula (1).The example of any composition comprises wavelength dispersion control agent, sugar ester, softening agent, UV light absorber, antioxidant and particulate etc.
< wavelength dispersion control agent >
Blooming of the present invention also can contain wavelength dispersion control agent.So-called " wavelength dispersion control agent " refers to the compound of the wavelength dependency regulating blooming to postpone.The preference of wavelength dispersion control agent comprises the compound recorded in the discoid compound and Japanese Unexamined Patent Publication 2010-163482 publication recorded in Japanese Unexamined Patent Publication 2001-166144 publication and Japanese Unexamined Patent Publication 2003-344655 publication.
Wavelength dispersion control agent preferably has maximum absorption in the wavelength region of 250nm ~ 400nm or the wavelength region of 270nm ~ 380nm.
Wavelength dispersion control agent can be used alone or is mixed with two or more.The addition of wavelength dispersion control agent preferably relative to thermoplastic resin 100 mass parts in the scope of 1.0 ~ 20 quality %, preferred in the scope of 1.5 ~ 15 quality % further, most preferably in the scope of 2.0 ~ 10 quality %.The addition means of wavelength dispersion control agent is added into thermoplastic resin solution's (rubber cement) after can dissolving wavelength decentralised control agent in the organic solvent of alcohol or methylene dichloride, dioxolane, or also can directly be added on in rubber cement composition.
Wavelength dispersion control agent can be added in the mixing solutions of thermoplastic resin in advance, also can add to arbitrary operation of curtain coating at the rubber cement making thermoplastic resin.In the latter case, make the solution of wavelength dispersion control agent and the dissolving of a small amount of thermoplastic resin be added into thermoplastic resin to be online dissolved in the rubber cement of solvent.This mixing preferably uses the such as on-line mixing device such as static mixer (Toray Engineering system), SWJ (in eastern beautiful silent oscillation pipe mixing tank Hi-Mixer) to carry out.
Together can add matting agent with wavelength dispersion control agent, also can add the additives such as Time delay control agent, softening agent, deterioration preventing agent, stripping promotor.
When using online mixing tank, preferably under high pressure concentrated dissolving; As long as pressurizing vessel can tolerate the pressure of regulation and can heat under elevated pressure, stirs.Pressurizing vessel is suitable for arranging the instrument class such as pressure warning unit, thermometer.Pressurize by being pressed into the method for the rare gas elementes such as nitrogen or being undertaken by the rising of heating the solvent vapour pressure caused.
Heating is preferably carried out from external container, the such as easy control of temperature of jacketing heat device, therefore preferably.Add the Heating temperature of solvent and preferably use more than the boiling point of solvent and the temperature of scope that can not seethe with excitement of this solvent, be set as the scope of such as 30 ~ 150 DEG C.At a set temperature, adjusting pressure makes solvent seethe with excitement.Cool after dissolving while take out from container or extract out from container with pump etc., use the coolings such as heat exchanger, provide it to masking.Cooling temperature now also can be cooled to normal temperature, but is cooled to the temperature of lower than boiling point 5 ~ 10 DEG C and carries out casting at temperature and can reduce cement viscosity, therefore preferably.
< sugar ester >
Blooming of the present invention is preferably containing the sugar ester beyond cellulose ester.This sugar ester so-called refers at least any one the compound containing furanose structure or pyranose structure.Sugar ester can be monose, also can be the polysaccharide of connection 2 ~ 12 sugared structures.And at least one of the OH base that sugared structure preferably has by sugar ester carries out the compound of esterification.The esterification yield of sugar ester is preferably present in more than 70% of the OH base in pyranose structure or furanose structure.
The example forming the sugar of sugar ester comprises glucose, semi-lactosi, seminose, fructose, wood sugar or pectinose, lactose, sucrose, GF3,1F-GF4, stachyose, maltose alcohol, Saccharum lactis, lactulose, cellobiose, maltose, procellose, trisaccharide maltose, raffinose or kestose.And then the example forming the sugar of sugar ester also comprises gentiobiose, gentianose, rough gentian tetrose, xylotriose, galactosyl sucrose etc.Certainly, sugar is not limited to these sugar.Form the sugared structure of sugar ester particularly preferably containing pyranose structure and furanose structure.
The preference forming the sugar of sugar ester is sucrose, kestose, GF3,1F-GF4, stachyose etc., more preferably sucrose.
In sugar ester, the whole OH base in pyranose structure or furanose structure or one are carried out a point esterification.Monocarboxylic acid for esterification is not particularly limited, and can use known aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate etc.The carboxylic acid used can be a kind, also can be mixing of more than two kinds.
Form the ester of sugar ester, the example of preferred aliphatic monocarboxylic acid comprises acetic acid, propionic acid, butyric acid, isopropylformic acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, nondecylic acid, eicosanoic acid, behenic acid, Lignoceric acid, cerinic acid, carboceric acid, montanic acid, myricyl acid, the saturated fatty acids such as n-Dotriacontanoic acid, undecylenic acid, oleic acid, Sorbic Acid, linolic acid, linolenic acid, arachidonic acid, the unsaturated fatty acidss etc. such as octylenic acid.
Form the ester of sugar ester, the example of preferred cycloaliphatic monocarboxylic comprises Cyclopentane carboxylic acid, hexahydrobenzoic acid, cyclooctanecarboxylic acid or their derivative.
Form the ester of sugar ester, the example of preferred aromatic monocarboxylate comprises aromatic monocarboxylate or their derivative that phenylformic acid, toluic acid etc. have imported alkyl in benzoic phenyl ring, the aromatic monocarboxylate, styracin, benzilic acid, biphenyl carboxylic acids, naphthalene monocarboxylic acid, tetralincarboxylic acid etc. of alkoxyl group have more than 2 phenyl ring.More specifically, comprise xylic acid, mellic acid, 3, 5-mesitylenic acid, 2, 3, 4-trimethylbenzene formic acid, γ-Yi Du acid, durylic acid, 2, 4, 6-trimethylbenzoic acid, α-Yi Du acid, cuminic acid, α-toluic acid, hydratropic acid, atropic acid, phenylpropionic acid, Whitfield's ointment, 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), between cresotinic 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, gallic acid, asarylic acid, amygdalic acid, to anisole oxyacetic acid, homovanillic acid, homoveratroyl, adjacent homoveratroyl, phthalonic acid, P-coumaric acid, particularly preferably phenylformic acid.
The ester of oligosaccharides can be used as the sugar ester in the present invention.Oligosaccharides makes amylase etc. act on enzyme and starch, sucrose etc. manufacture, and the example of preferred oligosaccharides comprises Fructus Hordei Germinatus oligose, isomalto Oligosaccharide, Nutriflora P, galactooligosaccharicomposition, wood oligose.
Sugar ester for condensation more than 1 and 12 with the compound of at least a kind of the pyranose structure shown in following general formula (A) or furanose structure.R in general formula (A)
11~ R
15, R
21~ R
25represent that carbonatoms is acyl group or the hydrogen atom of 2 ~ 22, m and n is respectively the integer of 0 ~ 12, and m+n is the integer of 1 ~ 12.
[chemical formula 27]
General formula (A)
R
11~ R
15, R
21~ R
25be preferably benzoyl, hydrogen atom.Benzoyl also can have substituent R
26(p is 0 ~ 5), can enumerate such as alkyl, alkenyl, alkoxyl group, phenyl and then, these alkyl, thiazolinyl, phenyl also can have substituting group.The ester of oligosaccharides is also by the method manufacture same with other sugar ester.
As the concrete example of the sugar ester used in the present invention, can enumerate: the middle compound recorded in Japanese Unexamined Patent Publication 2012-230154 publication paragraph [0130] ~ [0137] and Japanese Unexamined Patent Publication 2012-230282 publication paragraph [0077] ~ [0078], but the present invention is not limited thereto.
Blooming of the present invention, in order to suppress the variation of phase difference value and stabilization display grade, is preferably 0.5 ~ 30 quality % of blooming containing above-mentioned sugar ester, particularly preferably containing 5 ~ 30 quality %.
< softening agent >
Blooming of the present invention can contain softening agent.Softening agent is not particularly limited, but preferably selects from polycarboxylic acid ester plasticizer, oxyacetic acid ester plasticizer, phthalic ester plasticizer, fatty acid ester plasticiser, polyalcohol ester plasticizer, polyester softening agent, Acrylic Plasticizer etc.In blooming of the present invention containing two or more softening agent, preferably at least a kind is preferably polyalcohol ester plasticizer.
(polyalcohol ester plasticizer)
Polyalcohol ester plasticizer is the softening agent be made up of the aliphatic polyol of more than 2 yuan and the ester of monocarboxylic acid, preferably in molecule, has aromatic nucleus or cycloalkyl ring.Be preferably the aliphatic polybasic alcohol ester of 2 ~ 20 yuan.
The polyvalent alcohol of alkoxide softening agent of coming from different backgrounds and possess different abilities is represented by following general formula (a).
General formula (a) Ra-(OH)
n
At this, Ra represents the organic group of n valency, and n represents the positive integer of more than 2, the hydroxyl of OH basis representation alcoholic or phenol.
Come from different backgrounds and possess different abilities alkoxide softening agent, the example of preferred polyvalent alcohol comprises ribitol, arabitol, ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, 1, 2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, dibutylene glycol, 1, 2, 4-trihydroxybutane, 1, 5-pentanediol, 1, 6-hexylene glycol, hexanetriol, melampyrum, mannitol, 3-methylpentane-1, 3, 5-triol, tetramethyl ethylene ketone, Sorbitol Powder, TriMethylolPropane(TMP), trimethylolethane, Xylitol etc., but be not particularly limited.Particularly preferably triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, Sorbitol Powder, TriMethylolPropane(TMP), Xylitol.
The example of monocarboxylic acid of alkoxide softening agent of coming from different backgrounds and possess different abilities is not particularly limited, and can use known aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate etc.If use cycloaliphatic monocarboxylic, aromatic monocarboxylate, then from the viewpoint of improving water vapour permeability, retention, preferably.
As the example of preferred monocarboxylic acid, following monocarboxylic acid can be enumerated, but be not limited thereto.
The example of aliphatic monocarboxylic acid comprises and has the straight chain of carbonatoms 1 ~ 32 or the lipid acid of side chain.Carbonatoms more preferably 1 ~ 20, is particularly preferably 1 ~ 10.If containing acetic acid, then increase with cellulosic consistency, therefore preferably.Also preferred acetic acid and other monocarboxylic acid are carried out mixing using.
As preferred aliphatic monocarboxylic acid, can enumerate: the unsaturated fatty acids etc. such as saturated fatty acid, undecylenic acid, oleic acid, Sorbic Acid, linolic acid, linolenic acid, arachidonic acid of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, the acid of 2-ethyl-hexan, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, nondecylic acid, eicosanoic acid, behenic acid, Lignoceric acid, cerinic acid, carboceric acid, montanic acid, myricyl acid, n-Dotriacontanoic acid etc.
The example of preferred cycloaliphatic monocarboxylic comprises Cyclopentane carboxylic acid, hexahydrobenzoic acid, cyclooctanecarboxylic acid or their derivative.
The example of preferred aromatic monocarboxylate comprises aromatic monocarboxylate or their derivative that carboxylic acid, biphenyl carboxylic acids, naphthalene monocarboxylic acid, tetralincarboxylic acid etc. that phenylformic acid, toluic acid etc. imported the alkoxyl groups such as 1 ~ 3 alkyl, methoxyl group or oxyethyl group in benzoic phenyl ring have more than 2 phenyl ring.Particularly preferably phenylformic acid.
The carboxylic acid of ester of alkoxide softening agent of coming from different backgrounds and possess different abilities can be a kind, also can be combination of more than two kinds.In addition, the OH base in polyvalent alcohol all can carry out esterification, also a part can be retained with the state of OH base.
The molecular weight of polyalcohol ester plasticizer is not particularly limited, but is preferably the scope of 300 ~ 1500, the more preferably scope of 350 ~ 750.The large aspect of molecular weight due to not volatile, therefore preferably, from the viewpoint of water vapour permeability, with the consistency of thermoplastic resin, a preferably little side.
(oxyacetic acid ester plasticizer)
Oxyacetic acid ester plasticizer is not particularly limited, but preferably can use alkyl phthalic acyl group alkyl glycolate ester class.The example of alkyl phthalic acyl ethyl glycolate class comprises methyl phthalyl acid methyl esters, ethyl phthalyl acetoacetic ester, propyl group phthalyl propyl propionate, butyl phthalyl acid butyl ester, octyl phthalyl base oxyacetic acid monooctyl ester, methyl phthalyl acetoacetic ester, ethyl phthalyl acid methyl esters, ethyl phthalyl propyl propionate, methyl phthalyl acid butyl ester, ethyl phthalyl acid butyl ester, butyl phthalyl acid methyl esters, butyl phthalyethyl glycolate, propyl group phthalyl acid butyl ester, butyl phthalyl propyl propionate, the misery ester of methyl phthalyl, the misery ester of ethyl phthalyl, octyl phthalyl base methyl glycolate, octyl phthalyl base ethyl glycollate etc.
(phthalic ester plasticizer)
The example of phthalic ester plasticizer comprises diethyl phthalate, Dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate (DOP), dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate (DOP), dicyclohexyl phthalate, terephthalic acid dicyclohexyl maleate etc.
(citric acid ester plasticizer)
The example of citric acid ester plasticizer comprises citric acid acetyl three methyl esters, Triethyl citrate acetate, acetyl tributyl citrate etc.
(fatty acid ester plasticiser)
The example of fatty acid ester plasticiser comprises butyl oleate, methylacetyl ethanoyl ester, Uniflex DBS etc.
(phosphate plasticizer)
The example of phosphate plasticizer comprises triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate base diphenyl ester, octyl diphenyl phosphate, diphenyl phosphate Biphenyl Ester, tricresyl phosphate octyl group ester, tributyl phosphate etc.
(polycarboxylic acid ester plasticizer)
Polycarboxylic acid ester plasticizer is more than 2 yuan, the preferably 2 yuan ~ polycarboxylic acid of 20 yuan and the carboxylate of alcohol.In addition, aliphatic polycarboxylic acid is preferably 2 ~ 20 yuan, when aromatic polycarboxylic acid, ester ring type polycarboxylic acid, is preferably 3 yuan ~ 20 yuan.
Polycarboxylic acid is represented by following general formula (b).
General formula (b) Rb (COOH)
m(OH)
n
(wherein, the organic group of Rb represents (m+n) valency, 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 alcoholic or phenolic hydroxyl group.)
The example of preferred polycarboxylic acid comprises aromatic polycarboxylic acid or derivatives thereof more than as 3 valencys of trimellitic acid, trimesic acid, Pyromellitic Acid and so on, as the aliphatic polycarboxylic acid of succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, oxalic acid, fumaric acid, toxilic acid, tetrahydrophthalic acid and so on, the hydroxyl polycarboxylic acid etc. as tartrate, tartronic acid, oxysuccinic acid, citric acid and so on, but be not limited to these.Particularly use hydroxyl polycarboxylic acid, then the retention (can not volatilize from blooming) of softening agent improves, therefore preferably.
The alcohol of ester of carboxylic acid esters softening agent of coming from different backgrounds and possess different abilities also for known alcohol, phenols, can be not particularly limited.Be such as aliphatic saturated alcohols or the aliphatics unsaturated alcohol of the straight chain or side chain with carbonatoms 1 ~ 32.More preferably carbonatoms 1 ~ 20, is particularly preferably carbonatoms 1 ~ 10.In addition, also the aromatic alcohols or derivatives thereofs etc. such as the alicyclic alcohol such as cyclopentanol, hexalin or derivatives thereof, benzylalcohol, styryl carbinol can preferably be used.
The alcohols of ester of carboxylic acid esters softening agent of coming from different backgrounds and possess different abilities can be a kind, also can be mixing of more than two kinds.
When using hydroxyl polycarboxylic acid as polycarboxylic acid, monocarboxylic acid can be used the alcohol hydroxyl group of hydroxyl polycarboxylic acid or phenolic hydroxyl group esterification.Monocarboxylic acid is preferably aliphatic monocarboxylic acid, but is not limited thereto.
Aliphatic monocarboxylic acid preferably has the straight chain of carbonatoms 1 ~ 32 or the lipid acid of side chain.More preferably carbonatoms 1 ~ 20, is particularly preferably carbonatoms 1 ~ 10.As preferred aliphatic monocarboxylic acid, can enumerate: the unsaturated fatty acidss etc. such as saturated fatty acid, undecylenic acid, oleic acid, Sorbic Acid, linolic acid, linolenic acid, arachidonic acid such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, nondecylic acid, eicosanoic acid, behenic acid, Lignoceric acid, cerinic acid, carboceric acid, montanic acid, myricyl acid, n-Dotriacontanoic acid.
The example of preferred cycloaliphatic monocarboxylic can be enumerated: Cyclopentane carboxylic acid, hexahydrobenzoic acid, cyclooctanecarboxylic acid or their derivative.
The example of preferred aromatic monocarboxylate can be enumerated: monocarboxylic acid, biphenyl carboxylic acids, naphthalene monocarboxylic acid, tetralincarboxylic acid etc. that phenylformic acid, toluic acid etc. have imported alkyl in benzoic phenyl ring have aromatic monocarboxylate or their derivative of more than 2 phenyl ring.
The carboxylic acid that the alcohol hydroxyl group of hydroxyl polycarboxylic acid or phenolic hydroxyl group carry out esterification is particularly preferably acetic acid, propionic acid, phenylformic acid.
The molecular weight of polycarboxylic acid ester plasticizer is not particularly limited, but is preferably the scope of molecular weight 300 ~ 1000, the more preferably scope of 350 ~ 750.Improve from the viewpoint of the retention of softening agent, a preferably large side; From the viewpoint of water vapour permeability, with the consistency of cellulose ester, a preferably little side.
The acid number of polycarboxylic acid ester plasticizer is preferably below 1mgKOH/g, more preferably below 0.2mgKOH/g.By making acid number be above-mentioned scope, the environmental turbulence of delay is also inhibited, therefore preferably.Acid number refer in order in and the milligram number of potassium hydroxide required for acid (being present in the carboxyl in sample) contained in sample 1g.Acid number measures according to JIS K0070.
The more preferred example of polycarboxylic acid ester plasticizer can be enumerated: triethyl citrate, tributyl citrate, Triethyl citrate acetate (ATEC), acetyl tributyl citrate (ATBC), citric acid benzoyl tri-n-butyl, citric acid acetyl three phenyl ester, citric acid acetyl three benzyl ester, dibutyl tartrate, tartrate diacetyl dibutylester, tributyl trimellitate, Pyromellitic Acid four butyl ester etc., but is not limited to these.
(polyester softening agent)
Polyester softening agent such as having the polyester softening agent of aromatic nucleus or cycloalkyl ring in molecule.Polyester softening agent is such as the aromatic series end ester plasticizer shown in following general formula (c).
General formula (c) B-(G-A)
n-G-B
(in formula, B represents benzene monocarboxylic acid residue, G represents that the aklylene glycol residue of carbonatoms 2 ~ 12 or the aryl-diol residue of carbonatoms 6 ~ 12 or carbonatoms are the oxyalkylene diol residue of 4 ~ 12, A represents the alkylene dicarboxylic acids residue of carbonatoms 4 ~ 12 or aryl dicarboxylic acid's residue of carbonatoms 6 ~ 12, in addition, n represents the integer of more than 1.)
The polyester softening agent of general formula (c) is made up of the alkylene dicarboxylic acids residue shown in aklylene glycol residue, oxyalkylene diol residue or the aryl-diol residue shown in the benzene monocarboxylic acid residue shown in B, G, A or aryl dicarboxylic acid's residue.Polyester softening agent by with same being obtained by reacting of common polyester softening agent.
The example of the benzene monocarboxylic acid composition of polyester softening agent comprises phenylformic acid, p-tert-butyl benzoic acid, ortho-toluic acid, meta-toluic acid, paratolunitrile, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, benzaminic acid, acetoxy-benzoic acid, can be these one kind or two or more combination.
The example of the aklylene glycol composition of the carbonatoms 2 ~ 12 of polyester softening agent comprises ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butyleneglycol, 1, 3-butyleneglycol, 1, 2-propylene glycol, 2-methyl 1, ammediol, 1, 4-butyleneglycol, 1, 5-pentanediol, 2, 2-dimethyl-1, ammediol (neopentyl glycol), 2, 2-diethyl-1, ammediol (3, 3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1, 3 propylene glycol (3, 3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol, 1, 6-hexylene glycol, 2, 2, 4-trimethylammonium 1, 3-pentanediol, 2-ethyl 1, 3-hexylene glycol, 2-methyl 1, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-octadecandiol.These glycol can use with the form of one kind or two or more mixture.The particularly aklylene glycol of carbonatoms 2 ~ 12 and the excellent compatibility of cellulose ester, therefore particularly preferably.
As the oxyalkylene diol component of the carbonatoms 4 ~ 12 of polyester softening agent, such as have Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol etc., these glycol can use with the form of one kind or two or more mixture.
The example of the alkylene dicarboxylic acids composition of the carbonatoms 4 ~ 12 of polyester softening agent comprises succsinic acid, toxilic acid, fumaric acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid etc.These dicarboxylic acid can use with the form of one kind or two or more mixture respectively.As the arylidene dicarboxylic acid component of carbonatoms 6 ~ 12, there are phthalic acid, terephthalic acid, m-phthalic acid, 1,5-naphthalene dicarboxylic acids, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids etc.
The number-average molecular weight of polyester softening agent is preferably the scope of 300 ~ 1500, is more preferably the scope of 400 ~ 1000.In addition, its acid number is below 0.5mgKOH/g, and hydroxyl value is below 25mgKOH/g, and more preferably acid number is below 0.3mgKOH/g, hydroxyl value is below 15mgKOH/g.
(Acrylic Plasticizer)
(methyl) acrylic polymers as Acrylic Plasticizer can be weight-average molecular weight more than 3000 and the polymkeric substance X of less than 30000, and it is carried out copolymerization by the ethylene unsaturated monomer Xa in molecule to major general without aromatic nucleus and hydroxyl and the ethylene unsaturated monomer Xb that do not have aromatic nucleus and have a hydroxyl in molecule and obtained.
Or (methyl) acrylic polymers as Acrylic Plasticizer can be weight-average molecular weight more than 500 and the polymkeric substance Y of less than 3000, it is by being polymerized the ethylene unsaturated monomer Ya without aromatic nucleus and obtaining.
Preferred polymers X is represented by following general formula (X), and polymkeric substance Y is represented by following general formula (Y).
General formula (X) :-[CH
2-C (-Rc) (-CO
2rd)]
m-[CH
2-C (-Re) (-CO
2rf-OH)-]
n-[Xc]
p-
General formula (Y): Ry-[CH
2-C (-Rg) (-CO
2rh-OH)-]
k-[Yb]
q-
In formula (X) or formula (Y), Rc, Re, Rg represent H or methyl.Rd represents the alkyl or cycloalkyl of carbonatoms 1 ~ 12.Rf, Rh represent-CH
2-,-C
2h
4-or C
3h
6-.Ry represents the alkyl within hydroxyl, H or carbonatoms 3.Xc represents the monomeric unit that can be polymerized with Xa, Xb.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 softening agent, preferably contain in the scope relative to thermoplastic resin being 0.5 ~ 30 quality %, contain in the scope particularly preferably in 5 ~ 20 quality %.
[other resin]
Containing thermoplastic resin in blooming of the present invention, but also can comprise other the resin beyond the thermoplastic resin that mainly contains.The example of other resin comprises ether of cellulose resinoid, polycarbonate resin, polystyrene resins, polysulfones resin, polyester resin, polyarylate resinoid, acrylic resin, olefine kind resin (norbornene resin, cyclic olefin resinoid, cyclic conjugated diene resinoid, alicyclic vinyl ring type hydrocarbon resin etc.) etc.The preferred example of other resin comprises cellulose ester resinoid, polycarbonate resin, acrylic resin, cyclic olefin resinoid.When using other resin, in the scope of 5 ~ 70 quality % of the preferred blooming of its content.
[UV light absorber]
Blooming of the present invention can contain UV light absorber, also can contain two or more UV light absorber.The object of UV light absorber is, improve weather resistance by absorbing the ultraviolet of below 400nm, the transmitance particularly under optimal wavelength 370nm is less than 10%, is more preferably less than 5%, more preferably less than 2%.
UV light absorber is not particularly limited, such as, can enumerate: oxygen base benzophenone compound, benzotriazole compound, salicylate compounds, benzophenone compound, cyanoacrylate compound, compound in triazine class, nickel complex salt compounds, inorganic powder etc.
The concrete example of UV light absorber has the chloro-2-(3 of 5-, 5-bis--sec-butyl-2-hydroxy phenyl)-2H-benzotriazole, (2-2H-benzotriazole-2-base)-6-(straight chain and side chain dodecyl)-4-methylphenol, 2-hydroxyl-4 behzyloxybenzophenone, 2,4-behzyloxybenzophenone etc., in addition, there are the Tinuvin classes such as Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 928, these are the commercially available product of BASF Japanese firm, can preferably use.
UV light absorber is Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorption agent, triazine-based ultraviolet absorption agent, is particularly preferably Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorption agent.In addition, having the discoid compounds such as the compound of 1,3,5-triazines ring also can preferably as UV light absorber.
UV light absorber can be polymeric UV absorber; The particularly preferably UV light absorber of the polymer-type of No. 6-148430, Japanese Unexamined Patent Publication record.
Make an addition to rubber cement after the interpolation of UV light absorber can dissolve UV light absorber in the organic solvents such as the alcohol such as methyl alcohol, ethanol, butanols or methylene dichloride, methyl acetate, acetone, diox or their mixed solvent or be directly added in rubber cement component.In addition, the dispersion machine such as substance migration dissolver or sand mill that can not be dissolved in organic solvent as inorganic powder is added in rubber cement after disperseing in the solution of organic solvent and cellulose ester.
The content of the UV light absorber in blooming when the dry film thickness of blooming is 30 ~ 200 μm, the preferably scope of 0.5 ~ 10 quality %, the further scope of preferred 0.6 ~ 4 quality %.But kind, working conditions etc. according to UV light absorber will adjust.
[antioxidant]
Antioxidant is also referred to as deterioration preventing agent.When under the state that liquid crystal image display device etc. is placed on high humidity high temperature, sometimes cause the deterioration of blooming.Antioxidant such as postpones or suppresses blooming to decompose, phosphoric acid of its halogen due to the residual solvent amount in blooming or phosphoric acid class softening agent etc. and producing.
Antioxidant is preferred hindered phenol compound such as.The example of hindered phenol compound can be enumerated: 2, 6-bis--t-butyl-p-cresol, tetramethylolmethane-four [3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1, 6-hexylene glycol-bis-[3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], 2, 4-pair-(just pungent sulfenyl)-6-(4-hydroxyl-3, 5-bis--tertiary-butyl anilino)-1, 3, 5-triazine, 2, 2-sulfo--di ethylene bis [3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexa-methylene two (3, 5-bis--tertiary butyl-4-hydroxy-hydrocinnamamide), 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-bis--tertiary butyl-4-hydroxy benzyl) benzene, three-(3, 5-bis--tertiary butyl-4-hydroxy benzyl)-isocyanuric acid ester etc.Particularly preferably 2,6-bis--t-butyl-p-cresol, tetramethylolmethane-four [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester].
As antioxidant; also N can be combinationally used; the Phosphorus processing stabilizers such as the metal passivator of the hydrazine classes such as N '-bis-[3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionyl] hydrazine or three (2,4-bis--tert-butyl-phenyl) phosphorous acid ester
The addition of the antioxidant in blooming of the present invention in the scope relative to preferred 1ppm ~ 1.0% of the mass ratio of thermoplastic resin, the scope of preferred 10 ~ 1000ppm further.
[particulate]
Blooming of the present invention can be used for making sliding good containing particulate.The kinetic friction coefficient of the one side of blooming of the present invention is preferably the scope of 0.2 ~ 1.0.
Particulate can be mineral particulates, also can be organism particulate.The example of mineral particulates comprises silicon-dioxide, titanium dioxide, aluminum oxide, zirconium white, calcium carbonate, calcium carbonate, talcum, clay, burns till kaolin, burns till Calucium Silicate powder, calcium silicate hydrate, pure aluminium silicate, Magnesium Silicate q-agent and calcium phosphate.The example of organism particulate comprises tetrafluoroethylene, cellulose ethanoate, polystyrene, polymethylmethacrylate, polypropylmethacryla,es, polymethyl acrylate, polyethylencarbonate, styrene resinoid, silicone resin, polycarbonate resin, benzoguanamine resinoid, trimeric cyanamide resinoid, polyolefins powder, polyester resin, polyamide-based resin, polyimide based resin, or fluorinated ethylene propylene resinoid, the crushing and classification thing etc. of the organic high molecular compounds such as starch.And then the macromolecular compound synthesized by suspension polymerization, the macromolecular compound being formed as ball-type by spray-drying process or dispersion method etc. or mineral compound also can be used as particulate.Wherein, the particulate of particulate preferably containing silicon, particularly preferably silicon-dioxide.This is the turbidity in order to reduce blooming.
The scope of the preferred 5 ~ 400nm of the median size of the primary particle of particulate, the more preferably scope of 10 ~ 300nm.In blooming, particulate mainly contains with the form of the secondary aggregation body of particle diameter 0.05 ~ 0.3 μm.If the median size of the primary particle of particulate is the scope of 100 ~ 400nm, then preferably do not carry out condensing and containing in blooming with the form of primary particle yet.
The content of the particulate in blooming is preferably the scope of 0.01 ~ 1 quality %, particularly preferably the scope of 0.05 ~ 0.5 quality %.When the blooming of the multilayered structure utilizing casting method altogether to be formed, preferably at the particulate of this addition of film surface configuration.
The particulate of silicon-dioxide such as with Aerosil R972, R972V, R974, R812,200,200V, 300, the trade(brand)name of R202, OX50, TT600 (above Japanese Aerosil (strain) system) carries out commercially available.Zirconic particulate such as carries out commercially available with the trade(brand)name of Aerosil R976 and R811 (above Japanese Aerosil (strain) system).
The example of organism particulate comprises silicone resin, fluoro-resin and acrylic resin etc.Preferred silicone resin, particularly preferably there is the material of tridimensional network, such as commercially available with the trade(brand)name of Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120 and Tospearl 240 (being Toshiba's silicone (strain) system above).
Wherein, the turbidity that Aerosil 200V, Aerosil R972V make blooming keep lower, reduces the successful of frictional coefficient simultaneously, therefore, can particularly preferably use.
Arbitrary composition (various additive) in the solution containing thermoplastic resin before portion-wise addition to masking and rubber cement, also can prepare additive lysate and add online separately.Particularly in order to reduce the load of particulate to filtering material, a preferably online interpolation part or total amount.
When additive lysate being carried out online interpolation, in order to the Combination with rubber cement, preferably in additive lysate, add a small amount of thermoplastic resin.The amount of the thermoplastic resin in additive lysate is preferably the scope of 1 ~ 10 mass parts relative to solvent 100 mass parts, is more preferably the scope of 3 ~ 5 mass parts.
Online interpolation and mixing preferably use the such as on-line mixing device etc. such as static mixer (Toray Engineering system), SWJ (in eastern beautiful silent oscillation pipe mixing tank Hi-Mixer) to carry out.
The manufacture method > of < blooming
The manufacture method of blooming of the present invention is described.Blooming of the present invention can be manufactured by solution casting method, also can be made by melting curtain coating legal system.
The manufacture of blooming of the present invention is undertaken by following operation: make thermoplastic resin and additive be dissolved in solvent and prepare the operation of rubber cement; By the operation of rubber cement curtain coating on the annular metal supporting mass of lasting movement; The rubber cement of curtain coating is made reticulation and carries out dry operation; From the operation that metal support is peeled off; Carry out the operation stretched or width keeps; Carry out dry operation further; The film completed is carried out the operation reeled.
(rubber cement preparation section)
The operation preparing rubber cement is described.If the concentration of the thermoplastic resin in rubber cement is high, then in metal support, carries out the drying load after curtain coating reduce, therefore preferably.On the other hand, if the excessive concentration of the thermoplastic resin in rubber cement, then load when filtering increases, and filtering accuracy is deteriorated.Therefore, the scope of preferred 10 ~ 35 quality % of the concentration of the thermoplastic resin in rubber cement, the more preferably scope of 15 ~ 25 quality %.
The solvent of rubber cement is mixed solvent independent or of more than two kinds, if but be the good solvent of thermoplastic resin and the mixed solvent of poor solvent, then from the viewpoint of becoming to produce efficiency, preferably.Deliquescent from the viewpoint of thermoplastic resin, preferred good solvent is many.The scope of the preferred scope of the mixture ratio of good solvent and poor solvent to be good solvent be 70 ~ 98 quality %, poor solvent is the scope of 2 ~ 30 quality %.Good solvent is defined as, by the swelling Material Definitions of used thermoplastic resin that maybe can not dissolve individually for poor solvent by dissolving the solvent of thermoplastic resin used individually.When thermoplastic resin is cellulose ester, the kind of good solvent and poor solvent changes according to average acetify degree (degree of substitution with acetyl group).Such as acetone is good solvent for cellulosic acetic ester (degree of substitution with acetyl group 2.4), cellulose acetate propionate, is poor solvent for cellulosic acetic ester (degree of substitution with acetyl group 2.8).
The example of good solvent can be enumerated: the organic halogen compounds such as methylene dichloride and dioxolane, acetone, methyl acetate, methyl acetoacetate etc., be not particularly limited.Can particularly preferably enumerate methylene dichloride or methyl acetate.
The example of poor solvent can be enumerated: methyl alcohol, ethanol, propyl carbinol, hexanaphthene, pimelinketone etc., be not particularly limited.In addition, the content of the water in rubber cement is preferably the scope of 0.01 ~ 2 quality %.
By the solvent of dry removing and recovery rubber cement from film in film making process.Recycling design can be recycled.In recycling design, also trace, containing additive, such as softening agent, UV light absorber, polymkeric substance, monomer component etc., even if also can preferably recycle containing these, also can carry out refining recycling as required sometimes.
The dissolving of the thermoplastic resin in the preparation of rubber cement can use general method.If pressurizeed while heat, then can be heated to the temperature of more than the boiling point under normal pressure.If more than the boiling point of solvent at ambient pressure and under elevated pressure stirring and dissolving solution at the temperature of scope that can not seethe with excitement of solvent, then can prevent the generation of the non-solute of bulk being called as gel or powder ball.In addition, also preferred thermoplastic resin is mixed with poor solvent make it moistening or swelling after, add further good solvent and dissolve.
Pressurization by the method for the rare gas elementes such as press-in nitrogen or can be undertaken by the method for the vapour pressure adding thermogenesis solvent.Heating is preferably carried out from outside, on the other hand, and the easy control temperature of the pressurization of such as jacketing heat device, therefore preferably.
The thermoplastic resin that Heating temperature is high, its solvability improves, therefore preferably.On the other hand, if Heating temperature is too high, then reaction pressure uprises, and productivity reduces.Preferred Heating temperature is the scope of 45 ~ 120 DEG C, more preferably the scope of 60 ~ 110 DEG C, further the preferred scope of 70 DEG C ~ 105 DEG C.In addition, adjusting pressure makes solvent can not seethe with excitement at a set temperature.
The preparation of rubber cement also can preferably use hot-cold lysis method.Thermoplastic resin is made to be dissolved in methyl acetate equal solvent by hot-cold lysis method.
Then, the suitable filtering materials such as filter paper thermoplastic resin solution are used to filter.In order to remove insolubles etc., the filtering precision of filtering material is preferably less.But, if filtering precision is too small, then easily produce the blocking of filtering material.Therefore, the filter material of preferred below filtering precision 0.008mm, the more preferably filter material of the scope of 0.001 ~ 0.008mm, the further filter material of the preferred scope of 0.003 ~ 0.006mm.
The material of filtering material is not particularly limited, and can use common filtering material.The metal filtering materials such as plastic filter material and stainless steel such as polypropylene, teflon (registered trademark) do not have coming off of fiber, therefore preferably.Preferably by excessively filtering and reducing impurity, particularly bright spot foreign matter contained in the cellulose ester of raw material.
So-called bright spot foreign matter refers to and is configured with orthogonal polarization state by 2 polaroids, place blooming etc. betwixt, light is irradiated from the side of polaroid, when observing from the opposite side of polaroid, light spills and visible point (foreign matter) from opposition side, and the bright spot number with the diameter of more than 0.01mm is preferably 200/cm
2below.Be more preferably 100/cm
2below, more preferably 50/m
2below, more preferably 0 ~ 10/cm
2.In addition, the bright spot of preferred below 0.01mm is also few.
The filtration of thermoplastic resin solution is undertaken by usual method.If filtered at the temperature of scope that more than boiling point of solvent at ambient pressure and under elevated pressure solvent can not seethe with excitement, then the difference (being called differential pressure) of the filter pressure produced before and after filtering is little.Preferred temperature is the scope of 45 ~ 120 DEG C, more preferably the scope of 45 ~ 70 DEG C, more preferably the scope of 45 ~ 55 DEG C.The pressure of preferred filtration environment is little, is preferably below 1.6MPa, is more preferably below 1.2MPa, more preferably below 1.0MPa.
(curtain coating of rubber cement, drying, stripping process)
Then, curtain coating rubber cement.Minute surface precision work is preferably carried out in the surface of the metal support in curtain coating (casting) operation.The preferred Stainless Steel Band of metal support or or carry out electroplating the drum of precision work with foundry goods effects on surface.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 lower than the temperature of the boiling point of solvent.The curtain coating that the surface temperature of metal support is high, the rate of drying of reticulation can be accelerated, therefore preferably.On the other hand, if the surface temperature of metal support is too high, then produce foaming or planarity deterioration sometimes.Preferred supporting mass temperature is the scope of 0 ~ 40 DEG C, further the preferred scope of 5 ~ 30 DEG C.In addition, also preferably reticulation gelation is made by cool metal supporting mass and more to peel off from drum containing the state of residual solvent.
The method controlling the temperature of metal support is not particularly limited, and has the method for the method of blowing warm braw or cold wind and the rear-face contact making warm water and metal support.Use the method for control temperature of warm water effectively can carry out the transmission of heat, therefore, it is short that the temperature of metal support reaches constant time, preferably.When using warm braw, the wind that use temperature is higher than target temperature sometimes.
In order to improve the planarity of blooming, residual solvent amount in reticulation when peeling off from metal support preferably 10 ~ 150 quality %, the more preferably scope of 20 ~ 40 quality % or the scope of 60 ~ 130 quality %, is particularly preferably the scope of 20 ~ 30 quality % or the scope of 70 ~ 120 quality %.
In the present invention, residual solvent amount following formula defines.In following formula, " M " is the quality of reticulation or the film gathered any time in the mill or after manufacturing.This reticulation or film are heated the quality after 1 hour by " N " at 115 DEG C.
Residual solvent amount (quality %)={ (M-N)/N} × 100
(stretching process)
The reticulation peeled off from metal support preferably stretches.Specifically, preferably with the tenter machine mode holding the two ends of reticulation etc. with fixture etc. in the width direction (transverse direction) stretch.Peel off tension force and be preferably set to below 300N/m.
The reticulation peeled off from metal support preferably by stretching is to carry out specific refractory power control (control of delay).
Stretching such as or successively or simultaneously can carry out biaxial stretch-formed along the length direction of film (masking direction) or the direction vertical in face with it (i.e. width) uniaxial extension along two directions.Simultaneously biaxial stretch-formed also comprise to stretch along a direction make it shrink to the opposing party's tension force that relaxes.
The stretching ratio of mutually perpendicular biaxially oriented is preferably final is respectively set to the scope of 0.8 ~ 1.5 times in curtain coating direction, to be set to the scope of 1.1 ~ 2.5 times at width; Preferably be set to the scope of 0.9 ~ 1.0 times in curtain coating direction, be set to the scope of 1.2 ~ 2.0 times at width.
The scope that draft temperature is preferably 120 DEG C ~ 200 DEG C, the scope of more preferably 140 DEG C ~ 180 DEG C.Residual solvent during stretching in film preferably 20 ~ 0% scope, the more preferably scope of 15 ~ 0%.
The method of stretching reticulation is not particularly limited.Such as can enumerate: give peripheral speed difference to multiple roller and utilize the method that roller peripheral speed difference longitudinally stretches, the two ends fixing reticulation with fixture or pin betwixt, the method that the interval of fixture or pin is longitudinally stretched along direction of travel expansion, similarly transversely expansion and the method that transversely stretches or the method etc. that stretches along two directions in length and breadth along expansion simultaneously in length and breadth.Also these methods can be combined.In addition, when so-called tenter frame process, if drive clamp section by rear wheel drive mode, then stretching that can be smoothing, can reduce the danger such as fracture.
These width of film making process keep or the stretching of transverse direction is carried out preferably by tenter machine, pin tenter or clip tenter.In addition, can stretch throughput direction and width simultaneously, also can successively stretch.
(film drying process)
Preferably stretched film is carried out drying further, make residual solvent amount be below 1 quality %, more preferably below 0.1 quality %, is particularly preferably below 0 ~ 0.01 quality %.In film drying process, usually adopt by roller drying mode (the multiple rollers vertically configured alternately carry out dry mode to reticulation) or the mode of being carried reticulation drying by tenter machine mode.
The method of dry stretched film is not particularly limited, and generally speaking can carry out with hot blast, infrared rays, warming mill, microwave etc., but from the viewpoint of simplicity, preferably carry out with hot blast.Drying temperature in the drying process of reticulation preferably improves the scope next stage property of 40 ~ 200 DEG C.
In addition, at this, carry out describing to solution casting masking method, but do not hinder and make film by melting casting film legal system.
The characteristic > of < blooming
The film thickness of blooming of the present invention is not particularly limited, and is preferably the scope of 10 ~ 200 μm, is more preferably the scope of 10 ~ 100 μm, more preferably the scope of 20 ~ 60 μm.If in this scope, then can have both the improvement of the Water Vapour Permeability of the film thickness depending on film and the expression power of delay, therefore preferably.In addition, the cutting characteristic of the blooming of the thickness of this scope is also good.
The scope of the preferred 1 ~ 4m of the width of blooming of the present invention, the more preferably scope of 1.4 ~ 4m, is particularly preferably the scope of 1.6 ~ 3m.If more than 4m, be then difficult to conveying.
The Water Vapour Permeability of blooming of the present invention preferably 40 DEG C, be 10 ~ 1200g/m under 90%RH
2the scope of 24h.Water Vapour Permeability can measure according to the method recorded in JIS Z 0208:1976.
The elongation at break of blooming of the present invention is preferably the scope of 10 ~ 80%.Elongation at break is tried to achieve by carrying out measuring according to JIS-K7127-1999.
The visible light transmissivity of blooming of the present invention is preferably more than 90%, and more preferably more than 93%.Use the U-4000 recording spectrophotometer foundation of Inc. of Hitachi, carry out the visible light transmissivity (Tv) under mensuration 380 ~ 780nm according to JIS Z 8722 measuring method.
The mist degree of blooming of the present invention, preferably lower than 1%, is particularly preferably the scope of 0 ~ 0.1%.Haze meter (1001DP type, Japanese electric look industry (strain) system) is used to measure.
The humidity resistance of blooming of the present invention is evaluated by the dimensional change produced relative to humidity change.Undertaken by following method relative to the evaluation of the dimensional change of damp and hot change.To additional 2 places' mark (cross), the curtain coating direction of the blooming made.It is processed 1000 hours under temperature 60 C, relative humidity 90%RH.By light microscope determining mark before and after treatment (cross) distance each other.Size changing rate (%) is calculated by following formula.
Size changing rate (%)=[(a1-a2)/a1] × 100
A1: the distance before wet heat treatment
A2: the distance after wet heat treatment
If the protective film for polarizing plate of liquid crystal indicator makes size change because of moisture absorption, then produce uneven or that the change of phase difference value, the reduction producing contrast gradient or irregular colour are such problem.The polaroid protective film used in the liquid crystal indicator of particularly outdoor application easily significantly produces this problem.Therefore, when blooming of the present invention is used as the protective film for polarizing plate of liquid crystal indicator, size changing rate (%) preferably lower than 0.5%, more preferably less than 0.3%.If be such size changing rate, then can be evaluated as the blooming showing sufficient agent of low hygroscopicity.
Also can be coated with on blooming of the present invention and form liquid crystal layer or resin layer and further it stretched.The stacked film obtained thus can have the phase difference value of broad range further.
The purposes > of < blooming
Blooming of the present invention is preferably the functional membrane used in the various display unit such as liquid-crystal display, plasma display, OLED display.Specifically, blooming of the present invention can improve the optical compensation films etc. such as film, hard coat film, antiglare film, electrostatic prevention film, visible angle amplification for the polaroid protective film of liquid crystal indicator, phase retardation film, antireflection film, brightness.Typical case, blooming of the present invention is polaroid protective film, phase retardation film, optical compensation films.Blooming of the present invention can double as phase retardation film and polaroid protective film
(optical compensation films)
Liquid-crystal display use there is anisotropic liquid crystal material or polaroid, even if therefore viewed from front time can obtain good display, also there is the problem reducing so visible angle from display performance during oblique seeing.Therefore, in order to improve the performance of liquid-crystal display, need visible angle compensation plate.The index distribution of average liquid crystal cell is large at the thickness direction of unit, and in face, direction is less.Therefore, visible angle compensation plate must offset this anisotropy.That is, visible angle compensation plate there is film thickness direction specific refractory power specific surface in the little specific refractory power in direction, to have so-called negative uniaxiality structure very effective.Blooming of the present invention also can for having the optical compensation films of such function.
When blooming of the present invention is used for the liquid crystal cell of VA pattern, respectively can use the blooming (2 types) of 1 opening and closing meter 2 in the both sides of unit, also only can use blooming (1 type) at the upper and lower either side of unit.
In face shown in the preferred following formula of blooming of the present invention direction length of delay Ro 23 DEG C, under the environment of 55%RH and to measure wavelength be 590nm time in the scope of 40 ~ 150nm, in the scope of preferred 50nm ~ 130nm further.The length of delay Rth of thickness direction preferably 23 DEG C, under the environment of 55%RH and to measure wavelength be 590nm time in the scope of 70 ~ 350nm, in the scope of preferred 170nm ~ 270nm further.
These length of delays can use automatic birefringence meter KOBRA-WPR (prince measures machine) to measure.
Formula (I) Ro=(n
x-n
y) × d
Formula (II) Rth={ (n
x+ n
y)/2-n
z} × d
(n
xrepresent that in direction, specific refractory power is the specific refractory power of maximum direction x in the face of blooming; n
yrepresent the specific refractory power of direction y, described direction y direction in the face of blooming is vertical with described direction x; n
zrepresent the specific refractory power of the thickness direction z of blooming; D (nm) represents the thickness of blooming.)
Blooming of the present invention has slow axis or fast axle in face, and the axle angulation " θ 1 " in slow axis or fast axle and masking direction is preferably more than-1 ° and less than+1 °, is more preferably more than-0.5 ° and less than+0.5 °.θ 1 can be used as orientation angle and defines, and the mensuration of θ 1 can use automatic birefringence meter KOBRA-WPR (prince measures machine) to carry out.Meet the blooming liquid crystal indicator of above-mentioned relation containing θ 1, brightness of its display image is improved, and suppresses or prevents light leak, verily reproduction color in color liquid crystal display arrangement.
< polaroid >
Blooming of the present invention can be used for polaroid and possesses its liquid crystal indicator.Blooming of the present invention preferably adopts the film doubling as polaroid protective film and phase retardation film.Now, the phase retardation film preparing to be different from polaroid protective film is not needed.Therefore, can the thickness of reducer crystal device, can simplified manufacturing technique.
Polaroid has polarizer, and is pasted onto the polaroid protective film of one or both sides of polarizer.
So-called polarizer refers to the element of the light of the polarization plane by means of only certain orientation, and the polarizer representing type is polyvinyl alcohol polarizing coating, and it carries out to polyvinyl alcohol film the dye polarizing coating of iodine and the polarizing coating of dyeing dichroic dye.
Polarizer obtains as follows: by polyvinyl alcohol water solution masking, carries out uniaxial extension and dye or carry out uniaxial extension after dyeing it, then, preferably carries out weather resistance process with boron compound.The film thickness of the polarizer preferably scope of 5 ~ 30 μm, is particularly preferably the scope of 10 ~ 20 μm.
Polaroid of the present invention can make by general method.Saponification process is carried out to the surface of, the blooming of the present invention that is attached at polarizer.In iodine solution, dipping stretches and at least one side of polarizer that makes, uses fully saponified type polyvinyl alcohol water solution to fit blooming of the present invention.Can to fit at the another side of polarizer other existing polaroid protective 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 KONICA MINOLTA ADVANCED LAYERS (strain) of being make) etc.
< liquid crystal indicator >
Liquid crystal indicator of the present invention possesses the polaroid containing blooming of the present invention.Specifically, containing blooming of the present invention in the polaroid at least one side of liquid crystal cell configured; The film of the liquid crystal cell side of this polaroid is blooming of the present invention.
In liquid crystal indicator of the present invention, preferred polaroid fits in the one or both sides of liquid crystal cell via bonding coat.
The polaroid protective film that the face side of liquid crystal indicator of the present invention uses, except antiglare layer or transparent hard-coating layer, preferably has anti-reflection layer, antistatic backing, stain-proofing layer, back coating.
Blooming of the present invention or polaroid can be used for the liquid crystal indicator of STN, TN, OCB, HAN, VA (MVA, PVA), the various type of drive such as IPS, OCB.Be particularly preferred for VA (MVA, PVA) type liquid crystal indicator.Particularly namely be used in the liquid crystal indicator of the large picture of more than 30 types, painted when also can reduce the black display that light leak causes, can the visibility meter such as front contrast be improved.As mentioned above, the various visibility meter of liquid crystal indicator of the present invention are excellent.
Embodiment
Below, enumerate embodiment and the present invention is described particularly, but invention is not limited to these.In addition, use the expression of " part " or " % " in an embodiment, unless otherwise specified, then represent " mass parts " or " quality % ".
Embodiment 1
The details of the cellulose ester used in embodiment 1 is shown.
Cellulose ester A: the cellulose diacetate (in table, being designated as DAC) of the number-average molecular weight 70000 of degree of substitution with acetyl group 2.40
Cellulose ester B: the cellulose acetate propionate (being designated as CAP in table) of the number-average molecular weight 70000 of degree of substitution with acetyl group 1.58, propionyl substitution value 0.9, total acyl substitution 2.48
Cellulose ester C: the cellulosic triacetate (in table, being designated as TAC) of the number-average molecular weight 70000 of degree of substitution with acetyl group 2.85
The making > of < blooming 101
The preparation > of < particle dispersion liquid
After the particulate (Aerosil R972V Japan Aerosil (strain) system) of 11.3 mass parts and the ethanol dissolver of 84 mass parts are uniformly mixed 50 minutes, disperse with refiner (Manton-Gaulin).
The preparation > of < particulate annex solution 1
The particle dispersion liquid of 5 mass parts is slowly added in the well-beaten methylene dichloride (100 mass parts) in dissolving vessel.And then, carry out disperseing the particle diameter making offspring to become the size of regulation with masher.It is filtered with the Fine Met NF that Japanese smart line (strain) is made, prepares particulate annex solution.
The preparation > of the main rubber cement of <
The main rubber cement of preparation following compositions.First, in dissolved under pressure tank, methylene dichloride and ethanol is added.Generally stir while drop into cellulose ester A at the dissolved under pressure tank putting into solvent, be heated, stir and make it dissolve completely.
The composition > of the main rubber cement of <
[chemical formula 28]
And then above-mentioned additive component is dropped into encloses container, stirs and dissolve, the peace being used the long-pending filter paper (strain) of peace to make is amassed filter paper No.244 and is filtered, and prepares main rubber cement.Then, use endless belt casting device that rubber cement is carried out curtain coating with 1500mm width equably at temperature 31 DEG C on Stainless Steel Band supporting mass.The temperature of Stainless Steel Band controls to be 28 DEG C.
On Stainless Steel Band supporting mass, until be 75% carry out solvent evaporation to the residual solvent amount in the film of curtain coating (casting).Then, peel off from Stainless Steel Band supporting mass to peel off tension force 128N/m.The film of stripping is applied the heat of 142 DEG C while use tenter machine to stretch 24% in the width direction.The residual solvent stretched when starting is 17%.
Then, conveying is carried out while terminate drying in arid region with multiple roller.Drying temperature is 120 DEG C, conveyance tension is 122N/m.As above the blooming 101 that desciccator diaphragm thickness is 40 μm is obtained.
The making > of < blooming 102 ~ 141
In the making of blooming 101, only change as table 1 and table 2 using the kind of cellulose ester with as the kind and amount (mass parts) that postpone the exemplary compounds showing the compound shown in the general formula (1) of agent, in addition, blooming 102 ~ 131 of the present invention and the blooming 132 ~ 141 compared similarly is made.The addition of the cellulose ester of the cellulose ester A (DAC) used is replaced to be set to the mass parts identical with cellulose ester 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 "
Following evaluation is carried out to the blooming 101 ~ 141 made.Evaluation result is shown in table 1 and table 2.
(delay)
Abbe refractomecer (4T) is used to measure the mean refractive index of blooming.In addition, commercially available micrometer is used to measure the thickness of blooming.
Use birefringence meter KOBRA-WPR (prince measures machine (strain) system), to 23 DEG C, place under 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 thickness input following formula, try to achieve the value of the length of delay Ro in direction in face, the length of delay Rth of thickness direction.Also the direction of Simultaneously test slow axis.In following formula, n
xrepresent the largest refractive index in face, n
yrepresent and n
xthe specific refractory power of vertical direction, n
zrepresent the specific refractory power of film thickness direction, d represents the thickness (nm) of film.
Formula (I) Ro=(n
x-n
y) × d
Formula (II) Rth={ (n
x+ n
y)/2-n
z} × d
(internal haze value)
By the cellulose ethanoate film damping after more than 5 hours under the environment of 23 DEG C of 55%RH made, by following method evaluation internal haze value.
< internal haze determinator >
Use haze meter (turbidometer) (model: NDH 2000, Japanese electric look industry (strain) system)
Light source uses 5V9W halogen lamp, and light receiver uses silicon photocell (relative visibility spectral filter is housed).
In the mist degree mensuration of the film of cellulose ethanoate film of the present invention when being dripped on film by the solvent of the specific refractory power of film specific refractory power ± 0.05 with this device, its value is preferably less than 0.05.Condition determination measures according to JIS K-7136.
Internal haze is determined as follows carries out.Be described with Fig. 1 ~ Fig. 4.
First, the blank mist degree 1 of the measuring instrument beyond film is measured.
1. on the slide glass of cleaning, drip a glycerine (0.05ml).Now, note can not entering bubble in drop.Even if glass surface seems clean, sometimes also can be polluted, therefore, the glass after cleaning with clean-out system must be used.(with reference to Fig. 1.)。
2. load cover glass thereon.Even if not according to gland slide, glycerine also can be expanded.
3. arrange on haze meter, measure blank mist degree 1.
Then, the mist degree 2 of sample is comprised by following step measurements.
4. on slide glass, drip glycerine 0.05ml (with reference to Fig. 1.)。
5. load the sample film of mensuration thereon and bubble can not be entered (with reference to Fig. 2.)。
6. in sample film, drip glycerine 0.05ml (with reference to Fig. 3.)。
7. load cover glass thereon (with reference to Fig. 4.)。
8. the duplexer as above made (being upper cover glass/glycerine/sample film/glycerine/slide glass from above) is arranged on haze meter and measures mist degree 2.
9. calculate (mist degree 2)-(mist degree 1)=(internal haze of 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.
In addition, the slide glass used in said determination, glycerine are as described below.
Glass: MICRO SLIDE GLASS S9213 MATSUNAMI
Glycerine: Northeast chemistry deer superfine (purity >99.0%) specific refractory power 1.47 processed
(oozing out patience)
By the patience of oozing out of following explanation, weather resistance is evaluated.By blooming 80 DEG C, place 1000 hours under the hot and humid atmosphere of 90%RH after, visual observation oozing out (crystallization) with or without blooming surface.Result according to the observation, evaluates according to following benchmark.Evaluate A and B and be judged as practical no problem level.
A: the generation to oozing out completely unconfirmed on surface
B: confirm oozing out of part on surface a little
C: confirm a little on surface throughout whole ooze out
D: confirm clear and definite the oozing out throughout whole on surface
(humidity resistance: the dimensional change relative to damp and hot change)
At additional 2 places' mark (cross), the curtain coating direction of the blooming made and 60 DEG C, process 1000 hours under 90%RH, by the distance of light microscope determining mark before and after treatment (cross).According to measurement result, by following benchmark evaluation dimensional change, thus, as the durability evaluation humidity resistance of blooming.
Size changing rate (%)=[(a1-a2)/a1] × 100 (a1 represent wet heat treatment before distance, a2 represent the distance after wet heat treatment)
A: lower than 0.3%
B:0.3% ~ lower than 0.5%
C:0.5% ~ lower than 0.7%
More than D:0.7%
(Compatibility Evaluation)
Make the film before the stretching in the manufacture of blooming at 120 DEG C dry 15 minutes, used by the mist degree of this film haze meter (1001DP type, Japanese electric look industry (strain) system) to measure.According to measurement result, evaluate according to following benchmark.Evaluate A and B and be evaluated as practical no problem level.
A: mist degree is lower than 0.5%
B: mist degree is lower than 0.5 ~ 1.0%
C: mist degree is lower than 1.0 ~ 1.5%
D: mist degree is more than 1.5%
E: compound is separated out
(mist degree after stretching)
Haze meter (1001DP type, Japanese electric look industry (strain) system) is used to measure the mist degree of the blooming made.According to measurement result, evaluate according to following benchmark.Evaluate A and B and be judged as practical no problem level.
A: mist degree is lower than 0.5%
B: mist degree is 0.5 ~ lower than 1.0%
C: mist degree is 1.0 ~ lower than 1.5%
D: mist degree is more than 1.5%
E: compound is separated out
As shown in table 1 and table 2, the blooming 101 ~ 131 of known embodiment is compared with the blooming 132 ~ 141 of comparative example, the expression power postponed is excellent, and internal haze, consistency (mist degree) and weather resistance (oozing out patience) are good, it is practical excellent blooming.
From with the comparing of result of blooming 132 ~ 135 employing comparative compound C-001, C-002, C-004, if there is specific substituting group in the compound as delay performance agent, the then value step-down of internal haze, consistency and delay expression power improve.In addition, the poor compatibility of C-003 and C-005, compound is separated out in film, therefore, cannot carry out the mensuration of length of delay and the mensuration of internal haze.
From embodiment blooming 101 ~ 131, particularly 124 ~ 129 result, larger phase differential is shown containing the blooming postponing performance agent of the present invention, even if increase the addition postponing performance agent, also mix with cellulose ester, therefore, be the blooming of the excellence that internal haze is low, length of delay is high.
On the other hand, the length of delay of use TAC as cellulose ester and containing the blooming 141 postponing performance agent is not little, does not have 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, makes the blooming 201 ~ 206 of the thickness shown in table 3.Except the flow of rubber cement during curtain coating, make similarly to Example 1.Blooming 201 ~ 206 is evaluated similarly to Example 1.Now, the blooming 132 of making in embodiment 1 is added as comparative example.
In addition, by following evaluation method, fragility is evaluated.
(cutting adaptive)
The fragility cutting adaptive of following explanation is evaluated.Oil pressure type bench press is installed the lower cutter passing through upper cutter and 90 ° worn away of 60 °, makes 30 μm, its interval.Then, blooming is placed between two cutting knifes, cut out the sample of 100 width 90cm, length 100cm size with the lowering speed 6m/ of upper cutter minute continuously.Opticmicroscope is used to carry out observing the surface of fracture of each sample after cutting with 50 times.Cutting situation is compared.The sheet number of the film of some unfavorable condition such as statistics creates burr, splits, cannot cut off, cutting swarf, calculates fraction defective, carries out the evaluation of cutting adaptive according to following benchmark.Evaluate A and B and be judged as practical no problem level.
A: fraction defective is lower than 2%
B: fraction defective is lower than 2 ~ 5%
C: fraction defective is lower than 5 ~ 10%
D: fraction defective is lower than more than 10%
[table 3]
Clear and definite by table 3, the delay expression power of the blooming 201 ~ 206 of embodiment is excellent, and fragility (cutting adaptive) and weather resistance (oozing out patience) excellence.And then known, thickness is high especially in the above-mentioned effect of the blooming 202 ~ 205 of the scope of 20 ~ 60 μm.
The thickness of the blooming 132 of comparative example is 40 μm, but fragility (cutting adaptive) and weather resistance (oozing out patience) inequality.
Embodiment 3
The making of < polaroid and evaluation >
The polyvinyl alcohol film of thickness 120 μm is carried out uniaxial extension (temperature 110 DEG C, stretching ratio 5 times).The stretched film obtained is flooded 52 seconds in the aqueous solution be made up of iodine 0.069g, potassiumiodide 4.5g, water 100g, then, is immersed in by the aqueous solution of 60 DEG C that potassiumiodide 6.5g, boric acid 7.0g, water 100g are formed.Carried out washing, dry as becoming polarizer.
Then, according to the one side laminating blooming 101 ~ 141 and blooming 201 ~ 206 of following operation 1 ~ 5 at polarizer; And at another side laminating Konica Minolta TAC KC4UY (KONICA MINOLTA ADVANCED LAYERS (strain) cellulose ester membrane processed) of polarizer, make polaroid 101 ~ 141 and polaroid 201 ~ 206.
Operation 1: blooming 101 ~ 141, blooming 201 ~ 206 are flooded 95 seconds in the sodium hydroxide solution of the 2 moles/L of 60 DEG C, then, carries out washing and dry, obtains having carried out the blooming of saponification by with polarizer side of fitting.
Operation 2: polarizer is flooded 1 ~ 2 second in the polyvinyl alcohol caking agent groove of solids component 2 quality %, then, dabs off the too much caking agent being attached to polarizer.
Operation 3: the polarizer obtained in operation 2 is configured on the blooming processed in operation 1.
Operation 4: by the blooming of duplexer that obtains in operation 3 and polarizer with pressure 20 ~ 30N/cm
2, transfer rate is about 2m/ minute and fits.
Operation 5: in the drying machine of 80 DEG C, the polarizer of the duplexer made in operation 4 and Konica Minolta TAC KC4UY are fitted and dry 2 minutes, make polaroid 101 ~ 141 and polaroid 201 ~ 206.
The weather resistance of the polaroid of making is evaluated as follows.Show the result in table 4.
(photostabilization)
Measure the parallel transmitance (H0) and vertical transmitance (H90) of forcing deteriorated untreated samples.Degree of polarization P0 is calculated according to following formula by measured value.Then, each polaroid is implemented to force degradation treatment 500 hours in sunshine weather meter, under the condition that do not have a UV spectral filter.Then, again measure parallel transmitance (H0 ') and vertical transmitance (H90 '), calculate the degree of polarization P500 after forcing degradation treatment by measured value 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 of trying to achieve, carry out sunproof evaluation with following benchmark.Evaluate A and B and be judged as practical no problem level.
A: degree of polarization variable quantity is lower than 2%
B: degree of polarization variable quantity is more than 2% and lower than 10%
C: degree of polarization variable quantity is more than 10% and lower than 25%
D: degree of polarization variable quantity is more than 25%
(humidity resistance)
Prepare the polaroid of 3 500mm × 500mm.Carry out respectively wet heat treatment (condition: 70 DEG C, place 100 hours under 90%RH).2 polaroids are carried out stacked in the mode becoming vertical Niccol (crossed nicols) state.When measuring the one side irradiation light from polaroid, in the length of the blank parts that the edge portions of another side produces.Blank parts as evaluation object is set to blank parts the longest in multiple blank parts of each immediate vicinity generation of 4 edge portions of polaroid.The blank that edge portions produces to refer under vertical Niccol state not through the edge portions of polarisation of light sheet through the state of light, become the fault cause not showing image at the edge portions of polaroid.
Calculate the ratio of length relative to the length (500mm) on one side of polaroid of the blank parts of mensuration.Practical no problem level is judged as based on following benchmark evaluation humidity resistance, evaluation A and B by when this ratio.
A: the blank at edge is lower than 5% (as the level that polaroid is no problem)
B: the blank at edge is more than 5% and lower than 10% (as the level that polaroid is no problem)
C: the blank at edge is more than 10% and lower than 20% (level as polaroid uses reluctantly)
D: the blank at edge is more than 20% (as the in-problem level of polaroid)
[table 4]
| Polaroid No. | Blooming No. | Photostabilization | 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 |
Clear and definite by table 4, the polaroid 101 ~ 131 of embodiment and polaroid 201 ~ 206, compared with the polaroid 132 ~ 141 compared, are polaroid excellent in the practicality that photostabilization, humidity resistance are good.From with the comparing of result of polaroid 132 ~ 138 employing comparative compound C-001, C-002, C-003, C-004, C-005, the compound postponing performance agent, by having specific structure and substituting group, can realize problem to be solved by this invention.
According to the result of polaroid 101 ~ 131, particularly polaroid 124 ~ 129, the phase differential of the blooming containing delay performance agent of the present invention is large, even if increase the addition postponing to show agent, postpones performance agent also compatible with cellulose ester.Therefore, polaroid of the present invention is practical excellent polaroid.
Embodiment 4
The making of < liquid crystal indicator and evaluation >
Carry out making liquid crystal panel as follows to measure visible angle, the characteristic of evaluating liquid crystal device.The polaroid fitting in the two sides of liquid crystal cell in SONY system 40 escope KLV-40J3000 is peeled off.The polaroid 101 ~ 141 of alternative making and polaroid 201 ~ 206 are fitted in respectively the two sides of the glass surface of liquid crystal cell.The laminating carrying out polaroid makes the blooming of embodiment and comparative example be liquid crystal cell side, and the direction of the absorption axes of the polaroid of laminating is identical with the direction of the absorption axes of the polaroid of having fitted in advance.As above liquid crystal indicator 101 ~ 141 and liquid crystal indicator 201 ~ 206 is made respectively.
As above the liquid crystal indicator made is carried out to the evaluation of following record.The results are shown in table 6 and table 7.
(front contrast is uneven)
At the environment of 23 DEG C of 55%RH, the backlight of each liquid crystal indicator is lighted 1 week continuously.Then, the white display of liquid crystal indicator and the brightness of black display is measured from the normal direction of display frame.Measure and use ELDIM Inc. EZ-Contrast160D.The ratio of the brightness recorded is set to front contrast.Front contrast defines with formula (brightness of the black display of the brightness of the white display recorded from the normal direction of display unit/measure from the normal direction of display unit).
Measure the front contrast of any 5 of the display frame of liquid crystal indicator, evaluate with following benchmark.Evaluate A and B and be judged as practical no problem level.
A: front contrast is 0 ~ distribution lower than 5%, uneven little
B: front contrast is 5% ~ distribution lower than 10%, there is inequality a little
C: front contrast is the distribution of more than 10% is uneven large
(deterioration of visible angle)
Carry out visible angular measurement to the liquid crystal indicator placed 5 hours under the environment of 25 DEG C of 50%RH to determine.Then, this liquid crystal indicator is placed 5 hours under the environment of 25 DEG C of 20%RH, carry out visible angular measurement and determine.Then, this liquid crystal indicator is placed 5 hours under the environment of 23 DEG C of 80%RH, measure the visible angle of liquid crystal indicator.Finally, this liquid crystal indicator is placed 5 hours again under 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 of being carried out after this environment places 5 hours by liquid crystal indicator.In addition, fixed for visible angular measurement, in the display frame of the display of liquid crystal indicator mid point brilliant white and black display, use ELDIM Inc. EZ-Contrast160D, the angle that can maintain contrast gradient 10:1 is set to visible angle.
According to these measurement results, with the visible angle deterioration of following benchmark evaluation.Evaluate A and B and be judged as practical no problem level.
A: unconfirmed to visible angular variable
B: confirm visible angular variable a little
C: confirm visible angular variable
[table 5]
| Liquid crystal indicator No. | Polaroid No. | Front contrast | The deterioration of visible angle | 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 |
Clear and definite by table 5, possess the liquid crystal indicator 101 ~ 131 of polaroid 101 ~ 131 of the present invention and polaroid 201 ~ 206 and liquid crystal indicator 201 ~ 206 with employ comparative example polaroid 132 ~ 141 liquid crystal indicator 132 ~ 141 compared with, front contrast is not well, even if under the condition of humidity variation, visible angular variable is also few.As above known is the liquid crystal indicator of stabilizer pole and excellent in te pins of durability.
Compared from the result with the polaroid 132 ~ 138 employing comparative compound C-001, C-002, C-003, C-004, C-005, by postponing performance agent, there is specific structure and substituting group, problem to be solved by this invention can be realized.
Industrial utilizability
Blooming of the present invention is have high latency expression power, can suppress to ooze out and internal haze is low, fragility is excellent, photostabilization, blooming that humidity resistance is high in addition; therefore, particularly preferably can be used as the blooming of liquid crystal indicator, particularly use as the polaroid protective film with optical compensation function.Thus, the front contrast of liquid crystal indicator can be suppressed uneven, improve visible angle.
Nomenclature
GL slide glass
Gr glycerine
F sample film
Claims (10)
1. a blooming, it contains the compound shown in thermoplastic resin and following general formula (1),
[chemical formula 1]
General formula (1)
In general formula (1), X
1represent Sauerstoffatom or sulphur atom; Y
1represent Sauerstoffatom, sulphur atom, nitrogen-atoms or NR
41; Z
1represent Sauerstoffatom, nitrogen-atoms or sulphur atom; R
11, R
21and R
31represent substituting group, as with R
11the substituting group represented, represents alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, amino, alkylamino, arylamino, alkylthio, arylthio or heterocyclic radical, as with R
21and R
31the substituting group represented, represents alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, acyl amino, alkylsulfonyl, sulfonyloxy, amino, alkylthio or halogen atom respectively; R
41represent hydrogen atom or substituting group, as with R
41the substituting group represented, represents alkyl, cycloalkyl, alkoxyl group, aryl, aryloxy, acyl group, alkoxy carbonyl, aryloxycarbonyl, amino, alkylthio or halogen atom; 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.
2. blooming according to claim 1, wherein, the compound shown in described general formula (1) is the compound shown in following general formula (2),
[chemical formula 2]
General formula (2)
In general formula (2), X
2represent Sauerstoffatom or sulphur atom; Y
2represent Sauerstoffatom, sulphur atom, nitrogen-atoms or NR
42; Z
2represent Sauerstoffatom, nitrogen-atoms or sulphur atom; R
12and R
22represent substituting group; R
42represent hydrogen atom or substituting group; Substituent R
12, R
22and R
42respectively with the R in general formula (1)
11, R
21and R
41same meaning; M2 represents the integer of 0 ~ 4; N2 represents the integer of 0 ~ 4; Dotted portion represents singly-bound or double bond.
3. blooming according to claim 2, wherein, the compound shown in described general formula (2) is the compound shown in following general formula (3),
[chemical formula 3]
General formula (3)
In general formula (3), R
13and R
23represent substituting group, substituent R
13and R
23respectively with the R in general formula (1)
11and R
21same meaning; K3 represents the integer of 1 ~ 5; M3 represents the integer of 0 ~ 4.
4. blooming according to claim 3, wherein, the compound shown in described general formula (3) is the compound shown in following general formula (4),
[chemical formula 4]
General formula (4)
In general formula (4), R
14represent substituting group; Substituent R
14with the R in general formula (1)
11same meaning; K4 represents the integer of 1 ~ 5.
5. the blooming according to any one of Claims 1 to 4, wherein, described thermoplastic resin comprises cellulose ester.
6. blooming according to claim 5, wherein,
Described cellulose ester 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 ethanoyl; Y represents substitution value or its substitution value amounted to of propionyl or butyryl radicals.
7. the blooming according to any one of claim 1 ~ 6, wherein, the film thickness of described blooming is in the scope of 20 ~ 60 μm.
8. the blooming according to any one of claim 1 ~ 7, wherein, 23 DEG C, under the environment of 55%RH, when mensuration wavelength is 590nm, in face shown in following formula, the length of delay Ro in direction is in the scope of 20 ~ 150nm, and the length of delay Rth of thickness direction is in the scope of 70 ~ 350nm
Formula (I) Ro=(n
x-n
y) × d
Formula (II) Rth={ (n
x+ n
y)/2-n
z} × d
N
xrepresent that in direction, specific refractory power is the specific refractory power of maximum direction x in the face of blooming; n
yrepresent the specific refractory power of direction y, described direction y direction in the face of blooming is vertical with described direction x; n
zrepresent the specific refractory power of the thickness direction z of blooming; D (nm) represents the thickness of blooming.
9. a polaroid, it possesses the blooming according to any one of claim 1 ~ 8 at least one face of polarizer.
10. a liquid crystal indicator, it possesses polaroid according to claim 9 at least one face of liquid crystal cell.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012036272 | 2012-02-22 | ||
| JP2012-036272 | 2012-02-22 | ||
| PCT/JP2013/053450 WO2013125419A1 (en) | 2012-02-22 | 2013-02-14 | Optical film, polarizer, and liquid crystal display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104245851A true CN104245851A (en) | 2014-12-24 |
| CN104245851B CN104245851B (en) | 2016-12-21 |
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|---|---|---|---|
| CN201380010749.8A Expired - Fee Related CN104245851B (en) | 2012-02-22 | 2013-02-14 | Blooming, polaroid and liquid crystal indicator |
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| Country | Link |
|---|---|
| JP (1) | JPWO2013125419A1 (en) |
| CN (1) | CN104245851B (en) |
| WO (1) | WO2013125419A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109890902A (en) * | 2016-10-31 | 2019-06-14 | 东丽株式会社 | Comprising having the thermoplastic resin composition of the compound for the functional group for mutually forming the above hydrogen bond of at least two |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9581728B2 (en) * | 2012-12-13 | 2017-02-28 | Konica Minolta, Inc. | Retardation film, polarizing plate and liquid crystal display |
| KR101629076B1 (en) * | 2014-03-06 | 2016-06-09 | 주식회사 효성 | Norbornene-based retardation film, and polarizing plate and display device using the same |
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|---|---|---|---|---|
| JP2000111914A (en) * | 1998-09-30 | 2000-04-21 | Fuji Photo Film Co Ltd | Retardation raising agent for low fatty acid cellulose ester film, optical compensation sheet and liquid crystal display device |
| JP2006188718A (en) * | 2006-04-10 | 2006-07-20 | Fuji Photo Film Co Ltd | Retardation rise agent for film of cellulose lower fatty acid ester |
| CN1954023A (en) * | 2004-05-14 | 2007-04-25 | 富士胶片株式会社 | Optical cellulose acylate film, polarizing plate and liquid crystal display device |
| JP2009020399A (en) * | 2007-07-13 | 2009-01-29 | Konica Minolta Opto Inc | Optical film, polarizing plate and liquid crystal display |
| CN101981153A (en) * | 2008-03-31 | 2011-02-23 | 富士胶片株式会社 | Ultraviolet absorbent compositions |
| JP2012189664A (en) * | 2011-03-09 | 2012-10-04 | Konica Minolta Advanced Layers Inc | Optical film, and polarizing plate and liquid crystal display device using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103518151B (en) * | 2011-03-10 | 2016-09-28 | 柯尼卡美能达株式会社 | Phase retardation film, polaroid, liquid crystal indicator and compound |
-
2013
- 2013-02-14 CN CN201380010749.8A patent/CN104245851B/en not_active Expired - Fee Related
- 2013-02-14 JP JP2014500675A patent/JPWO2013125419A1/en active Pending
- 2013-02-14 WO PCT/JP2013/053450 patent/WO2013125419A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000111914A (en) * | 1998-09-30 | 2000-04-21 | Fuji Photo Film Co Ltd | Retardation raising agent for low fatty acid cellulose ester film, optical compensation sheet and liquid crystal display device |
| CN1954023A (en) * | 2004-05-14 | 2007-04-25 | 富士胶片株式会社 | Optical cellulose acylate film, polarizing plate and liquid crystal display device |
| JP2006188718A (en) * | 2006-04-10 | 2006-07-20 | Fuji Photo Film Co Ltd | Retardation rise agent for film of cellulose lower fatty acid ester |
| JP2009020399A (en) * | 2007-07-13 | 2009-01-29 | Konica Minolta Opto Inc | Optical film, polarizing plate and liquid crystal display |
| CN101981153A (en) * | 2008-03-31 | 2011-02-23 | 富士胶片株式会社 | Ultraviolet absorbent compositions |
| JP2012189664A (en) * | 2011-03-09 | 2012-10-04 | Konica Minolta Advanced Layers Inc | Optical film, and polarizing plate and liquid crystal display device using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109890902A (en) * | 2016-10-31 | 2019-06-14 | 东丽株式会社 | Comprising having the thermoplastic resin composition of the compound for the functional group for mutually forming the above hydrogen bond of at least two |
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|---|---|
| WO2013125419A1 (en) | 2013-08-29 |
| JPWO2013125419A1 (en) | 2015-07-30 |
| CN104245851B (en) | 2016-12-21 |
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