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CN102939550B - Phase retardation film and the image display device possessing this phase retardation film - Google Patents

Phase retardation film and the image display device possessing this phase retardation film Download PDF

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Publication number
CN102939550B
CN102939550B CN201180027074.9A CN201180027074A CN102939550B CN 102939550 B CN102939550 B CN 102939550B CN 201180027074 A CN201180027074 A CN 201180027074A CN 102939550 B CN102939550 B CN 102939550B
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retardation film
methyl
phase retardation
weight
film
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CN102939550A (en
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大西隆司
中昭夫
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C08F8/16—Lactonisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • G02F1/133637—Birefringent elements, e.g. for optical compensation characterised by the wavelength dispersion
    • 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
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The phase retardation film of the present invention comprises the layer being made up of resin combination, and described resin combination is included in main chain and has (methyl) acrylate copolymer 30 weight % of ring structure～95 weight % and cellulose ester polymer 5 weight %～70 weight %.Photoelastic coefficient and the moisture permeability of the phase retardation film of the present invention are low, the degree of freedom of the control of the wavelength dispersibility of phase contrast simultaneously is high, and the phase retardation film of the present invention for example, demonstrates the phase retardation film that the wavelength dispersibility of the anti-wavelength dispersibility of phase contrast or phase contrast is smooth.This phase retardation film is suitable for the purposes of the optical compensation in the image display devices such as liquid crystal indicator (LCD).

Description

Phase retardation film and the image display device possessing this phase retardation film
Technical field
The present invention relates to phase retardation film and possess the image display device of this film.
Background technology
In the past, the blooming headed by polarizer protection film and phase retardation film employed cellulose-based polymer.With by gathering The phase retardation film that the general polymer such as carbonic ester is constituted is different, and the phase retardation film being made up of cellulose-based polymer is the most extremely Wavelength dispersibility (the anti-wavelength dispersion of phase contrast that the shortest then phase contrast of wavelength of light is the least is demonstrated less in visible region Property).Thus, it is possible to expect the raising possessing the image display feature in the liquid crystal indicator (LCD) of this phase retardation film.But It is that origin is in the characteristic of cellulose-based polymer, and this phase retardation film has that poisture-penetrability is high, photoelastic coefficient big, may not obtain Problem to sufficiently large phase contrast.
Unlike this, in phase retardation film, employ main chain there is (methyl) acrylate copolymer of ring structure (with reference to specially Profit document 1: Japanese Unexamined Patent Publication 2008-9378 publication).Be there is the phase that (methyl) acrylate copolymer of ring structure is constituted by main chain Potential difference film has high transparent and a thermostability, on the other hand mechanical property, particularly flexible guarantee that aspect has problems.This phase The mechanical property of potential difference film is improved by interpolation or the stretching of the elastomer particles of rubber etc.But, with the addition of bullet In the case of elastomer particles, it is necessary to the cohesion of the granule that suppression is added, to guarantee the transparency as phase retardation film.Except this it Outward, as the phase retardation film constituted with by general polymer, main chain there is (methyl) acrylate copolymer of ring structure The phase retardation film constituted at least demonstrates the wavelength dispersibility (phase place that the shortest then phase contrast of wavelength of light is the biggest in visible region The positive wavelength dispersibility of difference).
In patent documentation 2 (Japanese Unexamined Patent Publication 2009-1744 publication), describe: main chain has (methyl) of ring structure Acrylate copolymer is useful as the modifying agent of cellulose ester membrane；By main chain being had (methyl) acroleic acid polymerization of ring structure Thing adds in cellulose ester membrane, can suppress to be transferred as, with horseback shape fault (back of the body fault), core, this film of representing Deformation fault；As an example of cellulose ester membrane, there is phase retardation film.But, in Japanese Unexamined Patent Publication 2009-1744 publication not Record and using which kind of degree, main chain had (methyl) acrylate copolymer of ring structure and add cellulose ester membrane to as modifying agent In, the most only describe to add in 100 part by weight of cellulose esters and be somebody's turn to do (methyl) acrylate copolymer 4 weight Amount～the example of 12 weight portions.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-9378 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-1744 publication
Summary of the invention
The problem that invention is to be solved
It is an object of the invention to provide a kind of phase retardation film, described phase retardation film comprises and is made up of resin combination The phase retardation film of layer, described resin combination comprises main chain and has (methyl) acrylate copolymer of ring structure and cellulose esters gathers Compound, photoelastic coefficient and the moisture permeability of described phase retardation film are low, simultaneously the degree of freedom of the control of the wavelength dispersibility of phase contrast High (for instance, it is possible to the wavelength dispersibility of the anti-wavelength dispersibility of display phase contrast or phase contrast is at least at visible region energy Enough smooth).
For solving the scheme of problem
The phase retardation film of the present invention comprises the layer being made up of resin combination (C), and described resin combination (C) comprises main chain Have (methyl) acrylate copolymer (A) 30 weight % of ring structure～95 weight % and cellulose ester polymer (B) 5 weight %～ 70 weight %.
The image display device of the present invention possesses the phase retardation film of the invention described above.
Invention effect
The phase retardation film of the present invention comprises the layer being made up of resin combination, and described resin combination is at the model of certain content Comprise main chain in enclosing and there is (methyl) acrylate copolymer (A) and the cellulosic polymer (B) of ring structure, thus become photoelasticity Coefficient and the phase retardation film that moisture permeability is low, the degree of freedom of the control of the wavelength dispersibility of phase contrast is high simultaneously.
Accompanying drawing explanation
Fig. 1 is the top view of an example of the phase retardation film schematically showing the present invention.
Detailed description of the invention
[(methyl) acrylate copolymer (A)]
(methyl) acrylate copolymer be have more than 50 weight % of entire infrastructure unit, be preferably more than 70 weight %, (methyl) acrylate more than more preferably 90 weight %, more than particularly preferably 95 weight %, more than most preferably 99 weight % The polymer of unit.(methyl) acrylate copolymer (A) can be for (methyl) acrylate list at the ring structure that main chain is had The derivant of unit.In this case, if (methyl) acrylic ester unit and 50 weights adding up to entire infrastructure unit of ring structure Amount more than %, then become (methyl) acrylate copolymer.
(methyl) acrylic ester unit is by such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) N-propyl, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the most own ester of (methyl) acrylic acid, (methyl) Cyclohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) benzyl acrylate, (methyl) acrylic acid bicyclopentyl oxygen Base ethyl ester, (methyl) acrylic acid bicyclo-pentyl ester, (methyl) acrylic acid chloromethyl ester, (methyl) acrylic acid-2-chloroethene ester, (methyl) third Olefin(e) acid-2-hydroxy methacrylate, (methyl) acrylic acid-3-hydroxy propyl ester, (methyl) acrylic acid own ester of-2,3,4,5,6-penta hydroxy group, (first Base) acrylic acid-2,3,4,5-tetrahydroxy pentyl ester, 2-(hydroxymethyl) acrylic acid methyl ester., 2-(hydroxymethyl) ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, 2-(hydroxymethyl) n-butyl acrylate, 2-(hydroxymethyl) tert-butyl acrylate etc. are single The construction unit that the polymerization of body is formed.(methyl) acrylate copolymer can have these two or more construction units.From The aspect of heat stability is set out, and (methyl) acrylate copolymer (A) preferably has methyl methacrylate (MMA) unit.
(methyl) acrylate copolymer (A) preferably has (methyl) the acrylate unit X shown in following formula (1) and makees For construction unit.
[chemical formula 1]
In formula (1), R1Be carbon number be the alkyl of 2～18, R2It is H (hydrogen atom) or CH3(methyl).R2During for H, formula (1) unit shown in is acrylate unit, R2For CH3Time, the unit shown in formula (1) is alkyl methacrylate list Unit.
If the resin combination molding of (methyl) acrylate copolymer and cellulose ester polymer, the then mist on surface will be comprised Degree improves, and the transparency of obtained molded body often reduces.Particularly, when this resin combination is shaped to film, this inclines To significantly.The film that the transparency reduces cannot use as phase retardation film.(methyl) acrylate copolymer (A) is comprising (methyl) third In the case of olefin(e) acid alkyl methacrylate unit X, the rising of this mist degree can be suppressed, obtain the phase retardation film that the transparency is excellent.
R1As long as the alkyl that carbon number is 2～18 does not the most limit.R1For example, ethyl (carbon number is 2), propyl group (carbon number is 3), butyl (carbon number is 4), amyl group (carbon number is 5), hexyl (carbon number is 6), (carbon is former for heptyl Subnumber is 7), octyl group (carbon number is 8), nonyl (carbon number is 9), decyl (carbon number is 10), (carbon is former for undecyl Subnumber is 11) and dodecyl (carbon number is 12) and their constitutional isomer.
In the entire infrastructure unit of (methyl) acrylate copolymer (A) shared by (methyl) acrylate unit X Ratio is different, more than for example, 5 weight % because of the concrete molecular structure of this unit X.Owing to can positively be inhibited on mist degree The effect risen, thus this ratio is preferably more than 10 weight %, is preferably more than 15 weight %.The most special to the upper limit of this ratio Limit, for example, 50 weight %.(methyl) alkyl acrylate list in the entire infrastructure unit of (methyl) acrylate copolymer (A) Unit's ratio shared by X is passed through1H nuclear magnetic resonance, NMR (1Or infrared spectroscopic analysis (IR) is obtained H-NMR).This ratio can by In the polymerization of (methyl) acrylate copolymer (A) use each monomer ratio and as required with reference to from monomer to formed (first Base) reaction mechanism of acrylate copolymer (A) and obtain.
(methyl) acrylate copolymer (A) can have (methyl) of more than two kinds acrylate unit X as structure Unit.
(methyl) acrylate copolymer (A) can have the construction unit in addition to (methyl) acrylic ester unit.This knot Structure unit be by such as (methyl) acrylic acid, styrene, vinyltoluene, α-methyl styrene, Alpha-hydroxy methyl styrene, Alpha-hydroxy ethyl styrene, acrylonitrile, methacrylonitrile, methallyl alcohol, 1-propenol-3, ethylene, propylene, 4-methyl-1-pentene, The monomers such as vinyl acetate, 2-hydroxymethyl-1-butylene, methyl vinyl ketone, NVP, N-VCz Polymerization and the construction unit that formed.
(methyl) acrylate copolymer (A) preferably has (methyl) acrylate unit X, MMA unit and 2-(hydroxyl Methyl) acrylic ester unit is as construction unit.(methyl) acrylate copolymer (A) preferably has (methyl) alkyl acrylate Unit X, MMA unit, 2-(hydroxymethyl) acrylic ester unit and N-VCz unit are as construction unit.These situations Under, further suppress the rising of mist degree, high optical characteristics can be obtained when making phase retardation film simultaneously.In the case of these, The content of the MMA unit in (methyl) acrylate copolymer (A) is preferably 10 weight %～80 weight %, more preferably 20 weight % ～60 weight %.The content of 2-(hydroxymethyl) acrylic ester unit is preferably 10 weight %～60 weight %, more preferably 20 weights Amount %～40 weight %.The content of unit X is preferably 5 weight %～70 weight %, more preferably 10 weight %～50 weight %.N-ethylene The content of base carbazole unit is preferably 1 weight %～20 weight %, more preferably 3 weight %～8 weight %.2-(hydroxymethyl) propylene Acid esters unit for example, 2-(hydroxymethyl) acrylic acid methyl ester. (MHMA) unit, 2-(hydroxymethyl) ethyl acrylate unit, 2- (hydroxymethyl) isopropyl acrylate unit, 2-(hydroxymethyl) n-butyl acrylate unit, 2-(hydroxymethyl) acrylic acid uncle Butyl ester unit.Wherein, preferably MHMA unit, 2-(hydroxymethyl) ethyl acrylate unit, from the transparency of phase retardation film and resistance to Hot aspect is set out, particularly preferred MHMA unit.
(methyl) acrylate copolymer (A) has ring structure at main chain.(methyl) acrylate copolymer (A) has at main chain Ring structure contributes to the phase retardation film of the present invention and demonstrates phase contrast and the rising of suppression mist degree in big face.
In addition, the glass transition temperature (Tg) that main chain has (methyl) acrylate copolymer (A) of ring structure is high, For example, more than 110 DEG C, according to the difference of the composition of this polymer, it is more than 120 DEG C and then is more than 130 DEG C.By comprising So having (methyl) acrylate copolymer (A) of high Tg, the thermostability of the phase retardation film of the present invention improves.The phase that thermostability is high Potential difference film can be configured at the vicinity of the radiating part of light source etc, is therefore suitable for the image display devices such as LCD.
The content of the ring structure in (methyl) acrylate copolymer (A) is preferably 25 weight %～90 weight %, is more preferably 35 weight %～90 weight %, particularly preferably 40 weight %～90 weight %.If the content of the ring structure in polymer (A) is more than 90 Weight %, then the mouldability of the resin combination comprising polymer (A) reduces, and is sometimes difficult to manufacture phase retardation film.
(methyl) acrylate copolymer (A) is to have such as ester group, imide or anhydride at the ring structure that main chain has The ring structure of base.
More specifically the example of ring structure is for take selected from lactonic ring structure, glutarimide structure, glutaric anhydride structure, N- For at least one in maleimide structure and maleic anhydride structure.These ring structures are for phase contrast in above-mentioned big face The degree helped is big.
Ring structure is preferably selected from least one in lactonic ring structure and glutarimide structure, more preferably lactonic ring Structure.Main chain has (methyl) acrylate copolymer of lactonic ring structure or glutarimide structure, particularly lactonic ring structure (A) birefringent wavelength dispersibility is the least.Therefore, the control of the wavelength dispersibility of the phase contrast in the phase retardation film of the present invention The degree of freedom of system is becoming higher between smooth wavelength dispersibility to anti-wavelength dispersibility.In addition, in main chain has (methyl) acrylate copolymer (A) of ester ring structure is the highest with the compatibility of cellulose ester polymer (B).High-compatibility helps Rising in suppression mist degree.
The concrete lactonic ring structure can having (methyl) acrylate copolymer (A) at main chain limits the most especially Fixed, can be such as 4～8 rings, due to the excellent in stability as ring structure, thus preferably 5 rings or 6 rings, more excellent Elect 6 rings as.The lactonic ring structure of 6 rings for example, structure disclosed in Japanese Unexamined Patent Publication 2004-168882 publication.Under due to State reason, preferably the structure shown in following formula (2): precursor (by making precursor carry out cyclized condensation reaction, obtains main chain and has interior (methyl) acrylate copolymer (A) of ester ring structure) polymerization yield high；Had by the cyclized condensation reaction of precursor (methyl) acrylate copolymer (A) of high lactonic ring content；Can be used for having the MMA unit polymer as construction unit Precursor；Etc..
[chemical formula 2]
In formula (2), R3、R4And R5It is independently of one another the organic residue of scope that hydrogen atom or carbon number are 1～20. Organic residue can comprise oxygen atom.
The alkyl of the scopes that carbon number is 1～20 such as organic residue e.g. methyl, ethyl, propyl group；Vinyl, propylene The carbon numbers such as base are the unsaturated fatty hydrocarbons base of the scope of 1～20；The carbon number such as phenyl, naphthyl is the scope of 1～20 Aromatic hydrocarbyl；In abovementioned alkyl, above-mentioned unsaturated fatty hydrocarbons base and above-mentioned aromatic hydrocarbyl, more than one hydrogen atom At least one the substituted group of group being selected from hydroxyl, carboxyl, ether and ester group.
Lactonic ring structure shown in formula (2) such as can be after comprising the monomer group copolymerization of MMA and MHMA, obtained by making Copolymer in adjacent MMA unit and MHMA unit dealcoholysis cyclizative condensation and formed.Now, R3For H, R4And R5For CH3。
(methyl) acrylate copolymer (A) in the case of main chain has lactonic ring structure, from cellulose ester polymer (B), the aspect of the particularly compatibility of cellulose acetate polymers set out, the content of the lactonic ring structure in polymer (A) is excellent Elect 25 weight %～90 weight %, more preferably 25 weight %～70 weight %, particularly preferably 30 weight %～60 weight %, optimum as Elect 35 weight %～60 weight % as.The content of the lactonic ring structure in (methyl) acrylate copolymer (A) can be special according to Japan The method described in 2001-151814 publication of opening is obtained.
The weight average molecular weight (Mw) of (methyl) acrylate copolymer (A) is preferably more than 80,000, more preferably more than 100,000. The dispersion (=weight average molecular weight Mw/ number-average molecular weight Mn) of the molecular weight in (methyl) acrylate copolymer (A) is preferably 3.5 Below, more preferably less than 3.Mw and the dispersion of (methyl) acrylate copolymer (A) can pass through gel permeation chromatography (GPC) obtain.When (methyl) acrylate copolymer (A) meets the scope of above-mentioned Mw and dispersion, a link of this polymer (A) Structure is suppressed.This improves the heat stability of the resin combination comprising polymer (A), contributes to having high intensity and desired The manufacture of phase retardation film of outward appearance.
(methyl) acrylate copolymer (A) can utilize known method manufacture.The ring structure of main chain is glutaric anhydride knot (methyl) acrylate copolymer (A) of structure or glutarimide structure such as can utilize WO2007/26659 publication or Method manufacture described in WO2005/108438 publication.The ring structure of main chain is maleic anhydride structure or N-replacement maleoyl (methyl) acrylate copolymer (A) of imine structure such as can utilize Japanese Laid-Open Patent Publication 57-153008 publication, Japanese Unexamined Patent Publication Method manufacture described in 2007-31537 publication.The ring structure of main chain is (methyl) acrylate copolymer of lactonic ring structure (A) Japanese Unexamined Patent Publication 2006-96960 publication, Japanese Unexamined Patent Publication 2006-171464 publication or Japanese Unexamined Patent Publication can such as be utilized Method manufacture described in 2007-63541 publication.
As an example, the manufacture method of (methyl) acrylate copolymer (A) to main chain with lactonic ring structure is said Bright.In the presence of arbitrary catalyst to strand in there is the polymer (a) of hydroxyl and ester group heat, carry out with de- The lactone cyclization condensation reaction of alcohol such that it is able to form this polymer (A).
Polymer (a) is such as formed by the polymerization of the monomer group that comprises the monomer shown in following formula (3).Polymer (A) have (methyl) the acrylate unit X shown in formula (1) as construction unit in the case of, polymer (a) such as can Reach the polymerization of the monomer group by comprising the monomer shown in following formula (3) and the monomer shown in following formula (4) and formed.
[chemical formula 3]
In formula (3), R6And R7It is independently of one another hydrogen atom or as the group illustrated in the organic residue in formula (2).Formula (3) monomer shown in provides hydroxyl and ester group by polymerization to the strand of polymer (a) is interior.
[chemical formula 4]
In formula (4), R8It is and the R of formula (1)1Same group.In formula (4), R9For H (hydrogen atom) or CH3(methyl).Formula (4) monomer ((methyl) alkyl acrylate monomer Y) shown in is by being polymerized as (methyl) acrylate unit X.
The concrete example of the monomer shown in formula (3) is 2-(hydroxymethyl) acrylic acid methyl ester., 2-(hydroxymethyl) acrylic acid second Ester, 2-(hydroxymethyl) isopropyl acrylate, 2-(hydroxymethyl) n-butyl acrylate, the tertiary fourth of 2-(hydroxymethyl) acrylic acid Ester.Wherein, preferably 2-(hydroxymethyl) acrylic acid methyl ester., 2-(hydroxymethyl) ethyl acrylate, from the transparency and thermostability Aspect is set out, particularly preferred 2-(hydroxymethyl) acrylic acid methyl ester. (MHMA).
The concrete example of the monomer shown in formula (4) is (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) propylene Acid butyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) acryllic acid monooctyl ester, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) lauryl base Ester.
Formula (3) in the monomer group of the formation of polymer (a), the monomer shown in (4) content can be according to institute's phase The molecular structure of (methyl) acrylate copolymer (A) hoped and adjust.
Monomer group for the formation of polymer (a) can comprise the monomer shown in formula of more than two kinds (3).This monomer group The monomer shown in formula of more than two kinds (4) can be comprised.
Monomer group for the formation of polymer (a) can comprise the monomer in addition to the monomer shown in formula (3), (4).This As long as the monomer of sample can be not particularly limited with the monomer of the monomer copolymerization shown in formula (3), (4).This monomer is for example, (methyl) acrylate in addition to the monomer shown in formula (3), (4).
It is somebody's turn to do the acrylate such as (methyl) acrylate for example, acrylic acid methyl ester., cyclohexyl acrylate, benzyl acrylate；First The methacrylates such as base acrylic acid methyl ester., cyclohexyl methacrylate, benzyl methacrylate.From the transparency and thermostability Aspect is set out, preferably MMA.
Monomer group for the formation of polymer (a) can comprise these (methyl) acrylate of more than two kinds.
Monomer group for the formation of polymer (a) can comprise (methyl) acrylic acid, styrene, vinyltoluene, α- One kind or two or more in the monomers such as methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate.Its In, (methyl) the acrylic acid content in this monomer group is preferably below below 30 weight %, more preferably 20 weight %, the most excellent Elect below below 10 weight %, most preferably 5 weight % as.If (methyl) acrylic acid content is more than 30 weight %, then in monomer group Polymerization process in carry out gelation sometimes.
When forming polymer (a) in the polymerization utilizing monomer group, as required, it is possible to use polymerization initiator.Polymerization Initiator for example, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, peroxide Change the organic peroxides such as benzoyl, tert-butylperoxy isopropyl carbonate, peroxidating tertiary pentyl-2-ethylhexanoate；2,2’- Azo two (isopropyl cyanide), 1,1 '-azo double (cyclohexane carbonitrile), 2,2 '-azo double (2,4-methyl pentane nitrile), 2,2 '-azo Two isopropylformic acid. dimethyl esters.Polymerization initiator can share two or more.The consumption of polymerization initiator can be according to contained by monomer group The combination of monomer and polymerizing condition suitably set.
Known cyclization catalyst is preferably used in the lactone cyclization condensation reaction of the dealcoholysis in concomitant polymerization thing (a).Ring Change esterification catalyst or the ester exchange catalysts such as catalyst for example, p-methyl benzenesulfonic acid.Can use acetic acid, propanoic acid, benzoic acid, The organic carboxyl acid class such as acrylic acid, methacrylic acid is as cyclization catalyst.Additionally, such as, such as Japanese Laid-Open Patent Publication 61-254608 As disclosed in publication and Japanese Laid-Open Patent Publication 61-261303 publication, it is possible to use alkali compounds；Organic carboxylic such as zinc acetate Hydrochlorate；Carbonate is as cyclization catalyst.
Cyclization catalyst can be organic phosphorus compound.This organic phosphorus compound for example, methyl phosphonous acid, ethyl Asia phosphine (wherein, these can be the alkyl as tautomer time phosphine for the phostonic acids such as acid, phenyl-phosphonite or aryl phosphonous acid Acid or arylphosphinic acid) and their monoesters or diester；Dimethylphosphinic acid, diethyl phosphinic acid, diphenyl phosphonic acid, benzene Dialkyl phosphinic acid, diaryl phosphinic acid or the alkylaryl phosphinic acid such as ylmethyl phosphinic acid, phenylethyl phosphinic acid and it Ester；The alkyl phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethyl phosphonic acids, phenyl-phosphonic acid or arylphosphonic acid and they Monoesters or diester；The alkyl Asia phosphinic acid of methyl Asia phosphinic acid, ethyl Asia phosphinic acid, phenyl Asia phosphinic acid etc. or sub-phosphine of aryl Acid and their ester；Methyl phosphite, phosphorous acid ethyl ester, phenyl-phosphite, dimethylphosphite, diethyl phosphite, Asia Monophosphite, diester or three esters such as diphenyl phosphate, NSC 6513, NSC 5284, triphenyl phosphite；Phosphoric acid Methyl ester, etherophosphoric acid, phosphoric acid-2-Octyl Nitrite, isodecyl ester, lauryl phosphate, phosphoric acid stearyl ester, the different stearyl ester of phosphoric acid, Phenyl phosphate, dimethyl phosphate, diethyl phosphate, di(2-ethylhexyl)phosphate-2-Octyl Nitrite, octyl phosphate, di(2-ethylhexyl)phosphate isodecyl ester, di(2-ethylhexyl)phosphate Lauryl, di(2-ethylhexyl)phosphate stearyl ester, the different stearyl ester of di(2-ethylhexyl)phosphate, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tricresyl phosphate are different The last of the ten Heavenly stems ester, tricresyl phosphate lauryl, tricresyl phosphate stearyl ester, the different stearyl ester of tricresyl phosphate, phosphate monoester, diester or three such as triphenyl phosphate Ester；Methylphosphine, ethyl phosphine, Phenylphosphine, dimethyl phosphine, diethyl phosphine, diphenylphosphine, trimethyl-phosphine, triethyl phosphine, triphenylphosphine Etc. mono-, di-or trialkyl (aryl) phosphine；Methyl dichloro phosphine, ethyl dichloro phosphine, phenyl dichloro phosphine, dimethyl chloride phosphine, diethyl chlorine The alkyl such as phosphine, chlorophosphonazo diphenylurea (aryl) halogen phosphine；Oxidation methyl phosphine, ethyl oxide phosphine, oxidation Phenylphosphine, cacodyl oxide base The oxidation lists such as phosphine, oxidation diethyl phosphine, diphenyl phosphine oxide, trimethylphosphine oxide, oxidation triethyl phosphine, triphenylphosphine oxide, Two or trialkyl (aryl) phosphine；The tetraalkylphosphonium halide such as tetramethyl phosphonium chloride phosphorus, chlorination tetraethyl phosphorus, tetraphenylphosphonium chloride (aryl) phosphorus.These organic phosphorus compounds of more than two kinds can be share.Wherein, owing to catalysis activity is high, coloring is low, because of And preferably alkyl (aryl) phosphonous acid, monophosphite or diester, phosphate monoester or diester, alkyl (aryl) phosphonic acids, more preferably Alkyl (aryl) phosphonous acid, monophosphite or diester, phosphate monoester or diester, particularly preferred alkyl (aryl) phosphonous acid, phosphorus Acid monoester or diester.
The cyclization catalyst of alkalescence can also be used.This cyclization catalyst for example, Japanese Unexamined Patent Publication 2009-144112 public affairs The compound of 12 race's elements described in report, particularly preferably zinc compound.Zinc compound for example, zinc acetate, zinc propionate, pungent The organic zinc compounds such as acid zinc；The inorganic zinc compounds such as zinc oxide, zinc chloride, zinc sulfate；Trifluoromethane sulfonic acid zinc etc. are containing fluorine Organic zinc compound.
Due to the unreacted reactive group that also trace is remaining after lactone cyclization condensation reaction, by obtained bag When resin combination containing (methyl) acrylate copolymer (A) is shaped to film, produce the friendship between foaming or polymer sometimes Connection.By adding the deactivator of cyclization catalyst after cyclized condensation reaction, it is possible to suppress this phenomenon.The interpolation of deactivator for The deterioration suppressing the cellulose ester polymer (B) that this resin combination comprised is the most effective.Cyclization catalyst many uses acid Matter or alkaline matter.In the case of cyclization catalyst is acidic materials, the deactivator of alkalescence is preferably used, in cyclisation catalysis In the case of agent is alkaline matter, the deactivator of acidity is preferably used.The deactivator for example, metal carboxylate of alkalescence, metal network Compound, metal-oxide, preferably metal carboxylate and metal-oxide, more preferably metal carboxylate.As long as not suppressing tree The physical property of oil/fat composition, then do not limit the metal for this deactivator, for example, the alkali metal such as lithium, sodium, potassium；Magnesium, calcium, The alkaline-earth metal such as strontium, barium；Zinc；Zirconium.Constitute the carboxylic acid for example, formic acid of metal carboxylate, acetic acid, propanoic acid, butanoic acid, valeric acid, oneself Acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid, tetradecylic acid, Palmic acid, stearic acid, behenic acid, tridecanoic acid, pentadecane Acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid.Metal network Organic principle in compound for example, acetylacetone,2,4-pentanedione.Metal-oxide for example, zinc oxide, calcium oxide, magnesium oxide, preferably oxygen Change zinc.Acid deactivator for example, organic phosphoric acid compound, carboxylic acid.Deactivator can share two or more.Shape to deactivator State does not limit, it is possible to have the forms such as solid-state, powder, dispersion, suspension, aqueous solution.
[cellulose ester polymer (B)]
Cellulose ester polymer (B) is not limited, for example, cellulose aromatic carboxylic acid ester polymer, cellulose fatty Acid ester polymer.The phase retardation film excellent owing to optical characteristics can be obtained, thus cellulosic polymer (B) is preferably cellulose Lower fatty acid ester polymer.Lower fatty acid refers to the fatty acid that carbon number is less than 5.Cellulose lower fatty acid ester gathers Compound for example, cellulose acetate, cellulose propionate, cellulose butyrate, neopentanoic acid cellulose.Cellulose ester polymer (B) can For the cellulose mixed fatty acid ester polymer such as cellulose-acetate propionate, cellulose acetate-butyrate.In this case, it is possible to realize Comprise the mechanical property of the film property of the resin combination (C) of this cellulosic polymer (B) and the phase retardation film of final acquisition Take into account.From the aspect with the compatibility of (methyl) acrylate copolymer (A), cellulose ester polymer (B) is preferably acetic acid Cellulose, particularly preferably cellulose triacetate or cellulose-acetate propionate.
The Mn of cellulose ester polymer (B) is preferably 50,000～150,000, more preferably 5.5 ten thousand～120,000, more preferably 60000～100,000.The Mw of cellulose ester polymer (B) is preferably 100,000～300,000, more preferably 100,000～250,000, further preferably It is 120,000～200,000.The dispersion (=Mw/Mn) of the molecular weight in cellulose ester polymer (B) be preferably 1.3～5.5, more preferably It is 1.5～5.0, more preferably 1.7～4.0, particularly preferably 2.0～3.5.
Cellulose ester polymer (B) can utilize known method manufacture.Such as, acetic anhydride, propionic andydride and/or fourth are used Anhydride, is substituted by acetyl group, propiono and/or butyl by conventional method by the hydroxyl of raw cellulose such that it is able to manufacture. Now, with reference to Japanese Unexamined Patent Publication 10-45804 publication and the method described in Japanese Kohyo 6-501040 publication.Need Illustrate, raw cellulose is not particularly limited, for example, timber slurry, cotton linters.Timber slurry can be pin The slurry of Ye Shu, it is also possible to be the slurry of broad leaf tree, the most acerose slurry.Go out in terms of fissility in time forming film Send out, preferably cotton linters.Cellulose ester polymer (B) can use two or more.
[resin combination (C)]
Resin combination (C) comprises main chain and has (methyl) acrylate copolymer (A) 30 weight %～95 weights of ring structure Measure % and cellulose ester polymer (B) 5 weight %～70 weight %.Resin combination (C) preferably comprises (methyl) acrylate copolymer (A) 50 weight %～90 weight % and cellulose ester polymer (B) 10 weight %～50 weight %, more preferably comprise (methyl) acrylic acid Polymer (A) 70 weight %～90 weight % and cellulose ester polymer (B) 10 weight %～30 weight %.
If the content of (methyl) acrylate copolymer (A) in resin combination (C) is excessive, then the phase contrast finally given The degree of freedom of the control of the wavelength dispersibility of the phase contrast in film reduces.On the other hand, if the cellulose in resin combination (C) The content of ester polymer (B) is excessive, then the photoelastic coefficient of the phase retardation film finally given and moisture permeability raise.
Resin combination (C) can comprise (methyl) of more than two kinds acrylate copolymer (A) and/or fiber of more than two kinds Element ester polymer (B).
As long as the effect of the present invention can be obtained, then resin combination (C) can comprise with in resin combination (C) Content is calculated as below 40 weight %, is preferably being polymerized except (methyl) acrylate copolymer (A) and cellulose esters below 10 weight % Polymer beyond thing (B).
The alkene such as this polymer for example, polyethylene, polypropylene, ethylene-propylene copolymer, poly-(4-methyl-1-pentene) gathers Compound；The halogen-containing polymer such as vinyl chloride, chlorinated ethylene resin；Polystyrene, styrene methyl methacrylate copolymerization The styrenics such as thing, SAN, acrylnitrile-butadiene-styrene copolymer；Poly-to benzene The polyester such as naphthalate, polybutylene terephthalate (PBT), PEN；Nylon 6, nylon66 fiber, Buddhist nun Dragon 610 polyamide such as grade；Polyacetals；Merlon；Polyphenylene oxide；Polyphenylene sulfide: polyether-ether-ketone；Polyethers nitrile；Polysulfones；Polyether sulfone；Poly- Oxygen benzene methyl；Polyamidoimide.
In these polymer, from (methyl) acrylate copolymer (A), particularly main chain, there is lactonic ring structure The aspect of the excellent compatibility of (methyl) acrylate copolymer (A) is set out, and preferably comprises the knot from cyanided vinyl monomer Structure unit and from the copolymer of construction unit of aromatic vinyl monomer, such as SAN.
As long as the effect of the present invention can be obtained, then resin combination (C) can comprise arbitrary material.This material is such as For UV absorbent；Antioxidant；The stabilizers such as resistance to light stabilizer, weathering stabilizers, heat stabilizer；Glass fibre, carbon are fine The reinforcing materials such as dimension；Near infrared ray absorption；The fire retardants such as three (dibromopropyl) phosphate ester, triallyl phosphate ester, stibium oxide； Anionic, cationic, the antistatic additive representated by surfactant of nonionic；Inorganic pigment, organic pigment, dyestuff Deng coloring agent；Organic filler, inorganic filler；Modifier；Anti-blocking agent；Dumb light agent；Acid supplement；Metal-inert agent； Plasticizer；Lubricant；The rubber mass polymers such as ASA or ABS.Content for example, 0 weight of these materials in resin combination (C) Measure %～5 weight %, be preferably 0 weight %～2 weight %, more preferably 0 weight %～0.5 weight %.
UV absorbent for example, benzophenone based compound, salicylate based compound, benzoate based compound, Three azole compounds and triazine based compound.Benzophenone based compound for example, 2,4 dihydroxyl benzophenone, the most pungent oxygen of 4- Base-2-dihydroxy benaophenonel, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2-hydroxyl-4-n-octyloxy hexichol first Double (4-benzoyl-3-the oxybenzone)-butane of ketone, double (5-benzoyl-4-hydroxyl-2-methoxyphenyl) methane, 1,4-. Salicylate based compound for example, salicylic acid-4-tert-butyl group phenyl ester.Benzoate based compound for example, 2,4-di-t-butyl Phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate.Three azole compounds for example, 2,2 '-di-2-ethylhexylphosphine oxide [4-(1,1,3, 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol], 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzene three Azoles, 2-(2H-benzotriazole-2-base)-paracresol, 2-(2H-benzotriazole-2-base)-4,6-are double (1-methyl isophthalic acid-phenylethyl) Phenol, 2 benzotriazole-2-base-4,6-DI-tert-butylphenol compounds, 2-[5-chlorine (2H)-benzotriazole-2-base]-4-methyl-6-(uncle Butyl) phenol, 2-(2H-benzotriazole-2-base)-4,6-DI-tert-butylphenol compounds, 2-(2H-benzotriazole-2-base)-4-(1,1, 3,3-tetramethyl butyl) phenol, 2-(2H-benzotriazole-2-base)-4-methyl-6-(3,4,5,6-tetrahydric phthalimide Ylmethyl) phenol, methyl 3-(3-(2H-benzotriazole-2-the base)-5-tert-butyl group-4-hydroxyphenyl) propionic ester/Liquid Macrogol Product, 2-(2H-benzotriazole-2-base)-6-(straight chain and branched dodecyl)-4-methylphenol, 2-(5-methyl- 2-hydroxyphenyl) benzotriazole, 2-[2-hydroxyl-3,5-double (bis (alpha, alpha-dimethylbenzyl) base) phenyl]-2H-benzotriazole, 3-(2H-benzene And triazole-2-base)-5-(1,1-dimethyl ethyl)-4-hydroxyl-C7-9 side chain and straight chained alkyl ester.Triazine based compound is such as For having 2,4-diphenyl-6-(2-hydroxyl-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxyl-4-second Phenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxyl-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl- (2-hydroxyl-4-butoxy phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxyl-4-butoxy phenyl)-1,3,5-three Piperazine, 2,4-diphenyl-6-(2-hydroxyl-4-Hexyloxy-phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(the pungent oxygen of 2-hydroxyl-4- Base phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxyl-4-dodecyl phenyl)-1,3,5-triazine, 2,4-bis- Phenyl-6-(2-hydroxyl-4-benzyloxy-phenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxyl-4-Butoxyethoxy)- Double [2-hydroxyl-4-butoxy phenyl]-6-(2,4-dibutoxy the phenyl)-1,3-5-triazine of 1,3,5-triazine, 2,4-, 2,4-are double (2,4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-alkoxyl-2-hydroxy propyloxy group)-5-α-cumyl phenyl]-s-triazine each Triazine skeleton and Alkoxy such as octyloxy, nonyl epoxide, the compound of the isometric chain alkoxy of decyloxy.As triazine system ultraviolet Absorbent, " Tinuvin 1577 ", " Tinuvin 460 ", " Tinuvin 477 " (being vapour bar speciality chemical manufacture) have city Selling, as triazole system UV absorbent, " ADKSTAB LA-31 " (rising sun electrochemical industry manufacture) is commercially available.
Resin combination (C) can comprise UV absorbent of more than two kinds.Resin combination (C) comprises ultraviolet and inhales In the case of receiving agent, the content of the UV absorbent in resin combination (C) is not particularly limited.Shape at phase retardation film Under state, its content is preferably 0.01 weight %～25 weight %, more preferably 0.05 weight %～10 weight %.If UV absorbent Content excessive, then the mechanical property of the phase retardation film finally given reduces sometimes, or phase retardation film xanthochromia sometimes.
Antioxidant for example, hindered phenol based compound, phosphorus series compound and chalcogenide compound.Resin combination (C) can Comprise antioxidant of more than two kinds.
Antioxidant can be phenol system compound, for example, n-octadecane base-3-(3,5-di-t-butyl-4-hydroxyphenyl) third Acid esters, n-octadecane base-3-(3,5-di-t-butyl-4-hydroxyphenyl) acetas, n-octadecane base-3,5-di-t-butyl-4-hydroxyl Yl benzoic acid ester, n-hexyl-3,5-di-t-butyl-4-hydroxyphenyl benzoate, dodecyl-3,5-di-t-butyl-4-hydroxyl Phenylbenzoate, new dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, dodecyl-β-(3,5-bis-uncle Butyl-4-hydroxyphenyl) propionic ester, ethyl-α-(4-hydroxyl-3,5-di-tert-butyl-phenyl) isobutyrate, octadecyl-α-(4- Hydroxyl-3,5-di-tert-butyl-phenyl) isobutyrate, octadecyl-α-(4-hydroxyl-3,5-di-t-butyl-4-hydroxyphenyl) propanoic acid Ester, 2-(the most pungent sulfenyl) ethyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester, 2-(the most pungent sulfenyl) the tertiary fourth of ethyl-3,5-two Base-4-hydroxyphenylacetic acids ester, 2-(n-octadecane base sulfenyl) ethyl-3,5-di-t-butyl-4-hydroxyphenylacetic acids ester, 2-(positive ten Eight alkyl sulfenyls) ethyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester, 2-(2-hydroxyeththylthio) the tertiary fourth of ethyl-3,5-two Base-4-HBA ester, diethylene glycol-ether be double-(3,5-di-t-butyl-4-hydroxy-pheny) propionic ester, 2-(positive 18 Alkyl sulfenyl) ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, the double [ethylene-3-(3,5-bis-of stearmide-N, N- The tert-butyl group-4-hydroxyphenyl) propionic ester], the double [ethylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) third of normal-butyl imino group-N, N- Acid esters], 2-(2-stearoyl-oxy ethylmercapto group) ethyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester, 2-(2-stearoyl-oxy Ethylmercapto group) ethyl-7-(the 3-methyl-5-tert-butyl group-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol double [3-(3,5-di-t-butyl- 4-hydroxyphenyl) propionic ester], ethylene glycol bis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], the double [3-(3,5-of neopentyl glycol Di-t-butyl-4-hydroxyphenyl) propionic ester], ethylene glycol bis-(3,5-di-t-butyl-4-hydroxyphenylacetic acids ester), glycerol-1-the hardest Fat acid ester-2,3-is double-and (3,5-di-t-butyl-4-hydroxyphenylacetic acids ester), tetramethylolmethane four-[3-(3 ', 5 '-di-t-butyl-4 '- Hydroxyphenyl) propionic ester], 1,1,1-trimethylolethane trimethacrylate-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], sorbose Alcohol six-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 2-ethoxy-7-(the 3-methyl-5-tert-butyl group-4-hydroxyphenyl) Propionic ester, 2-stearoyl-oxy ethyl-7-(the 3-methyl-5-tert-butyl group-4-hydroxyphenyl) heptanoate, the positive hexanediol of 1,6-are double [(3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester], tetramethylolmethane four (3,5-di-t-butyl-4-hydroxyhydrocinnamic acid Ester), double [1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propiono epoxide] ethyl]-2,4 of 3,9-, 8,10-tetra-oxaspiro [5,5]-hendecane.
The antioxidant (phenol system antioxidant) being made up of phenol system compound preferably with thioether system antioxidant or phosphoric acid system Antioxidant combination uses.About the content of the antioxidant of the both sides in resin combination (C), with (methyl) acroleic acid polymerization On the basis of the weight of thing (A), such as, phenol system antioxidant and thioether system antioxidant are respectively more than 0.01 weight %, and phenol system resists Oxidant and phosphoric acid system antioxidant are respectively more than 0.025 weight %.
Thioether system antioxidant for example, tetramethylolmethane four (3-lauryl thiopropionate), dilauryl-3,3 '-sulfur generation Dipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate.
Phosphoric acid system antioxidant for example, three (2,4-di-tert-butyl-phenyl) phosphite ester, 2-[[2,4,8,10-tetra-(1,1- Dimethyl ethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin English in heptan-6-base] epoxide] double [the 2-[[2,4,8,10-tetra-of-N, N- (1,1-dimethyl ethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin English in heptan-6-base] epoxide]-ethyl] ethamine, diphenyl Tridecyl phosphite, triphenyl phosphite, 2,2-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl) octyl group phosphite ester, double (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, Ji Wusi Double (2,6-di-t-butyl-4-aminomethyl phenyl) phosphite ester of alcohol.
The content of the antioxidant in resin combination (C) is not particularly limited, such as, be 0 weight %～10 weight %, It is preferably 0 weight %～5 weight %, more preferably 0.01 weight %～2 weight %, more preferably 0.05 weight %～1 weight %. If the content of antioxidant is excessive, then time by melt extruding by resin combination (C) molding phase retardation film, it some times happens that anti- Oxidant oozes out, or can produce crazing.
[phase retardation film]
Fig. 1 shows an example of the phase retardation film of the present invention.The phase retardation film 1 of the present invention shown in Fig. 1 is by resin combination The layer that thing (C) is formed is constituted, and described resin combination (C) comprises main chain and has (methyl) acrylate copolymer (A) of ring structure 30 weight %～95 weight % and cellulose ester polymer (B) 5 weight %～70 weight %.As required, the phase retardation film of the present invention Arbitrary layer in addition to can possessing the layer except being formed by resin combination (C), in order to obtain the effect of the present invention more reliably Really, as it is shown in figure 1, the layer preferably formed by resin combination (C) is constituted, i.e. be made up of resin combination (C).But, this layer Functional coat can be had on its surface.
The absolute value for example, 5 × 10 of the photoelastic coefficient of the light for wavelength 590nm in the phase retardation film of the present invention-12Pa-1Below.(resin combination (C) is comprised) (methyl) acroleic acid polymerization that phase retardation film according to the present invention is comprised (methyl) acrylate copolymer (A) in the phase retardation film of thing (A) and the kind of cellulose ester polymer (B) and the present invention With the difference of the content of cellulose ester polymer (B), this absolute value is 4 × 10-12Pa-1Below and then be 3 × 10-12Pa-1With Under.
In face shown by the phase retardation film of the present invention, phase contrast Re is different because of the extended state of this film, for wavelength The light of 590nm, in terms of the value of every 100 μm thickness, for example, more than 50nm.(the first that phase retardation film according to the present invention is comprised Base) acrylate copolymer (A) and the kind of cellulose ester polymer (B) and the present invention phase retardation film in (methyl) third The difference of the content of olefin(e) acid polymer (A) and cellulose ester polymer (B), in face, phase contrast Re is in terms of the value of every 100 μm thickness, For more than 140nm and then be more than 150nm and below 500nm.
The degree of freedom of the control of the wavelength dispersibility of the phase contrast in the phase retardation film of the present invention is high, such as, becomes display The anti-wavelength dispersibility of phase contrast or the smooth phase retardation film of the wavelength dispersibility of phase contrast.As concrete example, become for In the face of each light of wavelength 447nm, 590nm and 750nm, phase contrast Re (447), Re (590) and Re (750) meet formula 0.8 Re (447) phase retardation film of the relation of/Re (590) 1.2 and 0.8 Re (750)/Re (590) 1.2.The phase contrast of the present invention The preferred Re of film (447), Re (590) and Re (750) meet formula 0.8 Re (447)/Re (590) 1.1 and 0.9 Re (750)/ The relation of Re (590) 1.2, more preferably meets formula 0.8 Re (447)/Re (590) 1.0 and 1.0 Re (750)/Re The relation of (590) 1.2.
In terms of the value measured according to JIS Z0208, the moisture permeability of every 100 μ m thick in the phase retardation film of the present invention is such as For 300g/m2Less than 24 hours.(methyl) acrylate copolymer (A) that phase retardation film according to the present invention is comprised and fiber (methyl) acrylate copolymer (A) and cellulose esters in the kind of element ester polymer (B) and the phase retardation film of the present invention gather The difference of the content of compound (B), this value is 250g/m2Less than 24 hours, 200g/m2Less than 24 hours, 150g/m2·24 Below hour, 130g/m2Less than 24 hours and then be 120g/m2Less than 24 hours.
The phase retardation film of the present invention demonstrates that the height of (methyl) acrylate copolymer (A) having ring structure based on main chain is resistance to Hot, its Tg for example, more than 110 DEG C.(methyl) acrylate copolymer (A) that phase retardation film according to the present invention is comprised and (methyl) acrylate copolymer (A) in the kind of cellulose ester polymer (B) and the phase retardation film of the present invention and cellulose The difference of the content of ester polymer (B), Tg is more than 120 DEG C, more than 125 DEG C and then be more than 130 DEG C.
The thickness of the phase retardation film of the present invention is not particularly limited, such as, be 10 μm～500 μm, be preferably 20 μm～ 300 μm, particularly preferably 30 μm～100 μm.
Nz coefficient shown by the phase retardation film of the present invention in terms of the value of the light for wavelength 590nm, preferably smaller than 1.20, More preferably less than 1.15, more preferably less than 1.10 and more than 0.95.In by the face of phase retardation film, phase contrast is set to Re, time the phase contrast of thickness direction is set to Rth, Nz coefficient is by the value represented by formula Nz=(Rth/Re)+0.5.
In terms of the value measured according to JIS K7361-1, total light penetration of the phase retardation film of the present invention be preferably 85% with Above, more preferably more than 90%, more preferably more than 91%.
In terms of value when thickness 50 μm measured according to JIS 7165, the mist degree of the phase retardation film of the present invention be preferably 5% with Under, more preferably less than 3%, more preferably less than 1%.
In the phase retardation film of the present invention, as required, the surface of the layer being made up of resin combination (C) can be formed various Functional coat.Functional coat for example, antistatic layer；The adhesive linkage such as adhesive phase, cement layers；Easily adhesive linkage；Anti-dazzle (anti-dazzle) layer；The stain-proofing layers such as photocatalyst layer；Anti-reflecting layer；Hard conating；Ultraviolet screener layer, heat ray shielding layer, electromagnetism Ripple screen layer；Gas-barrier layer.
The purposes of the phase retardation film of the present invention is not particularly limited, it is possible to for the use as existing phase retardation film On the way.The phase retardation film of the present invention is suitable for the optical compensation in the image display devices such as LCD.Additionally, in addition to lcds, moreover it is possible to It is enough in various image display device, Optical devices.
As required, the phase retardation film of the present invention can be with other optics combination, such as with the state being bonded with each other Use.
The phase retardation film of the present invention can utilize known film forming method and film drawing process by resin combination (C), Or by making front (methyl) acrylate copolymer (A) of resin combination (C) and cellulose ester polymer (B) manufactures.Tool Say body, such as, resin combination (C) is shaped to film and makes former film (unstretching film), and obtained former film is carried out Stretching.
Film forming method for example, solution-casting method (solution casting method), extrusion by melting, rolling process, extrinsion pressing. Wherein, preferably solution-casting method, extrusion by melting.
The drawing process of former film can be suitable for known simple tension maneuver or biaxial tension maneuver.
Extrusion by melting for example, T modulus method and inflation method.In T modulus method, at the front-end configuration T mould of melt extruder, and roll up Around the film melt extruded from this T mould, thus obtain the former film of wound into rolls.Now, additionally it is possible to adjust temperature and the speed of winding Degree, applies stretching (simple tension) in the extrusion direction of film.
When melt extruding, the preferably aerofluxus oral area from melt extruder carries out the devolatilization of volatile ingredient.It addition, squeeze melted When going out, the filtration of preferably suitable resin combination based on polymer filter.
Solution-casting method typically has (1) dissolution process, (2) curtain coating operation and (3) drying process.Each operation can be suitable for Known maneuver.
As long as the detailed process of dissolution process can obtain comprising main chain has (methyl) acrylate copolymer of ring structure (A) the most do not limit with the solution of cellulose ester polymer (B).The solvent enabling the polymer of both sides to dissolve uses dichloromethane The good solvents such as alkane, methyl acetate, dioxolanes, meanwhile, it is capable to share the poor solvents such as methanol, ethanol, butanol.As long as dissolving fibre Dimension element ester polymer (B), then can use the polymer solvent used when being polymerized (methyl) acrylate copolymer (A).
Curtain coating operation can be suitable for known solution coating method.The method is for employing such as die coating machine, scraper for coating The coating process of machine, roll coater, comma coating machine, lip coating machine etc..
As long as the detailed process of drying process is by being formed film by the dry of the curtain coating coated film that formed of operation, then do not have It is particularly limited to.
[image display device]
The image display device of the present invention possesses the phase retardation film of the present invention.Thus, formed image display feature excellent, Such as high-contrast and the image display device at wide visible angle.
The image display device of the present invention for example, LCD.
Embodiment
Hereinafter, the present invention is illustrated in greater detail by embodiment.The present invention is not limited to embodiment described below.
[mean molecule quantity]
Weight average molecular weight (Mw) and number-average molecular weight (Mn) use gel permeation chromatography (GPC) according to following mensuration bar Part is obtained by polystyrene conversion.
Mensuration system: east Cao manufactures GPC system HLC-8220
Developing solvent: chloroform (with Wako Pure Chemical Industries Manufacturing, superfine)
Solvent flux: 0.6mL/ minute
Standard specimen: TSK polystyrene standard (east Cao manufacture, PS-oligomer test kit)
Mensuration lateral column is constituted: east Cao manufacture, and TSK-GEL super HZM-M 6.0 × 150,2 is connected in series
East Cao manufacture, TSK-GEL super HZ-L 4.6 × 35,1
Reference lateral column is constituted: east Cao manufacture, and TSK-GEL SuperH-RC 6.0 × 150,2 is connected in series
Column temperature: 40 DEG C
[glass transition temperature]
Glass transition temperature (Tg) is obtained according to JIS K7121.Specifically, differential scanning calorimetry (DSC) is used (Rigaku manufactures, DSC-8230), (programming rate is in a nitrogen atmosphere from room temperature, the sample of about 10mg to be warming up to 200 DEG C 20 DEG C/min), obtain DSC curve, this DSC curve be evaluated according to initial point method.Reference uses Alpha-alumina.
[melt flow rate (MFR) (MFR)]
About MFR, according to JIS K6874, test temperature is set to 240 DEG C, test load is set to 10kg and obtains.
[optical characteristics of phase retardation film]
About phase contrast Re and the phase of thickness direction in the face for the light of wavelength 590nm in made phase retardation film Potential difference Rth, uses phase retardation film optical material to check the device RETS-100 (big electronic manufacture) condition with angle of incidence 40 ° It is evaluated.In face, phase contrast Re is defined by formula Re=(nx-ny) × d, and the phase contrast Rth of thickness direction is by formula Rth=[(nx+ Ny)/2-nz] × d defined.Herein, nx is the refractive index of the slow-axis direction in face, ny be in face with nx vertical direction Refractive index, nz is the refractive index of the thickness direction of film, and d is the thickness (nm) of film.Slow-axis direction is refractive index maximum in face Direction.About the Nz coefficient of made phase retardation film, by the value of Re and Rth obtained as mentioned above, according to formula Nz coefficient= (Rth/Re)+0.5 calculate.
Additionally, to phase contrast Re in the face for the light of wavelength 447nm and 750nm in the phase retardation film made (447) similarly evaluate with Re (750), take and phase contrast Re in the above-mentioned face for the light of wavelength 590nm obtained (590) ratio, thus obtains the value of Re (447)/Re (590) and Re (750)/Re (590).
[the photoelastic coefficient Cd of phase retardation film]
About the photoelastic coefficient of the light for wavelength 590nm in made phase retardation film, use ellipsometer (JASCO manufactures, M-150) is evaluated.Specifically, made phase retardation film is cut into draw direction for long limit 20mm × 50mm and make mensuration sample, attach it to the photoelasticity measuring means of ellipsometer, parallel with draw direction Ground applies mechanical load 3 birefringences of measurement on one side of 5N～25N, by during the light of use wavelength 590nm, birefringence is relative In the slope of stress as photoelastic coefficient.
[moisture permeability]
About the moisture permeability of made phase retardation film, under the condition determination of 40 DEG C, obtain according to JIS Z0208.With Under table in show that the thickness of the phase retardation film with every 100 μm carries out the value converted.
[mist degree]
The mist degree of made phase retardation film uses scopometer (Japan's electricity color industry manufacture, NDH5000) to be evaluated.Need It is noted that and utilizes this scopometer to implement mensuration based on JIS K7165.Following table shows every 50 μm thickness Value.
(manufacturing example 1)
Reaction unit to the internal volume 30L (liter) possessing agitating device, temperature sensor, cooling tube and nitrogen ingress pipe Middle input methyl methacrylate (MMA) 6000g, 2-(hydroxymethyl) acrylic acid methyl ester. (MHMA) 3000g, methacrylic acid are just Butyl ester (BMA) 1000g and the mixed solvent of methyl iso-butyl ketone (MIBK) (MIBK) and methyl ethyl ketone (MEK) as polymer solvent (weight ratio 9:1) 6667g, leads to nitrogen wherein while being warming up to 105 DEG C.After starting with the backflow together that heats up, add Add the 6.0g as polymerization initiator peroxidating different n-nonanoic acid tert-pentyl ester (Arkema YOSHITOMI manufacture, trade name: Luperox 570), in above-mentioned mixed solvent 3315g, dissolve above-mentioned peroxidating different n-nonanoic acid uncle penta with dropping in 3 hours simultaneously Ester 12.0g and the solution that obtains, carry out polymerisation in solution under about 95 DEG C～the backflow of 110 DEG C, and then carries out 4 hours ripe Change.Polyreaction rate is 90.5%, and the content of the MHMA unit in obtained polymer is 29.7 weight %.
Then, in obtained polymeric solution, add octyl phosphate/dioctyl ester mixture (chemistry manufacture, the business of 20g The name of an article: Phoslex A-8) as the catalyst (cyclization catalyst) of cyclized condensation reaction, under about 85 DEG C～the backflow of 100 DEG C Carry out 2 hours cyclized condensation reactions.And then, with 240 DEG C of heating 90 in the autoclave being forced into a maximum of about of 2MPa in terms of gauge pressure After minute, by the devolatilization in vented twin-screw extruder of obtained polymeric solution, extrusion, obtain main chain and there is lactonic ring knot Transparent (methyl) acrylate copolymer (A-1) of structure.The weight average molecular weight of polymer (A-1) is 13.4 ten thousand, and MFR is 14.5g/ 10 minutes, Tg was 130 DEG C.
(embodiment 1)
Polymer (A-1) 90 weight portion made in example 1 and cellulose-acetate propionate (B-1) [acetyl group replacement will be manufactured Spend 2.5 weight %, hydroxyl substitution value 1.8 weight %, propiono substitution value 46 weight %, number-average molecular weight Mn=6.3 ten thousand, Weight-average molecular Amount Mw=17.5 ten thousand] 10 weight portions are dissolved in dichloromethane, and the solution obtained by stirring, by polymer (A-1) and acetate propionate Cellulose (B-1) uniformly mixes.Then, obtained mixed solution is under reduced pressure dried 1 hour in 120 DEG C, obtains solid-state Resin combination 100 weight portion.
Then, obtained resin combination utilizing compression molding forming machine with 220 DEG C of compression moldings, making thickness is 126 μ The film (unstretching film) of m.Then, made film utilize cupping machine (INSTRON manufacture) with draw ratio 2 times and draw Stretch temperature 133 DEG C and carry out simple tension in MD direction, obtain the stretched film (F1) that thickness is 85 μm.The evaluation knot of stretched film (F1) Fruit is listed in the table below 1.
(embodiment 2)
Polymer (A-1) 70 weight portion and cellulose-acetate propionate (B-1) 30 weight portion are dissolved in dichloromethane, and And make the former film that thickness is 120 μm, obtain the stretched film (F2) that thickness is 82 μm the most similarly to Example 1.Draw The evaluation result stretching film (F2) is listed in the table below 1.
(embodiment 3)
Polymer (A-1) 50 weight portion and cellulose-acetate propionate (B-1) 50 weight portion are dissolved in dichloromethane, and And make the former film that thickness is 118 μm, obtain the stretched film (F3) that thickness is 83 μm the most similarly to Example 1.Draw The evaluation result stretching film (F3) is listed in the table below 1.
(comparative example 1)
Polymer (A-1) 10 weight portion and cellulose-acetate propionate (B-1) 90 weight portion are dissolved in dichloromethane, and And to make thickness be the former film of 104 μm, and to make draft temperature be 135 DEG C, obtains thickness the most similarly to Example 1 It it is the stretched film (F4) of 72 μm.The evaluation result of stretched film (F4) is listed in the table below 1.
[table 1]
As shown in table 1, compared with the stretched film of comparative example 1, the moisture permeability of the stretched film of embodiment 1～3 and photoelasticity system Number is low, obtains phase contrast in big face, and Nz coefficient is little simultaneously.It addition, the phase contrast in the stretched film of embodiment 1～3 demonstrates Smooth wavelength dispersibility or anti-wavelength dispersibility.
(manufacturing example 2)
Reaction unit to the internal volume 30L (liter) possessing agitating device, temperature sensor, cooling tube and nitrogen ingress pipe Middle input methyl methacrylate (MMA) 52 weight portion, 2-(hydroxymethyl) acrylic acid methyl ester. (MHMA) 30 weight portion, methyl-prop Olefin(e) acid N-butyl (BMA) 18 weight portion and methyl iso-butyl ketone (MIBK) (MIBK) and methyl ethyl ketone (MEK) as polymer solvent Mixed solvent (weight ratio 9:1) 67 weight portion, leads to nitrogen wherein while being warming up to 105 DEG C.With heat up returning together After stream starts, add peroxidating different n-nonanoic acid tert-pentyl ester (the Arkema YOSHITOMI of 0.06 weight portion as polymerization initiator Manufacture, trade name: Luperox 570), dissolve above-mentioned in above-mentioned mixed solvent 33 weight portion with dropping in 3 hours simultaneously Peroxidating different n-nonanoic acid tert-pentyl ester 0.12 weight portion and the solution that obtains, carry out solution under about 95 DEG C～the backflow of 110 DEG C Polymerization, and then carry out the ripening of 4 hours.
Then, in obtained polymeric solution, add octyl phosphate/dioctyl ester mixture (chemistry of 0.2 weight portion Manufacture, trade name: Phoslex A-8) as the catalyst (cyclization catalyst) of cyclized condensation reaction, at about 85 DEG C～100 DEG C Backflow under carry out 2 hours cyclized condensation reactions.Further, and then in the autoclave being forced into a maximum of about of 2MPa in terms of gauge pressure with 240 DEG C are heated 90 minutes.Then, the processing speed that obtained polymeric solution is scaled 2.0kg/ hour with amount of resin is imported Barrel zone temperature is 260 DEG C, rotating speed is 100rpm, vacuum is 13.3hPa～400hPa (10mmHg～300mmHg), final vacuum Mouthful number is 1, front-seat QI KOU number is in the vented twin-screw extruder (φ=30mm, L/D=40) of 4, in this extruder Implement further carrying out and devolatilization of cyclized condensation reaction.Thereafter, it is in the polymer of molten condition from this extruder extrusion, Obtain main chain have lactonic ring structure, have simultaneously 18 weight % of entire infrastructure unit BMA unit (methyl) acrylic acid gather The granule of compound (A-2).The weight average molecular weight of polymer (A-2) is 12.6 ten thousand, and Tg is 123 DEG C.It should be noted that BMA is mono- Unit is (methyl) acrylate unit shown in formula (1), is R1For normal-butyl, R2For CH3The construction unit of (methyl).
(manufacturing example 3)
The amount making each monomer in input reaction unit is MMA60 weight portion, MHMA30 weight portion and BMA10 weight portion, Obtain main chain in the same manner as example 2 and there is lactonic ring structure, there are 10 weight % of entire infrastructure unit simultaneously with manufacturing in addition The granule of (methyl) acrylate copolymer (A-3) of BMA unit.The weight average molecular weight of polymer (A-3) is 13.4 ten thousand, and Tg is 130℃。
(manufacturing example 4)
Not putting into BMA in reaction unit, the amount making the MMA in input reaction unit is 70 weight portions, makes the amount of MHMA It is 30 weight portions, obtains main chain in addition in the same manner as manufacturing example 2 and there is lactonic ring structure, do not have shown in formula (1) simultaneously The granule of (methyl) acrylate copolymer (C-1) of construction unit.The weight average molecular weight of polymer (C-1) is 17.0 ten thousand, Tg It it is 122 DEG C.
(manufacturing example 5)
Reaction unit to the internal volume 30L (liter) possessing agitating device, temperature sensor, cooling tube and nitrogen ingress pipe Middle input MMA24.5 weight portion, MHMA26 weight portion, ethyl methacrylate (EMA) 45 weight portion, N-VCz (NVCz) 4.5 weight portions and the mixed solvent of toluene 86.5 weight portion and methanol 3.5 weight portion as polymer solvent, to Wherein lead to nitrogen while being warming up to 95 DEG C.After starting with the backflow together that heats up, add 0.01 weight as polymerization initiator Peroxidating-2 ethyl hexanoic acid the tert-pentyl ester (Arkema YOSHITOMI manufacture, trade name: Luperox 575) of amount part, simultaneously one Limit is dissolved above-mentioned peroxidating-2 ethyl hexanoic acid tert-pentyl ester 0.10 weight portion with dropping in 8 hours in toluene 10 weight portion and is obtained Solution, under about 90 DEG C～the backflow of 100 DEG C, carry out polymerisation in solution, and then carry out the ripening of 12 hours.
Then, in obtained polymeric solution, add octyl phosphate/dioctyl ester mixture (chemistry of 0.2 weight portion Manufacture, trade name: Phoslex A-8) as the catalyst (cyclization catalyst) of cyclized condensation reaction, at about 80 DEG C～100 DEG C Backflow under carry out 2 hours cyclized condensation reactions.Further, and then in the autoclave being forced into a maximum of about of 2MPa in terms of gauge pressure with 240 DEG C are heated 90 minutes.Then, obtained polymeric solution is under reduced pressure dried 1 hour in 240 DEG C, obtains main chain and have Lactonic ring structure, there is (methyl) acrylate copolymer (A-4) of the EMA unit of 45 weight % of entire infrastructure unit simultaneously.Poly- The weight average molecular weight of compound (A-4) is 17.0 ten thousand, and Tg is 122 DEG C.It should be noted that EMA unit is (first shown in formula (1) Base) acrylic ester unit is R1For ethyl, R2For CH3The construction unit of (methyl).
(manufacturing example 6)
The amount making each monomer in input reaction unit is MMA44.5 weight portion, MHMA26 weight portion, EMA25 weight portion With NVCz4.5 weight portion, obtain main chain in the same manner as example 5 and there is lactonic ring structure, there is all knots simultaneously with manufacturing in addition (methyl) acrylate copolymer (A-5) of the EMA unit of 25 weight % of structure unit.The weight average molecular weight of polymer (A-5) is 17.0 ten thousand, Tg are 129 DEG C.
(manufacturing example 7)
In reaction unit, do not put into EMA, make the amount of the MMA in input reaction unit be 69.5 weight portions, make MHMA's The amount that amount is 26 weight portions, make NVCz is 4.5 weight portions, obtains main chain in addition and have lactonic ring in the same manner as manufacturing example 5 Structure, not there is (methyl) acrylate copolymer (C-2) of the construction unit shown in formula (1) simultaneously.The weight average of polymer (C-2) Molecular weight is 16.3 ten thousand, and Tg is 138 DEG C.
(manufacturing example 8)
Polymer (A-2) 70 weight portion made in example 2 and cellulose-acetate propionate (B-1) [acetyl group replacement will be manufactured Degree be 2.5 weight %, hydroxyl substitution value be 1.8 weight %, propiono substitution value be 46 weight %, number-average molecular weight Mn=6.3 ten thousand, weight Average molecular weight Mw=17.5 ten thousand] 30 weight portions are dissolved in dichloromethane, and the solution obtained by stirring, by polymer (A-2) and second Acid cellulose propionate (B-1) uniformly mixes.Then, obtained mixed solution is under reduced pressure dried 1 hour in 120 DEG C, Resin combination 100 weight portion to solid-state.
Then, obtained resin combination utilizing compression molding forming machine with 220 DEG C of compression moldings, making thickness is 50 μm Unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 9)
Polymer (A-2) 50 weight portion and cellulose-acetate propionate (B-1) 50 weight portion are uniformly mixed, in addition with Manufacture example 8 and similarly obtain unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 10)
Polymer (A-2) is replaced to use and manufacture the polymer (A-3) made in example 3, in addition as manufacturing example 8 Ground obtains unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 11)
Polymer (A-2) is replaced to use and manufacture the polymer (C-1) made in example 4, in addition as manufacturing example 8 Ground obtains unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 12)
Polymer (A-2) is replaced to use and manufacture the polymer (A-4) made in example 5, in addition as manufacturing example 8 Ground obtains unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 13)
Polymer (A-4) 50 weight portion and cellulose-acetate propionate (B-1) 50 weight portion are uniformly mixed, in addition with Manufacture example 12 and similarly obtain unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 14)
Polymer (A-2) is replaced to use and manufacture the polymer (A-5) made in example 6, in addition as manufacturing example 8 Ground obtains unstretching film.The evaluation result of obtained film is listed in the table below 2.
(manufacturing example 15)
Polymer (A-2) is replaced to use and manufacture the polymer (C-2) made in example 7, in addition as manufacturing example 8 Ground obtains film.The evaluation result of obtained film is listed in the table below 2.
[table 2]
※ MMA: methyl methacrylate, MHMA:2-(hydroxymethyl) acrylic acid methyl ester.
BMA: n-BMA, EMA: ethyl methacrylate, NVCz:N-VCz
As shown in table 2, compared with the film manufacturing example 11,15, manufacture the mist degree of the film of example 8～10 and manufacture example 12～14 Little, the transparency is excellent.Further, the biggest then institute of content of the BMA unit in (methyl) acrylate copolymer or EMA unit is confirmed The tendency that the mist degree of film that makes is the least.In addition, according to (methyl) in the film manufacturing example 8～10 and manufacture example 12～14 The difference of the content of (methyl) acrylate copolymer (A) in the composition of acrylate copolymer (A) and made film, this film Moisture permeability and photoelastic coefficient lower than the moisture permeability of film and photoelastic coefficient manufacturing example 11,15.
(embodiment 4)
Use cupping machine (INSTRON manufacture), unstretching film (wherein, the thickness of this film made in example 8 will be manufactured It is 120 μm) carry out simple tension with draw ratio 2 times and draft temperature 128 DEG C in MD direction, obtain the stretching that thickness is 87 μm Film (phase retardation film).The evaluation result of obtained phase retardation film is listed in the table below 3.
(embodiment 5)
Use and manufacture the unstretching film (wherein, the thickness of this film is 120 μm) made in example 9, in addition with embodiment 4 Similarly obtain the stretched film (phase retardation film) that thickness is 85 μm.The evaluation result of obtained phase retardation film is listed in the table below 3.
(embodiment 6)
Use and manufacture the unstretching film (wherein, the thickness of this film is 120 μm) made in example 10, make the draft temperature be simultaneously 133 DEG C, obtain the stretched film (phase retardation film) that thickness is 82 μm the most similarly to Example 4.Obtained phase contrast The evaluation result of film is listed in the table below 3.
(embodiment 7)
Use and manufacture the unstretching film (wherein, the thickness of this film is 123 μm) made in example 12, make the draft temperature be simultaneously 127 DEG C, obtain the stretched film (phase retardation film) that thickness is 86 μm the most similarly to Example 4.Obtained phase contrast The evaluation result of film is listed in the table below 3.
(embodiment 8)
Use and manufacture the unstretching film (wherein, the thickness of this film is 121 μm) made in example 13, in addition with embodiment 4 similarly obtain the stretched film (phase retardation film) that thickness is 84 μm.The evaluation result of obtained phase retardation film is listed in the table below 3.
(embodiment 9)
Use and manufacture the unstretching film (wherein, the thickness of this film is 126 μm) made in example 14, in addition with embodiment 4 similarly obtain the stretched film (phase retardation film) that thickness is 87 μm.The evaluation result of obtained phase retardation film is listed in the table below 3.
[table 3]
As shown in table 3, each phase retardation film made in embodiment 4～9 demonstrates phase contrast Re and thickness side in big face To positive phase contrast Rth, and, about phase contrast Re in face, demonstrate anti-wavelength dispersibility.
It should be noted that about in embodiment 4～9 make phase retardation film shown by mist degree and with embodiment 4 The mist degree shown by stretched film similarly stretched the unstretching film made in manufacture example 11,15 and make, is converted into Identical thickness is identical with the mist degree shown by the unstretching film (manufacturing example 8～15) before corresponding stretching.It addition, about reality Execute in example 4～9 make the photoelastic coefficient shown by phase retardation film and the moisture permeability of every 100 μ m thick and with embodiment 4 Similarly to manufacture the unstretching film made in example 11,15 stretch and photoelastic coefficient shown by the stretched film that makes and The moisture permeability of every 100 μ m thick, with the photoelastic coefficient shown by the unstretching film (manufacture example 8～15) before corresponding stretching and Moisture permeability is identical.
The present invention is intended to and internal feature without departing from it, then can be applicable to other embodiment.This description Disclosed embodiment is the embodiment illustrated in all respects, but is not limited to this.The scope of the present invention is by above-mentioned The claim of unaccounted institute apposition illustrates, all changes in the implication impartial with claim and scope are all contained in In the scope of the present invention.
Industrial applicibility
The phase retardation film of the present invention can be used in the purposes as existing phase retardation film, such as can be used in Various image display devices headed by LCD and Optical devices.

Claims (10)

1. a phase retardation film, it comprises the layer being made up of resin combination (C), and described resin combination (C) is included in main chain There is (methyl) acrylate copolymer (A) 30 weight % of ring structure～95 weight % and cellulose ester polymer (B) 5 weight % ～70 weight %,
Described ring structure is selected from lactonic ring structure, glutarimide structure, glutaric anhydride structure, N-substituted maleimide amine knot At least one in structure and maleic anhydride structure,
The absolute value of the photoelastic coefficient of the light for wavelength 590nm of described phase retardation film is 5 × 10-12Pa-1Hereinafter,
In terms of the value measured according to JIS Z0208, the moisture permeability of every 100 μ m thick of described phase retardation film is 300g/m224 is little Time below.
2. phase retardation film as claimed in claim 1, wherein, described (methyl) acrylate copolymer (A) has following formula (1) institute (methyl) acrylate unit shown as construction unit,
[chemical formula 1]
In formula (1), R1Be carbon number be the alkyl of 2～18, R2It is H or CH3。
3. phase retardation film as claimed in claim 2, wherein, described (methyl) acrylate copolymer (A) has methacrylic acid Methyl ester unit and 2-(hydroxymethyl) acrylic ester unit.
4. phase retardation film as claimed in claim 2, wherein, described (methyl) acrylate copolymer (A) has methacrylic acid Methyl ester unit, 2-(hydroxymethyl) acrylic ester unit and N-VCz unit.
5. phase retardation film as claimed in claim 1, wherein, described (methyl) acrylate copolymer (A) has methacrylic acid Methyl ester unit.
6. phase retardation film as claimed in claim 1, wherein, described cellulose ester polymer (B) is cellulose acetate, acetic acid third Acid cellulose or cellulose acetate-butyrate.
7. phase retardation film as claimed in claim 1, wherein, described phase retardation film for wavelength 447nm, 590nm and 750nm Each light face in phase contrast Re (447), Re (590) and Re (750) meet following relation:
0.8 Re (447)/Re (590) 1.2, and
0.8≦Re(750)/Re(590)≦1.2。
8. phase retardation film as claimed in claim 1, wherein, the thickness measured according to JIS K7165 of described phase retardation film Mist degree during 50 μm is less than 5%.
9. phase retardation film as claimed in claim 1, wherein, the Nz coefficient of described phase retardation film is with the light for wavelength 590nm Value be calculated as less than 1.15,
Described Nz coefficient calculates according to formula Nz coefficient=(Rth/Re)+0.5, in wherein said phase retardation film for wavelength In the face of the light of 590nm, phase contrast Re is defined by formula Re=(nx-ny) × d, and the phase contrast Rth of thickness direction is by formula Rth= [(nx+ny)/2-nz] × d is defined, and herein, nx is the refractive index of the slow-axis direction in face, and ny is that face is interior vertical with nx The refractive index in direction, nz is the refractive index of the thickness direction of film, and d is the thickness of film, and this thickness unit is nm.
10. an image display device, it possesses the phase retardation film described in any one of claim 1～9.
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