TWI498362B - A method for producing a laminated optical film, a laminated optical film, a polarizing film, and a liquid crystal display device - Google Patents

A method for producing a laminated optical film, a laminated optical film, a polarizing film, and a liquid crystal display device Download PDF

Info

Publication number
TWI498362B
TWI498362B TW097145776A TW97145776A TWI498362B TW I498362 B TWI498362 B TW I498362B TW 097145776 A TW097145776 A TW 097145776A TW 97145776 A TW97145776 A TW 97145776A TW I498362 B TWI498362 B TW I498362B
Authority
TW
Taiwan
Prior art keywords
optical film
layer
laminated optical
film
group
Prior art date
Application number
TW097145776A
Other languages
Chinese (zh)
Other versions
TW200946570A (en
Inventor
Kei Tanaka
Chikara Isobe
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200946570A publication Critical patent/TW200946570A/en
Application granted granted Critical
Publication of TWI498362B publication Critical patent/TWI498362B/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133631—Birefringent elements, e.g. for optical compensation with a spatial distribution of the retardation value
    • 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
    • G02F1/133632—Birefringent elements, e.g. for optical compensation with refractive index ellipsoid inclined relative to the LC-layer surface
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

層合光學薄膜之製造方法、層合光學薄膜、偏光板及液晶顯示裝置Method for manufacturing laminated optical film, laminated optical film, polarizing plate and liquid crystal display device

本發明係有關實現液晶顯示裝置之優異之視角特性的層合光學薄膜與其製造方法，及使用該薄膜之偏光板及液晶顯示裝置。The present invention relates to a laminated optical film which realizes excellent viewing angle characteristics of a liquid crystal display device, a method for producing the same, and a polarizing plate and a liquid crystal display device using the same.

相位差薄膜一般係作為液晶顯示裝置之視角補償使用，防止斜向視角之漏光，防止對比降低。作為相位差薄膜使用之光學薄膜，例如有聚碳酸酯薄膜、聚酯薄膜、纖維素乙酸酯薄膜、環狀烯烴薄膜等。The phase difference film is generally used as a viewing angle compensation of a liquid crystal display device to prevent light leakage in a diagonal viewing angle and prevent contrast reduction. Examples of the optical film used as the retardation film include a polycarbonate film, a polyester film, a cellulose acetate film, and a cyclic olefin film.

其中，環狀烯烴薄膜因透明性、耐熱性、尺寸安定性、低光彈性等優異，因此作為相位差薄膜等之各種光學零件之材料而受矚目。Among them, the cyclic olefin film is excellent in transparency, heat resistance, dimensional stability, low photoelasticity, and the like, and is attracting attention as a material of various optical components such as a retardation film.

近年，除了以往之TN模式外，VA模式及IPS模式之高視角液晶模式已實用化，在要求高畫質之電視用途方面，液晶顯示裝置(液晶電視)已廣為普及。例如VA模式之液晶顯示裝置用之相位差薄膜，例如組合A板與C板之補償方式或組合1片或2片二軸性薄膜的補償方式對於視角改善效果特高，已為人知。In recent years, in addition to the conventional TN mode, the high viewing angle liquid crystal mode of the VA mode and the IPS mode has been put into practical use, and a liquid crystal display device (liquid crystal television) has been widely used for television applications requiring high image quality. For example, a retardation film for a liquid crystal display device of the VA mode, for example, a compensation method for combining the A plate and the C plate or a compensation method for combining one or two biaxial films is particularly high in the viewing angle improvement effect.

但是即使這些補償方式，對於由斜向觀看畫面時之顏色的變化(以下簡稱為色彩偏移)，例如黑顯示狀態下，本來應為黑色，卻可看見紫色著色等，視角補償不足。為了改善此問題時，需要具有在可見光區域，波長越短，相位差越小，波長越長，相位差越大之特性，即所謂逆波長分散性的相位差薄膜。例如專利文獻1係提案藉由相位差薄膜所用之樹脂之改質實現逆波長分散性的手法。但是藉由樹脂之改質很難確立樹脂製造條件，或損害薄膜之強度、透明性、安定性等，未到達廣泛實用化。However, even with these compensation methods, for the change in color when viewing the screen obliquely (hereinafter referred to as color shift), for example, in the black display state, it should be black, but purple coloring or the like can be seen, and the viewing angle compensation is insufficient. In order to improve this problem, it is necessary to have a characteristic that the phase difference is smaller in the visible light region, the phase difference is smaller, and the wavelength is longer, and the phase difference is larger, that is, a retardation film having a reverse wavelength dispersion property. For example, Patent Document 1 proposes a method of realizing reverse wavelength dispersion by reforming a resin used for a retardation film. However, it is difficult to establish the resin production conditions by the modification of the resin, or to impair the strength, transparency, stability, and the like of the film, and it has not reached widespread practical use.

樹脂之改質以外的方法，例如也有層合特定相位差的層，控制使合計之相位差成為逆波長分散性者。例如專利文獻2係提案藉由聚合性液晶所構成之相位差層與樹脂薄膜之層合，實現逆波長分散性的手法。但是聚合性液晶所構成之相位差層必須將數微米厚之層控制在數%之厚度偏差內等，製作難度高。而且，以此種層合的手法雖由正面方向觀測時，可得到所定之相位差值及逆波長分散性，但是由斜方觀測時，受光軸偏離之影響，而有無法得到所定之相位差，無法補償斜向之視角的問題。In addition to the modification of the resin, for example, a layer having a specific phase difference is laminated, and the total phase difference is controlled to be a reverse wavelength dispersion. For example, Patent Document 2 proposes a method of realizing reverse wavelength dispersion by laminating a phase difference layer composed of a polymerizable liquid crystal and a resin film. However, the retardation layer composed of the polymerizable liquid crystal must be controlled within a thickness variation of several micrometers, and the like, and the production difficulty is high. Further, when the method of lamination is observed from the front direction, the predetermined phase difference and the reverse wavelength dispersion can be obtained. However, when the oblique direction is observed, the optical axis deviation is affected, and the predetermined phase difference cannot be obtained. Can not compensate for the problem of the oblique view.

層合相位差層之其他的方法，例如專利文獻3提案以共擠壓法之薄膜製膜、相位差薄膜製作。但是各層之密著差，必須在層間夾著接著層，而有層構成及製造裝置變得複雜的問題。如上述，提高斜向之對比，且降低色彩偏移的手法仍未完全確立，需要改良。此外，對於行動電話、攜帶式遊戲機等之攜帶機器用或車用之液晶顯示裝置，除了上述優異的視角特性，還需要可在嚴苛環境下之長期使用的耐久性。Other methods of laminating the retardation layer, for example, Patent Document 3 proposes a film formation by a co-extrusion method or a retardation film. However, the adhesion between the layers is poor, and it is necessary to sandwich the interlayer between the layers, and the layer configuration and the manufacturing apparatus are complicated. As described above, the method of increasing the contrast of the oblique direction and reducing the color shift is still not fully established, and improvement is required. In addition, in addition to the above-described excellent viewing angle characteristics, a liquid crystal display device for a portable device or a portable game machine, such as a mobile phone or a portable game machine, requires durability for long-term use in a severe environment.

[專利文獻1]特開2006-225626號公報[Patent Document 1] JP-A-2006-225626

[專利文獻2]特開2006-268033號公報[Patent Document 2] JP-A-2006-268033

[專利文獻3]特開2004-133313號公報[Patent Document 3] JP-A-2004-133313

本發明係以提供對於液晶顯示裝置，由斜向觀看畫面時之對比高，或由斜向觀看畫面時之色彩偏移(Color Shift)量較小，可形成更均一的畫面顯示，同時提供耐久性優，外光映入較少之層合光學薄膜與其製造方法、及使用其之偏光板及液晶顯示裝置為課題。The present invention provides a more uniform color display for a liquid crystal display device when the viewing angle is obliquely viewed or when the viewing angle is obliquely viewed, thereby providing a more uniform screen display while providing durability. A laminated optical film having a high degree of excellent external light, a method for producing the same, a polarizing plate and a liquid crystal display device using the same are the subject matter.

本發明人有鑒於上述的狀況，精心検討的結果，發現可確保在專利文獻2中成為問題之由斜向觀看時之所定相位差及逆波長分散性，且可確保專利文獻3中成為問題之層合薄膜各層之密著性，遂完成本發明。In view of the above-mentioned situation, the present inventors have found that the phase difference and the reverse wavelength dispersion in the oblique direction when the problem is solved in Patent Document 2 can be ensured, and the problem in Patent Document 3 can be ensured. The adhesion of each layer of the laminated film is completed by the present invention.

本發明之層合光學薄膜之製造方法，其特徵係具有：將環狀烯烴系樹脂與乙烯基芳香族系樹脂藉由共擠壓法進行層合製膜，得到環狀烯烴系樹脂層(以下也稱為(A)層)與乙烯基芳香族系樹脂層(以下以稱為(B)層)被層合之原始薄膜(raw film)的步驟，將製得之原始薄膜在對於薄膜長度方向為正交方向，進行單軸拉伸的步驟，且得到滿足全部下述式(i)～(iii)表示之特性的層合光學薄膜。The method for producing a laminated optical film of the present invention is characterized in that a cyclic olefin-based resin and a vinyl aromatic resin are laminated by a co-extrusion method to obtain a cyclic olefin-based resin layer (hereinafter, Also referred to as a (A) layer) a step of laminating a raw film with a vinyl aromatic resin layer (hereinafter referred to as a (B) layer), the original film obtained is oriented for the film length The step of uniaxial stretching is performed in the orthogonal direction, and a laminated optical film satisfying all the characteristics represented by the following formulas (i) to (iii) is obtained.

R450≦R550≦R650...(i)R450≦R550≦R650...(i)

1.0≦R650/R550≦1.2...(ii)1.0≦R650/R550≦1.2...(ii)

70nm≦R550≦150nm...(iii)70nm≦R550≦150nm...(iii)

[上述式(i)～(iii)中、R450、R550、R650係依序表示在波長450nm、550nm、650nm之層合光學薄膜的面内相位差]。[In the above formulas (i) to (iii), R450, R550, and R650 sequentially show the in-plane retardation of the laminated optical film at wavelengths of 450 nm, 550 nm, and 650 nm].

這種本發明之層合光學薄膜之製造方法，其中環狀烯烴系樹脂較佳為由具有下述式(1)表示之結構單元及下述式(2)表示之結構單元的共聚物所構成者。In the method for producing a laminated optical film of the present invention, the cyclic olefin resin is preferably composed of a copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). By.

【化1】【化1】

[式(1)中，m係1以上之整數，p係0以上之整數，X係獨立以式：-CH=CH-表示之基或式：-CH2 CH2 -表示之基，R1 ～R4 係各自獨立表示下述(a)～(e)表示者或表示(f)或(g)。In the formula (1), m is an integer of 1 or more, p is an integer of 0 or more, and X is independently a group represented by the formula: -CH=CH- or a group represented by the formula: -CH 2 CH 2 -, R 1 The -R 4 system independently indicates the following (a) to (e) or (f) or (g).

(a)氫原子、(a) a hydrogen atom,

(b)鹵原子、(b) a halogen atom,

(c)含有具有氧原子、硫原子、氮原子或矽原子之連結基的取代或非取代之碳原子數1～30之烴基、(c) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which has a linking group having an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom,

(d)取代或非取代之碳原子數1～30之烴基、(d) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,

(e)極性基、(e) polar group,

(f)表示R1 與R2 、或R3 與R4 相互鍵結形成之亞烷基，未參與前述鍵結之R1 ～R4 係相互獨立表示選自前述(a)～(e)者，(f) represents an alkylene group in which R 1 and R 2 or R 3 and R 4 are bonded to each other, and R 1 to R 4 which are not involved in the aforementioned bonding are mutually independent and are selected from the above (a) to (e). By,

(g)表示R1 與R2 、R3 與R4 、或R2 與R3 相互鍵結形成之芳香環或非芳香環之單環或多環之烴環或雜環，未參與前述鍵結之R1 ～R4 係相互獨立表示選自前述(a)～(e)者]。(g) a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring representing an aromatic ring or a non-aromatic ring in which R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 are bonded to each other, and does not participate in the aforementioned bond R 1 to R 4 of the knot are independently selected from the above (a) to (e).

【化2】[Chemical 2]

[式(2)中，Y係以式：-CH=CH-表示之基或以式：-CH2 CH2 -表示之基，R5 ～R8 係各自獨立表示下述(a)～(e)表示者或表示(f)或(g)。[In the formula (2), Y is a group represented by the formula: -CH=CH- or a group represented by the formula: -CH 2 CH 2 -, and each of R 5 to R 8 independently represents the following (a) to ( e) Representation or representation (f) or (g).

(a)氫原子、(a) a hydrogen atom,

(b)鹵原子、(b) a halogen atom,

(c)含有具有氧原子、硫原子、氮原子或矽原子之連結基之取代或非取代之碳原子數1～30之烴基、(c) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms and having a linking group having an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom,

(d)取代或非取代之碳原子數1～30之烴基、(d) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,

(e)極性基、(e) polar group,

(f)表示R5 與R6 、或R7 與R8 相互鍵結形成之亞烷基，未參與前述鍵結之R5 ～R8 係相互獨立表示選自前述(a)～(e)者，(f) represents an alkylene group in which R 5 and R 6 or R 7 and R 8 are bonded to each other, and R 5 to R 8 which are not involved in the aforementioned bonding are mutually independent and are selected from the above (a) to (e). By,

(g)表示R5 與R6 、R7 與R8 、或R6 與R7 相互鍵結形成之芳香環或非芳香環之單環或多環之烴環或雜環，未參與前述鍵結之R5 ～R8 係相互獨立表示選自前述(a)～(e)者]。(g) a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring representing an aromatic ring or a non-aromatic ring in which R 5 and R 6 , R 7 and R 8 or R 6 and R 7 are bonded to each other, and does not participate in the aforementioned bond R 5 to R 8 in the knot are independent of each other and are selected from the above (a) to (e).

本發明之層合光學薄膜之製造方法，其中乙烯基芳香族系樹脂較佳為苯乙烯-(甲基)丙烯酸共聚物，或乙烯基芳香族系樹脂較佳為苯乙烯-順丁烯二酸酐共聚物。In the method for producing a laminated optical film of the present invention, the vinyl aromatic resin is preferably a styrene-(meth)acrylic copolymer, or the vinyl aromatic resin is preferably styrene-maleic anhydride. Copolymer.

本發明之層合光學薄膜之製造方法，其中環狀烯烴系樹脂層與乙烯基芳香族系樹脂層較佳為直接接觸。In the method for producing a laminated optical film of the present invention, the cyclic olefin-based resin layer and the vinyl aromatic resin layer are preferably in direct contact with each other.

本發明之層合光學薄膜之製造方法，其中環狀烯烴系樹脂與乙烯基芳香族系樹脂較佳為滿足下述式(iv)的關係。In the method for producing a laminated optical film of the present invention, the cyclic olefin resin and the vinyl aromatic resin preferably satisfy the relationship of the following formula (iv).

∣TgA(℃)-TgB(℃)∣≦20(℃)　...(iv)∣TgA(°C)-TgB(°C)∣≦20(°C) ...(iv)

[式中，TgA係表示環狀烯烴系樹脂之玻璃轉化溫度，TgB係表示乙烯基芳香族系樹脂之玻璃轉化溫度]。[In the formula, TgA represents the glass transition temperature of the cyclic olefin resin, and TgB represents the glass transition temperature of the vinyl aromatic resin].

本發明之層合光學薄膜之製造方法，其中環狀烯烴系樹脂之玻璃轉化溫度(TgA)及乙烯基芳香族系樹脂之玻璃轉化溫度(TgB)均為110℃以上較佳。In the method for producing a laminated optical film of the present invention, the glass transition temperature (TgA) of the cyclic olefin resin and the glass transition temperature (TgB) of the vinyl aromatic resin are preferably 110 ° C or higher.

本發明之層合光學薄膜，其特徵係環狀烯烴系樹脂層與乙烯基芳香族系樹脂層直接接觸，進行層合，且滿足全部下述式(i)～(iii)之特性者。In the laminated optical film of the present invention, the cyclic olefin-based resin layer is in direct contact with the vinyl aromatic resin layer, and is laminated, and all of the following formulas (i) to (iii) are satisfied.

R450≦R550≦R650...(i)R450≦R550≦R650...(i)

1.0≦R650/R550≦1.2...(ii)1.0≦R650/R550≦1.2...(ii)

70nm≦R550≦150nm...(iii)70nm≦R550≦150nm...(iii)

[上述式(i)～(iii)中，R450、R550、R650係依序表示在波長450nm、550nm、650nm之層合光學薄膜的面内相位差]。[In the above formulas (i) to (iii), R450, R550, and R650 sequentially show the in-plane retardation of the laminated optical film at wavelengths of 450 nm, 550 nm, and 650 nm].

本發明之層合光學薄膜，較佳為滿足下述式(v)者。The laminated optical film of the present invention preferably satisfies the following formula (v).

1.0≦NZ≦3.0...(v)1.0≦NZ≦3.0...(v)

[上述式(v)中，NZ係以NZ=(nx-nz)/(nx-ny)表示之係數，在波長550nm之值。其中nx係表示在層合光學薄膜面内之最大折射率，ny係表示在層合光學薄膜面内，與nx正交之方向的折射率，nz係表示與nx及ny正交之層合光學薄膜厚度方向的折射率。但是層合光學薄膜之平均折射率為Nave 時，以Nave =(nx+ny+nz)/3表示，Nave 係在層合光學薄膜中，環狀烯烴系樹脂層與乙烯基芳香族系樹脂層之各自之平均折射率藉由厚度比進行加權平均的值]。[In the above formula (v), NZ is a coefficient represented by NZ = (nx - nz) / (nx - ny), and has a value at a wavelength of 550 nm. Wherein nx represents the maximum refractive index in the plane of the laminated optical film, ny represents the refractive index in the direction perpendicular to nx in the plane of the laminated optical film, and nz represents the lamination optics orthogonal to nx and ny The refractive index in the thickness direction of the film. However, when the average refractive index of the laminated optical film is N ave , it is represented by N ave = (nx + ny + nz) / 3 , and N ave is in the laminated optical film, the cyclic olefin resin layer and the vinyl aromatic The average refractive index of each of the resin layers is a weighted average value by thickness ratio].

本發明之層合光學薄膜，其中環狀烯烴系樹脂之玻璃轉化溫度及乙烯基芳香族系樹脂之玻璃轉化溫度均為110℃以上較佳。In the laminated optical film of the present invention, the glass transition temperature of the cyclic olefin resin and the glass transition temperature of the vinyl aromatic resin are preferably 110 ° C or higher.

本發明之層合光學薄膜，其特徵係藉由上述層合光學薄膜之製造方法所得者。The laminated optical film of the present invention is characterized by the method for producing the above laminated optical film.

本發明之偏光板，其特徵係將上述本發明之層合光學薄膜，介由接著劑或黏著劑層合於偏光子之至少單面上所成者。這種本發明之偏光板，較佳為尚含有選自反射防止層及防眩層之至少1種的層。The polarizing plate of the present invention is characterized in that the laminated optical film of the present invention is laminated on at least one side of a polarizer via an adhesive or an adhesive. The polarizing plate of the present invention preferably further contains at least one layer selected from the group consisting of an antireflection layer and an antiglare layer.

本發明之液晶顯示裝置，其特徵係具有上述本發明之任一的偏光板者。A liquid crystal display device of the present invention is characterized in that it has the polarizing plate of any of the above-described inventions.

藉由本發明之層合光學薄膜，可得到對於液晶顯示裝置，由斜向觀看畫面時之對比高，或由斜向觀看畫面時之色彩偏移(Color Shift)量較小，可形成更均一的畫面顯示的液晶顯示裝置。According to the laminated optical film of the present invention, it is possible to obtain a higher uniformity when the screen is viewed obliquely from the liquid crystal display device, or a smaller color shift amount when viewing the image obliquely, thereby forming a more uniform color. A liquid crystal display device for screen display.

[實施發明之最佳形態][Best Mode for Carrying Out the Invention]

以下具體說明本發明。The invention is specifically described below.

[層合光學薄膜之製造方法][Method of Manufacturing Laminated Optical Film]

本發明之層合光學薄膜之製造方法，其係具有：將環狀烯烴系樹脂與乙烯基芳香族系樹脂藉由共擠壓法進行層合製膜，得到環狀烯烴系樹脂層與乙烯基芳香族系樹脂層被層合之原始薄膜的步驟，與將製得之原始薄膜在對於薄膜長度方向為正交方向，進行單軸拉伸的步驟。The method for producing a laminated optical film of the present invention comprises laminating a cyclic olefin resin and a vinyl aromatic resin by a co-extrusion method to obtain a cyclic olefin resin layer and a vinyl group. The step of laminating the original film of the aromatic resin layer and the step of uniaxially stretching the original film obtained in the direction perpendicular to the longitudinal direction of the film.

環狀烯烴系樹脂Cyclic olefin resin

本發明使用之環狀烯烴系樹脂，無特別限定，例如具有降冰片烯骨架之環狀烯烴系單體之開環(共)聚合物、開環(共)聚合物之氫化物、加成(共)聚合物或環狀烯烴系單體與共聚性之其他單體的共聚物、其氫化物等，較佳為具有以上述式(1)表示之結構單元(1)與以上述式(2)表示之結構單元(2)的共聚物。必要時可任意含有其他之結構單元。The cyclic olefin resin used in the present invention is not particularly limited, and examples thereof include a ring-opening (co)polymer of a cyclic olefin monomer having a norbornene skeleton, a hydrogenated product of a ring-opening (co)polymer, and addition ( A copolymer of a copolymer or a cyclic olefin monomer and another monomer having copolymerizability, a hydrogenated product thereof, etc., preferably having a structural unit (1) represented by the above formula (1) and having the above formula (2) ) a copolymer of the structural unit (2). Any other structural unit may be optionally included as necessary.

該共聚物係以下述式(3)表示之1種以上之單體(以下也稱為「單體(1)」)與下述式(4)表示之1種以上之單體(以下也稱為「單體(2)」)進行開環共聚所得。The copolymer is one or more monomers (hereinafter also referred to as "monomer (1)") represented by the following formula (3) and one or more monomers represented by the following formula (4) (hereinafter also referred to as It is obtained by ring-opening copolymerization of "monomer (2)").

【化3】[化3]

(式(3)中，m、p、R1 、R2 、R3 及R4 之定義係與式(1)之定義相同)。(In the formula (3), m, p, R 1 , R 2 , R 3 and R 4 are as defined in the formula (1)).

【化4】【化4】

(式(4)中，R5 、R6 、R7 及R8 之定義係與式(2)之定義相同)。(In the formula (4), R 5 , R 6 , R 7 and R 8 are as defined in the formula (2)).

式(1)～(4)中，R1 ～R8 係表示氫原子；鹵原子；可具有含氧、氮、硫或矽之連結基之取代或非取代之碳原子數1～30之烴基；或極性基。以下說明前述之原子及基。In the formulae (1) to (4), R 1 to R 8 represent a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing oxygen, nitrogen, sulfur or hydrazine; Or polar group. The aforementioned atoms and groups are explained below.

鹵原子例如有氟原子、氯原子及溴原子。The halogen atom has, for example, a fluorine atom, a chlorine atom, and a bromine atom.

碳原子數1～30之烴基例如有甲基、乙基、丙基等之烷基；環戊基、環己基等之環烷基；乙烯基、烯丙基、丙烯基等之烯基等。The hydrocarbon group having 1 to 30 carbon atoms may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; or an alkenyl group such as a vinyl group, an allyl group or a propylene group.

此外，上述取代或非取代之烴基可直接鍵結於環構造，或可介於連結基(linkage)鍵結。連結基例如有碳原子數1～10之2價烴基(例如-(CH2 )m -(式中，m為1～10之整數)表示之伸烷基)；含氧、氮、硫或矽之連結基(例如，羰基(-CO-)、羰氧基(-O(CO)-)、磺基(-SO2 -)、醚鍵(-O-)、硫醚鍵(-S-)、亞胺基(-NH-)、醯胺鍵(-NHCO-，-CONH-)、矽氧烷鍵(-Si(R2 )O-(式中，R係甲基、乙基等之烷基))；也可為含有此等之多種的連結者。Further, the above substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure or may be bonded to a linkage. The linking group is, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, -(CH 2 ) m - (wherein, m is an integer represented by an integer of 1 to 10); and oxygen, nitrogen, sulfur or hydrazine; a linking group (for example, a carbonyl group (-CO-), a carbonyloxy group (-O(CO)-), a sulfo group (-SO 2 -), an ether bond (-O-), a thioether bond (-S-) , an imido group (-NH-), a guanamine bond (-NHCO-, -CONH-), a decane bond (-Si(R 2 )O- (wherein, R is a methyl group, an ethyl group, etc. Base)); can also be a linker containing a variety of these.

極性基例如有羥基、碳原子數1～10之烷氧基、烷氧羰基、芳氧基羰基、氰基、醯胺基、含醯亞胺環之基、三有機矽烷氧基、三有機甲矽烷基、胺基、醯基、烷氧基甲矽烷基、含磺醯基之基及羧基等。更具體而言，上述烷氧基例如有甲氧基、乙氧基等；烷基羰氧基例如有甲氧基羰基、乙氧基羰基等；芳氧基羰基例如有苯氧基羰基、萘氧基羰基、芴氧基羰基、聯苯氧基羰基等；三有機矽氧烷基例如有三甲基矽烷氧基、三乙基矽烷氧基等；三有機甲矽烷基例如有三甲基甲矽烷基、三乙基乙矽烷基等；胺基例如有第1級胺基，而烷氧基甲矽烷基例如有三甲氧基甲矽烷基、三乙氧基甲矽烷基等。The polar group is, for example, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a decylamino group, a quinone ring containing a quinone ring, a triorganodecyloxy group, or a triorganomethane group. a decyl group, an amine group, a fluorenyl group, an alkoxycarbenyl group, a sulfonyl group-containing group, a carboxyl group, and the like. More specifically, the above alkoxy group is, for example, a methoxy group, an ethoxy group or the like; the alkylcarbonyloxy group is, for example, a methoxycarbonyl group, an ethoxycarbonyl group or the like; and the aryloxycarbonyl group is, for example, a phenoxycarbonyl group or a naphthalene group. An oxycarbonyl group, a decyloxycarbonyl group, a biphenyloxycarbonyl group or the like; a triorganophosphonyloxy group such as a trimethyldecyloxy group, a triethyldecyloxy group or the like; and a triorganosylalkyl group such as a trimethylcarbinyl group. And triethyl ethinyl group or the like; the amine group has, for example, a first-stage amine group, and the alkoxycarbenyl group has, for example, a trimethoxycarbenyl group, a triethoxycarbenyl group, or the like.

本發明中，環狀烯烴系樹脂之更具體的例有下述<1>～<3>所示之共聚物。其中，<3>所示之共聚物，因具有優異的熱安定性，光學特性優異，因此特佳。In the present invention, a more specific example of the cyclic olefin resin is a copolymer represented by the following <1> to <3>. Among them, the copolymer represented by <3> is particularly excellent because it has excellent thermal stability and excellent optical properties.

<1>單體(1)與單體(2)之開環共聚物。<1> A ring-opening copolymer of the monomer (1) and the monomer (2).

<2>單體(1)與單體(2)及其他之共聚性單體之開環共聚物。<2> A ring-opening copolymer of the monomer (1) and the monomer (2) and other copolymerizable monomers.

<3><1>及<2>之開環共聚物之氫化物。<3> <1> and <2> a hydrogenated product of a ring-opening copolymer.

<單體(1)><Monomer (1)>

結構單元(1)通常來自單體(1)。以下舉單體(1)之具體例，但是本發明不受這些具體例所限定。單體(1)可組合2種以上使用。四環[4.4.0.12,5 .17,10 ]-3-十二烯、五環[6.5.1.13,6 .02,7 .09,13 ]-4-十五碳烯、五環[7.4.0.12,5 .19,12 .08,13 ]-3-十五碳烯、三環[4.4.0.12,5 ]-3-十一烯、8-甲氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-乙氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-正丙氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-異丙氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-正丁氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-苯氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-甲氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-乙氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-正丙氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-異丙氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-正丁氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-苯氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯、五環[8.4.0.12,5 .19,12 .08,13 ]-3-十六烯、七環[8.7.0.13,6 .110,17 .112,15 .02,7 .011,16 ]-4-二十碳烯、七環[8.8.0.14,7 .111,18 .113,16 .03,8 .012,17 ]-5-二十一碳烯、8-亞乙基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-苯基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-苯基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-氟四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-氟甲基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-二氟甲基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-三氟甲基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-五氟乙基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8-二氟四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,9-二氟四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8-雙(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,9-雙(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-三氟甲基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9-三氟四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9-三(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9,9-四氟四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9,9-四(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8-二氟-9,9-雙(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,9-二氟-8,9-雙(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9-三氟-9-三氟甲基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9-三氟-9-三氟甲氧基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,8,9-三氟-9-五氟丙氧基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-氟-8-五氟乙基-9,9-雙(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,9-二氟-8-七氟異丙基-9-三氟甲基四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-氯-8,9,9-三氟四環[4.4.0.12,5 .17,10 ]-3-十二烯、8,9-二氯-8,9-雙(三氟甲基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-(2,2,2-三氟乙氧基羰基)四環[4.4.0.12,5 .17,10 ]-3-十二烯、8-甲基-8-(2,2,2-三氟乙氧基羰基)四環[4.4.0.12,5 .17,10 ]-3-十二烯等。The structural unit (1) is usually derived from the monomer (1). Specific examples of the monomer (1) are given below, but the present invention is not limited by these specific examples. The monomer (1) can be used in combination of two or more kinds. Tetracycline [4.4.0.1 2,5 .1 7,10 ]-3-dodecene, pentacyclic [6.5.1.1 3,6 .0 2,7 .0 9,13 ]-4-pentadecene, Five rings [7.4.0.1 2,5 .1 9,12 .0 8,13 ]-3-pentadecene, tricyclo[4.4.0.1 2,5 ]-3-undecene, 8-methoxy Carbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-ethoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene , 8-n-propoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-isopropoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7, 10 ]-3-dodecene, 8-n-butoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-phenoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8 -methyl-8-ethoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-Methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-phenoxycarbonyltetracyclo [4.4. 0.1 2,5 .1 7,10 ]-3-dodecene, pentacyclic [8.4.0.1 2,5 .1 9 , 12.0 8,13] -3-hexadecene, heptacyclo [8.7.0.1 3,6 .1 10,17 .1 12,15 .0 2,7 .0 11,16] -4- twenty Carbene, heptacyclo[8.8.0.1 4,7 .11 11,18 .1 13,16 .0 3,8 .0 12,17 ]-5- twenty- tencarbene , 8-ethylenetetracycline [ 4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-phenyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl- 8-phenyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-fluorotetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene , 8-fluoromethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-difluoromethyltetracycline [4.4.0.1 2,5 .1 7,10 ]- 3-dodecene, 8-trifluoromethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-pentafluoroethyltetracycline [4.4.0.1 2,5 . 1,7,10 ]-3-dodecene, 8,8-difluorotetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,9-difluorotetracycline [4.4 .0.1 2,5 .1 7,10 ]-3-dodecene, 8,8-bis(trifluoromethyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene , 8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-trifluoromethyltetracycline [4.4. 0.1 2,5 .1 7,10 ]-3-dodecene, 8,8,9-trifluorotetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,8 , 9-tris(trifluoromethyl)tetracyclo[4. 4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,8,9,9-tetrafluorotetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene , 8,8,9,9-tetrakis(trifluoromethyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,8-difluoro-9,9-double (Trifluoromethyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,9-difluoro-8,9-bis(trifluoromethyl)tetracyclo[4.4 .0.1 2,5 .1 7,10 ]-3-dodecene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3 -dodecene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,8,9-three Fluorine-9-pentafluoropropoxytetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bis(trifluoro Methyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracycline [4.4 .0.1 2,5 .1 7,10 ]-3-dodecene, 8-chloro-8,9,9-trifluorotetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-12 Alkene, 8,9-dichloro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-(2,2,2 -trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl ) Four rings [4.4.0.1 2,5 .1 7,10 ]-3-dodecene, etc.

這些中，較佳為使用分子内具有至少1個極性基的單體(1)。換言之，上述式(3)中，R1 及R3 為氫原子或碳原子數1～10之烴基，R2 及R4 為氫原子或一價有機基，R2 及R4 之至少一個為氫原子及烴基以外之極性基，提高與其他素材之密著性‧接著性，因此較佳。Among these, it is preferred to use a monomer (1) having at least one polar group in the molecule. In other words, in the above formula (3), R 1 and R 3 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2 and R 4 are a hydrogen atom or a monovalent organic group, and at least one of R 2 and R 4 is at least one of The polar group other than the hydrogen atom and the hydrocarbon group is preferred because it improves the adhesion to other materials and the adhesion.

共聚物中之極性基之含量係由所望之機能等來決定，無特別限定，為了提高與其他素材之密著性‧接著性時，全結構單元(1)中具有極性基的結構單元(1)通常為含有50莫耳%以上，較佳為70莫耳%以上，更佳為80莫耳%以上。全結構單元(1)只要是具有極性基者即可。因極性基之存在可提高共擠壓製膜時，與乙烯基芳香族系樹脂層之密著性。The content of the polar group in the copolymer is determined by the desired function and the like, and is not particularly limited. In order to improve the adhesion to other materials, the structural unit having a polar group in the entire structural unit (1) is used. It is usually contained in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more. The full structural unit (1) may be any one having a polar base. The adhesion to the vinyl aromatic resin layer during co-extrusion film formation can be improved by the presence of a polar group.

R2 及R4 之至少一個為式(5)：At least one of R 2 and R 4 is formula (5):

-(CH2 )n COOR9 　(5)-(CH 2 ) n COOR 9 (5)

[式中，n通常為0～5之整數，較佳為0～2之整數，更佳為0。R9 係一價有機基]。[wherein, n is usually an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0. R 9 is a monovalent organic group].

表示之極性基的單體(1)在容易控制所得之共聚物之玻璃轉化溫度與吸水性方面較佳。式(5)中，R9 表示之一價有機基，例如有甲基、乙基、丙基等之烷基；苯基、萘基、蒽基、聯苯基等之芳基；此外例如具有二苯基碸、四氫化芴等之芴類等之芳香環或喃環、醯亞胺環等之雜環的一價基等。The monomer (1) having a polar group is preferably used in terms of easy control of the glass transition temperature and water absorbability of the resulting copolymer. In the formula (5), R 9 represents a monovalent organic group such as an alkyl group having a methyl group, an ethyl group, a propyl group or the like; an aryl group such as a phenyl group, a naphthyl group, an anthracenyl group or a biphenyl group; An aromatic ring such as a diphenylanthracene or a tetrahydroanthracene, or a monovalent group of a heterocyclic ring such as an anthracene ring or a fluorene imine ring.

又，式(5)中，n係如上述，通常為0～5之整數，n之值越小，所得之共聚物之玻璃轉化溫度越高，因此較佳，特別是n為0的單體(1)係在合成容易的方面，較佳。Further, in the formula (5), n is usually an integer of 0 to 5 as described above, and the smaller the value of n, the higher the glass transition temperature of the resulting copolymer, and therefore it is preferable, particularly the monomer having n of 0. (1) It is preferred in terms of ease of synthesis.

上述式(3)中，式(5)表示之極性基所鍵結之碳原子再鍵結烷基時，可取得所得之共聚物之耐熱性與吸水性之平衡，故較佳。該烷基之碳數較佳為1～5，更佳為1～2，特佳為1。In the above formula (3), when the carbon atom bonded to the polar group represented by the formula (5) is bonded to the alkyl group, the balance between the heat resistance and the water absorbability of the obtained copolymer can be obtained, which is preferable. The carbon number of the alkyl group is preferably from 1 to 5, more preferably from 1 to 2, particularly preferably 1.

又，式(3)中，m為1，p為0的單體(1)可得到玻璃轉化溫度較高的共聚物，故佳。Further, in the formula (3), the monomer (1) wherein m is 1 and p is 0 is preferable because a copolymer having a high glass transition temperature can be obtained.

上述單體(1)之具體例中，特別是8-甲基-8-甲氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯可提高所得之共聚物之玻璃轉化溫度，幾乎不受吸水所造成之變形等不良影響，且可維持吸水性，以與其他材料之密著性及接著性良好，因此較佳。In the specific example of the above monomer (1), especially 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene can increase the copolymerization obtained. The glass transition temperature of the object is hardly affected by deformation due to water absorption, and the water absorbing property can be maintained, and the adhesion to other materials and the adhesion are good, which is preferable.

<單體(2)><Monomer (2)>

結構單元(2)係來自單體(2)。以下列舉單體(2)之具體例，但是本發明不限於這些具體例。又，單體(2)也可組合2種以上使用。The structural unit (2) is derived from the monomer (2). Specific examples of the monomer (2) are listed below, but the present invention is not limited to these specific examples. Further, the monomer (2) may be used in combination of two or more kinds.

雙環[2.2.1]庚-2-烯(降冰片烯)、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-甲氧羰基雙環[2.2.1]庚-2-烯、5-甲基-5-甲氧基羰基-雙環[2.2.1]庚-2-烯、5-苯氧羰基雙環[2.2.1]庚-2-烯、5-甲基-5-苯氧基羰基雙環[2.2.1]庚-2-烯、5-氰基雙環[2.2.1]庚-2-烯、5-亞乙基雙環[2.2.1]庚-2-烯、5-苯基雙環[2.2.1]庚-2-烯、5-(2-萘基)雙環[2.2.1]庚-2-烯(α，β之兩型皆可)、5-氟雙環[2.2.1]庚-2-烯、5-氟甲基雙環[2.2.1]庚-2-烯、5-三氟甲基雙環[2.2.1]庚-2-烯、5-五氟乙基雙環[2.2.1]庚-2-烯、5,5-二氟雙環[2.2.1]庚-2-烯、5,6-二氟雙環[2.2.1]庚-2-烯、5,5-雙(三氟甲基)雙環[2.2.1]庚-2-烯、5,6-雙(三氟甲基)雙環[2.2.1]庚-2-烯、5-甲基-5-三氟甲基雙環[2.2.1]庚-2-烯、5,5,6-三氟雙環[2.2.1]庚-2-烯、5,5,6-三(氟甲基)雙環[2.2.1]庚-2-烯、5,5,6,6-四氟雙環[2.2.1]庚-2-烯、5,5,6,6-四(三氟甲基)雙環[2.2.1]庚-2-烯、5,5-二氟-6,6-雙(三氟甲基)雙環[2.2.1]庚-2-烯、5,6-二氟-5,6-雙(三氟甲基)雙環[2.2.1]庚-2-烯、5,5,6-三氟-5-三氟甲基雙環[2.2.1]庚-2-烯、5-氟-5-五氟乙基-6,6-雙(三氟甲基)雙環[2.2.1]庚-2-烯、5,6-二氟-5-七氟-異丙基-6-三氟甲基雙環[2.2.1]庚-2-烯、5-氯-5,6,6-三氟雙環[2.2.1]庚-2-烯、5,6-二氯-5,6-雙(三氟甲基)雙環[2.2.1]庚-2-烯、5,5,6-三氟-6-三氟甲氧基雙環[2.2.1]庚-2-烯、5,5,6-三氟-6-七氟丙氧基雙環[2.2.1]庚-2-烯、5-(4-苯基苯基)雙環[2.2.1]庚-2-烯、4-(雙環[2.2.1]庚-5-烯-2-基)苯基磺醯基苯、三環[5.2.1.02,6 ]-8-癸烯、三環[4.3.0.12,5 ]癸-3,7-二烯(二環戊二烯)等。Bicyclo[2.2.1]hept-2-ene (norbornene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5 -methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1 Hept-2-ene, 5-methyl-5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, 5-AB Bicyclo[2.2.1]hept-2-ene, 5-phenylbicyclo[2.2.1]hept-2-ene, 5-(2-naphthyl)bicyclo[2.2.1]hept-2-ene (α , both of β can be), 5-fluorobicyclo[2.2.1]hept-2-ene, 5-fluoromethylbicyclo[2.2.1]hept-2-ene, 5-trifluoromethylbicyclo[2.2 .1]hept-2-ene, 5-pentafluoroethylbicyclo[2.2.1]hept-2-ene, 5,5-difluorobicyclo[2.2.1]hept-2-ene, 5,6-di Fluobicyclo[2.2.1]hept-2-ene, 5,5-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(trifluoromethyl)bicyclo[2.2 .1]hept-2-ene, 5-methyl-5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5,5,6-trifluorobicyclo[2.2.1]hept-2- Alkene, 5,5,6-tris(fluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,5,6,6-tetrafluorobicyclo[2.2.1]hept-2-ene, 5, 5,6,6-tetrakis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,5-difluoro-6,6-bis(trifluoro Bicyclo[2.2.1]hept-2-ene, 5,6-difluoro-5,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,5,6- Trifluoro-5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bis(trifluoromethyl)bicyclo[2.2.1]g 2-ene, 5,6-difluoro-5-heptafluoro-isopropyl-6-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-chloro-5,6,6-three Fluorobicyclo[2.2.1]hept-2-ene, 5,6-dichloro-5,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,5,6-three Fluoro-6-trifluoromethoxybicyclo[2.2.1]hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo[2.2.1]hept-2-ene, 5 -(4-phenylphenyl)bicyclo[2.2.1]hept-2-ene, 4-(bicyclo[2.2.1]hept-5-en-2-yl)phenylsulfonylbenzene, tricyclo[ 5.2.1.0 2,6 ]-8-decene, tricyclo[4.3.0.1 2,5 ]indole-3,7-diene (dicyclopentadiene), and the like.

這些當中，式(4)之R5 ～R8 均為氫原子或其中之一為碳原子數1～30之烴基，其他為氫原子之單體(2)因提高製得之光學用薄膜之韌性的效果大，故較佳，特別是R5 ~R8 均為氫原子，或其中之一為甲基、乙基或苯基，其他均為氫原子之單體，從耐熱性的觀點，較佳。而從合成之容易的觀點及提高樹脂之韌性、調整玻璃轉化溫度、良好之共擠壓，確保成形性的觀點，較佳為雙環[2.2.1]庚-2-烯(降冰片烯)、5-苯基雙環[2.2.1]庚-2-烯、三環[4.3.0.12,5 ]-癸-3,7-二烯(二環戊二烯)。Among these, R 5 to R 8 of the formula (4) are each a hydrogen atom or one of them is a hydrocarbon group having 1 to 30 carbon atoms, and the other monomer (2) which is a hydrogen atom is improved by the optical film obtained. It is preferable that the effect of toughness is large, and in particular, R 5 to R 8 are each a hydrogen atom, or one of them is a methyl group, an ethyl group or a phenyl group, and the other is a monomer of a hydrogen atom, from the viewpoint of heat resistance. Preferably. From the viewpoint of ease of synthesis, improvement of resin toughness, adjustment of glass transition temperature, and good co-extrusion, and ensuring formability, bicyclo [2.2.1] hept-2-ene (norbornene) is preferred. 5-phenylbicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 2,5 ]-indole-3,7-diene (dicyclopentadiene).

本發明中，單體(1)與單體(2)之使用比例通常以重量比為單體(1)：單體(2)=95:5~5:95，較佳為95:5~60:40，更佳為95:5~70:30，更佳為95:5~75:25。單體(1)之比例當大於上述範圍時，有時無法期待韌性改良的效果，相反的，單體(1)之比例當小於上述範圍時，玻璃轉化溫度降低，有時會產生耐熱性的問題。In the present invention, the ratio of the monomer (1) to the monomer (2) is usually in the weight ratio of the monomer (1): monomer (2) = 95:5 to 5:95, preferably 95:5~ 60:40, more preferably 95:5~70:30, more preferably 95:5~75:25. When the ratio of the monomer (1) is more than the above range, the effect of improving the toughness may not be expected. Conversely, when the ratio of the monomer (1) is less than the above range, the glass transition temperature is lowered, and heat resistance may occur. problem.

又為了提高與其他素材之密著性‧接著性時，在結構單元(1)及結構單元(2)之全量中，具有極性基的結構單元通常為含有50~95莫耳%，較佳為70~95莫耳%，更佳為80~95莫耳%以上。因極性基之存在，共擠壓製膜時，可提高與乙烯基芳香族系樹脂層之密著性。Further, in order to improve the adhesion to other materials and the adhesion, in the total amount of the structural unit (1) and the structural unit (2), the structural unit having a polar group usually contains 50 to 95 mol%, preferably 70~95% by mole, more preferably 80~95% by mole. When the film is formed by co-extrusion due to the presence of a polar group, the adhesion to the vinyl aromatic resin layer can be improved.

<其他的共聚性單體><Other copolymerizable monomers>

可與單體(1)及單體(2)共聚之其他共聚性單體，例如有環丁烯、環戊烯、環庚烯、環辛烯、三環[5.2.1.02,6 ]-3-癸烯等之環烯烴。環烯烴之碳數較佳為4~20，更佳為5~12。又，這些共聚性單體可用於改良相位差表現性、Tg調整、成形性改良等、樹脂改質。Other copolymerizable monomers copolymerizable with the monomer (1) and the monomer (2), for example, cyclobutene, cyclopentene, cycloheptene, cyclooctene, tricyclo[5.2.1.0 2,6 ]- a cycloolefin such as 3-decene. The carbon number of the cyclic olefin is preferably from 4 to 20, more preferably from 5 to 12. Further, these copolymerizable monomers can be used for improving the phase difference expression, Tg adjustment, moldability improvement, and the like, and resin modification.

又，可在聚丁二烯、聚異戊二烯、苯乙烯-丁二烯共聚物、乙烯-非共軛二烯共聚物、降冰片烯衍生物等之主鏈，含有烯烴不飽和鍵之不飽和烴系聚合物等之存在下，使單體(1)及單體(2)產生聚合。此時，所得之共聚物可作為耐衝擊性較大之樹脂的原料使用。Further, in the main chain of polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, norbornene derivative, etc., an olefin unsaturated bond may be contained. The monomer (1) and the monomer (2) are polymerized in the presence of an unsaturated hydrocarbon-based polymer or the like. In this case, the obtained copolymer can be used as a raw material of a resin having high impact resistance.

單體(1)及單體(2)與共聚性環狀單體或含有不飽和雙鍵之化合物之使用比例係[單體(1)＋單體(2)]：[共聚性環狀單體或含有不飽和雙鍵之化合物]以重量比較佳為100：0~50：50，更佳為100：0~60：40，特佳為100：0~70：30。The ratio of use of the monomer (1) and the monomer (2) to the copolymerizable cyclic monomer or the compound containing an unsaturated double bond is [monomeric (1) + monomer (2)]: [copolymerizable cyclic single The compound or the compound containing an unsaturated double bond is preferably 100:0 to 50:50, more preferably 100:0 to 60:40, and particularly preferably 100:0 to 70:30.

<開環聚合觸媒><Open-loop polymerization catalyst>

特定單體之開環聚合反應係於複分解(Metathesis)觸媒之存在下進行。此複分解觸媒係選自鎢化合物、鉬化合物及錸化合物之至少1種金屬化合物(以下稱為「(a)成分」)，與選自週期表IA族元素(例如Li、Na、K等)、IIA族元素(例如Mg、Ca等)、IIB族元素(例如Zn、Cd、Hg等)、IIIA族元素(例如B、Al等)、IVB族元素(例如Ti、Zr等)或IVA族元素(例如Si、Sn、Pb等)之化合物，且選自至少具有一個該元素與碳之鍵結或該元素與氫之鍵結者之至少一種化合物(以下稱為「(b)成分」)之組合所成者，為了提高觸媒活性時，可再含有添加劑(以下稱為「(c)成分」)。The ring opening polymerization of a specific monomer is carried out in the presence of a metathesis catalyst. The metathesis catalyst is selected from at least one metal compound of a tungsten compound, a molybdenum compound, and a ruthenium compound (hereinafter referred to as "(a) component)), and is selected from elements of Group IA of the periodic table (for example, Li, Na, K, etc.). , Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVB elements (eg, Ti, Zr, etc.) or Group IVA elements a compound (for example, Si, Sn, Pb, etc.), and is selected from at least one compound having at least one bond of the element and carbon or a bond of the element to hydrogen (hereinafter referred to as "(b) component)" In order to increase the activity of the catalyst, the additive may further contain an additive (hereinafter referred to as "(c) component").

構成上述(a)成分之較佳的金屬化合物之具體例有WCl6 、MoCl5 、ReOCl3 等之日本特開平1-240517號公報所記載的金屬化合物。Specific examples of the preferred metal compound constituting the above-mentioned component (a) include a metal compound described in JP-A No. 1-240517, such as WCl 6 , MoCl 5 or ReOCl 3 .

構成上述(b)成分之化合物的具體例有n-C4 H9 Li、(C2 H5 )3 Al、(C2 H5 )2 AlCl、(C2 H5 )15 AlCl15 、(C2 H5 )AlCl2 、甲基鋁氧烷、LiH等之日本特開平1-240517號公報所記載的化合物。Specific examples of the compound constituting the above component (b) are nC 4 H 9 Li, (C 2 H 5 ) 3 Al, (C 2 H 5 ) 2 AlCl, (C 2 H 5 ) 15 AlCl 15 , (C 2 H). 5 ) A compound described in JP-A-1-240517, such as AlCl 2 , methylaluminoxane or LiH.

上述(c)成分可使用例如醇類、醛類、酮類、胺類等，其他也可使用日本特開平1-240517號公報所示之化合物。For the component (c), for example, an alcohol, an aldehyde, a ketone, an amine or the like can be used, and other compounds such as those shown in JP-A-1-240517 can be used.

又，上述(a)(b)(c)成分以外之複分解觸媒可使用作為Graves’s觸媒之公知的釕化合物。Further, as the metathesis catalyst other than the above components (a), (b) and (c), a known ruthenium compound which is a Graves's catalyst can be used.

<氫化><hydrogenation>

上述<3>所示之氫化(共)聚合物之氫化率通常為50%以上，較佳為70%以上，更佳為90%以上，更佳為97%以上，特佳為99%以上。The hydrogenation ratio of the hydrogenated (co)polymer represented by the above <3> is usually 50% or more, preferably 70% or more, more preferably 90% or more, still more preferably 97% or more, and particularly preferably 99% or more.

本發明所使用之環狀烯烴系樹脂，在30℃之氯仿中，測定的固有黏度[ηinh ]較佳為0.2～5.0dl/g。The cyclic olefin resin used in the present invention has an intrinsic viscosity [η inh ] of preferably 0.2 to 5.0 dl/g as measured in chloroform at 30 °C.

又，環狀烯烴系樹脂之平均分子量係以凝膠滲透層析儀(GPC)所測定的聚苯乙烯換算之數平均分子量(Mn)較佳為8,000～100,000，重量平均分子量(Mw)較佳為20,000～300,000的範圍。Further, the average molecular weight of the cyclic olefin resin is preferably 8,000 to 100,000 in terms of polystyrene in terms of polystyrene conversion measured by a gel permeation chromatography (GPC), and the weight average molecular weight (Mw) is preferably. It is in the range of 20,000 to 300,000.

環狀烯烴系樹脂之玻璃轉化溫度(TgA)為了確保熱安定性及共擠壓成形性，較佳為100～250℃，更佳為110～180℃，特佳為120～170℃。本發明使用之環狀烯烴系樹脂薄膜係由含有如上述之環狀烯烴系樹脂之樹脂組成物所形成。樹脂組成物中，除了環狀烯烴系樹脂之外，必要時可在不損及發明效果的範圍內，添加抗氧化劑、熱穩定劑、光穩定劑、相位差調整劑、紫外線吸收劑、防靜電劑、分散劑、加工性提昇劑、氯捕捉劑、阻燃劑、結晶化核劑、防止黏連劑、防霧劑、脫模劑、顏料、有機或無機的填充材料、中和劑、滑劑、分解劑、金屬惰性劑、污染防止材料、抗菌劑或其他樹脂、熱可塑性彈性體等之公知的添加劑。The glass transition temperature (TgA) of the cyclic olefin resin is preferably from 100 to 250 ° C, more preferably from 110 to 180 ° C, even more preferably from 120 to 170 ° C, in order to ensure thermal stability and coextrusion moldability. The cyclic olefin resin film used in the present invention is formed of a resin composition containing the above cyclic olefin resin. In the resin composition, in addition to the cyclic olefin resin, an antioxidant, a heat stabilizer, a light stabilizer, a phase difference adjuster, an ultraviolet absorber, and an antistatic agent may be added as needed within a range that does not impair the effects of the invention. Agent, dispersant, processability enhancer, chlorine scavenger, flame retardant, crystallization nucleating agent, anti-adhesion agent, anti-fogging agent, mold release agent, pigment, organic or inorganic filler, neutralizer, slippery A known additive such as a agent, a decomposer, a metal inert agent, a contamination preventing material, an antibacterial agent or other resin, a thermoplastic elastomer or the like.

乙烯基芳香族系樹脂Vinyl aromatic resin

本發明使用之乙烯基芳香族系樹脂，較佳為具有下述式(6)表示之結構單元(6)。The vinyl aromatic resin used in the present invention preferably has a structural unit (6) represented by the following formula (6).

【化5】【化5】

[式(6)中，R10 係表示氫原子或甲基。R11 ～R13 係各自獨立表示氫原子；鹵原子；可具有含有氧、氮、硫或矽之連結基之取代或非取代之碳原子數1～30之烴基；極性基]。In the formula (6), R 10 represents a hydrogen atom or a methyl group. R 11 to R 13 each independently represent a hydrogen atom; a halogen atom; and a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; a polar group; which contains a linking group of oxygen, nitrogen, sulfur or hydrazine;

衍生結構單元(6)之單體的具體例有苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、o-甲基苯乙烯、p-三氟甲基苯乙烯、p-甲氧基苯乙烯、p-羥基苯乙烯、p-氯苯乙烯、p-硝基苯乙烯、p-胺基苯乙烯、p-羧基苯乙烯、p-苯基苯乙烯、p-tert丁氧基苯乙烯、2,4,6-三甲基苯乙烯等。這些單體可單獨或倂用兩種以上來使用。這些單體中，較佳為苯乙烯、α-甲基苯乙烯、p-羥基苯乙烯以單獨或倂用。Specific examples of the monomer of the derivatized structural unit (6) are styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-trifluoromethylstyrene, p-methoxy Styrene, p-hydroxystyrene, p-chlorostyrene, p-nitrostyrene, p-aminostyrene, p-carboxystyrene, p-phenylstyrene, p-tert butoxybenzene Ethylene, 2,4,6-trimethylstyrene, and the like. These monomers may be used singly or in combination of two or more. Among these monomers, styrene, α-methylstyrene, and p-hydroxystyrene are preferably used singly or in combination.

乙烯基芳香族系樹脂較佳為具有下述式(7)表示之結構單元(7)及/或下述式(8)表示之結構單元(8)。The vinyl aromatic resin preferably has a structural unit (7) represented by the following formula (7) and/or a structural unit (8) represented by the following formula (8).

【化6】【化6】

[式(7)中，X係氧原子或具有取代基之氮原子。式(8)中，R15 係氫原子或碳原子數1～30之烴基。碳原子數1～30之烴基例如有甲基、乙基、丙基等之烷基；環戊基、環己基等之環烷基；乙烯基、烯丙基、丙烯基等之烯基等。R14 係表示氫原子或甲基]。[In the formula (7), an X-based oxygen atom or a nitrogen atom having a substituent. In the formula (8), R 15 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group having 1 to 30 carbon atoms may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; or an alkenyl group such as a vinyl group, an allyl group or a propylene group. R 14 represents a hydrogen atom or a methyl group].

乙烯基芳香族系樹脂可為含有結構單元(7)與結構單元(8)兩者的結構，也可為含有結構單元(7)與結構單元(8)其中之一的結構。又，結構單元(7)之酸酐結構或醯亞胺結構可進行水解形成二羧酸結構或醯胺酸結構。The vinyl aromatic resin may have a structure including both the structural unit (7) and the structural unit (8), or may have a structure including one of the structural unit (7) and the structural unit (8). Further, the acid anhydride structure or the quinone imine structure of the structural unit (7) may be hydrolyzed to form a dicarboxylic acid structure or a proline structure.

衍生結構單元(7)之單體的具體例有順丁烯二酸酐、順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等之N取代順丁烯二醯亞胺類、順丁烯二酸及其衍生物、反丁烯二酸及其衍生物等。這些單體可單獨或倂用兩種類以上來使用。這些單體中，從耐熱性及與環狀烯烴系樹脂層之密著性的觀點，較佳為使用順丁烯二酸酐、N-苯基順丁烯二醯亞胺。Specific examples of the monomer of the derivatized structural unit (7) are N-substituted maleimide groups such as maleic anhydride, maleic acid imide, N-phenyl maleimide, and the like. , maleic acid and its derivatives, fumaric acid and its derivatives. These monomers may be used singly or in combination of two or more types. Among these monomers, maleic anhydride and N-phenyl maleimide are preferably used from the viewpoint of heat resistance and adhesion to the cyclic olefin resin layer.

衍生結構單元(8)之單體的具體例有、(甲基)丙烯酸、(甲基)丙烯酸甲酯等之(甲基)丙烯酸烷酯、(甲基)丙烯酸醯胺等。這些單體可單獨或倂用兩種類以上來使用。這些單體中，從耐熱性及與環狀烯烴系樹脂層之密著性的觀點，較佳為使用(甲基)丙烯酸、(甲基)丙烯酸甲酯。Specific examples of the monomer of the derivatized structural unit (8) include alkyl (meth)acrylate such as (meth)acrylic acid or methyl (meth)acrylate, and decylamine (meth)acrylate. These monomers may be used singly or in combination of two or more types. Among these monomers, (meth)acrylic acid or methyl (meth)acrylate is preferably used from the viewpoint of heat resistance and adhesion to the cyclic olefin-based resin layer.

本發明中，乙烯基芳香族系樹脂中之結構單元(6)與結構單元(7)及/或結構單元(8)之使用比例，通常以重量比表示時，結構單元(6)：[結構單元(7)＋結構單元(8)]=100:0～50:50，較佳為98:2～60:40，更佳為95:5～70:30。使用比例在上述範圍時，可調整玻璃轉化溫度、調整相位差表現性、確保共擠壓成形性、確保與環狀烯烴系樹脂層之密著性。In the present invention, when the ratio of the structural unit (6) to the structural unit (7) and/or the structural unit (8) in the vinyl aromatic resin is usually expressed by a weight ratio, the structural unit (6): [structure The unit (7) + structural unit (8)] = 100:0 to 50:50, preferably 98:2 to 60:40, more preferably 95:5 to 70:30. When the use ratio is in the above range, the glass transition temperature can be adjusted, the phase difference expression property can be adjusted, the co-extrusion moldability can be ensured, and the adhesion to the cyclic olefin-based resin layer can be ensured.

結構單元(7)、結構單元(8)之外，必要時可含有乙烯、丙烯、丁烯、丁二烯、異戊二烯、(甲基)丙烯腈、α-氯丙烯腈、乙酸乙烯酯、氯化乙烯等之其他的單體也作為共聚成分。In addition to the structural unit (7) and the structural unit (8), if necessary, ethylene, propylene, butene, butadiene, isoprene, (meth)acrylonitrile, α-chloroacrylonitrile, vinyl acetate may be contained. Other monomers such as chlorinated ethylene are also used as a copolymerization component.

本發明使用之乙烯基芳香族系樹脂係在30℃下之氯苯溶液(濃度0.5g/dL)中測定的對數黏度(η)較佳為0.1～3.0dL/g。又，以凝膠滲透層析儀(GPC)所測定的聚苯乙烯換算之重量平均分子量Mw通常為30,000～1,000,000，較佳為40,000～800,000，更佳為50,000～500,000。分子量太小時，有時所得之薄膜等之成形品的強度降低。分子量太大時，溶液黏度太高，有時用於本發明之樹脂組成物之生產性及加工性變差。The logarithmic viscosity (η) measured by the vinyl aromatic resin used in the present invention in a chlorobenzene solution (concentration: 0.5 g/dL) at 30 ° C is preferably from 0.1 to 3.0 dL/g. Further, the weight average molecular weight Mw in terms of polystyrene measured by a gel permeation chromatography (GPC) is usually 30,000 to 1,000,000, preferably 40,000 to 800,000, more preferably 50,000 to 500,000. When the molecular weight is too small, the strength of the molded article such as the obtained film may be lowered. When the molecular weight is too large, the viscosity of the solution is too high, and the productivity and workability of the resin composition of the present invention are sometimes deteriorated.

乙烯基芳香族系樹脂之分子量分布(Mw/Mn)通常為1.0～10，較佳為1.2～5.0，更佳為1.2～4.0。The molecular weight distribution (Mw/Mn) of the vinyl aromatic resin is usually from 1.0 to 10, preferably from 1.2 to 5.0, more preferably from 1.2 to 4.0.

本發明使用之乙烯基芳香族系樹脂，較佳為將衍生結構單元(6)、(7)、(8)之上述單體，在適當之聚合起始劑之存在下，產生聚合反應的方法來製造。聚合起始劑例如使用自由基聚合起始劑、陰離子聚合觸媒、配位聚合觸媒、陽離子聚合觸媒等，特佳為使用自由基聚合起始劑。The vinyl aromatic resin used in the present invention is preferably a method for producing a polymerization reaction by using the above-mentioned monomers of the derivatized structural units (6), (7), and (8) in the presence of a suitable polymerization initiator. To manufacture. As the polymerization initiator, for example, a radical polymerization initiator, an anionic polymerization catalyst, a coordination polymerization catalyst, a cationic polymerization catalyst, or the like is used, and a radical polymerization initiator is particularly preferably used.

聚合反應使用之自由基起始劑可使用產生自由基之公知的有機過氧化物或偶氮系之自由基聚合起始劑。多官能起始劑或容易產生脫氫反應的起始劑，可能會降低所得之苯乙烯系共聚物之線狀性，因此不理想。As the radical initiator used in the polymerization, a known organic peroxide or an azo radical polymerization initiator which generates a radical can be used. A polyfunctional initiator or an initiator which easily causes a dehydrogenation reaction may lower the linearity of the obtained styrene copolymer, which is not preferable.

有機過氧化物例如有二乙醯過氧化物、二苯醯過氧化物、二異丁醯過氧化物、二(2,4-二氯化苯醯)過氧化物、二(3,5,5-三甲基己醯)過氧化物、二辛醯過氧化物、二月桂醯過氧化物、二硬脂醯過氧化物、雙(4-(m-甲苯醯)苯醯)過氧化物等之二烷醯基過氧化物類；甲基乙基酮過氧化物、環己酮過氧化物、甲基環己酮過氧化物、乙醯丙酮過氧化物等之酮的過氧化物類；過氧化氫、t-丁基過氧化氫、a-異丙苯過氧化氫、p-萜烷過氧化氫、二異丙基苯過氧化氫、1,1,3,3-四甲基丁基過氧化氫、t-己基過氧化氫等之過氧化氫類；二-t-丁基過氧化物、二異丙苯基過氧化物、二月桂基過氧化物、a,a’-雙(t-丁基過氧)二異丙基苯、2,5-二甲基-2,5-雙(t-丁基過氧)己烷、t-丁基異丙苯基過氧化物、2,5-二甲基-2,5-雙(t-丁基過氧)己炔-3等之二烷基過氧化物類；t-丁基過氧化乙酸酯、t-丁基過氧化三甲基乙酸酯、t-己烷過氧化三甲基乙酸酯、1,1,3,3-四甲基丁基過氧化2-乙基己酸酯、2,5-二甲基-2,5-雙(2-乙基己醯過氧化)己烷、1-環己基-1-甲基乙基過氧化2-乙基己酸酯、t-己基過氧化2-乙基己酸酯、t-丁基過氧化2-乙基己酸酯、t-丁基過氧化異丁酸酯、t-丁基過氧化順丁烯二酸酯、t-丁基過氧化3,5,5-三甲基己酸酯、t-丁基過氧化月桂酸酯、2,5-二甲基-2,5-雙(m-甲苯醯過氧化)己烷、a,a’-雙(新癸醯過氧化)二異丙基苯、異丙苯基過氧化新癸酸酯、1,1,3,3-四甲基丁基過氧化新癸酸酯、1-環己基-1-甲基乙基過氧化新癸酸酯、t-己基過氧化新癸酸酯、t-丁基過氧化新癸酸酯、t-丁基過氧化苯甲酸酯、t-己基過氧化苯甲酸酯、雙(t-丁基過氧化)間苯二甲酸酯、2,5-二甲基-2,5-雙(苯醯過氧化)己烷、t-丁基過氧化m-甲苯醯基苯甲酸酯、3,3’,4,4’-四(t-丁基過氧羰基)二苯甲酮等之過氧化酯類；1,1-雙(t-己基過氧化)3,3,5-三甲基環己烷、1,1-雙(t-己基過氧化)環己烷、1,1-雙(t-丁基過氧化)3,3,5-三甲基環己烷、1,1-雙(t-丁基過氧化)環己烷、1,1-雙(t-丁基過氧化)環十二烷、2,2-雙(t-丁基過氧化)丁烷、n-丁基4,4-雙(t-丁基過氧化)三甲基乙酸酯、2,2-雙(4,4-二-t-丁基過氧化環己基)丙烷等之過氧化縮酮類；t-己基過氧化異丙基單碳酸酯、t-丁基過氧化異丙基單碳酸酯、t-丁基過氧化2-乙基己基單碳酸酯、t-丁基過氧化烯丙基單碳酸酯等之過氧化單碳酸酯類；二-sec-丁基過氧化二碳酸酯、二-n-丙基過氧化二碳酸酯、二異丙基過氧化二碳酸酯、雙(4-t-丁基環己基)過氧化二碳酸酯、二-2-乙氧基乙基過氧化二碳酸酯、二-2-乙基己基過氧化二碳酸酯、二-2-甲氧基丁基過氧化二碳酸酯、二(3-甲基-3-甲氧基丁基)過氧化二碳酸酯等之過氧化二碳酸酯類；其他可列舉t-丁基三甲基甲矽烷基過氧化物等,但是本發明可使用的有機過氧化物並不限於此等例示之化合物。The organic peroxides are, for example, diethyl hydrazine peroxide, diphenyl hydrazine peroxide, diisobutyl hydrazine peroxide, bis(2,4-dichlorophenylhydrazine) peroxide, and two (3, 5, 5-trimethylhexyl) peroxide, dioctyl peroxide, dilaurin peroxide, distearyl peroxide, bis(4-(m-toluene) benzoquinone) peroxide a peroxide such as a dimethyl ketone peroxide; a methyl ketone peroxide, a cyclohexanone peroxide, a methylcyclohexanone peroxide, an acetone acetone peroxide or the like Hydrogen peroxide, t-butyl hydroperoxide, a-cumyl hydroperoxide, p-decane hydrogen peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethyl Hydrogen peroxide such as butyl hydroperoxide or t-hexyl hydroperoxide; di-t-butyl peroxide, dicumyl peroxide, dilauryl peroxide, a, a'- Bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butyl cumyl peroxide a dialkyl peroxide of 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3; t-butyl peroxyacetate, t-butyl Over Trimethyl acetate, t-hexane trimethyl acetate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, 2,5-dimethyl 2-,5-bis(2-ethylhexyl peroxy)hexane, 1-cyclohexyl-1-methylethylperoxide 2-ethylhexanoate, t-hexylperoxide 2-ethyl Hexanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy maleate, t-butyl peroxidation 3, 5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluene peroxy)hexane, a, a'- Bis(new bismuth peroxide) diisopropylbenzene, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl- 1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxybenzoate, t-hexyl peroxidation Benzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(phenylhydrazine peroxy)hexane, t-butylperoxide m -toluene benzoate, 3,3',4,4'-tetrakis (t-butylperoxycarbonyl)benzophenone, etc. Oxidized esters; 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-double (t-butyl peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butyl peroxidation) Cyclododecane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)trimethylacetate, 2,2- Peroxy ketals such as bis(4,4-di-t-butylperoxycyclohexyl)propane; t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate a peroxymonocarbonate such as t-butylperoxide 2-ethylhexyl monocarbonate or t-butyl peroxyallyl monocarbonate; di-sec-butyl peroxydicarbonate, -n-propyl peroxydicarbonate, diisopropylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethylperoxide Carbonate, di-2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxydicarbonate Peroxydicarbonates such as esters; others may be t-butyl The base trimethylmethane alkyl peroxide or the like, but the organic peroxide usable in the present invention is not limited to the compounds exemplified above.

偶氮系自由基聚合起始劑例如有偶氮雙異丁腈、偶氮雙異戊腈、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-腈)、2-(胺基甲醯偶氮)異丁腈、2,2’-偶氮雙[2-甲基-N-{1,1-雙(羥基甲基)-2-羥基乙基}丙醯胺]、2,2’-偶氮雙[2-甲基-N-{2-(1-羥基丁基)}丙醯胺]、2,2’-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]、2,2’-偶氮雙[N-(2-丙基)-2-甲基丙醯胺]、2,2’-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2’-偶氮雙(N-環己基-2-甲基丙醯胺)、2,2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二硫酸鹽.二水合物、2,2’-偶氮雙[2-(3,4,5,6-四氫嘧啶-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-{1-(2-羥基乙基)-2-咪唑啉-2-基}丙烷]二氫氯化物、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2’-偶氮雙(2-甲基二乙基甲酮脒)二氫氯化物、2,2’-偶氮雙[N-(2-羧基乙基)-2-甲基-二乙基甲酮脒]、2,2’-偶氮雙(2-甲基二乙基甲酮胺肟)、二甲基2,2’-偶氮雙丁酸酯、4,4’-偶氮雙(4-氰基正戊酸)、2,2’-偶氮雙(2,4,4-三甲基戊烷)等,但本發明使用之偶氮系自由基聚合起始劑不限於此等例示之化合物。The azo-based radical polymerization initiators are, for example, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) , 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane -1-carbonitrile), 2-(aminomethyl azo azo) isobutyronitrile, 2,2'-azobis[2-methyl-N-{1,1-bis(hydroxymethyl)-2- Hydroxyethyl}propanolamine], 2,2'-azobis[2-methyl-N-{2-(1-hydroxybutyl)}propanamide], 2,2'-azobis [ 2-methyl-N-(2-hydroxyethyl)propanamide], 2,2'-azobis[N-(2-propyl)-2-methylpropanamide], 2,2' - azobis(N-butyl-2-methylpropanamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [2-(5-Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrogen Chloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate. Dihydrate, 2,2'-azobis[2-(3,4, 5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-{1-(2-hydroxyethyl)-2-imidazolin-2-yl} Propane]dihydrochloride, 2,2'-even Bis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methyldiethyl ketone oxime) dihydrochloride, 2,2'-azo double [N-(2-carboxyethyl)-2-methyl-diethyl ketone oxime], 2,2'-azobis(2-methyldiethyl ketone oxime), dimethyl 2 , 2'-azobisbutyrate, 4,4'-azobis(4-cyano-p-pentanoic acid), 2,2'-azobis(2,4,4-trimethylpentane) And the like, but the azo-based radical polymerization initiator used in the present invention is not limited to the compounds exemplified herein.

此等自由基起始劑之使用量係衍生乙烯基芳香族系樹脂之單體總量100莫耳%中,通常為0.01～5莫耳%,較佳為0.03～3莫耳%,更佳為0.05～2莫耳%。These radical initiators are used in an amount of 100 mol% based on the total amount of monomers derived from the vinyl aromatic resin, usually 0.01 to 5 mol%, preferably 0.03 to 3 mol%, more preferably It is 0.05 to 2 mol%.

此外,衍生前述乙烯基芳香族系樹脂之單體的共聚反應中,可使用觸媒。此觸媒並無特別限定,例如有習知的陰離子聚合觸媒、配位陰離子聚合觸媒、陽離子聚合觸媒等。Further, a catalyst may be used in the copolymerization reaction of the monomer from which the vinyl aromatic resin is derived. The catalyst is not particularly limited, and examples thereof include a conventional anionic polymerization catalyst, a coordination anionic polymerization catalyst, and a cationic polymerization catalyst.

衍生前述乙烯基芳香族系樹脂之單體的共聚反應係於上述聚合起始劑或觸媒之存在下，藉由以塊狀聚合法、溶液聚合法、沉澱聚合法、乳化聚合法、懸浮聚合法或塊狀-懸浮聚合法等之以往習知的方法進行共聚來進行。The copolymerization reaction of the monomer from which the vinyl aromatic resin is derived is carried out in the presence of the above polymerization initiator or catalyst by a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, an emulsion polymerization method, or a suspension polymerization. Conventional methods such as a method or a bulk-suspension polymerization method are carried out by copolymerization.

實施溶液聚合時所使用之溶劑只要是可溶解前述單體及聚合物者時，即無特別限定，較佳為環己酮等之烴系溶劑、甲苯等之芳香族烴系溶劑、甲基乙基酮等之酮系溶劑。溶劑之使用量係對於前述單體全量，較佳為0～3倍(重量比)的量。The solvent to be used in the solution polymerization is not particularly limited as long as it can dissolve the monomer and the polymer, and is preferably a hydrocarbon solvent such as cyclohexanone or an aromatic hydrocarbon solvent such as toluene or methyl b. A ketone solvent such as a ketone. The amount of the solvent to be used is preferably from 0 to 3 times by weight based on the total amount of the above monomers.

聚合反應時間通常為1～30小時，較佳為3～20小時，聚合反應溫度係依使用之自由基起始劑之種類而定，無特別限定，通常為40～180℃，較佳為50～120℃。The polymerization reaction time is usually 1 to 30 hours, preferably 3 to 20 hours, and the polymerization temperature is not particularly limited depending on the type of the radical initiator to be used, and is usually 40 to 180 ° C, preferably 50. ~120 ° C.

乙烯基芳香族系樹脂之玻璃轉化溫度(TgB)為了確保熱安定性及共擠壓成形性，較佳為110～200℃，更佳為120～170℃。本發明使用之乙烯基芳香族系樹脂薄膜可由如上述之含有乙烯基芳香族系樹脂之樹脂組成物所形成。樹脂組成物中，除了乙烯基芳香族系樹脂之外，必要時可在不損及發明效果的範圍內，添加抗氧化劑、熱穩定劑、光穩定劑、相位差調整劑、紫外線吸收劑、防靜電劑、分散劑、加工性提昇劑、氯捕捉劑、阻燃劑、結晶化核劑、防止黏達劑、防霧劑、脫模劑、顏料、有機或無機的填充材料、中和劑、滑劑、分解劑、金屬惰性劑、污染防止材料、抗菌劑或其他樹脂、熱可塑性彈性體等之公知的添加劑。The glass transition temperature (TgB) of the vinyl aromatic resin is preferably from 110 to 200 ° C, more preferably from 120 to 170 ° C, in order to ensure thermal stability and coextrusion moldability. The vinyl aromatic resin film used in the present invention can be formed from the above-described resin composition containing a vinyl aromatic resin. In the resin composition, in addition to the vinyl aromatic resin, an antioxidant, a heat stabilizer, a light stabilizer, a phase difference adjuster, an ultraviolet absorber, and an anti-antioxidant may be added as needed within a range that does not impair the effects of the invention. Electrostatic agent, dispersant, processability enhancer, chlorine scavenger, flame retardant, crystallization nucleating agent, anti-adhesion agent, anti-fogging agent, mold release agent, pigment, organic or inorganic filler, neutralizer, A known additive such as a slip agent, a decomposing agent, a metal inert agent, a contamination preventing material, an antibacterial agent or other resin, a thermoplastic elastomer or the like.

又，Noverchemicals 製 Dilark D332、Dilark D232、大日本油墨化學工業製RYU REXA14、RYU REXA15、CHI MEI製PN-177等之市販樹脂也可作為本發明之乙烯基芳香族系樹脂使用。Further, a commercially available resin such as Dilark D332, Dilark D232 manufactured by Nover Chemicals, RYU REXA14 manufactured by Dainippon Ink and Chemicals, RYU REXA15, and PN-177 manufactured by CHI MEI can also be used as the vinyl aromatic resin of the present invention.

得到原始薄膜的步驟Step of obtaining the original film

得到環狀烯烴系樹脂層(A層)與乙烯基芳香族系樹脂層(B層)被層合之原始薄膜的方法係藉由共擠壓的層合製膜。具體而言，例如有共擠壓T模法、共擠壓吹塑法、共擠壓層合法等。本發明從製造效率、強度之確保、光學特性、相位差控制的觀點，較佳為使用A層/B層之二層所構成之層合光學薄膜、A層/B層/A層之三層所構成之層合光學薄膜及B層/A層/B層之三層所構成之層合光學薄膜。二層所構成之層合光學薄膜係在光學特性(透明性)、相位差控制方面更佳，三層所構成之層合光學薄膜係在防止薄膜之曲翹，得到力學強度方面更佳。A method of obtaining an original film in which a cyclic olefin-based resin layer (layer A) and a vinyl aromatic resin layer (layer B) are laminated is a film formed by co-extrusion lamination. Specifically, there are, for example, a co-extrusion T-die method, a co-extrusion blow molding method, a co-extrusion lamination method, and the like. The present invention preferably uses a laminated optical film composed of two layers of the A layer/B layer, and a layer of the A layer/B layer/A layer from the viewpoints of manufacturing efficiency, strength assurance, optical characteristics, and phase difference control. A laminated optical film comprising a laminated optical film and three layers of a B layer/A layer/B layer. The laminated optical film composed of the two layers is more preferable in terms of optical characteristics (transparency) and phase difference control, and the laminated optical film composed of the three layers is excellent in mechanical strength in preventing warpage of the film.

共擠壓法之擠壓溫度係以樹脂適合擠壓製膜之溶融黏度來適當選擇，其中A層、B層較佳為200～350℃，更佳為230～300℃，更佳為240～280℃。A層之擠壓溫度與B層之擠壓溫度之溫度差係當兩樹脂在T模内或餵料塊(feed block)内接觸時，不會因溫度變化造成溶融黏度過度變化，成形性變差的情形，較佳為50℃以内，更佳為30℃以内，更佳為20℃以内。構成A層與B層之樹脂之溶融黏度之差係為了確保成形性，特別是各層之厚度之均一性，較佳為5倍以内，更佳為3倍以内，更佳為2倍以内。The extrusion temperature of the co-extrusion method is appropriately selected according to the melt viscosity of the resin suitable for extrusion film formation, wherein the A layer and the B layer are preferably 200 to 350 ° C, more preferably 230 to 300 ° C, more preferably 240 to 280 ° C. The temperature difference between the extrusion temperature of layer A and the extrusion temperature of layer B is such that when the two resins are contacted in the T-die or in the feed block, the melt viscosity is not excessively changed due to temperature change, and the formability is changed. In the case of a poor condition, it is preferably within 50 ° C, more preferably within 30 ° C, and even more preferably within 20 ° C. The difference in the melt viscosity of the resin constituting the layer A and the layer B is preferably within 5 times, more preferably within 3 times, more preferably within 2 times, in order to ensure formability, particularly the uniformity of the thickness of each layer.

本發明使用之環狀烯烴系樹脂與乙烯基芳香族系樹脂係因彼此之密著性優，因此薄膜層間不需要設置接著層、黏著層，或實施電暈處理、電漿處理、底漆處理等之易接著處理。藉由共擠壓之熱融黏，在A層與B層直接接觸的狀態下，可得到充分的密著強度。又，即使進行拉伸處理後，A層與B層之密著性也保持良好。Since the cyclic olefin resin and the vinyl aromatic resin used in the present invention are excellent in adhesion to each other, it is not necessary to provide an adhesive layer or an adhesive layer between the film layers, or to perform corona treatment, plasma treatment, or primer treatment. Wait for the easy processing. By the thermal fusion of the co-extrusion, a sufficient adhesion strength can be obtained in a state where the layer A and the layer B are in direct contact. Moreover, even after the stretching treatment, the adhesion between the A layer and the B layer was kept good.

所得之原始薄膜較佳為在寬度方向、長度方向之厚度皆為均一。厚度偏差係造成所得之層合光學薄膜之相位差偏差的原因，影響組裝於液晶顯示裝置時之顯示均一性。因此，以產生厚度偏差之原因的模線(因T模唇受傷等所造成之長度方向的線)、交叉痕跡(cross mark)(長度方向之週期性的厚度變動)等較少為佳。又，導致點狀之缺點如量點或漏光漏等顯示不良之凝膠、異物等也是較少為佳。這些可藉由例如使用具有聚合物過濾器之擠壓機、溶融樹脂之滯留時間最佳化、降低齒輪泵之脈動、T模唇之研磨或表面處理、轉印輥、剝離輥之平滑化、表面處理等來抑制。原始薄膜之各層之厚度分布較佳為±10%以内，更佳為±5%以内，特佳為±2%以内。The resulting original film preferably has a uniform thickness in both the width direction and the length direction. The thickness deviation causes a variation in the phase difference of the obtained laminated optical film, and affects display uniformity when assembled in a liquid crystal display device. Therefore, it is preferable that a mold line (a line in the longitudinal direction due to a T-die lip injury or the like), a cross mark (a periodic thickness variation in the longitudinal direction), and the like are caused. Further, it is less preferable that a defect such as a spot or a light leakage or the like, such as a gel or foreign matter, which is poor in display, is caused. These can be achieved, for example, by using an extruder having a polymer filter, optimizing the residence time of the molten resin, reducing the pulsation of the gear pump, grinding or surface treatment of the T-die lip, smoothing of the transfer roller, the peeling roller, Surface treatment or the like is suppressed. The thickness distribution of each layer of the original film is preferably within ±10%, more preferably within ±5%, and particularly preferably within ±2%.

拉伸步驟Stretching step

具有相位差薄膜之功能之本發明的層合光學薄膜可藉由將上述原始薄膜進行拉伸處理來製造。層合光學薄膜進行拉伸的方法可使用以往之公知的方法係在對於薄膜長度方向為正交方向、即寬度方向使用單軸拉伸較佳。具體而言，使用拉幅器在寬度方向進行單軸拉伸的方法較佳。因此，可展現本發明之優異的相位差特性。The laminated optical film of the present invention having the function of a retardation film can be produced by subjecting the above-mentioned original film to a stretching treatment. The method of stretching the laminated optical film can be preferably carried out by using a conventionally known method in which the uniaxial stretching is performed in the direction orthogonal to the longitudinal direction of the film, that is, in the width direction. Specifically, a method of performing uniaxial stretching in the width direction using a tenter is preferred. Therefore, the excellent phase difference characteristics of the present invention can be exhibited.

本發明之製造方法之拉伸步驟中，拉伸溫度係依據環狀烯烴系樹脂之Tg(TgA)與乙烯基芳香族系樹脂之Tg(TgB)來決定，此對於調整相位差而言較理想。具體而言，在(TgA與TgB之較低者的值)-10(℃)～(TgA與TgB之較高者的值)+30(℃)之範圍，較佳為(TgA與TgB之較低者的值)-5(℃)～(TgA與TgB之較高者的值)+20(℃)的範圍。In the stretching step of the production method of the present invention, the stretching temperature is determined depending on the Tg (TgA) of the cyclic olefin resin and the Tg (TgB) of the vinyl aromatic resin, which is preferable for adjusting the phase difference. . Specifically, in the range of (the lower value of TgA and TgB) -10 (° C.) to (the value of the higher of TgA and TgB) + 30 (° C.), it is preferable (the ratio of TgA to TgB) The value of the lower is -5 (°C) to (the value of the higher of TgA and TgB) +20 (°C).

又，TgA與TgB之關係係滿足下述式(iv)為佳。Further, the relationship between TgA and TgB is preferably satisfied by the following formula (iv).

|TgA-TgB|≦20(℃)　...(iv)|TgA-TgB|≦20(°C) ...(iv)

上述式(iv)之值較佳為|TgA-TgB|≦15(℃)，更佳為|TgA-TgB|≦12(℃)，特佳為|TgA-TgB|≦10(℃)。The value of the above formula (iv) is preferably |TgA-TgB|≦15 (°C), more preferably |TgA-TgB|≦12 (°C), and particularly preferably |TgA-TgB|≦10 (°C).

藉由使拉伸溫度、TgA及TgB在上述範圍內，可藉由拉伸同時控制A層及B層各自之相位差，容易得到層合光學薄膜之目的之特性(式(i)、式(ii)、式(iii)及式(v)表示的特性等)。藉此可實現對比高，由斜向觀看畫面時之色彩偏移較小的液晶顯示裝置。此外可得到在高溫下之耐久性優異的層合光學薄膜。By setting the stretching temperature, TgA and TgB within the above range, it is possible to easily control the characteristics of the laminated optical film by stretching and controlling the phase difference between the A layer and the B layer (formula (i), formula ( Ii), characteristics expressed by formula (iii) and formula (v), etc.). Thereby, a liquid crystal display device having a high contrast and a small color shift when the screen is viewed obliquely can be realized. Further, a laminated optical film excellent in durability at a high temperature can be obtained.

TgA及TgB均為110℃以上為佳，為了確保熱安定性及拉伸加工性，更佳為110～200℃，特佳為120～170℃。Both TgA and TgB are preferably 110 ° C or more, and more preferably 110 to 200 ° C, particularly preferably 120 to 170 ° C, in order to ensure thermal stability and tensile processability.

本發明之製造方法係拉伸倍率通常為1.1～10倍，較佳為1.2～7倍，更佳為1.3倍～5倍。特別是對於薄膜長度方向為正交方向，進行單軸拉伸之橫單軸拉伸，較佳為拉深1.3～5倍。藉由橫單軸拉伸，本發明之層合光學薄膜係光軸(面内之最大折射率方向)對於薄膜長度方向成為正交方向，因此層合光學薄膜與偏光子可以輥對輥接著，因此提高生產性。拉伸倍率在上述範圍時，相位差薄膜之光軸、相位差值、NZ係數、或這些之薄膜面内之分布可適當控制，可實現對比高，由斜向觀看畫面時之色彩偏移較小，且可均勻之畫面顯示的液晶顯示裝置。The production method of the present invention is usually 1.1 to 10 times, preferably 1.2 to 7 times, more preferably 1.3 to 5 times. In particular, the transverse uniaxial stretching of the film in the longitudinal direction of the film in the direction of the uniaxial stretching is preferably 1.3 to 5 times. By transverse uniaxial stretching, the optical axis (in-plane maximum refractive index direction) of the laminated optical film of the present invention is orthogonal to the longitudinal direction of the film, so that the laminated optical film and the polarizer can be roll-to-roll, Therefore, productivity is improved. When the stretching ratio is in the above range, the optical axis, the phase difference value, the NZ coefficient, or the distribution in the in-plane of the film of the retardation film can be appropriately controlled, and the contrast can be high, and the color shift when viewing the image obliquely is higher. A liquid crystal display device that is small and can be displayed on a uniform screen.

[層合光學薄膜][Laminated optical film]

本發明之層合光學薄膜係上述A層與B層直接接觸，進行層合所成。層合A層與B層的方法除上述的共擠壓法之外，可利用乾式層合等之薄膜層合成形方法、基材樹脂薄膜上塗佈樹脂溶液之塗佈成形方法等之公知的方法，從製造效率等之觀點，最佳為共擠壓法。In the laminated optical film of the present invention, the layer A and the layer B are directly contacted and laminated. In the method of laminating the A layer and the B layer, in addition to the coextrusion method described above, a known method of forming a film layer such as dry lamination or a coating forming method of coating a resin solution on a base resin film can be used. The method is preferably a co-extrusion method from the viewpoint of manufacturing efficiency and the like.

層合光學薄膜之長度方向之長度較佳為50m以上，更佳為100m以上。這種長薄膜通常為薄膜筒的形態取用。又，薄膜之寬度較佳為1000mm以上，更佳為1500mm以上，特佳為2000mm以上。The length of the laminated optical film in the longitudinal direction is preferably 50 m or more, and more preferably 100 m or more. Such long films are usually used in the form of a film cylinder. Further, the width of the film is preferably 1000 mm or more, more preferably 1500 mm or more, and particularly preferably 2000 mm or more.

本發明之層合光學薄膜無特別限定，從使用性或光軸與相位差值之調整上而言，薄膜厚度通常為10～400μm，較佳為20～300μm，特佳為20～200μm。The laminated optical film of the present invention is not particularly limited, and the thickness of the film is usually from 10 to 400 μm, preferably from 20 to 300 μm, particularly preferably from 20 to 200 μm, in terms of usability or adjustment of optical axis and phase difference.

又，厚度之偏差較少時，相位差值之偏差減少，可得到顯示品質之均一性，因此較佳。層合光學薄膜之厚度偏差之範圍係平均值±10%以内，較佳為平均值±5%以内，更佳為平均值±2%以内。Further, when the variation in thickness is small, the variation in the phase difference value is reduced, and uniformity in display quality can be obtained, which is preferable. The thickness deviation of the laminated optical film is within ±10% of the average value, preferably within ±5% of the average value, and more preferably within ±2% of the average value.

本發明之層合光學薄膜可為未拉伸之薄膜，或經拉伸的薄膜，為了滿足式(i)～(iii)及較佳為滿足式(v)所記載之特性，較佳為經拉伸的薄膜。The laminated optical film of the present invention may be an unstretched film or a stretched film, and in order to satisfy the characteristics described in the formula (i) to (iii) and preferably satisfy the formula (v), it is preferred that Stretched film.

本發明之層合光學薄膜，特佳為藉由本發明之層合光學薄膜之製造方法所形成。The laminated optical film of the present invention is particularly preferably formed by the method for producing a laminated optical film of the present invention.

層合光學薄膜之光學特性Optical properties of laminated optical films

本發明之層合光學薄膜，其特徵係層合光學薄膜之相位差之測定值滿足全部下述式(i)～(iii)之特性者。In the laminated optical film of the present invention, the measured value of the phase difference of the laminated optical film satisfies all the characteristics of the following formulas (i) to (iii).

R450≦R550≦R650…(i)R450≦R550≦R650...(i)

1.0≦R650/R550≦1.2…(ii)1.0≦R650/R550≦1.2...(ii)

70nm≦R550≦150nm…(iii)70nm≦R550≦150nm...(iii)

[上述式(i)～(iii)中，R450、R550、R650係依序表示在波長450nm、550nm、650nm之層合光學薄膜的面内相位差]。[In the above formulas (i) to (iii), R450, R550, and R650 sequentially show the in-plane retardation of the laminated optical film at wavelengths of 450 nm, 550 nm, and 650 nm].

上述(i)及(ii)係表示相位差之波長分散性，上述(i)係表示越長波長時，面内相位差越大，即所謂具有逆波長分散性。此乃是防止通過層合光學薄膜之光的偏光狀態因波長而異，且降低由斜向觀看畫面時之色彩偏移量上所需要的特性。上述(ii)之值係表示逆波長分散性的程度。為了減少色彩偏移量，進行良好的視角補償時，此值越大越佳，較佳為1.01~1.18，更佳為1.02~1.18。上述(iii)係表示薄膜面内相位差的量。VA模式之液晶顯示裝置用之相位差薄膜可使用將A板與C板組合之補償方式，此時具有A板之功能之面内相位差係於(iii)所示之範圍，較佳為75nm~145nm，更佳為75nm~140nm。因滿足上述(iii)可得到良好的對比，同時滿足上述(i)及(ii)可降低色彩偏移，可進一步提高由斜向觀察時之對比。The above (i) and (ii) show the wavelength dispersion of the phase difference, and the above (i) shows that the longer the in-plane phase difference, the larger the in-plane phase difference, that is, the reverse wavelength dispersion property. This is to prevent the polarization state of the light passing through the laminated optical film from being different depending on the wavelength, and to reduce the characteristics required for the color shift amount when viewing the image obliquely. The value of the above (ii) indicates the degree of reverse wavelength dispersion. In order to reduce the color shift amount, when the viewing angle compensation is good, the larger the value, the better, preferably 1.01 to 1.18, more preferably 1.02 to 1.18. The above (iii) represents the amount of phase difference in the in-plane of the film. The phase difference film for the liquid crystal display device of the VA mode can be compensated by combining the A plate and the C plate. In this case, the in-plane phase difference of the function of the A plate is in the range shown in (iii), preferably 75 nm. ~145 nm, more preferably 75 nm to 140 nm. A good contrast can be obtained by satisfying the above (iii), and satisfying the above (i) and (ii) can reduce the color shift, and the contrast when viewed obliquely can be further improved.

為了得到顯示品質之均一性時，薄膜寬度方向、長度方向因場所所造成之相位差之偏差越少越佳。上述(ii)之R650/R550之偏差的範圍較佳為±0.04以内，更佳為±0.03以内，特佳為±0.02以內。上述(iii)之R550之偏差之範圍較佳為±7nm以内，更佳為±5nm以内，特佳為±3nm以内。In order to obtain uniformity of display quality, the deviation of the phase difference caused by the place in the width direction and the longitudinal direction of the film is preferably as small as possible. The range of the deviation of R650/R550 in the above (ii) is preferably within ±0.04, more preferably within ±0.03, and particularly preferably within ±0.02. The range of the deviation of R550 of the above (iii) is preferably within ±7 nm, more preferably within ±5 nm, and particularly preferably within ±3 nm.

同樣的，為了得到顯示品質之均一性時，因場所所造成之光軸之偏差越少越佳，與薄膜長度方向正交之薄膜寬度方向為基準時，較佳為±2°以内，更佳為±1°以内，更佳為±0.7°以内，特佳為±0.5°以内。Similarly, in order to obtain the uniformity of the display quality, the variation of the optical axis due to the place is preferably as small as possible, and when the film width direction orthogonal to the longitudinal direction of the film is the reference, it is preferably within ±2°, more preferably It is within ±1°, more preferably within ±0.7°, and particularly preferably within ±0.5°.

本發明之層合光學薄膜，較佳為滿足下述式(v)者。The laminated optical film of the present invention preferably satisfies the following formula (v).

1.0≦NZ≦3.0...(v)1.0≦NZ≦3.0...(v)

[上述式(v)中，NZ係以NZ=(nx-nz)/(nx-ny)表示之係數，在波長550nm之值，其中nx係表示在層合光學薄膜面内之最大折射率，ny係表示在層合光學薄膜面内，與nx正交之方向的折射率，nz係表示與nx及ny正交之層合光學薄膜厚度方向的折射率，但是層合光學薄膜之平均折射率為Nave 時，以Nave =(nx+ny+nz)/3表示，Nave 係在層合光學薄膜中，A層與B層之各自之平均折射率藉由厚度比進行加權平均的值]。[In the above formula (v), NZ is a coefficient expressed by NZ = (nx - nz) / (nx - ny) at a wavelength of 550 nm, where nx represents the maximum refractive index in the plane of the laminated optical film, The ny system indicates the refractive index in the direction orthogonal to nx in the plane of the laminated optical film, and the nz indicates the refractive index in the thickness direction of the laminated optical film orthogonal to nx and ny, but the average refractive index of the laminated optical film When N ave is N ave = (nx + ny + nz) / 3, N ave is in the laminated optical film, and the average refractive index of each of the A layer and the B layer is weighted and averaged by the thickness ratio. ].

上述(v)係被稱為NZ係數的數值，表示層合光學薄膜之面内相位差與厚度方向相位差之平衡的數值。計算NZ係數時，測定層合光學薄膜之面内相位差與斜向相位差(通常為遲相軸傾斜的狀態下，由極角40°入射時的值)，使用薄膜合計厚度及薄膜平均折射率進行數值計算得到nx、ny、nz，然後NZ=(nx-nz)/(nx-ny)。但是本發明之層合光學薄膜的情形，因A層與B層之平均折射率不同，因此無法直接測定Nave 來取得。The above (v) is a numerical value called the NZ coefficient, and represents a numerical value in which the phase difference between the in-plane phase difference and the thickness direction of the laminated optical film is balanced. When the NZ coefficient is calculated, the in-plane phase difference and the oblique phase difference of the laminated optical film (usually the value when incident at a polar angle of 40° in a state where the slow axis is inclined) are measured, and the total thickness of the film and the average refractive index of the film are used. The rate is numerically calculated to obtain nx, ny, nz, and then NZ = (nx - nz) / (nx - ny). However, in the case of the laminated optical film of the present invention, since the average refractive indices of the A layer and the B layer are different, it is not possible to directly measure N ave .

因此，本發明係將層合光學薄膜之平均折射率Nave 係在權宜上，將A層與B層之各自的平均折射率以厚度比加權平均後的值。換言之，當A層之平均折射率為Nave A，厚度為dA(μm)，B層之平均折射率為Nave B、厚度為dB(μm)時，Nave =(dA×Nave A＋dB×Nave B)/(dA+dB)，且對nx、ny、nz進行數值計算，決定NZ。Therefore, in the present invention, the average refractive index N ave of the laminated optical film is set to an appropriate value, and the average refractive index of each of the A layer and the B layer is weighted and averaged by the thickness ratio. In other words, when the average refractive index of the A layer is N ave A, the thickness is dA (μm), the average refractive index of the B layer is N ave B, and the thickness is dB (μm), N ave = (dA × N ave A + dB × N ave B) / (dA + dB), and numerical calculations for nx, ny, and nz determine NZ.

各層之厚度dA、dB係將各層剝離後，各層之厚度以接觸式微量計測定或層合光學薄膜之剖面以顯微鏡觀察或以公知的非接觸式測定法，例如使用光干涉式膜厚測定裝置計測。其中，以測定精度佳、非破壞、線上(on line)、非線上皆可測定之光干涉式膜厚測定較佳。The thickness dA and dB of each layer are peeled off, and the thickness of each layer is measured by a contact micrometer or the cross section of the laminated optical film is observed by a microscope or a known non-contact measurement method, for example, an optical interference film thickness measuring device is used. Measurement. Among them, the measurement of the optical interference film thickness which is excellent in measurement accuracy, non-destructive, on-line, and off-line is preferable.

A層及/或B層各自為2層以上時，例如A層/B層/A層之3層構成時，dA係2層以上之A層之厚度的合計值，dB係2層以上之B層之厚度的合計值。When each of the A layer and/or the B layer is two or more layers, for example, when the three layers of the A layer, the B layer, and the A layer are formed, the total value of the thickness of the A layer of the two layers of dA is equal to or greater than the thickness of the two layers of the D layer. The total value of the thickness of the layer.

NZ係數係接近1時，接近正(Positive)A板，與VA液晶之補償方式之組合A板與C板之補償方式一致，對比較佳，因此較理想。較佳為1.0～2.5，更佳為1.0～2.0。NZ係數未達1之薄膜不具有逆波長分散性。When the NZ coefficient is close to 1, it is close to the positive A plate, and the compensation method of the VA liquid crystal is the same as the compensation method of the A plate and the C plate, and the comparison is preferable, so it is preferable. It is preferably 1.0 to 2.5, more preferably 1.0 to 2.0. A film having a NZ coefficient of less than 1 does not have reverse wavelength dispersion.

各層之光學特性(面内相位差)Optical properties of each layer (in-plane phase difference)

本發明之構成層合光學薄膜之A層與B層係各自具有理想之相位差值及相位差波長分散性。但是層合的狀態時，無法測定A層與B層各自單獨之相位差，因此，將A層與B層由層合光學薄膜上剝離，各自測定相位差或由構成A層與B層之聚合物之各自之相位差波長分散性與層合光學薄膜之相位差波長分散性，計算A層與B層之相位差值，或將僅有A層之薄膜與僅有B層之薄膜與層合光學薄膜相同條件下，進行拉伸，藉由各自測定相位差，可確認各層的特性。波長450nm、550nm下之A層之面内相位差為R450A、R550A，波長450nm、550nm下之B層之面内相位差為R450B、R550B時，調整各層以滿足下述條件(vi)～(x)。The layer A and the layer B of the laminated optical film of the present invention each have an ideal phase difference and phase difference wavelength dispersion. However, in the laminated state, the phase difference between the A layer and the B layer cannot be measured. Therefore, the A layer and the B layer are peeled off from the laminated optical film, and the phase difference is measured or the polymerization of the A layer and the B layer is formed. The phase difference wavelength dispersion of the respective materials and the phase difference wavelength dispersion of the laminated optical film, the phase difference between the A layer and the B layer is calculated, or the film of only the A layer and the film of the B layer only are laminated. The optical film was stretched under the same conditions, and the phase difference was measured to confirm the characteristics of each layer. When the in-plane retardation of the layer A at wavelengths of 450 nm and 550 nm is R450A or R550A, and the in-plane retardation of the layer B at wavelengths of 450 nm and 550 nm is R450B or R550B, the layers are adjusted to satisfy the following conditions (vi) to (x). ).

R450A/R550A≦1.04...(vi)R450A/R550A≦1.04...(vi)

200nm≦R550A≦400nm...(vii)200nm ≦R550A≦400nm...(vii)

1.04<R450B/R550B...(viii)1.04<R450B/R550B...(viii)

100nm≦R550B≦300nm...(ix)100nm ≦R550B≦300nm...(ix)

R550A>R550B...(x)R550A>R550B...(x)

A層與B層滿足上述式(vi)～(x)時，層合光學薄膜滿足上述式(i)～(iii)，可減少由斜向觀看液晶顯示裝置時之色彩偏移，同時可提高對比。A層與B層係固有雙折射之正負不同，因此同時拉伸作為層合光學薄膜之A層與B層時，A層與B層之最大折射率方向係彼此正交。因此，彼此抵銷面内相位差，而層合光學薄膜之面内相位差R550係以R550A-R550B表示。藉由上述式(x)，層合光學薄膜之光軸係在與薄膜長度方向正交的方向，可與偏光予以輥對輥接著，提高偏光板之生產性。When the layer A and the layer B satisfy the above formulas (vi) to (x), the laminated optical film satisfies the above formulas (i) to (iii), and the color shift when the liquid crystal display device is viewed obliquely can be reduced, and the thickness can be improved. Compared. The positive and negative intrinsic birefringence of the A layer and the B layer are different. Therefore, when the A layer and the B layer are laminated as the laminated optical film, the maximum refractive index directions of the A layer and the B layer are orthogonal to each other. Therefore, the in-plane phase difference is offset from each other, and the in-plane retardation R550 of the laminated optical film is represented by R550A-R550B. According to the above formula (x), the optical axis of the laminated optical film is aligned in the direction orthogonal to the longitudinal direction of the film, and the polarized light can be applied to the roll to improve the productivity of the polarizing plate.

使用本發明之層合光學薄膜之製造方法，以上述拉伸溫度及拉伸倍率，在薄膜寬度方向進行拉伸，各層以1次拉伸處理可滿足上述式(vi)～(x)，同時層合光學薄膜整體可滿足上述式(i)～(iii)。因此，本發明之層合光學薄膜之製造方法係生產性非常優異。According to the method for producing a laminated optical film of the present invention, the film is stretched in the film width direction at the stretching temperature and the stretching ratio, and each layer is subjected to the first stretching treatment to satisfy the above formulas (vi) to (x). The laminated optical film as a whole can satisfy the above formulas (i) to (iii). Therefore, the method for producing a laminated optical film of the present invention is extremely excellent in productivity.

上述式(vi)及(viii)係表示各層之相位差之波長分散性。A層之R450A/R550A係小於B層之R450B/R550B，而A層之波長分散性係在每個波長下，不太變化之平坦的波長分散或隨著波長變大，相位差也變大的逆波長分散。B層之波長分散性相較於A層時，隨著波長變大，相位差變小，即所謂的正波長分散。A層與B層滿足此特性，因而A層與B層互相抵銷相位差時，層合光學薄膜滿足上述式(i)及(ii)之特性。The above formulae (vi) and (viii) show the wavelength dispersion of the phase difference of each layer. The R450A/R550A of the A layer is smaller than the R450B/R550B of the B layer, and the wavelength dispersion of the A layer is at each wavelength, and the flat wavelength which is not changed is dispersed or the phase difference becomes larger as the wavelength becomes larger. Reverse wavelength dispersion. When the wavelength dispersion of the layer B is larger than that of the layer A, the phase difference becomes smaller as the wavelength becomes larger, that is, the so-called positive wavelength dispersion. The layer A and the layer B satisfy this characteristic, and thus the layered optical film satisfies the characteristics of the above formulas (i) and (ii) when the layer A and the layer B cancel each other out of phase.

A層及/或B層各自為2層以上時，例如A層/B層/A層之3層構成的情形，R450A、R550A係2層以上之A層之相位差的合計值，R450B、R550B係2層以上之B層之相位差的合計值。When each of the A layer and/or the B layer is two or more layers, for example, in the case of three layers of the A layer, the B layer, and the A layer, the total value of the phase difference between the R layer A and the R550A two or more layers A, R450B, R550B The total value of the phase differences of the B layers of two or more layers.

在得到顯示品質之均一性的觀點，A層、B層均為因場所造成之相位差之偏差較少為佳。(vi)及(viii)之偏差之範圍較佳為±0.03以内，更佳為±0.02以内，特佳為±0.01以内。(vii)及(ix)表示之R550A及R550B之偏差的範圍較佳為±7nm以内，更佳為±5nm以内，特佳為±3nm以内。From the viewpoint of obtaining uniformity of display quality, it is preferable that the A layer and the B layer have less variation in phase difference due to the place. The range of the deviation of (vi) and (viii) is preferably within ±0.03, more preferably within ±0.02, and particularly preferably within ±0.01. The range of the deviation between R550A and R550B indicated by (vii) and (ix) is preferably within ±7 nm, more preferably within ±5 nm, and particularly preferably within ±3 nm.

為了得到顯示品質之均一性時，因場所造成之各層之光軸偏差較少為佳。A層之光軸係以薄膜寬度方向為基準時，較佳為±2度以内，更佳為±1度以内，更佳為±0.7度以内，特佳為±0.5度以内。B層之光軸係以薄膜長度方向為基準時，較佳為±2度以内，更佳為±1度以内，更佳為±0.7度以内，特佳為±0.5度以内。In order to obtain uniformity of display quality, it is preferable that the optical axis deviation of each layer due to the place is small. The optical axis of the A layer is preferably within ±2 degrees, more preferably within ±1 degree, more preferably within ±0.7 degrees, and more preferably within ±0.5 degrees, based on the film width direction. The optical axis of the layer B is preferably within ±2 degrees, more preferably within ±1 degree, more preferably within ±0.7 degrees, and more preferably within ±0.5 degrees, based on the length direction of the film.

為了得到顯示品質之均一性的觀點，A層、B層均為因場所造成之厚度偏差較少為佳。dA、dB之偏差範圍係與層合光學薄膜整體肢厚度偏差之範圍同樣，各自為平均值±10%以内，較佳為平均值±5%以内，更佳為平均值±2%以内。In order to obtain uniformity of display quality, it is preferable that both the A layer and the B layer have small thickness variations due to the place. The deviation range of dA and dB is the same as the range of the total limb thickness deviation of the laminated optical film, and each is within ±10% of the average value, preferably within ±5% of the average value, and more preferably within ±2% of the average value.

A層與B層之厚度比率只要是各層及層合光學薄膜整體之光學特性在較佳之範圍時，無特別限定，在控制相位差上，具體而言，為了以1次之橫拉伸處理而展現所定相位差，較佳為A層之厚度比率係層合光學薄膜整體之20～90%，更佳為30～80%，更佳為40～80%。(A層及/或B層各含有2層以上時，各層之厚度合計，以對於全A層之層合光學薄膜整體之厚度比率表示)。The thickness ratio of the A layer and the B layer is not particularly limited as long as the optical properties of the entire layer and the laminated optical film as a whole are in a preferable range, and in particular, in order to control the phase difference, specifically, in order to perform the horizontal stretching treatment once The thickness ratio of the layer A is preferably from 20 to 90%, more preferably from 30 to 80%, still more preferably from 40 to 80%, based on the total thickness of the layer A. (When each of the A layer and/or the B layer contains two or more layers, the total thickness of each layer is expressed by the thickness ratio of the entire laminated optical film of the entire A layer).

同樣的，為了得到顯示品質之均一性時，因場所造成之NZ之偏差較少為佳。NZ之偏差範圍係平均值±0.3以内，較佳為平均值±0.2以内，更佳為平均值±0.1以内。Similarly, in order to obtain uniformity of display quality, it is preferable that the deviation of NZ due to the place is small. The deviation range of NZ is within ±0.3 of the average value, preferably within ±0.2 of the average value, and more preferably within ±0.1 of the average value.

本發明之層合光學薄膜之NZ係數為了滿足上述式(v)時，構成層合光學薄膜之A層與B層具有各自較佳之NZ係數的範圍。但是層合的狀態下，無法得到A層與B層各自單獨之NZ係數，因此，採用將A層與B層由層合光學薄膜上剝離，各自測定相位差，得到NZ係數，或將僅有A層之薄膜與僅有B層之薄膜與層合光學薄膜相同條件下，進行拉伸，藉由各自測定相位差，得到各層之大概之NZ係數的方法。A層之NZ係數為NZA，B層之NZ係數為NZB時，調整以滿足下述式(xi)及(xii)。When the NZ coefficient of the laminated optical film of the present invention satisfies the above formula (v), the layer A and the layer B constituting the laminated optical film have respective preferred ranges of NZ coefficients. However, in the laminated state, the individual NZ coefficients of the A layer and the B layer cannot be obtained. Therefore, the A layer and the B layer are peeled off from the laminated optical film, and the phase difference is measured to obtain the NZ coefficient, or only A film of the A layer and a film of only the B layer are stretched under the same conditions as the laminated optical film, and the approximate NZ coefficient of each layer is obtained by measuring the phase difference. The NZ coefficient of the A layer is NZA, and when the NZ coefficient of the B layer is NZB, it is adjusted to satisfy the following formulas (xi) and (xii).

1.0≦NZA≦1.7　...(xi)1.0≦NZA≦1.7 ...(xi)

-1.0≦NZB≦0　...(xii)-1.0≦NZB≦0 ...(xii)

[上述式(xi)中，NZA係以NZA=(nxA-nzA)/(nxA-nyA)表示之係數，波長550nm下之值。式中，nxA係A層之面内之最大折射率，nyA係在A層之面内，與nxA正交之方向的折射率，nzA係與nxA及nyA正交之A層之厚度方向的折射率，Nave A=(nxA+nyA+nzA)/3。上述式(xii)中，NZB係以NZB=(nxB-nzB)/(nxB-nyB)表示之係數，波長550nm下之值。式中，nxB係B層之面内之最大折射率，nyB係在B層之面内，與nyB正交之方向的折射率，nzB係與nxB及nyB正交之B層之厚度方向的折射率，Nave B=(nxB+nyB+nzB)/3]。[In the above formula (xi), NZA is a coefficient expressed by NZA = (nxA - nzA) / (nxA - nyA), and a value at a wavelength of 550 nm. In the formula, the maximum refractive index in the plane of the nxA-based layer A, nyA is in the plane of the layer A, the refractive index in the direction orthogonal to nxA, and the refractive index in the thickness direction of the layer A in which the nzA is orthogonal to nxA and nyA. Rate, N ave A = (nxA + nyA + nzA) / 3. In the above formula (xii), NZB is a coefficient expressed by NZB=(nxB-nzB)/(nxB-nyB) and a value at a wavelength of 550 nm. In the formula, the maximum refractive index in the plane of the nxB-based B layer, nyB is in the plane of the B layer, the refractive index in the direction orthogonal to nyB, and the refractive index in the thickness direction of the B layer orthogonal to nxB and nyB Rate, N ave B = (nxB + nyB + nzB) / 3].

上述式(xi)係相當於在環狀烯烴系樹脂層進行橫拉伸時所展現之相位差，nxA係拉伸方向，即薄膜寬度方向，nyA係與拉伸方向正交，即薄膜長度方向。折射率橢圓體係一般稱為正(Positive)A板。上述式(xii)係相當於在乙烯基芳香族系樹脂層進行橫拉伸時所展現之相位差，nxB係與拉伸方向正交，即薄膜長度方向，nyB係拉伸方向，即薄膜寬度方向。折射率橢圓體係一般被稱為負(negative)A板。層合光學薄膜之NZ無法由NZA及NZB以單純計算得到，與以波因卡球(Poincare sphere)表示之A層之偏光狀態的變化與B層之偏光狀態之變化的結果有關聯。The above formula (xi) corresponds to a phase difference exhibited when the cyclic olefin-based resin layer is transversely stretched, and the nxA-based stretching direction, that is, the film width direction, and the nyA-based direction is orthogonal to the stretching direction, that is, the film length direction. . The refractive index elliptical system is generally referred to as a Positive A plate. The above formula (xii) corresponds to a phase difference exhibited when the vinyl aromatic resin layer is transversely stretched, and the nxB system is orthogonal to the stretching direction, that is, the film longitudinal direction, and the nyB stretching direction, that is, the film width. direction. The refractive index elliptical system is generally referred to as a negative A plate. The NZ of the laminated optical film cannot be simply calculated from NZA and NZB, and is related to the change in the polarization state of the A layer represented by the Poincare sphere and the change in the polarization state of the B layer.

NZA與NZB有較佳之範圍，較佳為(NZA+NZB)/2=0.1～0.8，更佳為(NZA+NZB)/2=0.2～0.8，更佳為(NZA+NZB)/2=0.3～0.7。NZA與NZB滿足此範圍時，層合光學薄膜不論從哪方向觀看，也具有逆波長分散性，不論由哪方向觀看，也不會產生因各層之光軸偏離而無法得到所定相位差的問題，因色彩偏移減少而提高面板特性。NZA越小，越能提高面板特性，較佳為1.0～1.6，更佳為1.0～1.5。同時，NZB越大者，越能提高面板特性，較佳為-0.6～0，更佳為-0.5～0。使各層之NZ係數在上述範圍時，由斜向觀測時也具有所定之相位差，使液晶顯示裝置之斜視角之色彩偏移減少，同時可提高對比。NZA and NZB have a preferred range, preferably (NZA + NZB) / 2 = 0.1 to 0.8, more preferably (NZA + NZB) / 2 = 0.2 to 0.8, more preferably (NZA + NZB) / 2 = 0.3 ~0.7. When NZA and NZB satisfy this range, the laminated optical film has reverse wavelength dispersion regardless of the direction from which it is viewed, and the problem that the predetermined phase difference cannot be obtained due to the deviation of the optical axes of the respective layers does not occur in any direction. Increased panel characteristics due to reduced color shift. The smaller the NZA, the more the panel characteristics can be improved, preferably from 1.0 to 1.6, more preferably from 1.0 to 1.5. At the same time, the larger the NZB, the more the panel characteristics can be improved, preferably -0.6 to 0, more preferably -0.5 to 0. When the NZ coefficient of each layer is in the above range, the phase difference is also observed from the oblique direction, so that the color shift of the oblique viewing angle of the liquid crystal display device is reduced, and the contrast can be improved.

在得到顯示品質之均一性方面，NZA、NZB均為因場所造成之偏差較少為佳。NZA、NZB之偏差範圍較佳為各自平均值±0.2以内，更佳為平均值±0.1以内。In terms of the uniformity of display quality, both NZA and NZB are less likely to be biased by the location. The deviation range of NZA and NZB is preferably within ±0.2 of the respective average value, more preferably within ±0.1 of the average value.

[偏光板][Polarizer]

本發明之偏光板，其係在至少一面上具有含有相位差薄膜之功能之本發明之層合光學薄膜者，較佳為偏光子(偏光膜)之至少單面上層合上述本發明之層合光學薄膜之構成者。構成本發明之偏光板之偏光子，例如對於聚乙烯醇(PVA)或PVA之一部分進行甲醛化之聚合物等所構成之薄膜，以適當的順序或方法實施以碘或二色性染料等所構成之二色性物質之染色處理、拉伸處理、交聯處理等所得的薄膜，自然光入射時，成為直線偏光而透過者。特佳為使用光之透過率高，偏光度優異者。The polarizing plate of the present invention is a laminated optical film of the present invention having a function of a retardation film on at least one side, preferably at least one side of a polarizer (polarizing film) is laminated on the above-described laminated layer of the present invention. The constituent of the optical film. The polarizer constituting the polarizing plate of the present invention is, for example, a film composed of a polyvinyl alcohol (PVA) or a polymer obtained by subjecting a part of PVA to a formaldehyde, or the like, in an appropriate order or method, using iodine or a dichroic dye. The film obtained by the dyeing treatment, the stretching treatment, the crosslinking treatment, and the like of the constituent dichroic material is transmitted as a linearly polarized light when the natural light is incident. It is particularly good for those who use light with high transmittance and excellent polarization.

構成偏光板之偏光子的厚度一般適合使用5～80μm者，但是本發明不受此限定。偏光子除了上述PVA系薄膜外，只要是具有同樣特性者，其他薄膜也可使用。例如有對於環狀烯烴系樹脂所構成之薄膜，以適當的順序或方法實施染色處理、拉伸處理、交聯處理等所得者，或塗佈二色性物質之溶液，使之配向者，或為線柵(WireGrid)型之偏光子。The thickness of the polarizer constituting the polarizing plate is generally suitably 5 to 80 μm, but the present invention is not limited thereto. The polarizer may be used in addition to the PVA film as described above, as long as it has the same characteristics. For example, a film composed of a cyclic olefin resin may be subjected to a dyeing treatment, a stretching treatment, a crosslinking treatment, or the like in an appropriate order or method, or a solution of a dichroic substance may be applied to orient it, or It is a wire grid type photon.

通常，偏光板係由偏光子、相位差薄膜、保護薄膜所構成，但是本發明係以構成偏光板之相位差薄膜的形態，將層合光學薄膜介於接著劑或黏著劑，貼合於偏光子之至少一面來使用。層合光學薄膜可在A層側與偏光子貼合，或在B層側與偏光子貼合。這種偏光板係因相位差薄膜為耐熱性、耐濕性、耐藥品性等之性狀優異，且具有作為保護薄膜之充分的功能，因此偏光子上被層合具有作為相位差薄膜之功能之本發明之層合光學薄膜的面上，可不必在另外層合保護薄膜。本發明之偏光板為僅在偏光子之單面被層合具有作為相位差薄膜之功能之本發明之層合光學薄膜的構成時，偏光子之另一面可被層合例如三乙醯基纖維素(TAC)、環狀烯烴系樹脂薄膜、丙烯酸系樹脂薄膜等之公知的保護薄膜。Usually, the polarizing plate is composed of a polarizer, a retardation film, and a protective film. However, in the form of a retardation film constituting a polarizing plate, the laminated optical film is interposed with an adhesive or an adhesive, and is bonded to polarized light. Use at least one side of the child. The laminated optical film may be bonded to the polarizer on the A layer side or to the polarizer on the B layer side. Such a polarizing plate is excellent in properties such as heat resistance, moisture resistance, and chemical resistance, and has a sufficient function as a protective film. Therefore, the polarizer is laminated to have a function as a retardation film. On the surface of the laminated optical film of the present invention, it is not necessary to additionally laminate the protective film. The polarizing plate of the present invention is a structure in which a laminated optical film of the present invention having a function as a retardation film is laminated on only one side of a polarizer, and the other side of the polarizer can be laminated, for example, a triethylene fluorene fiber. A known protective film such as a TAC, a cyclic olefin resin film, or an acrylic resin film.

本發明之層合光學薄膜與偏光子之貼合、保護薄膜與偏光子之貼合係將各層介於感壓接著劑、熱硬化接著劑、光硬化性接著劑等之公知之接著劑或黏著劑，予以接著來製造。黏著劑、接著劑較佳為透明性優者，具體而言，例如天然橡膠、合成橡膠、乙酸乙烯/氯乙烯共聚物、聚乙烯醚、聚乙烯醇、丙烯酸系樹脂、改性聚烯烴系樹脂等之黏著劑及具有羥基、胺基等之官能基之前述樹脂等中添加含有異氰酸酯基之化合物等硬化劑的硬化型黏著劑；聚胺基甲酸乙酯系之乾層合用接著劑；合成橡膠系接著劑；環氧系接著劑等。The lamination of the laminated optical film of the present invention and the polarizer, and the bonding of the protective film and the polarizer are a known adhesive or adhesion of each layer to a pressure-sensitive adhesive, a thermosetting adhesive, a photocurable adhesive, or the like. The agent is then manufactured. The adhesive and the adhesive are preferably excellent in transparency, and specifically, for example, natural rubber, synthetic rubber, vinyl acetate/vinyl chloride copolymer, polyvinyl ether, polyvinyl alcohol, acrylic resin, modified polyolefin resin. a curing adhesive which adds a curing agent such as a compound containing an isocyanate group to the above-mentioned resin having a functional group such as a hydroxyl group or an amine group; a polyurethane-based dry laminating adhesive; synthetic rubber An adhesive; an epoxy-based adhesive or the like.

本發明之偏光板較佳為尚含有選自反射防止層及防眩層之至少1種的層，且設置於與偏光子相反側之保護薄膜面的外側為佳。The polarizing plate of the present invention preferably further contains at least one layer selected from the group consisting of an antireflection layer and an antiglare layer, and is preferably provided on the outer side of the protective film surface on the side opposite to the polarizer.

這些層可藉由將熱硬化性樹脂組成物或光硬化性樹脂組成物以凹版塗佈、模塗佈、縫隙(slot)塗佈等公知之塗佈方法塗佈，必要時進行乾燥後，硬化所形成。這些層可直接設置於保護薄膜上，或可使用基材薄膜，設置於其上，將該基材薄膜貼合於保護薄膜所形成。又，將保護薄膜或基材薄膜與偏光子貼合之前，可形成該層，或可與偏光子貼合後，形成該層。These layers can be applied by a known coating method such as gravure coating, die coating, or slot coating by using a thermosetting resin composition or a photocurable resin composition, and if necessary, drying and hardening. Formed. These layers may be directly provided on the protective film, or a base film may be used, and the base film may be attached to the protective film. Further, the layer may be formed before the protective film or the base film is bonded to the polarizer, or may be formed by bonding with a polarizer.

反射防止層通常由低折射率層所構成，為了進一步提高反射防止性能時，可具有低折射率層與高折射率層之層合構造，又為了確保耐擦傷性，可具有硬塗層。層合順序係由接近保護薄膜之側開始，較佳為硬塗層/高折射率層/低折射率層之順序來層合。必要時，在低折射率層與高折射率層之間、或硬塗層與高折射率層之間可具有中折射率層。這些層可藉由濺鍍或蒸鍍等來形成，較佳為藉由如上述之硬化性組成物之塗佈來形成。The antireflection layer is usually composed of a low refractive index layer, and may have a laminated structure of a low refractive index layer and a high refractive index layer in order to further improve the reflection preventing performance, and may have a hard coat layer in order to secure scratch resistance. The lamination sequence is laminated from the side close to the protective film, preferably in the order of the hard coat layer/high refractive index layer/low refractive index layer. If necessary, there may be a medium refractive index layer between the low refractive index layer and the high refractive index layer, or between the hard coat layer and the high refractive index layer. These layers can be formed by sputtering, vapor deposition, or the like, and are preferably formed by coating the above-described curable composition.

形成低折射率層及高折射率層用之組成物，例如有公知的硬化性組成物。例如黏結劑樹脂有環氧系樹脂、酚系樹脂、三聚氰胺系樹脂、醇酸系樹脂、氰酸酯系樹脂、丙烯酸系樹脂、聚酯系樹脂、胺甲酸乙酯系樹脂、矽氧烷樹脂等含有一種以上，低折射率層形成用組成物係含有含氟化合物，高折射率層形成用組成物係含有高折射率之無機粒子，例如氧化矽、氧化鋁、氧化鋯、氧化錫、二氧化鈰、鈧氧、氟化鎂等金屬氧化物粒子。The composition for forming the low refractive index layer and the high refractive index layer is, for example, a known curable composition. For example, the binder resin may be an epoxy resin, a phenol resin, a melamine resin, an alkyd resin, a cyanate resin, an acrylic resin, a polyester resin, an urethane resin, a decane resin, or the like. The composition for forming a low refractive index layer contains a fluorine-containing compound, and the composition for forming a high refractive index layer contains inorganic particles having a high refractive index, such as cerium oxide, aluminum oxide, zirconium oxide, tin oxide, and dioxide. Metal oxide particles such as ruthenium, osmium, and magnesium fluoride.

低折射率層及高折射率層之折射率及厚度可使用公知的範圍，但是為了提高反射防止效果，低折射率層之折射率(25℃，波長589nm下之平均折射率)較佳為1.45以下，低折射率層之厚度較佳為50～300nm。又，高折射率層之折射率(25℃、波長589nm下之平均折射率)較佳為大於低折射率層之折射率0.05以上的折射率，厚度較佳為50～10,000nm。The refractive index and thickness of the low refractive index layer and the high refractive index layer may be in a known range, but in order to improve the reflection preventing effect, the refractive index of the low refractive index layer (25 ° C, average refractive index at a wavelength of 589 nm) is preferably 1.45. Hereinafter, the thickness of the low refractive index layer is preferably from 50 to 300 nm. Further, the refractive index of the high refractive index layer (25 ° C, average refractive index at a wavelength of 589 nm) is preferably a refractive index larger than a refractive index of the low refractive index layer of 0.05 or more, and the thickness is preferably 50 to 10,000 nm.

硬塗層之構成材料可使用公知的材料。這種材料例如有矽氧烷樹脂、丙烯酸樹脂、三聚氰胺樹脂、環氧樹脂等之1種以上，可含有金屬氧化物等之無機粒子。硬塗層可為具有後述之作為防眩層之效果者。As the constituent material of the hard coat layer, a known material can be used. The material may be, for example, one or more of a phthalic acid resin, an acrylic resin, a melamine resin, and an epoxy resin, and may contain inorganic particles such as a metal oxide. The hard coat layer may be one having an effect as an antiglare layer described later.

又，硬塗層之厚度無特別限定，較佳為2～10μm。Further, the thickness of the hard coat layer is not particularly limited, but is preferably 2 to 10 μm.

防眩層係使用通常在層表面具有凹凸，展現防眩性的層，表面之中心線平均粗度較佳為0.1～1.0μm的層。形成該防眩層用之組成物較佳為使用含有有機粒子及/或無機粒子的硬化性組成物。用於硬化性組成物之黏結劑樹脂可使用上述之反射防止膜形成用之硬化性組成物的黏結劑樹脂。較佳之防眩性係該層之Haze為5～65%，全光線透過率為80～98%。The antiglare layer is a layer which has irregularities on the surface of the layer and exhibits an antiglare property, and the center line average roughness of the surface is preferably 0.1 to 1.0 μm. The composition for forming the antiglare layer is preferably a curable composition containing organic particles and/or inorganic particles. As the binder resin used for the curable composition, the above-described binder resin for forming a curable composition for preventing the film formation can be used. The preferred anti-glare property is that the layer has a Haze of 5 to 65% and a total light transmittance of 80 to 98%.

[液晶顯示裝置][Liquid Crystal Display Device]

本發明之液晶顯示裝置係具有上述本發明之偏光板者，較佳為具有上述本發明之偏光板。本發明之液晶顯示裝置係由斜向觀看畫面時之對比高，且由斜向觀看畫面時之色彩偏移量較小，且具有光學不均較小的層合光學薄膜或偏光板，因此可均勻顯示表示，同時用於嚴苛環境下之長期使用之耐久性優異，無外光映入。The liquid crystal display device of the present invention has the above-described polarizing plate of the present invention, and preferably has the above-described polarizing plate of the present invention. The liquid crystal display device of the present invention has a high contrast when viewing the image obliquely, and has a small color shift amount when viewing the image obliquely, and has a laminated optical film or a polarizing plate having a small optical unevenness, so that Uniform display and excellent durability for long-term use in harsh environments, no external light.

[實施例][Examples]

以下依據實施例更具體說明本發明，但本發明不受這些實施例所限定。此外，下述實施例及比較例中，「份」以及「%」在不特別聲明時，係指「重量份」及「重量%」。室溫係指25℃。The present invention will be more specifically described below based on the examples, but the present invention is not limited by the examples. In the following examples and comparative examples, "parts" and "%" mean "parts by weight" and "% by weight" unless otherwise stated. Room temperature means 25 ° C.

以下之實施例、比較例中，各種測定及評價係以下述方式進行。In the following examples and comparative examples, various measurements and evaluations were carried out in the following manner.

[聚合反應率][Polymerization rate]

將秤量後之聚合反應溶液置入鋁製容器中，在加熱至300℃之加熱板上，加熱至恆溫為止，除去殘留單體及溶劑後，計測殘留之聚合物重量，由與理論上之聚合物生成量之比，求得反應率。The weighed polymerization reaction solution is placed in an aluminum container, heated to a constant temperature on a hot plate heated to 300 ° C, and the residual monomer and solvent are removed, and the residual polymer weight is measured, and theoretically polymerized. The ratio of the amount of the substance produced is used to determine the reaction rate.

[氫化率][Hydration rate]

核磁共振分光計(NMR)係使用Bruker公司製AVANCE500，在測定溶劑為d-氯仿中測定1 H-NMR。藉由5.1～5.8ppm之亞乙烯基、3.7ppm之甲氧基、0.6～2.8ppm之脂肪族質子之積分值，算出單體之組成後，計算氫化率。For the nuclear magnetic resonance spectrometer (NMR), 1 H-NMR was measured using a AVANCE 500 manufactured by Bruker Co., Ltd., and the measurement solvent was d-chloroform. The hydrogenation ratio was calculated by calculating the composition of the monomer from the integral value of the vinylidene group of 5.1 to 5.8 ppm, the methoxy group of 3.7 ppm, and the aliphatic proton of 0.6 to 2.8 ppm.

[玻璃轉化溫度(Tg)][Glass transition temperature (Tg)]

使用熱量示差掃描分析儀(精工儀器公司製、商品名：DSC6200)，遵照日本工業規格K7121，以昇溫速度：20℃/min之條件進行測定。Using a calorimeter scanning analyzer (manufactured by Seiko Instruments Inc., trade name: DSC6200), the measurement was carried out under the conditions of a temperature increase rate of 20 ° C/min in accordance with Japanese Industrial Standard K7121.

[重量平均分子量(Mw)及分子量分布(Mw/Mn)][Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)]

使用凝膠滲透層析儀(東曹(股)製HLC-8220GPC，依序連結管柱：東曹(股)製HXL -H、TSK gel G7000HXL 、TSKgel GMHXL 2隻、TSK gel G2000HXL ；溶劑：四氫呋喃；流速：1mL/min；樣品濃度：0.7～0.8重量%；注入量：70μL；測定溫度：40℃；檢出儀：RI(40℃)；標準物質：東曹(股)製TSK標準聚苯乙烯)，測定重量平均分子量(Mw)及分子量分布(Mw/Mn)。前述Mn為數平均分子量。Using a gel permeation chromatography (HLC-8220GPC manufactured by Tosoh Corporation), the columns were connected in sequence: H XL -H, TSK gel G7000H XL , TSKgel GMH XL 2, TSK gel G2000H XL , manufactured by Tosoh Corporation. Solvent: tetrahydrofuran; flow rate: 1 mL/min; sample concentration: 0.7 to 0.8% by weight; injection amount: 70 μL; measurement temperature: 40 ° C; detector: RI (40 ° C); standard material: Tosoh (stock) system TSK standard polystyrene), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured. The aforementioned Mn is a number average molecular weight.

[對數黏度][logarithmic viscosity]

使用Ubbelohde型黏度計在氯仿中，樣品濃度0.5g/dL、30℃下測定對數黏度。The logarithmic viscosity was measured using a Ubbelohde type viscometer in chloroform at a sample concentration of 0.5 g/dL at 30 °C.

[厚度][thickness]

以光學顯微鏡觀察測定層合光學薄膜之剖面。剖面不適合顯微鏡觀察時，將剖面部分包埋於環氧樹脂中，使用大和光機(股)製microtome RV-240進行薄切片，使剖面明確後，以光學顯微鏡觀察測定。The cross section of the laminated optical film was measured by an optical microscope. When the cross section is not suitable for microscopic observation, the cross-section is partially embedded in an epoxy resin, and thinly sectioned using a microtome RV-240 manufactured by a Yamato Optical Co., Ltd., and the cross section is made clear, and then observed by an optical microscope.

[相位差][phase difference]

使用自動雙折射計(王子計測機器(股)製、KOBRA-21ADH)進行測定。將波長478.8nm、546.0nm、629.3nm、747.3nm下之實測值以Cauchy之公式進行歸納計算，求得波長450nm、550nm、650nm下之薄膜面内相位差R450、R550、R650。薄膜面内相位差與遲相軸傾斜的狀態，由極角40度之斜向相位差、薄膜厚度及薄膜平均折射率求得NZ係數。The measurement was performed using an automatic birefringence meter (manufactured by Oji Scientific Instruments Co., Ltd., KOBRA-21ADH). The measured values at wavelengths of 478.8 nm, 546.0 nm, 629.3 nm, and 747.3 nm were calculated by Cauchy's formula, and the in-plane retardation R450, R550, and R650 at wavelengths of 450 nm, 550 nm, and 650 nm were obtained. In the state in which the phase difference between the in-plane of the film and the retardation axis are inclined, the NZ coefficient is obtained from the oblique phase difference of the polar angle of 40 degrees, the film thickness, and the average refractive index of the film.

[單體透過率、偏光度][Monomer transmittance, polarization]

使用日本分光(股)製V-7300測定偏光板之單體透過率及偏光度。The monomer transmittance and the degree of polarization of the polarizing plate were measured using a V-7300 manufactured by JASCO Corporation.

[液晶顯示裝置之對比等測定][Measurement of comparison of liquid crystal display devices, etc.]

使用ELDIM(股)製之「EZ Contrast-XL88」，在照度11x以下之暗室中測定液晶面板之亮度、視角、對比及色彩偏移。The brightness, viewing angle, contrast, and color shift of the liquid crystal panel were measured in a dark room having an illuminance of 11 x or less using "EZ Contrast-XL88" manufactured by ELDIM Co., Ltd.

[層合光學薄膜層間之密著性][Adhesion between laminated optical film layers]

將層合光學薄膜以雙面膠帶貼於玻璃板上，各層間***切割刀，產生剝離的方法確認密著性，依據以下之基準進行評價。The laminated optical film was attached to a glass plate with a double-sided tape, and a dicing blade was inserted between each layer, and the peeling method was used to confirm the adhesion, and the evaluation was performed based on the following criteria.

A：切割刀無法***層間，也未剝離。A: The cutter cannot be inserted between the layers and is not peeled off.

B：切割刀***層間，可製作剝離處，但是未連續剝離。B: The dicing blade was inserted between the layers to make a peeling place, but it was not continuously peeled off.

C：切割刀***層間，由該剝離處產生連續剝離。C: The dicing blade was inserted between the layers, and continuous peeling occurred from the peeling.

[反射防止層、防眩層之密著性][Adhesion of anti-reflection layer and anti-glare layer]

使用賽璐酚膠帶(「CT24」，Niban(股)製)以JIS-D0202所記載的方法實施棋盤格剝離試驗，依據以下之基準進行評價。The checkerboard peeling test was carried out by the method described in JIS-D0202 using a cellophane tape ("CT24", manufactured by Niban Co., Ltd.), and evaluated based on the following criteria.

A：殘留格數係100格中為100格。A: The number of residual cells is 100 cells in 100 cells.

B：殘留格數係100格中為90格以上。B: The number of residual cells is 90 or more in 100 cells.

C：殘留格數係100格中為未達90格。C: The number of residual lattices is less than 90 grids in 100 grids.

[環境試驗(相位差變化)][Environmental test (phase difference change)]

對於製作之層合光學薄膜測定乾熱試驗：95℃下500小時、濕熱試驗：85℃、相對濕度85%下500小時、熱衝擊試驗：-40℃下進行30分鐘與85℃下30分鐘來回為1循環，在200循環之3個條件下，測定前後面内相位差之變化量(%)，依據以下之基準進行評價。For the fabricated laminated optical film, the dry heat test was carried out: 500 hours at 95 ° C, damp heat test: 85 ° C, 500 ° at a relative humidity of 85%, thermal shock test: 30 minutes at -40 ° C and 30 minutes at 85 ° C For one cycle, the amount of change (%) of the phase difference between the front and the back was measured under three conditions of 200 cycles, and the evaluation was performed based on the following criteria.

A：相位差之變化量在3條件下均為±2%以内，且外觀無變化。A: The amount of change in the phase difference was within ±2% under the conditions of 3, and the appearance did not change.

B：相位差之變化量在3條件下均為±3%以内，且外觀無變化。B: The amount of change in the phase difference was within ±3% under the conditions of 3, and the appearance did not change.

C：相位差之變化量在各條件下均超過±3%。或以目視確認有變形、白化、龜裂或層間之剝離等外觀之變化。C: The amount of change in phase difference exceeds ±3% under each condition. Or visually confirm the change in appearance such as deformation, whitening, cracking, or peeling between layers.

[環境試驗(塗膜之變化)][Environmental test (change of coating film)]

對於設置反射防止層、防眩層的保護薄膜，置於上述3條件下，試驗前後檢查該層之外觀變化或層間剝離之有無，依據以下之基準進行評價。The protective film provided with the antireflection layer and the antiglare layer was subjected to the above three conditions, and the appearance change of the layer or the presence or absence of interlayer peeling was examined before and after the test, and evaluation was performed based on the following criteria.

A：3條件下，外觀皆無變化。Under the condition of A:3, there is no change in appearance.

B：白化、變黃等，顏色稍微變化。B: whitening, yellowing, etc., the color changes slightly.

C：以目視發現變形、龜裂或層間之剝離等，有明顯之外觀變化。C: Visually, deformation, cracking, or peeling between layers was observed, and there was a noticeable change in appearance.

[反射率][Reflectivity]

將設置反射防止層之保護薄膜(與偏光子貼合之前或由偏光板剝離的狀態)之無反射防止層之面，以黑色噴霧塗裝，藉由分光反射率測定裝置(組合大型試料室積分球附屬裝置150-09090之分光光度計U-3410、日立製作所(股)製)，由反射防止層測定波長340～700nm範圍下之反射率進行評價。具體而言，以鋁之蒸鍍膜之反射率為基準(100%)，測定在380～780nm之範圍下之反射防止層用層合體(反射防止膜)之反射率。The surface of the non-reflection preventing layer on which the protective film of the antireflection layer (before being bonded to the polarizer or peeled off from the polarizing plate) is applied by black spray, and the spectral reflectance measuring device (combined large sample integration) The spectrophotometer U-3410 of the ball attachment device 150-09090, manufactured by Hitachi, Ltd., was evaluated by the reflection preventing layer at a reflectance in the range of 340 to 700 nm. Specifically, the reflectance of the antireflection layer laminate (antireflection film) in the range of 380 to 780 nm is measured based on the reflectance of the aluminum vapor deposited film (100%).

[Haze(霧值)及全光線透過率][Haze (haze value) and total light transmittance]

對於與偏光子貼合之前或由偏光板剝離的狀態之保護薄膜，使用霧度計HZ-2(Suga試驗機(股)製)，藉由JIS K7105所記載的方法測定Haze及全光線透過率。Haze and total light transmittance were measured by a method described in JIS K7105 using a haze meter HZ-2 (manufactured by Suga Tester Co., Ltd.) for a protective film in a state before being bonded to a polarizer or peeled off from a polarizing plate. .

[合成例1]環狀烯烴系樹脂(A1)之合成[Synthesis Example 1] Synthesis of cyclic olefin resin (A1)

將8-甲基-8-甲氧基羰基四環[4.4.0.12,5 .17,10 ]-3-十二烯215份、雙環[2.2.1]庚-2-烯35份、1-己烯(分子量調節劑)18份、甲苯(開環聚合反應用溶劑)750份投入經氮取代之反應容器內，將此溶液加熱至60℃。接著，反應容器内之溶液中添加聚合觸媒：三乙基鋁(1.5莫耳/1)之甲苯溶液0.62份、以t-丁醇及甲醇改性之六氯化鎢(t-丁醇：甲醇：鎢=0.35莫耳：0.3莫耳：1莫耳)之甲苯溶液(濃度0.05莫耳/1)3.7份，此溶液以80℃加熱攪拌3小時，使產生開環聚合反應得到開環聚合物溶液。此聚合反應之聚合轉化率為97%，對於製得之開環聚合物，在30℃之氯仿中測定之對數黏度為0.75dl/g。VIII parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, 35 parts of bicyclo [2.2.1]hept-2-ene, 18 parts of 1-hexene (molecular weight modifier) and 750 parts of toluene (solvent for ring-opening polymerization reaction) were placed in a reaction vessel substituted with nitrogen, and the solution was heated to 60 °C. Next, a solution of a polymerization catalyst: 0.62 parts of a toluene solution of triethylaluminum (1.5 mol/1) and tungsten hexachloride (t-butanol modified with t-butanol and methanol) were added to the solution in the reaction vessel. Methanol: tungsten = 0.35 mol: 0.3 mol: 1 mol) toluene solution (concentration 0.05 mol / 1) 3.7 parts, this solution was heated and stirred at 80 ° C for 3 hours to cause ring-opening polymerization to obtain ring-opening polymerization Solution. The polymerization conversion ratio of this polymerization reaction was 97%, and the logarithmic viscosity measured in chloroform at 30 ° C was 0.75 dl / g for the obtained ring-opened polymer.

將如上述所得之開環聚合物溶液1,000份注入高壓鍋內，此開環聚合物溶液中添加RuHCl(CO)[P(C6 H5 )3 ]3 0.12份，在氫氣壓100kg/cm2 、反應溫度165℃之條件下，加熱攪拌3小時進行氫化反應。將製得之反應溶液(氫化聚合物溶液)進行冷卻後，釋放氫氣體壓力。將此反應溶液注入大量甲醇中，將凝固物分離回收，經乾燥後得到氫化聚合物(以下為環狀烯烴系樹脂(A1))。1,000 parts of the ring-opening polymer solution obtained as described above was injected into an autoclave, and 0.12 parts of RuHCl(CO)[P(C 6 H 5 ) 3 ] 3 was added to the ring-opening polymer solution at a hydrogen pressure of 100 kg/cm 2 , The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a reaction temperature of 165 °C. After the obtained reaction solution (hydrogenated polymer solution) is cooled, the hydrogen gas pressure is released. This reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter referred to as a cyclic olefin resin (A1)).

如此製得之樹脂A1，其氫化率為99.9%，玻璃轉化溫度為125℃，數平均分子量(Mn)為32,000，重量平均分子量(Mw)係137,000，分子量分布(Mw/Mn)係4.29，對數黏度係0.69dl/g。The resin A1 thus obtained had a hydrogenation rate of 99.9%, a glass transition temperature of 125 ° C, a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a molecular weight distribution (Mw/Mn) of 4.29, logarithm. The viscosity is 0.69 dl/g.

[合成例2]環狀烯烴系樹脂(A2)之合成[Synthesis Example 2] Synthesis of cyclic olefin resin (A2)

除了使用四環[4.4.0.12,5 .17,10 ]-3-十二烯53份、8-亞乙基四環[4.4.0.12,5 .17,10 ]-3-十二烯46份、三環[4.3.0.12,5 ]-癸-3,7-二烯66份，1-己烯(分子量調節劑)之添加量為22份，開環聚合反應用溶劑為使用環己烷取代甲苯外，與合成例1同樣得到氫化聚合物(以下為環狀烯烴系樹脂(A2))。In addition to the use of four rings [4.4.0.1 2,5 .1 7,10 ]-3-dodecene 53 parts, 8-ethylene tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-10 46 parts of diene, 66 parts of tricyclo[4.3.0.1 2,5 ]-indole-3,7-diene, 22 parts of 1-hexene (molecular weight modifier), and solvent for ring-opening polymerization A hydrogenated polymer (hereinafter referred to as a cyclic olefin resin (A2)) was obtained in the same manner as in Synthesis Example 1 except that toluene was replaced with cyclohexane.

製得之樹脂A2其氫化率係99.9%，玻璃轉化溫度(Tg)係125℃，Mn係30,000，Mw為122,000，分子量分布(Mw/Mn)為4.07，對數黏度為0.63dl/g。The obtained resin A2 had a hydrogenation ratio of 99.9%, a glass transition temperature (Tg) of 125 ° C, a Mn system of 30,000, a Mw of 122,000, a molecular weight distribution (Mw/Mn) of 4.07, and a logarithmic viscosity of 0.63 dl/g.

[合成例3]乙烯基芳香族系樹脂(B1)之合成[Synthesis Example 3] Synthesis of Vinyl Aromatic Resin (B1)

在具備攪拌機、冷凝器、溫度計之玻璃燒瓶中加入苯乙烯127.87g(1.23mol)、順丁烯二酸酐13.33g(0.136mol)、溶劑：甲苯75g及自由基起始劑：1,1’-偶氮雙(環己烷-1-腈)0.67g(2.7mmol)，加熱至90℃，使產生反應15小時。取出此聚合液之一部份，測定反應率，得到85%。又，測定分子量得到Mw=129,900，Mw/Mn=2.00。In a glass flask equipped with a stirrer, a condenser, and a thermometer, 127.87 g (1.23 mol) of styrene, 13.33 g (0.136 mol) of maleic anhydride, 75 g of toluene, and a radical initiator: 1,1'- were added. Azobis(cyclohexane-1-carbonitrile) 0.67 g (2.7 mmol) was heated to 90 ° C to cause a reaction for 15 hours. A part of this polymerization liquid was taken out, and the reaction rate was measured to obtain 85%. Further, the molecular weight was measured to obtain Mw = 129,900 and Mw / Mn = 2.00.

將製得之聚合反應溶液以四氫呋喃稀釋，使之在大量之甲醇中凝固，將聚合物回收‧純化，以80℃之真空乾燥機乾燥2天。分別測定製得之聚合物之分子量、對數黏度，得到Mw=131，910(Mw/Mn=1.88)，對數黏度η=0.44dL/g，收率為80%。以NMR所分析之共聚組成比係如投入的值。所得之聚合物係苯乙烯-順丁烯二酸酐之共聚物，玻璃轉化溫度係122℃。製得之乙烯基芳香族系共聚物(樹脂)當作為B1。The obtained polymerization reaction solution was diluted with tetrahydrofuran, solidified in a large amount of methanol, and the polymer was recovered and purified, and dried in a vacuum dryer at 80 ° C for 2 days. The molecular weight and logarithmic viscosity of the obtained polymer were respectively measured to obtain Mw = 131, 910 (Mw / Mn = 1.88), logarithmic viscosity η = 0.44 dL / g, and the yield was 80%. The copolymer composition ratio analyzed by NMR is, for example, an input value. The obtained polymer was a copolymer of styrene-maleic anhydride at a glass transition temperature of 122 °C. The obtained vinyl aromatic copolymer (resin) was designated as B1.

[合成例4]乙烯基芳香族系樹脂(B4)之合成[Synthesis Example 4] Synthesis of Vinyl Aromatic Resin (B4)

在具備攪拌機、冷凝器、溫度計之玻璃燒瓶中加入苯乙烯145.6g(1.40mol)、溶劑：甲苯75g及自由基起始劑：1,1’-偶氮雙(環己烷-1-腈)0.67g(2.7mmol)，加熱至90℃，使產生反應15小時。取出此聚合液之一部份，測定反應率，得到93%。In a glass flask equipped with a stirrer, a condenser, and a thermometer, 145.6 g (1.40 mol) of styrene, solvent: 75 g of toluene, and a radical initiator: 1,1'-azobis(cyclohexane-1-carbonitrile) were added. 0.67 g (2.7 mmol) was heated to 90 ° C to cause a reaction for 15 hours. A part of this polymerization liquid was taken out, and the reaction rate was measured to obtain 93%.

將製得之聚合反應溶液以四氫呋喃稀釋，使之在大量之甲醇中凝固，將聚合物回收‧純化，以80℃之真空乾燥機乾燥2天。分別測定製得之聚合物之分子量、對數黏度，得到Mw=168，300(Mw/Mn=1.68)、對數黏度η=0.42dL/g、收率為87%。所得之聚合物係聚苯乙烯，玻璃轉化溫度係102℃。製得之乙烯基芳香族系共聚物(樹脂)當作為B4。The obtained polymerization reaction solution was diluted with tetrahydrofuran, solidified in a large amount of methanol, and the polymer was recovered and purified, and dried in a vacuum dryer at 80 ° C for 2 days. The molecular weight and logarithmic viscosity of the obtained polymer were measured to obtain Mw = 168,300 (Mw / Mn = 1.68), logarithmic viscosity η = 0.42 dL / g, and yield of 87%. The obtained polymer was polystyrene, and the glass transition temperature was 102 °C. The obtained vinyl aromatic copolymer (resin) was used as B4.

[調製例1]水系接著劑之調製[Modulation Example 1] Preparation of water-based adhesive

將蒸餾水250份注入反應容器中，再將丙烯酸丁酯90份、甲基丙烯酸2-羥乙酯8份、二乙烯基苯2份及油酸鉀0.1份添加於該反應容器內，再使用TEFLON(註冊商標)製攪拌葉片攪拌進行分散處理。該反應容器內經氮取代後，將該體系升溫至50℃，添加過硫酸鉀0.2份後開始聚合。經過2小時後，再添加過硫酸鉀0.1份，此體系升溫至80℃，繼續聚合反應1小時得到聚合物分散液。250 parts of distilled water was poured into the reaction vessel, and 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene and 0.1 parts of potassium oleate were added to the reaction vessel, and TEFLON was used. The (stacked trademark) stirring blade is stirred and dispersed. After the inside of the reaction vessel was replaced with nitrogen, the system was heated to 50 ° C, and 0.2 part of potassium persulfate was added to initiate polymerization. After 2 hours, 0.1 part of potassium persulfate was further added, and the system was heated to 80 ° C, and the polymerization reaction was continued for 1 hour to obtain a polymer dispersion.

其次使用蒸發器將聚合物分散液濃縮至固形分濃度成為70%，得到丙烯酸酯系聚合物之水系分散體所構成之水系接著劑(具有極性基之接著劑)。Next, the polymer dispersion was concentrated using an evaporator to a solid content concentration of 70% to obtain a water-based adhesive (adhesive having a polar group) composed of an aqueous dispersion of an acrylate-based polymer.

構成上述製得之水系接著劑之丙烯酸酯系聚合物係以GPC法測得之Mn為69,000，而Mw為135,000，在30℃之氯仿中測定之對數黏度為1.2dL/g。The acrylate-based polymer constituting the water-based adhesive prepared above had a Mn of 69,000 as measured by a GPC method and a Mw of 135,000, and a logarithmic viscosity of 1.2 dL/g as measured in chloroform at 30 °C.

[調製例2]硬塗層用塗佈液之調製[Preparation Example 2] Preparation of coating liquid for hard coat layer

在遮蔽紫外線之容器中，將表面以不飽和基改質之平均粒徑20μm之二氧化矽粒子之甲基乙基酮/異丙醇分散液86份(固形分為30份)、二季戊四醇六丙烯酸酯65份、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉基丙烷-1-酮5份、MIBK 44份在50℃下，攪拌2小時得到均勻溶液之硬塗層用塗佈液。在鋁皿上秤取此塗佈液2g後，在120℃之加熱板上乾燥1小時，秤量得到固形分含量為50重量%。In a container for shielding ultraviolet rays, 86 parts of methyl ethyl ketone/isopropanol dispersion of cerium oxide particles having an average particle diameter of 20 μm whose surface is modified with an unsaturated group (solid content is 30 parts), dipentaerythritol 65 parts of acrylate, 5 parts of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, and 44 parts of MIBK were stirred at 50 ° C for 2 hours. A coating solution for a hard coat layer of a homogeneous solution. After 2 g of this coating liquid was weighed on an aluminum dish, it was dried on a hot plate at 120 ° C for 1 hour, and the solid content was weighed to 50% by weight.

[調製例3]低折射率層用塗佈液之調製[Preparation Example 3] Modulation of coating liquid for low refractive index layer

以氮氣充分取代之內容積2.0L之附有電磁攪拌器的不銹鋼製高壓鍋後，投入乙酸乙酯400g、全氟(丙基乙烯醚)53.2g、乙基乙烯醚36.1g、羥乙基乙烯醚44.0g、過氧化月桂醯1.00g、含偶氮基之聚二甲基矽氧烷(VPS1001(商品名)、和光純藥工業(股)製))6.0g及非離子性反應性乳化劑(NE-30(商品名)、旭電化工業(股)製)20g，然後以乾冰-甲醇冷卻至-50℃後，再度以氮氣除去體系內之氧氣。After replacing 2.0 L of a stainless steel pressure cooker with a magnetic stirrer, which was sufficiently substituted with nitrogen, 400 g of ethyl acetate, 53.2 g of perfluoro(propyl vinyl ether), 36.1 g of ethyl vinyl ether, and hydroxyethyl vinyl ether were charged. 44.0g, oxidized lauryl quinone 1.00g, azo-containing polydimethyl methoxy oxane (VPS1001 (trade name), and Wako Pure Chemical Industries, Ltd.)) 6.0g and nonionic reactive emulsifier ( After 20 g of NE-30 (trade name) and manufactured by Asahi Kasei Co., Ltd., and then cooled to -50 ° C with dry ice-methanol, the oxygen in the system was again removed by nitrogen.

接著，投入六氟丙烯120g，開始升溫。高壓鍋內之溫度達60℃時之壓力為5.3×105 pa。其後，以70℃攪拌20小時繼續反應，當壓力降為1.7×105 pa的時點，將高壓鍋進行水冷，停止反應。到達室溫後，釋出未反應單體，開啟高壓鍋，得到固形分濃度26.4%之聚合物溶液。將所得聚合物溶液投入甲醇中，使聚合物析出後，以甲醇洗淨，於50℃下真空乾燥得到220g之含羥基之含氟聚合物。Next, 120 g of hexafluoropropylene was introduced, and the temperature was raised. The pressure in the autoclave at a temperature of 60 ° C was 5.3 × 10 5 pa. Thereafter, the reaction was continued by stirring at 70 ° C for 20 hours, and when the pressure was lowered to 1.7 × 10 5 Pa, the autoclave was water-cooled to stop the reaction. After reaching room temperature, unreacted monomers were released, and the autoclave was opened to obtain a polymer solution having a solid concentration of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, and then washed with methanol, and vacuum-dried at 50 ° C to obtain 220 g of a hydroxyl group-containing fluoropolymer.

接著，具備電磁攪拌機、玻璃製冷卻管及溫度計之容量1L之可分離燒瓶中，投入上述含羥基之含氟聚合物50.0g、聚合抑制劑：2,6-二-t-丁基甲基苯酚0.01g及甲基液丁酮(MIBK)370g，在20℃下，含羥基之含氟聚合物溶解於MIBK中，進行攪拌直到溶液成為透明、均勻為止。Next, 50.0 g of the hydroxyl group-containing fluoropolymer and a polymerization inhibitor: 2,6-di-t-butylmethylphenol 0.01 g were placed in a separable flask having a capacity of 1 L in a magnetic stirrer, a glass cooling tube, and a thermometer. And methyl ketone (MIBK) 370g, the hydroxyl group-containing fluoropolymer was dissolved in MIBK at 20 ° C, and stirred until the solution became transparent and uniform.

其次，此體系中添加2-甲基丙烯醯氧基乙基異氰酸酯15.1g，攪拌直到溶液均勻為止，然後添加二丁基錫二月桂酸酯0.1g開始反應，體系之溫度保持55～65℃，繼續攪拌5小時，得到含有乙烯性不飽和基之含氟素聚合物之MIBK溶液。得到此溶液之固形分含量為15.0重量%。Next, 15.1 g of 2-methylpropenyloxyethyl isocyanate was added to the system, and the mixture was stirred until the solution was homogeneous. Then, 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was maintained at 55 to 65 ° C, and stirring was continued. After 5 hours, a MIBK solution of a fluorine-containing polymer containing an ethylenically unsaturated group was obtained. The solid content of this solution was found to be 15.0% by weight.

將上述含有乙烯性不飽和基之含氟素聚合物之MIBK溶液507g(固形分為76g)、表面以不飽和基改質之平均粒徑45nm之二氧化矽粒子之甲基乙基酮分散液65.6g(固形分為21g)、光聚合起始劑：1-羥基環己基苯基酮(Irgacure184，Ciba‧Speciality‧Chemicals製)3g及MIBK 1424.4g注入附有攪拌機之玻璃製可分離燒瓶中，室溫下攪拌1小時得到均勻之低折射率層用塗佈液。得到此塗佈液之固形分濃度為5.0重量%。507 g (solid content: 76 g) of the MIBK solution containing the ethylenically unsaturated group-containing fluoropolymer, and methyl ethyl ketone dispersion of cerium oxide particles having an average particle diameter of 45 nm whose surface is modified with an unsaturated group 65.6 g (solid content: 21 g), photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba‧Speciality ‧ Chemicals) 3 g and MIBK 1424.4 g were poured into a glass separable flask equipped with a stirrer. The mixture was stirred at room temperature for 1 hour to obtain a uniform coating liquid for a low refractive index layer. The solid content concentration of this coating liquid was 5.0% by weight.

[調製例4]防眩層兼硬塗層用塗佈液之調製[Preparation Example 4] Preparation of antiglare layer and coating liquid for hard coat layer

將季戊四醇三丙烯酸酯(東亞合成(股)製，商品名「Aronix M-305」(比重1.179))90.0份、平均粒徑1.5μm之二氧化矽粒子(東曹‧silica(股)製、商品名「Nioseal E-200」(比重2.150))10.0質量份及光聚合起始劑：1-羥基環己基苯基酮(Irgacure184，Ciba‧Speciality‧Chemicals製)5.0份添加於丙二醇單甲醚中，進行混合調製固形分濃度30重量%之塗佈液。90.0 parts of pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-305" (specific gravity 1.179)) and cerium oxide particles having an average particle diameter of 1.5 μm (made by Tosoh ‧silica) "Nioseal E-200" (specific gravity: 2.150)) 10.0 parts by mass and a photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba‧Speciality ‧ Chemicals) 5.0 parts was added to propylene glycol monomethyl ether, A coating liquid having a solid concentration of 30% by weight was prepared by mixing.

[製造例1]偏光子之製造[Manufacturing Example 1] Manufacturing of polarizer

將膜厚120μm之卷狀之聚乙烯醇(以下也稱為「PVA」)製薄膜於碘濃度為0.03重量%、碘化鉀濃度為0.5重量%之30℃水溶液的染色浴中，連續地以拉伸倍率3倍在長度方向進行單軸拉伸(前拉伸)後，於硼酸濃度為5重量%、碘化鉀濃度為8重量%之水溶液為55℃的交聯浴中，再以拉伸倍率2倍在長度方向進行單軸拉伸(後拉伸)後，乾燥處理、捲取得到卷狀之偏光子。A film made of a roll of polyvinyl alcohol (hereinafter also referred to as "PVA") having a thickness of 120 μm was continuously stretched in a dyeing bath of an aqueous solution of 30° C. having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. After uniaxial stretching (pre-stretching) in the longitudinal direction at a magnification of 3 times, the aqueous solution having a boric acid concentration of 5% by weight and a potassium iodide concentration of 8% by weight was 55 ° C in a crosslinking bath, and then a draw ratio of 2 times. After uniaxial stretching (post-stretching) in the longitudinal direction, the film is dried and wound into a roll of polarized light.

[製造例2]光學薄膜(負C板)及偏光板之製造[Manufacturing Example 2] Production of Optical Film (Negative C Plate) and Polarizing Plate

將合成例1製得之環狀烯烴系樹脂(A1)之薄膜卷(150μm)以拉伸溫度133℃、拉伸倍率1.6倍進行縱拉伸，接著以拉伸溫度135℃、拉伸倍率2.4倍進行拉幅器橫拉伸，得到厚度68μm的拉伸薄膜。所得之拉伸薄膜之面内相位差R550=0～2nm，平均Rth=190nm。(Rth係表示厚度方向相位差之指標之一，以{(nx+ny)/2-nz}×d表示。nx係表示光學薄膜測定點之面内的最大折射率、ny係表示在面内，與nx正交之方向的折射率、nz係表示與nx及ny正交之拉伸薄膜厚度方向的折射率，d係測定點的薄膜厚度(nm))。The film roll (150 μm) of the cyclic olefin resin (A1) obtained in Synthesis Example 1 was longitudinally stretched at a stretching temperature of 133 ° C and a draw ratio of 1.6 times, followed by a stretching temperature of 135 ° C and a draw ratio of 2.4. The tenter was stretched in the transverse direction to obtain a stretched film having a thickness of 68 μm. The in-plane retardation of the obtained stretched film was R550 = 0 to 2 nm, and the average Rth was 190 nm. (Rth is one of the indexes indicating the phase difference in the thickness direction, and is represented by {(nx+ny)/2-nz}×d. nx is the maximum refractive index in the plane of the measurement point of the optical film, and ny is expressed in the plane. The refractive index in the direction orthogonal to nx, nz represents the refractive index in the thickness direction of the stretched film orthogonal to nx and ny, and d is the film thickness (nm) at the measurement point.

將此薄膜於製造例1製得之偏光子之單面上，調整卷狀的薄膜，使用調製例1製得之水系接著劑連續黏貼兩者，而在偏光子之另一面上，使用由濃度5%的PVA水溶液所成之接著劑黏貼皂化處理後之80μm厚之三乙酸纖維素(以下也稱「TAC」)製薄膜，得到偏光板(P0)。所得之偏光板的單體透過率為42.1%，偏光度為99.9%。This film was applied to one surface of the polarizer obtained in Production Example 1, and the roll-shaped film was adjusted, and the water-based adhesive prepared in Preparation Example 1 was continuously adhered to both, and on the other side of the polarizer, the concentration was used. A film made of a 5% PVA aqueous solution was adhered to a film of 80 μm thick cellulose triacetate (hereinafter also referred to as "TAC") after saponification treatment to obtain a polarizing plate (P0). The obtained polarizing plate had a monomer transmittance of 42.1% and a degree of polarization of 99.9%.

[實施例1][Example 1] <層合光學薄膜(F1)之製造><Manufacture of laminated optical film (F1)>

將環狀烯烴系樹脂(A1)粒與乙烯基芳香族系樹脂(B1)粒分別使用乾燥空氣流通之熱風乾燥機，以100℃乾燥5小時。將這些顆粒使用具有65mmΦ螺旋及50mmΦ螺旋之2系列的熔融擠壓成形機，以熔融樹脂溫度260℃、T模唇開口寬600mm之條件下進行共擠壓成形，得到A1層(150μm)/B1層(140μm)之構成之未拉伸層合光學薄膜卷。The cyclic olefin resin (A1) particles and the vinyl aromatic resin (B1) particles were each dried at 100 ° C for 5 hours using a hot air dryer through which dry air was passed. These pellets were subjected to co-extrusion molding using a two-stage melt extrusion molding machine having a 65 mm Φ spiral and a 50 mm Φ spiral at a molten resin temperature of 260 ° C and a T lip opening width of 600 mm to obtain an A1 layer (150 μm) / B1. An unstretched laminated optical film roll of a layer (140 μm).

將此層合光學薄膜卷以拉伸溫度128℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度148μm之層合光學薄膜(F1)。製得之層合光學薄膜之面内相位差R450=79nm、R550=90nm、R650=96nm，NZ=1.65。確認此層合光學薄膜之密著性時，得知未剝離，密著性良好。又環境試驗的結果，3條件下，相位差之變化量皆為±2%以内，末發現外觀變化。The laminated optical film roll was transversely stretched by a tenter at a stretching temperature of 128 ° C and a stretching ratio of 2.0 times to obtain a laminated optical film (F1) having a thickness of 148 μm. The in-plane retardation of the obtained laminated optical film was R450 = 79 nm, R550 = 90 nm, R650 = 96 nm, and NZ = 1.65. When the adhesion of the laminated optical film was confirmed, it was found that the film was not peeled off, and the adhesion was good. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was within ±2%, and the appearance was found to change.

<偏光板(P1)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P1) and evaluation of liquid crystal display device>

將製得之層合光學薄膜(F1)於製造例1製得之偏光子之單面上，調整卷狀的薄膜(使偏光子之吸收軸的拉伸方向與層合光學薄膜之拉伸方向正交)，使乙烯基芳香族系樹脂層面向偏光子側，使用調製例1製得之水系接著劑連續黏貼兩者，而在偏光子之另一面上，使用由濃度5%的PVA水溶液所構成之接著劑黏貼作為保護薄膜之經皂化處理後之80μm厚的三乙酸纖維素(TAC)薄膜，得到偏光板(P1)。所得之偏光板的單體透過率及偏光度分別為42.1%及99.9%。The obtained laminated optical film (F1) was applied to one side of the polarizer prepared in Production Example 1, and the roll-shaped film was adjusted (the stretching direction of the absorption axis of the polarizer and the stretching direction of the laminated optical film) Orthogonally, the vinyl aromatic resin layer was faced to the polarizer side, and the water-based adhesive prepared in Preparation Example 1 was continuously adhered to both, and on the other side of the polarizer, a PVA aqueous solution having a concentration of 5% was used. The constituting adhesive was adhered to a 80 μm thick cellulose triacetate (TAC) film as a protective film, and a polarizing plate (P1) was obtained. The monomer transmittance and the degree of polarization of the obtained polarizing plate were 42.1% and 99.9%, respectively.

為了評價此偏光板的特性，因此將黏貼於三星電子(股)製液晶電視(型號LN40R81BD)之液晶面板之觀察者側之前面及背面的偏光板及相位差薄膜予以剝離，此剝離處上，使用丙烯酸系透明黏著薄膜，將製造例2製得之負C板偏光板(P0)貼合於背面，將偏光板(P1)貼合於前面，且各自與原來被貼合之偏光板之透過軸相同的狀態予以貼合。此時背面、前面及偏光板之相位差薄膜(層合光學薄膜)在液晶經胞側的狀態下，予以貼合。In order to evaluate the characteristics of the polarizing plate, the polarizing plate and the retardation film which are adhered to the front side and the back side of the viewer side of the liquid crystal panel of the LCD TV (model LN40R81BD) of Samsung Electronics Co., Ltd. are peeled off. Using a acrylic transparent adhesive film, the negative C plate polarizing plate (P0) obtained in Production Example 2 was attached to the back surface, and the polarizing plate (P1) was attached to the front surface, and each of them was passed through the polarizing plate which was originally bonded. The same state of the shaft is attached. At this time, the retardation film (laminated optical film) of the back surface, the front surface, and the polarizing plate is bonded to each other in a state in which the liquid crystal is on the cell side.

測定具有此偏光板之液晶電視的對比，在全方位、極角0～80度之範圍內，最大值：5260、最小值：110之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.03。The contrast of the liquid crystal television having the polarizing plate was measured. In the range of omnidirectional and polar angles of 0 to 80 degrees, the maximum value was 5260 and the minimum value was 110, and no unevenness was visually observed. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.03.

[實施例2][Embodiment 2] <層合光學薄膜(F2)之製造><Manufacture of laminated optical film (F2)>

除了環狀烯烴系樹脂(A1)與乙烯基芳香族系樹脂(B2)使用Noverchemicals公司製Dilark D332(苯乙烯-順丁烯二酸酐共聚物(順丁烯二酸酐含有率15%)、Tg：128℃)外，與實施例1同樣得到A1層(150μm)/B2層(120μm)之構成的未拉伸層合光學薄膜卷。將此層合光學薄膜卷以拉伸溫度130℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度136μm之層合光學薄膜(F2)。製得之層合光學薄膜之面内相位差R450=82nm、R550=92nm、R650=98nm，NZ=1.72。確認此層合光學薄膜之密著性時，未剝離，且密著性良好。又環境試驗的結果，3條件下，相位差之變化量皆為±2%以内，未發現外觀變化。In addition to the cyclic olefin-based resin (A1) and the vinyl aromatic resin (B2), Dilark D332 (a styrene-maleic anhydride copolymer content (15%) and Tg: manufactured by Nover Chemicals Co., Ltd.) was used. An unstretched laminated optical film roll having an A1 layer (150 μm)/B2 layer (120 μm) was obtained in the same manner as in Example 1 except for 128 ° C. This laminated optical film roll was transversely stretched by a tenter at a stretching temperature of 130 ° C and a stretching ratio of 2.0 times to obtain a laminated optical film (F2) having a thickness of 136 μm. The in-plane retardation of the obtained laminated optical film was R450 = 82 nm, R550 = 92 nm, R650 = 98 nm, and NZ = 1.72. When the adhesion of the laminated optical film was confirmed, it was not peeled off, and the adhesion was good. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was within ±2%, and no change in appearance was observed.

<偏光板(P2)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P2) and evaluation of liquid crystal display device>

除了使用層合光學薄膜(F2)取代層合光學薄膜(F1)外，與實施例1同樣得到偏光板(P2)。測定偏光板之單體透過率及偏光度，分別測得42.0%及99.9%。除了使用偏光板(P2)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：5110、最小值：100之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.04。A polarizing plate (P2) was obtained in the same manner as in Example 1 except that the laminated optical film (F2) was used instead of the laminated optical film (F1). The monomer transmittance and the degree of polarization of the polarizing plate were measured and found to be 42.0% and 99.9%, respectively. In the same manner as in the first embodiment, except that the polarizing plate (P2) was used instead of the polarizing plate (P1), the contrast of the liquid crystal television was measured, and the maximum value was measured in the range of 0 to 80 degrees in all directions and polar angles: 5110, the minimum value. : A higher value of 100, no unevenness was visually observed. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.04.

<偏光板(P2’)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P2') and evaluation of liquid crystal display device>

除了以水系接著劑貼合偏光子與層合光學薄膜時，環狀烯烴系樹脂層面向偏光子側外，與上述偏光板(P2)同樣得到偏光板(P2’)。測定偏光板之單體透過率及偏光度，分別測得42.0%及99.9%。除了使用偏光板(P2’)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：5080、最小值：100之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.04。When the polarizing film and the laminated optical film are bonded together with a water-based adhesive, the cyclic olefin-based resin layer faces the polarizer side, and a polarizing plate (P2') is obtained in the same manner as the polarizing plate (P2). The monomer transmittance and the degree of polarization of the polarizing plate were measured and found to be 42.0% and 99.9%, respectively. In the same manner as in the first embodiment, except that the polarizing plate (P2') was used instead of the polarizing plate (P1), the comparison of the liquid crystal television was measured, and the maximum value was measured in the range of 0 to 80 degrees in the omnidirectional and polar angles: 5080, minimum. Value: A higher value of 100, and no unevenness was visually observed. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.04.

[實施例3][Example 3] <層合光學薄膜(F3)之製造><Manufacture of laminated optical film (F3)>

除了使用環狀烯烴系樹脂(A1)與乙烯基芳香族系樹脂(B3)為DIC(股)製RYU REXA14(苯乙烯-甲基丙烯酸共聚物、Tg：129℃)外，與實施例1同樣得到A1層(150μm)/B3層(110μm)之構成之未拉伸層合光學薄膜卷。將此層合光學薄膜卷以拉伸溫度130℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度130μm之層合光學薄膜(F3)。製得之層合光學薄膜之面内相位差R450=81nm、R550=91nm、R650=96nm，NZ=1.74。確認此層合光學薄膜之密著性，發現未剝離，密著性良好。又環境試驗的結果，3條件下，相位差之變化量皆為±2%以内，未發現外觀變化。The same procedure as in Example 1 except that the cyclic olefin resin (A1) and the vinyl aromatic resin (B3) were RYU REXA14 (styrene-methacrylic acid copolymer, Tg: 129 ° C) manufactured by DIC Co., Ltd. An unstretched laminated optical film roll having an A1 layer (150 μm) / a B3 layer (110 μm) was obtained. This laminated optical film roll was transversely stretched by a tenter at a stretching temperature of 130 ° C and a stretching ratio of 2.0 times to obtain a laminated optical film (F3) having a thickness of 130 μm. The in-plane retardation of the obtained laminated optical film was R450 = 81 nm, R550 = 91 nm, R650 = 96 nm, and NZ = 1.74. The adhesion of the laminated optical film was confirmed, and it was found that it was not peeled off, and the adhesion was good. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was within ±2%, and no change in appearance was observed.

<偏光板(P3)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P3) and evaluation of liquid crystal display device>

除了使用層合光學薄膜(F3)取代層合光學薄膜(F1)外，與實施例1同樣得到偏光板(P3)。測定偏光板之單體透過率及偏光度，分別測得42.0%及99.9%。除了使用偏光板(P3)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：5050、最小值：100之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.04。A polarizing plate (P3) was obtained in the same manner as in Example 1 except that the laminated optical film (F3) was used instead of the laminated optical film (F1). The monomer transmittance and the degree of polarization of the polarizing plate were measured and found to be 42.0% and 99.9%, respectively. Except that the polarizing plate (P3) was used instead of the polarizing plate (P1), the comparison of the liquid crystal television was measured in the same manner as in the first embodiment, and the maximum value was measured in the range of 0 to 80 degrees in the omnidirectional and polar angles: 5050, the minimum value. : A higher value of 100, no unevenness was visually observed. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.04.

[實施例4][Example 4] <層合光學薄膜(F4)之製造><Manufacture of laminated optical film (F4)>

除了層合構成為A1層(75μm)/B3層(110μm)/A1層(75μm)之3層構成外，與實施例3同樣得到未拉伸層合光學薄膜卷。將此層合光學薄膜卷以拉伸溫度130℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度130μm之層合光學薄膜(F4)。製得之層合光學薄膜之面内相位差R450=84nm、R550=93nm、R650=99nm，NZ=1.82。確認此層合光學薄膜之密著性，發現未剝離，密著性良好。又環境試驗的結果，3條件下，相位差之變化量皆為±2%以内，未發現外觀變化。An unstretched laminated optical film roll was obtained in the same manner as in Example 3 except that the laminate was composed of a three-layer structure of an A1 layer (75 μm)/B3 layer (110 μm)/A1 layer (75 μm). This laminated optical film roll was transversely stretched by a tenter at a stretching temperature of 130 ° C and a stretching ratio of 2.0 times to obtain a laminated optical film (F4) having a thickness of 130 μm. The in-plane retardation of the obtained laminated optical film was R450 = 84 nm, R550 = 93 nm, R650 = 99 nm, and NZ = 1.82. The adhesion of the laminated optical film was confirmed, and it was found that it was not peeled off, and the adhesion was good. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was within ±2%, and no change in appearance was observed.

<偏光板(P4)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P4) and evaluation of liquid crystal display device>

使用層合光學薄膜(F4)取代層合光學薄膜(F1)，面向偏光子之側成為(因3層層合，所以必然的)環狀烯烴系樹脂層外，與實施例1同樣得到偏光板(P4)。測定製得之偏光板之單體透過率及偏光度，分別測得41.9%及99.9%。除了使用偏光板(P4)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：4890、最小值：90之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.05。A laminated optical film (F4) was used instead of the laminated optical film (F1), and a polarizing plate was obtained in the same manner as in Example 1 except that the side facing the polarizer became a cyclic olefin-based resin layer (which is inevitably laminated by three layers). (P4). The monomer transmittance and the degree of polarization of the obtained polarizing plate were measured and found to be 41.9% and 99.9%, respectively. In the same manner as in the first embodiment, the contrast of the liquid crystal television was measured except that the polarizing plate (P4) was used instead of the polarizing plate (P1), and the maximum value was measured in the range of omnidirectional and polar angles of 0 to 80 degrees: 4890, the minimum value. : A higher value of 90, no unevenness was observed visually. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.05.

[實施例5][Example 5] <層合光學薄膜(F5)之製造><Manufacture of laminated optical film (F5)>

除了使用環狀烯烴系樹脂(A2)與乙烯基芳香族系樹脂(B2)為Noverchemicals製Dilark D332外，與實施例1同樣得到A2層(150μm)/B2層(130μm)之構成的未拉伸層合光學薄膜卷。此層合光學薄膜卷以拉伸溫度130℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度133μm的層合光學薄膜(F5)。製得之層合光學薄膜之面内相位差R450=82nm、R550=91nm、R650=96nm，NZ=1.72。確認此層合光學薄膜之密著性時，發現層間一部份剝離，但是剝離途中，材料破壞。又環境試驗的結果，3條件下，相位差之變化量皆為±2%以内，未發現外觀變化。An unstretched A2 layer (150 μm)/B2 layer (130 μm) was obtained in the same manner as in Example 1 except that the cyclic olefin resin (A2) and the vinyl aromatic resin (B2) were Dilark D332 manufactured by Nover Chemicals. Laminated optical film roll. This laminated optical film roll was transversely stretched by a tenter at a stretching temperature of 130 ° C and a stretching ratio of 2.0 times to obtain a laminated optical film (F5) having a thickness of 133 μm. The in-plane retardation of the obtained laminated optical film was R450 = 82 nm, R550 = 91 nm, R650 = 96 nm, and NZ = 1.72. When the adhesion of the laminated optical film was confirmed, it was found that a part of the interlayer was peeled off, but the material was broken during the peeling. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was within ±2%, and no change in appearance was observed.

<偏光板(P5)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P5) and evaluation of liquid crystal display device>

使用層合光學薄膜(F5)取代層合光學薄膜(F1)外，與實施例1同樣得到偏光板(P5)。測定製得之偏光板之單體透過率及偏光度，分別測得42.0%及99.9%。除了使用偏光板(P5)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：4970、最小值：100之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.04。A polarizing plate (P5) was obtained in the same manner as in Example 1 except that the laminated optical film (F5) was used instead of the laminated optical film (F1). The monomer transmittance and the degree of polarization of the obtained polarizing plate were measured and found to be 42.0% and 99.9%, respectively. In the same manner as in the first embodiment, the contrast of the liquid crystal television was measured except that the polarizing plate (P5) was used instead of the polarizing plate (P1), and the maximum value was measured in the range of 0 to 80 degrees in all directions and polar angles: 4970, the minimum value. : A higher value of 100, no unevenness was visually observed. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.04.

[比較例1][Comparative Example 1] <光學薄膜(F6)之製造><Manufacture of Optical Film (F6)>

將環狀烯烴系樹脂(A1)以單獨進行擠壓成形，得到A1之薄膜卷(150μm)。將A1之薄膜卷以拉伸溫度140℃、拉伸倍率3.0倍進行拉幅器橫拉伸，得到厚度55μm之光學薄膜(F6)。此光學薄膜之面内相位差R450=121nm、R550=120nm、R650=119nm，NZ=1.33。又環境試驗的結果，3條件下，相位差之變化量皆在±2%以内，未發現外觀變化。The cyclic olefin resin (A1) was separately extruded to obtain a film roll (150 μm) of A1. The film roll of A1 was transversely stretched by a tenter at a stretching temperature of 140 ° C and a stretching ratio of 3.0 times to obtain an optical film (F6) having a thickness of 55 μm. The in-plane retardation of the optical film was R450 = 121 nm, R550 = 120 nm, R650 = 119 nm, and NZ = 1.33. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was within ±2%, and no change in appearance was observed.

<偏光板(P6)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P6) and evaluation of liquid crystal display device>

使用光學薄膜(F6)取代層合光學薄膜(F1)外，與實施例1同樣得到偏光板(P6)。測定製得之偏光板之單體透過率及偏光度，分別測得41.8%及99.9%。除了使用偏光板(P6)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：5160、最小值：85之較高的數值，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0~60度之色彩偏移為Δu’v’=0.11。光學薄膜F6因不具有逆波長分散性，因此Δu’v’值稍微變大，未改善色彩偏移。A polarizing plate (P6) was obtained in the same manner as in Example 1 except that the optical film (F6) was used instead of the laminated optical film (F1). The monomer transmittance and the degree of polarization of the obtained polarizing plate were measured and found to be 41.8% and 99.9%, respectively. In the same manner as in the first embodiment, except that the polarizing plate (P6) was used instead of the polarizing plate (P1), the comparison of the liquid crystal television was measured, and the maximum value was measured in the range of 0 to 80 degrees in the omnidirectional and polar angles: 5160, the minimum value. A higher value of :85, no unevenness was visually observed. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.11. Since the optical film F6 does not have reverse wavelength dispersion, the value of Δu'v' is slightly increased, and the color shift is not improved.

[比較例2][Comparative Example 2] <層合光學薄膜(F7)之製造><Manufacture of laminated optical film (F7)>

除使用環狀烯烴系樹脂(A2)與乙烯基芳香族系樹脂(B4)外，與實施例1同樣得到A2層(130μm)/B4層(130μm)之構成之未拉伸層合光學薄膜卷。此層合光學薄膜卷以拉伸溫度130℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度133μm的層合光學薄膜(F7)。製得之層合光學薄膜之面内相位差R450=258nm、R550=255nm、R650=252nm，NZ=1.45。確認此層合光學薄膜之密著性時，發現層間容易剝離。又環境試驗的結果，在乾熱試驗時，相位差之變化量超過5%，在溼熱試驗及熱衝擊試驗時，層間產生剝離。An unstretched laminated optical film roll having an A2 layer (130 μm)/B4 layer (130 μm) was obtained in the same manner as in Example 1 except that the cyclic olefin resin (A2) and the vinyl aromatic resin (B4) were used. . This laminated optical film roll was transversely stretched by a tenter at a stretching temperature of 130 ° C and a stretching ratio of 2.0 times to obtain a laminated optical film (F7) having a thickness of 133 μm. The in-plane retardation of the obtained laminated optical film was R450 = 258 nm, R550 = 255 nm, R650 = 252 nm, and NZ = 1.45. When the adhesion of the laminated optical film was confirmed, it was found that the layers were easily peeled off. Further, as a result of the environmental test, the amount of change in the phase difference exceeded 5% in the dry heat test, and peeling occurred between the layers in the damp heat test and the thermal shock test.

<偏光板(P7)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P7) and evaluation of liquid crystal display device>

使用層合光學薄膜(F7)取代層合光學薄膜(F1)外，與實施例1同樣得到偏光板(P7)。測定製得之偏光板之單體透過率及偏光度，分別測得42.0%及99.9%。除了使用偏光板(P7)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：5320、最小值：5。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.22。層合光學薄膜(F7)所用之乙烯基芳香族系樹脂(B4)之玻璃轉化溫度低，進行拉伸時，B4層未具有所定的相位差，層合光學薄膜未具有較理想之相位差，因此正面對比無問題，但是斜向之對比差，色彩偏移也多。A polarizing plate (P7) was obtained in the same manner as in Example 1 except that the laminated optical film (F7) was used instead of the laminated optical film (F1). The monomer transmittance and the degree of polarization of the obtained polarizing plate were measured and found to be 42.0% and 99.9%, respectively. In the same manner as in the first embodiment, except that the polarizing plate (P7) was used instead of the polarizing plate (P1), the comparison of the liquid crystal television was measured, and the maximum value was measured in the range of 0 to 80 degrees in the omnidirectional and polar angles: 5320, the minimum value. : 5. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.22. The vinyl aromatic resin (B4) used for the laminated optical film (F7) has a low glass transition temperature, and when stretched, the B4 layer does not have a predetermined phase difference, and the laminated optical film does not have a desired phase difference. Therefore, there is no problem with the frontal contrast, but the oblique contrast is poor and the color shift is also large.

[比較例3][Comparative Example 3] <層合光學薄膜(F8)之製造><Manufacture of laminated optical film (F8)>

將環狀烯烴系樹脂(A1)以單獨進行擠壓成形，得到A1之薄膜卷(150μm)。將A1之薄膜卷以拉伸溫度130℃、拉伸倍率2.0倍進行拉幅器橫拉伸，得到厚度77μm之光學薄膜。此光學薄膜之面内相位差R450=263nm、R550=260nm、R650=257nm，NZ=1.38。The cyclic olefin resin (A1) was separately extruded to obtain a film roll (150 μm) of A1. The film roll of A1 was stretched transversely by a tenter at a stretching temperature of 130 ° C and a draw ratio of 2.0 times to obtain an optical film having a thickness of 77 μm. The in-plane retardation of the optical film was R450 = 263 nm, R550 = 260 nm, R650 = 257 nm, and NZ = 1.38.

接著，將配向膜用之聚醯亞胺溶液以金屬線棒塗佈於PET薄膜上，以80℃之溫風乾燥1分鐘，再以100℃之溫風乾燥2分鐘後，將此聚醯亞胺配向膜之表面進行摩擦處理。聚合性向列性液晶溶液以金屬線棒塗佈於此配向膜上，以100℃乾燥2分鐘後，使用高壓水銀燈，以700mJ/cm2 照射UV，使聚合性向列性液晶化合物產生聚合。將此液晶硬化膜自PET薄膜剝離，測定相位差，R450=174nm、R550=165nm、R650=159nm，NZ=1.02，厚度為2μm。Next, the polyimine solution for the alignment film was coated on the PET film with a metal bar, dried at 80 ° C for 1 minute, and then dried at 100 ° C for 2 minutes. The surface of the amine alignment film is subjected to a rubbing treatment. The polymerizable nematic liquid crystal solution was applied onto the alignment film by a metal bar, and dried at 100 ° C for 2 minutes, and then irradiated with UV at 700 mJ/cm 2 using a high pressure mercury lamp to polymerize the polymerizable nematic liquid crystal compound. The liquid crystal cured film was peeled off from the PET film, and the phase difference was measured, and R450 = 174 nm, R550 = 165 nm, R650 = 159 nm, NZ = 1.02, and thickness was 2 μm.

使用丙烯酸系透明黏著薄膜，使製得之液晶硬化膜在上述光學薄膜上，光軸方向(面内之最大折射率方向)互相正交的狀態，予以貼合，得到層合光學薄膜(F8)。製得之層合光學薄膜之面内相位差R450=89nm、R550=95nm、R650=98nm，NZ=3.80。又環境試驗的結果，3條件下，相位差之變化量係最大2.3%，外觀無變化。By using an acrylic transparent adhesive film, the obtained liquid crystal cured film is bonded to the optical film in a state in which the optical axis direction (the maximum refractive index direction in the plane) is orthogonal to each other to obtain a laminated optical film (F8). . The in-plane retardation of the obtained laminated optical film was R450 = 89 nm, R550 = 95 nm, R650 = 98 nm, and NZ = 3.80. As a result of the environmental test, under the condition of 3, the amount of change in the phase difference was at most 2.3%, and the appearance did not change.

<偏光板(P8)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P8) and evaluation of liquid crystal display device>

除使用層合光學薄膜(F8)取代層合光學薄膜(F1)，液晶硬化層面向偏光子側外，與實施例1同樣得到偏光板(P8)。測定製得之偏光板之單體透過率及偏光度，分別測得41.9%及99.9%。除了使用偏光板(P8)取代偏光板(P1)外，與實施例1同樣，測定液晶電視的對比，在全方位、極角0～80度之範圍內，測得最大值：4900、最小值：15，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’V’=0.15。層合液晶硬化膜的F8係薄膜面内相位差R450、R550、R650係成為逆波長分散性，無問題，但是因斜向之相位差異常，造成NZ係數未在理想的範圍內。因此正面對比無問題，但是斜向之對比差，且色彩偏移也多。A polarizing plate (P8) was obtained in the same manner as in Example 1 except that the laminated optical film (F8) was used instead of the laminated optical film (F1), and the liquid crystal hardened layer was faced to the polarizer side. The monomer transmittance and the degree of polarization of the obtained polarizing plate were measured and found to be 41.9% and 99.9%, respectively. In the same manner as in the first embodiment, the comparison of the liquid crystal television was carried out except that the polarizing plate (P8) was used instead of the polarizing plate (P1), and the maximum value was measured in the range of 0 to 80 degrees in the omnidirectional and polar angles: 4900, the minimum value. :15, no unevenness was found by visual inspection. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'V' = 0.15. The F8-based film in-plane phase difference R450, R550, and R650 of the laminated liquid crystal cured film have reverse-wavelength dispersibility, and there is no problem. However, the phase difference in the oblique direction is abnormal, and the NZ coefficient is not in an ideal range. Therefore, there is no problem with the frontal contrast, but the oblique contrast is poor and the color shift is also large.

[參考例][Reference example]

將預先貼合於液晶電視之相位差薄膜自偏光板剝離，作為參考，藉由上述方法實施環境試驗，結果3條件下之相位差之變化量係最大5%，、試驗樣品產生曲翹。The retardation film which was previously bonded to the liquid crystal television was peeled off from the polarizing plate. As a reference, an environmental test was carried out by the above method. As a result, the amount of change in the phase difference under the conditions of 3 was 5%, and the test sample was warped.

以上之結果中，層合光學薄膜之評價結果如表1所示，偏光板及液晶顯示裝置之評價結果及作為參考，由上述液晶電視，將偏光板剝離前之面板特性如表2所示。As a result of the above evaluation, the evaluation results of the laminated optical film are shown in Table 1. The evaluation results of the polarizing plate and the liquid crystal display device and the reference panel characteristics before the peeling of the polarizing plate from the liquid crystal television are shown in Table 2.

[實施例6][Embodiment 6] <附反射防止層之偏光板(P1-1)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P1-1) with reflection preventing layer and evaluation of liquid crystal display device>

將調製例2製作之硬塗層塗佈液以金屬線棒塗佈於與實施例1使用之保護薄膜相同之TAC薄膜的單面上，以80℃乾燥2分鐘後，使用高壓水銀燈，以600mJ/cm2 照射UV，使聚合，製作厚度4μm之硬化膜。將調製例3製作之低折射率層用塗佈液以金屬線棒塗佈於形成硬塗層的面上，以80℃乾燥2分鐘後，使用高壓水銀燈，以600mJ/cm2 照射UV，使聚合，製作厚度100nm之硬化膜，得到附反射防止層之保護薄膜。測定製得之保護薄膜的反射率，在380～780nm下為2.4%以下，確認具有反射防止效果。又，Haze係0.5%，全光線透過率係94.2%。反射防止層之密著性優異，環境試驗的結果，3條件下，均未發現因反射防止層所造成之外觀變化或層的剝離。The hard coat layer coating liquid prepared in Preparation Example 2 was applied to one surface of the TAC film which was the same as the protective film used in Example 1 by a wire bar, and dried at 80 ° C for 2 minutes, and then a high pressure mercury lamp was used at 600 mJ. /cm 2 was irradiated with UV, and polymerization was carried out to prepare a cured film having a thickness of 4 μm. The coating liquid for a low refractive index layer prepared in Preparation Example 3 was applied to a surface on which a hard coat layer was formed by a metal bar, and dried at 80 ° C for 2 minutes, and then irradiated with UV at 600 mJ/cm 2 using a high pressure mercury lamp. Polymerization was carried out to prepare a cured film having a thickness of 100 nm, and a protective film with an antireflection layer was obtained. The reflectance of the obtained protective film was measured to be 2.4% or less at 380 to 780 nm, and it was confirmed that the reflection preventing effect was obtained. Further, Haze is 0.5%, and the total light transmittance is 94.2%. The adhesion preventing layer was excellent in adhesion, and as a result of the environmental test, no change in appearance or peeling of the layer due to the antireflection layer was observed under the conditions of 3.

除了實施例1中之保護薄膜使用上述附反射防止層之保護薄膜外，與實施例1同樣得到偏光板(P1-1)。使用製得之偏光板(P1-1)，與實施例1同樣測定液晶電視的對比，在全方位、極角0～80度之範圍內，最大值：5210、最小值：105，目視未發現不均。又，黑顯示狀態下，方位角45度時，測得極角0～60度之色彩偏移為Δu’v’=0.04。又，黑顯示時之外光映入的情形減少。A polarizing plate (P1-1) was obtained in the same manner as in Example 1 except that the protective film of the antireflection layer was used as the protective film of Example 1. Using the obtained polarizing plate (P1-1), the comparison of the liquid crystal television was measured in the same manner as in Example 1. In the range of omnidirectional and polar angles of 0 to 80 degrees, the maximum value was 5210 and the minimum value was 105, and visual observation was not found. Uneven. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.04. Moreover, the situation in which the external light is reflected in the black display is reduced.

[實施例7][Embodiment 7] <附反射防止層之偏光板(P1-2)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P1-2) with reflection preventing layer and evaluation of liquid crystal display device>

將調製例4製作之防眩層兼硬塗層用塗佈液以金屬線棒塗佈於與實施例1使用之保護薄膜相同之TAC薄膜的單面上，以80℃乾燥2分鐘後，使用高壓水銀燈，以600mJ/cm2 照射UV，使聚合，製作厚度4μm之硬化膜，得到附防眩層之保護薄膜。製得之保護薄膜的Haze係25%，全光線透過率係93.0%，形成防眩層的面可抑制外光(螢光燈)之閃耀。防眩層之密著性優異，環境試驗的結果，3條件下，均未發現因防炫層所造成之外觀變化或層的剝離。The coating liquid for the antiglare layer and the hard coat layer prepared in Preparation Example 4 was applied to one surface of the TAC film similar to the protective film used in Example 1 by a metal bar, and dried at 80 ° C for 2 minutes, and then used. The high-pressure mercury lamp was irradiated with UV at 600 mJ/cm 2 to carry out polymerization to prepare a cured film having a thickness of 4 μm to obtain a protective film with an anti-glare layer. The Haze system of the protective film obtained was 25%, and the total light transmittance was 93.0%, and the surface forming the antiglare layer suppressed the glare of the external light (fluorescent lamp). The anti-glare layer was excellent in adhesion, and as a result of the environmental test, no change in appearance or peeling of the layer due to the anti-glare layer was observed under the conditions of 3.

除了實施例1中之保護薄膜使用上述附防炫層之保護薄膜外，與實施例1同樣得到偏光板(P1-2)。使用製得之偏光板(P1-2)，與實施例1同樣測定液晶電視的對比，在全方位、極角0～80度之範圍內，最大值：5200、最小值：105，目視未發現不均。又，黑顯示狀態下，方位角45度時，測定極角0～60度之色彩偏移為Δu’v’=0.03。又，黑顯示時之外光映入，閃耀的情形減少。A polarizing plate (P1-2) was obtained in the same manner as in Example 1 except that the protective film of the first embodiment was used as the protective film of the first embodiment. Using the obtained polarizing plate (P1-2), the comparison of the liquid crystal television was measured in the same manner as in Example 1. In the range of omnidirectional and polar angles of 0 to 80 degrees, the maximum value was 5,200 and the minimum value was 105, and visual observation was not found. Uneven. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.03. In addition, when the black display is displayed, the external light is reflected, and the situation of the flare is reduced.

[實施例8][Embodiment 8] <附防炫層之偏光板(P1-4)之製造及液晶顯示裝置之評價><Manufacture of polarizing plate (P1-4) with anti-glare layer and evaluation of liquid crystal display device>

將實施例1製得之層合光學薄膜(F1)於製造例1製得之偏光子之單面上，調整卷狀的薄膜(使偏光子之吸收軸的拉伸方向與層合光學薄膜之拉伸方向正交)，使乙烯基芳香族系樹脂層面向偏光子側，使用調製例1製得之水系接著劑連續黏貼兩者，而在偏光子之另一面上，將合成例1製得之環狀烯烴系樹脂(A1)之薄膜卷(60μm厚度)使用調製例1得到之水系接著劑，連續黏貼兩者，得到偏光板(P1-3)。測定製得之偏光板的單體透過率及偏光度，分別測得42.3%及99.9%。The laminated optical film (F1) obtained in Example 1 was applied to one side of the polarizer prepared in Production Example 1, and the roll-shaped film was adjusted (the stretching direction of the absorption axis of the polarizer and the laminated optical film were adjusted). The stretching direction was orthogonal, and the vinyl aromatic resin layer was faced to the polarizer side, and the water-based adhesive prepared in Preparation Example 1 was continuously adhered to both, and the synthesis example 1 was obtained on the other side of the polarizer. The film roll (60 μm thickness) of the cyclic olefin resin (A1) was continuously adhered using the water-based adhesive obtained in Preparation Example 1 to obtain a polarizing plate (P1-3). The monomer transmittance and the degree of polarization of the obtained polarizing plate were measured and found to be 42.3% and 99.9%, respectively.

將調製例4製作之防眩層兼硬塗層塗佈液以金屬線棒塗佈於此偏光板之偏光子保護薄膜的環狀烯烴系樹脂薄膜面上，以80℃乾燥2分鐘後，使用高壓水銀燈，以600mJ/cm2 照射UV，使之聚合，製作厚度5μm之硬化膜，得到附防眩層之保護薄膜(P1-4)。形成防眩層的面可抑制外光(螢光燈)之閃耀。將保護薄膜由偏光板上剝離，進行防眩層兼附硬塗層之保護薄膜的評價，結果Haze為30%，全光線透過率係93.3%。又，環境試驗的結果，3條件下，均未發現因防炫層所造成之外觀變化或層的剝離。The antiglare layer and the hard coat layer coating liquid prepared in Preparation Example 4 were applied to the surface of the cyclic olefin resin film of the polarizer protective film of the polarizing plate by a metal bar, and dried at 80 ° C for 2 minutes, and then used. The high pressure mercury lamp was irradiated with UV at 600 mJ/cm 2 to polymerize it to prepare a cured film having a thickness of 5 μm to obtain a protective film (P1-4) having an antiglare layer. The surface on which the anti-glare layer is formed suppresses the flare of the external light (fluorescent lamp). The protective film was peeled off from the polarizing plate, and the protective film of the antiglare layer and the hard coat layer was evaluated. As a result, Haze was 30%, and the total light transmittance was 93.3%. Further, as a result of the environmental test, no change in appearance or peeling of the layer due to the antiglare layer was observed under the conditions of 3 conditions.

使用偏光板(P1-4)取代偏光板(P1)，與實施例1同樣測定液晶電視的對比，在全方位、極角0～80度之範圍內，最大值：5230、最小值：105，目視未觀察到不均勻。又，黑顯示狀態下，在方位角45度時，測得極角0～60度之色彩偏移為Δu’v’=0.03。又，黑顯示時之外光映入，閃耀的情形減少。The polarizing plate (P1-4) was used instead of the polarizing plate (P1), and the comparison of the liquid crystal television was measured in the same manner as in the first embodiment. In the range of omnidirectional and polar angles of 0 to 80 degrees, the maximum value was 5230 and the minimum value was 105. No unevenness was observed visually. Further, in the black display state, when the azimuth angle is 45 degrees, the color shift of the polar angle of 0 to 60 degrees is measured as Δu'v' = 0.03. In addition, when the black display is displayed, the external light is reflected, and the situation of the flare is reduced.

對於預先貼合於液晶電視之偏光板表面的防眩層，與基材之保護薄膜一同剝離，實施環境試驗，確認塗膜稍微變黃。The antiglare layer previously adhered to the surface of the polarizing plate of the liquid crystal television was peeled off together with the protective film of the substrate, and an environmental test was performed to confirm that the coating film was slightly yellowed.

實施例6～8之評價結果及預先貼合於上述液晶電視之偏光板之評價結果如表3所示。The evaluation results of Examples 6 to 8 and the evaluation results of the polarizing plates previously attached to the above liquid crystal television are shown in Table 3.

[產業上之利用性][Industrial use]

本發明之層合光學薄膜及偏光板可用於各種光學零件。例如有液晶電視、液晶監視器、行動電話、汽車導航、攜帶式遊戲機、數位資訊終端等之各種液晶顯示裝置、液晶投影機、電致發光顯示元件或設置ITO等之透明導電膜之觸控面板等。也可作為使用於光碟之記錄、播放裝置之光學系的波長板、使用於相機等之光學系之遮斷近紅外線的薄膜來使用。The laminated optical film and polarizing plate of the present invention can be used for various optical parts. For example, there are various liquid crystal display devices such as a liquid crystal television, a liquid crystal monitor, a mobile phone, a car navigation, a portable game machine, a digital information terminal, a liquid crystal projector, an electroluminescence display element, or a transparent conductive film provided with ITO or the like. Panels, etc. It can also be used as a wavelength plate for an optical system used for recording and playback of optical disks, and a film for blocking near-infrared rays used in an optical system such as a camera.

Claims (11)

一種層合光學薄膜之製造方法，其特徵係具有：將環狀烯烴系樹脂與乙烯基芳香族系樹脂直接接觸藉由共擠壓法進行層合製膜，得到環狀烯烴系樹脂層與乙烯基芳香族系樹脂層被層合之原始薄膜的步驟，將製得之原始薄膜在對於薄膜長度方向為正交方向，進行單軸拉伸的步驟，且得到滿足全部下述式(i)~(iii)表示之特性的層合光學薄膜，R450≦R550≦R650...(i) 1.0≦R650/R550≦1.2...(ii) 70nm≦R550≦150nm...(iii)[上述式(i)~(iii)中、R450、R550、R650係依序表示在波長450nm、550nm、650nm之層合光學薄膜的面內相位差]其中前述環狀烯烴系樹脂為由具有下述式(1)表示之結構單元及下述式(2)表示之結構單元的共聚物所構成， [式(1)中，m係1以上之整數，p係0以上之整數，X係獨立以式：-CH=CH-表示之基或式：-CH2 CH2 -表示之基，R1 ~R4 係各自獨立表示下述(a)~(e)表示者或表示(f)或(g)，(a)氫原子、(b)鹵原子、(c)含有具有氧原子、硫原子、氮原子或矽原子之連結基的取代或非取代之碳原子數1~30之烴基、(d)取代或非取代之碳原子數1~30之烴基、(e)極性基、(f)表示R1 與R2 、或R3 與R4 相互鍵結形成之亞烷基，未參與前述鍵結之R1 ~R4 係相互獨立表示選自前述(a)~(e)者，(g)表示R1 與R2 、R3 與R4 、或R2 與R3 相互鍵結 形成之芳香環或非芳香環之單環或多環之烴環或雜環，未參與前述鍵結之R1 ~R4 係相互獨立表示選自前述(a)~(e)者] [式(2)中，Y係以式：-CH=CH-表示之基或以式：-CH2 CH2 -表示之基，R5 ~R8 係各自獨立表示下述(a)~(e)表示者或表示(f)或(g)，(a)氫原子、(b)鹵原子、(c)含有具有氧原子、硫原子、氮原子或矽原子之連結基之取代或非取代之碳原子數1~30之烴基、(d)取代或非取代之碳原子數1~30之烴基、(e)極性基、(f)表示R5 與R6 、或R7 與R8 相互鍵結形成之亞烷基，未參與前述鍵結之R5 ~R8 係相互獨立表示選自前述(a)~(e)者，(g)表示R5 與R6 、R7 與R8 、或R6 與R7 相互鍵結形成之芳香環或非芳香環之單環或多環之烴環或雜環，未參與前述鍵結之R5 ~R8 係相互獨立表示選自前述(a)~ (e)者]其中乙烯基芳香族系樹脂為苯乙烯-(甲基)丙烯酸共聚物。A method for producing a laminated optical film, comprising: forming a cyclic olefin resin layer and ethylene by directly bonding a cyclic olefin resin and a vinyl aromatic resin by a co-extrusion method; a step of laminating the original film of the base aromatic resin layer, and pulverizing the original film obtained in the direction orthogonal to the longitudinal direction of the film, and satisfying all of the following formula (i)~ (iii) A laminated optical film of the characteristics indicated, R450≦R550≦R650...(i) 1.0≦R650/R550≦1.2...(ii) 70nm≦R550≦150nm...(iii) [The above formula (i) to (iii), R450, R550, and R650 sequentially show the in-plane retardation of the laminated optical film at wavelengths of 450 nm, 550 nm, and 650 nm. The cyclic olefin-based resin has the following formula ( 1) a structural unit represented by the structural unit represented by the following formula (2), In the formula (1), m is an integer of 1 or more, p is an integer of 0 or more, and X is independently a group represented by the formula: -CH=CH- or a group represented by the formula: -CH 2 CH 2 -, R 1 The ~R 4 groups independently represent the following (a) to (e) or represent (f) or (g), (a) a hydrogen atom, (b) a halogen atom, and (c) an oxygen atom or a sulfur atom. a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, (e) a polar group, (f) An alkylene group represented by R 1 and R 2 or R 3 and R 4 bonded to each other, and R 1 to R 4 which are not involved in the aforementioned bonding are independently selected from the above (a) to (e), g) a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring representing an aromatic ring or a non-aromatic ring in which R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 are bonded to each other, and does not participate in the aforementioned bonding R 1 to R 4 are independent of each other and are selected from the above (a) to (e). [In the formula (2), Y is a group represented by the formula: -CH=CH- or a group represented by the formula: -CH 2 CH 2 -, and each of R 5 to R 8 independently represents the following (a) to ( e) represents or represents (f) or (g), (a) a hydrogen atom, (b) a halogen atom, (c) a substituted or unsubstituted group containing a linking group having an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom. a hydrocarbon group having 1 to 30 carbon atoms, (d) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, (e) a polar group, and (f) each represents R 5 and R 6 or R 7 and R 8 The alkylene group formed by bonding, the R 5 to R 8 groups not participating in the aforementioned bonding are independent of each other and are selected from the above (a) to (e), and (g) represents R 5 and R 6 , R 7 and R 8 . Or a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring in which an aromatic ring or a non-aromatic ring which is bonded to R 6 and R 7 is bonded to each other, and R 5 to R 8 which are not involved in the aforementioned bonding are mutually independent and are selected from the foregoing ( a)~(e)] wherein the vinyl aromatic resin is a styrene-(meth)acrylic acid copolymer. 如申請專利範圍第1項之層合光學薄膜之製造方法，其中環狀烯烴系樹脂與乙烯基芳香族系樹脂為滿足下述式(iv)的關係，｜TgA(℃)-TgB(℃)｜≦20(℃)...(iv)[式中，TgA係表示環狀烯烴系樹脂之玻璃轉化溫度，TgB係表示乙烯基芳香族系樹脂之玻璃轉化溫度]。 The method for producing a laminated optical film according to the first aspect of the invention, wherein the cyclic olefin resin and the vinyl aromatic resin satisfy the relationship of the following formula (iv), |TgA(°C)-TgB(°C) ≦20 (°C) (iv) [In the formula, TgA represents the glass transition temperature of the cyclic olefin resin, and TgB represents the glass transition temperature of the vinyl aromatic resin]. 如申請專利範圍第1項之層合光學薄膜之製造方法，其中環狀烯烴系樹脂之玻璃轉化溫度(TgA)及乙烯基芳香族系樹脂之玻璃轉化溫度(TgB)均為110℃以上。 The method for producing a laminated optical film according to the first aspect of the invention, wherein the glass transition temperature (TgA) of the cyclic olefin resin and the glass transition temperature (TgB) of the vinyl aromatic resin are both 110 ° C or higher. 一種層合光學薄膜，其特徵係環狀烯烴系樹脂層與乙烯基芳香族系樹脂層直接接觸，進行層合，且滿足全部下述式(i)~(iii)之特性者，R450≦R550≦R650...(i) 1.0≦R650/R550≦1.2...(ii) 70nm≦R550≦150nm...(iii)[上述式(i)~(iii)中，R450、R550、R650係依序表示在波長450nm、550nm、650nm之層合光學薄膜的面內相位差]。 A laminated optical film characterized in that a cyclic olefin-based resin layer is in direct contact with a vinyl aromatic-based resin layer, and is laminated, and satisfies all the characteristics of the following formulas (i) to (iii), R450≦R550 ≦R650...(i) 1.0≦R650/R550≦1.2...(ii) 70nm≦R550≦150nm...(iii) [R450, R550, R650 in the above formula (i)~(iii) The in-plane retardation of the laminated optical film at wavelengths of 450 nm, 550 nm, and 650 nm is sequentially indicated. 如申請專利範圍第4項之層合光學薄膜，其係滿足下述式(v)者， 1.0≦NZ≦3.0...(v)[上述式(v)中，NZ係以NZ=(nx-nz)/(nx-ny)表示之係數，在波長550nm之值，其中nx係表示在層合光學薄膜面內之最大折射率，ny係表示在層合光學薄膜面內，與nx正交之方向的折射率，nz係表示與nx及ny正交之層合光學薄膜厚度方向的折射率，但是層合光學薄膜之平均折射率為Nave 時，以Nave =(nx+ny+nz)/3表示，Nave 係在層合光學薄膜中，環狀烯烴系樹脂層與乙烯基芳香族系樹脂層之各自之平均折射率藉由厚度比進行加權平均的值]。The laminated optical film of claim 4, which satisfies the following formula (v), 1.0 ≦ NZ ≦ 3.0 (v) [in the above formula (v), NZ is NZ = (nx) -nz)/(nx-ny) represents a coefficient at a wavelength of 550 nm, where nx represents the maximum refractive index in the plane of the laminated optical film, and ny is represented in the plane of the laminated optical film, orthogonal to nx The refractive index in the direction, nz represents the refractive index in the thickness direction of the laminated optical film orthogonal to nx and ny, but when the average refractive index of the laminated optical film is N ave , N ave = (nx + ny + nz ) / 3 represents, N ave based on the laminated optical film, the resin layer and an average refractive index of the aromatic vinyl-based resin layer of each of the cyclic olefin-based ratio by the thickness weighted average value]. 如申請專利範圍第4項之層合光學薄膜，其中環狀烯烴系樹脂之玻璃轉化溫度及乙烯基芳香族系樹脂之玻璃轉化溫度均為110℃以上。 The laminated optical film of claim 4, wherein the glass transition temperature of the cyclic olefin resin and the glass transition temperature of the vinyl aromatic resin are both 110 ° C or higher. 一種層合光學薄膜，其特徵係藉由申請專利範圍第1項之層合光學薄膜之製造方法所得者。 A laminated optical film obtained by the method for producing a laminated optical film according to claim 1 of the patent application. 一種偏光板，其特徵係將申請專利範圍第4~7項中任一項之層合光學薄膜，介由接著劑或黏著劑層合於偏光子之至少單面上所成者。 A polarizing plate characterized by laminating an optical film according to any one of claims 4 to 7, which is formed by laminating an adhesive or an adhesive on at least one side of a polarizer. 如申請專利範圍第8項之偏光板，其中尚含有選自反射防止層及防眩層之至少1種的層。 The polarizing plate of claim 8 which further comprises at least one layer selected from the group consisting of an antireflection layer and an antiglare layer. 一種液晶顯示裝置，其特徵係具有申請專利範圍第8項之偏光板者。 A liquid crystal display device characterized by having a polarizing plate of claim 8 of the patent application. 一種液晶顯示裝置，其特徵係具有申請專利範圍第9項之偏光板者。A liquid crystal display device characterized by having a polarizing plate of claim 9th.
TW097145776A 2007-11-30 2008-11-26 A method for producing a laminated optical film, a laminated optical film, a polarizing film, and a liquid crystal display device TWI498362B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2007311283 2007-11-30
JP2008021666 2008-01-31
JP2008057816 2008-03-07

Publications (2)

Publication Number Publication Date
TW200946570A TW200946570A (en) 2009-11-16
TWI498362B true TWI498362B (en) 2015-09-01

Family

ID=40988141

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097145776A TWI498362B (en) 2007-11-30 2008-11-26 A method for producing a laminated optical film, a laminated optical film, a polarizing film, and a liquid crystal display device

Country Status (3)

Country Link
JP (2) JP5375043B2 (en)
KR (1) KR20090056904A (en)
TW (1) TWI498362B (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5724177B2 (en) * 2009-12-16 2015-05-27 日本ゼオン株式会社 Method for producing multilayer film and retardation film
US9442233B2 (en) 2010-12-06 2016-09-13 Nitto Denko Corporation Anti-reflection circularly polarizing plate for organic EL display and organic EL display
JP2013083956A (en) * 2011-09-30 2013-05-09 Nippon Shokubai Co Ltd Phase difference film, polarizing plate, and image display device
JP6176827B2 (en) * 2012-03-14 2017-08-09 日東電工株式会社 Optical film roll
JP6128115B2 (en) * 2012-03-30 2017-05-17 日本ゼオン株式会社 Retardation film laminate, method for producing the same, and liquid crystal display device
KR102057611B1 (en) 2013-05-27 2019-12-20 삼성전자주식회사 Inverse dispertion phase retardation film and display having the same
JPWO2016031946A1 (en) * 2014-08-29 2017-07-20 富士フイルム株式会社 Brightness enhancement film and liquid crystal display device
CN107076904B (en) * 2014-09-17 2019-11-12 日本瑞翁株式会社 Circular polarizing disk, the wave plate of broadband λ/4 and organic electroluminescence display device and method of manufacturing same
JP6266556B2 (en) * 2015-03-20 2018-01-24 富士フイルム株式会社 Laminated film and method for producing the same
JP7056573B2 (en) * 2016-10-31 2022-04-19 日本ゼオン株式会社 Wideband wavelength film and its manufacturing method and circularly polarizing film manufacturing method
JP7059936B2 (en) * 2016-10-31 2022-04-26 日本ゼオン株式会社 Wideband wavelength film and its manufacturing method and circularly polarizing film manufacturing method
KR20210004981A (en) 2018-04-27 2021-01-13 니폰 제온 가부시키가이샤 Broadband wavelength film and its manufacturing method, and manufacturing method of circular polarizing film
WO2019208512A1 (en) 2018-04-27 2019-10-31 日本ゼオン株式会社 Broadband wavelength film, production method for same, and production method for circularly polarizing film
JP7398187B2 (en) * 2018-05-29 2023-12-14 大日本印刷株式会社 Optical laminate, circularly polarizing plate and display panel using the same
KR20210070272A (en) * 2018-09-28 2021-06-14 니폰 제온 가부시키가이샤 Optical film and manufacturing method thereof, optical laminate and liquid crystal display device
KR20220093109A (en) * 2019-10-29 2022-07-05 니폰 제온 가부시키가이샤 Retardation film, manufacturing method thereof, and circularly polarizing plate
JPWO2022145172A1 (en) * 2020-12-28 2022-07-07
KR20230124554A (en) * 2020-12-28 2023-08-25 니폰 제온 가부시키가이샤 Multilayer films, optical films and manufacturing methods

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002040258A (en) * 1999-12-16 2002-02-06 Fuji Photo Film Co Ltd Phase-difference plate, its manufacturing method, circular polarizing plate utilizing the same, half-wave length plate and reflection type liquid crystal display device
TW200634071A (en) * 2004-12-27 2006-10-01 Jsr Corp Thermoplastic resin composition, optical film and retardation film
JP2006268033A (en) * 2005-02-25 2006-10-05 Fuji Photo Film Co Ltd Optical compensation sheet, polarizing plate, and liquid crystal display

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4171168B2 (en) * 2000-10-03 2008-10-22 富士フイルム株式会社 Production method of retardation plate
JP2003090912A (en) * 2001-07-11 2003-03-28 Fuji Photo Film Co Ltd Optical retardation plate
JP2004163684A (en) * 2002-11-13 2004-06-10 Nippon Zeon Co Ltd Laminated phase-difference film and its manufacture method
JP2005112994A (en) * 2003-10-07 2005-04-28 Mitsubishi Engineering Plastics Corp Thermoplastic resin composition
JP2006058540A (en) * 2004-08-19 2006-03-02 Jsr Corp Optical film, polarizer plate and liquid crystal display
JP2007108529A (en) * 2005-10-14 2007-04-26 Jsr Corp Method for producing phase difference film, phase difference film and its use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002040258A (en) * 1999-12-16 2002-02-06 Fuji Photo Film Co Ltd Phase-difference plate, its manufacturing method, circular polarizing plate utilizing the same, half-wave length plate and reflection type liquid crystal display device
TW200634071A (en) * 2004-12-27 2006-10-01 Jsr Corp Thermoplastic resin composition, optical film and retardation film
JP2006268033A (en) * 2005-02-25 2006-10-05 Fuji Photo Film Co Ltd Optical compensation sheet, polarizing plate, and liquid crystal display

Also Published As

Publication number Publication date
KR20090056904A (en) 2009-06-03
JP2009237533A (en) 2009-10-15
TW200946570A (en) 2009-11-16
JP2009237534A (en) 2009-10-15
JP5375043B2 (en) 2013-12-25

Similar Documents

Publication Publication Date Title
TWI498362B (en) A method for producing a laminated optical film, a laminated optical film, a polarizing film, and a liquid crystal display device
JP5186926B2 (en) Method for producing laminated optical film, laminated optical film and use thereof
JP4178810B2 (en) Thermoplastic norbornene resin-based optical film
JP3735366B2 (en) Birefringent material for optical film
JP5135799B2 (en) Thermoplastic resin composition, optical film and stretched film
JP3912159B2 (en) Optical film, method for producing the same, and polarizing plate
JP4799320B2 (en) Negative A retardation film and liquid crystal display device using the same
JP2007108529A (en) Method for producing phase difference film, phase difference film and its use
KR20170011306A (en) Optical film, manufacturing method thereof and display device
JP4172310B2 (en) Polarizer
JP3815790B1 (en) Retardation film, optical film, liquid crystal panel, liquid crystal display device, and image display device
JP5186991B2 (en) Method for producing laminated optical film, laminated optical film, polarizing plate and liquid crystal display device
JP5251214B2 (en) Method for producing laminated optical film, laminated optical film and use thereof
JP2010060618A (en) Polarizing plate with laminate optical film and liquid crystal display device provided with the same
JP5374820B2 (en) Thermoplastic resin composition and optical film comprising the same
JP2008102498A (en) Method for producing retardation film, retardation film and its use
KR20070043701A (en) Novel modified polymer, process for producing the same, and use of said novel modified polymer
KR20080027203A (en) Process for producing retardation film, retardation film and use thereof
TW202016184A (en) Optical film, method for manufacturing same, optical layered body, and liquid crystal display device
JP2009244609A (en) Method for manufacturing laminated optical film, laminated optical film, and application of the same
JP4701715B2 (en) Optical film manufacturing method and optical film
JP5560551B2 (en) Liquid crystal panel and optical film set for liquid crystal panel
JP2004339406A (en) Optical film, its manufacturing method and image display device
JP4080200B2 (en) Retardation film and liquid crystal display device
TWI837452B (en) Circular polarizing plate with anti-reflection layer and image display device using the circular polarizing plate with anti-reflection layer