JP2001350017A - Optical retardation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical retardation film having superior adhesive property, low gas permeability, superior dimensional stability and little retardation unevenness, and an optical retardation plate. SOLUTION: The optical retardation film and the optical retardation plate comprise a film composed of a thermoplastic saturated norbornene resin and have 100 to 1,500 nm for residual phase difference.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phase plate comprising a norbornene-based resin and having a specific residual retardation, and more particularly to a phase plate having excellent adhesiveness, low gas permeability, excellent dimensional stability, and its retardation. The present invention relates to a retardation plate having less unevenness.

[0002]

2. Description of the Related Art A retardation plate is used in a liquid crystal display.
Used to change the relative phase of the polarized light components. As the retardation plate, a film or sheet having birefringence is used, and conventionally, a film obtained by stretching and orienting a polymer film such as polyvinyl alcohol or triacetyl cellulose has been used. However, since these polymer materials have a large photoelastic coefficient, the retardation is greatly changed by a slight stress, and thus there is a problem in the uniformity and stability of the screen of the liquid crystal display. Also,
In liquid crystal displays, there is a demand to widen the viewing angle. In particular, in the TFT method, a retardation plate with a small retardation is preferred, but in a conventional material, since the photoelastic coefficient is large, a retardation plate with a small retardation is made. This requires strict management, and it has been difficult to manufacture with good yield. A film made of a norbornene-based resin has a small retardation and a high uniformity due to a small photoelastic coefficient of the material itself. Therefore, a film made of norbornene is disclosed in JP-A-4-36120 and JP-A-5-2108. A retardation plate comprising a film of a base resin has been proposed.

[0003] In these publications, it is mentioned that if the water absorption is high like polycarbonate, the retardation changes, which is not preferable, and a norbornene resin having a water absorption of 0.05% or less can be easily obtained. It is supposed to be. However, norbornene-based polymers have a wide range of constitutions, and not all of them have a water absorption of 0.05% or less. In order to reduce the water absorption to 0.05% or less, the norbornene-based polymer can be achieved only by using a so-called polyolefin composed of only carbon and hydrogen or a composition partially containing halogen. When these are used as a retardation plate, use of a water-based pressure-sensitive adhesive results in low water vapor permeability and poor wettability with water, so that good adhesion to glass serving as a substrate is not obtained. In addition, when a solution-based pressure-sensitive adhesive is used, there have been problems in that the phase difference is easily changed and the adhesion to glass is deteriorated.

[0004]

The present invention relates to a retardation plate made of a norbornene-based resin and having a specific residual retardation. The retardation plate has excellent adhesion, low gas permeability, excellent dimensional stability, and its retardation. An object of the present invention is to provide a phase difference plate with less unevenness.

[0005]

SUMMARY OF THE INVENTION The present invention provides a film comprising a thermoplastic saturated norbornene resin and having a residual retardation of 100 nm or more and 1500 nm or less. The present invention also provides a retardation plate in which the above retardation film is laminated on a transparent substrate. Preferred in the above is a retardation film in which a retardation film is laminated on a transparent substrate via an adhesive or an adhesive. In addition, a glass plate is preferable as the transparent substrate, and a water-dispersed acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive. Further, the above retardation film has a water vapor permeability of 40 ° C. and 90% RH.
20 g / m ² · 24 h with 25 μm film under the conditions of
Those having r or more are preferable. Further, a retardation plate in which an antireflection film is laminated on one side or both sides of the above retardation film is also a preferable embodiment.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic norbornene-based resin used in the present invention includes the following polymers. Ring-opening polymer of monomer represented by the following general formula (I) (hereinafter, referred to as “specific monomer”) Ring-opening copolymer of specific monomer and copolymerizable monomer Hydrogenated polymer of ring (co) polymer After cyclization of the ring-opened (co) polymer by Friedel-Crafts reaction, hydrogenated (co) polymer Specific monomer and unsaturated double bond-containing compound Saturated copolymer with

[0007]

Embedded image

[In the formula, R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group. You may. R ¹ and R ² or R ³ and R ⁴
May be integrated to form a divalent hydrocarbon group,
R ¹ or R ² and R ³ or R ⁴ are bonded to each other,
It may form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. The cyclic polyolefin-based resin [component (A)] obtained from the above specific monomer may contain one or more polar groups in the molecular structure from the viewpoint of improving the adhesion to the substrate. preferable.

[0009] The <specific monomer> The preferred specific monomer, in the above formula (I), a hydrocarbon group of R ¹ and R ³ is hydrogen atom or a C1-10, R ² and R
⁴ is a hydrogen atom or a monovalent organic group, at least one of R ² and R ⁴ represents a polar group other than a hydrogen atom and a hydrocarbon group, m is an integer of 0 to 3, p is 0 to 3 And m + p is 0 to 4 (more preferably 0 to 2, particularly preferably 1). Also, of the specific monomers, the formula - (CH ₂₎ a specific monomer having a polar group represented by _n COOR ⁵ has a thermoplastic resin composition obtained high glass transition temperature and low moisture absorption It is preferable in that it becomes a thing. In the above formula according to the polar group, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group. In addition, n is generally 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained thermoplastic resin composition is higher. Further, the specific monomer in which n is 0 is preferable. It is preferable in that the synthesis is easy. Further, in the above general formula (I), R ¹ or R ³ is preferably an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, particularly preferably 1 to 2. It is. In particular, the alkyl group is the above formula - is preferably coupled to (CH ₂₎ the same carbon atom and the carbon atom to which the polar group is bonded, represented by _n COOR ^5. Further, the specific monomer in which m is 1 in the general formula (I) is preferable in that a thermoplastic resin composition having a high glass transition temperature can be obtained.

The specific monomer represented by the above general formula (I)
The following compounds may be mentioned as specific examples. Bi
Cyclo [2.2.1] hept-2-ene, tricyclo
[5.2.1.0^2,6 ] -8-decene, tetracyclo
[4.4.0.1^2,5 . 1^7,10] -3-Dodecene, pen
Tacyclo [6.5.1.1^3,6 . 0^2,7 . 0^9,13] -4
-Pentadecene, pentacyclo [7.4.0.1^2,5 .
1^9,12. 0^8,13] -3-pentadecene, tricyclo
[4.4.0.1^2,5 ] -3-undecene, 5-methyl
Bicyclo [2.2.1] hept-2-ene, 5-ethyl
Bicyclo [2.2.1] hept-2-ene, 5-methoxy
Cycarbonylbicyclo [2.2.1] hept-2-e
5-methyl-5-methoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-cyanobicyclo
[2.2.1] Hept-2-ene, 8-methoxycarbo
Nyltetracyclo [4.4.0.1^2,5 . 1^7,10] -3
-Dodecene, 8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5 . 1^7,10] -3-dodecene, 8-
n-propoxycarbonyltetracyclo [4.4.0.
1^2,5 . 1^7,10] -3-dodecene, 8-isopropoxy
Carbonyltetracyclo [4.4.0.1^2,5 .
1^7,10] -3-dodecene, 8-n-butoxycarbonyl
Tetracyclo [4.4.0.1^2,5 . 1^7,10] -3-do
Decene, 8-methyl-8-methoxycarbonyltetracy
Black [4.4.0.1^2,5 . 1 ^7,10-3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5 . 1 ^7,10] -3-dodecene, 8-
Methyl-8-n-propoxycarbonyltetracyclo
[4.4.0.1^{2, Five} . 1^7,10] -3-dodecene, 8-
Methyl-8-isopropoxycarbonyltetracyclo
[4.4.0.1^{2, Five} . 1^7,10] -3-dodecene, 8-
Methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, dime
Tanooctahydronaphthalene, ethyl tetracyclod
Decene, 6-ethylidene-2-tetracyclododecene,
Trimethanooctahydronaphthalene, pentacyclo
[8.4.0.1^2,5 . 1^9,12. 0^8,13] -3-Hexa
Decene, heptacyclo [8.7.0.1^3,6 . 1
^10,17 . 1^12,15 . 0^2,7 . 0^11,16] -4-Eicose
Heptacyclo [8.8.0.1^4,7 . 1^11,18 . 1
^13,16 . 0^3,8 . 0^12,17] -5-heneicosen, 5
-Ethylidenebicyclo [2.2.1] hept-2-e
8-ethylidenetetracyclo [4.4.0.1
^2,5 . 1^7,10] -3-dodecene, 5-phenylbicyclo
[2.2.1] Hept-2-ene, 8-phenyltetra
Cyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
5-fluorobicyclo [2.2.1] hept-2-
Ene, 5-fluoromethylbicyclo [2.2.1] hep
To-2-ene, 5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-pentafluoroethyl
Bicyclo [2.2.1] hept-2-ene, 5,5-di
Fluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2
-Ene, 5,5-bis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,6-bis (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-trifluoromethylbicyclo
[2.2.1] Hept-2-ene, 5,5,6-triff
Fluorobicyclo [2.2.1] hept-2-ene, 5,
5,6-tris (fluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6,6-tetrafluoro
Lobicyclo [2.2.1] hept-2-ene, 5,5
6,6-tetrakis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,5-difluoro
-6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5,
6-bis (trifluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6-trifluoro-5
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoro-iso-propyl-6-trifluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Chloro-5,6,6-trifluorobicyclo [2.2.
1] Hept-2-ene, 5,6-dichloro-5,6-bi
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,5,6-trifluoro-6-trif
Fluoromethoxybicyclo [2.2.1] hept-2-e
, 5,5,6-trifluoro-6-heptafluorop
Lopoxybicyclo [2.2.1] hept-2-ene, 8
-Fluorotetracyclo [4.4.0.1^2,5 .
1^7,10] -3-Dodecene, 8-fluoromethyltetracy
Black [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1
^2,5 . 1^7,10] -3-Dodecene, 8-trifluoromethyl
Letetracyclo [4.4.0.1^2,5 . 1^7,10] -3-
Dodecene, 8-pentafluoroethyltetracyclo
[4.4.0.1^2,5 . 1^7,10-3-dodecene, 8,
8-difluorotetracyclo [4.4.0.1^2,5 . 1
^7,10] -3-dodecene, 8,9-difluorotetracycline
B [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5 . 1 ^7,10-3-dodecene, 8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.1.^2,5 . 1 ^7,10] -3-dodecene, 8-methyl
-8-trifluoromethyltetracyclo [4.4.0.
1^2,5 . 1 ^7,10] -3-dodecene, 8,8,9-triff
Fluorotetracyclo [4.4.0.1^2,5 . 1^7,10]-
3-dodecene, 8,8,9-tris (trifluoromethyl
Le) tetracyclo [4.4.0.1^{2, Five} . 1^7,10] -3
-Dodecene, 8,8,9,9-tetrafluorotetracy
Black [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) te
Toracyclo [4.4.0.1^2,5 . 1^7,10] -3-Dode
Sen, 8,8-difluoro-9,9-bis (trifluoro
Romethyl) tetracyclo [4.4.0.1^2,5 .
1^7,10] -3-dodecene, 8,9-difluoro-8,9
-Bis (trifluoromethyl) tetracyclo [4.4.
0.1^2,5 . 1^7,10] -3-dodecene, 8,8,9-
Trifluoro-9-trifluoromethyltetracyclo
[4.4.0.1^2,5 . 1^7,10-3-dodecene, 8,
8,9-trifluoro-9-trifluoromethoxytet
Lacyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8,8,9-trifluoro-9-pentafluorop
Lopoxytetracyclo [4.4.0.1^2,5 . 1^7,10]
-3-dodecene, 8-fluoro-8-pentafluoroe
Cyl-9,9-bis (trifluoromethyl) tetracyclyl
B [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8,9-difluoro-8-heptafluoroiso-pro
Pill-9-trifluoromethyltetracyclo [4.4.
0.1^2,5 . 1^7,10] -3-Dodecene, 8-chloro-
8,9,9-trifluorotetracyclo [4.4.0.
1^2,5 . 1^7,10] -3-dodecene, 8,9-dichloro-
8,9-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5 . 1^7,10] -3-dodecene, 8-
(2,2,2-trifluoroethoxycarbonyl) tetra
Lacyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8-methyl-8- (2,2,2-trifluoroethene
Xycarbonyl) tetracyclo [4.4.0.1^2,5 .
1^7,10] -3-dodecene and the like.

Among these specific monomers, 8-methyl-
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1^7,10-3-Dodecene, 8-ethylidenetetra
Cyclo [4.4.0.1^2,5 . 1^7,10-3-Dodese
8-ethyltetracyclo [4.4.0.1^2,5 . 1
^7,10] -3-dodecene, pentacyclo [7.4.0.1
^2,5 . 1^9,12. 0^8,13-3-pentadecene
The polymer obtained by ring-opening polymerization has a high glass transition temperature and
It is preferable in that it has low hygroscopicity.
-Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1.^2,5 . 1^7,10] -3-dodecene is preferred.
The above specific monomer does not necessarily have to be used alone,
The ring-opening copolymerization reaction can be carried out using two or more kinds.

<Copolymerizable Monomer> In the ring-opening polymerization step for obtaining the component (A), the above-mentioned specific monomer may be subjected to ring-opening polymerization alone. Ring-opening copolymerization with a copolymerizable monomer may be carried out. Specific examples of the copolymerizable monomer used in this case include cyclobutene, cyclopentene, cycloheptene, cyclooctene, tricyclo [5.2.1.0.
^{2, 6]} -3-decene, 5-ethylidene-2-norbornene, it can be mentioned cycloolefins such as dicyclopentadiene. The carbon number of the cycloolefin is preferably from 4 to 20, more preferably from 5 to 12. Specified in the presence of unsaturated hydrocarbon-based polymers containing a carbon-carbon double bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene The monomer may be subjected to ring-opening polymerization. The hydrogenated product of the ring-opening polymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Ring-Opening Polymerization Catalyst> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) a group IA element (eg, Li, Na, K, etc.) of the periodic table of deming; and a group IIA element (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn,
Cd, Hg, etc.), Group IIIB elements (eg, B, Al, etc.), Group IVA elements (eg, Ti, Zr, etc.) or IV
A catalyst which is a compound of a group B element (for example, Si, Sn, Pb, etc.) and which is a combination with at least one selected from those having at least one element-carbon bond or element-hydrogen bond. . In this case, in order to increase the activity of the catalyst, an additive (c) described below may be added.

W, Mo or a suitable component (a)
As a typical example of the compound of Re, WCl₆ , MoCl
_Five , ReOCl_Three Japanese Patent Application Laid-Open No. 1-240517
The compounds described can be mentioned. Specific examples of the component (b) include nC_Four H₉ Li, (C
_Two H_Five )_Three Al, (C _Two H_Five )_Two AlCl, (C_Two H
_Five )_1.5 AlCl_1.5 , (C_Two H_Five ) AlCl_Two, Meth
JP-A-1-240517 such as lualumoxane and LiH
The compounds described in the gazette can be mentioned. Additive
Typical examples of the component (c) include alcohols and aldehydes.
Hydrates, ketones, amines, etc. are preferably used.
Although it is possible, it is further disclosed in JP-A-1-240517.
Compounds can be used.

The amount of the metathesis catalyst used is such that the molar ratio of the component (a) to the specific monomer is such that “component (a): specific monomer” is usually 1: 500 to 1: 50000. , Preferably in the range of 1: 1000 to 1: 10000. The ratio of the component (a) to the component (b) is such that “(a) :( b)” is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio. . The ratio of the component (a) to the component (c) is “(c) :( a)” in molar ratio.
Is 0.005: 1 to 15: 1, preferably 0.05: 1
７7: 1.

<Molecular Weight Controlling Agent> The molecular weight of the ring-opened polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight controlling agent must be present in the reaction system. It is preferable to adjust by.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, among which 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent (solvent for dissolving the specific monomer, the metathesis catalyst and the molecular weight modifier) used in the ring-opening polymerization reaction include pentane, hexane, heptane, octane, nonane, and the like. Alkanes such as decane; cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutane;
Halogenated alkanes such as bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene;
Compounds such as aryl; ethyl acetate, n-butyl acetate,
Saturated carboxylic esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane can be used, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is such that “solvent: specific monomer (weight ratio)” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. . The molecular weight of the cyclic olefin polymer used in the present invention is preferably in the range of 0.2 to 5 in intrinsic viscosity (ηinh).

<Hydrogenation catalyst> The ring-opened (co) polymer obtained as described above can be used as the component (A) as it is. It is preferred to use as component (A). The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening (co) polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to the solution.
C., preferably at 20-180.degree. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of the homogeneous catalyst include nickel / naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octanoate / n-butyllithium, titanocene dichloride /
Examples include diethylaluminum monochloride, rhodium acetate, rhodium chlorotris (triphenylphosphine), ruthenium dichlorotris (triphenylphosphine), ruthenium chlorohydrocarbonyltris (triphenylphosphine), and ruthenium dichlorocarbonyltris (triphenylphosphine). it can. The form of the catalyst may be powdery or granular. These hydrogenation catalysts are used in such a ratio that the “ring-opening (co) polymer: hydrogenation catalyst (weight ratio)” is 1: 1 × 10 ⁻⁶ to 1: 2. As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated by heating during molding or use as a product. . Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably 95% or more, and especially 98% or more.
% Or more.

<Unsaturated Double Bond-Containing Compound Constituting a Saturated Copolymer> In order to obtain the component (A) composed of a saturated copolymer, the unsaturated dibond used in the copolymerization reaction with a specific monomer is obtained. Examples of the heavy bond-containing compound include olefin compounds having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, propylene, and butene.

<Catalyst Used for Obtaining Saturated Copolymer>
Copolymerization reaction between specific monomer and unsaturated double bond-containing compound
The catalysts used for vanadium compounds and organic
A catalyst comprising a luminium compound is used. Vanaji
The compound represented by the general formula VO (OR)_a X_b Or
V (OR)_c X _d (Where R is a hydrocarbon group, 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d
≦ 4, 3 ≦ c + d ≦ 4) a vanadium compound represented by the following formula:
Alternatively, these electron donor adducts are used. Electronic
Donors include alcohols, phenols, ketones, and alcohols.
Esters of aldehydes, carboxylic acids, organic or inorganic acids
, Ether, acid amide, acid anhydride, alkoxysilane
Oxygen-containing electron donors such as ammonia, amines, nitrites
And nitrogen-containing electron donors such as isocyanate and the like.
It is. As an organoaluminum compound catalyst component,
At least one aluminum-carbon bond or aluminum
At least one selected from those having an um-hydrogen bond
Seeds are used. The ratio of catalyst components to vanadium atoms
Aluminum atom ratio (Al / V) of 2 or more
From 2 to 50, particularly preferably from 3 to 20.
You.

<Solvent used for obtaining saturated copolymer>
Examples of the solvent used in the copolymerization reaction between the specific monomer and the unsaturated double bond-containing compound include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclohexane and methylcyclohexane. And aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives thereof. Of these, cyclohexane is preferable.

The intrinsic viscosity (ηinh) of the component (A) used in the present invention, measured in chloroform at 30 ° C., is 0.1.
It is preferably from 2 to 5 dl / g. More preferably, it is 0.4 to 4 dl / g, and if it exceeds 5 dl / g, the solution viscosity becomes too high and the processability deteriorates, which is not preferable. If it is less than 0.2 dl / g, the film strength decreases. . As the molecular weight of the component (A), the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is from 8,000 to
1,000,000, weight average molecular weight (Mw) 20,
Those having a range of 000 to 3,000,000 are preferable.

The saturated water absorption at 23 ° C. of the ring-opened polymer or hydrogenated product obtained as described above is 0.1 to 1% by weight.
Is preferably within the range. When the saturated water absorption is within this range, the retardation is uniform, the adhesion between the obtained retardation film and the glass substrate is excellent, no peeling or the like occurs during use, and an antioxidant. It is also excellent in compatibility with, and can be added in large amounts. In addition, the above saturated water absorption is 23% according to ASTM D570.
It is a value obtained by immersing in water for 1 week and measuring the weight gain. If the saturated water absorption is less than 0.1%, the adhesion to the glass substrate is poor, and peeling is liable to occur. If it exceeds 1%, the retardation film is liable to undergo dimensional change due to water absorption.

The norbornene-based resin used in the present invention may contain known thermoplastic resins, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles, etc. as long as transparency and heat resistance are not impaired. good.

Further, additives such as an antioxidant may be added to the norbornene resin used in the present invention. Examples of such additives as antioxidants include the following. Antioxidants; 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,
3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
Methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 , 2'-dioxy-3,3 '
-Di-t-butyl-5,5'-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- (β- (3
-T-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy) ethyl], 2,4,8,10-tetraoxyspiro [5.5] undecane, tris (2,4
-Di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl) -4-methylphenyl) phosphite, 2,2-methylenebis (4,
6-di-t-butylphenyl) octyl phosphite;
It can be stabilized by adding an ultraviolet absorber, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like. Further, an additive such as a lubricant may be added for the purpose of improving workability.

The amount of the antioxidant to be added is generally 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the specific polymer. The retardation film and the retardation plate of the present invention can be formed into a film or a sheet of a specific polymer by a melt molding method, a solution casting method, or the like. As the melt molding method, a solvent casting method or a T-die method is preferably used. The thickness of the film or sheet is usually 25 to 700 μm, preferably 50 to 700 μm.
It is 600 μm, more preferably 70 to 500 μm.
As the stretching method, a known uniaxial stretching method, that is, a transverse uniaxial stretching method using a tenter method, a compression stretching method between rolls, a longitudinal uniaxial stretching method using rolls having different circumferential distances, and the like can be used. Alternatively, biaxial stretching may be performed in which the film is stretched in a range that does not affect the orientation of the molecule, and then stretched in a uniaxial direction to orient the molecule.

Of the films obtained as described above, the stretched film has a certain retardation value because the molecules are oriented by stretching, and the retardation is determined by the retardation of the sheet before stretching, the stretching ratio, and the stretching ratio. The temperature and the thickness of the oriented film can be controlled. When the sheet before stretching has a constant thickness, the absolute value of the retardation tends to be larger as the film has a larger stretching ratio, so that it is possible to obtain a stretched oriented film having a desired retardation by changing the stretching ratio. it can. The film obtained by such a method has a retardation measured by a polarizing microscope of 5 to 900 nm. In the above, the retardation value was measured using an ellipsometer DVA-36LS manufactured by Mizojiri Optical Co., Ltd.
This is a value measured at 3 nm.

The variation in the retardation is preferably as small as possible, and the variation in the retardation at a wavelength of 633 nm is preferably ± 20% or less. Particularly preferably, it is ± 5% or less. When the variation of the retardation exceeds ± 20%, it is difficult to say that the phase plate is an optically uniform phase plate, and when used in an optical disk reproducing apparatus, the resolution of a signal is deteriorated and the reproducing performance is hardly obtained.

The retardation film and the retardation plate of the present invention are used as an optical disk reproducing device and a liquid crystal display. In this case, another film, sheet, or substrate can be used by being laminated on the retardation film or retardation plate of the present invention. When laminating, an adhesive or an adhesive can be used. As these pressure-sensitive adhesives and adhesives, those excellent in transparency are preferable. Specific examples include natural rubber, synthetic rubber, vinyl acetate / vinyl chloride copolymer, polyvinyl ether, acrylic, modified polyolefin, and isocyanate. Examples of the adhesive include a curable adhesive to which a curing agent such as a nate is added, an adhesive for dry lamination in which a polyurethane resin solution and a polyisocyanate resin solution are mixed, a synthetic rubber adhesive, and an epoxy adhesive. Further, the retardation film and the retardation plate of the present invention, in order to improve the workability of lamination with other film sheets, substrates, etc., in advance, an adhesive layer or,
An adhesive layer can be laminated. When laminating,
As the pressure-sensitive adhesive or adhesive, the above-mentioned pressure-sensitive adhesive or adhesive can be used.

In the present invention, the retardation of the retardation film is from 100 to 1500 nm, preferably from 200 to 1500 nm.
1000 nm. When the retardation is less than 100 nm, the effect as a retardation film is not exhibited, and 1500
If the phase difference exceeds nm, phase difference unevenness occurs, making it difficult to align polarized light in a certain direction.

In the present invention, an antireflection film can be laminated on one side or both sides of the retardation film or the retardation plate. As a method of forming the anti-reflection film, for example, a fluorine-based copolymer is dissolved in an organic solvent, and the solution is cast on a film using a bar coater or the like. Coating, heating using a press, and curing. The heating conditions are preferably a temperature of 80 to 165 ° C, more preferably 100 to 150 ° C, and a time is preferably 10 minutes to 3 hours, and more preferably 30 minutes to 2 hours. The thickness of the obtained antireflection film is preferably from 5 to 200.
0 nm, more preferably 10 to 1000 nm, particularly preferably 50 to 200 nm. If it is less than 5 nm, the antireflection effect cannot be exhibited, and if it exceeds 2,000 nm, the thickness of the coating film tends to be uneven, and the appearance and the like are undesirably deteriorated.

In the present invention, the retardation film can be used as a retardation plate by laminating it on a transparent substrate such as a glass plate. In that case, the retardation film can be laminated via an adhesive or an adhesive. A transparent adhesive or adhesive is preferably used. Among them, acrylic ones are preferred. A particularly preferable pressure-sensitive adhesive is a water-dispersed acrylic pressure-sensitive adhesive, which is preferable in that the occurrence of phase difference unevenness in the phase difference film can be suppressed. The water vapor permeability of the retardation film of the present invention is 25 μm under the conditions of 40 ° C. and 90% RH.
m thickness is 20 g / m ² · 24 hr or more, preferably 30 g / m ² · 24 hr or more, particularly preferably 40 to 5
00 g / m ² · 24 hr. 20g water vapor permeability
If it is less than / m ² · 24 hr, water as a solvent for the pressure-sensitive adhesive will not diffuse, resulting in swelling and peeling in a subsequent step.

When the retardation film or the retardation plate of the present invention is used for an optical disk reproducing apparatus, the optical disk reproducing apparatus includes a digital information terminal, a navigation, a liquid crystal monitor, a CD-ROM, a writable CD, and a rewritable D.
Recording devices such as VD and OA equipment using them, C
For example, the present invention can be used for an audio reproducing device such as D, an image reproducing device such as a DVD, an AV device using the same, a game machine using the above-described CD, DVD, and the like.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

[0035] <Synthesis Example 1> 8-methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^2.5 , 1 ^7.10] -
A reaction vessel in which 250 parts of 3-dodecene (specific monomer), 18 parts of 1-hexene (molecular weight modifier) and 750 parts of toluene were replaced with nitrogen was charged, and the solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. (0.35 mol: 0.3 mol: 1 mol) in toluene solution (concentration: 0.05 mol / l) was added, and the system was heated and stirred at 80 ° C. for 3 hours for ring opening. The polymerization reaction was performed to obtain a ring-opened polymer solution. The polymerization conversion in this polymerization reaction was 97%, and the intrinsic viscosity (η _inh ) of the obtained ring-opened polymer measured in chloroform at 30 ° C was 0.65 dl / g.

4,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and RuHCl (CO) [P (C ₆ H _{5 3} ] ₃
0.48 parts were added, and the hydrogen gas pressure was 100 kg / cm ² ,
Under the condition of a reaction temperature of 165 ° C., the mixture was heated and stirred for 3 hours to carry out a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and collect the coagulated material.
This was dried to obtain a hydrogenated polymer (specific cyclic polyolefin resin).

The hydrogenated polymer thus obtained (hereinafter referred to as “resin (a)”). ¹ H-NM
The hydrogenation rate measured using R was 99.9%. The glass transition temperature (Tg) of the resin (a) measured by the DSC method was 170 ° C. Further, the resin (a) is subjected to a GPC method (solvent:
When the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were measured with tetrahydrofuran), the number average molecular weight (Mn) was 39,000, the weight average molecular weight (Mw) was 116,000, and the molecular weight distribution ( (Mw / Mn) was 2.97. The saturation water absorption at 23 ° C. of the resin (a) was 0.4%. The intrinsic viscosity (η _inh ) of the resin (a) measured in chloroform at 30 ° C. was 0.67 dl / g.

<Synthesis Example 2> 6-methyl-1,4,5,8
Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 10 parts of a 15% solution of triethylaluminum in cyclohexane as a polymerization catalyst, 5 parts of triethylamine, and 20% cyclohexane of titanium tetrachloride The solution was added with 10 parts of a solution and subjected to a ring-opening polymerization reaction in cyclohexane to obtain a ring-opened polymer solution. The ring-opening polymer solution thus obtained was charged into an autoclave, a nickel catalyst was added to the ring-opening polymer solution, and a hydrogen gas pressure of 40 kg / cm ² Under a condition of a reaction temperature of 165 ° C., the mixture was heated and stirred for 4 hours to carry out a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. The reaction solution was poured into a large amount of methanol to separate and collect a coagulated product, which was dried to obtain a powdered hydrogenated polymer.

The hydrogenated polymer thus obtained (hereinafter referred to as “resin (b)”). ¹ H-NM
The hydrogenation rate measured using R was 99.9%. The glass transition temperature (Tg) of the resin (b) measured by the DSC method was 142 ° C. Further, the resin (b) is subjected to a GPC method (solvent:
When the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were measured with tetrahydrofuran), the number average molecular weight (Mn) was 40,000, the weight average molecular weight (Mw) was 118,000, and the molecular weight distribution ( (Mw / Mn) was 2.95. Further, the saturated water absorption of the resin (b) at 23 ° C. was measured to be 0.05%. The intrinsic viscosity (η _inh ) of the resin (b) measured in chloroform at 30 ° C. was 0.69 dl / g.

<Preparation Example 1> The resin (a) obtained in Synthesis Example 1 was dissolved in toluene to a concentration of 30%.
Using a bar coater, a PET film (Lumirror, manufactured by Toray Industries, Inc.) was applied so as to have a film thickness of 188 μm, and this was subjected to primary drying at 50 ° C. and then to secondary drying at 90 ° C. Remove the resin film peeled from the PET film
It was set to -1. The amount of residual solvent in the obtained film was 0.9
%Met. This film was heated to 170 ° C. in a tenter and stretched 1.3 times at a stretching speed of 400% / min.
This operation is repeated twice to have a phase difference of 835 nm.
A 115 μm retardation film was obtained.

<Comparative Production Example 1> Polymethyl methacrylate resin “Acrypet VH” (manufactured by Mitsubishi Rayon Co., Ltd.)
Was subjected to a melt extrusion method using an extruder equipped with a T die to produce a resin film (comparative resin film) having a thickness of 0.05 mm. Here, the melting temperature was 230 ° C., and the temperature of the take-off roll was 80 ° C. The resin film thus obtained (hereinafter referred to as “resin film (PMMA)”
That. ) Was measured for thickness variation using a dial-type thickness gauge, and the average thickness (188 μm) was measured.
m) within ± 5%. This was stretched in the same manner as in Production Example 1 to obtain a retardation film having a retardation of 700 nm.

<Comparative Production Example 2> A resin film (comparative resin film) having a thickness of 188 μm was produced from the resin (b) obtained in Synthesis Example 2 by a melt extrusion method using an extruder equipped with a T-die. did. Here, the melting temperature is 270 ° C.
The temperature of the take-off roll was 130 ° C. The resin film thus obtained (hereinafter referred to as “resin film (b-
1) ". ) Was measured for variations in thickness using a dial-type thickness gauge, and the average thickness (1) was measured.
88 μm) within ± 5%. This was stretched in the same manner as in Production Example 1 to obtain a retardation film having a retardation of 830 nm.

Preparation Example 1 A reaction vessel was charged with 250 parts of distilled water, and 90 parts of butyl acrylate was added to the reaction vessel.
8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene, and 0.1 part of potassium oleate were added. This is stirred by a Teflon (registered trademark) stirring blade.
Stirred. After the inside of the reaction vessel was replaced with nitrogen, the temperature of the system was raised to 50 ° C., and 0.2 parts of potassium persulfate was added to initiate polymerization. After 2 hours, potassium persulfate 0.1%
The system was heated to 80 ° C., and the polymerization reaction was continued for 1 hour to obtain a polymer dispersion. Next, this polymer dispersion was concentrated using an evaporator until the solid content concentration became 70%, thereby obtaining an aqueous pressure-sensitive adhesive A-1 consisting of an aqueous dispersion of an acrylate polymer.

<Preparation Example 2> In Preparation Example 1, 2 of the monomer was used.
A water-based pressure-sensitive adhesive A-2 was obtained in the same manner except that -hydroxyethyl methacrylate was changed to methacrylic acid.

<Comparative Preparation Example 1> 180 parts of toluene was charged into an autoclave, and 90 parts of butyl acrylate and 10 parts of 2-hydroxyethyl methacrylate were added to the autoclave. After the inside of the autoclave was replaced with nitrogen, the temperature of the system was raised to 80 ° C., 0.2 part of lauroyl peroxide was added, and the temperature of the system was further raised to 110 ° C. to initiate polymerization. After 2 hours, the system is
The temperature was raised to 35 ° C., and the polymerization reaction was continued for 2 hours to obtain a polymer solution. Then, the polymer solution was concentrated using an evaporator until the solid content concentration became 70%, thereby obtaining an organic solvent-based pressure-sensitive adhesive composed of a toluene solution of an acrylate polymer.

The pressure-sensitive adhesive thus obtained (hereinafter, referred to as
It is called "solution-type pressure-sensitive adhesive (B-1)". When the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were measured by GPC method (solvent: tetrahydrofuran) for the acrylate-based polymer constituting ()), the number average molecular weight (Mn) was 39. 000, weight average molecular weight (Mw) is 94,000, molecular weight distribution (Mw)
/ Mn) was 2.41. In addition, a solution-type adhesive (B
About -1), the intrinsic viscosity (η _inh ) measured in chloroform at 30 ° C. was 0.55 dl / g.

Reference Example 1 Production of Fluorine-Based Copolymer A 2.0-liter stainless steel autoclave equipped with an electromagnetic stirrer was sufficiently purged with nitrogen gas.
(A) Perfluoro (propyl vinyl ether) 53.2
g, (b-1) ethyl vinyl ether (EVE)
7g, (b-2) hydroxybutyl vinyl ether (H
BVE) 26.4 g, (e) Adecaria Soap NE-30 (manufactured by Asahi Denka Kogyo KK) as a nonionic reactive emulsifier, 20.0 g, and (c) VPS-1001 (number average molecular weight) as an azo group-containing polydimethylsiloxane. 70-90,000
3.0 g of Wako Pure Chemical Industries, Ltd.) and 1.0 g of lauroyl peroxide (LPO) were charged, cooled to −50 ° C. with dry ice-methanol, and oxygen in the system was removed again with nitrogen gas. Next, 120 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. When the temperature in the autoclave reaches 60 ° C., the pressure is 6.
1 kgf / cm ² was shown. Thereafter, the reaction was continued under stirring at 60 ° C. for 20 hours, and the pressure was increased to ^2.5 kgf / cm ^2.
The autoclave was cooled with water at the point of time when the reaction was lowered to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution. The obtained polymer solution was poured into methanol to precipitate a polymer, followed by washing with methanol and vacuum drying at 50 ° C. to obtain 220 g of a fluorine-based copolymer. A 0.5% solution of the obtained fluorine-based copolymer in tetrahydrofuran (THF) was prepared and subjected to GPC measurement. The number average molecular weight of the obtained polymer was 35,000.

<Example 1> The water-based pressure-sensitive adhesive (A-1) obtained in Preparation Example 1 was applied to the surface of a release film “Vinasheet” (manufactured by Fujimori Kogyo Co., Ltd.) using a bar coater. A coated film having a thickness of 6 μm was formed, and the coated film was dried at 80 ° C. for 2 minutes to prepare a transfer film. Then
Dry coating film of the transfer film [water-based adhesive (A-1)]
Was transferred to the surface of the resin film (a-1) having a thickness of 115 μm obtained in Preparation Example 1. The fluoropolymer prepared in Reference Example 2 was dissolved in methyl isobutyl ketone (MIBK) at a concentration of 10% on the back side of the thus-prepared retardation film coated with the pressure-sensitive adhesive, and cast using a bar coater. The composition was applied on the above film and cured by heating at 120 ° C. for 1 hour using a press to form a 122 μm antireflection film. A retardation plate having the antireflection film formed on one surface was attached to glass, and the retardation plate was evaluated. Table 1 shows the evaluation results.

<Example 2> The present invention was carried out in the same manner as in Example 1 except that the aqueous adhesive (A-2) obtained in Preparation Example 2 was used instead of the aqueous adhesive (A-1). Was manufactured.

Comparative Example 1 Comparative Example 1 was repeated in the same manner as in Example 1 except that the resin film (a-1) was replaced with the 115 μm-thick resin film (PMMA) obtained in Comparative Preparation Example 1. A retardation plate was manufactured. <Comparative Example 2> Instead of the resin film (a-1), the 115 μm-thick resin film (b-
A retardation plate for comparison was manufactured in the same manner as in Example 1 except that 1) was used.

Comparative Example 3 The procedure of Example 1 was repeated, except that the aqueous pressure-sensitive adhesive (A-1) was replaced by the solution-type pressure-sensitive adhesive (B-1) obtained in Comparative Adjustment Example 1. A retardation plate for comparison was manufactured. <Comparative Example 4> Using a resin film (b-1) instead of the resin film (a-1) and using a solution type adhesive (B-1) instead of the aqueous adhesive (A-1). A comparative polarizing plate was manufactured in the same manner as in Example 1 except for the above.

<Evaluation of retardation plate> The following physical properties were measured for each of the retardation plates obtained in Examples 1 and 2 and Comparative Examples 1 to 4. (1) Initial adhesion strength (C ₀ ) between retarder and glass,
(2) adhesive strength after exposure to a high temperature and high humidity environment (C),
(3) The dimensional change rate due to exposure to a high temperature and high humidity environment was measured. Here, as the “high-temperature and high-humidity environment”, a temperature and humidity of 85 ° C. were measured by a constant temperature and humidity tester (Tabayspec).
An environment with a relative humidity of 80% was realized, and each of the polarizing plates was left in this environment for 300 hours. (4) The phase difference plate is cut to the size of the A-4 plate, the dispersion of the in-plane phase difference is divided into 10 in the longitudinal direction at intervals of 3 cm, and the phase difference is measured by the automatic birefringence meter KOBRA-21ADH (Oji Scientific ( (Manufactured by Co., Ltd.). (5) The water vapor permeability was measured using a film obtained by press-molding a resin using a L80-5000 type water vapor permeability meter manufactured by Lysy AG, at 40 ° C. and 90% RH. The results are shown in Table 1.

[0053]

[Table-1]

[0054]

The retardation film and the retardation plate of the present invention are made of norbornene-based resin and have a specific residual retardation, and have excellent adhesiveness, low gas permeability and excellent dimensional stability, and This has the effect of reducing the phase difference unevenness.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 65:00 G02B 1/10 A F-term (reference) 2H049 BA06 BA25 BB41 BB51 BB65 BC03 BC14 BC22 2K009 AA04 BB11 CC21 DD02 DD06 4F071 AA69 AA78 AA81 AA88 AF08Y AF29Y AH19 BB02 BB07 BC01 BC12

Claims (7)

[Claims] 1. A film comprising a thermoplastic saturated norbornene-based resin having a residual retardation of 100 nm or more and 1
Retardation film of 500 nm or less 2. A retardation plate wherein the retardation film according to claim 1 is laminated on a transparent substrate. 3. A retardation plate wherein the retardation film according to claim 1 is laminated on a transparent substrate via an adhesive or an adhesive. 4. The retardation plate according to claim 2, wherein the transparent substrate is a glass plate. 5. The retardation plate according to claim 2, wherein the pressure-sensitive adhesive is a water-dispersed acrylic pressure-sensitive adhesive. 6. Conditions at a water vapor permeability of 40 ° C. and 90% RH.
20 g / m below with 25 μm film ^Two・ 24 hours or more
The retardation film according to claim 1, wherein 7. A retardation film according to claim 1, wherein an anti-reflection film is laminated on one or both surfaces of the retardation film.