CN102236120A - Optical film, polarizer protective film, polarizing plate and image display device - Google Patents
Optical film, polarizer protective film, polarizing plate and image display device Download PDFInfo
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- CN102236120A CN102236120A CN2011101020456A CN201110102045A CN102236120A CN 102236120 A CN102236120 A CN 102236120A CN 2011101020456 A CN2011101020456 A CN 2011101020456A CN 201110102045 A CN201110102045 A CN 201110102045A CN 102236120 A CN102236120 A CN 102236120A
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- C08L33/04—Homopolymers or copolymers of esters
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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
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G—PHYSICS
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- 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
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Abstract
The invention provides an optical film, a polarizer protective film, a polarizing plate and an image display device. The optical film in the invention comprises a (methyl) acrylic acid polymer (c) with an N- substitute maleimide unit (a) and a (methyl) acrylic acid ester unit (b) as the structural unit. The N- substitute maleimide unit (a) is a structural unit applying effect of positive fixing double refraction upon the (methyl) acrylic acid polymer (c). The (methyl) acrylic acid ester unit (b) is a structural unit applying effect of negative fixing double refraction upon the (methyl) acrylic acid polymer (c). The optical film in the invention displays an inplane phase difference Re in the range of 0nm to 10nm, and a thickness direction phase Rth in the range of -10nm to 10nm with respective to light with wavelength of 589nm. The optical film in the invention is a bidirectional stretching film. Although the optical film is a bidirectional stretching film, the displayed phase direction is small and high heat resistance is provided.
Description
Technical field
The present invention relates to a kind of as the low blooming of the phase differential of biaxial stretching film.In addition, the present invention relates to polarizer protection film, polaroid and image display device.
Background technology
In recent years, the market of the such flat type image display device of liquid crystal indicator (LCD) enlarges.In image display device, use blooming.For blooming, not only require the transparency, and the corresponding optical characteristics of tightly being adjusted like that with the optical design of image display device of requirement.One of optical characteristics is a phase differential.For example, used polarizer protection film in the polaroid for LCD requires to approach zero phase differential.In the blooming used macromolecular material demonstrate usually based on along the direction of high polymer main chain and with the direction of this main chain quadrature between the different birefringence of refractive index.Therefore, when only selecting the high macromolecular material of the transparency, can not get can be used for the little blooming of phase differential of polarizer protection film.
By using the little macromolecular material of above-mentioned refringence, can obtain the little blooming of phase differential.Such material is the such cellulose derivative of triacetyl cellulose typically.But the phase differential of the thickness direction of the blooming that is formed by cellulose derivative is big, and is therefore, big for the birefringence from the incident light of vergence direction.The angle of visibility characteristic of the big picture image display device that the shown such birefringent characteristic of cellulose derivative makes image display device, particularly developing in recent years reduces.
Macromolecular material beyond the cellulose derivative can be used for polarizer protection film.Patent documentation 1 (TOHKEMY 2000-206333 communique) discloses the film formed polarizer protection film of two-way stretch by polymethylmethacrylate (PMMA).The speciality that this polarizer protection film has little phase differential and comes from PMMA, for example, good processing and forming, high skin hardness, high light penetration and low wavelength dependency.
Therewith mutually independently, as the macromolecular material that can be used for blooming, known (methyl) acrylate copolymer that on main chain, has ring structure.Compare glass transition temperature (Tg) height at (methyl) acrylate copolymer that has ring structure on the main chain with (methyl) acrylate copolymer that on main chain, does not have ring structure.High Tg is implemented in the blooming of thermotolerance aspect excellence.In image display device for example, can easily be configured in position at the blooming of excellence aspect the thermotolerance near heat units such as light sources.In addition, also have various advantages in the practicality at the blooming of excellence aspect the thermotolerance.Patent documentation 2 (TOHKEMY 2007-31537 communique) discloses a kind of by substituent A r
1The blooming that forms for the multipolymer of the N-substituted maleimide amine ring structure of aromatic group and (methyl) acrylic ester unit.The blooming of patent documentation 2 is not a polarizer protection film, and it shows the interior phase differential of big face of maximum 400nm.
Patent documentation 1: TOHKEMY 2000-206333 communique
Patent documentation 2: TOHKEMY 2007-31537 communique
Summary of the invention
Used PMMA has intrinsic birefringence in the patent documentation 1, although it is less.Therefore, disclosed polarizer protection film demonstrates the phase differential of the thickness direction that is produced by two-way stretch in the patent documentation 1.The angle of visibility characteristic that the phase place official post of thickness direction possesses the image display device of this polarizer protection film reduces.In addition, the Tg of PMMA is low, is about 100 ℃.Therefore, in reality, be difficult to this polarizer protection film is used for the image display device of requirement high-fire resistance.
On the other hand, the resin molding that is formed by the multipolymer with patent documentation 2 disclosed N-substituted maleimide amine structures is positioned on the main chain of this multipolymer owing to N-substituted maleimide amine structure, thereby hard, is short of aspect flexible.Can be by stretching this resin molding, improve intensity and flexible and so on mechanical property, can use as blooming.In fact, the blooming of patent documentation 2 is a stretched film.But, by stretching, produce the birefringence that comes from N-substituted maleimide amine structure, therefore be difficult to use as requiring to approach the polarizer protection film of zero little phase differential.
In addition, by two-way stretch, the mechanical property of intensity and flexible and so on resin molding is compared when carrying out unilateral stretching and is improved.But, compare with unilateral stretching, during two-way stretch, the phase difference variable of thickness direction is big usually.For polarizer protection film, expect that not only phase differential is as far as possible little in the face, and the phase differential of expectation thickness direction is also as far as possible little.
The object of the present invention is to provide a kind of blooming, though it is a biaxial stretching film, shown phase differential is little, have high-fire resistance.
Blooming of the present invention comprises (methyl) acrylate copolymer (c) ((メ タ) ア Network リ Le polymer (c)), should (methyl) acrylate copolymer (c) has N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b) as structural unit.Above-mentioned N-substituted maleimide amine unit (a) is to have to give the structural unit of just intrinsic birefringent effect to above-mentioned (methyl) acrylate copolymer (c).Above-mentioned (methyl) acrylic ester unit (b) is to have the structural unit of above-mentioned (methyl) acrylate copolymer (c) being given negative intrinsic birefringent effect.What blooming of the present invention was shown is more than the 0nm and below the 10nm for phase differential Re in the face of the light of wavelength 589nm.The shown phase differential Rth for the thickness direction of the light of wavelength 589nm of blooming of the present invention is-more than the 10nm and below the 10nm.Blooming of the present invention is a biaxial stretching film.
Herein, with the slow axis (Rather-late Xiang Shaft in the face of above-mentioned blooming) refractive index of direction is made as nx, with the fast axle (Jin Xiang Shaft in above-mentioned) refractive index of direction be made as ny, with the refractive index of the thickness direction of above-mentioned blooming be made as nz, when the thickness of above-mentioned blooming is made as d, the phase differential Rth of phase differential Re and thickness direction is respectively by formula Re=(nx-ny) * d and formula Rth={ (nx+ny)/defined value of 2-nz} * d in the face.
Have the structural unit of giving just intrinsic birefringent effect to polymkeric substance and be meant, when forming the homopolymer of this structural unit, this homopolymer shows just intrinsic birefringent structural unit.Have the structural unit of giving negative intrinsic birefringent effect to polymkeric substance and be meant that when forming the homopolymer of this structural unit, this homopolymer shows negative intrinsic birefringent structural unit.
Strand at polymkeric substance is in the layer (for example film) of uniaxial orientation, the intrinsic birefringent positive and negative of polymkeric substance can be judged based on following " n1-n2 ": among the light perpendicular to the interarea incident of this layer, " layer refractive index n 1 " is the refractive index with respect to the layer of the vibration component parallel with the direction (axis of orientation) of molecular chain orientation in this layer, " refractive index n 2 of layer " is the refractive index with respect to the layer of the vibration component vertical with axis of orientation, and the value that deducts " refractive index n 2 of layer " from " refractive index n 1 of layer " is " n1-n2 ".For each polymkeric substance, intrinsic birefringent value can be utilized based on the calculating of its molecular structure and try to achieve.
Polarizer protection film of the present invention is made of the blooming of the invention described above.
Polaroid of the present invention possesses the polarizer protection film and the polariscope of the invention described above.
Image display device of the present invention possesses the blooming of the invention described above.
In the present invention, (methyl) acrylate copolymer (c) is used for blooming, and described (methyl) acrylate copolymer (c) has N-substituted maleimide amine unit (a) (its have give just intrinsic birefringent effect to polymkeric substance) and (methyl) acrylic ester unit (b) (its have give negative intrinsic birefringent effect to polymkeric substance) as structural unit.Thus, can realize a kind of blooming, although it is a biaxial stretching film, its shown phase differential is little, have high-fire resistance.
Description of drawings
Fig. 1 is the sectional view that schematically shows an example of blooming of the present invention.
Fig. 2 is the sectional view that schematically shows an example of polarizer protection film of the present invention.
Fig. 3 is the sectional view that schematically shows an example of polaroid of the present invention.
Fig. 4 is the sectional view that schematically shows an example of image display device of the present invention.
Embodiment
The following describes preferred implementation of the present invention.The present invention is not limited to following embodiment.
[(methyl) acrylate copolymer (c)]
Used (methyl) acrylate copolymer (c) has N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b) as structural unit in the blooming of the present invention.N-substituted maleimide amine unit (a) has gives just intrinsic birefringent molecular structure to (methyl) acrylate copolymer (c) with this unit.
N-substituted maleimide amine unit (a) is preferably has the N-alkyl substituted maleimide amine of polymkeric substance being given just intrinsic birefringent effect.As substituent alkyl for example is 1～20 alkyl for carbon number, is preferably carbon number and is 1～20 aliphatic alkyl.Alkyl can be straight chain shape, chain and ring-type.N-substituted maleimide amine unit (a) for example is the structural unit from each monomers such as N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, N-normal-butyl maleimide, N-isobutyl maleimide, N-tert-butyl group maleimide, N-n-hexyl maleimide, N-2-ethylhexyl maleimide, N-dodecyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-benzyl maleimides.(methyl) acrylate copolymer (c) can comprise in these N-substituted maleimide amine units more than a kind or 2 kinds.From the aspect that the thermal stability and the optical characteristics of blooming uprises, N-substituted maleimide amine unit (a) is preferably N-cyclohexyl maleimide amine unit especially.
Need to prove, such shown in patent documentation 2 (TOHKEMY 2007-31537 communique), with aromatic group Ar
1Usually have as substituent N-substituted maleimide amine unit (for example, N-phenylmaleimide unit, N-chlorphenyl maleimide amine unit, N-aminomethyl phenyl maleimide amine unit, N-methoxyphenyl maleimide amine unit, N-naphthyl maleimide amine unit) and to give negative intrinsic birefringent effect polymkeric substance.
(methyl) acrylic ester unit (b) has gives negative intrinsic birefringent molecular structure to (methyl) acrylate copolymer (c) with this unit.
In (methyl) acrylate copolymer (c), N-substituted maleimide amine unit (a) has the just intrinsic birefringent effect of giving, and (methyl) acrylic ester unit (b) has the negative intrinsic birefringent effect of giving.Therefore, as (methyl) acrylate copolymer (c) of the multipolymer of structural unit when being stretched, cancel out each other by the birefringence that both structural unit produces with both.Thus, be all little blooming of phase differential Rth of interior phase differential Re of biaxial stretching film face and thickness direction although can obtain.
To give negative intrinsic birefringent effect to polymkeric substance just unqualified as long as have for (methyl) acrylic ester unit (b).(methyl) acrylic ester unit (b) for example is from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid chloromethyl ester, (methyl) acrylic acid-2-chloroethene ester, methacrylic acid-2-hydroxy methacrylate, (methyl) acrylic acid-3-hydroxy propyl ester, (methyl) acrylic acid-2,3,4,5, the own ester of 6-penta hydroxy group, (methyl) acrylic acid-2,3,4, the structural unit of each monomer such as 5-tetrahydroxy pentyl ester.(methyl) acrylate copolymer (c) can comprise in these (methyl) acrylic ester unit more than a kind or 2 kinds.From the aspect that the thermal stability and the optical characteristics of blooming uprises, (methyl) acrylic ester unit (b) is preferably methyl methacrylate (MMA) unit especially.Need to prove that the blooming that is formed by the PMMA as the homopolymer of MMA unit demonstrates particularly by two-way stretch that the phase differential Rth of thickness direction becomes big tendency.
It is above and 30 quality % following, more preferably 5 quality % are above and 25 quality % are following, more preferably 8 quality % are above and 22 quality % are following, it is above and below the 22 quality % to be preferably 10 quality % especially that the content of the N-substituted maleimide amine unit (a) in (methyl) acrylate copolymer (c) is preferably 5 quality %.It is above and 95 quality % following, more preferably 75 quality % are above and 95 quality % are following, more preferably 78 quality % are above and 92 quality % are following, it is above and below the 90 quality % to be preferably 78 quality % especially that the content of (methyl) acrylic ester unit (b) in (methyl) acrylate copolymer (c) is preferably 70 quality %.Under N-substituted maleimide amine unit (a) in (methyl) acrylate copolymer (c) and the situation of content in these scopes of (methyl) acrylic ester unit (b), although can obtain for the shown phase differential of biaxial stretching film littler, have a higher stable on heating blooming.In addition, although be biaxial stretching film, in whole visible domain (approximately more than the 380nm and below the 750nm), the phase differential Rth of phase differential Re and thickness direction is inhibited in the face.
Have N-substituted maleimide amine unit (a) as structural unit by (methyl) acrylate copolymer (c), the glass transition temperature (Tg) of this polymkeric substance (c) is improved.Thus, the thermotolerance that contains the blooming of this polymkeric substance (c) is improved.The Tg of (methyl) acrylate copolymer (c) for example is more than 110 ℃.According to the kind and the content of N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b), the Tg of (methyl) acrylate copolymer (c) is more than 115 ℃, more than 120 ℃, further be more than 125 ℃.Because the Tg of (methyl) acrylate copolymer (c) is so high, thereby blooming of the present invention is suitable for the image display device that the radiator body that power supply, light source and semiconductor circuit is such is contained in narrow space to high-density.The upper limit to the Tg of (methyl) acrylate copolymer (c) is not particularly limited, and is easy to the aspect but become from this polymkeric substance and the moulding that contains the resin combination of this polymkeric substance, is preferably below 200 ℃.
In addition, the content of N-substituted maleimide amine unit (a) is many more, and the Tg of (methyl) acrylate copolymer (c) is high more.But, when this content surpasses 30 quality %, the many tendencies of quantitative change that remain in the monomer in (methyl) acrylate copolymer (c) are arranged.Under the many situation of the amount of residual monomer, the operation reduction when sometimes the resin combination that contains (methyl) acrylate copolymer (c) being carried out processing and forming, the throughput rate of blooming reduces.
N-substituted maleimide amine unit (a) is the ring structure on the main chain that is positioned at (methyl) acrylate copolymer (c).As the ring structure on the main chain that imports to (methyl) acrylate copolymer in order to adjust Tg and/or optical characteristics, also known maleic anhydride structure and glutaric anhydride structure.Compare with (methyl) acrylate copolymer that has these other ring structure on main chain, (methyl) acrylate copolymer (c) with N-substituted maleimide amine unit (a) is difficult to take place thermal decomposition.Utilize this feature, for example (methyl) acrylate copolymer (c) and the resin combination that contains this polymkeric substance (c) (are for example being carried out melt filteration, utilize the melt filteration of polymer filter) and/or during melt molding, can suppress the foaming that the thermal decomposition by (methyl) acrylate copolymer (c) causes.Foaming becomes the optical defect of blooming.Therefore, to have on main chain that blooming of the present invention that ring structure suppressed (methyl) acrylate copolymer (c) of the foaming that caused by thermal decomposition is suitable for the image display device be the optical applications of representative although contain.
The weight-average molecular weight of (methyl) acrylate copolymer (c) is preferably 2,000～1, and 000,000, more preferably 10,000～500,000, more preferably 50,000～300,000.
(methyl) acrylate copolymer (c) just can have structural unit (d) except that N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b) as long as can obtain effect of the present invention.The content of the structural unit (d) in (methyl) acrylate copolymer (c) be preferably 0～10 quality %, more preferably 0～5 quality %, more preferably 0～2 quality %, be preferably 0～1 quality % especially.
Structural unit (d) in (methyl) acrylate copolymer (c) is from carrying out the structural unit of the monomer of polymerization with " being the monomer of N-substituted maleimide amine unit (a) by being polymerized " and " being the monomer of (methyl) acrylic ester unit (b) by being polymerized " the two monomer.Structural unit (d) for example is from acrylic acid, methacrylic acid, butenoic acid, maleic anhydride, 2-(hydroxymethyl) acrylic acid, 2-(hydroxyethyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid three ring [5.2.1.0
2,6] last of the ten Heavenly stems-8-base ester ((メ タ) ア Network リ Le acid ジ シ Network ロ ペ Application タ ニ Le), (methyl) acrylic acid three ring [5.2.1.0
2,6] last of the ten Heavenly stems-8-base-oxygen ethyl ester ((メ タ) ア Network リ Le acid ジ シ Network ロ ペ Application タ ニ Le オ キ シ エ チ Le), styrene, vinyltoluene, α-Jia Jibenyixi, alpha-hydroxymethyl styrene, α-hydroxyethylbenzene ethene, vinyl cyanide, methacrylonitrile, methallyl alcohol, allyl alcohol, ethene, propylene, 4-methyl-1-pentene, vinyl acetate, 2-hydroxymethyl-1-butylene, methyl vinyl ketone, the N-vinyl pyrrolidone, the structural unit of each monomer such as N-vinylcarbazole.As long as can obtain effect of the present invention, (methyl) acrylate copolymer (c) can have the structural unit (d) more than 2 kinds.
Structural unit (d) has for example suppressed that the Tg of (methyl) acrylate copolymer (c) becomes too high, therefore can join in this polymkeric substance (c).
[blooming]
One example of blooming of the present invention shown in Fig. 1.Blooming 1 shown in Figure 1 comprises (methyl) acrylate copolymer (c), should (methyl) acrylate copolymer (c) has N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b) as structural unit.Typically, blooming 1 is formed by the resin combination that contains (methyl) acrylate copolymer (c).
Blooming 1 shows more than the 0nm and phase differential Re in the face below the 10nm for the light of wavelength 589nm.Blooming 1 is for more than the light demonstration-10nm of wavelength 589nm and the phase differential Rth of the thickness direction below the 10nm.The phase differential Rth of phase differential Re and thickness direction all demonstrates less phase differential in the face of blooming 1, is suitable as polarizer protection film and uses.Particularly, the phase differential Rth of thickness direction means for a short time in the image display device of big picture and can guarantee sufficient angle of visibility characteristic.
Blooming 1 is a biaxial stretching film.By two-way stretch, blooming 1 is as blooming, particularly demonstrate sufficient mechanical property (for example, intensity and flexible) as polarizer protection film.Usually, in biaxial stretching film, even suppressed phase differential Re in the face, the phase differential Rth that also has thickness direction becomes big tendency.But although blooming 1 is a biaxial stretching film, the phase differential Rth of thickness direction is also little.
Composition according to the material that constitutes blooming 1 utilizes two-way stretch, and as blooming, when particularly demonstrating sufficient mechanical property as polarizer protection film, the phase differential Rth of phase differential Re and/or thickness direction further diminishes in the face.In blooming 1, for phase differential Re in the face of the light of wavelength 589nm be preferably more than the 0nm and less than 10nm, more preferably more than the 0nm and below the 5nm, more preferably more than the 0nm and below the 3nm, be preferably more than the 0nm especially and below the 2nm.In blooming 1, for the phase differential Rth of the thickness direction of the light of wavelength 589nm be preferably-more than the 5nm and below the 5nm, more preferably-more than the 3nm and below the 3nm, more preferably-more than the 2nm and below the 2nm.It is the image display device of representative that the blooming 1 of the interior phase differential Re of face that demonstration is so little and/or the phase differential Rth of thickness direction is particularly suitable for LCD.Can obtain good angle of visibility characteristic, contrast-response characteristic.
Blooming 1 is by two-way stretch, and as blooming, when particularly demonstrating sufficient mechanical property as polarizer protection film, the phase differential Rth of phase differential Re and thickness direction is little in the face in whole visible domain.For example, be more than the 0nm and below the 10nm at phase differential Re in the face of the light of the light of wavelength 400nm and wavelength 750nm.According to the composition of the material that constitutes blooming 1, be more than the 0nm and below the 5nm, more than the 0nm and below the 3nm, further for more than the 0nm and below the 2nm at phase differential Re in the face of the light of the light of wavelength 400nm and wavelength 750nm.For example, the phase differential Rth at the thickness direction of the light of the light of wavelength 400nm and wavelength 750nm be-more than the 10nm and below the 10nm.According to the composition of the material that constitutes blooming 1, at the phase differential Rth of the thickness direction of the light of the light of wavelength 400nm and wavelength 750nm be-more than the 5nm and below the 5nm ,-more than the 3nm and below the 3nm, further be-more than the 2nm and below the 2nm.
Blooming 1 be preferably more than the 0nm at phase differential Re in the face of the light of wavelength 400nm and wavelength 750nm and below the 5nm, at the phase differential Rth of the thickness direction of the light of wavelength 400nm and wavelength 750nm be preferably-more than the 10nm and below the 10nm.
The birefringence of the film thickness direction of representing with Rth/d of blooming 1 is preferably-2 * 10
-4More than and 2 * 10
-4Below, more preferably-1 * 10
-4More than and 1 * 10
-4Below, more preferably-0.5 * 10
-4More than and 0.5 * 10
-4Below.In above-mentioned scope, the birefringence of the thickness direction of blooming 1 is little, and the setting degree of freedom of the thickness of this film is improved thus.More particularly, needn't make the thickness of blooming 1 too small, just can set and take into full account intensity and flexible thickness.That is, by being set in the above-mentioned scope, the intensity of blooming 1 and flexible aspect favourable.Need to prove that Rth is that d is the thickness (unit is nm) of blooming at the phase differential (unit is nm) of the thickness direction of the blooming of the light of wavelength 589nm.
Blooming 1 has N-substituted maleimide amine unit (a) (methyl) acrylate copolymer (c) as structural unit owing to comprising, therefore excellence aspect thermotolerance.The Tg of blooming 1 for example is more than 110 ℃.According to the content of the composition of (methyl) acrylate copolymer (c) and this polymkeric substance (c) in the blooming 1, the Tg of blooming 1 is more than 115 ℃, more than 120 ℃, further be more than 125 ℃.Blooming 1 with so high Tg is suitable for the image display device that the radiator body that power supply, light source and semiconductor circuit is such is contained in narrow space to high-density.Blooming 1 with high Tg for example can easily be configured in the position of heat units such as close light source in image display device, the design freedom that therefore possesses the image display device of this film 1 also is improved.The upper limit to the Tg of blooming 1 is not particularly limited, but from the aspect of the mouldability of this film 1, be preferably below 200 ℃, more preferably below 180 ℃.
It is above and 100 quality % following, more preferably 70 quality % are above and 100 quality % are following, more preferably 80 quality % are above and 100 quality % are following, it is above and below the 100 quality % to be preferably 90 quality % especially that the content of (methyl) acrylate copolymer (c) in the blooming 1 is preferably 60 quality %.Blooming 1 can be formed by (methyl) acrylate copolymer (c).
Blooming 1 can contain the material except that (methyl) acrylate copolymer (c), and the content of this material is counted less than 40 quality %, is preferably less than 10 quality % with the content in the resin combination that constitutes blooming 1.
This material for example is the thermoplastic resin that has compatibility with this polymkeric substance (c) except that (methyl) acrylate copolymer (c).This thermoplastic resin for example is tygon, polypropylene, ethylene-propylene copolymer, poly-olefin polymers such as (4-methyl-1-pentenes); Polymer containing halogens such as vinyl chloride, ethlyene dichloride base resin; Styrene polymers such as polystyrene, styrene-methylmethacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene (ABS) segmented copolymer; Polymethylmethacrylate etc. (methyl) acrylate copolymer; Polyester such as polyethylene terephthalate, polybutylene terephthalate, PEN; Cellulose esters such as triacetyl cellulose; Polyamide such as nylon 6, nylon 66, NYLON610; Polyacetal: polycarbonate; Polyphenylene oxide; Polyphenylene sulfide: polyetheretherketone; The polyethers nitrile; Polysulfones; Polyethersulfone; The polyoxy benzene methyl; Polyamidoimide.
This material for example is an adjuvant.Adjuvant for example is ultraviolet light absorbers such as benzotriazole system, benzophenone series, salicylate system, benzoic ether system, triazine system; Antioxidants such as phenol system, phosphoric acid system, thioether system; Phase differential rising agent, phase differential depressant equiphase difference are adjusted agent; Stabilizing agents such as phase differential stabilizing agent, fast light stabilizing agent, weather-proof stabilizing agent, thermal stabilizer; Reinforcing material such as glass fibre, carbon fiber; Near infrared ray absorption; Fire retardants such as three (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; With negative ion system, kation system, nonionic is that surfactant is the antistatic agent of representative; Colorants such as inorganic pigment, organic pigment, dyestuff; Organic filler, inorganic filler; Modifier; Plastifier; Lubricant; Fire retardant; Rubber polymer such as ASA, ABS etc.The addition of these adjuvants in blooming 1 for example is more than the 0 quality % and below the 5 quality %, be preferably more than the 0 quality % and below the 2 quality %, more preferably more than the 0 quality % and below the 0.5% quality %.If the addition of adjuvant is too much, then when forming blooming 1, is easy to generate and oozes out and/or crazing.
Thickness to blooming 1 is unqualified.The thickness of blooming 1 for example is that 5 μ m are above and 250 μ m following, it is above and 150 μ m are following, more preferably 20 μ m are above and below the 80 μ m to be preferably 10 μ m.Under the situation of thickness, sometimes as the insufficient strength of blooming less than 5 μ m.If thickness is greater than 250 μ m, then the birefringence of film becomes excessive sometimes.
Manufacture method to blooming 1 is unqualified.Method that can application of known is made blooming 1.For example, will contain the resin combination moulding of (methyl) acrylate copolymer (c) and form film, resulting film will be carried out two-way stretch, make blooming 1 thus.
The method that the resin combination moulding is formed film is not particularly limited, is moulding by casting for example, melt extrudes moulding, compression moulding.
As mentioned above, (methyl) acrylate copolymer (c) is difficult to take place thermal decomposition.Therefore, blooming 1 can preferably utilize the moulding manufacturing that melt extrudes.
Melt extruding moulding for example implements at the resin combination that contains (methyl) acrylate copolymer (c).For example, other the mixers such as components utilising Omni (オ system ニ) mixer in (methyl) acrylate copolymer (c) and this resin combination are carried out premixed after, from mixing roll, extrude mixing resulting potpourri, can form resin combination thus.Mixing roll can be suitable for known mixing roll (for example, single screw extrusion machine, the such extruder of double screw extrusion machine) and pressurization kneader.
For melt extruding moulding, for example carry out according to T modulus method, blow moulding.The temperature (forming temperature) that melt extrudes moulding be preferably more than 200 ℃ and below 350 ℃, more preferably more than 250 ℃ and below 300 ℃, more preferably more than 255 ℃ and below 300 ℃, be preferably more than 260 ℃ especially and below 300 ℃.
When utilizing the T modulus method, reel, can obtain being wound on the film on the roller by will the film of extruding the extruder of T mould being installed from leading section.At this moment, can be by control coiling temperature and speed, can be at film extrude direction stretched (unilateral stretching).
Using in melt extruding moulding under the situation of extruder, the kind of extruder is not particularly limited, can be single screw rod, twin-screw and multiscrew.The resin combination that contains (methyl) acrylate copolymer (c) in order to make fully plastifies and obtains good mixing state, the L/D value of extruder (L is that length, the D of the machine barrel of extruder is the internal diameter of machine barrel) be preferably more than 10 and 100 following, more preferably 15 or more and below 80, more preferably more than 20 and below 60.The L/D value less than 10 situation under, abundant plasticizing resin composition sometimes, and can not obtain good mixing state.Under the L/D value surpassed 100 situation, shear heat evolution excessively was applied to resin combination, so the composition that resin combination the contained easy thermal decomposition that becomes.
In this case, the design temperature of machine barrel is preferably more than 200 ℃ and below 350 ℃, more preferably more than 250 ℃ and below 320 ℃.Design temperature less than 200 ℃ situation under, the melt viscosity that contains the resin combination of (methyl) acrylate copolymer (c) becomes too high, the throughput rate of film reduces.Surpass under 350 ℃ the situation at design temperature, thermal decomposition takes place in composition that resin combination contained easily sometimes.
In melt extruding moulding, use under the situation of extruder, the shape of extruder is not particularly limited.Extruder preferably has the open row gas port portion more than 1.By using such extruder, can attract to divide from open row gas port portion and vent one's spleen.Thus, the amount that remains in the volatile ingredient in the resulting film reduces.To vent one's spleen in order attracting to divide, for example to make open row gas port portion be in decompression state from open row gas port portion.The vacuum tightness of this moment in the pressure (absolute pressure) of open row gas port portion be preferably 1.3hPa above and 931hPa is following, more preferably more than the 13.3hPa and below the 798hPa.Pressure in open row gas port portion is higher than under the situation of 931hPa, and volatile ingredient and/or the monomer that decomposition produced by the composition that resin combination contained remain in the resulting film easily.On the other hand, in the industrial level that is difficult to the pressure of open row gas port portion is remained below 1.3hPa.
When melt extruding moulding, preferably, the resin combination that contains (methyl) acrylate copolymer (c) that uses polymer filter will be in molten condition carries out melt filteration.By melt filteration, the foreign matter that is present in the resin combination is removed.Therefore, reduce the optical defect in the blooming finally obtain and the amount of apparent shortcoming.As mentioned above, (methyl) acrylate copolymer (c) is difficult to take place thermal decomposition, therefore is difficult to produce foaming when melt filteration.But, can become the reason of the shortcoming that in resulting film, produces perforation, current mark and this class of flow liner in the melt filteration under the too high temperature.These shortcomings particularly take place when film continuously shaped easily.Consider these situations, in order to shorten the residence time of said composition in polymer filter by the melt temperature that reduces resin combination, the temperature that melt extrudes moulding for example is more than 200 ℃ and below 350 ℃, be preferably more than 250 ℃ and below 320 ℃.
Formation to polymer filter is not particularly limited.Can be fit to use the polymer filter that has disposed multi-disc leaf dish-type filtrator in the enclosure.The filter material of leaf dish-type filtrator can use metallic fiber nonwoven fabric slug type, metal powder sintered type, many stack-up types of wire gauze or mixed type that they are combined in any.Most preferred metal fabric nonwoven cloth slug type.
Filtering accuracy to polymer filter is not particularly limited.Filtering accuracy is generally below the 15 μ m, is preferably below the 10 μ m, more preferably below the 5 μ m.Under filtering accuracy was situation below the 1 μ m, the residence time of resin combination in polymer filter was elongated, thereby the hot deterioration of said composition strengthens.In addition, the throughput rate of film reduces.Surpass under the situation of 15 μ m at filtering accuracy, removing of the foreign matter that is contained in the resin combination becomes insufficient easily.
Shape to polymer filter is not particularly limited.Polymer filter is for example for having resin flow port more than 2, have the interior flow pattern of resin stream in newel (セ Application タ one Port one Le); The inner peripheral surface of the summit more than 2 in cross section or the face in cross section and leaf dish filtrator joins, has in the outside of newel the outer flow pattern of the stream of resin.From the few aspect of the delay of resin, the outer flow pattern of preferred use.
The residence time of resin in polymer filter be preferably below 20 minutes, more preferably below 10 minutes, more preferably below 5 minutes.The inlet of polymer filter is pressed and the outlet of this filtrator presses that for example to be respectively 3MPa above and 15MPa is following and 0.3MPa is above and below the 10MPa in the melt filteration.The pressure loss in the melt filteration (pressure differential that the inlet of polymer filter is pressed and outlet is pressed) is preferably more than the 1MPa and below the 15MPa.Under the situation of the pressure loss less than 1MPa, the stream of resin combination by polymer filter is easy to generate and departs from.The reason that departs from the quality reduction that is resulting film of stream.Surpass under the situation of 15MPa in the pressure loss, polymer filter is damaged easily.
The melt filteration of utilizing polymer filter can also be when forming resin combination except can implementing when melt extruding moulding etc. be implemented arbitrarily opportunity.
During with the resin combination melt filteration,, make the pressure stabilityization of the resin combination in the polymer filter preferably by between extruder and polymer filter, gear-type pump being set.
The film that utilizes the various methods of forming to obtain is then formed blooming 1 by two-way stretch.During shaping membrane, under the situation that has applied unilateral stretching,, form biaxial stretching film by the unilateral stretching of being left.
As long as it is can obtain blooming 1, just unqualified to the method for two-way stretch.Two-way stretch for example can be these the 2 grades of stretchings of longitudinal stretching-cross directional stretch.Two-way stretch for example can be longitudinal stretching-cross directional stretch-longitudinal stretching or the such 3 grades of stretchings (the perhaps multistage stretching more than 3 grades) of cross directional stretch-longitudinal stretching-cross directional stretch.Blooming 1 is a biaxial stretching film, therefore, and the homogeneity excellence of intensity height, thickness.For unstretching film,, when using, do not have full intensity as blooming though shown phase differential is little.The unilateral stretching film is being easy to generate anisotropy aspect optical characteristics and the intensity, and shown phase differential is big.
Unqualified to draft temperature.Draft temperature is preferably near the temperature of Tg of the resin combination that contains (methyl) acrylate copolymer (c).Draft temperature for example for more than Tg-20 ℃ and below Tg+50 ℃, be preferably more than Tg-10 ℃ and below Tg+30 ℃.Draft temperature less than Tg-20 ℃ situation under, film breaks easily during stretching.Draft temperature greater than Tg+50 ℃ situation under, can not fully obtain the effect that stretches and produced.Draw speed is not particularly limited, for example be 10%/minute more than and 20000%/minute below, be preferably 100%/minute more than and 10000%/minute below.Draw speed less than 10%/minute situation under, elongated up to the time of finishing stretching, so the manufacturing cost of blooming uprises.Surpass 20000% at draw speed/minute situation under, film breaks easily during stretching.
Draw ratio be preferably more than 1.2 times in the area ratio and below 25 times, more preferably more than 1.5 times and below 15 times, more preferably more than 2 times and below 10 times.Draw ratio less than 1.2 times situation under, can not obtain sufficient mechanical property (for example, intensity and flexible).When draw ratio surpasses 25 times, not only can not get increasing its above draw ratio and the benefit brought, and film breaks easily when stretching.
Stablize for the optical characteristics and the mechanical property that make blooming, after the stretching, can implement thermal treatment (annealing) as required.
On the surface of blooming of the present invention, can form various functional coating layers as required.Functional coating layer for example is stain-proofing layer, anti-reflecting layer, hard membrane layer, UV-preventing layer, heat ray shielding layer, electromagnetic shielding layer, the gas-barrier layer of antistatic layer, adhesive phase, adhesive linkage, easy adhesive linkage, anti-dazzle (non glare) layer, photocatalyst layer etc.
Purposes to blooming of the present invention is not particularly limited.Blooming of the present invention is based on little phase differential, high transparent and high-fire resistance, and is suitable for following purposes.This purposes for example is the optics diaphragm, specifically, the diaphragm of the substrate of various CDs (VD, CD, DVD, MD, LD etc.), is used for the polarizer protection film of the polaroids that image display device possessed such as LCD.Can use blooming of the present invention as angle of visibility compensate film, optical diffusion film, reflectance coating, antireflection film, antiglare film, brightness enhancement film, conductive film for touch screen, phase retardation film (wherein, be below the 10nm at phase differential Re in the face of the light of wavelength 589nm and the phase differential Rth of thickness direction for-more than the 10nm and below the 10nm) etc. blooming.Blooming of the present invention is particularly suitable as polarizer protection film and uses.
[polarizer protection film and polaroid]
One example of polarizer protection film of the present invention shown in Fig. 2.Polarizer protection film 2 shown in Figure 2 is made of blooming of the present invention.That is, polarizer protection film 2 comprises (methyl) acrylate copolymer (c), should (methyl) acrylate copolymer (c) has N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b) as structural unit.N-substituted maleimide amine unit (a) is to have to give the structural unit of just intrinsic birefringent effect to (methyl) acrylate copolymer (c).(methyl) acrylic ester unit (b) is to have the structural unit of (methyl) acrylate copolymer (c) being given negative intrinsic birefringent effect.Polarizer protection film 2 shows more than the 0nm and phase differential Re in the face below the 10nm for the light of wavelength 589nm.Polarizer protection film 2 is for more than the light demonstration-10nm of wavelength 589nm and the phase differential Rth of the thickness direction below the 10nm.Polarizer protection film 2 is a biaxial stretching film.
One example of polaroid of the present invention has been shown among Fig. 3.Polaroid 3 shown in Figure 3 possesses polarizer protection film 2 of the present invention and polariscope 4.The a pair of polarizer protection film 2 of polariscope 4 usefulness comes clamping.Polariscope 4 is in contact with one another with polarizer protection film 2.
Unqualified to polariscope 4, can be according to adopting suitable arbitrarily polariscope as polaroid 3 needed functions.Polariscope 4 is for example for being adsorbed with such dichroic substance of iodine or dichroic dye and the film that has carried out unilateral stretching on the such hydrophilic macromolecule film of the partly-hydrolysed film of polyvinyl alcohol (PVA) (PVA) mesentery, part formalizing PVA mesentery, vinyl-vinyl acetate copolymer (EVA); The polyenoid of the processed thing of use PVA or the desalination acid treatment thing of Polyvinylchloride is an alignment films.The film that wherein preferably is adsorbed with dichroic substance on the PVA mesentery and has carried out unilateral stretching is as polariscope 4.This polariscope demonstrates high polarized light dichroic ratio.Thickness to polariscope 4 is unqualified, is generally about 1～80 μ m.
Polaroid 3 is typically made by polarizer protection film 2 and polariscope 4 are carried out lamination by adhesive linkage.Specifically, for example, become the binder compositions of adhesive linkage after being coated on drying on the surface of any one party in being selected from polariscope 4 or polarizer protection film 2, then drying is carried out in both applyings.The coating process of binder compositions for example is roller method, spray-on process, infusion process.Contain in binder compositions under the situation of metallic compound colloid, be coated with binder compositions greater than the mode of the mean grain size of metallic compound colloidal solid with the thickness of dried adhesive linkage.Baking temperature typically be more than 5 ℃ and below 150 ℃, be preferably more than 30 ℃ and below 120 ℃.Typically be drying time more than 120 seconds, be preferably more than 300 seconds.
As long as polaroid of the present invention possesses at least 1 polarizer protection film 2.
Polarizer protection film of the present invention and polaroid are suitable for image display device.Image display device for example is electroluminescence (EL) display screen panel, plasma panel plate (PDP), Field Emission Display (FED:FieldEmission Display), LCD.LCD possesses liquid crystal cell and is configured in the polaroid of at least one side interarea of liquid crystal cell.This polaroid is suitable for polaroid of the present invention.
[image display device]
Image display device of the present invention possesses blooming of the present invention.Blooming for example is a polarizer protection film.Image display device for example is el panel panel, PDP, FED, LCD.
Formation to the image display device (image display device of the present invention) that possesses blooming of the present invention is not particularly limited, and can suitably possess parts such as power supply, backlight unit, operating portion as required.
One example of the structure of the image displaying part in the image display device of the present invention has been shown among Fig. 4.Image displaying part 11 shown in Figure 4 is the image displaying part of LCD, the backlight 8 that is disposed on a pair of polaroid 3a, the 3b that it possesses liquid crystal cell 5, dispose according to the mode of holding liquid crystal box 5 and the face of the side in the laminate of liquid crystal cell 5 and polaroid 3a, 3b.A pair of polarizer protection film 2a, 2b that each polaroid 3a, 3b possess polariscope 4a, 4b and dispose according to this polariscopic mode of clamping; 2c, 2d.Liquid crystal cell 5 has known structure, for example has liquid crystal layer, glass substrate, transparency electrode, alignment films etc.Backlight 8 has known structure, for example possesses light source, reflector plate, light guide plate, diffusing panel (weigh in the hand and fall apart), diffusion sheet, prismatic lens, brightness enhancement film etc.
In image displaying part 11, at least 1 that for example is selected among 4 polarizer protection film 2a～2d is blooming of the present invention.Whole polarizer protection films can be blooming of the present invention.Image displaying part 11 can further have blooming and optics arbitrarily such as phase retardation film or optical compensation films as required.This blooming can be blooming of the present invention.This optics can possess blooming of the present invention.
Image display device of the present invention can possess polarizer protection film of the present invention and/or polaroid of the present invention.
Embodiment
Below by embodiment the present invention is described in further detail.The present invention is not limited to following embodiment.
The evaluation method of the polymkeric substance and the blooming of made in the present embodiment at first is shown.
[glass transition temperature (Tg)]
The Tg of polymkeric substance utilizes the starting point method to try to achieve based on the regulation of JIS K7121.Specifically, (Rigaku makes, and DSC-8230), sample that will about 10mg under nitrogen atmosphere is warming up to 200 ℃ (programming rate is 20 ℃/minute) by normal temperature, is estimated by the DSC curve that obtains to use differential scanning calorimeter.Reference uses Alpha-alumina.
[weight-average molecular weight]
The weight-average molecular weight of polymkeric substance utilizes gel permeation chromatography (GPC) to try to achieve by polystyrene conversion.It is as follows to measure used device and condition determination.
System: eastern Cao makes the HLC-8220 of GPC system
The mensuration lateral column constitutes
Guard column: eastern Cao makes, TSKguard column SuperHZ-L
Separating column: eastern Cao makes, and 2 of TSKgel SuperHZM-M are connected in series
The reference lateral column constitutes
Reference column: eastern Cao makes, TSKgel SuperH-RC
Launch solvent: methenyl choloride (pure pharmaceutical worker already makes with light, superfine)
Launch the flow of solvent: 0.6mL/ minute
Standard sample: TSK polystyrene standard (eastern Cao makes, PS-oligomer kit (オ リ go マ one キ Star ト))
Column temperature: 40 ℃
[thickness of film]
The thickness d of film (μ m) uses Digimatic milscale (manufacturing of Mitutoyo society) to measure.
[refractive index anisotropy]
(Japanese OTSUKA electronics is made, and RETS-100) measures to use phase retardation film optical material testing fixture for the phase differential Rth of phase differential Re and thickness direction in the face of the film of each light of wavelength 400nm, 589nm and 750nm.
Need to prove, the phase difference value Rth of thickness direction is in the thickness d of the mean refractive index of the film that obtains measuring with Abbe refractometer (ア Star ベ flexion rate Meter), film, film is tilted after respectively value of three-dimensional refractive index nx, the ny of phase differential (Re (40 °)) in 40 ° of faces of being measured and film and nz, obtains according to following formula.About nx, ny and nz, as mentioned above.
The phase differential Rth (nm) of thickness direction=(nx+ny)/2-nz} * d (nm)
[foaminess test]
The following evaluation of the foaminess of polymkeric substance.At first, the polymkeric substance of drying is filled in the machine barrel of melt indexer of JIS K7210 regulation.Then, with the machine barrel of having filled polymkeric substance 280 ℃ keep 20 minutes after, the polymkeric substance in the front end of line material shape extruder barrel of machine barrel.The generation number of the bubble more than the major diameter 0.5mm that exists between the top graticule of the line material that obtains like this with visual instrumentation and the bottom graticule is estimated it with the number in every 1g polymkeric substance.Metewand is as follows.
◎ (excellent): below 1
Zero (very): more than 2 and below 5
△ (can): more than 6 and less than 10
* (can not): more than 10
(Production Example 1)
In the reactor that has possessed stirring apparatus, temperature sensor, cooling tube and nitrogen ingress pipe, drop into methyl methacrylate (MMA) 45 mass parts, N-cyclohexyl maleimide (CHMI) 5 mass parts and as toluene 50 mass parts of polymer solvent, to wherein feed nitrogen on one side be warming up to 105 ℃ on one side.Be accompanied by intensification, beginning refluxes, interpolation is as the different n-nonanoic acid tert-pentyl ester of the peroxidating of polymerization initiator (lucky rich manufacturing of ア ト Off イ Na, trade name: Le ペ ロ Star Network ス 570) 0.04 mass parts the time, on one side with dripping different n-nonanoic acid tert-pentyl ester 0.16 mass parts of above-mentioned peroxidating in 4 hours, under about 105～110 ℃ backflow, carry out solution polymerization on one side, further carry out 4 hours slaking.Next, with resulting polymer solution under reduced pressure, in 200 ℃ of dryings 1 hour, obtain having CHMI unit and MMA unit transparent solid as (methyl) acrylate copolymer (A-1) of structural unit.The weight-average molecular weight of polymkeric substance (A-1) is 230,000, and Tg is 126 ℃.The evaluation result that the foaminess of polymkeric substance (A-1) is tested is " zero (very) ".The CHMI unit is for to give just intrinsic birefringent structural unit to polymkeric substance.The MMA unit is for giving negative intrinsic birefringent structural unit to polymkeric substance.The content of CHMI unit is that the content of 10 quality %, MMA unit is 90 quality % in the polymkeric substance (A-1).
(Production Example 2)
The inventory of MMA and CHMI is set at 40 mass parts and 10 mass parts respectively, with the time set of slaking is 5 hours, and the baking temperature of resulting polymeric solution is set at 220 ℃, in addition, obtain having CHMI unit and MMA unit transparent solid similarly to Example 1 as (methyl) acrylate copolymer (A-2) of structural unit.The weight-average molecular weight of polymkeric substance (A-2) is 220,000, and Tg is 128 ℃.The evaluation result that the foaminess of polymkeric substance (A-2) is tested is " ◎ (excellent) ".The content of the CHMI unit in the polymkeric substance (A-2) is that the content of 20 quality %, MMA unit is 80 quality %.
(embodiment 1)
Utilize press-forming machine under 250 ℃ forming temperature, to be pressed in the polymkeric substance (A-1) of made in the Production Example 1, obtain the film (B-1) of thickness 152 μ m.Next, (the smart mechanism of Japan is done manufacturing to utilize bidirectional tensile tester, X-6S), draft temperature be 146 ℃, draw speed be 1000%/minute stretching condition under, with the film (B-1) of made according to the order of vertical and horizontal respectively with the draw ratio two-way stretch one by one of 2 times and 1.5 times.Need to prove, vertically be meant so-called MD direction, laterally be meant so-called TD direction.After the two-way stretch, from test unit, take out film and cooling rapidly, obtain the biaxial stretching film (C-1) of thickness 55 μ m.The Tg of resulting film (C-1) is 126 ℃, be 1.2nm, be-3.9nm for phase differential Re in the face of the light of wavelength 589nm for the phase differential Rth of the thickness direction of this light, be 1.3nm, be-6.2nm for phase differential Re in the face of the light of wavelength 400nm, be 2.0nm, be-2.8nm for the phase differential Rth of the thickness direction of this light for phase differential Re in the face of the light of wavelength 750nm for the phase differential Rth of the thickness direction of this light.
(embodiment 2)
Utilize press-forming machine under 255 ℃ forming temperature, to be pressed in the polymkeric substance (A-2) of made in the Production Example 2, obtain the film (B-2) of thickness 138 μ m.Next, (the smart mechanism of Japan is done manufacturing to utilize bidirectional tensile tester, X-6S), draft temperature be 148 ℃, draw speed be 1000%/minute stretching condition under, with the film (B-2) of made according to the order of vertical and horizontal respectively with 2 times and 1.5 times of draw ratio two-way stretches one by one.After the two-way stretch, from test unit, take out film and cooling rapidly, obtain the biaxial stretching film (C-2) of thickness 43 μ m.The Tg of resulting film (C-2) is 128 ℃, be 0.4nm, be 0.8nm for phase differential Re in the face of the light of wavelength 589nm for the phase differential Rth of the thickness direction of this light, be 0.3nm, be 1.0nm for phase differential Re in the face of the light of wavelength 400nm, be 0.4nm, be 0.8nm for the phase differential Rth of the thickness direction of this light for phase differential Re in the face of the light of wavelength 750nm for the phase differential Rth of the thickness direction of this light.
(comparative example 1)
With polymethylmethacrylate (Sumitomo Chemical manufacturing, trade name: SUMIPEX EX) utilize press-forming machine under 230 ℃ forming temperature, to be pressed, obtain the film (B-3) of thickness 146 μ m.Next, (the smart mechanism of Japan is done manufacturing to utilize bidirectional tensile tester, X-6S), draft temperature be 129 ℃, draw speed be 1000%/minute stretching condition under, with the film (B-3) of made according to the order of vertical and horizontal respectively with the draw ratio two-way stretch one by one of 2 times and 1.5 times.After the two-way stretch, from test unit, take out film and cooling rapidly, obtain the biaxial stretching film (C-3) of thickness 51 μ m.The Tg of resulting film (C-3) is 109 ℃, be 6.1nm, be-11.1nm for phase differential Re in the face of the light of wavelength 589nm for the phase differential Rth of the thickness direction of this light, be 6.2nm, be-12.4nm for phase differential Re in the face of the light of wavelength 400nm, be 5.7nm, be-10.8nm for the phase differential Rth of the thickness direction of this light for phase differential Re in the face of the light of wavelength 750nm for the phase differential Rth of the thickness direction of this light.
Evaluation result for the test of the foaminess of polymethylmethacrylate used in the comparative example 1 is " * (can not) ".
The evaluation result of embodiment and comparative example is summarized in following table 1.Need to prove that Rth/d is the value for the light of wavelength 589nm.
Table 1
As shown in table 1, in embodiment 1 and 2, particularly in embodiment 2, for the shown phase differential of resulting biaxial stretching film, the phase differential Rth of phase differential Re and thickness direction has all diminished in the face.Confirm in addition, in embodiment 1 and 2, particularly in embodiment 2, in whole visible domain, the phase differential Rth of phase differential Re and thickness direction diminishes in the face.And, among the embodiment 1 and 2 among used polymkeric substance, the particularly embodiment 2 used polymkeric substance be difficult to take place thermal decomposition, the foaming when having suppressed the film moulding.
Industrial applicibility
Blooming of the present invention is suitable for various image display devices (liquid crystal indicator, organic EL display, PDP etc.).
Claims (9)
1. blooming, this blooming comprises (methyl) acrylate copolymer (c), should (methyl) acrylate copolymer (c) has N-substituted maleimide amine unit (a) and (methyl) acrylic ester unit (b) as structural unit,
Described N-substituted maleimide amine unit (a) is to have to give the structural unit of just intrinsic birefringent effect to described (methyl) acrylate copolymer (c),
Described (methyl) acrylic ester unit (b) is to have to give the structural unit of bearing intrinsic birefringent effect to described (methyl) acrylate copolymer (c),
This blooming for phase differential Re in the face of the light of wavelength 589nm be more than the 0nm and below the 10nm, for the phase differential Rth of the thickness direction of described light for-more than the 10nm and below the 10nm,
This blooming is a biaxial stretching film,
Herein, with the refractive index of the slow-axis direction in the face of described blooming be made as nx, with the refractive index of the quick shaft direction in described be made as ny, with the refractive index of the thickness direction of described blooming be made as nz, when the thickness of described blooming is made as d, the phase differential Rth of phase differential Re and thickness direction is respectively by formula Re=(nx-ny) * d and formula Rth={ (nx+ny)/defined value of 2-nz} * d in the face.
2. blooming as claimed in claim 1, wherein, described N-substituted maleimide amine unit (a) is a cyclohexyl maleimide amine unit.
3. blooming as claimed in claim 1, wherein, described (methyl) acrylic ester unit (b) is a methyl methacrylate units.
4. blooming as claimed in claim 1, wherein,
The content of the described N-substituted maleimide amine unit (a) in described (methyl) acrylate copolymer (c) is more than the 5 quality % and below the 30 quality %,
The content of described (methyl) acrylic ester unit (b) in described (methyl) acrylate copolymer (c) is more than the 70 quality % and below the 95 quality %.
5. blooming as claimed in claim 1, wherein,
Described the interior phase differential Re for the light of the light of wavelength 400nm and wavelength 750nm of this blooming is below the 5nm,
The phase differential Rth for the described thickness direction of the light of the light of wavelength 400nm and wavelength 750nm of this blooming is-more than the 10nm and below the 10nm.
6. blooming as claimed in claim 1, wherein, the glass transition temperature of described blooming is more than 110 ℃.
7. polarizer protection film, it is made of each described blooming in the claim 1～6.
8. polaroid, it possesses described polarizer protection film of claim 7 and polariscope.
9. image display device, it possesses each described blooming in the claim 1～6.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010098358 | 2010-04-22 | ||
| JP2010-098358 | 2010-04-22 |
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| CN102236120A true CN102236120A (en) | 2011-11-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011101020456A Pending CN102236120A (en) | 2010-04-22 | 2011-04-22 | Optical film, polarizer protective film, polarizing plate and image display device |
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| Country | Link |
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| JP (3) | JP5912277B2 (en) |
| KR (1) | KR101774056B1 (en) |
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| JP6591166B2 (en) * | 2015-01-27 | 2019-10-16 | 株式会社日本触媒 | Optical film, use thereof and manufacturing method thereof |
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| KR20180079613A (en) * | 2016-12-30 | 2018-07-11 | 주식회사 효성 | Heat resistant anti hazing resin film |
| KR101912124B1 (en) | 2017-12-11 | 2018-10-29 | (주)유티아이 | optical filter cell array structure and manufacturing method of optical filter cell array structure thereby |
| KR20210022709A (en) * | 2018-07-31 | 2021-03-03 | 코니카 미놀타 가부시키가이샤 | Optical film, polarizing plate, and manufacturing method of optical film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031537A (en) * | 2005-07-26 | 2007-02-08 | Teijin Dupont Films Japan Ltd | Stretched film and polarizing plate using stretched film |
| CN101156092A (en) * | 2005-03-31 | 2008-04-02 | 株式会社日本触媒 | Polarizer protective film, polarizer, and image display device |
| CN101228198A (en) * | 2005-08-04 | 2008-07-23 | 株式会社日本触媒 | low birefringence copolymer |
| CN101389987A (en) * | 2006-02-28 | 2009-03-18 | 株式会社日本触媒 | Retardation film |
| WO2009134098A2 (en) * | 2008-04-30 | 2009-11-05 | 주식회사 엘지화학 | Optical film, and an electronic information device comprising the same |
| CN101679710A (en) * | 2007-06-14 | 2010-03-24 | 株式会社日本触媒 | Thermoplastic resin composition, resin molded article and polarizer protective film using same, and method for producing resin molded article |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002328232A (en) * | 2001-05-02 | 2002-11-15 | Kanegafuchi Chem Ind Co Ltd | Film, protective film for polarizer and polarizing plate |
| AT500555B1 (en) * | 2003-06-13 | 2009-11-15 | Cytec Surface Specialties At | SELF-NETWORKING AQUEOUS POLYURETHANE ISOLATIONS |
| JP2006208587A (en) * | 2005-01-26 | 2006-08-10 | Fuji Photo Film Co Ltd | Cellulose acylate film and optical compensation sheet, polarizing plate and liquid crystal display device using the film |
| JP4928187B2 (en) * | 2005-08-04 | 2012-05-09 | 株式会社日本触媒 | Low birefringence copolymer |
| CN101796086A (en) * | 2007-09-04 | 2010-08-04 | 电气化学工业株式会社 | Thermoplastic copolymer resin and its optical molding |
| KR20090076754A (en) * | 2008-01-08 | 2009-07-13 | 주식회사 엘지화학 | Optical film, retardation film, protective film and liquid crystal display device comprising the same |
| JP5306710B2 (en) * | 2008-06-02 | 2013-10-02 | 富士フイルム株式会社 | Liquid crystal display device, acrylic film and method for producing the same |
-
2011
- 2011-03-31 JP JP2011080083A patent/JP5912277B2/en active Active
- 2011-04-21 KR KR1020110037179A patent/KR101774056B1/en active Active
- 2011-04-22 CN CN2011101020456A patent/CN102236120A/en active Pending
-
2014
- 2014-11-21 JP JP2014236609A patent/JP2015057664A/en active Pending
-
2016
- 2016-06-07 JP JP2016113446A patent/JP2016173602A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156092A (en) * | 2005-03-31 | 2008-04-02 | 株式会社日本触媒 | Polarizer protective film, polarizer, and image display device |
| JP2007031537A (en) * | 2005-07-26 | 2007-02-08 | Teijin Dupont Films Japan Ltd | Stretched film and polarizing plate using stretched film |
| CN101228198A (en) * | 2005-08-04 | 2008-07-23 | 株式会社日本触媒 | low birefringence copolymer |
| CN101389987A (en) * | 2006-02-28 | 2009-03-18 | 株式会社日本触媒 | Retardation film |
| CN101679710A (en) * | 2007-06-14 | 2010-03-24 | 株式会社日本触媒 | Thermoplastic resin composition, resin molded article and polarizer protective film using same, and method for producing resin molded article |
| WO2009134098A2 (en) * | 2008-04-30 | 2009-11-05 | 주식회사 엘지화학 | Optical film, and an electronic information device comprising the same |
| WO2009134098A3 (en) * | 2008-04-30 | 2010-03-11 | 주식회사 엘지화학 | Optical film, and an electronic information device comprising the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151761A (en) * | 2014-08-15 | 2014-11-19 | 吴江市德佐日用化学品有限公司 | Mirror surface special-purposed resin composition and preparation method thereof |
| CN107849201A (en) * | 2015-08-21 | 2018-03-27 | 株式会社日本触媒 | Block copolymer |
| CN106990458A (en) * | 2015-10-01 | 2017-07-28 | 三星电子株式会社 | Optical film and its manufacture method and the display device including it |
| CN106990458B (en) * | 2015-10-01 | 2019-11-15 | 三星电子株式会社 | Optical film, manufacturing method thereof, and display device including same |
| CN109181194A (en) * | 2017-10-17 | 2019-01-11 | Skc株式会社 | Optical film and liquid crystal display device including the same |
| CN113927879A (en) * | 2017-10-27 | 2022-01-14 | 3M创新有限公司 | Shaped optical film, method of shaping optical film, and curved reflective polarizer |
| CN113927879B (en) * | 2017-10-27 | 2024-07-19 | 3M创新有限公司 | Shaping optical film, method of shaping optical film, and curved reflective polarizer |
| CN112105971A (en) * | 2018-05-11 | 2020-12-18 | 住友化学株式会社 | Polarizing plate and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110118092A (en) | 2011-10-28 |
| JP2015057664A (en) | 2015-03-26 |
| JP2016173602A (en) | 2016-09-29 |
| KR101774056B1 (en) | 2017-09-12 |
| JP2011242754A (en) | 2011-12-01 |
| JP5912277B2 (en) | 2016-04-27 |
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