KR20080027203A - Method for producing retardation film, retardation film and use thereof - Google Patents

Abstract

The present invention provides a norbornene-based resin-containing retardation film having an optical axis in the transverse direction and excellent in reverse wavelength dispersion even after stretching, and having a small NZ coefficient, and a method for producing the retardation film, comprising the retardation film Provide a film roll.

The present invention extends the norbornene-based resin-containing film in a range of 2 to 5 times in the width direction of the film roll under specific temperature conditions, thereby obtaining a retardation film in which the optical axis is in the width direction of the film roll while having reverse wavelength dispersion. It provides a method for producing a retardation film, characterized in that.

Description

The manufacturing method of retardation film, retardation film, and its use {PROCESS FOR PRODUCING RETARDATION FILM, RETARDATION FILM AND USE THEREOF}

The present invention comprises a norbornene-based resin, is excellent in the wavelength dispersion of the retardation, and having a optical axis in the film width direction, a method for producing a retardation film and a retardation film, a polarizing plate comprising the retardation film and a polarizer, using these The present invention relates to a liquid crystal display device. Moreover, this invention relates to the film roll of retardation film which has an optical axis in the width direction, and the manufacturing method of the polarizing plate using the same.

The norbornene-based resin has high glass transition temperature due to the rigidity of the main chain structure, and because of the presence of bulky groups in the main chain structure, it is amorphous and has high light transmittance, and also has low birefringence due to low birefringence anisotropy. It is attracting attention as a transparent thermoplastic resin which has the characteristics and is excellent in heat resistance, transparency, and optical characteristics.

By using the above characteristics, for example, optical disks, optical lenses, optical fibers, transparent plastic bases, low dielectric materials, retardation plates, protective films for polarizing plates, electronic and optical materials such as substrates for liquid crystal display elements, optical semiconductor sealing, etc. Application of norbornene-based resins in fields such as sealing materials has been studied.

The norbornene-based resin is further subjected to stretching orientation to become a retardation film that provides uniform and stable retardation to transmitted light. In general, however, the retardation film has a function of providing retardation (birefringence) to transmitted light obtained by stretching orientation, and the characteristic that the absolute value of the retardation (birefringence) of transmitted light becomes smaller as the wavelength of the transmitted light becomes longer (hereinafter referred to as "negative wavelength"). Dependencies "). For this reason, the function which provides the transmitted light with a phase difference of 1/4 wavelength in the whole visible light region (400-800 nm) required for a reflection type | mold semi-transmissive liquid crystal display etc. (in this invention, phase difference is It was very difficult to obtain a retardation film with retardation). Moreover, in order to obtain the retardation film which has a function which provides the transmitted light with the phase difference of 1/2 wavelength, which is required for the liquid crystal projector, for example, it was necessary to laminate | stack a film in conventional norbornene-type resin. In the lamination of the films, not only the processes such as bonding, cutting, and bonding are complicated, but also the film thickness of the optical film obtained is large, and it is difficult to thin the retardation film which is recently required.

In order to solve the said subject, the optical film which shows the characteristic (henceforth "reverse wavelength dispersion | distribution") which the absolute value of the phase difference of transmitted light becomes large as a wavelength becomes long wavelength is needed. As an optical film which shows the said reverse wavelength dispersion property, in the following patent documents 1 and 2 and the nonpatent literature 1, the retardation film containing specific cellulose acetate type resin, the retardation film containing polycarbonate resin, norbornene system A retardation film or the like comprising a thermoplastic resin composition having a resin and a styrene resin has been proposed.

However, in the film containing the cellulose acetate-based resin, there are problems in terms of changes in properties due to absorption, heat resistance, and the like. In polycarbonate-based resins, the glass transition temperature is high, and stretching at high temperatures is required. Because of the large photoelastic coefficient, optical deformation due to stress occurs. Moreover, in the film obtained from the thermoplastic resin composition which has norbornene-type resin and styrene resin, when extending | stretching, there exists a problem that extending | stretching process becomes difficult, for example, the stress at the time of extending | stretching or the stress nonuniformity at the time of extending | stretching arises. When the film roll is laterally stretched, it is consequently constrained in the film length direction, so that the value of NZ is generally 1.50 or more, and the optical axis of the retardation film is in the width direction of the film roll. It was difficult to obtain.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2000-137116

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-337222

[Non-Patent Document 1] Polymer Journal, Vol. 61, no. 1, 89-94 (2004)

The present invention provides a norbornene-based resin-containing retardation film having an optical axis in the transverse direction and excellent in reverse wavelength dispersion even after stretching, and having a small NZ coefficient, and a method for producing the retardation film, comprising the retardation film Let it be a subject to provide a film roll. Moreover, this invention makes it a subject to provide the polarizing plate containing the said retardation film and a polarizer, and the liquid crystal display device using these. In addition, the present invention provides a method for producing a high performance polarizing plate with good manufacturing efficiency by using a retardation film or a film roll according to the present invention, excellent transparency, excellent dimensional stability under high temperature and high humidity environment, and a simple method. It is a task to do it.

Method for producing a retardation film of the present invention is a norbornene-based resin-containing film in a range of 2 to 5 times in the width direction of the film roll under the temperature conditions of Tg to Tg + 50 ℃ based on the glass transition temperature (Tg) of the film. By extending | stretching, ratio Re (650) / Re (550) of phase difference Re (550) in wavelength 550nm and phase difference Re (650) in wavelength 650nm exists in the range of 1.03-1.18, and phase difference in wavelength 550nm Characterized by obtaining a retardation film in which the optical axis is in the width direction of the film roll while the ratio Re (450) / Re (550) of the Re (550) and the retardation Re (450) at a wavelength of 450 nm is in a range of less than 1.0. do.

In the manufacturing method of the retardation film of this invention, norbornene-type resin containing a norbornene-type resin containing structure unit (henceforth also called "structural unit (I)") represented by following formula (I) (hereinafter, "norbornene-type It is preferable that it is a film formed by forming a film of resin (I) ".

<Formula I>

In Formula I, m and n are each independently an integer of 0 to 2,

X is a group represented by the formula -CH = CH- or a group represented by the formula -CH ₂ CH _2- ,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently a hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom; And an atom or group selected from the group consisting of a polar group, s, t, u are each independently an integer of 0 to 3)

In the manufacturing method of the retardation film of this invention, norbornene-type resin containing film (A) norbornene-type resin which has a structural unit represented by following formula (1) or following formula (2) is also called "norbornene-type resin (A)" And a vinyl polymer having a polar group (B) (hereinafter also referred to as "vinyl polymer (B)").

(Formula (1) of, m is 0, 1, or 2, X is independently a group or the formula -CH ₂ CH ₂ represented by the formula -CH = CH- - are each independently a group represented by the, A ¹ to A ⁴ Hydrogen atom; halogen atom; substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group containing oxygen, nitrogen, sulfur or silicon; or a polar group)

(In Formula 2, X is independently a group represented by the formula -CH = CH- or a group represented by the formula -CH ₂ CH _2- , and A ⁵ to A ¹⁰ are each independently a hydrogen atom; a halogen atom; Substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group comprising nitrogen, sulfur or silicon; or a polar group)

In the manufacturing method of the retardation film of this invention, the (B) styrene-type copolymer which has a structural polymer (B1) represented by the following general formula (B1), and the structural unit (B2) represented by the following general formula (B2) has a polar group (following) , Also referred to as "specific styrenic copolymer".

<Formula B1>

<Formula B2>

(In Formula B1 and Formula B2, R represents a hydrogen atom or a methyl group, and in Formula B2, R ⁰ may be a hydrogen atom; a halogen atom; and may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom). Substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or represents a polar group)

In the manufacturing method of the retardation film of this invention, it is preferable that a retardation film is a 1/4 (lambda) plate.

The retardation film of this invention was obtained by the manufacturing method of the retardation film of the said invention, It is characterized by the above-mentioned.

The retardation film of the present invention contains a norbornene-based resin, the ratio Re (650) / Re (550) of the phase difference Re (550) at a wavelength of 550 nm and the phase difference Re (650) at a wavelength of 650 nm is 1.03 to 1.18. The ratio Re (450) / Re (550) of the phase difference Re (550) at a wavelength of 550 nm and the phase difference Re (450) at a wavelength of 450 nm is in a range of less than 1.0. The displayed NZ coefficient is in the range of 0.90 to 1.40, and the phase difference Re 550 is in the range of 100 to 300 nm.

NZ coefficient = (nx-nz) / (nx-ny)

[Wherein nx represents the maximum refractive index in the film plane, ny represents the refractive index in the direction perpendicular to nx in the film plane, and nz represents the refractive index in the thickness direction of the film (each at a wavelength of 550 nm)]

The polarizing plate of this invention is characterized by bonding the retardation film of this invention to at least one surface of a polarizer.

The film roll of this invention contains the retardation film of this invention, has an optical axis in the width direction of a film roll, and is characterized by the phase difference of transmitted light having reverse wavelength dispersion.

The manufacturing method of the polarizing plate of this invention is made to adhere | attach both continuously, matching the longitudinal direction of the film roll of this invention, and the longitudinal direction of the polarizer which has an absorption axis in a longitudinal direction. The polarizing plate of this invention was obtained by the manufacturing method of this polarizing plate of this invention, It is characterized by the above-mentioned.

The liquid crystal display device of this invention is characterized by using the retardation film of this invention or the polarizing plate of this invention.

According to the present invention, a norbornene-based resin-containing retardation film having excellent transparency, low gas permeability, excellent dimensional stability, optical axis in the width direction, excellent reverse wavelength dispersion, and low NZ coefficient, It is possible to provide a method for producing a retardation film. In particular, in the present invention, since the optical axis in the film plane is in the film width direction, a roll type retardation film having a small NZ coefficient can be obtained, and the retardation film has reverse wavelength dispersion in the visible light region, and is preferable in the whole visible light region. The manufacturing method of retardation film and retardation film which can manufacture the retardation film which provide the to a transmitted light can be provided.

Moreover, according to this invention, by using the phase difference film which concerns on this invention, it is excellent in transparency, it is excellent in dimensional stability even in a high temperature, high humidity environment, and can manufacture a high performance polarizing plate by a simple method with favorable manufacturing efficiency, The polarizing plate The manufacturing method of the present invention can be provided, and also the liquid crystal display device using the said retardation film or a polarizing plate can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<Norbornene-based resin>

As the norbornene-based resin according to the present invention, a monomer containing a compound obtained by ring-opening (co) polymerizing a monomer containing a compound having a norbornene skeleton and hydrogenated as needed and a compound having a norbornene skeleton Any resin obtained by addition (co) polymerization can be used. In this invention, resin obtained by ring-opening (co) polymerizing the monomer containing the compound which has a norbornene skeleton among these, and hydrogenating as needed is used preferably. In particular, the norbornene-based resin (I) having the above-mentioned structural unit (I) is preferably used as a resin having excellent reverse wavelength dispersion. In addition, the above-mentioned norbornene-based resin (A) is preferably used because it is easy to adjust reverse characteristics such as reverse wavelength dispersibility and to adjust properties such as moldability by mixing with the vinyl polymer (B).

Norbornene system  Monomer

Norbornene-based resin (I) is obtained by ring-opening (co) polymerizing a monomer containing a compound represented by the following general formula Im, preferably by hydrogenation.

<Formula Im>

In Formula I, m and n are each independently an integer of 0 to 2,

X is a group represented by the formula -CH = CH- or a group represented by the formula -CH ₂ CH _2- ,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently a hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom; And an atom or group selected from the group consisting of a polar group, s, t, u are each independently an integer of 0 to 3)

Here, as a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned.

As a hydrocarbon group of 1-30 carbon atoms, For example, Alkyl groups, such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups such as vinyl group and allyl group; Alkylidene groups such as ethylidene group and propylidene group; Aromatic groups, such as a phenyl group, a naphthyl group, and anthracenyl group, etc. are mentioned. These hydrocarbon groups may be substituted, and examples of the substituent include halogen atoms such as fluorine, chlorine and bromine, phenylsulfonyl group and cyano group.

In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded through a linkage. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example,-(CH ₂ ) _q- (q is an alkylene group represented by an integer of 1 to 10)); A linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom (for example, a carbonyl group (-CO-), a carbonyloxy group (-COO-), a sulfonyl group (-SO _2- ), a sulfonyl ester group) (-SO ₂ -O-), ether bond (-O-), thioether bond (-S-), imino group (-NH-), amide bond (-NHCO-), siloxane bond (-Si (R ₂ ) O- (here, R is an alkyl group such as methyl or ethyl)) or two or more thereof are combined and connected.

Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, and a triorganosilyl group , An amino group, acyl group, alkoxysilyl group, sulfonyl group, and carboxyl group. More specifically, as said alkoxy group, a methoxy group, an ethoxy group, etc. are mentioned, for example; Examples of the carbonyloxy group include alkylcarbonyloxy groups such as acetoxy group and propionyloxy group, and arylcarbonyloxy groups such as benzoyloxy group; As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned, for example; Examples of the aryloxycarbonyl group include phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, biphenylyloxycarbonyl group, and the like; Examples of the triorganosiloxy group include trimethylsiloxy group, triethylsiloxy group, and the like; Examples of the triorganosilyl group include trimethylsilyl group and triethylsilyl group; A primary amino group etc. are mentioned as an amino group, For example, a trimethoxy silyl group, a triethoxy silyl group, etc. are mentioned as an alkoxy silyl group.

On the other hand, four R ⁸ and R ⁹ in the formula Im are each an independent atom or group.

As the stereoisomer of the site where the spiro aromatic structure and the cyclocyclic structure connect in the norbornene-based compound (Im), an exo body and an endo body exist, but their composition is not particularly limited, It can select suitably according to a characteristic. In particular, when producing norbornene-based resin by ring-opening (co) polymerization and hydrogenation, since norbornene-based compound (Im) provides "negative birefringence" to the (co) polymer, By appropriately copolymerizing "with other norbornene-based monomers to be provided to the (co) polymer, birefringence can also be suitably desired. On the other hand, the birefringence positive and negative referred to herein is obtained from the refractive index change generated when the film is uniaxially stretched, and the property in which the refractive index in the stretching direction is larger than the refractive index in the vertical direction with respect to the stretching direction is "positive birefringence", on the contrary, stretching. The property that the refractive index of the direction becomes small is defined as "negative birefringence."

In addition, when a functional group (for example, an ester group, an alkoxy group, etc.) having a large polarization is introduced with respect to the substituent on the aromatic ring, the wavelength dependence of birefringence can be increased.

As said norbornene-type monomer (Im), it is obtained by reducing 5-norbornene-2,3-dicarboxylic anhydride which is the Diels-Alder reaction product of maleic anhydride and cyclopentadiene, for example. The spiro compound etc. which are synthesize | combined by modifying norbornene dimethanol with a suitable leaving group (tosyl group, a halogen atom, etc.), and then reacting with a fluorene derivative anion are mentioned. As a norbornene-type monomer (Im) used preferably by this invention, the following compounds can be illustrated more specifically.

Specific examples of norbornene-based monomers (Im)

Examples of norbornene-based monomers ( Im ) represented by m = n = 0

(1) spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene],

(2) spiro [2,7-difluorofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(3) spiro [2,7-dichlorofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(4) spiro [2,7-dibromofluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(5) spiro [2-methoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(6) spiro [2-ethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(7) spiro [2-phenoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(8) spiro [2,7-dimethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(9) spiro [2,7-diethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(10) spiro [2,7-diphenoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(11) spiro [3,6-dimethoxyfluorene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(12) spiro [9,10-dihydroanthracene-9,8'-tricyclo [4.3.0.1 ^2.5 ] [3] decene],

(13) spiro [fluorene-9,8 '-[2] methyltricyclo [4.3.0.1 ^2.5 ] [3] decene],

(14) spiro [fluorene-9,8 '-[10] methyltricyclo [4.3.0.1 ^2.5 ] [3] decene],

<Example of norbornene derivatives represented by m = 1, n = 0

(15) spiro [fluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(16) spiro [2,7-difluorofluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(17) spiro [2,7-dichlorofluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(18) spiro [2,7-dibromofluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(19) spiro [2-methoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(20) spiro [2-ethoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(21) spiro [2-phenoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(22) spiro [2,7-dimethoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(23) spiro [2,7-diethoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(24) spiro [2,7-diphenoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(25) spiro [3,6-dimethoxyfluorene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene],

(26) Spiro [9,10-dihydroanthracene-9,11'-pentacyclo [6.5.1.1 ^3.6 .0 ^2.7 .0 ^9.13 ] [4] pentadecene].

Examples of norbornene-based monomers ( Im ) represented by m = 1, n = 1

(27) spiro [fluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(28) spiro [2,7-difluorofluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(29) spiro [2,7-dichlorofluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(30) spiro [2,7-dibromofluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(31) spiro [2-methoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(32) spiro [2-ethoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(33) spiro [2-phenoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(34) spiro [2,7-dimethoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(35) spiro [2,7-diethoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(36) spiro [2,7-diphenoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(37) spiro [3,6-dimethoxyfluorene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene],

(38) Spiro [9,10-dihydroanthracene-9,13'-hexacyclo [7.7.0.1 ^3.6 .1 ^10.16 .0 ^2.7 .0 ^11.15 ] [4] octadecene].

Examples of norbornene-based monomers ( Im ) represented by m = 0 and n = 1

(39) spiro [fluorene-9,10'-tetracyclo [7.4.0.0 ^8.12 .1 ^2.5 ] [3] tetradecene],

(40) spiro [fluorene-9,10 '-[7] methyltetracyclo [7.4.0.0 ^8.12 .1 ^2.5 ] [3] tetradecene].

In addition, for example, the following compounds in which a substituent is further added to the compound represented by the formula Im can also be preferably used as a monomer.

(41) spiro [fluorene-9,10 '-[1] methyltetracyclo [7.4.0.0 ^8.12 .1 ^2.5 ] [3] tetradecene].

In the production of norbornene-based resin according to the present invention, these norbornene-based monomers (Im) may be used alone, or may be used in combination of two or more thereof.

In the present invention, particularly in the production of norbornene-based ring-opening (co) polymers, monomers containing m = 0, n = 0 and u = 0 in the above-mentioned formula (Im) among the norbornene-based compounds (Im) are used. It is preferable. Such monomers are preferable because they can be synthesized relatively easily, the monomers are easily obtained, and the ring-opening (co) polymers obtained and the hydrogenated products thereof combine heat resistance and toughness.

In norbornene-type resin (I), although it does not specifically limit as a monomer which can be used by copolymerizing with the compound represented by the said Formula (Im), For example, the compound represented by following formula (1m) is mentioned. In addition, the compound represented by following formula (1m) is used as a monomer which comprises structural unit (1) in norbornene-type resin (A).

<1m>

In Formula 1m, m and A ¹ to A ⁴ are m, 0, 1 or 2, and A ¹ to A ⁴ each independently represent a hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 30, preferably 1 to 10, carbon atoms which may have a linking group comprising oxygen, nitrogen, sulfur or silicon; Or a polar group. Preferably, at least one of A ¹ to A ⁴ is a polar group, and at least one of the other A ¹ to A ⁴ is a hydrocarbon group having 1 to 10 carbon atoms.

In the general formula (1m), for example, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, A triorgano silyl group, an amino group, an acyl group, an alkoxy silyl group, a sulfonyl group, a carboxyl group, etc. are mentioned. More specifically, as said alkoxy group, a methoxy group, an ethoxy group, etc. are mentioned, for example; Examples of the carbonyloxy group include alkylcarbonyloxy groups such as acetoxy group and propionyloxy group, and arylcarbonyloxy groups such as benzoyloxy group; As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned, for example; Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, biphenylyloxycarbonyl group, and the like; Examples of the triorganosiloxy group include trimethylsiloxy group, triethylsiloxy group, and the like; Examples of the triorganosilyl group include trimethylsilyl group and triethylsilyl group; Primary amino group is mentioned as an amino group, For example, a trimethoxy silyl group, a triethoxy silyl group, etc. are mentioned as an alkoxy silyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

As a hydrocarbon group of 1-10 carbon atoms, For example, Alkyl groups, such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups, such as a vinyl group, an allyl group, and a propenyl group, etc. are mentioned.

In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded through a linkage. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by-(CH ₂ ) _m- (wherein m is an integer of 1 to 10)); Linking groups containing oxygen, nitrogen, sulfur or silicon (e.g. carbonyl group (-CO-), oxycarbonyl group (-O (CO)-), sulfone group (-SO _2- ), ether bond (-O-) , Thioether bond (-S-), imino group (-NH-), amide bond (-NHCO-, -CONH-), siloxane bond (-OSi (R ₂ )-(where R is methyl, ethyl, etc.) Alkyl group)) and the like, and may be a linking group including a plurality of these groups.

As the compound represented by formula 1m, specifically, for example, as a non-cyclin [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, hexahydro cyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hept-4-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5- Methyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxycarbonyl- Bicyclo [2.2.1] hept-2-ene, 5-methyl-6-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-6-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methyl-8-ethoxy Carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methyl-8-n-propoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-ene, 8-methyl-8-isopropoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-methyl-8-n- Butoxycarbonyl-Tet Cyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca- Although 3-yen etc. are mentioned, It is not limited to these examples.

In the present invention, it is preferable that the polar group in the compound represented by Chemical Formula 1m is a group represented by the following Chemical Formula a. That is, the compound represented by Chemical Formula 1m is preferably one or more of A ¹ to A ⁴ is a group represented by the following Chemical Formula a.

<Formula a>

-(CH ₂ ) _p COOA '

(In formula a, p is 0 or an integer of 1-5, A 'is a C1-C15 hydrocarbon group.)

In the above formula (a), the smaller the value of n and the smaller the number of carbon atoms of A ', the higher the glass transition temperature of the copolymer obtained and the higher the heat resistance. That is, n is usually 0 or an integer of 1 to 5, preferably 0 or 1, and A 'is usually a hydrocarbon group having 1 to 15 carbon atoms, but preferably an alkyl group having 1 to 3 carbon atoms. Especially as a norbornene-type compound which has such a carboxylic acid ester group, 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3- dodecene is the manufacturing method which is easy. It is preferable at one point. On the other hand, examples of the hydrocarbon group represented by A 'include alkyl groups such as methyl group, ethyl group and propyl group, aryl groups such as phenyl group and aralkyl groups such as benzyl group, and preferably methyl group, ethyl group and phenyl group. And a methyl group is particularly preferable. p is an integer of 0 or more, and particularly preferably 0.

In addition, in the said Formula (1m), when an alkyl group is further bonded to the carbon atom which the polar group represented by the said Formula (a) couple | bonded, it is preferable in order to balance the heat resistance and the water absorption (wetness) of the copolymer obtained. Do. It is preferable that carbon number of the said alkyl group is 1-5, More preferably, it is 1-2, Especially preferably, it is 1.

In Formula 1m, when A ¹ , A ² , A ³ , and A ⁴ are bonded to each other to form a monocyclic or polycyclic group that may have a hetero atom, the monocyclic or polycyclic formed may be an aromatic ring or a non-aromatic ring. In the formula (1m), an example of the case where A ¹ , A ² , A ³ and A ⁴ are bonded to each other to form a ring structure is partially shown below.

In addition, as a monomer component which can be copolymerized, the compound represented by following formula (2m) is mentioned. In addition, the compound represented by following formula (2m) is used as a monomer which comprises structural unit (2) in norbornene-type resin (A).

<Formula 2m>

In Formula 2m, A ⁵ to A ¹⁰ are each independently a hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group including oxygen, nitrogen, sulfur or silicon; Or a polar group.

In Chemical Formula 2m, a halogen atom, a hydrocarbon group and a polar group are the same as those described in connection with Chemical Formula 1m.

As a compound represented by such a chemical formula 2m, it is concrete, for example

Tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

8-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-ethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-isopropyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-phenyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7,7-dimethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-methyl-8-ethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

8-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-phenoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-methyl-7-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

8-methyl-8-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-fluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

8-fluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7-chloro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

8-chloro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7,7-difluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7,8-difluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene,

7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] deca-3-ene etc. are mentioned, It is not limited to these examples.

In addition, after (co) polymerization using the compound represented by the following Formula 2m 'instead of the compound represented by the above Formula 2m, a 5-membered ring may be hydrogenated as necessary.

<Formula 2m '>

As the compound represented by the formula (2m '), for example,

Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (DCP),

7-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

8-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

9-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-ethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-phenyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-phenoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-methyl-7-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-fluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7,8-difluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene,

7-chloro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, and the like, but are not limited to these examples. Among them, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene is particularly preferably used.

In the production of norbornene-based resin (I) according to the present invention, the monomers described above are polymerized or copolymerized.

In the present invention, in addition to the norbornene-based compounds exemplified above, other copolymerizable compounds (copolymerizable compounds) can be used as part of the monomer. Specific examples of the copolymerizable compound include cycloalkane such as cyclobutene, cyclopentene, cyclooctene and cyclododecene; Non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatene; Low polymers having a double bond such as polybutadiene, polyisoprene, styrene-butadiene, ethylene-non-conjugated diene polymer; Etc. can be mentioned. In the monomer, the norbornene-based compound / copolymerizable compound is preferably in the range of 100/0 to 50/50 by weight, more preferably 100/0 to 60/40.

Norbornene-based resin (I) according to the present invention can be obtained by ring-opening (co) polymerizing the monomers described above.

Ring opening (co) polymer

Although it does not specifically limit as a ring-opening (co) polymer of the monomer containing the compound which has a norbornene skeleton, and its hydrogenated substance, For example, the norbornene-type polymer which has a structural unit (1) represented by the said General formula (1) is mentioned. Can be.

In Formula 1, m is 0, 1 or 2, X is independently a group represented by the formula -CH = CH-, or a group represented by the formula -CH ₂ CH _2- , A ¹ to A ⁴ are each independently Hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group including oxygen, nitrogen, sulfur or silicon; Or a polar group. Preferably, at least one of A ¹ to A ⁴ is a polar group, and at least one of the other A ¹ to A ⁴ is a hydrocarbon group having 1 to 10 carbon atoms.

The structural unit represented by Formula 1 is derived from a norbornene-based compound represented by Formula 1m by ring-opening (co) polymerization and hydrogenation as necessary.

Moreover, as a ring-opening (co) polymer of the monomer containing the compound which has a norbornene frame | skeleton, and its hydrogenated substance, the norbornene-type polymer which has a structural unit represented by the said Formula (2) is mentioned, for example.

The structural unit represented by the formula (2) is ring-opened (co) polymerized the norbornene-based compound represented by the formula (2m), hydrogenated as necessary, or the ring-opened norbornene-based compound represented by the formula (2m ') It can obtain by superposing | polymerizing and hydrogenating.

When norbornene-type resin which concerns on this invention has a structural unit (I), it is preferable to contain structural unit (I) normally 2 mol% or more, preferably 5 mol% or more in all the structural units.

In the norbornene-based resin, the structural unit (I) preferably has m = 0, n = 0, and u = 0 in the general formula (I). The norbornene-based ring-opening (co) polymer having such a structural unit (I) is preferable because it has both heat resistance and toughness, and can easily synthesize monomers for inducing the structural unit.

Moreover, it is preferable that such norbornene-type resin is 0.2-5.0, Preferably it is 0.3-4.0, More preferably, it is 0.35-3.0, and the intrinsic viscosity [(eta)] measured with a ubelide-type viscometer in a chloroform solution. Further, in the molecular weight measurement by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion), the number average molecular weight (Mn) is usually from 1,000 to 500,000, preferably from 2000 to 300,000, more preferably from 5000 It is 300,000, and a weight average molecular weight (Mw) is 5000-5 million normally, Preferably it is 10,000-1 million, More preferably, it is 10,000-500,000. When the intrinsic viscosity [η] is less than 0.2, the number average molecular weight (Mn) is less than 1000, or the weight average molecular weight (Mw) is less than 5000, the strength of the molded product obtained from the norbornene-based ring-opening (co) polymer may be significantly lowered. It is not desirable because there is. On the other hand, when the intrinsic viscosity [η] is 5.0 or more, the number average molecular weight (Mn) is 500,000 or more, or the weight average molecular weight (Mw) is 2 million or more, the melt viscosity of the norbornene-based ring-opening (co) polymer or its hydrogenated substance or It is not preferable because the solution viscosity may become too high to obtain a film of a desired property.

The norbornene-based resin (I) having the structural unit (I) represented by the formula (I) has excellent transparency, heat resistance and low water absorption, and has reverse wavelength dispersion when a retardation film is produced. Especially preferably, it can use.

It is preferable that norbornene-type resin (I) contains 2 weight% or more of structural unit (I). When the ratio of the structural unit (I) in all the structural units is smaller than 2/98, reverse wavelength dispersibility may not be obtained, and desired characteristics may not be obtained when stretching in the width direction of the film roll.

In addition, norbornene-based resin (A) having a structural unit represented by the formula (1) or (2) has excellent transparency, heat resistance and low water absorption, and is also used in combination with a vinyl-based polymer (B) to reverse wavelength dispersion. It is also easy to express and to adjust characteristics, such as moldability, and can use preferably in this invention.

Ring opening (co) polymerization catalyst

The ring-opening (co) polymerization reaction of the monomer can be carried out in the presence of a metathesis catalyst.

As the catalyst for ring-opening polymerization to be used in the present invention, the catalyst described in Olefin Metathesis and Metathesis Polymerization (K.J. IVIN, J.C.MOL, Academic Press 1997) is preferably used.

As such a catalyst, for example, (a) one or more selected from compounds of W, Mo, Re and V, Ti, and (b) Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, Al As a compound such as Si, Sn, Pb, or the like, a metathesis polymerization catalyst including a combination with one or more selected from those having one or more of the above element-carbon bonds or the above element-hydrogen bonds may be mentioned. This catalyst may be one to which additive (c) described later is added to increase the activity of the catalyst. Examples of other catalysts include (d) metathesis catalysts containing a periodic table of Groups 4 to 8 transition metal-carbene complexes, metallacyclobutane complexes, and the like which do not use a crude catalyst.

Representative examples of the compounds of W, Mo, Re and V, Ti suitable as the component (a) include WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl ₄ and the like described in JP-A-240517 The compound can be mentioned.

Examples of the component (b) _{nC 4 H 9 Li, (C} 2 H 5) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1 .5, (C 2 H 5) AlCl 2 The compound of Unexamined-Japanese-Patent No. 1-240517, such as methylalumoxane and LiH, is mentioned.

As representative examples of the component (c), which is an additive, alcohols, aldehydes, ketones, amines and the like can be preferably used, but further, the compounds disclosed in Japanese Patent Application Laid-Open No. Hei 1-240517 can be used.

Representative examples of the catalyst (d) include W (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CH tBu) (O tBu) ₂ , Mo (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CH tBu) (O tBu) ₂ , Ru (= CHCH = CPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (= CHPh) (PC ₆ H ₁₁ ) ₂ Cl ₂ .

As the usage-amount of a metathesis catalyst, "(a) component: whole monomer" is usually 1 in the molar ratio of the said (a) component and all monomers (norbornene-type monomer (Im), (IIm) and other copolymerizable monomer. It is preferable that it is the range which becomes: 500-1: 500000, Preferably it is the range which becomes 1: 1000-1: 100000. The ratio of component (a) to component (b) is preferably in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30, in terms of metal atomic ratio. . In addition, when the said (c) additive is added to this metathesis catalyst, the ratio of (a) component and (c) component has a molar ratio of "(c) :( a)" of 0.005: 1 to 15: 1, preferably Is preferably in the range of 0.05: 1 to 7: 1. In addition, the amount of the catalyst (d) used is in a molar ratio of the component (d) and the total monomers such that the "component (d): all monomers" is usually 1:50 to 1: 50000, preferably 1: 100 to 1: 1. It is preferable that it is the range which becomes 10000.

Molecular weight regulator

Although the molecular weight control of a ring-opening (co) polymer can be performed also by the polymerization temperature, the kind of catalyst, and the kind of solvent, in this invention, it is preferable to adjust by coexisting a molecular weight modifier in a reaction system. Here, as a preferable molecular weight modifier, alpha olefins and styrene, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, are mentioned, for example. Among these, 1-butene and 1-hexene are especially preferable. These molecular weight modifiers can be used individually or in mixture of 2 or more types. As the usage-amount of a molecular weight modifier, it is preferable that it is 0.001-0.6 mol, preferably 0.02-0.5 mol with respect to 1 mol of all the monomers provided for a ring-opening (co) polymerization reaction.

Ring-opening (co) polymerization solvent

As a solvent used in a ring-opening (co) polymerization reaction, ie, a solvent which dissolves a norbornene-based monomer, a metathesis catalyst, and a molecular weight regulator, for example, alkanes such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated alkanes such as chlorobutane, bromine hexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform and tetrachloroethylene; Compounds such as aryl; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane; And ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane and the like, and these may be used alone or in combination. In this invention, an aromatic hydrocarbon is preferable in these.

As a usage-amount of a solvent, "solvent: all monomers (weight ratio)" is the quantity which is usually 1: 1-10: 1, It is preferable that it is the quantity which becomes 1: 1-1: 51 preferably.

Hydrogenation

In the present invention, the norbornene-based resin which is a norbornene-based ring-opening (co) polymer can be produced only by the above-described ring-opening (co) polymerization, but it is preferable to further hydrogenate the ring-opening (co) polymer obtained in the ring-opening (co) polymerization. . In the ring-opening (co) polymerization alone, the norbornene-based ring-opening (co) polymer of the present invention obtained is an olefinically unsaturated group in which all of X in the structural units represented by the above-described formulas (1), (2) or (I) are represented by the formula -CH = CH- The state of The ring-opening (co) polymer of the present invention may be used as it is, but in view of heat stability, it is preferable that the olefinically unsaturated group is a hydrogenated substance in which X is converted into a group represented by -CH ₂ -CH _2- . However, the hydrogenated substance used in this invention means that the said olefinic unsaturated group was hydrogenated, and the aromatic ring of the side chain based on the norbornene-type monomer is not hydrogenated substantially.

On the other hand, as a ratio to hydrogenate, it is preferable that it is 90 mol% or more, Preferably it is 95% or more, More preferably, it is 97% or more of the sum of X in the structural unit represented by the said Formula (1), (2) or I. The higher the ratio of hydrogenation, the more stable the (co) polymer, and the more preferable the coloring and deterioration due to heat are suppressed.

In the production method of the present invention, when the hydrogenation reaction has a side chain aromatic ring based on the norbornene-based compound which is a monomer, it is preferable that the hydrogenation reaction is carried out under conditions that are not substantially hydrogenated. For this reason, it is usually carried out by adding a hydrogenation catalyst to the solution of the ring-opening (co) polymer and acting hydrogen at normal pressure to 30 MPa, preferably 2 to 20 MPa, more preferably 3 to 18 MPa. desirable.

As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, both a well-known heterogeneous catalyst and a homogeneous catalyst can be used. As a heterogeneous catalyst, the solid catalyst which supported noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. As the homogeneous catalyst, nickel naphthenate / triethylaluminum, bis (acetylacetonate) nickel (II) / triethylaluminum, cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum monochloride, acetic acid Rhodium, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium have. The form of the catalyst may be powder or granular. In addition, this hydrogenation reaction catalyst can be used individually by 1 type or in combination of 2 or more types.

These hydrogenated catalysts need to be adjusted in amount so that the aromatic ring of the side chain based on the monomers is not substantially hydrogenated, but the "opening (co) polymer: hydrogenated catalyst (weight ratio)" is usually 1: 1 ×. 10 ^-6 to 1: 2 is preferably used in a proportion of.

Addition (co) polymers

The norbornene-based resin according to the present invention may be an addition (co) polymer of a monomer containing the above-mentioned norbornene-based compound. As a method for obtaining an addition (co) polymer, all known methods can be adopted, and it can be obtained by addition (co) polymerizing a monomer using an addition polymerization catalyst.

As an addition polymerization catalyst for obtaining an addition (co) polymer, one or more types usually selected from a titanium compound, a zirconium compound and a vanadium compound and an organic aluminum compound as a crude catalyst are used.

Here, titanium tetrachloride, titanium trichloride, etc. are mentioned as a titanium compound, bis (cyclopentadienyl) zirconium chloride, bis (cyclopentadienyl) zirconium dichloride, etc. are mentioned as a zirconium compound.

As the vanadium compound, the formula VO (OR) _a X _b or V (OR) _c X _d (where R is a hydrocarbon group and X is a halogen atom, 0≤a≤3, 0≤b≤3, 2≤ a vanadium compound represented by (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4), or an electron donating adduct thereof.

Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes, and nitrogen-containing electrons such as ammonia, amines, nitriles, and isocyanates. Electron donors and the like.

As the organoaluminum compound as the crude catalyst, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

In the above, for example, the ratio of the vanadium compound to the organoaluminum compound in the case of using a vanadium compound is 2 or more, preferably 2 to 50, particularly preferably 2 to 50, particularly preferably a ratio of aluminum atoms to vanadium atoms. Preferably in the range of 3 to 20.

As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. In addition, molecular weight control of the obtained saturated polymer is normally performed using hydrogen.

Norbornene system  Suzy

In this invention, it is preferable to make intrinsic viscosity [(eta)] obtained by measuring the chloroform solution of norbornene-type resin with a ubelide viscometer normally 0.2-5.0, Preferably it is 0.3-4.0, More preferably, it is 0.35-3.0. Further, the number average molecular weight (Mn) according to the measurement of the molecular weight by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion) is usually from 1,000 to 500,000, preferably from 2000 to 300,000, and more preferably from 5000. It is preferable to set to 300,000, and to make a weight average molecular weight (Mw) normally 5000-2 million, Preferably it is 10,000-1 million, More preferably, it is 10,000-500,000. Here, when the intrinsic viscosity [η] is less than 0.2, Mn is less than 1000, or Mw is less than 5000, the strength of the molded product using the obtained ring-opening (co) polymer may be remarkably lowered. On the other hand, when intrinsic viscosity [(eta)] is 5.0 or more, Mn is 500,000 or more, or Mw is 2 million or more, the melt viscosity or solution viscosity of norbornene-type resin may become high too much, and shaping | molding of a film may become difficult.

The norbornene-based resin according to the present invention has excellent transparency, heat resistance and low water absorption, and in particular, the norbornene-based resin having the above-mentioned structural unit (I) has a specific birefringence wavelength dependency. When such a norbornene-based resin is used, under the conditions of the present invention of uniaxial stretching, the NZ coefficient tends to come out to a desired value, and a phase difference film having good reverse wavelength dispersion can be easily produced.

The norbornene-based resin according to the present invention can be used by adding various additives, if desired. As the additive, for example, 2,6-di-t-butyl-4-methylphenol, 2,2-methylenebis (4-ethyl-6-t-butylphenol) and 2,5-di-t-butylhydroquinone , Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4-thiobis- (6-t-butyl-3-methylphenol ), Phenols such as 1,1'-bis (4-hydroxyphenyl) cyclohexane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propiolate, and hydroquinones Antioxidant or phosphorus system, such as a tris (4-methoxy-3, 5- diphenyl) phosphite, a tris (nonylphenyl) phosphite, and a tris (2, 4-di-t-butylphenyl) phosphite An antioxidant is mentioned, The oxidation stability of norbornene-type resin can be improved by adding 1 type, or 2 or more types of these antioxidants. Further, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2, -methylenebis [4- (1,1,3,3-tetramethylbutyl Ultraviolet absorbers such as) -6-[(2H-benzotriazol-2-yl) phenol]], and the light resistance of the norbornene-based resin of the present invention can be improved by adding them. Moreover, additives, such as a lubricant, can also be added for the purpose of improving workability.

<Vinyl polymer>

The vinyl polymer (B) used for this invention is characterized by having a polar group. Preferred polar groups include hydroxyl groups, acid anhydride groups (also including acid chlorides), amide groups, carboxyl groups and the like, and hydroxyl groups, acid anhydride groups, and amide groups in order to increase compatibility with norbornene-based resins (A). Especially preferably, it is used.

Moreover, it is preferable that a vinyl polymer (B) is a polymer which has a structural unit derived from an aromatic vinylic monomer.

Vinyl  Monomer

As a monomer which provides a hydroxyl group as a polar group to a vinyl polymer (B), it is p-hydroxy styrene, (alpha) -methyl- p-hydroxy styrene, 2-methyl-4- hydroxy styrene, 3, 4- dihydride Hydroxy styrenes such as oxy styrene; Hydroxyalkyl (meth) acrylate type monomers, such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, are mentioned. Of these, α-methyl-p-hydroxystyrene is preferable in the hydroxystyrene monomer, and 2-hydroxyethyl (meth) acrylate is preferable in the hydroxyalkyl (meth) acrylate monomer.

Moreover, as a monomer which provides an acid anhydride group as a polar group to a vinyl-type polymer (B), maleic anhydride, a citraconic acid anhydride, a cis-1-cyclohexene-1,2- anhydrous dicarboxylic acid, 3-methyl-cis Acid anhydride group-containing monomers such as -1-cyclohexene-1,2-anhydrous dicarboxylic acid and 4-methyl-cis-1-cyclohexene-1,2-anhydrous dicarboxylic acid, acryloyl chloride, and methacryl Acid chloride containing monomers, such as a loyl chloride, are mentioned. Of these, acid anhydride-containing monomers are preferred, and maleic anhydride is particularly preferred.

As a monomer which provides an amide group as a polar group in a vinyl polymer (B), N-phenyl (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide, etc. are mentioned.

Moreover, acrylic acid, methacrylic acid, itaconic acid is mentioned as a monomer which provides a carboxyl group as a polar group to a vinyl polymer (B).

The monomers providing these polar groups may be used alone or in combination of two or more as a copolymerization component.

As a specific example of an aromatic vinyl monomer other than the said monomer, Styrene; Alkyl-substituted styrenes, such as (alpha) -methylstyrene, (beta) -methylstyrene, and p-methylstyrene; Halogen-substituted styrenes such as 4-chlorostyrene and 4-bromostyrene; Vinyl benzyl alcohols; alkoxy substituted styrenes such as p-methoxy styrene, p-t-butoxy styrene and m-t-butoxy styrene; Vinyl benzoic acids such as 3-vinyl benzoic acid and 4-vinyl benzoic acid; Vinyl benzoic acid esters such as methyl-4-vinyl benzoate and ethyl-4-vinyl benzoate; 4-vinylbenzyl acetate; 4-acetoxy styrene; Amide styrenes such as 2-butylamide styrene, 4-methylamide styrene and p-sulfonamide styrene; Amino styrenes such as 3-amino styrene, 4-amino styrene, 2-isopropenyl aniline, vinyl benzyl dimethylamine; Nitrostyrenes such as 3-nitrostyrene and 4-nitrostyrene; Cyanostyrenes such as 3-cyanostyrene and 4-cyanostyrene; Vinylphenylacetonitrile; Aryl styrene, such as phenyl styrene, etc. are mentioned. These monomers can use 2 or more types as a copolymerization component. Among them, styrene and α-methyl styrene are preferable because they are easily obtained industrially and inexpensive.

As a monomer which provides the other structural unit of a vinyl type polymer (B), For example, vinyl cyanide monomers, such as an acrylonitrile and methacrylonitrile; (Meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate; Maleimide monomers, such as N-phenylmaleimide, etc. are mentioned. Among them, vinyl cyanide monomers are preferable in view of polymerizability.

As a combination of the monomer especially used for the synthesis | combination of a vinyl type polymer (B), styrene / (alpha)-methyl- p-hydroxy styrene, styrene / (alpha)-methyl- p-hydroxy styrene / acrylonitrile, styrene / Maleic anhydride, styrene / maleic anhydride / acrylonitrile, styrene / N-phenylacrylamide / acrylic acid, and the like.

Especially, the specific styrene copolymer which has a structural unit (B1) represented by the said Formula (B1) and a structural unit (B2) represented by the said Formula (B2) is excellent in compatibility with norbornene-type resin, and is easy to film It is especially preferable at the point from which the film excellent in transparency is obtained.

Certain styrene-based copolymers are polymerized by styrene and / or α-methylstyrene with a monomer represented by the following formula b (hereinafter also referred to as “monomer (b)”) in the presence of a radical initiator, followed by monomer (b) It is preferable to convert O-R 'group in a derived structural unit to OH group, and to manufacture it.

<Formula b>

In Formula b, R and R ⁰ have the same meaning as in Formula B2, and R 'is an acetyl group, t-butyl group, t-butoxycarbonyl group, -CH (OR ^a ) (R ^b ), or -SiR ^a ₃ R ^a and R ^b each independently represent an alkyl group having 1 to 6 carbon atoms, or R ^a and R ^b are linked to each other to represent a hydrocarbon group having 1 to 6 carbon atoms.)

As R and R ⁰ , a hydrogen atom is preferable. As R ', an acetyl group and t-butyl group are especially preferable.

In addition, the styrene and / or α-methylstyrene is preferably styrene alone.

In addition, the specific styrene copolymer may include structural units derived from the other vinyl monomers described above as other structural units.

Radical  polymerization Initiator

When synthesize | combining the vinyl polymer (B) used for this invention by radical polymerization, the well-known organic peroxide which generate | occur | produces a free radical, or an azobis type radical polymerization initiator can be used.

Examples of the organic peroxide include diacetyl peroxide, dibenzoyl peroxide, diisobutyroyl peroxide, di (2,4-dichlorobenzoyl) peroxide, di (3,5,5-trimethylhexanoyl) peroxide and di Diacyl peroxides such as octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide and bis {4- (m-toluyl) benzoyl} peroxide;

Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide and acetylacetone peroxide;

Hydrogen peroxide, t-butylhydroperoxide, α-cumene hydroperoxide, p-mentane hydroperoxide, diisopropylbenzenehydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, t-hexyl Hydroperoxides such as dropper oxide;

Di-t-butylperoxide, dicumylperoxide, dilaurylperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t- Dialkyl peroxides such as butyl peroxy) hexane, t-butyl cumyl peroxide and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyn-3;

t-butylperoxy acetate, t-butylperoxy pivalate, t-hexyl peroxy pivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5-dimethyl-2 , 5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5 -Dimethyl-2,5-bis (m-toluoylperoxy) hexane, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3, 3-tetramethylbutylperoxy neodecanoate, 1-cyclohexyl-1-methylethylperoxy neodecanoate, t-hexyl peroxy neodecanoate, t-butylperoxy neododecanoate, t- Butyl peroxy benzoate, t-hexyl peroxybene Eights, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy m-toluoylbenzoate, 3,3 ', 4, Peroxy esters such as 4'-tetra (t-butylperoxycarbonyl) benzophenone;

1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3 , 3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylper Peroxy ketals such as oxy) butane, n-butyl 4,4-bis (t-butylperoxy) pivalate and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane ;

t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-butyl peroxy allyl monocarbonate, etc. Peroxy monocarbonates;

Di-sec-butylperoxydicarbonate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2 -Ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydica Peroxydicarbonates such as carbonate;

In addition, t-butyl trimethylsilyl peroxide etc. are mentioned, The organic peroxide used for this invention is not limited to these exemplary compounds.

Examples of azobis radical polymerization initiators include azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azo. Bis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carba Moyl azo) isobutyronitrile, 2,2'-azobis [2-methyl-N- {1,1-bis (hydroxymethyl) -2-hydroxyethyl} propionamide], 2,2'-azo Bis [2-methyl-N- {2- (1-hydroxybutyl)} propionamide], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2 , 2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 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) prop Pan] dihydrochloride, 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'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2 , 2'-azobis [N- (2-carboxyethyl) -2-methyl-propionamidine], 2,2'-azobis (2-methylpropionamide oxime), dimethyl 2,2'-azobisbutyrate , 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2,4,4-trimethylpentane), and the like, but there are azobis radical polymerization initiators used in the present invention. Is not limited to these exemplary compounds.

The use amount of these radical initiators is usually 0.01 to 5 mol%, preferably 0.03 to 3 mol%, more preferably 0.05 to 2 mol% in 100 mol% of the vinyl monomers total amount.

In addition, a catalyst may be used for the copolymerization reaction of the vinyl monomer. This catalyst is not specifically limited, For example, a well-known anion polymerization catalyst, a coordination anion polymerization catalyst, a cationic polymerization catalyst, etc. are mentioned.

The vinyl polymer (B) used in the present invention is a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, an emulsion polymerization method, a suspension polymerization method or a bulk-suspension polymerization method in the presence of the polymerization initiator or catalyst. It is obtained by copolymerizing by conventionally well-known methods, such as these.

OH Conversion process to crossroads

The specific styrene copolymer which is preferably used in the present invention can be obtained by polymerizing the monomer and then converting the O-R 'group in the structural unit derived from the monomer (b) to an OH group. As a result, for example, R ′ of the monomer (b) is released to form the structural unit represented by the above formula (B2).

Examples of the conversion reaction include a method of converting to alcoholic or hydrolysis in the presence of an acid or a base, a method of heating and converting under acidic conditions, a method of converting only by heating, and a method of converting using fluoride ions. have. These are suitably employ | adopted according to the structure of R 'in O-R' group.

Vinyl  polymer

In the vinyl polymer (B) thus obtained, the proportion of the structural unit having a polar group to the total 100% by weight of the total structural units, that is, the structural unit derived from the monomer providing the polar group is usually 1 to 40% by weight, preferably Preferably it is 1-30 weight%, More preferably, it is 2-20 weight%. If the ratio of the structural unit which has a polar group exists in the said range, it is preferable at the point of compatibility and low water absorption. Moreover, the ratio of the structural unit derived from an aromatic vinylic monomer is 60-99 weight% normally, Preferably it is 70-99 weight%, More preferably, it is 80-98 weight%. When the ratio of the structural unit derived from an aromatic vinylic monomer exists in the said range, it is preferable at the point of compatibility with norbornene-type resin (A).

In addition, in the specific styrene copolymer, the content of the structural unit (B2) is usually 0.1 to 50 mol%, preferably 0.2 to 40 mol%, more preferably 0.3 to 35 mol in 100 mol% of the total structural units. %to be. If it is in the said numerical range, since the norbornene-type resin (A) and the specific styrene-type copolymer both have the solvent which shows favorable solubility, it is preferable.

The vinyl polymer (B) has a number average molecular weight (Mn) in terms of polystyrene as measured by gel permeation chromatography (GPC), usually 3,000 to 500,000, preferably 5,000 to 400,000, more preferably 10,000 to 250,000, and a weight average The molecular weight (Mw) is usually 500 to 1,000,000, preferably 5,000 to 800,000, more preferably 20,000 to 500,000. If the molecular weight is too small, the strength of the resulting film may be low, and if the molecular weight is too large, the solution viscosity may be too high to deteriorate the productivity or processability of the thermoplastic resin composition according to the present invention.

Moreover, the molecular weight distribution (Mw / Mn) of a vinyl polymer (B) is 1.0-10 normally, Preferably it is 1.2-5, More preferably, it is 1.2-4.

Tg of a vinyl polymer (B) is 75-140 degreeC normally, Preferably it is 80-130 degreeC, More preferably, it is 90-130 degreeC. When Tg is too low, there exists a possibility that Tg of a thermoplastic resin composition may fall and a problem may arise in heat resistance, and the problem that the change of the optical characteristic by the temperature of the molded article and film obtained may become large. On the other hand, when Tg is too high, there exists a tendency for intensity | strength to fall extremely.

<Norbornene-based resin film>

In the method for producing a retardation film of the present invention, a film containing the above-described norbornene-based resin or a composition of a norbornene-based resin and a vinyl-based polymer (hereinafter, these are also simply referred to as "resins") is used. As a method of manufacturing a film from norbornene-type resin, the method of shape | molding norbornene-type resin by the melt-molding method, such as the melt-extrusion method, or the solution casting method (solvent casting method), etc. is mentioned.

Examples of the solvent casting method include a method of dissolving or dispersing the resin in a solvent to form a liquid having an appropriate concentration, pouring or applying the resin onto a suitable carrier, and drying the resin, and then peeling it from the carrier.

When dissolving or dispersing the resin in a solvent, the concentration of the resin is usually 0.1 to 90% by weight, preferably 1 to 50% by weight, more preferably 10 to 35% by weight. When the density | concentration of the said resin is made less than the above, it becomes difficult to ensure the thickness of a film. In addition, problems such as difficulty in obtaining surface smoothness of the film due to foaming due to evaporation of the solvent occur. On the other hand, the concentration exceeding the above is not preferable because the solution viscosity becomes so high that the thickness and the surface of the optical film obtained become difficult to be uniform. In addition, the viscosity of the solution at room temperature is usually 1 to 1,000,000 (mPa · s), preferably 10 to 100,000 (mPa · s), more preferably 100 to 100,000 (mPa · s), particularly preferably Is 1,000 to 10,000 (mPa · s).

Examples of the solvent used herein include aromatic solvents such as benzene, toluene, and xylene, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and 1-methoxy-2-propanol, diacetone alcohol, acetone, and cyclohexa. Ketone solvents such as rice paddy, methylethyl ketone, 4-methyl-2-pentanone, cyclohexanone, ethylcyclohexanone, and 1,2-dimethylcyclohexane, ester solvents such as methyl lactate and ethyl lactate, 2 Halogen-containing solvents such as 2,3,3-tetrafluoro-1-propanol, methylene chloride and chloroform, ether solvents such as tetrahydrofuran and dioxane, alcohol solvents such as 1-pentanol and 1-butanol Can be mentioned.

Further, in addition to SP value (solubility parameter) is usually 10 to 30 (MPa ^1/2), preferably from 10 to 25 (MPa ^1/2), more preferably from 15 to 25 (MPa ^1/2), in particular When preferably using a solvent of 15 to 20 (MPa ^1/2) range, the surface uniformity and optical characteristics can be obtained a good film.

The said solvent can be used individually or in combination of 2 or more types. When using 2 or more types of solvents together, SP value as a mixture can be calculated | required from the weight ratio, For example, in the case of 2 types of mixtures, the weight fraction of each solvent makes W1, W2, and SP values SP1 and SP2. The SP value of a mixed solvent can be calculated | required as the value computed by following formula (2).

SP value = W1, SP1 + W2, SP2

In the preparation of the resin solution, the temperature when dissolving the resin in a solvent may be room temperature or high temperature. A uniform solution is obtained by stirring sufficiently. On the other hand, when coloring as needed, you may add the dye and the coloring agent of a pigment suitably to a solution.

In addition, a leveling agent may be added to improve the surface smoothness of the film. If it is a general leveling agent, all can be used, For example, a fluorine-type nonionic surfactant, a special acrylic resin type leveling agent, a silicone type leveling agent, etc. can be used.

As a method for producing the film of the present invention by the solvent casting method, the solution is formed using a die or a coater, a polyester film such as a metal drum, a steel belt, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or polytetra. The method of apply | coating on a base material, such as a fluoroethylene belt etc., drying and removing a solvent after that and peeling a film from a base material is mentioned generally. Moreover, it can manufacture by apply | coating a resin solution to a base material using means, such as spraying, a brush, roll spin coating, and immersion, drying and removing a solvent after that, and peeling a film from a base material. In addition, thickness, surface smoothness, etc. can also be controlled by repetition of application | coating.

In addition, when using a polyester film as a base material, the surface-treated film can be used. As a surface treatment method, the hydrophilization treatment method currently performed, for example, the method of laminating | stacking acrylic resin and sulfonic acid base containing resin with a coating or a laminate, or the method of improving the hydrophilicity of a film surface by corona discharge treatment etc. are mentioned. Can be.

There is no restriction | limiting in particular about the drying (solvent removal) process of the said solvent casting method, Although it can carry out by the method generally used, for example, passing the inside of a drying furnace through many rollers, If bubbles are generated by evaporation, the properties of the film are significantly lowered. Therefore, in order to avoid this, it is preferable to set the drying step to two or more steps, and to control the temperature or air volume in each step.

Moreover, the amount of residual solvent in a film is 10 weight% or less normally, Preferably it is 5 weight% or less, More preferably, it is 1 weight% or less, Especially preferably, it is 0.5 weight% or less. Here, when the amount of residual solvent is more than 10 weight%, when the said film is actually used, the dimensional change with time becomes large and it is unpreferable. Moreover, since Tg becomes low by the residual solvent and heat resistance also falls, it is unpreferable.

On the other hand, in order to perform the extending process mentioned later preferably, it is necessary to adjust the said residual solvent amount suitably within the said range. Specifically, the amount of residual solvent is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight, more preferably 1 to 0.1% by weight in order to stably and uniformly express the phase difference in the stretching orientation. Can be. By remaining a trace amount of the solvent, the stretching processing may be easy or the control of the phase difference may be easy.

The thickness of the norbornene-based resin film used in the present invention is usually 1 to 500 µm, preferably 1 to 300 µm, and more preferably 1 to 200 µm (1000 to 200000 nm). In the case of a thickness of less than 1 μm, handling becomes difficult substantially. On the other hand, when it is 500 micrometers or more, what is called a "wound trace" arises when a film is wound in roll shape, and handling in post processing etc. may become difficult.

The thickness distribution of the film of the present invention is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 1% of the average value. In addition, the variation in thickness per cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, particularly preferably 0.5% or less. By performing thickness control in this way, the phase difference nonuniformity at the time of extending | stretching orientation can be prevented.

<Method of manufacturing retardation film>

In the present invention, the above-mentioned norbornene-based resin film is stretched in the range of 2 to 5 times, preferably 2.5 to 4 times, more preferably 3 to 4 times in the width direction of the film roll to produce a retardation film. In this retardation film, the polymer chain of norbornene-type resin of a film material is oriented in the width direction (horizontal direction) of a film roll, has an optical axis in the width direction of a film roll, and provides retardation to transmitted light.

The optical axis at this time is within 0 ± 10 degrees, preferably within 0 ± 5 degrees, more preferably within 0 ± 1 degrees, and most preferably within 0 ± 0.5 degrees when the film width direction is 0 degrees. By including an optical axis in this range, when using a polarizing plate, contrast ratio can be raised and it is preferable.

The stretching speed of the film in the transverse direction is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, and particularly preferably 100 to 500% / min.

The stretching processing temperature is usually Tg to Tg + 50 ° C, preferably Tg + 5 to Tg + 30 ° C, more preferably Tg + 10 ° C to Tg + 20 ° C based on the glass transition temperature Tg of the norbornene-based resin used in the present invention. When it is in the said range, since preferable optical characteristic value is obtained and it becomes possible to suppress generation | occurrence | production of phase difference nonuniformity, it is preferable.

Although the stretched film can be cooled as it is, it is preferable to hold and heat-fix at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes under a temperature atmosphere of Tg-20 ° C to Tg. Do. Thereby, there exists little change of the phase difference of transmitted light with time, and a stable phase difference film is obtained.

The dimensional shrinkage rate by heating of the retardation film which concerns on this invention is 1% or less normally, when it heats at 80 degreeC for 500 hours, Preferably it is 0.5% or less, More preferably, it is 0.1% or less.

In the present invention, the dimensional shrinkage ratio is appropriately selected by appropriately selecting the film forming method, the condition, the stretching method, the condition, or the heat fixation condition in which the specific monomer or other copolymerizable monomer which is a raw material of the norbornene-based resin used is appropriately selected. It can be in the said range.

In the stretched film as described above, molecules are oriented by stretching to provide retardation to transmitted light. The retardation (retardation, Re) of the film can be controlled by stretching ratio, stretching temperature, or film thickness. For example, when the film thickness before extending | stretching is the same, since the absolute value of the phase difference of transmitted light tends to become large, the film with a big draw ratio is large, and by changing a draw ratio, the retardation film which provides a desired phase difference to transmitted light can be obtained. On the other hand, when the draw ratio is the same, since the absolute value of the phase difference of transmitted light tends to become larger as the thickness of the film before extending | stretching is thick, the phase difference film which provides a desired phase difference to transmitted light by changing the thickness of the film before extending | stretching can be obtained. . In addition, since the absolute value of the phase difference of transmitted light tends to become large in the above drawing process temperature range, the retardation film which provides a desired phase difference to transmitted light by changing extending | stretching temperature can be obtained.

On the other hand, retardation (Retardation): Re is a value defined by the following equation (3).

Re = (nx-ny) × d

Here, d represents the optical path length, nx is the maximum refractive index in the film plane, ny is the refractive index in the direction perpendicular to nx in the film plane.

The thickness of the retardation film obtained by stretching as mentioned above becomes like this. Preferably it is 0.1-300 micrometers, More preferably, it is 0.5-200 micrometers, Especially preferably, it is 1-150 micrometers, Most preferably, it is 1-100 micrometers. By making thickness thin, it can respond largely to the miniaturization and thickness reduction required for the product of the field | area where retardation film is used. The thickness of retardation film can be controlled by selecting the thickness of the film before extending | stretching suitably, and selecting a draw ratio suitably. For example, the thickness of retardation film can be made thin by thinning the film before extending | stretching, or extending draw ratio.

The retardation value of the retardation film, that is, the value of the retardation provided to the transmitted light is determined by the effect required for the retardation film, and may also vary depending on the wavelength of the transmitted light, and the wavelength of the transmitted light is not uniquely determined. The value at 550 nm is usually 1 to 1000 nm, preferably 10 to 500 nm, more preferably 100 to 300 nm, particularly preferably 100 to 150 nm and most preferably 1 / 4λ. 1 / 4λ represents a phase difference of approximately 1/4 to a wavelength of 550 nm of transmitted light, that is, a phase difference film expressing a phase difference of 138 ± 15 nm, preferably 138 ± 10 nm. It is substantially difficult to control the retardation value to less than 1 nm, the retardation film which has a retardation value exceeding 1000 nm is not only difficult to manufacture, but also it may be difficult to ensure the uniformity of the retardation mentioned later.

Moreover, it is preferable that the phase difference of the light which permeate | transmitted the retardation film is high in the surface, and the variation in wavelength 550nm is usually ± 20% or less, Preferably it is 10% or less, More preferably, ± 1% or less. When the variation in the phase difference exceeds the range of ± 20%, when used in a liquid crystal display device or the like, color unevenness may occur and performance as a display may deteriorate.

In addition, the retardation film according to the present invention preferably has reverse wavelength dispersion in the visible light region. That is, the ratio Re (650) / Re (550) of the phase difference Re (550) at wavelength 550nm and the phase difference Re (650) at wavelength 650nm is in the range of 1.03 to 1.18, and the phase difference Re at wavelength 550nm. The ratio Re (450) / Re (550) of phase difference Re (450) at (550) and wavelength 450nm is in the range of less than 1.0.

More preferably, the ratio Re (650) / Re (550) of the phase difference Re (550) at the wavelength 550 nm and the phase difference Re (650) at the wavelength 650 nm is in the range of 1.05 to 1.18, and at the wavelength 550 nm. The ratio Re (450) / Re (550) of the phase difference Re (550) and the phase difference Re (450) at a wavelength of 450 nm is in a range of 0.8 to less than 1.0.

In addition, the retardation film according to the present invention has a value of its NZ coefficient of 0.90 to 1.40, preferably 0.95 to 1.20, particularly preferably 1.00 to 1.15. Moreover, distribution (change) in the film surface of the said NZ coefficient becomes like this. Preferably it is within 20% of center value, More preferably, it is within 10% of center value. By controlling NZ coefficient in this range, the viewing angle characteristic at the time of using for a liquid crystal display can be obtained favorably. On the other hand, as described above, the NZ coefficient is defined as (nx-nz) / (nx-ny).

In this invention, the retardation film which has such reverse wavelength dispersion can be obtained easily by selection of norbornene-type resin which is a raw material. As a norbornene-based resin which is preferable for producing a retardation film having reverse wavelength dispersion, a norbornene-based resin having a structural unit (I) represented by the above-mentioned general formula (I) is particularly preferable, but the present invention is not limited thereto. The norbornene-type polymer other than the above which provides reverse wavelength dispersibility to a film, the resin composition containing 2 or more types of norbornene-type polymers, and the resin composition containing a norbornene-type polymer and another polymer can be used.

<Method of manufacturing polarizing plate>

Polarizer

The polarizer which is used in the manufacturing method of the polarizing plate of this invention, and comprises the polarizing plate which concerns on this invention can be formed by adsorbing and orienting an iodine or a dichroic dye to a polymer film. It is preferable that the polarizer which comprises the polarizing plate of this invention contains a polyvinyl alcohol (PVA) type film.

As a polarizer containing a PVA system film, if it has a function as a polarizer, it will not specifically limit, For example, after making an PVA film adsorb | suck iodine, PVA iodine polarizing film obtained by uniaxial stretching in a boric acid bath; A PVA dye-based polarizing film obtained by uniaxially stretching the resultant dye by directly adsorbing a high dichroic dye onto the PVA film; PVA-polyvinylene polarizing film which adsorbed and extended | stretched iodine to PVA film, and made it into the polyvinylene structure; PVA metal polarizing film which made metals, such as gold, silver, mercury, iron, adsorb | suck to a PVA film; A near-ultraviolet polarizing film treated with a PVA film with a boric acid solution containing potassium iodide and sodium thiosulfate; The polarizing film etc. which have a dichroic dye in the surface and / or inside of the PVA system film containing modified PVA containing a cationic group in a molecule | numerator are mentioned.

It does not specifically limit also about the manufacturing method of the polarizer containing a PVA system film, For example, The method of adsorbing iodine ion after extending | stretching a PVA system film; A method of dyeing a PVA film with a dichroic dye and then stretching the film; A method of dyeing with a dichroic dye after stretching the PVA film; A method of stretching the dichroic dye after printing the PVA film; After extending | stretching a PVA system film, the method of printing a dichroic dye, etc. are mentioned. More specifically, iodine is dissolved in a potassium iodine solution to prepare higher iodine ions, the iodine ions are adsorbed onto a PVA film, stretched, and then immersed in an aqueous solution of 1-4% boric acid at a bath temperature of 30 to 40 ° C. The method of manufacturing a polarizing film, or the PVA film similarly boric-acid-processed and extending | stretching about 3 to 7 times in the uniaxial direction, immersed in 0.05-5% aqueous solution of dichroic dye at bath temperature 30-40 degreeC, and adsorb | sucking dye, 80 And the method of drying and heat-fixing at 100 degreeC and manufacturing a polarizing film, etc. are mentioned.

It is preferable that the polarizer used by this invention has an absorption axis in a vertical direction. The polarizer which has an absorption axis in a vertical direction can be manufactured by extending | stretching a polymer film by longitudinal uniaxial stretching.

·glue

In the manufacturing method of the polarizing plate of this invention, it is preferable to perform adhesion | attachment of the retardation film and polarizer obtained by the method mentioned above using an adhesive or an adhesive agent. As an adhesive or adhesive agent, the water-based adhesive agent which melt | dissolved PVA in water, the adhesive agent which has a polar group, or the adhesive agent which has a polar group (henceforth these are also called "polar group containing adhesive agent") is used preferably.

As a polar group which a polar group containing adhesive agent has, ester groups, such as a halogen atom and a halogen atom containing group, a carboxyl group, a carbonyl group, a hydroxyl group, an alkyl ester group, an aromatic ester group, an amino group, an amide group, a cyano group, an ether group, an acyl group, a silyl ether A group, a thioether group, etc. are mentioned. In these, a carboxyl group, a carbonyl group, a hydroxyl group, and an ester group are preferable. Moreover, it is preferable that a polar group containing adhesive agent is an aqueous adhesive or an aqueous adhesive agent. As a preferable polar group containing adhesive agent used in order to adhere | attach a specific resin film, the aqueous dispersion of an acrylic ester polymer is mentioned.

The acrylic ester polymer constituting the polar group-containing adhesive agent can be obtained by polymerizing a monomer composition comprising an acrylic ester and a polar group-containing monomer. Here, as acrylate ester, ethyl acrylate, propyl acrylate, cyclohexyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. are mentioned. Moreover, as a polar group which a polar group containing monomer has, ester groups, such as a halogen atom and a halogen atom containing group, a carboxyl group, a carbonyl group, a hydroxyl group, an alkyl ester group, and an aromatic ester group, an amino group, an amide group, a cyano group, an ether group, an acyl group, a silyl ether A group, a thioether group, etc. are mentioned, Among these, a carboxyl group, a carbonyl group, a hydroxyl group, and an ester group are preferable, and a hydroxyl group and a carboxyl group are especially preferable. As a specific example of a preferable polar group containing monomer, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, etc. are mentioned. It is preferable that the ratio of the acrylic ester and the polar group-containing monomer provided for the synthesis of the acrylic ester polymer is about 0.5 to 15 parts by weight of the polar group-containing monomer relative to 100 parts by weight of the acrylic ester polymer.

Moreover, it is preferable to use diene monomers, such as divinylbenzene, as a monomer provided in the synthesis | combination of an acrylic ester polymer. The acrylic ester polymer obtained by polymerizing a composition containing an acrylic ester, a polar group-containing monomer, and a diene monomer can form a high strength adhesive layer. Here, it is preferable that the usage-amount of a diene monomer is 0-10 weight part with respect to 100 weight part of acrylic ester polymers. When the usage-amount of a diene monomer exceeds 10 weight part, an adhesive layer or an adhesive bond layer becomes hard.

As a polymerization method for obtaining an acrylic ester polymer, an emulsion polymerization method, suspension polymerization method, solution polymerization method, etc. are mentioned. On the other hand, when non-polar solvents, such as toluene and xylene, are used as a polymerization solvent, when using the adhesive obtained, a shift | offset | difference between a polarizer which is a to-be-adhered body and retardation film, etc. may occur easily, and it is unpreferable.

As molecular weight of the acrylic ester polymer which comprises a polar group containing adhesive agent, it is preferable that the number average molecular weights (Mn) of polystyrene conversion measured by GPC analysis are 5,000-500,000, More preferably, it is 10,000-200,000, The weight average molecular weight It is preferable that (Mw) is 15,000-1,000,000, More preferably, it is 20,000-500,000, Its preferable molecular weight distribution (Mw / Mn) is 1.2-5, More preferably, it is 1.4-3.6.

In the polar group-containing adhesive agent which can be used in the present invention, a crosslinking agent such as isocyanate or butylated melamine, an ultraviolet absorber, or the like can be added. Here, addition of the crosslinking agent to a polar group containing adhesive agent is normally performed just before apply | coating the said polar group containing adhesive agent.

Manufacturing method of polarizing plate

In the present invention, the polarizing plate is bonded to one side and / or the other side of the polarizer including a PVA-based film, the retardation film obtained from the norbornene-based resin film, using a polar group-containing adhesive agent, and heated and pressed to a polarizer It can manufacture by bonding (complexing) and retardation film.

In manufacture of a polarizing plate, a retardation film is adhere | attached on at least one surface of a polarizer so that the absorption axis of a polarizer and the optical axis of a retardation film may go straight.

Since the retardation film obtained by the manufacturing method of this invention has an optical axis in the horizontal direction, and is usually obtained as a film roll, it adheres continuously with the film roll of a polarizer which has an absorption axis in a longitudinal direction, and what is called roll to roll. can do. That is, the polarizing plate can be manufactured by making the longitudinal direction of retardation film match the longitudinal direction of the polarizer which has an absorption axis in a longitudinal direction, and sticking them together continuously. For this reason, according to the manufacturing method of the polarizing plate of this invention, after cut | disconnecting the retardation film which has an optical axis in the longitudinal direction according to the width | variety of a polarizer, it makes it adhere to each other, making the direction of a retardation film direct to the absorption axis of a polarizer. Manufacturing of the polarizing plate which was used can be performed continuously, and manufacturing efficiency can be improved further.

In the manufacturing method of the polarizing plate of this invention, although the norbornene-type resin retardation film obtained by the manufacturing method of this invention is used, since this retardation film is low in gas permeability and excellent in moisture resistance, it can also serve as a protective film. It is not necessary to use the protective film which a conventionally well-known polarizing plate has other than retardation film normally. For this reason, in the manufacturing method of the polarizing plate of this invention, it is not necessary to adhere | attach the protective film which protects a polarizer other than retardation film separately, and the fall of the transmittance | permeability by the number of films to be laminated | stacked and the quantity of adhesives used is large, and many films Not only can the problems such as deterioration of precision due to adhesion be greatly reduced, but also the manufacturing process can be simplified, and the polarizing plate can be made thinner and lighter.

Moreover, especially in the manufacturing method of the polarizing plate of this invention, when a retardation film has reverse wavelength dispersion and shows a larger phase difference as the longer wavelength is visible in visible region, the polarizing plate which provides a preferable phase difference to transmitted light in a wide wavelength range is obtained. Lose.

The polarizing plate obtained by this invention is excellent in transparency, excellent in dimensional stability even in a high temperature, high humidity environment, and also thin and lightweight, and high performance.

<Example>

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, in the following, "part" and "%" mean "weight part" and "weight%" unless there is particular notice.

The measuring method of various physical property values in this invention is shown below.

Glass transition temperature ( Tg )

The extrapolation glass transition start temperature (henceforth simply a glass transition temperature (Tg)) was calculated | required according to Japanese Industrial Standard K7121 using the differential scanning calorimeter (The Seiko Instruments company make, brand name: DSC6200).

Saturated water absorption

Based on ASTMD570, the sample was immersed in 23 degreeC water for 1 week, and the weight change before and behind immersion was measured and calculated | required.

Total light transmittance, Haze

It measured using the haze meter (HGM-2DP type | mold) made by Suga Shikinki Corporation.

Yellowness  index( YI , Yellow degree)

The C-light 2 ° visual permeation measurement was performed 3 times using SM color computer SM-7-CH by the Suga Shikeki Co., Ltd., and the average value was calculated | required (a measurement sample: the toluene solution containing 10 weight% resin). 20 g, measuring cell: cylindrical glass cell with an internal diameter of 60 mm and a height of 30 mm).

Transmitted light Phase difference

Retardation (Re) when light incident on the film perpendicularly was measured using "RETS" manufactured by Otsuka Denshi Co., Ltd. for each wavelength.

NZ  Coefficient

Nx, ny, and nz in wavelength 550nm were measured using "RETS" by Otsuka Denshi Co., Ltd., and it calculated and calculated | required by following formula (1).

<Equation 1>

NZ coefficient = (nx-nz) / (nx-ny)

Optical axis Orientation angle )

The optical axis (orientation angle) and distribution in a film plane were measured using "RETS" by Otsuka Denshi Corporation. On the other hand, the film length direction was 90 degrees, and the film width direction was defined as 0 degree.

Transmittance and Polarization Degree of Polarizer

The transmittance and polarization degree of the polarizing plate were measured using "RETS" manufactured by Otsuka Denshi Co., Ltd. The measurement wavelength was 550 nm.

Film thickness distribution

It measured using the film thickness distribution measuring apparatus (made by MOCON).

Luminance, viewing angle and Contrast Ratio  Measure

The luminance, viewing angle, and contrast ratio of the liquid crystal panel were measured in a dark room using the luminance meter LS-110 manufactured by Minolta Co., Ltd ..

Residue Solvent

The sample was dissolved in methylene chloride, and the obtained solution was analyzed using gas chromatography (GC-7A manufactured by Shimadzu Corporation).

Polymer molecular structure

It measured in deuterated chloroform using the superconducting nuclear magnetic resonance absorption apparatus (NMR, Bruker make, brand name: AVANCE500).

Weight average molecular weight ( Mw ) And molecular weight distribution ( Mw Of Mn )

Gel permeation chromatography (HLC-8220GPC manufactured by Tosoh Corporation, column: guard column H _XL- H manufactured by Tosoh Corporation, TSK gel G7000H _XL , TSK gel GMH _XL 2, TSK gel G2000H _XL) 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: Doso Co., Ltd. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using the TSK standard polystyrene of manufacture. In addition, said Mn is a number average molecular weight.

Logarithmic viscosity

Measurements were made at 30 ° C. in chloroform (sample concentration: 0.5 g / dL) using an Ubbelohde viscometer.

Synthesis Example 1

<Synthesis of Resin A using Spiro [Fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endomer, see formula (A) below) as one of the monomers>

2285 g (25.9 mol) of cis-2-butene-1,4-diol, 1715 g (13.0 mol) of dicyclopentadiene, and pentaerythritol tetrakis [3- (3,5-di-) as a polymerization inhibitor t-butyl-4-hydroxyphenyl) propionate] 40 g was placed in an autoclave and reacted at 175 ° C for 9 hours. 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene (boiling point: 150 ° C / 4mmHg) was isolated from the obtained reaction mixture by distillation under reduced pressure at a yield of 50%.

750 g (4.9 mol) of 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 1855 g (9.73 mol) of p-toluenesulfonyl chloride, and 5904 g of tetrahydrofuran were obtained. 1287 g (23 mol) of potassium hydroxide were slowly added while maintaining the solution temperature at 10 DEG C or lower. After completion of the addition, the reaction was further performed at a temperature of 10 ° C. or lower for 12 hours. After completion of the reaction, unreacted potassium hydroxide and by-product salt were filtered off and concentrated to give a white solid. The obtained solid was washed with 1500 g of hexane, and the insoluble part was filtered and dried in vacuo to give 5,6-di (p-toluenesulfonyloxymethyl) bicyclo [2.2.1] hept-2-ene in a yield of 75%. lost.

1586 g (3.4 mol) of 5,6-di (p-toluenesulfonyloxymethyl) bicyclo [2.2.1] hept-2-ene and 569 g (3.4 mol) of fluorene were dissolved in 8000 g of dimethyl sulfoxide. The temperature was adjusted to 20 ° C. 253 g (6.9 mol) of sodium hydride containing 35 weight% of liquid paraffins was gradually added and stirred to this solution, maintaining the temperature of 25 degrees C or less. After the reaction for 8 hours, 5000 g of methanol was poured into the reaction mixture and stirred at 20 ° C for 1 hour, after which the precipitate was recovered by filtration. The solid obtained was washed again with 3000 g of methanol. As a result of drying, 716 g (yield 74%) of spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene] of a milky solid was obtained.

73 parts of spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene] (endomer) (specific monomer) thus obtained, and 8-methyl-8-methoxycarb 177 parts of carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (specific monomer), 9 parts of 1-hexene (molecular weight regulator), and 750 parts of toluene (solvent for ring-opening polymerization reaction) nitrogen It put in the substituted reaction container, and this solution was heated to 60 degreeC. Next, in the solution in the reaction vessel, 0.62 parts of toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst, and tungsten chloride (t-butanol: methanol: tungsten = 0.35 mol) modified with t-butanol and methanol: 3.7 parts of a toluene solution (concentration 0.05 mol / l) of 0.3 mol: 1 mol) was added, and this system was heat-opened-polymerized by stirring at 80 degreeC for 3 hours, and the ring-opening polymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%, and the logarithmic viscosity measured in 30 degreeC chloroform with respect to the obtained ring-opened polymer was 0.52 dl / g.

1,000 parts of the ring-opening polymer solution thus obtained were placed in an autoclave, and 0.12 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution, and the hydrogen gas pressure was 100 kg / cm ² and the reaction temperature. Hydrogenation was performed by heat-stirring for 3 hours on conditions of 165 degreeC.

After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was discharged. The reaction solution was poured into a large amount of methanol to separate and collect the coagulum, and dried to obtain a hydrogenated polymer (hereinafter referred to as "resin A").

As a result of measuring the various physical properties about obtained resin A, the hydrogenation rate was 99.9%, and the glass transition temperature (Tg) measured by DSC method was measured by 184 degreeC and GPC method (solvent: tetrahydrofuran). Mn in polystyrene conversion was 18,000, Mw was 74,000, and the molecular weight distribution (Mw / Mn) was 4.06 and the logarithmic viscosity in 30 degreeC chloroform was 0.54 dl / g.

Synthesis Example 2

Using 250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (specific monomer) and 18 parts of 1-hexene (molecular weight regulator) A hydrogenated polymer (hereinafter referred to as "resin B") was obtained in the same manner as in Synthesis example 1 except for the above.

As a result of measuring various physical properties of the resin B thus obtained, the hydrogenation rate measured using ¹ H-NMR was 99.9%, and the glass transition temperature (Tg) measured by the DSC method was 165 ° C and the GPC method (solvent). : The number average molecular weight (Mn) of polystyrene conversion measured by tetrahydrofuran) is 32,000, the weight average molecular weight (Mw) is 137,000, and the molecular weight distribution (Mw / Mn) is 4.29, 23% of saturated water absorption at 23 degreeC. , SP value of 19 (MPa ^1/2), inherent viscosity of from 30 ℃ of chloroform was 0.78 dl / g.

Synthesis Example 3

25 parts by weight of 5-methoxycarbonyl-5-methylbicyclo [2.2.1] -2-heptene (Formula Y) in a glass flask equipped with a stirrer, a condenser and a thermometer, 8-methoxycarbonyl-8- 50 parts by weight of methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (Formula X), 150 parts by weight of toluene and 3.18 parts by weight of 1-hexene were charged and heated to 80 ° C. 0.030 parts by weight of triethylaluminum and 0.0510 parts by weight of a WCl ₆ methanol modified catalyst (anhydrous methanol: PhPOCl ₂ : WCl ₆ = 103: 630: 427 (weight ratio)) were added to initiate the reaction. After 9 minutes and 30 seconds from the start of the reaction, the reactor internal temperature reached 112 ° C, the highest achieved temperature. As a result of sampling at this time, the reaction rates of the monomer represented by the following formula (Y) and the monomer represented by the following formula (X) were 86.1% and 88.1%, respectively. After 10 seconds from reaching the highest temperature, 5 parts by weight of the monomer represented by the following formula (X) was further added dropwise over 12 minutes, and further reacted for 1 hour. The reaction rates of the monomer represented by the following general formula (Y) and the monomer represented by the following general formula (X) after the reaction were 96.2% and 97.2%, respectively.

110 parts by weight of toluene and 0.0418 parts by weight of RuH (OCO-C ₆ H ₄ -C ₅ H ₁₁ ) (CO) (PPh ₃ ) ₂ were added as a hydrogenation catalyst, and hydrogen substitution was carried out three times to increase the pressure to 8 MPa. Thereafter, the temperature of the reaction solution was raised to 160 ° C, the pressure was set at 10 MPa, and hydrogenation reaction was performed for 3 hours. ^The hydrogenation rate determined by <^1> H-NMR analysis was 99.9 or more.

After completion of the reaction, 100 parts by weight of toluene was added and diluted, and 3 parts by weight of distilled water, 0.72 parts by weight of lactic acid and 0.00214 parts by weight of hydrogen peroxide were added and heated at 60 ° C for 30 minutes. Then 234 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes. Cooling to 25 ° C. separated the two layers. 333 weight part of supernatant liquid was removed, 202 weight part of toluene, and 3 weight part of water were added, and it heated at 60 degreeC for 30 minutes. Then 132 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes. Cooling to 25 ° C. separated the two layers. Again 333 parts by weight of the supernatant was removed, 202 parts by weight of toluene and 3 parts by weight of water were added, followed by heating at 60 ° C. for 30 minutes. Then 132 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes. Cooling to 25 ° C. separated the two layers. Finally, after removing 333 parts by weight of the supernatant, the lower polymer solution was diluted to 20% of the polymer concentration, and three stages of filtration were performed using filters having 2.0 µm, 1.0 µm, and 0.2 µm pore diameters, respectively. The yield of the polymer calculated | required from the weight and concentration of the obtained polymer solution was 92%. A part of this solution was dried and analyzed and found to be YI = 0.31, eta = 0.64, Mw = 101450, Mn = 36658, and Tg = 137 ° C. The obtained polymer solution was referred to as polymer solution C.

Synthesis Example 4

340 parts of styrene, 50 parts of pt-butoxystyrene, 183 parts of toluene as a solvent, and 1.30 parts of 1,1'- azobis (cyclohexane-1-carbonitrile) as a radical initiator were added to the reaction apparatus provided with a stirring blade, After heating to 90 ° C. for 10 hours, 0.43 parts of 1,1′-azobis (cyclohexane 1-carbonitrile) were further added, and the reaction was further performed at 90 ° C. for 10 hours. A part of this polymerization liquid was taken out and the reaction rate was measured, and it was 92%. Moreover, as a result of measuring molecular weight, Mw = 126,700 and Mw / Mn = 2.00.

After adding and diluting 195 parts of toluene in the obtained polymerization reaction solution, 78 parts of methanol and 1.0 part of concentrated sulfuric acid were added, and it heated at 60 degreeC and made it react for 8 hours. Then, 2.63 parts of 50.5 weight% sodium lactate aqueous solution were added, and stirring was continued at 60 degreeC for 30 minutes.

After adding 389 parts of toluene to this reaction liquid and mixing it uniformly, 779 parts of methanol were added, and extraction was performed at 60 degreeC for 1 hour. It was cooled to 30 DEG C or lower and left to stand for 1 hour to separate the lower layer solution containing the polymer and the upper layer solution containing almost no polymer. Only this upper solution was separated and removed. After adding 381 parts of toluene to the remaining lower layer solution and mixing it uniformly, 534 parts of methanol were added and extraction was performed at 60 degreeC again for 1 hour. It was cooled to 30 DEG C or lower and left to stand for 1 hour to separate the lower layer solution containing the polymer and the upper layer solution containing almost no polymer. After adding 381 parts of toluene and 534 parts of methanol and allowing to cool, the operation of separating and removing the upper layer was further repeated twice to obtain a polymer solution containing a polymer, toluene, and methanol. As a result of measuring the polymer concentration in this polymer solution, it was 30 weight%, and the yield computed from the obtained solution weight was 90%. The solution was subjected to three stages of filtration using filters of 2.0 mu m, 1.0 mu m, and 0.2 mu m pore diameters, respectively. As a result of drying and analyzing a part of the obtained solution, the copolymer composition ratio determined by Mw = 129,208, Mw / Mn = 1.90, Tg = 111 ° C, and ¹³ C-NMR is as a feed ratio, and the conversion ratio of butoxy group to OH group is 98% It was. The obtained polymer solution was referred to as polymer solution D.

100 parts of polymer solution C obtained in Synthesis Example 3, 28.6 parts of polymer solution D obtained in Synthesis Example 4, and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl as antioxidant) ) Propionate] methane 0.086 parts were added and mixed uniformly. Resin C was obtained by desolvating this solution to 20 mmHg at 240 degreeC using the twin-screw extruder of 50 mm (L / D = 13.2). The obtained resin C was analyzed and found to be YI = 0.9, Mw = 110,000, Mw / Mn = 2.36, Tg = 123 ° C. (single peak) and residual toluene = 900 ppm.

Production Example 1 Preparation of Resin Film A

The resin A was dissolved in toluene so as to have a concentration of 30% (solution viscosity at room temperature is 30,000 mPa · s), and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4) as an antioxidant. -Hydroxyphenyl) propionate] was added at 0.1 part by weight with respect to 100 parts by weight of polymer, and the flow rate of the solution was controlled so that the pressure difference was stabilized within 0.4 MPa using a metal fiber sintered filter having a pore diameter of 5 µm manufactured by Nippon Pole. It was filtered while. PET film based on 100 µm thick hydrophilic (simple adhesive) surface treatment of the obtained polymer solution in an acrylic acid system using an INVEX lab coater manufactured by Inoue Kinzo Kogyo Co., Ltd., installed in a clean room of grade 1000. ), Lumila U94), and apply | coated so that the film thickness after drying might be set to 200 micrometers, and after drying this initially at 50 degreeC, it peeled from PET film and performed secondary drying at 90 degreeC. Thus obtained film was made into the resin film A. The amount of residual solvent of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 183 degreeC. In addition, the film thickness variation was 1 micrometer (0.5%).

Production Example 2 Preparation of Resin Film B

A resin film B having a thickness of 200 μm was obtained in the same manner as in Production Example 1, except that Resin B was used instead of Resin A. The amount of residual solvent of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 164 degreeC. In addition, the film thickness variation was 1 micrometer (0.5%).

Production Example 3 Preparation of Resin Film C

A resin film C having a thickness of 290 μm was obtained in the same manner as in Production Example 1 except that Resin C was used instead of Resin A. The residual solvent amount of the obtained film was 0.1%, the total light transmittance was 93%, and the glass transition temperature (Tg) was 123 ° C. In addition, the film thickness variation was 1 micrometer (0.5%).

Example 1

The resin film A (thickness 200 micrometers, width direction 600mm) obtained by the manufacture example 1 was continuously extended | stretched at 193 degreeC (Tg + 10 degreeC) using the horizontal uniaxial stretching machine which can transversely stretch roll film, and a strain rate It extended | stretched by the draw ratio 3.0 time so that it might become 500% / min. Furthermore, after extending | stretching and slow cooling continuously for about 1 minute between 173 degreeC ovens after extending | stretching, the film edge part was slit and wound up in the roll shape of width 1450mm width, and retardation film A was obtained. With respect to this retardation film A, each phase difference Re (450), Re (550), Re at the optical axis (orientation angle) (the film width direction is set to 0 ° as a reference), thickness d, wavelength 450 nm, 550 nm, and 650 nm. (650), and the results of measuring the NZ coefficient and the film appearance are shown in Table 1. This retardation film was a 1/4 (lambda) film of an optical axis in the width direction, achieved the optical characteristic whose NZ coefficient is 1.1, and also the external appearance was favorable. Moreover, the reverse wavelength dispersion of retardation film was also favorable. Moreover, the phase difference variation was also good within 1%.

Example 2

Resin film C (thickness 290 micrometers, width direction 600mm) obtained by the manufacture example 3 was continuously extended | stretched temperature 137 degreeC (Tg + 14 degreeC) using the horizontal uniaxial stretching machine which can transversely stretch roll film, and a strain rate It extended | stretched by the draw ratio 4.0 time so that it might become 500% / min. Furthermore, after extending | stretching and slow cooling continuously for about 1 minute between 113 degreeC ovens after extending | stretching, the film edge part was slit and wound up in the roll shape of width 1450mm width, and retardation film B was obtained. Retardation film Re (450), Re (550), Re at the optical axis (orientation angle) (the film width direction is 0 °), thickness d, wavelength 450 nm, 550 nm, and 650 nm with respect to the retardation film B. (650), and the results of measuring the NZ coefficient and the film appearance are shown in Table 1. This retardation film was a 1/4 (lambda) film of an optical axis in the width direction, achieved the optical characteristic whose NZ coefficient is 1.2, and also the external appearance was favorable. Moreover, the reverse wavelength dispersion of retardation film was also favorable. Moreover, the phase difference variation was also good within 1%.

Comparative Example 1

Retardation film C was produced like Example 1 except the film to be used was made into the resin film B obtained by the manufacture example 2, the process temperature at the time of extending | stretching was 194 degreeC (Tg + 30 degreeC), and the slow cooling temperature was 154 degreeC. It was. The results are shown in Table 1 in the same manner as in Example 1. This retardation film was a 1/4 (lambda) plate of an optical axis in the width direction, achieved the optical characteristic whose NZ coefficient is 1.3, and also the external appearance was favorable. In addition, the variation in phase difference was 2%. However, the phase difference did not show reverse wavelength dispersion.

Comparative Example 2

Retardation film D was produced in the same manner as in Example 1 except that the draw ratio was increased to 1.5 times. The results are shown in Table 1 as in Example 1. In this retardation film, the optical axis was a 1/4 lambda plate in the width direction, and the retardation showed reverse wavelength dispersion and the appearance was also good. In addition, the variation in phase difference was 2%. However, the NZ coefficient was 1.5.

<Production example of the water-based adhesive>

250 parts of distilled water was put into a reaction container, 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene, and 0.1 part of potassium oleate were added, and this was stirred with Teflon (registered trademark). It stirred by the blade and disperse | distributed.

After nitrogen-substituting the said reaction container, this system was heated up to 50 degreeC, 0.2 part of potassium persulfate was added, and superposition | polymerization was started. After 2 hours, 0.1 part of potassium persulfate was further added, the system was heated to 80 ° C, and the polymerization reaction was continued over 1 hour to obtain a polymer dispersion. Subsequently, this polymer dispersion liquid was concentrated until the solid content concentration became 70% using the evaporator, and the water-based adhesive (pressure-sensitive adhesive which has a polar group) containing the aqueous dispersion of an acrylic ester polymer was obtained.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of polystyrene conversion were measured by GPC method (solvent: tetrahydrofuran) with respect to the acrylic ester polymer constituting the aqueous adhesive thus obtained, and Mn was 69,000. And Mw were 135,000 and the logarithmic viscosity measured in chloroform at 30 degreeC was 1.2 dl / g.

Example 3

The film of roll type polyvinyl alcohol (henceforth "PVA") was preliminarily stretched by 3 times of draw ratio continuously in the dyeing bath of 30 degreeC aqueous solution whose iodine concentration is 0.03 weight%, and potassium iodide concentration is 0.5 weight%. Thereafter, in a 55 ° C crosslinking bath of an aqueous solution having a boric acid concentration of 5% by weight and a potassium iodide concentration of 8% by weight, the film was further stretched by a draw ratio twice, dried and wound to obtain a roll-shaped polarizer.

Next, the retardation film A obtained in Example 1 is made to match a roll-shaped film to one surface of the polarizer (the optical axis existing in the width direction of the absorption axis of the polarizing plate and the retardation film becomes straight), and Both of them were continuously bonded using an aqueous adhesive, and a film made of triacetyl cellulose (hereinafter also referred to as "TAC") having a thickness of 80 µm was adhered to the other side using an adhesive containing a 5% aqueous PVA solution. Polarizing plate A was obtained. As a result of examining the transmittance | permeability and polarization degree of the obtained polarizing plate, it was 44.0% and 99.9%, respectively.

Example 4

In order to evaluate the characteristic of the said polarizing plate, the polarizing plate adhere | attached on the observer side of the liquid crystal panel of the liquid crystal television (LC-13B1-S) by Sharp Corp. which employs ASV system low reflection black TFT liquid crystal, and The retardation film was peeled off, and the polarizing plate A was bonded to this peeled spot in the same manner as the transmission axis of the polarizing plate originally adhered so that the retardation film of the polarizing plate became the liquid crystal cell side.

As a result of confirming the contrast ratio in the azimuth angle of 45 degrees and the polar angle 60 degree direction of the liquid crystal television which has this polarizing plate, it was a numerical value high as 70. Moreover, as a result of confirming the viewing angle (region of contrast ratio 10 or more) from all directions, it was confirmed that it was 175 degrees or more in all of the up-down, left-right, and inclination directions. Further, in the black display state, the color shift phenomenon at the polar angle of 0 degrees to 60 degrees was visually confirmed at 45 degrees of azimuth, and as a result, it was favorable without discoloration.

Example 5

A polarizing plate B was obtained in the same manner as in Example 3 except that the retardation film B was used. As a result of examining the transmittance | permeability and polarization degree of the obtained polarizing plate, it was 44.0% and 99.9%, respectively.

Moreover, except having used the said polarizing plate B, it carried out similarly to Example 4, and confirmed the contrast ratio in 45 degree azimuth angle and 60 degree direction of the liquid crystal television which has this polarizing plate, and was high numerical value as 68. Moreover, as a result of confirming the viewing angle (region of contrast ratio 10 or more) from all directions, it was confirmed that it was 175 degrees or more in all of the up-down, left-right, and inclination directions. Further, in the black display state, the color shift phenomenon at the polar angle of 0 degrees to 60 degrees was visually confirmed at 45 degrees of azimuth, and as a result, it was favorable without discoloration.

Comparative Example 3

Except having used the retardation film C, it carried out similarly to Example 3, and obtained the polarizing plate C. As a result of examining the transmittance | permeability and polarization degree of the obtained polarizing plate, it was 44.0% and 99.9%, respectively.

In addition, except having used the said polarizing plate C, it carried out similarly to Example 4, and confirmed the contrast ratio in 45 degrees of azimuth angles and a 60 degree polarity direction of the liquid crystal television which has this polarizing plate, and was 60. In addition, as a result of confirming the viewing angle (region with a contrast ratio of 10 or more) from all directions, it was confirmed that it was 165 degrees in all of the up, down, left, and right directions. In addition, visually confirming the color shift phenomenon at the polar angle of 0 degrees to 60 degrees at the azimuth angle of 45 degrees in the black display state, the state which became blue purple was confirmed.

Comparative Example 4

Except having used the retardation film D, it carried out similarly to Example 3, and obtained the polarizing plate D. As a result of examining the transmittance | permeability and polarization degree of the obtained polarizing plate, it was 44.0% and 99.9%, respectively.

In addition, the contrast ratio in the azimuth angle of 45 degrees and the polar angle 60 degree direction of the liquid crystal television with this polarizing plate was confirmed similarly to Example 4 except having used the said polarizing plate D, and it was 55. Moreover, as a result of confirming the viewing angle (region of contrast ratio 10 or more) from all directions, it was confirmed that it was 155 degrees in all the up-down, left-right, and inclination directions. In addition, as a result of visually confirming the color shift phenomenon at a polar angle of 0 degrees to 60 degrees at the azimuth angle of 45 degrees in the black display state, the reddish violet state was confirmed.

Claims (12)

The phase difference in wavelength 550 nm is extended | stretched by norbornene-type resin containing film in 2 to 5 times the range of the film roll width direction on the basis of the glass transition temperature (Tg) of the said film under the temperature conditions of Tg-Tg + 50 degreeC. The ratio Re (650) / Re (550) of Re (550) and phase difference Re (650) at wavelength 650 nm is in the range of 1.03 to 1.18, and at phase difference Re (550) and wavelength 450nm at wavelength 550nm. The retardation film of which the optical axis is in the width direction of a film roll is obtained, while ratio Re (450) / Re (550) of retardation Re (450) is in the range below 1.0, The manufacturing method of the retardation film characterized by the above-mentioned. The method for producing a retardation film according to claim 1, wherein the norbornene-based resin-containing film is a film formed by forming a norbornene-based resin having a structural unit represented by the following formula (I). <Formula I>

In Formula I, m and n are each independently an integer of 0 to 2, X is a group represented by the formula -CH = CH- or a group represented by the formula -CH ₂ CH _2- , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are each independently a hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom; And an atom or group selected from the group consisting of a polar group, s, t, u are each independently an integer of 0 to 3) The norbornene-based resin-containing film according to claim 1, wherein the norbornene-based resin-containing film (A) has a composition of a norbornene-based resin having a structural unit represented by the following formula (1) or (2) and a vinyl polymer having a polar group (B) It is a film formed, The manufacturing method of retardation film characterized by the above-mentioned. <Formula 1>

In Formula 1, m is 0, 1 or 2, X is independently a group represented by the formula -CH = CH- or a group represented by the formula -CH ₂ CH _2- , and A ¹ to A ⁴ are each Independently a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group comprising oxygen, nitrogen, sulfur or silicon; or a polar group) <Formula 2>

(In Formula 2, X is independently a group represented by the formula -CH = CH- or a group represented by the formula -CH ₂ CH _2- , and A ⁵ to A ¹⁰ are each independently a hydrogen atom; a halogen atom; Substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group comprising nitrogen, sulfur or silicon; or a polar group) The vinyl polymer having a polar group (B) is a styrene copolymer having a structural unit (B1) represented by the following general formula (B1) and a structural unit (B2) represented by the following general formula (B2). Method for producing a film. <Formula B1>

<Formula B2>

(In Formula B1 and Formula B2, R represents a hydrogen atom or a methyl group, and in Formula 2, R ⁰ may have a linking group including a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom). Substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or represents a polar group) The retardation film is a 1/4 (lambda) plate, The manufacturing method of the retardation film of Claim 1 characterized by the above-mentioned. It was obtained by the manufacturing method of Claim 1, The retardation film characterized by the above-mentioned. Containing norbornene-based resin, the ratio Re (650) / Re (550) of the phase difference Re (550) at a wavelength of 550 nm and the phase difference Re (650) at a wavelength of 650 nm is in the range of 1.03 to 1.18. The ratio Re (450) / Re (550) of the phase difference Re (550) at 550 nm and the phase difference Re (450) at a wavelength of 450 nm is in a range of less than 1.0, and the NZ coefficient represented by the following formula (1) is 0.90: And a phase difference Re (550) in the range of 100 to 300 nm. <Equation 1> NZ coefficient = (nx-nz) / (nx-ny) [Wherein nx represents the maximum refractive index in the film plane, ny represents the refractive index in the direction perpendicular to nx in the film plane, and nz represents the refractive index in the thickness direction of the film (each at a wavelength of 550 nm)] The retardation film of Claim 6 or 7 is stuck to at least one surface of a polarizer, The polarizing plate characterized by the above-mentioned. The retardation film of Claim 6 or 7 which has an optical axis in the width direction of a film roll, The film roll characterized by the above-mentioned. The longitudinal direction of the film roll of Claim 9, and the longitudinal direction of the polarizer which has an absorption axis in a longitudinal direction are made to match, and both are continuously bonded, The manufacturing method of the polarizing plate characterized by the above-mentioned. It was obtained by the method of Claim 10, The polarizing plate characterized by the above-mentioned. The retardation film of Claim 6 or 7 or the polarizing plate of Claim 11 is used, The liquid crystal display device characterized by the above-mentioned.