WO2006112304A1 - Polarizing plate and process for producing the same - Google Patents

Polarizing plate and process for producing the same Download PDF

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Publication number
WO2006112304A1
WO2006112304A1 PCT/JP2006/307662 JP2006307662W WO2006112304A1 WO 2006112304 A1 WO2006112304 A1 WO 2006112304A1 JP 2006307662 W JP2006307662 W JP 2006307662W WO 2006112304 A1 WO2006112304 A1 WO 2006112304A1
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WO
WIPO (PCT)
Prior art keywords
film
based resin
norbornene
polarizing plate
polyurethane
Prior art date
Application number
PCT/JP2006/307662
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French (fr)
Japanese (ja)
Inventor
Yosuke Fukuse
Naoki Sugiyama
Masayuki Sekiguchi
Original Assignee
Jsr Corporation
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Publication date
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Priority to JP2007521196A priority Critical patent/JPWO2006112304A1/en
Publication of WO2006112304A1 publication Critical patent/WO2006112304A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Definitions

  • the present invention relates to a polarizing plate. More specifically, the present invention relates to a norbornene-based resin film and
  • the present invention also relates to a polarizing plate bonded with a polarizing film with high strength.
  • a polarizing plate (polarizing film) used for a liquid crystal display or the like is usually formed from a substrate (optical film) having excellent transparency and a polarizing film (polarizer).
  • the polarizing plate may be formed from a film (retardation film) obtained by stretching an optical film and having a function of imparting a retardation to transmitted light, and a polarizing film.
  • Patent Document 1 proposes a polarizing film in which a norbornene-based resin sheet is laminated as a protective layer on a polarizing film.
  • Patent Document 1 JP-A-6-51117
  • the present invention is intended to solve the problems associated with the prior art as described above, and is excellent in adhesion between an optical film and a polarizing film, and has characteristics such as heat resistance and chemical resistance.
  • the objective is to provide a highly reliable polarizing plate that is resistant to peeling and deformation even after long-term use.
  • the polarizing plate according to the present invention is a polarizing plate in which a norbornene-based resin film and a polarizing film are laminated via an adhesive layer, and the adhesive layer includes a polyether polyol and a polyisocyanate. It is formed from a mixture of a polyurethane-based resin obtained by reacting a Natetoi compound and a polybulal alcohol-based resin, and the total of the polyurethane-based resin and the polybulu alcohol-based resin in the adhesive layer is 100.
  • the solid content weight ratio (polyurethane-based resin Z-polybulal alcohol-based resin) relative to parts by weight is 90ZlO to 70Z30.
  • the norbornene-based resin film is preferably a film made of resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1). ,.
  • Ri to R 4 are each independently a hydrogen atom; a halogen atom; or oxygen, nitrogen, Represents a monovalent group that may contain thio or keium.
  • R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form an alkylidene group, or R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 And may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring.
  • X represents 0 or an integer of 1 to 3
  • y represents 0 or 1. However, when X is 0, y is also 0.
  • the norbornene-based resin film is preferably a retardation film.
  • the adhesive layer further contains a water-soluble epoxy compound, and a solid content weight ratio with respect to a total of 100 parts by weight of the polyurethane resin and the water-soluble epoxy compound in the adhesive layer.
  • a water-soluble epoxy compound preferably 97Z3 to 82Z18.
  • the method for producing a polarizing plate according to the present invention comprises a polyurethane-based resin and a polyhydric alcohol-based product obtained by reacting a norbornene-based resin film surface with a polyether polyol and a polyisocyanate compound. Mixing force with rosin is also formed, and the solid content weight ratio (polyurethane reinforced resin Z polyvinyl alcohol-based reinforced resin) is 90ZlO to 70Z30 with respect to 100 parts by weight of the total of polyurethane-based resin and polybulal alcohol-based resin. It is characterized by adhering to the polarizing film through an adhesive layer.
  • the surface of the norbornene-based resin film is pretreated with a corona discharge electron dose of 70 to 100 WZm 2 Zmin.
  • the present invention has a good polarizing function, excellent adhesion between an optical film and a polarizing film, and excellent properties such as heat resistance and chemical resistance, and can be peeled off even after long-term use.
  • a polarizing plate having excellent durability and resistance to deformation and high reliability.
  • the polarizing plate of the present invention is a polarizing plate in which a norbornene-based resin film and a polarizing film are bonded via an adhesive layer formed with a mixture force of polyurethane-based resin and polyvinyl alcohol-based resin. .
  • the norbornene-based resin constituting the norbornene-based resin film used in the present invention is A resin obtained by (co) polymerizing a monomer composition containing at least one norbornene-based compound, or a resin obtained by hydrogenating this resin as required.
  • Examples of the norbornene compound contained in the monomer composition include a norbornene compound represented by the following formula.
  • Ri to R 4 each independently represent a hydrogen atom; a halogen atom; or a monovalent group that may contain oxygen, nitrogen, iodo, or silicon.
  • the monovalent group include a monovalent organic group, a cyano group, and an amino group.
  • examples of the monovalent organic group include a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, which may have a linking group containing oxygen, nitrogen, iodo or silicon.
  • X represents 0 or an integer of 1 to 3
  • y represents 0 or 1. However, when X force, y is also 0.
  • R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form an alkylidene group.
  • R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 may be bonded to each other to form a monocyclic or polycyclic carbocyclic ring or a monocyclic or polycyclic heterocyclic ring.
  • “scale 1 and R 2 are bonded to each other to form an alkylidene group” means that either R 1 or R 2 is removed and the remaining group is bonded to the ring structure by a double bond. This means a state (the following formula (1 ′)).
  • Examples of the carbocycle or heterocycle include alicyclic and aromatic rings.
  • the norbornene-based compound represented by the above formula (1) may be used alone or in combination of two or more.
  • Examples of the norbornene-based compound represented by the above formula (1) include the following compounds, but are not limited to these compounds.
  • the kind and amount of the norbornene compound used in the present invention are appropriately selected according to the required properties of the resin.
  • a structure containing at least one selected atom in the molecule (hereinafter referred to as oxygen atom, nitrogen atom, ion atom, and key atom)
  • a compound having a “polar structure” is preferable in terms of excellent adhesion and adhesion to other materials.
  • R 1 and R 3 are a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R 2 and R 4 is a polar structure
  • a compound having a hydrogen atom and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable in that the water absorption (wet) property of the resulting resin is low.
  • a norbornene-based compound in which the group having a polar structure is a group represented by the following formula (2) is preferably used because of a good balance between the heat resistance and water absorption (wet) property of the resulting resin.
  • R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms
  • z represents 0 or an integer of 1 to 10.
  • z is 0 or an integer from 1 to 3. Furthermore, a monomer in which z is 0 is preferable in that its synthesis is easy.
  • R in the above formula (2) tends to decrease the water absorption (wetness) of the resulting hydrogenated polymer as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining the property, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.
  • a compound in which an alkyl group having 1 to 3 carbon atoms, in particular a methyl group, is bonded to the carbon atom to which the group represented by the above formula (2) is bonded It is preferable in terms of (wet) balance.
  • a compound in which X is 0 or 1, and y is 0 is a highly reactive polymer with a high yield, and a polymer having high heat resistance. It is preferably used because it is easy to obtain hydrogenated products and industrially.
  • a monomer copolymerizable with the norbornene-based compound is included in the monomer composition within a range without impairing the effects of the present invention. Can be polymerized.
  • These copolymerizable monomers include, for example, cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclootaten and cyclododecene; non-cyclic such as 1,4-cyclootatagene, dicyclopentagen and cyclododecatriene. Conjugated cyclic polynes can be mentioned.
  • copolymerizable monomers may be used alone or in combination of two or more.
  • the norbornene-based resin polymerization method used in the present invention is not particularly limited as long as the monomer composition containing the norbornene-based compound can be polymerized. Polymerization can be carried out by ring polymerization or addition polymerization.
  • Production of the polymer by ring-opening polymerization can be carried out by a known ring-opening polymerization reaction for norbornene-based compounds.
  • a monomer composition containing the norbornene-based compound is mixed with a polymerization catalyst, a polymerization reaction solvent, And, if necessary, it can be produced by ring-opening polymerization using a molecular weight regulator.
  • the monomer composition when polymerized by a ring-opening (co) polymerization reaction, it is preferably performed in the presence of a metathesis catalyst.
  • Compound (A) Compound power having W, Mo and Re At least one selected compound (hereinafter referred to as Compound (A)),
  • (B) Periodic table of Deming Group IA elements (for example, Li, Na, K, etc.), Group elements (for example, Mg, Ca, etc.), Group elements (for example, Zn, Cd, Hg, etc.), Group III elements (E.g., ⁇ , A1, etc.), IVA group elements (e.g., Si, Sn, Pb, etc.), or IVB group elements (e.g., Ti, Zr, etc.) that are bonded to carbon or With this element and hydrogen A compound having at least one bond of at least one selected compound (hereinafter referred to as compound (B)) and
  • Group IA elements for example, Li, Na, K, etc.
  • Group elements for example, Mg, Ca, etc.
  • Group elements for example, Zn, Cd, Hg, etc.
  • Group III elements E.g., ⁇ , A1, etc.
  • IVA group elements e.g., Si, Sn, Pb, etc.
  • IVB group elements e.g.,
  • Compound (A) includes W, Mo or Re halides, oxyhalides, alkoxy halides, alkoxides, carboxylates, (oxy) acetylethylacetonates, carboxyl complexes, and acetonitrile complexes. , Hydride complexes, and derivatives thereof, or combinations thereof, and those halides, oxyhalides, and alkoxyhalides that are preferred for the compounds of W and Mo are particularly preferred in view of polymerization activity and practicality. preferable. Also, a mixture of two or more compounds that produce the compound by reaction may be used. In addition, these compounds are suitable complexing agents such as P (C H)
  • the compound (A) includes WCl, WCl, WCl, WBr, WF, WI, MoCl, MoCl, M
  • Mo (OC H) CI Mo (OC H), MoO (acac), W (OCOR), W (OC H) CI
  • MoCl Mo (OC H) CI
  • WCl W (OC H) CI
  • etc. are particularly preferred.
  • Examples of the compound (B) include: n—C H Li, n—C H Na ⁇ C H Na ⁇ CH Mgl, C H MgBr
  • Al, (C 3 H 4) Al and the like are preferable.
  • additive (C) that can be used together with the compound (A) and the compound (B)
  • alcohols, aldehydes, ketones, amines and the like can be preferably used.
  • (1) to (9) can be exemplified.
  • Cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane;
  • Amides such as N, N-jetylformamide, N, N-dimethylacetamide, amines such as aline, morpholine and piperidine, and azo compounds such as azobenzene;
  • N—-troso compounds such as N—-trosodimethylamine, N—-trosodiphenylamine;
  • the amount of the metathesis catalyst used is usually such that the molar ratio of the compound (A) to the total monomers used for polymerization (compound (8): total monomers) is 1: 500 to 1:50, 000, preferably 1: 1,000 to 1:10
  • the ratio of the compound (A) to the compound (B) is 1: 1 by metal atom ratio.
  • (b) Polymerization solvent Solvents used in the ring-opening polymerization reaction are those in which the monomer composition or catalyst to be used for polymerization dissolves and the catalyst is not deactivated, and the produced ring-opening polymer dissolves.
  • alkanes such as pentane, hexane, heptane, octane, nonane, decane
  • cycloalkanes such as cyclohexane, cycloheptane, cyclootatan, decalin, norbornane
  • benzene, toluene Aromatic hydrocarbons such as xylene, ethylbenzene, and cumene
  • Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibutamide, chlorophonolem, tetrachloroethylene
  • Halogenated aryl compounds such as chlorobenzene
  • Such a solvent can be used not only as a solvent for dissolving the norbornene compound, copolymerizable monomer and Z or metathesis catalyst, but also as a solvent constituting the molecular weight regulator solution.
  • the amount of the solvent used is a weight ratio between the solvent and the monomer composition used for polymerization (solvent: monomer composition) force usually 1: 1 to: L0: 1, preferably 1: 1 to An amount of 5: 1 is desirable.
  • the molecular weight of the resulting ring-opened polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent, but can also be adjusted by allowing a molecular weight regulator to coexist in the reaction system. .
  • Suitable molecular weight regulators include ⁇ -o, such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. And olefins such as styrene, 4-methyl styrene, 2-methyl styrene, 4-ethyl styrene, among which 1-butene and 1-hexene are Particularly preferred. These molecular weight regulators can be used alone or in admixture of two or more.
  • the amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.01 to 0.5 mol, with respect to 1 mol of the monomer subjected to the ring-opening polymerization reaction. .
  • the ring-opening polymer can be obtained by ring-opening polymerization of the norbornene-based compound, or ring-opening copolymerization of the norbornene-based compound and a copolymerizable monomer.
  • Norbornene in the presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain, such as conjugated gen compounds such as styrene butadiene copolymer, ethylene non-conjugated gen copolymer, and polynorbornene. It is also possible to ring-open polymerization a monomer composition containing a compound.
  • the production of the polymer by addition (co) polymerization can be carried out by a known addition polymerization reaction with a norbornene compound, and a monomer composition containing the norbornene compound is prepared as a polymerization catalyst, If necessary, it can be produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight regulator.
  • polymerization catalyst used in the addition polymerization examples include single catalysts and multi-component catalysts such as palladium, nickel, conoleto, titanium and zirconium listed in (a-1) to (a-3) below.
  • the polymerization catalyst used in the present invention is not limited to these.
  • a combination of a palladium complex having a ⁇ or ⁇ , ⁇ bond and an organoaluminum or super strong acid salt can be mentioned.
  • a palladium complex having a ⁇ or ⁇ , ⁇ bond and an organoaluminum or super strong acid salt can be mentioned.
  • Di-chloro-bibis (6-methoxybicyclo [2.2.1] hept-2-ene 1-end 5 ⁇ , 2 ⁇ ) Pd, methylalumoxane (abbreviated as “MAO”), AgSbF and AgBF
  • Nickel compounds and cobalt compounds include nickel or cobalt organic carbonates, organic phosphites, organic phosphates, organic sulfonates, ⁇ -diketone compounds, etc. More specifically, for example, nickel 2-ethylhexanoate, nickel naphthenate, cobalt naphthenate, nickel oleate, nickel dodecanoate, cobalt dodecanoate, cobalt neodecanoate, dibutyl phosphorus Nickel phosphate, nickel dibutyl phosphate, nickel dioctyl phosphate, nickel salt of dibutyl phosphate, nickel dodecylbenzenesulfonate, rhodium nickel sulfonate, bis (acetylacetate) nickel, bis (ethylacetoacetate) ) Nickel.
  • Examples thereof include compounds obtained by modifying the organic carboxylate of nickel with a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, and hexafluoroacetone.
  • a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, and hexafluoroacetone.
  • Nickel gen or triene coordination complexes such as dichloro (1,5-cyclohexane [( 3 crotyl) (1,5 cyclooctagen) nickel] hexafluorophosphate, and its tetrafluoroborate complex, tetrakis [3,5-bis (trifluoromethyl)] borate complex; (1 , 5, 9 Cyclododecatriene) nickel; bis (norbornagen) nickel; nickel complexes such as bis (1, 5 cyclooctagen) nickel.
  • complexes in which ligands having atoms such as ⁇ , ⁇ , and ⁇ are coordinated to nickel or cobalt such as bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dichloride.
  • Nickel complexes such as Ni (where Anth is 9-anthracel, Ph is phenol,
  • Cy is an abbreviation for cyclohexyl
  • Titanium and zirconium compounds include [t-BunSiMe (Me Cp)] TiCl, (Me Cp)
  • Flu is an abbreviation for fluorenyl
  • super strong acids examples include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, trifluoroacetic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, and tetrafluoroboric acid.
  • Lewis acid compounds include complexes of boron trifluoride with ethers, amines, phenols, etc., aluminum trifluoride ethers, amines, phenols, etc.
  • Examples of the ionic boron compound include triphenyl carbe tetrakis (pentafluorophenol) borate, triphenyl carbatetrakis [3,5-bis (trifluoromethyl) tiv] borate, triphenyl carbe Umtetrakis (2, 4, 6-trifluorofluoroborate), triphenylcarboltetraphorate, tributinole ammo-tetrakis (pentafluorophenol) borate, N, N-dimethyl-rumum tetrakis (pentafluoro) Rofe) borate, N, N-Jetyl-Ru tetrakis (pentafluorophenol) borate, N, N-Di-Fuylureum tetrakis (pentafluorophenol) borate and the like.
  • organoaluminum compound examples include alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, and butylalumoxane; trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, jetylaluminum chloride, Examples thereof include alkylaluminum compounds and halogenated alkylaluminum compounds such as tilaluminum fluoride, ethylaluminum sesquichloride, and ethylaluminum dichloride; a mixture of the alkylalumoxane compound and the alkylaluminum compound.
  • alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, and butylalumoxane
  • trimethylaluminum triethylaluminum, triisobutylaluminum, di
  • the transition metal compound is 0.02 to: LOO mmol atom per 1 mol of the monomer.
  • organoaluminum compounds multicomponent systems (1) and (2)
  • the compound is 1 to 5,000 moles per mole of metal atoms of the transition metal compound.
  • a super strong acid, Lewis acid or ionic boron compound is used in combination (multi-component system (2))
  • these compounds are 0.1 to L00 mol per 1 mol of the metal atom of the transition metal compound. It is.
  • any monomer composition or catalyst to be used for the polymerization can be dissolved and the catalyst is not deactivated, and the produced addition polymer can be dissolved.
  • alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane
  • aliphatic hydrocarbon solvents such as hexane, heptane, and octane
  • Aromatic hydrocarbon solvents Halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, black benzene, and dichlorobenzene. These can be used alone or in admixture of two or more.
  • the molecular weight of the norbornene-based addition polymer to be produced can be adjusted by adding hydrogen or a-olefin to the polymerization system as a molecular weight regulator.
  • the molecular weight of the resulting norbornene-based addition polymer decreases as the molecular weight regulator added increases.
  • the polymer obtained by the ring-opening polymerization reaction has an olefinic unsaturated bond in the molecule.
  • the polymer may have an olefinic unsaturated bond in the molecule. Since the olefinic unsaturated bond present in the polymer molecule may cause deterioration of gelling and the like over time, it is necessary to carry out a hydrogenation reaction to convert this olefinically unsaturated bond into a saturated bond. preferable.
  • the hydrogenation reaction is carried out by a conventional method, that is, a known hydrogenation catalyst is added to a solution of a polymer containing an olefinic unsaturated bond, and normal pressure to 300 atm, preferably 3 to 200 atm.
  • the hydrogen gas can be reacted at 0 to 200 ° C, preferably 20 to 180 ° C.
  • the hydrogenation rate of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more, as measured by 500 MHz, ⁇ -NMR. Most preferably, it is 99% or more.
  • the aromatic group does not cause deterioration such as coloring over time or gelation, but rather, mechanical properties and optical properties. Since it may have an advantageous effect on properties, it is not necessary to hydrogenate such aromatic groups.
  • the hydrogenation catalyst those used in the usual hydrogenation reaction of olefinic compounds can be used.
  • the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.
  • heterogeneous catalyst examples include a solid catalyst in which a noble metal catalyst material such as radium, platinum, nickel, rhodium, or ruthenium is supported on a carrier such as carbon, silica, alumina, or titanium. Can do.
  • a noble metal catalyst material such as radium, platinum, nickel, rhodium, or ruthenium is supported on a carrier such as carbon, silica, alumina, or titanium.
  • Homogeneous catalysts include nickel naphthenate, Z triethyl chloride, nickel acetyl acetate, z triethyl aluminum, oxalate cobalt, Zn-butyl lithium, titanocene dichloride, Z jetyl aluminum monochloride, rhodium acetate, chlorotris (Triphenylphosphine) rhodium, dichlorotris (trifluorophosphine) ruthenium, chlorohydrocarbonyltris (trifluorophosphine) ruthenium, dichlorocarbo-trithris (triphenylphosphine) ruthenium
  • These catalysts may be powder or granular.
  • These hydrogenation catalysts are usually the weight ratio of ring-opened polymer and the hydrogenation catalyst (ring-opening polymer: hydrogenation catalyst) is, 1: 1 X 10- 6 ⁇ 1 : 2 become ratio Used in.
  • the norbornene-based resin used in the present invention has an intrinsic viscosity [7?] In a black mouth form of 30 ° C, preferably 0.2-2. Odl / g, more preferably 0.35-: L Odl / g, especially
  • the number average molecular weight (Mn) force in terms of polystyrene measured by gel permeation chromatography is preferably 5,000 to 1,000,000, more preferably 0.4 to 0.85 dlZg. 10,000 to 500,000, particularly preferably 150,000 to 250,000, and a weight average molecular weight (Mw) of 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, particularly preferably 30,000 to 50 It is desirable that When the intrinsic viscosity [r?], Number average molecular weight, and weight average molecular weight are in the above ranges,
  • Norbornene-based resin has excellent mechanical strength, and a norbornene-based resin-made substrate (film) that is not easily damaged can be obtained.
  • the glass transition temperature (Tg) of the norbornene-based resin is usually 120 ° C or higher, preferably 130 ° C or higher, more preferably 150 ° C or higher.
  • Tg glass transition temperature
  • the adhesion strength of the dielectric multilayer film to the base material is improved, and a norbornene-based resin substrate (film) having excellent anti-nodal and reflow properties can be obtained.
  • the saturated water absorption of the norbornene-based rosin is usually 1% by weight or less, preferably 0.
  • the saturated water absorption is in the above range, the resin substrate (film) obtained from this resin has excellent durability against water absorption (wet) deformation over time and also excellent adhesion.
  • the saturated water absorption is within the above range, deterioration of the image sensor due to moisture can be prevented particularly when used for the light-transmitting lid of the package for housing the solid-state image sensor.
  • the saturated water absorption is a value obtained by immersing in water at 23 ° C for 1 week and measuring the increased weight according to ASTM D570.
  • additives such as an antioxidant and an ultraviolet absorber can be further added to the norbornene-based resin within a range not impairing the effects of the present invention.
  • Antioxidants include, for example, 2,6 di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, tetrax [methylene 1- (3,5-di-tert-butyl 4-hydroxyphenol) propionate] methane.
  • ultraviolet absorbers examples include 2,4-dihydroxybenzophenone and 2-hydroxy
  • These additives produce norbornene-based resinous resin substrates (films) used in the present invention.
  • it may be mixed with norbornene-based resin or the like, or may be pre-mixed by adding it when producing norbornene-based resin.
  • the addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05-2.0 parts by weight with respect to 100 parts by weight of norbornene-based resin. Part is desirable.
  • the norbornene-based resin film used in the present invention can be more suitably formed by directly melt-molding the norbornene-based resin or by dissolving in a solvent and casting (casting).
  • the norbornene-based resin film used in the present invention can be produced by melt-molding the norbornene-based resin or the resin composition containing the norbornene-based resin and the additive.
  • melt molding method include injection molding, melt extrusion molding, and blow molding.
  • the norbornene-based resin film used in the present invention is prepared by casting a liquid resin composition in which the norbornene-based resin and, if necessary, the additive are dissolved in a solvent, onto a suitable base material. It can also be manufactured by removing.
  • the liquid resin composition is applied onto a substrate such as a steel belt, a steel drum, or a polyester film, the solvent is dried, and then the coating film is peeled off from the substrate. A fat film can be obtained.
  • the amount of residual solvent in the norbornene-based resin film obtained by the above method is preferably as small as possible, usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight. % Or less.
  • the residual solvent amount is in the above range, a norbornene-based resin film having a desired function that hardly deforms or changes in properties with time can be obtained.
  • the thickness of the norbornene-based resin film used in the present invention is not particularly limited, but is usually 5 to 500 ⁇ m, preferably 10 to 150 ⁇ m, more preferably 20 to: LOO ⁇ m. Is desirable. If the film thickness is in the above range, a film with sufficient strength can be obtained, In addition, a film having good birefringence, transparency, and appearance can be obtained.
  • the norbornene-based resin film used in the present invention desirably has a light transmittance of usually 80% or more, preferably 85% or more, more preferably 90% or more.
  • the norbornene-based resin film used in the present invention may be subjected to a surface treatment for the purpose of improving the adhesiveness to the adhesive layer described later.
  • a surface treatment examples include primer treatment, plasma treatment, corona treatment, alkali treatment, and coating treatment.
  • the norbornene-based resin film and the adhesive layer can be firmly adhered by using corona treatment in particular.
  • the corona treatment conditions in this case the irradiation amount of the corona discharge electrons l ⁇ 1000WZm 2 Zmin is preferably fixture 10 ⁇ 100W / m 2 / min, more preferably tool 70 ⁇ : LOOWZm 2 / min is most preferred.
  • the irradiation amount is in the above range, the treatment effect does not reach the inside of the film, and a sufficient surface modification effect can be obtained without altering the film.
  • this corona treatment may be performed not only on the surface in contact with the adhesive layer but also on the opposite surface.
  • the atmosphere during corona treatment is not particularly limited, and examples include corona treatment under an air atmosphere, nitrogen atmosphere, oxygen atmosphere, or argon atmosphere, and the effect of surface treatment and operability. It is preferable to perform corona treatment in an air atmosphere.
  • the effect of the surface treatment can be expressed using the pure water contact angle as an index, and the pure water contact angle is preferably 50 to 70 deg, more preferably 40 to 50 deg.
  • the norbornene-based resin film used in the present invention can be used as a phase difference film by performing a stretching treatment.
  • the stretching method a method of uniaxially stretching or biaxially stretching the resin film is used.
  • the stretching speed is usually 1 to 5,000% Z minutes, preferably 50 to 1,000% Z minutes, more preferably 100 to 1,000% Z minutes. is there.
  • the intersecting angle of the two stretching axes is appropriately determined according to the properties required for the target optical film (retardation film), and is not particularly limited, but is usually in the range of 60 to 120 degrees. is there.
  • the stretching speed is usually 1 to 5,000% Z minutes, preferably 50 to 1,000% Z minutes, more preferably 100 to 1,000% Z minutes, and particularly preferably 100 to 1,000% Z minutes. It is 500% Z and may be the same or different in each stretching direction.
  • the stretching temperature is not particularly limited, but Tg ⁇ 30 ° C, preferably Tg ⁇ 15 ° C, based on the glass transition temperature (Tg) of the norbornene-based resin used. Preferably, it is in the range of Tg ⁇ 5 to Tg + 15 ° C.
  • the draw ratio is appropriately determined according to the properties required for the target optical film and is not particularly limited, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, and more preferably. Is 1.03 to 3 times.
  • the stretched film may be cooled as it is, but it is kept at a temperature atmosphere of Tg—20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 to 60 minutes. It is preferable to cool later.
  • Tg—20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 to 60 minutes. It is preferable to cool later.
  • Tg—20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 to 60 minutes. It is preferable to cool later.
  • the film subjected to the stretching treatment as described above can give a retardation to transmitted light as a result of the orientation of the molecules by the stretching treatment. This retardation is determined by the stretching ratio and the stretching temperature. Alternatively, it can be controlled by the thickness of the film.
  • the thickness of the norbornene-based resin film used as the retardation film is not particularly limited, but is usually 5 to 500 111, preferably 10 to 150 111, and more preferably 20 to 100 m. It is desirable.
  • an adhesive is prepared by dispersing a mixture of polyurethane-based resin and polybulal alcohol-based resin, preferably in water, and applying, drying, for example, to form an adhesive layer.
  • polyurethane resin in the present invention, any one of a one-component type composed of a compound having an isocyanate group at the terminal and a two-component type composed of a main agent having a hydroxyl group at the terminal and a hardener having an isocyanate group is used.
  • a polyurethane-based resin may be used.
  • the one-component polyurethane-based resin can be obtained, for example, by reacting a polyol-one compound with a polyisocyanate compound.
  • the main component of the two-component polyurethane resin includes a polyol compound, and the curing agent includes a polyisocyanate compound.
  • the polyurethane-based resin used in the present invention is stably dissolved or dispersed in an organic solvent and Z or water, and further improves the coating property of the adhesive and the adhesiveness between the substrate and the adhesive layer. For this reason, it is also preferable to add a hydrophilic group-containing compound in addition to the above-described polyo-alkyl compound and polyisocyanate compound.
  • a polyether polyol is particularly preferably used as the polio Louis compound from the viewpoint of sufficient adhesiveness when the obtained adhesive exhibits sufficient adhesiveness.
  • polyether polyols examples include poly (alkylene glycols) such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol; two or more types of ion polymerization Polyether polyols obtained by ring-opening copolymerization of functional cyclic compounds; ion-polymerizable cyclic compounds, cyclic imines such as ethyleneimine, cyclic ratatonic acids such as ⁇ -propiolactone and glycolic acid lactide, or dimethylcyclohexane Polyether polyols obtained by ring-opening copolymerization with polysiloxanes; polyether polyols obtained by ring-opening addition polymerization of one or more ion-polymerizable cyclic compounds to polyhydric alcohols, etc. . These ion-polymerizable cyclic compounds may be randomly ring
  • Examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, 1,2 butylene oxide, butene-1-oxide, isobuteneoxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2 —Methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexeneoxy , Styrene oxide, epichlorohydrin, glycidyl metatalylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, buroxetane, butyltetrahydrofuran, burcyclohexenoxide, phenyl And cyclic ethers such as sidyl ether, butyl daricidyl ether, and g
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, bisphenolanol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, hydroquinone, naphthohydroquinone, alcohol Intrahydroquinone, 1,4-cyclohexanediol, tricyclodecanediol, tricyclodecane dimethanol, pentacyclopentadecanediol, pentacyclopentadecane dimethanol and the like can be mentioned. These can be used alone or in combination of two or more.
  • polytetramethylene glycol is preferred, with polytetramethylene glycol and polyhexamethylene glycol being preferred.
  • a polyisocyanate usually used for producing a polyurethane resin can be used without any particular limitation.
  • polyisocyanate compounds can be used alone or in combination of two or more.
  • these polyisocyanate compounds the viewpoint of not impairing the transparency of the polarizing plate.
  • Isocyanate compounds having an alicyclic structure and no aromatic ring are preferred.
  • Sophorone diisocyanate And methylenebis (4-cyclohexylisocyanate) is particularly preferred.
  • the hydrophilic group-containing compound has at least one active hydrogen atom in the molecule, and at least one functional group selected from a group force consisting of a carboxylic acid group and a sulfonic acid group.
  • An ionic compound is mentioned.
  • Such hydrophilic group-containing compounds include, for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, and sulfolic acid.
  • the polyurethane-based resin used in the present invention is a reaction of the above-mentioned polyol compound, a polyisocyanate compound, and, if necessary, a hydrophilic group-containing compound, usually in the presence of a urethanization catalyst. Can be manufactured. A manufacturing method is not specifically limited, A conventionally well-known method is applicable.
  • Examples of the urethane catalyst include copper naphthenate, conol naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4-diazabicyclo [2.2.2] otatan, 2, 6, 7 Trimethyl 1,4 diazabicyclo [2.2.2] octane.
  • the urethanization catalyst is preferably used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of reactants.
  • the reaction temperature is usually 10 to 90 ° C, particularly 30 to 80 ° C.
  • the weight-average molecular weight of the polyurethane-based resin used in the present invention is a polystyrene equivalent value measured by gel permeation chromatography, and is usually 1,000 to 200,000, preferably Preferably it is 30,000-150,000.
  • the polyurethane resin is desirably water-soluble.
  • polyurethane-based resin for example, Hydran WLS-201
  • WLS-202 Commercially available products such as WLS-202, WLS-210, WLS-213, WLS-220 (manufactured by Oisomoto Ink Industries Co., Ltd.) can also be used.
  • polybulal alcohol-based resin used in the present invention examples include polybutyl alcohols such as partially kenpolypolyvalol and fully saponified polybulal alcohol; modified polybulls such as carboxyl group-modified polybulal alcohol and acetocetyl group-modified polybulal alcohol. Mention may be made of bull alcohol.
  • the weight average molecular weight of the polyvinyl alcohol-based resin used in the present invention is a polystyrene conversion value measured by gel permeation chromatography, and is usually 22,000 to 130,000, preferably 30,000 to 88, 000, more preferably 44,000 to 75,000
  • the polyvinyl alcohol-based resin may be used in combination with a compound having a functional group capable of reacting with a hydroxyl group such as an isocyanate group as a component for crosslinking them.
  • polyalcohol-based resin is usually used by dissolving it in water. In order to improve the wettability to substrates and films, a small amount of water-soluble solvents such as alcohol and ketones are used. It is also preferable to add.
  • the adhesive used in the present invention further includes a curing agent, a tackifier, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, a thermal polymerization inhibitor, a leveling agent, an interface.
  • Activators, storage stabilizers, plasticizers, lubricants, fillers, anti-aging agents, wettability improvers, coating surface improvers, and the like can be blended.
  • an epoxy-based curing agent when a carboxyl group is introduced into a polyurethane-based resin with the above hydrophilic group-containing compound, it is preferable to use an epoxy-based curing agent.
  • the epoxy curing agent used in the present invention is not particularly limited as long as it has at least one epoxy group in the molecule.
  • bisphenol type epoxy compounds novolak type epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, glycidylamine type epoxy compounds, halogenated epoxy compounds Etc.
  • the epoxy curing agent used in the present invention is preferably a water-soluble epoxy compound from the viewpoint of the adhesive being preferably an aqueous solution.
  • bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether; phenol novolak type epoxy compounds, cresol novolac type epoxy compounds Novolac epoxy compounds such as compounds;
  • 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl Aliphatic epoxy compounds such as ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether;
  • Halogenated epoxy compounds such as brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether; glycidylamine type epoxy compounds such as tetraglycidylaminophenol methane Such as things.
  • polyalkylene glycol polyglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin.
  • epoxy compounds can also be used as epoxy resins obtained by polymerizing one kind or two or more kinds in an appropriate range in advance.
  • epoxy compound used in the present invention a polymer of a conjugated gen monomer is used.
  • a copolymer of a conjugated gen monomer and a compound having an ethylenically unsaturated bond group a copolymer of a gen monomer and a compound having an ethylenically unsaturated bond group, or a natural rubber (co)
  • a polymer obtained by epoxidizing the polymer can also be used.
  • polyethylene glycol glycidyl ether is preferred.
  • an epoxy hardener for example, a commercially available product such as "CR-5L” (manufactured by Dainippon Ink & Chemicals, Inc.) can be used.
  • the adhesive used in the present invention is an adhesive in which a mixture of the polyurethane-based resin and the polyvinyl alcohol-based resin is preferably dispersed in water.
  • the dispersed adhesive can be suitably manufactured by adding the polyvinyl alcohol-based resin to the aqueous solution of the polyurethane-based resin.
  • the amount of polybulal alcohol-based resin contained in the above-mentioned adhesive is based on 100 parts by weight of the solid content of the resin (polybulal alcohol-based resin + polyurethane-based resin) in the adhesive.
  • the solid content is 10 to 30 parts by weight, preferably 15 to 25 parts by weight, and most preferably 20 parts by weight.
  • the solid content weight ratio (polyurethane resin Z epoxy curing agent) is preferably 97Z3 to 82Z18, more preferably 93Z7 to 84Z16.
  • the adhesive is preferably diluted with water so that the solid content is preferably 5 to 30 wt%, more preferably 10 to 20 wt%.
  • the adhesive is preferably used within 24 hours, more preferably within 1 hour after preparation, from the viewpoint of suppressing precipitation and separation of components, deterioration of adhesion and deterioration of appearance. And are preferred.
  • the polarizing film used in the present invention has a function as a polarizing film, that is, the incident light is divided into two polarization components orthogonal to each other, only one of them is allowed to pass, and the other component is absorbed or dispersed.
  • the polarizing film is not particularly limited as long as it has a function, and any polarizing film can be used.
  • Examples of the polarizing film that can be used in the present invention include polybulal alcohol (hereinafter abbreviated as "PVA") 'iodine polarizing film; PVA film in which dichroic dye is adsorbed and oriented on a PVA film.
  • Dye-based polarizing film Polyphenylene polarizing film formed by polyhydration by dehydration reaction of PVA film or polyvinyl chloride film; PVA film made of modified PVA containing cationic groups in the molecule Examples thereof include a polarizing film having a dichroic dye on the surface and Z or inside. Of these, PVA'iodine polarizing films are preferred.
  • the method for producing the polarizing film used in the present invention is not particularly limited, and conventionally known methods can be applied. For example, after stretching a PVA film, adsorb iodine ions, after dyeing a PVA film with a dichroic dye, stretch it, after stretching a PVA film, dye it with a dichroic dye, two colors After printing a functional dye on PVA film, Examples thereof include a stretching method and a method of printing a dichroic dye after stretching a PVA film.
  • iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, which are adsorbed on a PVA film and stretched, and then bathed in a 1-5 wt% boric acid aqueous solution.
  • Examples include a method of producing a polarizing film by immersing in a dichroic dye aqueous solution at a bath temperature of 30 to 40 ° C to adsorb the dye, followed by drying at 80 to LO at 0 ° C and heat-fixing. .
  • the thickness of the polarizing film used in the present invention is not particularly limited, but is 10 to 50 m, preferably 15 to 45 ⁇ m.
  • These polarizing films may be used as they are for the production of the polarizing plate according to the present invention, but the surfaces in contact with the adhesive layer can also be used after being subjected to corona discharge treatment or plasma treatment.
  • the polarizing plate of the present invention is a polarizing plate in which the norbornene-based resin film and the polarizing film are bonded via the adhesive.
  • the method for producing such a polarizing plate is not particularly limited.
  • an adhesive is uniformly applied to one surface of a norbornene-based resin film or a polarizing film, and the other film (film) is applied to the coated surface.
  • a method of overlapping and bonding with a roll or the like and drying may be used.
  • the thickness of the adhesive layer after drying is preferably 0.01 to 50 m, more preferably 0.1 to 30 / ⁇ ⁇ , and particularly preferably 1 to 5 /. It is preferable to apply so that ⁇ .
  • the thickness of the adhesive layer after drying is in the above range, the transparency of the polarizing plate is maintained, and the norbornene-based resin film and the polarizing film are bonded with sufficient adhesive force, and the delamination of these layers is prevented. Hard to happen.
  • the temperature at the time of applying the adhesive is usually in the range of 15 to 40 ° C, and the bonding temperature is usually in the range of about 15 to 30 ° C.
  • dry treatment is performed to remove water and other solvents contained in the adhesive.
  • the drying temperature at this time is usually in the range of 30 to 85 ° C, preferably 40 to 80 ° C.
  • the polyurethane-based resin and the polyvinyl alcohol-based resin have a solids weight ratio (polyurethane-based resin Z-polybulal alcohol-based resin). It is included in the range of 5-50 / 50, preferably 90 / 10-70 / 30. However, the total weight (solid content) of the polyurethane resin and the polyvinyl alcohol resin is 100.
  • the above-mentioned adhesive is applied to both surfaces of the polarizing film to adhere the norbornene-based resin film.
  • a norbornene-based resin film is laminated on one surface of the polarizing film and a film (for example, a protective film) made of other resin is laminated on the other surface, the above-mentioned film is formed on both surfaces of the polarizing film.
  • a norbornene-based resin film and other film made of a resin may be adhered by applying an adhesive, and the above-mentioned adhesive is used for bonding the polarizing film and the norbornene-based resin film.
  • Different adhesives may be used for bonding the film to other resin films.
  • an adhesive substantially made of polyvinyl alcohol-based resin may be used.
  • the polarizing plate according to the present invention has a good polarizing function, and the norbornene-based resin film and the polarizing film are firmly bonded to each other, and has excellent characteristics such as heat resistance and chemical resistance. In addition, it has high reliability that resists peeling, deformation, phase change, etc. even during long-term use, and has excellent durability.
  • a polarizing plate can be suitably used for applications such as a liquid crystal display device.
  • the glass transition temperature, total light transmittance, polarization degree, retardation of transmitted light, pure water contact angle, adhesion, moisture resistance test, and dry heat test were measured by the following methods.
  • Tg glass transition temperature
  • Total light transmittance was measured using a haze meter (HGM-2DP type) manufactured by Suga Test Instruments Co., Ltd.
  • the polarization at a wavelength of 547.7 nm was measured using “KOBRA-21ADHZPR” manufactured by Oji Scientific Instruments.
  • a water droplet with a diameter of 1.5 mm is formed at the tip of the needle, and it is brought into contact with the surface of the norbornene resin film.
  • the water droplet is transferred to the norbornene resin film, and the contact angle is determined by the contact angle between the water droplet and the pure water contact surface of the norbornene resin film. Measured using a total (Kyowa Interface Chemical Co., Ltd., AD-31)
  • the polarizing plate was stored for 500 hours in an environment of a temperature of 40 ° C and a relative humidity of 95%, and then various evaluations were performed.
  • the polymerization conversion rate in this copolymerization reaction was 97%, and the intrinsic viscosity (7?) Of the obtained ring-opening copolymer in 30 ° C of chloroform was measured. It was 65dlZg
  • the hydrogenation reaction was performed by heating and stirring under the conditions for 3 hours.
  • the INVEX Lab Coater made by Inoue Metal Industry installed in a Class 1000 clean room, it was hydrophilized with an acrylic acid-based surface treatment agent (easy-to-adhesive), and its thickness was 100 / zm. It was applied on a T film ("Lumirror U94" manufactured by Toray Industries, Inc.). Next, the obtained liquid layer was subjected to a primary drying treatment at 50 ° C., and further subjected to a secondary drying treatment at 90 ° C., and then the PET film force was also peeled off to obtain a 100 m thick resin film (hereinafter referred to as “the resin film”). “Resin film (a-2)”) was formed. The obtained resin film (a-2) had a residual solvent amount of 0.5% by weight and a total light transmittance of 93% or more.
  • a resin film having a residual solvent amount of 0.4 wt% and a thickness of 80 m (hereinafter, also referred to as “wax film (a-3)"), and a method similar to the above, A resin film having a residual solvent amount of 0.3% by weight and a thickness of 50 m (hereinafter also referred to as “resin film (a-4)”) was formed.
  • the total light transmittances of the obtained resin film (a-3) and resin film (a-4) were both 93% or more.
  • the obtained resin film (a-2) was heated in a tenter to 140 ° C (Tg + 10 ° C) and stretched in the longitudinal direction in the film plane at a stretch rate of 300% Z. Then, the film is stretched 1.3 times in the transverse direction in the film plane, and then in this state for 1 minute under an atmosphere of 110 ° C (Tg—20 ° C) The film was cooled while being held, further cooled at room temperature, and then taken out from the tenter to obtain a retardation film (hereinafter also referred to as “retardation film (a-5)”).
  • retardation film (a-5) a retardation film
  • the obtained resin film (a-3) was heated in a tenter to 140 ° C (Tg + 10 ° C), and the lateral width in the film plane was kept constant at a stretching rate of 300% Z. While maintaining this state for 1.3 minutes in an atmosphere of 110 ° C (Tg-20 ° C), while maintaining this state for 1 minute, and further cooling at room temperature, By taking out, a retardation film (hereinafter also referred to as “retardation film (a-6)”) was obtained.
  • the obtained resin film (a-4) was heated to 140 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the longitudinal direction of the film at a stretch rate of 300% Z. Then, the film is stretched 1.1 times in the lateral direction in the film plane, and then cooled in an atmosphere of 110 ° C. (Tg—20 ° C.) for 1 minute, and further at room temperature. After cooling, the film was taken out from the tenter to obtain a retardation film (hereinafter also referred to as “retardation film (a-7)”).
  • retardation film (a-7) a retardation film
  • retardation films (a-5), (a-6) and (a-7) After producing retardation films (a-5), (a-6) and (a-7) in the same manner as in Production Example 1, the obtained retardation films (a-5), (a-6) ) And (a-7) are subjected to corona treatment in the atmosphere under the condition that the corona discharge electron dose is 100 WZm 2 Zmin, and the retardation film (a-5,), ( & 6,) I got a joy (& -7).
  • the pure water contact angle on the surface of these retardation films was 40 deg. Retardation ⁇ (550), retardation j8 (550), and film thickness of the obtained retardation films (a-5,), (a-6,) and (a-7,) were measured. The results are shown in Table 1.
  • the obtained resin film (f-2) was heated in a tenter to 165 ° C (Tg + 10 ° C) and stretched in the longitudinal direction in the film plane at a stretching rate of 300% Z for 1.03 times. Then, the film was stretched 1.03 times in the transverse direction in the film plane, and then cooled in an atmosphere of 135 ° C (Tg—20 ° C) for 1 minute while maintaining the temperature at room temperature. After cooling, a retardation film (hereinafter also referred to as “retardation film (f5)”) was obtained by taking it out from the tenter.
  • the obtained resin film (f-3) is heated in a tenter to 165 ° C (Tg + 10 ° C), and the transverse width in the film plane is kept constant at a stretching rate of 300% Z. While maintaining this state, the film was stretched 1.03 times in the longitudinal direction, cooled in this condition for 1 minute in an atmosphere of 135 ° C (Tg-20 ° C), further cooled at room temperature, and then from the inside of the tenter. By taking out, a retardation film (hereinafter, also referred to as “retardation film (f-6)”) was obtained.
  • retardation film (f6) retardation ⁇ (550), retardation
  • the results are shown in Table 1.
  • the obtained resin film (f 4) was heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched 1.01 times in the longitudinal direction in the film plane at a stretching rate of 300% Z. Then, the film was stretched 1.01 times in the lateral direction in the film plane, and then cooled in this state for 1 minute in an atmosphere of 135 ° C (Tg-20 ° C), and further cooled at room temperature, By removing from the inside of the tenter, a retardation film (hereinafter, also referred to as “retardation film ( ⁇ -7)”) was obtained.
  • retardation film ( ⁇ -7) retardation film
  • PC Polycarbonate resin (A 2700)
  • a polyurethane resin emulsion (hereinafter also referred to as “polyurethane resin (B-1)”) having a polystyrene-reduced weight average molecular weight of 120,000 and a nonvolatile content of 35% by weight was obtained.
  • the obtained polyurethane-based resin aqueous solution and polyvinyl alcohol-based resin aqueous solution are mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and the solid content concentration is 15% by weight.
  • a mixed adhesive (b-1) was prepared.
  • Preparation Example 3 Mixing with a solid content concentration of 15% by weight in the same manner as in Preparation Example 1, except that 100 parts of polyurethane resin (B-2) was used instead of WLS-201 manufactured by Dainippon Ink & Chemicals, Inc. Adhesive (b-3) was prepared.
  • the solids concentration was 15 in the same manner as in Preparation Example 1 except that WLS-201 manufactured by Dainippon Ink & Chemicals, Inc. and polyvinyl alcohol-based resin were mixed at a solid weight ratio of 95: 5.
  • a weight percent mixed adhesive (b-4) was prepared.
  • the solids concentration is 15 in the same manner as in Preparation Example 1 except that WLS-201 manufactured by Dainippon Ink & Chemicals, Inc. and polyvinyl alcohol-based resin are mixed at a solid weight ratio of 50:50.
  • a weight percent mixed adhesive (b 5) was prepared.
  • Dainippon Ink & Chemicals, Inc. WLS-201 (Solid content 35% by weight aqueous solution) 100 parts, Dainippon Ink & Chemicals CR-5L (100% active ingredient) ) 5 parts was added, and water was further added to dilute to a solid content concentration of 15% by weight to prepare an adhesive (g-l).
  • Wako Pure Chemical Industries, Ltd. 163—03045 (molecular weight 22000, saponification degree 88 mol 0 /.) was diluted with water to a solid content concentration of 15% by weight. 2) was prepared.
  • the solids concentration is 15 as in Preparation Example 1 except that WLS-201 manufactured by Dainippon Ink and Chemicals, Inc. and polyvinyl alcohol-based resin are mixed at a solid weight ratio of 50:50.
  • a weight percent mixed adhesive (g-3) was prepared.
  • a mixed adhesive (g-5) having a solid content concentration of 15% by weight was prepared in the same manner as Preparation Example 1 except that the amount of CR-5L manufactured by Dainippon Ink & Chemicals, Inc. was changed to 5 parts. .
  • Polyvinyl alcohol (hereinafter abbreviated as “PVA”) is spread in a dyeing bath at a temperature of 30 ° C. with an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. Pre-stretched at a stretch ratio of 3 times, and then stretched at a stretch ratio of 2 times in a 55 ° C crosslinking bath consisting 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 post-stretched at, and then dried to obtain a polarizing film (hereinafter also referred to as “polarizer (1)”).
  • polarizer (1) polarizing film
  • a polarizing plate was obtained in the same manner as in Example 1 except that the mixed adhesive (b-4) or (b-5) obtained in Preparation Example 4 or 5 was used as the adhesive. [0196] When the obtained polarizing plate was evaluated for adhesiveness, the adhesive strength was all rank 2. Furthermore, after each obtained polarizing plate was stored under wet heat or dry heat, the adhesion was evaluated. The results are shown in Table 2.
  • the retardation films (a-5,), (a-6,) and (a-7 ') obtained in Preparation Example 2 were bonded together in the combinations shown in Table 2.
  • a polarizing plate was obtained in the same manner as in 1.
  • the adhesive strength of the polarizing plate of the present invention was rank 1 or 2, which was a usable level.
  • the rank 2 polarizing plate was improved to rank 1 by corona treatment.
  • retardation film As the retardation film, the same as in Example 1 except that the retardation films (f 5), (f-6) and (f 7) obtained in Comparative Preparation Example 1 were bonded in the combinations shown in Table 2. A polarizing plate was obtained.
  • the adhesive (g-1) or (g 2) obtained in Comparative Preparation Examples 1 to 5, or A polarizing plate was obtained in the same manner as in Example 1 except that the mixed adhesive (g-3), (g-4) or (g-5) was used.
  • Polarizing plate composition retardation film 1 Z polarizer (1) Z retardation film 2
  • composition of polarizing plate retardation film 1 / polarizer (1) / retardation film 2

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Laminated Bodies (AREA)

Abstract

A polarizing plate comprising a norbornene resin film and a polarizing film superposed thereon through an adhesive layer, characterized in that the adhesive layer is formed from a mixture of a polyvinyl alcohol resin with a polyurethane resin obtained by reacting a polyether polyol with a polyisocyanate compound and that the proportions of the solid ingredients (polyurethane resin/polyvinyl alcohol resin) in the adhesive layer is from 90/10 to 70/30 in terms of ratio by weight, with the sum of the polyurethane resin and the polyvinyl alcohol resin being 100 parts by weight.

Description

明 細 書  Specification
偏光板およびその製造方法  Polarizing plate and manufacturing method thereof
技術分野  Technical field
[0001] 本発明は偏光板に関する。より詳しくは、本発明は、ノルボルネン系榭脂フィルムと [0001] The present invention relates to a polarizing plate. More specifically, the present invention relates to a norbornene-based resin film and
、偏光膜とが高強度で接着された偏光板に関する。 The present invention also relates to a polarizing plate bonded with a polarizing film with high strength.
背景技術  Background art
[0002] 液晶ディスプレイなどに用いられる偏光板 (偏光フィルム）は、通常、透明性に優れ た基板 (光学フィルム）と、偏光膜 (偏光子)とから形成される。また、当該偏光板は、 光学フィルムを延伸して得られる、透過光に位相差を付与する機能を有するフィルム (位相差フィルム）と、偏光膜とから形成されていてもよい。  A polarizing plate (polarizing film) used for a liquid crystal display or the like is usually formed from a substrate (optical film) having excellent transparency and a polarizing film (polarizer). In addition, the polarizing plate may be formed from a film (retardation film) obtained by stretching an optical film and having a function of imparting a retardation to transmitted light, and a polarizing film.
[0003] 従来、偏光板の基板または位相差フィルムとして用いられる光学フィルムとしては、 ポリカーボネートフィルム、ポリエステルフィルム、アセテートフィルムなどが用いられ ていた。しかしながら、ポリカーボネートフィルムやポリエステルフィルムを用いた偏光 板では、光弾性係数が大きぐ微小な応力変化などにより透過光に付与する位相差 を変化させる場合があり、また、アセテートフィルムは、耐熱性が低ぐ吸水性が高い ため、これを用いた偏光板は、使用環境によっては変形しやすいという問題があった  Conventionally, polycarbonate films, polyester films, acetate films, and the like have been used as optical films used as polarizing plate substrates or retardation films. However, in a polarizing plate using a polycarbonate film or a polyester film, the phase difference imparted to transmitted light may change due to a small stress change with a large photoelastic coefficient, and the acetate film has low heat resistance. Because of its high water absorption, there is a problem that polarizing plates using this material are easily deformed depending on the usage environment.
[0004] 一方、ノルボルネン系榭脂は、透明性、耐熱性、耐薬品性等に優れることから、各 種光学部品の材料として注目されている。そして、特許文献 1には、偏光膜にノルボ ルネン系榭脂シートを保護層として積層した偏光フィルムが提案されている。 [0004] On the other hand, norbornene-based resin is attracting attention as a material for various optical components because it is excellent in transparency, heat resistance, chemical resistance and the like. Patent Document 1 proposes a polarizing film in which a norbornene-based resin sheet is laminated as a protective layer on a polarizing film.
[0005] しカゝしながら、ノルボルネン系榭脂と他の榭脂素材とは、接着性が悪!、ため、ノルボ ルネン榭脂フィルムを用いた偏光板は製造が困難であった。また、長期使用におい ては剥がれを生じやすいという問題があった。さらに、偏光板には耐傷付き性や反射 防止性能を向上させるために一方の面にハードコート処理などの表面処理を施す場 合があるが、この場合も長期使用においては剥がれが発生するなどの問題があった 。このため、ノルボルネン系榭脂フィルムを用い、かつ接着性にも優れた偏光板の開 発が強く求められていた。 特許文献 1：特開平 6— 51117号公報 [0005] However, since norbornene-based resin and other resin materials have poor adhesion, it is difficult to produce a polarizing plate using a norbornene-based resin film. In addition, there is a problem that peeling tends to occur during long-term use. Furthermore, in order to improve the scratch resistance and antireflection performance of the polarizing plate, a surface treatment such as a hard coat treatment may be applied to one surface, but in this case as well, peeling may occur during long-term use. There was a problem. For this reason, there has been a strong demand for the development of a polarizing plate using a norbornene-based resin film and having excellent adhesion. Patent Document 1: JP-A-6-51117
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明は、上記のような従来技術に伴う問題を解決しょうとするものであって、光学 フィルムと偏光膜との接着性に優れ、かつ、耐熱性、耐薬品性などの特性にも優れ、 長期使用においても剥離、変形などが生じにくぐ高い信頼性を有する偏光板を提 供することを目的としている。 [0006] The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in adhesion between an optical film and a polarizing film, and has characteristics such as heat resistance and chemical resistance. The objective is to provide a highly reliable polarizing plate that is resistant to peeling and deformation even after long-term use.
課題を解決するための手段  Means for solving the problem
[0007] 本発明者らは、上記問題点を解決すべく鋭意研究した結果、偏光板の製造にぉ 、 てノルボルネン系榭脂フィルムと偏光膜とを接着する際に、ポリウレタン系榭脂とポリ ビュルアルコール系榭脂とを特定の割合で含有する混合物を用いることにより、偏光 板の特性を損なうことなぐ上記フィルム (膜)を強固に接着できることを見出し、本発 明を完成するに至った。 [0007] As a result of diligent research to solve the above problems, the present inventors have found that, when a norbornene-based resin film and a polarizing film are bonded to each other during the production of a polarizing plate, It has been found that the use of a mixture containing a specific proportion of butyl alcohol-based resin can firmly bond the film (film) without impairing the characteristics of the polarizing plate, and has completed the present invention.
[0008] すなわち、本発明に係る偏光板は、ノルボルネン系榭脂フィルムと偏光膜とが接着 剤層を介して積層された偏光板であって、前記接着剤層がポリエーテルポリオールと ポリイソシァネートイ匕合物とを反応させてなるポリウレタン系榭脂とポリビュルアルコー ル系榭脂との混合物から形成され、該接着剤層中のポリウレタン系榭脂とポリビュル アルコール系榭脂との合計 100重量部に対して固形分重量比 (ポリウレタン系榭脂 Zポリビュルアルコール系榭脂）が 90ZlO〜70Z30であることを特徴とする。  That is, the polarizing plate according to the present invention is a polarizing plate in which a norbornene-based resin film and a polarizing film are laminated via an adhesive layer, and the adhesive layer includes a polyether polyol and a polyisocyanate. It is formed from a mixture of a polyurethane-based resin obtained by reacting a Natetoi compound and a polybulal alcohol-based resin, and the total of the polyurethane-based resin and the polybulu alcohol-based resin in the adhesive layer is 100. The solid content weight ratio (polyurethane-based resin Z-polybulal alcohol-based resin) relative to parts by weight is 90ZlO to 70Z30.
[0009] 前記ノルボルネン系榭脂フィルムは、下記式（1)で表される少なくとも 1種の化合物 を含む単量体を (共)重合して得られた榭脂からなるフィルムであることが好ま 、。  [0009] The norbornene-based resin film is preferably a film made of resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1). ,.
[0010] [化 1]  [0010] [Chemical 1]
Figure imgf000003_0002
Figure imgf000003_0002
Figure imgf000003_0001
Figure imgf000003_0001
[0011] (式（1)中、 Ri〜R4は、各々独立に水素原子;ハロゲン原子;または酸素、窒素、ィォ ゥもしくはケィ素を含有していてもよい 1価の基を表す。 R1と R2、または R3と R4とが相 互に結合してアルキリデン基を形成していてもよぐあるいは、 R1と R2、 R3と R4、または R2と R3とが相互に結合して単環または多環の炭素環または複素環を形成してもよい 。 Xは 0または 1〜3の整数、 yは 0または 1を表す。ただし、 Xが 0のとき、 yも 0である。） 前記ノルボルネン系榭脂フィルムは位相差フィルムであることが好ましい。 [In the formula (1), Ri to R 4 are each independently a hydrogen atom; a halogen atom; or oxygen, nitrogen, Represents a monovalent group that may contain thio or keium. R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form an alkylidene group, or R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 And may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring. X represents 0 or an integer of 1 to 3, and y represents 0 or 1. However, when X is 0, y is also 0. The norbornene-based resin film is preferably a retardation film.
[0012] 前記接着剤層が、さらに水溶性エポキシィ匕合物を含有し、該接着剤層中のポリウレ タン樹脂と水溶性エポキシィ匕合物との合計 100重量部に対して、固形分重量比 (ポリ ウレタン榭脂 Z水溶性エポキシィ匕合物）が 97Z3〜82Z18であることが好ましい。  [0012] The adhesive layer further contains a water-soluble epoxy compound, and a solid content weight ratio with respect to a total of 100 parts by weight of the polyurethane resin and the water-soluble epoxy compound in the adhesive layer. (Polyurethane resin Z water-soluble epoxy compound) is preferably 97Z3 to 82Z18.
[0013] 本発明に係る偏光板の製造方法は、ノルボルネン系榭脂フィルム表面を、ポリエー テルポリオールとポリイソシァネートイ匕合物とを反応させてなるポリウレタン系榭脂とポ リビュルアルコール系榭脂との混合物力も形成され、ポリウレタン系榭脂とポリビュル アルコール系榭脂との合計 100重量部に対して固形分重量比 (ポリウレタン系榭脂 Zポリビニルアルコール系榭脂）が 90ZlO〜70Z30である接着剤層を介して偏光 膜と接着することを特徴とする。  [0013] The method for producing a polarizing plate according to the present invention comprises a polyurethane-based resin and a polyhydric alcohol-based product obtained by reacting a norbornene-based resin film surface with a polyether polyol and a polyisocyanate compound. Mixing force with rosin is also formed, and the solid content weight ratio (polyurethane reinforced resin Z polyvinyl alcohol-based reinforced resin) is 90ZlO to 70Z30 with respect to 100 parts by weight of the total of polyurethane-based resin and polybulal alcohol-based resin. It is characterized by adhering to the polarizing film through an adhesive layer.
[0014] 本発明に係る偏光板の製造方法にお!ヽては、前記ノルボルネン系榭脂フィルム表 面を、予めコロナ放電電子の照射量 70〜100WZm2Zminでコロナ処理することが 好ましい。 [0014] In the method for producing a polarizing plate according to the present invention, it is preferable that the surface of the norbornene-based resin film is pretreated with a corona discharge electron dose of 70 to 100 WZm 2 Zmin.
発明の効果  The invention's effect
[0015] 本発明によれば、良好な偏光機能を有し、光学フィルムと偏光膜との接着性に優れ 、かつ、耐熱性、耐薬品性、などの特性にも優れ、長期使用においても剥離、変形な どが生じにくぐ耐久性に優れ、高い信頼性を有する偏光板を得ることができる。 発明を実施するための最良の形態  [0015] According to the present invention, it has a good polarizing function, excellent adhesion between an optical film and a polarizing film, and excellent properties such as heat resistance and chemical resistance, and can be peeled off even after long-term use. Thus, it is possible to obtain a polarizing plate having excellent durability and resistance to deformation and high reliability. BEST MODE FOR CARRYING OUT THE INVENTION
[0016] 以下、本発明について具体的に説明する。 [0016] The present invention will be specifically described below.
[0017] 本発明の偏光板は、ノルボルネン系榭脂フィルムと偏光膜とが、ポリウレタン系榭脂 およびポリビニルアルコール系榭脂の混合物力 形成された接着剤層を介して接着 された偏光板である。  The polarizing plate of the present invention is a polarizing plate in which a norbornene-based resin film and a polarizing film are bonded via an adhesive layer formed with a mixture force of polyurethane-based resin and polyvinyl alcohol-based resin. .
[0018] <ノルボルネン系榭脂フィルム >  [0018] <Norbornene-based resin film>
本発明に用いられるノルボルネン系榭脂フィルムを構成するノルボルネン系榭脂は 、ノルボルネン系化合物を少なくとも 1種含む単量体組成物を (共)重合して得 榭脂、または、必要に応じてこの樹脂に水素添加して得られた榭脂である。 The norbornene-based resin constituting the norbornene-based resin film used in the present invention is A resin obtained by (co) polymerizing a monomer composition containing at least one norbornene-based compound, or a resin obtained by hydrogenating this resin as required.
[0019] (単量体組成物）  [0019] (Monomer composition)
前記単量体組成物に含まれるノルボルネン系化合物としては、たとえば、下窗 )で表されるノルボルネン系化合物を挙げることができる。  Examples of the norbornene compound contained in the monomer composition include a norbornene compound represented by the following formula.
[0020] [化 2] [0020] [Chemical 2]
Figure imgf000005_0001
Figure imgf000005_0001
[0021] 式（1)中、 Ri〜R4は、各々独立に水素原子;ハロゲン原子;または酸素、窒素、ィォ ゥもしくはケィ素を含有していてもよい 1価の基を表す。前記 1価の基としては、 1価の 有機基、シァノ基、アミノ基などが挙げられる。さらに、 1価の有機基としては、酸素、 窒素、ィォゥもしくはケィ素を含む連結基を有していてもよい、置換または非置換の 炭素数 1〜15の炭化水素基などが挙げられる。 Xは 0または 1〜3の整数、 yは 0また は 1を表す。ただし、 X力 のとき、 yも 0である。 In the formula (1), Ri to R 4 each independently represent a hydrogen atom; a halogen atom; or a monovalent group that may contain oxygen, nitrogen, iodo, or silicon. Examples of the monovalent group include a monovalent organic group, a cyano group, and an amino group. Furthermore, examples of the monovalent organic group include a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, which may have a linking group containing oxygen, nitrogen, iodo or silicon. X represents 0 or an integer of 1 to 3, and y represents 0 or 1. However, when X force, y is also 0.
[0022] また、 R1と R2、または R3と R4とが相互に結合してアルキリデン基を形成して 、てもよ ぐあるいは、 R1と R2、 R3と R4、または R2と R3とが相互に結合して単環もしくは多環の 炭素環または単環もしくは多環の複素環を形成してもよい。ここで、「尺1と R2とが相互 に結合してアルキリデン基を形成する」とは、 R1と R2のいずれか一方が脱離し、残りの 基が 2重結合により環構造と結合して 、る状態（下記式（1 ' ) )を意味する。 R3と R4の 場合も同様である。また、上記炭素環または複素環としては、脂環式、芳香族環が挙 げられる。 [0022] Alternatively, R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form an alkylidene group. Alternatively, R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 may be bonded to each other to form a monocyclic or polycyclic carbocyclic ring or a monocyclic or polycyclic heterocyclic ring. Here, “scale 1 and R 2 are bonded to each other to form an alkylidene group” means that either R 1 or R 2 is removed and the remaining group is bonded to the ring structure by a double bond. This means a state (the following formula (1 ′)). The same applies to R 3 and R 4 . Examples of the carbocycle or heterocycle include alicyclic and aromatic rings.
[0023] [化 3]  [0023] [Chemical 3]
Figure imgf000005_0002
[0024] 上記式（1)で表されるノルボルネン系化合物は 1種単独で用いてもよいし、 2種以 上を併用してもよい。
Figure imgf000005_0002
[0024] The norbornene-based compound represented by the above formula (1) may be used alone or in combination of two or more.
[0025] 上記式（1)で表されるノルボルネン系化合物としては、たとえば、以下の化合物が 例示できるが、これらの化合物に限定されるものではない。  [0025] Examples of the norbornene-based compound represented by the above formula (1) include the following compounds, but are not limited to these compounds.
ビシクロ [2. 2. 1]ヘプトー 2—ェン（ノルボルネン）  Bicyclo [2. 2. 1] heptoe-2-en (norbornene)
5—メチル一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5-methylbicyclo [2. 2. 1] hepto-2
5 ェチル一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5 ethyl 1 bicyclo [2. 2. 1] heptoe 2
5 シクロへキシル一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5 Cyclohexyl bibicyclo [2.2.1] hepto 2
5—フエ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン  5- Hue-Rubicyclo [2. 2. 1] heptoe 2
5— (4—ビフエ-ル）一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5— (4-biphenyl) monobicyclo [2. 2. 1] heptoe 2
5—メトキシカルボ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン  5-Methoxycarbo-rubicyclo [2.2.1] hepto-2
5 フエノキシカルボ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン  5 Phenoxycarbo-rubicyclo [2.2.1] hepto-2
5 フエノキシェチルカルボ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン  5 Fuenoxychetylcarbo-rubicyclo [2. 2. 1] heptou 2
5 フエ-ルカルポ-ルォキシ—ビシクロ [2. 2. 1]ヘプトー 2 ェン  5 Fe-l-polyoxy-bicyclo [2. 2. 1] hepto-2
5—メチル 5—メトキシカルボ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン  5-Methyl-5-methoxycarbo-rubicyclo [2. 2. 1] hepto-2
5—メチル 5 フエノキシカルボ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン  5-methyl-5-phenoxycarbo-rubicyclo [2. 2. 1] hepto-2
5—メチル 5 フエノキシェチルカルボ-ルービシクロ [2. 2. 1]ヘプトー 2 ェン 5 —ビュル一ビシクロ [2. 2. 1]ヘプトー 2—ェン  5—Methyl 5 phenoxycetylcarbo-rubicyclo [2. 2. 1] hepto 2 -en 5 —Bulbibicyclo [2. 2. 1] hepto 2—en
5 ェチリデン一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5 Ethylidene-bicyclo [2. 2. 1] heptoe 2
5, 5 ジメチルービシクロ [2. 2. 1]ヘプトー 2 ェン  5, 5 Dimethyl-bicyclo [2.2.1] hepto-2
5, 6 ジメチルービシクロ [2. 2. 1]ヘプトー 2 ェン  5, 6 Dimethyl-bicyclo [2.2.1] hepto-2
5 フルオロービシクロ [2. 2. 1]ヘプトー 2 ェン  5 Fluorobicyclo [2. 2. 1] hepto-2
5 クロ口一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5 Black-and-white bicyclo [2. 2. 1] heptoe 2
5 ブロモ一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5 Bromo-bibicyclo [2. 2. 1] hepto-2
5, 6 ジフルオロービシクロ [2. 2. 1]ヘプトー 2 ェン  5, 6 Difluoro-bicyclo [2. 2. 1] hepto-2
5, 6 ジクロロ一ビシクロ [2. 2. 1]ヘプトー 2 ェン  5, 6 Dichlorobicyclo [2. 2. 1] hepto-2
5, 6 ジブ口モービシクロ [2. 2. 1]ヘプトー 2 ェン  5, 6 Jib mouth mobicyclo [2. 2. 1] heptoe 2
5 ヒドロキシ一ビシクロ [2. 2. 1]ヘプトー 2 ェン 5 ヒドロキシェチル一ビシクロ [2. 2. 1]ヘプトー 2 ェン 5 Hydroxybicyclo [2. 2. 1] hepto-2 5 Hydroxyethyl bicyclo [2. 2. 1] hepto-2
5 シァノービシクロ [2. 2. 1]ヘプトー 2 ェン  5 Cyanobicyclo [2.2.1] Heptou 2
5 アミノービシクロ [2. 2. 1]ヘプトー 2 ェン  5 Amino-bicyclo [2. 2. 1] hepto-2
トリシクロ [4. 3. 0. I2'5]デカー 3 ェン Tricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
トリシクロ [4. 4. 0. I2'5]ゥンデ力一 3 ェン Tricyclo [4. 4. 0. I 2 ' 5 ]
7—メチル一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7-Methyl monotricyclo [4. 3. 0. I 2 ' 5 ]
7 ェチル一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 ethyl tricyclo [4. 3. 0. I 2 ' 5 ]
7 シクロへキシル一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン7 Cyclohexyl Monotricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7 フエ-ル一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Fertritricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7— (4 ビフエ-ル）一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7, 8 ジメチル一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7— (4 Biphenyl) monotricyclo [4. 3. 0. I 2 ' 5 ] Deca 3 3, 7, dimethyl mono tricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7, 8, 9 トリメチルートリシクロ [4. 3. 0. I2'5]デカ— 3 ェン7, 8, 9 Trimethyl-tricyclo [4. 3. 0. I 2 ' 5 ] Deca-3
8—メチル一トリシクロ [4. 4. 0. I2'5]ゥンデ力一 3 ェン 8—Methyl monotricyclo [4. 4. 0. I 2 ' 5 ]
8 フエ-ル一トリシクロ [4. 4. 0. I2'5]ゥンデ力一 3 ェン 7 フルォロ一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 8 Ferritricyclo [4. 4. 0. I 2 ' 5 ] Wunde force 1 3 7 Fluorotricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7 クロロートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Chlorotricyclo [4. 3. 0. I 2 ' 5 ]
7 プロモートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Promotricyclo [4. 3. 0. I 2 ' 5 ]
7, 8 ジクロロ一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7, 8 Dichlorotricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7, 8, 9 トリクロロートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン7, 8, 9 Trichloro-tricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7 クロロメチルートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Chloromethyl-tricyclo [4. 3. 0. I 2 ' 5 ]
7 ジクロロメチルートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン7 Dichloromethyl-tricyclo [4. 3. 0. I 2 ' 5 ]
7 トリクロロメチルートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン7 Trichloromethyl-tricyclo [4. 3. 0. I 2 ' 5 ]
7 ヒドロキシ一トリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Hydroxy monotricyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7 シァノートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Sinat Recyclo [4. 3. 0. I 2 ' 5 ] Deca 3
7 アミノートリシクロ [4. 3. 0. I2'5]デカ一 3 ェン 7 Amino-tricyclo [4. 3. 0. I 2 ' 5 ]
テトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン Tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
ペンタシクロ [7. 4. 0. I2'5. I8'11. 07'12]ペンタデカー 3 ェン へキサシクロ [8. 4. 0. I2'5. I7'14. I9'12. 08'13]ヘプタデカー 3 ェン 8—メチルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン Pentacyclo [7. 4. 0. I 2 '5 . I 8' 11. 0 7 '12] Pentadeka to 3 E down Kisashikuro [8. 4. 0. I 2' 5 . I 7 '14. I 9' 12 . 0 8 '13] Heputadeka 3 E down 8—Methyl-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
8 ェチルーテトラシクロ [4. 4. 0. I2'5. 17。]ドデ力一 3 ェン 8 Ethyl-tetracyclo [4. 4. 0. I 2 ' 5. 1 7 . ] Dode Rikiichi 3
8 シクロへキシル一テトラシクロ [4. 4. 0. I2'5. 1"。]ドデ力一 3 ェン 8 Cyclohexyl monotetracyclo [4. 4. 0. I 2 ' 5 .1 ".]
8 フエ二ルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 -ェン 8 Henriru Tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3 -Yen
8—（4ービフエ-ル）ーテトラシクロ [4. 4. 0. I2'5. I7'10]ド、デカー 3 -ェン 8- (4-biphenyl) -tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8—メトキシカルボ-ルーテトラシクロ [4. 4. 0. I2'5. l7'10]ドデ力一 3 ェン 8-Methoxycarbo-rutetracyclo [4. 4. 0. I 2 ' 5. l 7 ' 10 ]
8 フエノキシカルボ-ルーテトラシクロ [4. 4. 0. I2'5. l7'10]ドデ力一 3 ェン 8 Phenoxycarbo-rutetracyclo [4. 4. 0. I 2 ' 5. L 7 ' 10 ]
8 フエノキシェチルカルボ-ルーテトラシクロ [4. 4. 0. I2'5. l7'10]ドデ力一 3 ェン8 Fuenoxycetylcarbo-rutetracyclo [4. 4. 0. I 2 ' 5. L 7 ' 10 ]
8 フエニルカルボニルォキシ一テトラシクロ [4. 4. 0. I2'5. 1"°]ドデ力一 3 ェン8 phenylalanine carbonyl O carboxymethyl one tetracyclo [4. 4. 0. I 2 '5 . 1 "°] de de force one 3 E down
8—メチル 8—メトキシカルボ-ル一テトラシクロ [4. 4. 0. I2'5. l7'10]ドデ力一 3— ェン 8-Methyl 8-Methoxycarborutetracyclo [4. 4. 0. I 2 ' 5. l 7 ' 10 ]
8—メチル 8 フエノキシカルボ-ルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力一 3 ーェン 8—Methyl 8 phenoxycarbo-rutetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8—メチル 8 フエノキシェチルカルボ二ルーテトラシクロ [4. 4. 0. I2'5. l7'10]ドデ カー 3—ェン 8-Methyl 8 phenoxycetylcarbonyl tetracyclo [4. 4. 0. I 2 ' 5. L 7 ' 10 ] dodeca 3-en
8 ビニルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデカー 3 ェン 8 Vinyl-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dodeca 3
8 ェチリデン一テトラシクロ [4. 4. 0. I2,5. I7'10]ドデ力一 3 ェン 8 Echiriden one tetracyclo [4. 4. 0. I 2,5. I 7 '10] dodecane force one 3 E down
8, 8 ジメチルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン 8, 8 Dimethyl-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
8, 9 ジメチルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力一 3 ェン 8, 9 Dimethyl-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8 フルォロ一テトラシクロ [4. 4. 0. I2,5. 1"。]ドデ力一 3 ェン 8 Furuoro one tetracyclo [4. 4. 0. I 2,5. 1 ".] De de force one 3 E down
8 クロローテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン 8 Chloro-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
8 ブロモ一テトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力一 3 ェン 8 Bromo monotetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8, 8 ジクロロ一テトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン 8, 8 Dichloromonotetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
8, 9一ジクロローテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン 8, 9 dichloro-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
8, 8, 9, 9—テトラクロローテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力— 3 ェン 8, 8, 9, 9—Tetrachloro-tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ] Dode force — 3
8 ヒドロキシ一テトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力一 3 ェン 8 Hydroxy monotetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8 ヒドロキシェチルーテトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力一 3 ェン 8 Hydroxyethyl tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8—メチル 8 ヒドロキシェチル一テトラシクロ [4. 4. 0. I2'5. l7'10]ドデ力一 3 ェン 8—シァノ一テトラシクロ [4. 4. 0. I2'5. I7'10]ドデ力一 3—ェン 8-methyl 8 hydroxyethyl monotetracyclo [4. 4. 0. I 2 ' 5. L 7 ' 10 ] 8-Cyanol tetracyclo [4. 4. 0. I 2 ' 5. I 7 ' 10 ]
8—ァミノ一テトラシクロ [4. 4. 0. I2'5. 17。]ドデ力一 3—ェン 8-Aminomonotetracyclo [4. 4. 0. I 2 ' 5. 1 7 . ] Power of Dode 3—Yen
本発明で用いられるノルボルネン系化合物の種類および使用量は、求められる榭 脂の特性に応じて適宜選択される。  The kind and amount of the norbornene compound used in the present invention are appropriately selected according to the required properties of the resin.
[0026] 上記式（1)で表されるノルボルネン系化合物のうち、酸素原子、窒素原子、ィォゥ 原子およびケィ素原子力 選ばれた少なくとも 1種の原子を分子内に少なくとも 1個 含む構造 (以下、「極性構造」という）を有する化合物が、他の素材との接着性や密着 性に優れている点で好ましい。特に、上記式（1)中、 R1および R3が水素原子または 炭素数 1〜3の炭化水素基、好ましくは水素原子またはメチル基であり、 R2または R4 のいずれか一つが極性構造を有する基であって他が水素原子または炭素数 1〜3炭 化水素基である化合物は、得られる榭脂の吸水 (湿)性が低くなる点で好ましい。さら に、極性構造を有する基が下記式（2)で表わされる基であるノルボルネン系化合物 は、得られる榭脂の耐熱性と吸水 (湿)性とのバランスがよぐ好ましく用いられる。 [0026] Among the norbornene-based compounds represented by the above formula (1), a structure containing at least one selected atom in the molecule (hereinafter referred to as oxygen atom, nitrogen atom, ion atom, and key atom) A compound having a “polar structure” is preferable in terms of excellent adhesion and adhesion to other materials. In particular, in the above formula (1), R 1 and R 3 are a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R 2 and R 4 is a polar structure A compound having a hydrogen atom and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable in that the water absorption (wet) property of the resulting resin is low. Furthermore, a norbornene-based compound in which the group having a polar structure is a group represented by the following formula (2) is preferably used because of a good balance between the heat resistance and water absorption (wet) property of the resulting resin.
[0027] - (CH ) COOR (2)  [0027]-(CH) COOR (2)
2 z  2 z
式 (2)中、 Rは置換または非置換の炭素数 1〜15の炭化水素基を表し、 zは 0また は 1〜 10の整数を表す。  In the formula (2), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10.
[0028] 上記式（2)において、 zの値が小さいものほど得られる重合体の水素添加物のガラ ス転移温度が高くなり耐熱性に優れるので、 zが 0または 1〜3の整数であることが好 ましぐさらに、 zが 0である単量体はその合成が容易である点で好ましい。また、上記 式（2)における Rは、炭素数が多いほど得られる重合体の水素添加物の吸水 (湿)性 が低下する傾向にあるが、ガラス転移温度が低下する傾向もあるので、耐熱性を保 持する観点力 は炭素数 1〜10の炭化水素基が好ましぐ特に炭素数 1〜6の炭化 水素基であることが好まし 、。  [0028] In the above formula (2), the smaller the value of z, the higher the glass transition temperature of the resulting polymer hydrogenated product and the better the heat resistance, so z is 0 or an integer from 1 to 3. Furthermore, a monomer in which z is 0 is preferable in that its synthesis is easy. In addition, R in the above formula (2) tends to decrease the water absorption (wetness) of the resulting hydrogenated polymer as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining the property, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.
[0029] 上記式（1)において、上記式（2)で表される基が結合した炭素原子に炭素数 1〜3 のアルキル基、特にメチル基が結合している化合物は、耐熱性と吸水 (湿)性のバラ ンスの点で好ましい。さらに、上記式（1)において、 Xが 0または 1であり yが 0である化 合物は、反応性が高ぐ高収率で重合体が得られること、また、耐熱性が高い重合体 水素添加物が得られること、さらに工業的に入手しやすいことから好適に用いられる [0030] 本発明に用いられるノルボルネン系榭脂を得るにあたっては、本発明の効果を損な わな 、範囲で前記ノルボルネン系化合物と共重合可能な単量体を単量体組成物に 含ませて重合することができる。 [0029] In the above formula (1), a compound in which an alkyl group having 1 to 3 carbon atoms, in particular a methyl group, is bonded to the carbon atom to which the group represented by the above formula (2) is bonded, It is preferable in terms of (wet) balance. Furthermore, in the above formula (1), a compound in which X is 0 or 1, and y is 0 is a highly reactive polymer with a high yield, and a polymer having high heat resistance. It is preferably used because it is easy to obtain hydrogenated products and industrially. [0030] In obtaining the norbornene-based resin used in the present invention, a monomer copolymerizable with the norbornene-based compound is included in the monomer composition within a range without impairing the effects of the present invention. Can be polymerized.
[0031] これらの共重合可能な単量体としては、たとえば、シクロブテン、シクロペンテン、シ クロヘプテン、シクロオタテン、シクロドデセンなどの環状ォレフィン； 1, 4ーシクロオタ タジェン、ジシクロペンタジェン、シクロドデカトリェンなどの非共役環状ポリェンを挙 げることができる。  [0031] These copolymerizable monomers include, for example, cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclootaten and cyclododecene; non-cyclic such as 1,4-cyclootatagene, dicyclopentagen and cyclododecatriene. Conjugated cyclic polynes can be mentioned.
[0032] これらの共重合性単量体は、 1種単独で用いてもよいし 2種以上を併用してもよい。  [0032] These copolymerizable monomers may be used alone or in combination of two or more.
[0033] (重合方法） [0033] (Polymerization method)
本発明に用いられるノルボルネン系榭脂の重合方法にっ 、ては、上記ノルボルネ ン系化合物を含む単量体組成物の重合が可能である限り、特に制限されるものでは ないが、たとえば、開環重合または付加重合によって重合することができる。  The norbornene-based resin polymerization method used in the present invention is not particularly limited as long as the monomer composition containing the norbornene-based compound can be polymerized. Polymerization can be carried out by ring polymerization or addition polymerization.
[0034] (1)開環重合 [0034] (1) Ring-opening polymerization
開環重合による重合体の製造は、ノルボルネン系化合物についての公知の開環重 合反応により行うことができ、前記ノルボルネン系化合物を含む単量体組成物を、重 合触媒、重合反応用溶媒、および必要に応じて分子量調節剤を用いて、開環重合さ せること〖こよって製造することができる。  Production of the polymer by ring-opening polymerization can be carried out by a known ring-opening polymerization reaction for norbornene-based compounds. A monomer composition containing the norbornene-based compound is mixed with a polymerization catalyst, a polymerization reaction solvent, And, if necessary, it can be produced by ring-opening polymerization using a molecular weight regulator.
[0035] (a)重合触媒 [0035] (a) Polymerization catalyst
本発明において、単量体組成物の重合を開環（共)重合反応により行う場合は、メ タセシス触媒の存在下で行うことが好ま 、。  In the present invention, when the monomer composition is polymerized by a ring-opening (co) polymerization reaction, it is preferably performed in the presence of a metathesis catalyst.
[0036] このメタセシス触媒は、 [0036] This metathesis catalyst is
(A) W、 Moおよび Reを有する化合物力 選ばれた少なくとも 1種の化合物（以下、 化合物 (A)という）と、  (A) Compound power having W, Mo and Re At least one selected compound (hereinafter referred to as Compound (A)),
(B)デミングの周期律表 IA族元素（たとえば Li、 Na、 Kなど）、 ΠΑ族元素（たとえば、 Mg、 Caなど）、 ΠΒ族元素（たとえば、 Zn、 Cd、 Hgなど）、 ΙΠΑ族元素（たとえば、 Β、 A1など）、 IVA族元素（たとえば、 Si、 Sn、 Pbなど）、または IVB族元素（たとえば、 Ti 、 Zrなど）を有する化合物であって、この元素と炭素との結合またはこの元素と水素と の結合を少なくとも 1つ有する化合物力 選ばれる少なくとも 1種の化合物（以下、化 合物（B)という）と (B) Periodic table of Deming Group IA elements (for example, Li, Na, K, etc.), Group elements (for example, Mg, Ca, etc.), Group elements (for example, Zn, Cd, Hg, etc.), Group III elements (E.g., Β, A1, etc.), IVA group elements (e.g., Si, Sn, Pb, etc.), or IVB group elements (e.g., Ti, Zr, etc.) that are bonded to carbon or With this element and hydrogen A compound having at least one bond of at least one selected compound (hereinafter referred to as compound (B)) and
の組み合わせ力もなる触媒である。また、触媒の活性を高めるために、後述の添加剤 (C)をさらに添カロしてもよい。  It is a catalyst that can also be combined. In order to increase the activity of the catalyst, an additive (C) described later may be further added.
[0037] 化合物（A)としては、 W、 Moあるいは Reのハロゲン化物、ォキシハロゲン化物、ァ ルコキシハロゲン化物、アルコキシド、カルボン酸塩、（ォキシ）ァセチルァセトネート 、カルボ-ル錯体、ァセトニトリル錯体、ヒドリド錯体、およびその誘導体、あるいはこ れらの組み合わせが挙げられ、重合活性、実用性の点から、 Wおよび Moの化合物 が好ましぐこれらのハロゲン化物、ォキシハロゲン化物およびアルコキシハロゲン化 物が特に好ましい。また、反応によって前記化合物を生成する 2種以上の化合物の 混合物を用いてもよい。さらに、これらの化合物は適当な錯化剤、たとえば P (C H )  [0037] Compound (A) includes W, Mo or Re halides, oxyhalides, alkoxy halides, alkoxides, carboxylates, (oxy) acetylethylacetonates, carboxyl complexes, and acetonitrile complexes. , Hydride complexes, and derivatives thereof, or combinations thereof, and those halides, oxyhalides, and alkoxyhalides that are preferred for the compounds of W and Mo are particularly preferred in view of polymerization activity and practicality. preferable. Also, a mixture of two or more compounds that produce the compound by reaction may be used. In addition, these compounds are suitable complexing agents such as P (C H)
6 5 5 6 5 5
、 C H Nなどによって錯ィ匕されていてもよい。 , C H N, etc.
5 5  5 5
[0038] ィ匕合物 (A)としては、 WCl、 WCl、 WCl、 WBr、 WF、 WI、 MoCl、 MoCl、 M  [0038] The compound (A) includes WCl, WCl, WCl, WBr, WF, WI, MoCl, MoCl, M
6 5 4 6 6 6 5 4 oCl、 ReCl、 WOC1、 MoOCl、 ReOCl、 ReOBr、 W(OC H ) 、 WCl (OC H ) 6 5 4 6 6 6 5 4 oCl, ReCl, WOC1, MoOCl, ReOCl, ReOBr, W (OC H), WCl (OC H)
3 3 4 3 3 3 6 5 6 2 6 53 3 4 3 3 3 6 5 6 2 6 5
、 Mo (OC H ) CI、 Mo (OC H ) 、 MoO (acac) 、 W (OCOR) 、 W (OC H ) CI, Mo (OC H) CI, Mo (OC H), MoO (acac), W (OCOR), W (OC H) CI
4 2 5 2 3 2 5 5 2 2 5 2 5 2 34 2 5 2 3 2 5 5 2 2 5 2 5 2 3
、 W(CO) 、 Mo (CO) 、 Re (CO) 、 ReOBr - P (C H ) 、 WCl - P (C H ) 、 WCl , W (CO), Mo (CO), Re (CO), ReOBr-P (C H), WCl-P (C H), WCl
6 6 2 10 3 6 5 3 5 6 5 3 6 6 6 2 10 3 6 5 3 5 6 5 3 6
•C H N、 W(CO) - P (C H ) 、 W (CO) · (CH CN)などが挙げられる。これらの化• C H N, W (CO)-P (C H), W (CO) · (CH CN), etc. These
5 5 5 6 5 3 3 3 3 5 5 5 6 5 3 3 3 3
合物のうち、 MoCl、 Mo (OC H ) CI、 WCl、 W (OC H ) CIなどが特に特に好ま  Of the compounds, MoCl, Mo (OC H) CI, WCl, W (OC H) CI, etc. are particularly preferred.
5 2 5 2 3 6 2 5 2 3  5 2 5 2 3 6 2 5 2 3
しい。  That's right.
[0039] 化合物（B)としては、 n— C H Li、 n— C H Naゝ C H Naゝ CH Mgl、 C H MgBr  [0039] Examples of the compound (B) include: n—C H Li, n—C H Na ゝ C H Na ゝ CH Mgl, C H MgBr
4 5 5 11 5 5 3 2 5 4 5 5 11 5 5 3 2 5
、 CH MgBrゝ n-C H MgCl、 (C H ) Al、 t— C H MgCl、 CH =CHCH MgCl、, CH MgBr ゝ n-C H MgCl, (C H) Al, t— C H MgCl, CH = CHCH MgCl,
3 3 7 6 5 3 4 9 2 23 3 7 6 5 3 4 9 2 2
(C H ) Znゝ（C H ) Cdゝ CaZn (C H ) 、 (CH ) B、（C H ) B、 (n-C H ) B、（C(C H) Zn ゝ (C H) Cd ゝ CaZn (C H), (CH) B, (C H) B, (n-C H) B, (C
2 5 2 2 5 2 2 5 4 3 3 2 5 3 4 9 32 5 2 2 5 2 2 5 4 3 3 2 5 3 4 9 3
H ) Al、 (CH ) A1C1、 (CH ) Al CI、 CH A1C1、（C H ) Al、 LiAl (C H ) 、（CH) Al, (CH) A1C1, (CH) Al CI, CH A1C1, (C H) Al, LiAl (C H), (C
3 3 3 2 3 3 2 3 3 2 2 5 3 2 5 2 23 3 3 2 3 3 2 3 3 2 2 5 3 2 5 2 2
H ) Al— O (C H ) 、（C H ) A1C1、 C H A1C1、（C H ) A1H、（iso— C H ) AIHH) Al—O (C H), (C H) A1C1, C H A1C1, (C H) A1H, (iso—C H) AIH
5 3 2 5 2 2 5 2 2 5 2 2 5 2 4 9 25 3 2 5 2 2 5 2 2 5 2 2 5 2 4 9 2
、（C H ) AIOC H、 (iso -C H ) Al、（C H ) Al CI、 (CH ) Gaゝ (CH ) Sn、 (n, (C H) AIOC H, (iso -C H) Al, (C H) Al CI, (CH) Ga ゝ (CH) Sn, (n
2 5 2 2 5 4 9 3 2 5 3 2 3 3 4 3 42 5 2 2 5 4 9 3 2 5 3 2 3 3 4 3 4
— C H ) Sn、（C H ) SiH、 (n-C H ) Al、 (n-C H ) Al、 LiH、 NaH、 B H、— C H) Sn, (C H) SiH, (n-C H) Al, (n-C H) Al, LiH, NaH, B H,
4 9 4 2 5 3 6 13 3 4 17 3 2 64 9 4 2 5 3 6 13 3 4 17 3 2 6
NaBH、 AIH、 LiAlH、 BiHおよび TiHなどが挙げられる。また反応によってこれNaBH, AIH, LiAlH, BiH and TiH. This also depends on the reaction
4 3 4 4 4 4 3 4 4 4
らの化合物を生成する 2種以上の化合物の混合物を用いることもできる。これらの化 合物のうち、（CH ) Al、 (CH ) A1C1、 (CH ) Al CI、 CH AlCl、（C H ) Al、 (C Mixtures of two or more compounds that produce these compounds can also be used. These Of the compounds, (CH) Al, (CH) A1C1, (CH) Al CI, CH AlCl, (CH) Al, (C
3 3 3 2 3 3 2 3 3 2 2 5 3 2 3 3 3 2 3 3 2 3 3 2 2 5 3 2
H ) AlCl, (C H ) AlCl 、 C H AlCl、（C H ) A1H、 (C H ) AIOC H、（C HH) AlCl, (C H) AlCl, C H AlCl, (C H) A1H, (C H) AIOC H, (C H
5 2 2 5 1.5 1.5 2 5 2 2 5 2 2 5 2 2 5 2 55 2 2 5 1.5 1.5 2 5 2 2 5 2 2 5 2 2 5 2 5
) A1CN、 (C H ) Al、 (iso-C H ) Al、（iso— C H ) A1H、 (C H ) Al、（C H )) A1CN, (C H) Al, (iso-C H) Al, (iso— C H) A1H, (C H) Al, (C H)
2 3 7 3 4 9 3 4 9 2 6 13 3 8 17 32 3 7 3 4 9 3 4 9 2 6 13 3 8 17 3
Al、 (C H ) Alなどが好ましい。 Al, (C 3 H 4) Al and the like are preferable.
6 5 5  6 5 5
[0040] 前記化合物 (A)および化合物（B)とともに用いることのできる添加剤（C)としては、 アルコール類、アルデヒド類、ケトン類、アミン類などが好適に用いることができ、たと えば以下の（1)〜（9)を例示することができる。  [0040] As the additive (C) that can be used together with the compound (A) and the compound (B), alcohols, aldehydes, ketones, amines and the like can be preferably used. (1) to (9) can be exemplified.
(1)単体ホウ素、 BF、： BCl、 B (0— n— C H )、 (C H O ) 、： BF、 B O、 H BOな  (1) simple boron, BF, BCl, B (0— n— C H), (C H O), BF, B O, H BO
3 3 4 9 3 2 5 3 2 2 3 3 3 どのホウ素の非有機金属化合物、 Si (OC H )などのケィ素の非有機金属化合物；  3 3 4 9 3 2 5 3 2 2 3 3 3 Non-organometallic compounds of boron, non-organometallic compounds of silicon such as Si (OC H);
2 5 4  2 5 4
(2)アルコール類、ヒドロバーオキシド類およびパーォキシド類；  (2) alcohols, hydrobaroxides and peroxides;
(3)水;  (3) water;
(4)酸素；  (4) oxygen;
(5)アルデヒドおよびケトンなどのカルボ-ル化合物およびその重合物；  (5) Carbon compounds such as aldehydes and ketones and polymers thereof;
(6)エチレンォキシド、ェピクロルヒドリン、ォキセタンなどの環状エーテル類；  (6) Cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane;
(7) N, N—ジェチルホルムアミド、 N, N—ジメチルァセトアミドなどのアミド類、ァ-リ ン、モルホリン、ピぺリジンなどのアミン類およびァゾベンゼンなどのァゾ化合物； (7) Amides such as N, N-jetylformamide, N, N-dimethylacetamide, amines such as aline, morpholine and piperidine, and azo compounds such as azobenzene;
(8) N— -トロソジメチルァミン、 N— -トロソジフエ-ルァミンなどの N— -トロソ化合 物； (8) N—-troso compounds such as N—-trosodimethylamine, N—-trosodiphenylamine;
(9)トリクロルメラミン、 N—クロルサクシノイミド、フエ-ルスルフエ-ルクロリドなどの S - Cほたは N - C1基を含む化合物。  (9) Compounds containing S—C or N—C1 groups such as trichloromelamine, N-chlorosuccinimide, and phenylsulfur chloride.
[0041] メタセシス触媒の使用量は、前記化合物 (A)と重合に供される全単量体のモル比（ 化合物（八）：全単量体）が、通常1 : 500〜1 : 50, 000、好ましくは 1 : 1, 000〜1 : 10 [0041] The amount of the metathesis catalyst used is usually such that the molar ratio of the compound (A) to the total monomers used for polymerization (compound (8): total monomers) is 1: 500 to 1:50, 000, preferably 1: 1,000 to 1:10
, 000となる量力望まし ヽ。 , 000 000 is desired.
[0042] 化合物 (A)と化合物 (B)との割合 (ィ匕合物 (A)：ィ匕合物 (B) )は、金属原子比で 1 : 1[0042] The ratio of the compound (A) to the compound (B) (the compound (A): the compound (B)) is 1: 1 by metal atom ratio.
〜 1： 50、好ましくは 1： 2〜 1： 30が望まし!/、。 ~ 1: 50, preferably 1: 2 ~ 1: 30!
[0043] 化合物 (A)と化合物（C)との割合 (化合物（C)：化合物 (A) )は、モル比で 0. 005： [0043] The ratio of compound (A) to compound (C) (compound (C): compound (A)) is 0.005 in molar ratio:
1〜15： 1、好ましくは 0. 05 : 1〜7： 1が望ましい。  1 to 15: 1, preferably 0.05: 1 to 7: 1 is desirable.
[0044] (b)重合溶媒 開環重合反応において用いられる溶媒としては、重合に供される単量体組成物や 触媒等が溶解し、かつ触媒が失活することがなぐまた、生成した開環重合体が溶解 するものであれば特に限定されないが、たとえば、ペンタン、へキサン、ヘプタン、ォ クタン、ノナン、デカンなどのアルカン類；シクロへキサン、シクロヘプタン、シクロオタ タン、デカリン、ノルボルナンなどのシクロアルカン類；ベンゼン、トルエン、キシレン、 ェチルベンゼン、クメンなどの芳香族炭化水素；クロロブタン、ブロモへキサン、塩化 メチレン、ジクロロエタン、へキサメチレンジブ口ミド、クロロホノレム、テトラクロロェチレ ンなどのハロゲン化アルカン；クロ口ベンゼンなどのハロゲン化ァリール化合物；酢酸 ェチル、酢酸 n—ブチル、酢酸 iso—ブチル、プロピオン酸メチル、ジメトキシェタンな どの飽和カルボン酸エステル類；ジブチルエーテル、テトラヒドロフラン、ジメトキシェ タンなどのエーテル類などを挙げることができる。これらは単独で、または 2種以上を 混合して用いることができる。なお、このような溶媒は、前記ノルボルネン系化合物、 共重合性単量体および Zまたはメタセシス触媒を溶解するための溶媒の他、分子量 調節剤溶液を構成する溶媒としても用いることができる。 [0044] (b) Polymerization solvent Solvents used in the ring-opening polymerization reaction are those in which the monomer composition or catalyst to be used for polymerization dissolves and the catalyst is not deactivated, and the produced ring-opening polymer dissolves. For example, alkanes such as pentane, hexane, heptane, octane, nonane, decane; cycloalkanes such as cyclohexane, cycloheptane, cyclootatan, decalin, norbornane; benzene, toluene, Aromatic hydrocarbons such as xylene, ethylbenzene, and cumene; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibutamide, chlorophonolem, tetrachloroethylene; Halogenated aryl compounds such as chlorobenzene ; Ethyl acetate, n-butyl acetate, acetic acid iso Butyl, methyl propionate, which saturated carboxylic acid esters such dimethoxy E Tan; dibutyl ether, tetrahydrofuran, and the like ethers such as Jimetokishe Tan. These can be used alone or in admixture of two or more. Such a solvent can be used not only as a solvent for dissolving the norbornene compound, copolymerizable monomer and Z or metathesis catalyst, but also as a solvent constituting the molecular weight regulator solution.
[0045] 溶媒の使用量は、溶媒と重合に供する単量体組成物との重量比 (溶媒:単量体組 成物）力 通常 1： 1〜： L0 : 1、好ましくは 1： 1〜5： 1となる量が望ましい。  [0045] The amount of the solvent used is a weight ratio between the solvent and the monomer composition used for polymerization (solvent: monomer composition) force usually 1: 1 to: L0: 1, preferably 1: 1 to An amount of 5: 1 is desirable.
[0046] (c)分子量調節剤  [0046] (c) Molecular weight regulator
得られる開環重合体の分子量は、重合温度、触媒の種類、溶媒の種類によって調 節することも可能であるが、分子量調節剤を反応系に共存させることによつても調節 することができる。  The molecular weight of the resulting ring-opened polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent, but can also be adjusted by allowing a molecular weight regulator to coexist in the reaction system. .
[0047] 好適な分子量調節剤としては、たとえばエチレン、プロペン、 1—ブテン、 1—ペン テン、 1—へキセン、 1—ヘプテン、 1—オタテン、 1—ノネン、 1—デセンなどの α—ォ レフイン類；およびスチレン、 4—メチルスチレン、 2—メチルスチレン、 4—ェチルスチ レンなどの芳香族ビ-ルイ匕合物類を挙げることができ、これらのうち、 1—ブテン、 1— へキセンが特に好ましい。これらの分子量調節剤は単独で、または 2種以上を混合し て用いることができる。  [0047] Suitable molecular weight regulators include α-o, such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. And olefins such as styrene, 4-methyl styrene, 2-methyl styrene, 4-ethyl styrene, among which 1-butene and 1-hexene are Particularly preferred. These molecular weight regulators can be used alone or in admixture of two or more.
[0048] 分子量調節剤の使用量は、開環重合反応に供される単量体 1モルに対して、通常 0. 005〜0. 6モル、好ましくは 0. 01〜0. 5モルである。 [0049] (d)その他の重合条件 [0048] The amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.01 to 0.5 mol, with respect to 1 mol of the monomer subjected to the ring-opening polymerization reaction. . [0049] (d) Other polymerization conditions
前記開環重合体は、前記ノルボルネン系化合物を開環重合させて、もしくは前記ノ ルボルネン系化合物と共重合性単量体とを開環共重合させて得ることができる力 ポ リブタジエン、ポリイソプレンなどの共役ジェン化合物、スチレン ブタジエン共重合 体、エチレン 非共役ジェン共重合体、ポリノルボルネンなど、主鎖に炭素 炭素間 二重結合を 2つ以上含む不飽和炭化水素系ポリマーなどの存在下でノルボルネン系 化合物を含む単量体組成物を開環重合させてもょ ヽ。  The ring-opening polymer can be obtained by ring-opening polymerization of the norbornene-based compound, or ring-opening copolymerization of the norbornene-based compound and a copolymerizable monomer. Norbornene in the presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain, such as conjugated gen compounds such as styrene butadiene copolymer, ethylene non-conjugated gen copolymer, and polynorbornene. It is also possible to ring-open polymerization a monomer composition containing a compound.
[0050] (2)付加重合  [0050] (2) Addition polymerization
付カ卩（共)重合による重合体の製造は、ノルボルネン系化合物にっ 、ての公知の付 加重合反応により行うことができ、前記ノルボルネン系化合物を含む単量体組成物を 、重合触媒、必要に応じて重合反応用溶媒、および必要に応じて分子量調節剤を用 いて、付加重合させることによって製造することができる。  The production of the polymer by addition (co) polymerization can be carried out by a known addition polymerization reaction with a norbornene compound, and a monomer composition containing the norbornene compound is prepared as a polymerization catalyst, If necessary, it can be produced by addition polymerization using a solvent for polymerization reaction and, if necessary, a molecular weight regulator.
[0051] (a)重合触媒  [0051] (a) Polymerization catalyst
付加重合に用いられる重合触媒としては、たとえば、下記 (a—l)〜（a— 3)に挙げ られるパラジウム、ニッケル、コノ レト、チタニウムおよびジルコニウムなどの単一触媒 や多成分系触媒が挙げられるが、本発明に用いられる重合触媒はこれらに限定され るものではない。  Examples of the polymerization catalyst used in the addition polymerization include single catalysts and multi-component catalysts such as palladium, nickel, conoleto, titanium and zirconium listed in (a-1) to (a-3) below. However, the polymerization catalyst used in the present invention is not limited to these.
[0052] (a— 1)単一触媒系  [0052] (a— 1) Single catalyst system
〔Pd(CH CN)〕〔BF〕、  (Pd (CH CN)) (BF),
3 4 4 2  3 4 4 2
[Pd(PhCN)〕〔SbF〕、  [Pd (PhCN)] (SbF),
4 6  4 6
〔（ 3 クロチル） Pd (シクロォクタ 1, 5 ジェン）〕〔PF〕、 [( 3 crotyl) Pd (cycloocta 1, 5 gen)] [PF],
6  6
〔（ 3 クロチル） Ni (シクロォクタ一 1, 5 ジェン）〕〔B(3, 5— (CF) CF)〕、 [( 3 crotyl) Ni (cycloocta-1, 5 gen)] [B (3, 5— (CF) CF)],
3 2 6 3 4 3 2 6 3 4
〔（ 3 クロチル） Ni (シクロォクタ 1, 5 ジェン）〕〔PF〕、〔（ 7? 3—ァリル） Ni (シク [(3 crotyl) Ni (Shikurookuta 1, 5 Zhen)] [PF], [(7: 3 -? Ariru) Ni (Sik
6  6
ロォクタ一 1, 5—ジェン）〕〔B(CF)〕、 〔（7? 3—クロチル） Ni (シクロォクタ一 1, 5-Loctator 1, 5-gen)] [B (CF)], [(7? 3 -Crotyl) Ni (Cycloocta 1, 5-
6 5 4 6 5 4
ジェン）〕〔SbF〕、  Gen)] [SbF],
6  6
トルエン .Ni(CF) 、  Toluene.Ni (CF),
6 5 2  6 5 2
ベンゼン 'Ni CF)、  Benzene 'Ni CF),
6 5 2  6 5 2
メシチレン 'Ni(CF) 、 ェチルエーテル .Ni(C F )、などの遷移金属化合物が挙げられる。 Mesitylene 'Ni (CF), Transition metal compounds such as ethyl ether, Ni (CF 3), and the like.
6 5 2  6 5 2
[0053] (a— 2)多成分系触媒系（1)  [0053] (a-2) Multi-component catalyst system (1)
σまたは σ , π結合を有するパラジウム錯体と有機アルミニウムまたは超強酸塩の 組み合わせが挙げられる。具体的には、  A combination of a palladium complex having a σ or σ, π bond and an organoaluminum or super strong acid salt can be mentioned. In particular,
ジ一 ークロロ一ビス（6—メトキシビシクロ〔2. 2. 1〕ヘプトー 2 ェン一エンド一 5 σ , 2 π ) Pdと、メチルアルモキサン（「MAO」と略す）、 AgSbFおよび AgBFから選ば  Di-chloro-bibis (6-methoxybicyclo [2.2.1] hept-2-ene 1-end 5 σ, 2 π) Pd, methylalumoxane (abbreviated as “MAO”), AgSbF and AgBF
6 4 れた化合物との組み合わせ、〔（ 7? 3—ァリール） PdCl〕 と、 AgSbFまたは AgBFとの 6 (4) in combination with [(7? 3 — aryl) PdCl] and AgSbF or AgBF
2 6 4 組み合わせ、〔（シクロォクタ一 1, 5 ジェン） Pd (CH ) C1〕と PPhと NaB〔3, 5— (C  2 6 4 combination, [(Cycloocta 1, 5 Gen) Pd (CH) C1], PPh and NaB [3, 5— (C
3 3  3 3
F ) C H〕 との組み合わせなどが挙げられる。  F) and C H].
3 2 6 3 4  3 2 6 3 4
[0054] (a— 3)多成分触媒系（2)  [0054] (a-3) Multi-component catalyst system (2)
(I)ニッケル化合物、コバルト化合物、チタニウム化合物およびジルコニウム化合物 から選ばれた遷移金属化合物と、（II)超強酸、ルイス酸およびイオン性ホウ素化合 物から選ばれた化合物と、 (III)有機アルミニウム化合物との 3成分力 なる組み合わ せが挙げられる。  (I) a transition metal compound selected from nickel compounds, cobalt compounds, titanium compounds and zirconium compounds; (II) a compound selected from super strong acids, Lewis acids and ionic boron compounds; and (III) organoaluminum compounds. And the combination of the three components.
[0055] (I)遷移金属化合物  [0055] (I) Transition metal compound
(I 1)ニッケルィ匕合物、コバルト化合物  (I 1) Nickel compound, cobalt compound
ニッケル化合物およびコバルトィ匕合物としては、ニッケルまたはコバルトの有機カル ボン酸塩、有機亜リン酸塩、有機リン酸塩、有機スルホン酸塩、 β—ジケトンィ匕合物 など力も選ばれたィ匕合物が挙げられ、より具体的には、たとえば、 2—ェチルへキサ ン酸ニッケル、ナフテン酸ニッケル、ナフテン酸コバルト、ォレイン酸ニッケル、ドデカ ン酸ニッケル、ドデカン酸コバルト、ネオデカン酸コバルト、ジブチル亜リン酸ニッケル 、ジブチルリン酸ニッケル、ジォクチルリン酸ニッケル、リン酸ジブチルエステルの-ッ ケル塩、ドデシルベンゼンスルホン酸ニッケル、 ρ トルエンスルホン酸ニッケル、ビス (ァセチルァセトナート）ニッケル、ビス（ェチルァセトアセテート）ニッケルなどが挙げ られる。  Nickel compounds and cobalt compounds include nickel or cobalt organic carbonates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds, etc. More specifically, for example, nickel 2-ethylhexanoate, nickel naphthenate, cobalt naphthenate, nickel oleate, nickel dodecanoate, cobalt dodecanoate, cobalt neodecanoate, dibutyl phosphorus Nickel phosphate, nickel dibutyl phosphate, nickel dioctyl phosphate, nickel salt of dibutyl phosphate, nickel dodecylbenzenesulfonate, rhodium nickel sulfonate, bis (acetylacetate) nickel, bis (ethylacetoacetate) ) Nickel.
[0056] 前記ニッケルの有機カルボン酸塩を六フッ化アンチモン酸、四フッ化ホウ素酸、トリ フロロ酢酸、六フッ化アセトンなどの超強酸で変性したィ匕合物なども挙げられる。  [0056] Examples thereof include compounds obtained by modifying the organic carboxylate of nickel with a super strong acid such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, and hexafluoroacetone.
[0057] また、ニッケルのジェンもしくはトリェン配位錯体、たとえば、ジクロロ（1, 5 シクロ ォクタジェン）ニッケル；〔（ 3 クロチル）（1, 5 シクロォクタジェン）ニッケル〕へキ サフロロホスフェート、およびそのテトラフロロボレート錯体、テトラキス〔3, 5—ビス（ト リフロロメチル）〕ボレート錯体；（1, 5, 9 シクロドデカトリェン）ニッケル；ビス（ノルボ ルナジェン）ニッケル；ビス（ 1 , 5 シクロォクタジェン）ニッケルなどのニッケル錯体な ども挙げられる。 [0057] Nickel gen or triene coordination complexes such as dichloro (1,5-cyclohexane [( 3 crotyl) (1,5 cyclooctagen) nickel] hexafluorophosphate, and its tetrafluoroborate complex, tetrakis [3,5-bis (trifluoromethyl)] borate complex; (1 , 5, 9 Cyclododecatriene) nickel; bis (norbornagen) nickel; nickel complexes such as bis (1, 5 cyclooctagen) nickel.
[0058] さらに、ニッケルまたはコバルトに Ρ、 Ν、 Οなどの原子を有する配位子が配位した錯 体、たとえば、ビス（トリフエ-ルホスフィン）ニッケルジクロライド、ビス（トリフエ-ルホス フィン）ニッケルジブロマイド、ビス（トリフエ-ルホスフィン）コバルトジブロマイド、ビス〔 トリ（2—メチルフエ-ル）ホスフィン〕ニッケルジクロライド、ビス〔トリ（4—メチルフエ- ル）ホスフィン〕ニッケルジクロライド、ビス〔Ν— (3— t—ブチルサリシリデン）フエ-ル アミネート〕ニッケル、 Ni [PhC (O) CH〕 (Ph)、 Ni (OC (C H ) PPh) (H) (PCy )、 N  [0058] Further, complexes in which ligands having atoms such as Ρ, Ν, and 配 are coordinated to nickel or cobalt, such as bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dichloride. Bromide, bis (triphenylphosphine) cobalt dibromide, bis [tri (2-methylphenol) phosphine] nickel dichloride, bis [tri (4-methylphenol) phosphine] nickel dichloride, bis [Ν- (3- t-butylsalicylidene) phenol aminate] nickel, Ni [PhC (O) CH] (Ph), Ni (OC (CH) PPh) (H) (PCy), N
6 4 3 i〔OC (0) (C H ) P〕 (H) (PPh )、ビス（1, 5 シクロォクタジェン）ニッケルと PhC (  6 4 3 i [OC (0) (C H) P] (H) (PPh), bis (1,5 cyclooctagen) nickel and PhC (
6 4 3  6 4 3
0) CH = PPhとの反応物、 [2, 6—（i—Pr) C H N = CHC H (O) (Anth) ] (Ph)  0) Reaction with CH = PPh, [2, 6— (i—Pr) C H N = CHC H (O) (Anth)] (Ph)
3 2 6 3 6 3  3 2 6 3 6 3
(PPh ) Niなどのニッケル錯体（ここで、 Anthは 9—アントラセ-ル、 Phはフエ-ル、 (PPh) Nickel complexes such as Ni (where Anth is 9-anthracel, Ph is phenol,
3 Three
Cyはシクロへキシルの略称である）が挙げられる。  Cy is an abbreviation for cyclohexyl).
[0059] (I 2)チタニウム、ジルコニウム化合物 [0059] (I 2) Titanium, zirconium compound
チタニウム、ジルコニウム化合物としては、〔t— BuNSiMe (Me Cp)〕TiCl、（Me  Titanium and zirconium compounds include [t-BunSiMe (Me Cp)] TiCl, (Me
4 2 4 4 2 4
Cp) (O-iPr C H ) TiCl、（Me Cp)TiCl、（Me Cp)Ti(OBu) 、 [t-BuNSiMe Cp) (O-iPr C H) TiCl, (Me Cp) TiCl, (Me Cp) Ti (OBu), [t-BuNSiMe
2 6 3 2 4 3 4 3 2 2 6 3 2 4 3 4 3 2
FlujTiMe、〔t— BuNSiMe FlujTiCl、 Et (lnd) ZrCl、 Ph C (Ind) (Cp) ZrCl FlujTiMe, [t— BuNSiMe FlujTiCl, Et (lnd) ZrCl, Ph C (Ind) (Cp) ZrCl
2 2 2 2 2 2 2 2 2 2 2 2 2 2
、 iPr (Cp) (Flu) ZrCl、 iPr (3—tert—But—Cp) (ind) ZrCl、 iPr (Cp) (ind) ZrCl , IPr (Cp) (Flu) ZrCl, iPr (3—tert—But—Cp) (ind) ZrCl, iPr (Cp) (ind) ZrCl
2 2  twenty two
、 Me Si (Ind) ZrCl、 Cp ZrCl、（Cpはシクロペンタジェ -ル、 Indはインデュル、 , Me Si (Ind) ZrCl, Cp ZrCl, (Cp is cyclopentagel, Ind is indur,
2 2 2 2 2 2 2 2 2 2 2 2
Fluはフルォレニルの略称である）などが挙げられる。  Flu is an abbreviation for fluorenyl).
[0060] (Π)超強酸、ルイス酸およびイオン性ホウ素化合物 [0060] (ii) Super strong acid, Lewis acid and ionic boron compound
超強酸としては、たとえば、へキサフロロアンチモン酸、へキサフロロリン酸、へキサ フロロ砒酸、トリフロロ酢酸、フロロ硫酸、トリフロロメタンスルホン酸、テトラフロロホウ酸 Examples of super strong acids include hexafluoroantimonic acid, hexafluorophosphoric acid, hexafluoroarsenic acid, trifluoroacetic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, and tetrafluoroboric acid.
、テトラキス（ペンタフロロフエ-ル）ホウ酸、テトラキス〔3, 5—ビス（トリフロロメチル）フ ェ -ル〕ホウ酸、 p—トルエンスルホン酸、ペンタフロロプロピオン酸などが挙げられる [0061] ルイス酸化合物としては、たとえば、三フッ化ホウ素とエーテル、ァミン、フエノール などとの錯体、三フッ化アルミニウムのエーテル、ァミン、フエノールなどの錯体、トリス (ペンタフロロフエ-ル）ボラン、トリス〔3, 5—ビス（トリフロロメチル）フエ-ル〕ボランな どのホウ素化合物；三塩化アルミニウム、三臭化アルミニウム、ェチルアルミニウムジ クロライド、ェチルアルミニウムセスキク口ライド、ジェチルアルミニウムフロライド、トリ（ ペンタフロロフエ-ル）アルミニウムなどのアルミニウム化合物；へキサフロロアセトン、 へキサクロ口アセトン、クロラエル、へキサフロロメチルェチルケトンなどのルイス酸性 を示す有機ハロゲン化合物；四塩化チタン、ペンタフロロアンチモンなどのルイス酸 性を示すィ匕合物などが挙げられる。 , Tetrakis (pentafluorophenol) boric acid, tetrakis [3,5-bis (trifluoromethyl) phenol] boric acid, p-toluenesulfonic acid, pentafluoropropionic acid, etc. [0061] Examples of Lewis acid compounds include complexes of boron trifluoride with ethers, amines, phenols, etc., aluminum trifluoride ethers, amines, phenols, etc. complexes, tris (pentafluorophenol) borane, Boron compounds such as tris [3,5-bis (trifluoromethyl) phenol] borane; aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, ethylaluminum sesquich mouthride, jetylaluminum fluoride , Aluminum compounds such as tri (pentafluorophenyl) aluminum; organic halogen compounds exhibiting Lewis acidity such as hexafluoroacetone, hexachloroacetone, chlorael, hexafluoromethylethyl ketone; titanium tetrachloride, pentafluoroル イ ス showing Lewis acidity such as antimony Things and the like.
[0062] イオン性ホウ素化合物としては、たとえば、トリフエ-ルカルベ-ゥムテトラキス（ペン タフルォロフエ-ル）ボレート、トリフエ-ルカルベ-ゥムテトラキス [3, 5—ビス（トリフ ルォロメチル）フエ-ル]ボレート、トリフエ-ルカルベ-ゥムテトラキス（2, 4, 6—トリフ ルォロフエ-ル）ボレート、トリフエ-ルカルベ-ゥムテトラフエ-ルポレート、トリブチノレ アンモ-ゥムテトラキス（ペンタフルォロフエ-ル）ボレート、 N, N—ジメチルァ-リュウ ムテトラキス（ペンタフルォロフエ-ル）ボレート、 N, N—ジェチルァ-リュウムテトラキ ス（ペンタフルォロフエ-ル）ボレート、 N, N—ジフエ-ルァユリ-ゥムテトラキス（ペン タフルォロフエ-ル）ボレートなどが挙げられる。  [0062] Examples of the ionic boron compound include triphenyl carbe tetrakis (pentafluorophenol) borate, triphenyl carbatetrakis [3,5-bis (trifluoromethyl) fehl] borate, triphenyl carbe Umtetrakis (2, 4, 6-trifluorofluoroborate), triphenylcarboltetraphorate, tributinole ammo-tetrakis (pentafluorophenol) borate, N, N-dimethyl-rumum tetrakis (pentafluoro) Rofe) borate, N, N-Jetyl-Ru tetrakis (pentafluorophenol) borate, N, N-Di-Fuylureum tetrakis (pentafluorophenol) borate and the like.
[0063] (III)有機アルミニウム化合物  [0063] (III) Organoaluminum compound
有機アルミニウム化合物としては、たとえば、メチルアルモキサン、ェチルアルモキ サン、ブチルアルモキサンなどのアルキルアルモキサン化合物；トリメチルアルミ-ゥ ム、トリェチルアルミニウム、トリイソブチルアルミニウム、ジイソブチルアルミニウムヒド リド、ジェチルアルミニウムクロライド、ジェチルアルミニウムフルオライド、ェチルアル ミニゥムセスキク口ライド、ェチルアルミニウムジクロライドなどのアルキルアルミニウム 化合物およびハロゲン化アルキルアルミニウム化合物；前記アルキルアルモキサン化 合物と前記アルキルアルミニウム化合物との混合物などが挙げられる。  Examples of the organoaluminum compound include alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, and butylalumoxane; trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, jetylaluminum chloride, Examples thereof include alkylaluminum compounds and halogenated alkylaluminum compounds such as tilaluminum fluoride, ethylaluminum sesquichloride, and ethylaluminum dichloride; a mixture of the alkylalumoxane compound and the alkylaluminum compound.
[0064] これら触媒成分は、たとえば、以下の範囲の使用量で用いられる。  [0064] These catalyst components are used, for example, in amounts used within the following ranges.
[0065] 遷移金属化合物は単量体 1モルに対して、 0. 02〜： LOOミリモル原子である。有機 アルミニウム化合物を併用する場合 (多成分系（1)および (2) )には、有機アルミ-ゥ ム化合物は遷移金属化合物の金属原子 1モルに対して 1〜5, 000モルである。さら に、超強酸、ルイス酸またはイオン性ホウ素化合物を併用する場合 (多成分系（2) ) には、これらの化合物は遷移金属化合物の金属原子 1モルに対して 0. 1〜： L00モル である。 [0065] The transition metal compound is 0.02 to: LOO mmol atom per 1 mol of the monomer. When using organoaluminum compounds (multicomponent systems (1) and (2)), The compound is 1 to 5,000 moles per mole of metal atoms of the transition metal compound. Furthermore, when a super strong acid, Lewis acid or ionic boron compound is used in combination (multi-component system (2)), these compounds are 0.1 to L00 mol per 1 mol of the metal atom of the transition metal compound. It is.
[0066] (b)重合溶媒 [0066] (b) Polymerization solvent
付加重合反応において用いられる溶媒としては、重合に供される単量体組成物や 触媒等が溶解してかつ触媒が失活することがなぐまた、生成した付加重合体が溶解 するものであれば特に限定されないが、たとえば、シクロへキサン、シクロペンタン、メ チルシクロペンタンなどの脂環式炭化水素溶媒;へキサン、ヘプタン、オクタンなどの 脂肪族炭化水素溶媒;トルエン、ベンゼン、キシレン、メシチレンなどの芳香族炭化水 素溶媒；ジクロロメタン、 1, 2—ジクロロエタン、 1, 1—ジクロロェタン、テトラクロ口エタ ン、クロ口ベンゼン、ジクロロベンゼンなどのハロゲン化炭化水素溶媒などを挙げるこ とができる。これらは単独で、または 2種以上を混合して用いることができる。  As the solvent used in the addition polymerization reaction, any monomer composition or catalyst to be used for the polymerization can be dissolved and the catalyst is not deactivated, and the produced addition polymer can be dissolved. Although not particularly limited, for example, alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; toluene, benzene, xylene, mesitylene, etc. Aromatic hydrocarbon solvents: Halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, black benzene, and dichlorobenzene. These can be used alone or in admixture of two or more.
[0067] (c)分子量調節剤  [0067] (c) Molecular weight regulator
本発明では、製造するノルボルネン系付加重合体の分子量の調節を、分子量調節 剤として重合系内に水素あるいは aーォレフインを添加することにより行うこともできる 。生成するノルボルネン系付加重合体の分子量は、添加する分子量調節剤が多い ほど低下する。  In the present invention, the molecular weight of the norbornene-based addition polymer to be produced can be adjusted by adding hydrogen or a-olefin to the polymerization system as a molecular weight regulator. The molecular weight of the resulting norbornene-based addition polymer decreases as the molecular weight regulator added increases.
[0068] (水素添加反応）  [0068] (Hydrogenation reaction)
前記開環重合反応により得られる重合体は、その分子中にォレフィン性不飽和結 合を有している。また、前記付加重合反応においても、重合体がその分子中にォレフ イン性不飽和結合を有する場合がある。重合体分子中に存在するォレフイン性不飽 和結合は経時着色ゃゲルイ匕等の劣化の原因となる場合があるので、このォレフィン 性不飽和結合を飽和結合に変換する水素添加反応を行うことが好ましい。  The polymer obtained by the ring-opening polymerization reaction has an olefinic unsaturated bond in the molecule. In the addition polymerization reaction, the polymer may have an olefinic unsaturated bond in the molecule. Since the olefinic unsaturated bond present in the polymer molecule may cause deterioration of gelling and the like over time, it is necessary to carry out a hydrogenation reaction to convert this olefinically unsaturated bond into a saturated bond. preferable.
[0069] 水素添加反応は、通常の方法、すなわちォレフィン性不飽和結合を含有する重合 体の溶液に公知の水素添加触媒を添加し、これに常圧〜 300気圧、好ましくは 3〜2 00気圧の水素ガスを 0〜200°C、好ましくは 20〜180°Cで作用させることによって行 うことができる。 [0070] 水素添カ卩重合体の水素添カ卩率は、 500MHz、 ^— NMRで測定した値で通常 50 %以上、好ましく 70%以上、より好ましくは 90%以上、特に好ましくは 98%以上、最 も好ましくは 99%以上である。水素添加率が高いほど、水素添加重合体は熱や光に 対する安定性が優れており、成形体として使用した場合に長期にわたって安定した 特性を得ることができるため好まし 、。 [0069] The hydrogenation reaction is carried out by a conventional method, that is, a known hydrogenation catalyst is added to a solution of a polymer containing an olefinic unsaturated bond, and normal pressure to 300 atm, preferably 3 to 200 atm. The hydrogen gas can be reacted at 0 to 200 ° C, preferably 20 to 180 ° C. [0070] The hydrogenation rate of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more, as measured by 500 MHz, ^ -NMR. Most preferably, it is 99% or more. The higher the hydrogenation rate, the more preferable the hydrogenated polymer is because of its excellent stability to heat and light, and when it is used as a molded product, it can obtain stable characteristics over a long period of time.
[0071] 前記方法で得られた重合体がその分子内に芳香族基を有する場合、この芳香族 基は経時着色やゲル化等劣化の原因とはならず、むしろ、機械的特性や光学的特 性において有利な作用を及ぼすこともあるため、このような芳香族基については必ず しも水素添加する必要はな 、。  [0071] When the polymer obtained by the above method has an aromatic group in the molecule, the aromatic group does not cause deterioration such as coloring over time or gelation, but rather, mechanical properties and optical properties. Since it may have an advantageous effect on properties, it is not necessary to hydrogenate such aromatic groups.
[0072] 水素添加触媒としては、通常のォレフィン性ィ匕合物の水素添加反応に用いられるも のを使用することができる。この水素添加触媒としては、不均一系触媒および均一系 触媒が挙げられる。  [0072] As the hydrogenation catalyst, those used in the usual hydrogenation reaction of olefinic compounds can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.
[0073] 不均一系触媒としては、ノ《ラジウム、白金、ニッケル、ロジウム、ルテニウムなどの貴 金属触媒物質を、カーボン、シリカ、アルミナ、チタ-ァなどの担体に担持させた固体 触媒を挙げることができる。均一系触媒としては、ナフテン酸ニッケル Zトリェチルァ ルミ-ゥム、ニッケルァセチルァセトナート zトリェチルアルミニウム、オタテン酸コバ ルト Zn—ブチルリチウム、チタノセンジクロリド Zジェチルアルミニウムモノクロリド、酢 酸ロジウム、クロロトリス（トリフエ-ルホスフィン）ロジウム、ジクロロトリス（トリフエ-ルホ スフイン）ルテニウム、クロロヒドロカルボニルトリス（トリフエ-ルホスフィン）ルテニウム、 ジクロロカルボ-ルトリス（トリフエ-ルホスフィン)ルテニウムなどを挙げることができる [0073] Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as radium, platinum, nickel, rhodium, or ruthenium is supported on a carrier such as carbon, silica, alumina, or titanium. Can do. Homogeneous catalysts include nickel naphthenate, Z triethyl chloride, nickel acetyl acetate, z triethyl aluminum, oxalate cobalt, Zn-butyl lithium, titanocene dichloride, Z jetyl aluminum monochloride, rhodium acetate, chlorotris (Triphenylphosphine) rhodium, dichlorotris (trifluorophosphine) ruthenium, chlorohydrocarbonyltris (trifluorophosphine) ruthenium, dichlorocarbo-trithris (triphenylphosphine) ruthenium
。これらの触媒は、粉末でも粒状でもよい。 . These catalysts may be powder or granular.
[0074] これらの水素添加触媒は、通常、開環重合体と水素添加触媒との重量比（開環重 合体:水素添加触媒)が、 1： 1 X 10— 6〜1： 2となる割合で使用される。 [0074] These hydrogenation catalysts are usually the weight ratio of ring-opened polymer and the hydrogenation catalyst (ring-opening polymer: hydrogenation catalyst) is, 1: 1 X 10- 6 ~1 : 2 become ratio Used in.
[0075] (ノルボルネン系榭脂の特性） [0075] (Characteristics of norbornene-based resin)
本発明に用いられるノルボルネン系榭脂は、 30°Cのクロ口ホルム中における固有 粘度〔 7?〕 が好ましくは 0. 2〜2. Odl/g,さらに好ましくは 0. 35〜： L Odl/g,特に  The norbornene-based resin used in the present invention has an intrinsic viscosity [7?] In a black mouth form of 30 ° C, preferably 0.2-2. Odl / g, more preferably 0.35-: L Odl / g, especially
inh  inh
好ましくは 0. 4〜0. 85dlZgであり、ゲルパーミエーシヨンクロマトグラフィーで測定し たポリスチレン換算の数平均分子量 (Mn)力好ましくは 5000〜100万、さらに好まし くは 1万〜 50万、特に好ましくは 1. 5万〜 25万であり、重量平均分子量 (Mw)が 1万 〜200万、さらに好ましくは 2万〜 100万、特に好ましくは 3万〜 50万であることが望 ましい。固有粘度〔 r?〕 、数平均分子量および重量平均分子量が上記範囲にあると The number average molecular weight (Mn) force in terms of polystyrene measured by gel permeation chromatography is preferably 5,000 to 1,000,000, more preferably 0.4 to 0.85 dlZg. 10,000 to 500,000, particularly preferably 150,000 to 250,000, and a weight average molecular weight (Mw) of 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, particularly preferably 30,000 to 50 It is desirable that When the intrinsic viscosity [r?], Number average molecular weight, and weight average molecular weight are in the above ranges,
uih  uih
、ノルボルネン系榭脂は機械的強度に優れ、破損しにくいノルボルネン系榭脂製基 板 (フィルム）が得られる。  Norbornene-based resin has excellent mechanical strength, and a norbornene-based resin-made substrate (film) that is not easily damaged can be obtained.
[0076] また、前記ノルボルネン系榭脂のガラス転移温度 (Tg)は、通常 120°C以上、好まし くは 130°C以上、さらに好ましくは 150°C以上である。 Tgが上記範囲内にあると、誘 電体多層膜の基材への密着強度が向上し、さらに耐ノ、ンダリフロー性に優れたノル ボルネン系榭脂製基板 (フィルム）が得られる。  [0076] Further, the glass transition temperature (Tg) of the norbornene-based resin is usually 120 ° C or higher, preferably 130 ° C or higher, more preferably 150 ° C or higher. When the Tg is within the above range, the adhesion strength of the dielectric multilayer film to the base material is improved, and a norbornene-based resin substrate (film) having excellent anti-nodal and reflow properties can be obtained.
[0077] また、前記ノルボルネン系榭脂の飽和吸水率は、通常 1重量％以下、好ましくは 0.  [0077] Further, the saturated water absorption of the norbornene-based rosin is usually 1% by weight or less, preferably 0.
1〜0. 8重量％である。飽和吸水率が上記範囲にあると、この榭脂から得られた榭脂 基板 (フィルム）は、経時的に吸水 (湿)変形しにくぐ耐久性に優れ、さらに接着性に も優れている。また、飽和吸水率が上記範囲内にあることにより、特に固体撮像素子 収納用パッケージの透光性蓋体に用いた場合には、撮像素子の水分による劣化を 防止できる。なお、前記飽和吸水率は ASTM D570に従い、 23°Cの水中で 1週間 浸漬して増加重量を測定することにより得られる値である。  1 to 0.8% by weight. When the saturated water absorption is in the above range, the resin substrate (film) obtained from this resin has excellent durability against water absorption (wet) deformation over time and also excellent adhesion. In addition, when the saturated water absorption is within the above range, deterioration of the image sensor due to moisture can be prevented particularly when used for the light-transmitting lid of the package for housing the solid-state image sensor. The saturated water absorption is a value obtained by immersing in water at 23 ° C for 1 week and measuring the increased weight according to ASTM D570.
[0078] (その他成分）  [0078] (Other ingredients)
本発明においては、本発明の効果を損なわない範囲において、ノルボルネン系榭 脂にさらに、酸化防止剤、紫外線吸収剤等の添加剤を添加することができる。  In the present invention, additives such as an antioxidant and an ultraviolet absorber can be further added to the norbornene-based resin within a range not impairing the effects of the present invention.
[0079] 酸化防止剤としては、たとえば、 2, 6 ジ—tーブチルー 4 メチルフエノール、 2, 2'—ジォキシー 3, 3'—ジー tーブチルー 5, 5 '—ジメチルジフエニルメタン、テトラキ ス [メチレン一 3— (3, 5—ジ一 t—ブチル 4—ヒドロキシフエ-ル）プロピオネート]メ タンなどが挙げられる。  [0079] Antioxidants include, for example, 2,6 di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, tetrax [methylene 1- (3,5-di-tert-butyl 4-hydroxyphenol) propionate] methane.
[0080] 紫外線吸収剤としては、たとえば、 2, 4ージヒドロキシベンゾフエノン、 2 ヒドロキシ [0080] Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone and 2-hydroxy
4ーメトキシベンゾフエノンなどが挙げられる。また、後述する溶液キャスティング法 によりノルボルネン系榭脂製基板 (フィルム）を製造する場合には、レべリング剤や消 泡剤を添加することで榭脂基板 (榭脂フィルム）の製造を容易にすることができる。  4-methoxybenzophenone and the like can be mentioned. In addition, when a norbornene-based resinous resin substrate (film) is manufactured by the solution casting method described later, the production of a resinous resin substrate (resin film) can be facilitated by adding a leveling agent or an antifoaming agent. can do.
[0081] これら添加剤は、本発明に用いられるノルボルネン系榭脂製基板 (フィルム)を製造 する際に、ノルボルネン系榭脂などとともに混合してもよいし、ノルボルネン系榭脂を 製造する際に添加することにより予め配合してもよい。また、添加量は、所望の特性 に応じて適宜選択されるが、ノルボルネン系榭脂 100重量部に対して、通常 0. 01〜 5. 0重量部、好ましくは 0. 05-2. 0重量部であることが望ましい。 [0081] These additives produce norbornene-based resinous resin substrates (films) used in the present invention. In this case, it may be mixed with norbornene-based resin or the like, or may be pre-mixed by adding it when producing norbornene-based resin. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05-2.0 parts by weight with respect to 100 parts by weight of norbornene-based resin. Part is desirable.
[0082] (ノルボルネン系榭脂フィルムの製造方法）  [0082] (Method for producing norbornene-based resin film)
本発明に用いられるノルボルネン系榭脂フィルムは、前記ノルボルネン系榭脂を直 接溶融成形することにより、あるいは溶媒に溶解してキャスティング (キャスト成形)す ること〖こより好適に成形することができる。  The norbornene-based resin film used in the present invention can be more suitably formed by directly melt-molding the norbornene-based resin or by dissolving in a solvent and casting (casting).
[0083] (A)溶融成形  [0083] (A) Melt molding
本発明に用いられるノルボルネン系榭脂フィルムは、前記ノルボルネン系榭脂、ま たは前記ノルボルネン系榭脂と前記添加剤とを含有する榭脂組成物を溶融成形する ことにより製造することができる。溶融成形方法としては、たとえば、射出成形、溶融 押出成形あるいはブロー成形などを挙げることができる。  The norbornene-based resin film used in the present invention can be produced by melt-molding the norbornene-based resin or the resin composition containing the norbornene-based resin and the additive. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.
[0084] (B)キャスティング  [0084] (B) Casting
本発明に用いられるノルボルネン系榭脂フィルムは、前記ノルボルネン系榭脂およ び必要に応じて前記添加剤を溶媒に溶解した液状榭脂組成物を適切な基材の上に キャスティングして溶剤を除去することにより製造することもできる。たとえば、スチー ルベルト、スチールドラムあるいはポリエステルフィルム等の基材の上に、上記液状榭 脂組成物を塗布して溶剤を乾燥させ、その後、基材から塗膜を剥離することにより、ノ ルボルネン系榭脂フィルムを得ることができる。  The norbornene-based resin film used in the present invention is prepared by casting a liquid resin composition in which the norbornene-based resin and, if necessary, the additive are dissolved in a solvent, onto a suitable base material. It can also be manufactured by removing. For example, the liquid resin composition is applied onto a substrate such as a steel belt, a steel drum, or a polyester film, the solvent is dried, and then the coating film is peeled off from the substrate. A fat film can be obtained.
[0085] 前記方法で得られたノルボルネン系榭脂フィルム中の残留溶剤量は可能な限り少 ない方が好ましぐ通常 3重量％以下、好ましくは 1重量％以下、さらに好ましくは 0. 5重量％以下である。残留溶剤量が上記範囲にあると、フィルムの経時的な変形や 特性変化が起こりにくぐ所望の機能を有するノルボルネン系榭脂フィルムを得ること ができる。  [0085] The amount of residual solvent in the norbornene-based resin film obtained by the above method is preferably as small as possible, usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight. % Or less. When the residual solvent amount is in the above range, a norbornene-based resin film having a desired function that hardly deforms or changes in properties with time can be obtained.
[0086] 本発明で用いられるノルボルネン系榭脂フィルムの厚さは、特に限定されないが、 通常 5〜500 μ m、好ましくは 10〜150 μ m、さらに好ましくは 20〜： LOO μ mであるこ とが望ましい。フィルムの厚さが上記範囲にあると、十分な強度のフィルムが得られ、 また、複屈折性、透明性、外観性が良好なフィルムを得ることができる。 [0086] The thickness of the norbornene-based resin film used in the present invention is not particularly limited, but is usually 5 to 500 µm, preferably 10 to 150 µm, more preferably 20 to: LOO µm. Is desirable. If the film thickness is in the above range, a film with sufficient strength can be obtained, In addition, a film having good birefringence, transparency, and appearance can be obtained.
[0087] 本発明で用いられるノルボルネン系榭脂フィルムは、光透過性が通常 80%以上、 好ましくは 85%以上、より好ましくは 90%以上であるのが望ましい。  [0087] The norbornene-based resin film used in the present invention desirably has a light transmittance of usually 80% or more, preferably 85% or more, more preferably 90% or more.
[0088] また、本発明で用いられるノルボルネン系榭脂フィルムは、後述する接着剤層との 接着性を高める目的で表面処理を施したものであってもよい。当該表面処理としては 、プライマー処理、プラズマ処理、コロナ処理、アルカリ処理、コーティング処理等が 挙げられる。  [0088] In addition, the norbornene-based resin film used in the present invention may be subjected to a surface treatment for the purpose of improving the adhesiveness to the adhesive layer described later. Examples of the surface treatment include primer treatment, plasma treatment, corona treatment, alkali treatment, and coating treatment.
[0089] 上記表面処理のうち、とりわけコロナ処理を用いることにより、ノルボルネン系榭脂フ イルムと接着剤層を強固に密着することができる。この場合のコロナ処理条件としては 、コロナ放電電子の照射量が l〜1000WZm2Zminが好ましぐ 10~100W/m2 /minがより好ましぐ 70〜： LOOWZm2/minが最も好ましい。照射量が上記範囲に あると、フィルムの内部にまで処理効果が及ばず、フィルムを変質させずに十分な表 面改質効果が得られる。また、このコロナ処理は接着剤層と当接する面のみならず、 その反対側の面に施してもよい。また、コロナ処理をする際の雰囲気は特に制限はな いが、たとえば、空気雰囲気下や窒素雰囲気下、酸素雰囲気下、あるいはアルゴン 雰囲気下等でのコロナ処理が挙げられ、表面処理効果と操作性から空気雰囲気下 でコロナ処理することが好まし 、。 [0089] Among the above surface treatments, the norbornene-based resin film and the adhesive layer can be firmly adhered by using corona treatment in particular. The corona treatment conditions in this case, the irradiation amount of the corona discharge electrons l~1000WZm 2 Zmin is preferably fixture 10 ~ 100W / m 2 / min, more preferably tool 70~: LOOWZm 2 / min is most preferred. When the irradiation amount is in the above range, the treatment effect does not reach the inside of the film, and a sufficient surface modification effect can be obtained without altering the film. Further, this corona treatment may be performed not only on the surface in contact with the adhesive layer but also on the opposite surface. The atmosphere during corona treatment is not particularly limited, and examples include corona treatment under an air atmosphere, nitrogen atmosphere, oxygen atmosphere, or argon atmosphere, and the effect of surface treatment and operability. It is preferable to perform corona treatment in an air atmosphere.
[0090] 上記表面処理の効果は、純水接触角を指標として表すことができ、純水接触角の 値が 50〜70degであることが好ましぐより好ましくは 40〜50degである。  [0090] The effect of the surface treatment can be expressed using the pure water contact angle as an index, and the pure water contact angle is preferably 50 to 70 deg, more preferably 40 to 50 deg.
[0091] <位相差フィルムの製造方法 >  [0091] <Method for producing retardation film>
本発明で用いられるノルボルネン系榭脂フィルムは、延伸処理を施すことにより位 相差フィルムとして使用することができる。  The norbornene-based resin film used in the present invention can be used as a phase difference film by performing a stretching treatment.
[0092] 延伸処理の方法としては、榭脂フィルムを一軸延伸または二軸延伸する方法が用 いられる。  [0092] As the stretching method, a method of uniaxially stretching or biaxially stretching the resin film is used.
[0093] 一軸延伸処理の場合、延伸速度は、通常 1〜5, 000%Z分であり、好ましくは 50 〜1, 000%Z分であり、より好ましくは 100〜1, 000%Z分である。  [0093] In the case of the uniaxial stretching treatment, the stretching speed is usually 1 to 5,000% Z minutes, preferably 50 to 1,000% Z minutes, more preferably 100 to 1,000% Z minutes. is there.
[0094] 二軸延伸処理の場合には、同時に二方向に延伸処理を行う方法、一軸延伸処理 した後にこの延伸処理した方向と異なる方向に延伸処理する方法を適用することが できる。このとき、 2つの延伸軸の交わり角度は、目的とする光学フィルム (位相差フィ ルム）に要求される特性に応じて適宜決定され、特に限定されないが、通常、 60〜1 20度の範囲である。また、延伸速度は、通常 1〜5, 000%Z分であり、好ましくは 50 〜1, 000%Z分であり、さらに好ましくは 100〜1, 000%Z分であり、特に好ましく は 100〜500%Z分であり、各延伸方向で同じであってもよぐ異なっていてもよい。 [0094] In the case of biaxial stretching, a method of performing stretching in two directions at the same time, or a method of performing stretching in a direction different from the direction of stretching after uniaxial stretching has been applied. it can. At this time, the intersecting angle of the two stretching axes is appropriately determined according to the properties required for the target optical film (retardation film), and is not particularly limited, but is usually in the range of 60 to 120 degrees. is there. The stretching speed is usually 1 to 5,000% Z minutes, preferably 50 to 1,000% Z minutes, more preferably 100 to 1,000% Z minutes, and particularly preferably 100 to 1,000% Z minutes. It is 500% Z and may be the same or different in each stretching direction.
[0095] 延伸処理温度は、特に限定されるものではな 、が、用いるノルボルネン系榭脂のガ ラス転移温度 (Tg)を基準として、 Tg± 30°C、好ましくは Tg± 15°C、さらに好ましく は Tg— 5〜Tg+ 15°Cの範囲である。延伸処理温度を上記範囲内に設定することに より、得られる延伸フィルムに位相差ムラが発生することを抑制することができ、また、 屈折率楕円体の制御が容易となる点で好ましい。  [0095] The stretching temperature is not particularly limited, but Tg ± 30 ° C, preferably Tg ± 15 ° C, based on the glass transition temperature (Tg) of the norbornene-based resin used. Preferably, it is in the range of Tg−5 to Tg + 15 ° C. By setting the stretching treatment temperature within the above range, it is possible to suppress the occurrence of uneven retardation in the obtained stretched film, and it is preferable in that the refractive index ellipsoid can be easily controlled.
[0096] 延伸倍率は、目的とする光学フィルムに要求される特性に応じて適宜決定され、特 に限定されないが、通常は 1. 01〜10倍、好ましくは 1. 03〜5倍、さらに好ましくは 1 . 03〜3倍である。延伸倍率が上記範囲にあると、得られる延伸フィルムの位相差を 容易に制御することができる。延伸処理されたフィルムは、そのまま冷却してもよいが 、 Tg— 20°C〜Tgの温度雰囲気下に少なくとも 10秒間以上、好ましくは 30秒間〜 6 0分間、さらに好ましくは 1〜60分間保持した後に冷却することが好ましい。これによ り、透過光の位相差の経時変化が少なくて安定した位相差フィルムが得られる。  [0096] The draw ratio is appropriately determined according to the properties required for the target optical film and is not particularly limited, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, and more preferably. Is 1.03 to 3 times. When the draw ratio is in the above range, the retardation of the obtained stretched film can be easily controlled. The stretched film may be cooled as it is, but it is kept at a temperature atmosphere of Tg—20 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 to 60 minutes. It is preferable to cool later. Thus, a stable retardation film can be obtained with little change over time in the retardation of transmitted light.
[0097] 上記のようにして延伸処理が施されたフィルムは、延伸処理により分子が配向した 結果、透過光に位相差を付与することができるが、この位相差は、延伸倍率、延伸温 度あるいはフィルムの厚さなどにより制御することができる。  [0097] The film subjected to the stretching treatment as described above can give a retardation to transmitted light as a result of the orientation of the molecules by the stretching treatment. This retardation is determined by the stretching ratio and the stretching temperature. Alternatively, it can be controlled by the thickness of the film.
[0098] 位相差フィルムとして用いられるノルボルネン系榭脂フィルムの厚さは、特に限定す るものではないが、通常5〜500 111、好ましくは10〜150 111、さらに好ましくは 20 〜 100 mであることが望ましい。  [0098] The thickness of the norbornene-based resin film used as the retardation film is not particularly limited, but is usually 5 to 500 111, preferably 10 to 150 111, and more preferably 20 to 100 m. It is desirable.
[0099] <接着剤層 >  [0099] <Adhesive layer>
本発明では、ポリウレタン系榭脂およびポリビュルアルコール系榭脂の混合物を、 好ましくは水に分散させて接着剤を調製し、これを、たとえば塗布、乾燥して接着剤 層を形成する。  In the present invention, an adhesive is prepared by dispersing a mixture of polyurethane-based resin and polybulal alcohol-based resin, preferably in water, and applying, drying, for example, to form an adhesive layer.
[0100] (ポリウレタン系榭脂） 本発明では、上記ポリウレタン系榭脂として、末端にイソシァネート基を有する化合 物からなる一液型と、末端にヒドロキシ基を有する主剤とイソシァネート基を有する硬 ィ匕剤とからなる二液型のいずれのポリウレタン系榭脂を使用してもよい。 [0100] (Polyurethane resin) In the present invention, as the polyurethane-based resin, any one of a one-component type composed of a compound having an isocyanate group at the terminal and a two-component type composed of a main agent having a hydroxyl group at the terminal and a hardener having an isocyanate group is used. A polyurethane-based resin may be used.
[0101] 上記一液型ポリウレタン系榭脂は、たとえば、ポリオ一ルイ匕合物とポリイソシァネート 化合物とを反応させることによって得ることができる。また、上記二液型ポリウレタン系 榭脂の主剤としてはポリオ一ルイ匕合物が挙げられ、硬化剤としてはポリイソシァネート 化合物が挙げられる。  [0101] The one-component polyurethane-based resin can be obtained, for example, by reacting a polyol-one compound with a polyisocyanate compound. In addition, the main component of the two-component polyurethane resin includes a polyol compound, and the curing agent includes a polyisocyanate compound.
[0102] 本発明に用いられるポリウレタン系榭脂を安定的に有機溶剤および Zまたは水に 溶解または分散させ、さらに接着剤の塗工性、および基材と接着剤層との接着性を 向上させるために、上記ポリオ一ルイ匕合物およびポリイソシァネートイ匕合物にカ卩えて 、親水基含有化合物を添加することも好ましい。  [0102] The polyurethane-based resin used in the present invention is stably dissolved or dispersed in an organic solvent and Z or water, and further improves the coating property of the adhesive and the adhesiveness between the substrate and the adhesive layer. For this reason, it is also preferable to add a hydrophilic group-containing compound in addition to the above-described polyo-alkyl compound and polyisocyanate compound.
[0103] (ポリオール化合物）  [0103] (Polyol compound)
ポリオ一ルイ匕合物としては、得られる接着剤が十分な接着性を発現すると!/ヽぅ観点 から、ポリエーテルポリオールが特に好ましく用いられる。  A polyether polyol is particularly preferably used as the polio Louis compound from the viewpoint of sufficient adhesiveness when the obtained adhesive exhibits sufficient adhesiveness.
[0104] ポリエーテルポリオールとしては、たとえば、ポリエチレングリコール、ポリプロピレン グリコール、ポリテトラメチレングリコール、ポリへキサメチレングリコール、ポリヘプタメ チレングリコール、ポリデカメチレングリコールなどのポリ（アルキレングリコール）；2種 以上のイオン重合性環状ィ匕合物を開環共重合させて得られるポリエーテルポリオ一 ル;イオン重合性環状化合物と、エチレンィミン等の環状イミン類、 β プロピオラクト ン、グリコール酸ラクチド等の環状ラタトン酸またはジメチルシクロポリシロキサン類と を開環共重合させたポリエーテルポリオール；多価アルコールに 1種または 2種以上 のイオン重合性環状ィ匕合物を開環付加重合させて得られるポリエーテルポリオール などが挙げられる。これらのイオン重合性環状ィ匕合物はランダムに開環 (共)重合さ れて 、てもよ 、し、ブロック状に開環（共)重合されて!、てもよ!/、。  [0104] Examples of polyether polyols include poly (alkylene glycols) such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol; two or more types of ion polymerization Polyether polyols obtained by ring-opening copolymerization of functional cyclic compounds; ion-polymerizable cyclic compounds, cyclic imines such as ethyleneimine, cyclic ratatonic acids such as β-propiolactone and glycolic acid lactide, or dimethylcyclohexane Polyether polyols obtained by ring-opening copolymerization with polysiloxanes; polyether polyols obtained by ring-opening addition polymerization of one or more ion-polymerizable cyclic compounds to polyhydric alcohols, etc. . These ion-polymerizable cyclic compounds may be randomly ring-opened (co) polymerized, or may be ring-opened (co-) polymerized in a block form!
[0105] 上記イオン重合性環状化合物としては、たとえば、エチレンォキシド、プロピレンォ キシド、 1, 2 ブチレンォキシド、ブテン— 1ーォキシド、イソブテンォキシド、 3, 3— ビスクロロメチルォキセタン、テトラヒドロフラン、 2—メチルテトラヒドロフラン、 3—メチ ルテトラヒドロフラン、ジォキサン、トリオキサン、テトラオキサン、シクロへキセンォキシ ド、スチレンォキシド、ェピクロルヒドリン、グリシジルメタタリレート、ァリルグリシジルェ 一テル、ァリルグリシジルカーボネート、ブタジエンモノォキシド、イソプレンモノォキ シド、ビュルォキセタン、ビュルテトラヒドロフラン、ビュルシクロへキセンォキシド、フ ェニルダリシジルエーテル、ブチルダリシジルエーテル、安息香酸グリシジルエステ ル等の環状エーテル類が挙げられる。 Examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, 1,2 butylene oxide, butene-1-oxide, isobuteneoxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2 —Methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexeneoxy , Styrene oxide, epichlorohydrin, glycidyl metatalylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, buroxetane, butyltetrahydrofuran, burcyclohexenoxide, phenyl And cyclic ethers such as sidyl ether, butyl daricidyl ether, and glycidyl ester benzoate.
[0106] 上記多価アルコールとしては、エチレングリコール、プロピレングリコール、グリセリン 、トリメチロールプロパン、ペンタエリスリトール、ビスフエノーノレ A、ビスフエノール F、 水添ビスフエノール A、水添ビスフエノール F、ハイドロキノン、ナフトハイドロキノン、ァ ントラハイドロキノン、 1, 4ーシクロへキサンジオール、トリシクロデカンジオール、トリ シクロデカンジメタノール、ペンタシクロペンタデカンジオール、ペンタシクロペンタデ カンジメタノール等が挙げられる。これらは単独でまたは 2種以上を組み合わせて用 いることがでさる。  [0106] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, bisphenolanol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, hydroquinone, naphthohydroquinone, alcohol Intrahydroquinone, 1,4-cyclohexanediol, tricyclodecanediol, tricyclodecane dimethanol, pentacyclopentadecanediol, pentacyclopentadecane dimethanol and the like can be mentioned. These can be used alone or in combination of two or more.
[0107] 上記ポリエーテルポリオールのうち、ポリテトラメチレングリコール、ポリへキサメチレ ングリコールが好ましぐポリテトラメチレングリコールが特に好ましい。  [0107] Of the above polyether polyols, polytetramethylene glycol is preferred, with polytetramethylene glycol and polyhexamethylene glycol being preferred.
[0108] (ポリイソシァネートイ匕合物）  [0108] (Polyisocyanate compound)
ポリイソシァネートイ匕合物としては、通常ポリウレタン榭脂の製造に用いられるポリイ ソシァネートを特に制限なく使用できる。たとえば、 2, 4 トリレンジイソシァネート、 2 , 6 トリレンジイソシァネート、 1, 3 キシリレンジイソシァネート、 1, 4 キシリレンジ イソシァネート、 1, 5 ナフタレンジイソシァネート、 m フエ二レンジイソシァネート、 p—フエ-レンジイソシァネート、 3, 3，ージメチノレー 4, 4，ージフエ-ルメタンジィソシ ァネート、 4, 4'ージフエ-ルメタンジイソシァネート、 3, 3，ージメチルフエ-レンジィ ソシァネート、 4, 4，ービフエ-レンジイソシァネート、 1, 6 へキサンジイソシァネー ト、イソホロンジイソシァネート、メチレンビス（4 シクロへキシノレイソシァネート）、 2, 2 , 4 トリメチルへキサメチレンジイソシァネート、ビス（2—イソシァネートェチル）フマ レート、 6—イソプロピル一 1, 3 フエ-ルジイソシァネート、 4 ジフエ-ルプロパン ジイソシァネート、リジンジイソシァネート、水添ジフエニルメタンジイソシァネート、水 添キシリレンジイソシァネート、テトラメチルキシリレンジイソシァネート、 2, 5 (または 6 )—ビス (イソシァネートメチル）ービシクロ [2. 2. 1]ヘプタン等が挙げられる。これら のポリイソシァネートイ匕合物は、単独であるいは 2種類以上を組み合わせて用いるこ とができる。これらのポリイソシァネートイ匕合物のうち、偏光板の透明性を損なわない という観点力 脂環構造を有し芳香環を有さないイソシァネートイ匕合物が好ましぐィ ソホロンジイソシァネートおよびメチレンビス（4ーシクロへキシルイソシァネート）が特 に好ましい。 As the polyisocyanate compound, a polyisocyanate usually used for producing a polyurethane resin can be used without any particular limitation. For example, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4 xylylene diisocyanate, 1,5 naphthalene diisocyanate, m Naphthalate, p-phenolic diisocyanate, 3, 3, -dimethylolene 4, 4, di-dimethanemethane diisocyanate, 4,4'-dimethanemethane diisocyanate, 3, 3, -dimethylphenolic diisocyanate, 4, 4 , -Biphenol-diisocyanate, 1,6 hexane diisocyanate, isophorone diisocyanate, methylene bis (4 cyclohexenoyl isocyanate), 2, 2, 4 trimethylhexamethylene diisocyanate Bis (2-isocyanateethyl) fumarate, 6-isopropyl-1,3-diisocyanate, 4 diphenylpro Diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2, 5 (or 6) -bis (isocyanate methyl) -Bicyclo [2.2.1] heptane and the like. these These polyisocyanate compounds can be used alone or in combination of two or more. Of these polyisocyanate compounds, the viewpoint of not impairing the transparency of the polarizing plate. Isocyanate compounds having an alicyclic structure and no aromatic ring are preferred. Sophorone diisocyanate And methylenebis (4-cyclohexylisocyanate) is particularly preferred.
[0109] (親水基含有化合物）  [0109] (Hydrophilic group-containing compound)
上記親水基含有ィ匕合物としては、分子中に少なくとも 1個以上の活性水素原子を 有し、かつカルボン酸基、スルホン酸基力 なる群力 選ばれる少なくとも 1個以上の 官能基を含有するイオン性化合物が挙げられる。  The hydrophilic group-containing compound has at least one active hydrogen atom in the molecule, and at least one functional group selected from a group force consisting of a carboxylic acid group and a sulfonic acid group. An ionic compound is mentioned.
[0110] このような親水性基含有ィ匕合物としては、たとえば、 2 ォキシエタンスルホン酸、フ エノールスルホン酸、スルホ安息香酸、スルホ琥珀酸、 5—スルホイソフタル酸、スル ファ-ル酸、 1, 3 フエ-レンジァミン一 4, 6 ジスルホン酸、 2, 4 ジアミノトルェ ン 5—スルホン酸等のスルホン酸ィ匕合物およびこれらの誘導体、ならびに (メタ）ァ クリル酸、ポリ（メタ）アクリル酸、 2, 2—ジメチロールプロピオン酸、 2, 2—ジメチロー ル酪酸、 2, 2 ジメチロール吉草酸、ジォキシマレイン酸、 2, 6 ジォキシ安息香酸 、 3, 4ージァミノ安息香酸等のカルボン酸含有化合物およびこれらの誘導体が挙げ られる。  [0110] Such hydrophilic group-containing compounds include, for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, and sulfolic acid. 1,3 phenylenediamine 4,6 disulfonic acid, 2,4 diaminotoluene 5-sulfonic acid compounds such as 5-sulfonic acid and their derivatives, and (meth) acrylic acid, poly (meth) acrylic acid 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2 dimethylolvaleric acid, dioxymaleic acid, 2,6 dioxybenzoic acid, 3,4-diaminobenzoic acid and other carboxylic acid-containing compounds and their Derivatives.
[0111] 本発明に用いられるポリウレタン系榭脂は、上記ポリオ一ルイ匕合物とポリイソシァネ ート化合物と、必要に応じて親水性基含有化合物とを、通常、ウレタン化触媒の存在 下で反応させることにより製造することができる。製造方法は特に限定されず、従来 公知の方法を適用することができる。  [0111] The polyurethane-based resin used in the present invention is a reaction of the above-mentioned polyol compound, a polyisocyanate compound, and, if necessary, a hydrophilic group-containing compound, usually in the presence of a urethanization catalyst. Can be manufactured. A manufacturing method is not specifically limited, A conventionally well-known method is applicable.
[0112] 上記ウレタンィ匕触媒としては、ナフテン酸銅、ナフテン酸コノ レト、ナフテン酸亜鉛 、ラウリル酸ジ n—ブチルスズ、トリェチルァミン、 1, 4ージァザビシクロ〔2. 2. 2〕オタ タン、 2, 6, 7 トリメチル 1, 4 ジァザビシクロ〔2. 2. 2〕オクタン等が挙げられる。 上記ウレタン化触媒は、反応物の総量 100重量部に対して 0. 01〜1重量部用いる ことが好ましい。また、反応温度は、通常 10〜90°C、特に 30〜80°Cが好ましい。  [0112] Examples of the urethane catalyst include copper naphthenate, conol naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4-diazabicyclo [2.2.2] otatan, 2, 6, 7 Trimethyl 1,4 diazabicyclo [2.2.2] octane. The urethanization catalyst is preferably used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of reactants. The reaction temperature is usually 10 to 90 ° C, particularly 30 to 80 ° C.
[0113] 本発明で用いられるポリウレタン系榭脂の重量平均分子量は、ゲルパーミエーショ ンクロマトグラフィーで測定したポリスチレン換算値で、通常 1, 000〜200, 000、好 ましくは 30, 000-150, 000である。また、本発明で使用する接着剤がポリビュルァ ルコール系榭脂を含有し、溶媒として好ましくは水を使用する観点から、ポリウレタン 系榭脂は水溶性であることが望ましい。 [0113] The weight-average molecular weight of the polyurethane-based resin used in the present invention is a polystyrene equivalent value measured by gel permeation chromatography, and is usually 1,000 to 200,000, preferably Preferably it is 30,000-150,000. In addition, from the viewpoint of using a poly (vinyl alcohol) resin in the present invention and preferably using water as a solvent, the polyurethane resin is desirably water-soluble.
[0114] 本発明では、このようなポリウレタン系榭脂として、たとえば、ハイドラン WLS— 201[0114] In the present invention, as such polyurethane-based resin, for example, Hydran WLS-201
、 WLS— 202、 WLS— 210、 WLS— 213、 WLS— 220 (大曰本インキイ匕学工業（ 株)製)等の市販品を使用することもできる。 Commercially available products such as WLS-202, WLS-210, WLS-213, WLS-220 (manufactured by Oisomoto Ink Industries Co., Ltd.) can also be used.
[0115] (ポリビュルアルコール系榭脂） [0115] (Polybulol alcohol-based fat)
本発明に用いられるポリビュルアルコール系榭脂としては、部分ケンィ匕ポリビュルァ ルコール、完全ケン化ポリビュルアルコールなどのポリビュルアルコール；カルボキシ ル基変性ポリビュルアルコール、ァセトァセチル基変性ポリビュルアルコールなどの 変性ポリビュルアルコールを挙げることができる。  Examples of the polybulal alcohol-based resin used in the present invention include polybutyl alcohols such as partially kenpolypolyvalol and fully saponified polybulal alcohol; modified polybulls such as carboxyl group-modified polybulal alcohol and acetocetyl group-modified polybulal alcohol. Mention may be made of bull alcohol.
[0116] これらのうち、部分ケン化ポリビュルアルコールが好ましい。 [0116] Of these, partially saponified polybutyl alcohol is preferred.
[0117] このようなポリビュルアルコール系榭脂として、たとえば、 163— 03045 (和光純薬（ 株)）等の市販品を使用することもできる。  [0117] Commercially available products such as, for example, 163-03045 (Wako Pure Chemical Industries, Ltd.) can also be used as such polybulal alcoholic resin.
[0118] 本発明で用いられるポリビニルアルコール系榭脂の重量平均分子量は、ゲルパー ミエーシヨンクロマトグラフィーで測定したポリスチレン換算値で、通常 22, 000〜13 0, 000、好ましく 30, 000〜88, 000、さらに好ましくは、 44, 000〜75, 000である  [0118] The weight average molecular weight of the polyvinyl alcohol-based resin used in the present invention is a polystyrene conversion value measured by gel permeation chromatography, and is usually 22,000 to 130,000, preferably 30,000 to 88, 000, more preferably 44,000 to 75,000
[0119] また、上記ポリビニルアルコール系榭脂は、これらを架橋する成分としてイソシァネ ート基などの水酸基と反応しうる官能基を有する化合物と併用してもよい。さらに、ポ リビュルアルコール系榭脂は通常、水に溶解させて用いられる力 基板やフィルムへ の濡れ性を向上させるため、アルコール、ケトン類などの水への溶解性に優れた溶 剤を少量添加することも好まし 、。 [0119] In addition, the polyvinyl alcohol-based resin may be used in combination with a compound having a functional group capable of reacting with a hydroxyl group such as an isocyanate group as a component for crosslinking them. In addition, polyalcohol-based resin is usually used by dissolving it in water. In order to improve the wettability to substrates and films, a small amount of water-soluble solvents such as alcohol and ketones are used. It is also preferable to add.
[0120] (その他の成分）  [0120] (Other ingredients)
本発明で用いられる接着剤には、さらに、硬化剤、粘着付与剤、酸化防止剤、着色 剤、紫外線吸収剤、光安定剤、シランカップリング剤、熱重合禁止剤、レべリング剤、 界面活性剤、保存安定剤、可塑剤、滑剤、フィラー、老化防止剤、濡れ性改良剤、塗 面改良剤等を配合することができる。 [0121] 特に、上記親水基含有ィ匕合物によりポリウレタン系榭脂中にカルボキシル基を導入 した場合には、エポキシ系硬化剤を用いることが好ま 、。 The adhesive used in the present invention further includes a curing agent, a tackifier, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, a thermal polymerization inhibitor, a leveling agent, an interface. Activators, storage stabilizers, plasticizers, lubricants, fillers, anti-aging agents, wettability improvers, coating surface improvers, and the like can be blended. [0121] In particular, when a carboxyl group is introduced into a polyurethane-based resin with the above hydrophilic group-containing compound, it is preferable to use an epoxy-based curing agent.
[0122] 本発明に用いられるエポキシ系硬化剤は、分子内に少なくとも一つのエポキシ基を 有しているものであれば特に制限されるものではない。たとえば、ビスフエノール型ェ ポキシ化合物、ノボラック型エポキシィ匕合物、脂環式エポキシ化合物、脂肪族ェポキ シ化合物、芳香族エポキシィ匕合物、グリシジルァミン型エポキシィ匕合物、ハロゲンィ匕 エポキシィ匕合物等が挙げられる。  [0122] The epoxy curing agent used in the present invention is not particularly limited as long as it has at least one epoxy group in the molecule. For example, bisphenol type epoxy compounds, novolak type epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, glycidylamine type epoxy compounds, halogenated epoxy compounds Etc.
[0123] また、本発明に用いられるエポキシ系硬化剤は、接着剤が好ましくは水溶液である t 、う観点から、水溶性エポキシィ匕合物であることが望ま 、。  [0123] The epoxy curing agent used in the present invention is preferably a water-soluble epoxy compound from the viewpoint of the adhesive being preferably an aqueous solution.
[0124] 具体的には、ビスフエノール Aジグリシジルエーテル、ビスフエノール Fジグリシジル エーテル、ビスフエノール Sジグリシジルエーテル等のビスフエノール型エポキシ化合 物；フエノールノボラック型エポキシィ匕合物、クレゾ一ルノボラック型エポキシィ匕合物等 のノボラック型エポキシ化合物；  [0124] Specifically, bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether; phenol novolak type epoxy compounds, cresol novolac type epoxy compounds Novolac epoxy compounds such as compounds;
3, 4 エポキシシクロへキシノレメチノレー 3' , 4'—エポキシシクロへキサン力ノレボキシ レート、 2- (3, 4 エポキシシクロへキシルー 5, 5—スピロ 3, 4 エポキシ）シクロ へキサン メタ ジォキサン、ビス（3, 4—エポキシシクロへキシルメチル）アジペート 、ビュルシクロへキセンオキサイド、 4—ビュルエポキシシクロへキサン、ビス（3, 4— エポキシ 6—メチノレシクロへキシノレメチノレ）アジペート、 3, 4 エポキシ 6—メチ ルシクロへキシルー 3' , 4' エポキシ 6'—メチルシクロへキサンカルボキシレート 、メチレンビス（3, 4—エポキシシクロへキサン）、ジシクロペンタジェンジェポキサイド 、エチレングリコールのジ（3, 4—エポキシシクロへキシルメチル）エーテル、エチレン ビス（3, 4—エポキシシクロへキサンカルボキシレート）、エポキシ化テトラベンジルァ ルコール、ラタトン変性 3, 4—エポキシシクロへキシルメチル 3' , 4'—エポキシシク 口へキサンカルボキシレート、ラタトン変性エポキシ化テトラヒドロべンジルアルコール 、シクロへキセンオキサイド、水添ビスフエノール Aジグリシジルエーテル、水添ビスフ ェノール Fジグリシジルエーテル、水添ビスフエノール ADジグリシジルエーテル等の 脂環式エポキシィ匕合物類；  3, 4 Epoxycyclohexenolemethynole 3 ′, 4′—Epoxycyclohexane force noroxylate, 2- (3,4 Epoxycyclohexylene 5, 5-spiro 3, 4 epoxy) cyclohexane meta dioxane, Bis (3,4-epoxycyclohexylmethyl) adipate, butylcyclohexene oxide, 4-butylepoxycyclohexane, bis (3,4-epoxy 6-methylenocyclohexenolemethinole) adipate, 3, 4 epoxy 6-methylcyclohexane Xylou 3 ', 4' Epoxy 6'-Methylcyclohexanecarboxylate, Methylenebis (3,4-Epoxycyclohexane), Dicyclopentagenjepoxide, Diethyl of ethylene glycol (3,4-Epoxycyclohexylmethyl) Ether, ethylene bis (3,4-epoxycyclohexanecarboxylate) , Epoxidized tetrabenzyl alcohol, rataton-modified 3, 4-epoxycyclohexylmethyl 3 ', 4'-epoxy cyclohexane hexane carboxylate, rataton-modified epoxidized tetrahydrobenzyl alcohol, cyclohexene oxide, hydrogenated bisphenol Alicyclic epoxy compounds such as A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether;
1, 4 ブタンジオールジグリシジルエーテル、 1, 6 へキサンジオールジグリシジル エーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエー テル等の脂肪族エポキシィヒ合物； 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl Aliphatic epoxy compounds such as ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether;
臭素化ビスフエノール Aジグリシジルエーテル、臭素化ビスフエノール Fジグリシジル エーテル、臭素化ビスフエノール Sジグリシジルエーテル等のハロゲン化エポキシ化 合物；テトラグリシジルァミノフエ-ルメタン等のグリシジルァミン型エポキシィ匕合物 などが挙げられる。  Halogenated epoxy compounds such as brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether; glycidylamine type epoxy compounds such as tetraglycidylaminophenol methane Such as things.
[0125] また、上記エポキシィ匕合物以外に、ポリエチレングリコールジグリシジルエーテル、 ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコールポリグリ シジルエーテル類；エチレングリコール、プロピレングリコール、グリセリンなどの脂肪 族多価アルコールに 1種または 2種以上のアルキレンオキサイドを付加することにより 得られるポリエーテルポリオールのポリグリシジルエーテル類;脂肪族長鎖二塩基酸 のジグリシジルエステル類；脂肪族高級アルコールのモノグリシジルエーテル類；フエ ノール、クレゾール、ブチルフエノールまたはこれらにアルキレンオキサイドを付カロし て得られるポリエーテルアルコールのモノグリシジルエーテル類；高級脂肪酸のダリ シジノレエステノレ類；エポキシィヒ大豆油、エポキシステアリン酸プチノレ、エポキシステア リン酸ォクチル、エポキシ化アマ-油なども用いることができる。  [0125] Besides the above epoxy compounds, polyalkylene glycol polyglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin. Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; phenols, Cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; darisidinoestenoles of higher fatty acids; epoxies Soybean oil, Puchinore epoxystearate, Okuchiru epoxystearate, epoxidized linseed - oil or the like can also be used.
[0126] これらのエポキシィ匕合物は、 1種また 2種以上を予め適宜好適な範囲で重合したェ ポキシ榭脂として使用することもできる。 [0126] These epoxy compounds can also be used as epoxy resins obtained by polymerizing one kind or two or more kinds in an appropriate range in advance.
[0127] また、本発明に用いられるエポキシィ匕合物として、共役ジェン系モノマーの重合体[0127] Further, as the epoxy compound used in the present invention, a polymer of a conjugated gen monomer is used.
、共役ジェン系モノマーとエチレン性不飽和結合基を有する化合物との共重合体、 ジェン系モノマーとエチレン性不飽和結合性基を有する化合物との共重合体、また は天然ゴム等の（共)重合体を、エポキシィ匕した重合体も用いることができる。 , A copolymer of a conjugated gen monomer and a compound having an ethylenically unsaturated bond group, a copolymer of a gen monomer and a compound having an ethylenically unsaturated bond group, or a natural rubber (co) A polymer obtained by epoxidizing the polymer can also be used.
[0128] これらのうち、ポリエチレングリコールグリシジルエーテルが好ましい。 Of these, polyethylene glycol glycidyl ether is preferred.
[0129] このようなエポキシ系硬ィ匕剤としては、たとえば、「CR— 5L」（大日本インキ化学ェ 業 (株)製)などの市販品を用いることもできる。 [0129] As such an epoxy hardener, for example, a commercially available product such as "CR-5L" (manufactured by Dainippon Ink & Chemicals, Inc.) can be used.
[0130] (接着剤の調製） [0130] (Preparation of adhesive)
本発明に用いられる接着剤は、上記ポリウレタン系榭脂およびポリビニルアルコー ル系榭脂の混合物を、好ましくは水に分散させた接着剤である。前記混合物を水に 分散させた接着剤は、上記ポリウレタン系榭脂の水溶液に、上記ポリビニルアルコー ル系榭脂を添加することにより好適に製造することができる。 The adhesive used in the present invention is an adhesive in which a mixture of the polyurethane-based resin and the polyvinyl alcohol-based resin is preferably dispersed in water. The mixture into water The dispersed adhesive can be suitably manufactured by adding the polyvinyl alcohol-based resin to the aqueous solution of the polyurethane-based resin.
[0131] 上記接着剤に含まれるポリビュルアルコール系榭脂の量は、接着剤中の榭脂（ポリ ビュルアルコール系榭脂 +ポリウレタン系榭脂）の固形分 100重量部に対して、榭脂 固形分で 10〜30重量部、好ましくは 15〜25重量部、最も好ましくは 20重量部であ る。また、上記エポキシ系硬化剤を使用する場合、ポリウレタン榭脂とエポキシ系硬 ィ匕剤との合計を 100重量部とすると、固形分重量比 (ポリウレタン榭脂 Zエポキシ系 硬化剤）が、好ましくは 97Z3〜82Z18、より好ましくは 93Z7〜84Z16である。  [0131] The amount of polybulal alcohol-based resin contained in the above-mentioned adhesive is based on 100 parts by weight of the solid content of the resin (polybulal alcohol-based resin + polyurethane-based resin) in the adhesive. The solid content is 10 to 30 parts by weight, preferably 15 to 25 parts by weight, and most preferably 20 parts by weight. Further, when using the above epoxy curing agent, if the total of the polyurethane resin and the epoxy curing agent is 100 parts by weight, the solid content weight ratio (polyurethane resin Z epoxy curing agent) is preferably 97Z3 to 82Z18, more preferably 93Z7 to 84Z16.
[0132] また、上記接着剤は、塗工性の観点から、固形分濃度が好ましくは 5〜30重量％、 より好ましくは 10〜20重量％となるように、水で希釈することが望ましい。  [0132] From the viewpoint of coatability, the adhesive is preferably diluted with water so that the solid content is preferably 5 to 30 wt%, more preferably 10 to 20 wt%.
[0133] また、この接着剤は、含有成分の沈殿や分離、接着性の低下や外観悪化を抑制で きる点で、調製後、好ましくは 24時間以内、さらに好ましくは 1時間以内に使用するこ とが好ましい。  [0133] In addition, the adhesive is preferably used within 24 hours, more preferably within 1 hour after preparation, from the viewpoint of suppressing precipitation and separation of components, deterioration of adhesion and deterioration of appearance. And are preferred.
[0134] <偏光膜 >  [0134] <Polarizing film>
本発明で用いられる偏光膜としては、偏光膜としての機能、すなわち、入射光を互 いに直行する 2つの偏光成分に分け、その一方のみを通過させ、他の成分を吸収ま たは分散させる働きを有する膜であれば特に限定されず、いずれの偏光膜も用いる ことができる。  The polarizing film used in the present invention has a function as a polarizing film, that is, the incident light is divided into two polarization components orthogonal to each other, only one of them is allowed to pass, and the other component is absorbed or dispersed. The polarizing film is not particularly limited as long as it has a function, and any polarizing film can be used.
[0135] 本発明で用いることのできる偏光膜としては、たとえば、ポリビュルアルコール (以下 、「PVA」と略す） 'ヨウ素系偏光膜; PVA系フィルムに二色性染料を吸着配向させた PVA ·染料系偏光膜; PVA系フィルムの脱水反応やポリ塩化ビニルフィルムの脱塩 酸反応により、ポリェンを形成させたポリェン系偏光膜;分子内にカチオン性基を含 有する変性 PVAからなる PVA系フィルムの表面および Zまたは内部に二色性染料 を有する偏光膜などが挙げられる。これらのうち、 PVA'ヨウ素系偏光膜が好ましい。  [0135] Examples of the polarizing film that can be used in the present invention include polybulal alcohol (hereinafter abbreviated as "PVA") 'iodine polarizing film; PVA film in which dichroic dye is adsorbed and oriented on a PVA film. Dye-based polarizing film; Polyphenylene polarizing film formed by polyhydration by dehydration reaction of PVA film or polyvinyl chloride film; PVA film made of modified PVA containing cationic groups in the molecule Examples thereof include a polarizing film having a dichroic dye on the surface and Z or inside. Of these, PVA'iodine polarizing films are preferred.
[0136] 本発明で用いられる偏光膜の製造方法は特に限定されず、従来公知の方法を適 用することができる。たとえば、 PVA系フィルムを延伸後、ヨウ素イオンを吸着させる 方法、 PVA系フィルムを二色性染料による染色後、延伸する方法、 PVA系フィルム を延伸後、二色性染料で染色する方法、二色性染料を PVA系フィルムに印刷後、 延伸する方法、 PVA系フィルムを延伸後、二色性染料を印刷する方法などが挙げら れる。より具体的には、ヨウ素をヨウ化カリウム溶液に溶解して、高次のヨウ素イオンを 作り、このイオンを PVAフィルムに吸着させて延伸し、次いで 1〜5重量％ホウ酸水溶 液に浴温度 30〜40°Cで浸漬して偏光膜を製造する方法；あるいは、 PVAフィルムを 上記と同様にホウ酸処理して一軸方向に 3〜7倍程度延伸した後、 0. 05〜5重量％ の二色性染料水溶液に浴温度 30〜40°Cで浸漬して染料を吸着し、次 、で 80〜： LO 0°Cで乾燥して熱固定して偏光膜を製造する方法などが挙げられる。 [0136] The method for producing the polarizing film used in the present invention is not particularly limited, and conventionally known methods can be applied. For example, after stretching a PVA film, adsorb iodine ions, after dyeing a PVA film with a dichroic dye, stretch it, after stretching a PVA film, dye it with a dichroic dye, two colors After printing a functional dye on PVA film, Examples thereof include a stretching method and a method of printing a dichroic dye after stretching a PVA film. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, which are adsorbed on a PVA film and stretched, and then bathed in a 1-5 wt% boric acid aqueous solution. A method for producing a polarizing film by immersing at 30 to 40 ° C; or, after the PVA film is treated with boric acid in the same manner as described above and stretched about 3 to 7 times in a uniaxial direction, 0.05 to 5% by weight Examples include a method of producing a polarizing film by immersing in a dichroic dye aqueous solution at a bath temperature of 30 to 40 ° C to adsorb the dye, followed by drying at 80 to LO at 0 ° C and heat-fixing. .
[0137] 本発明で用いられる偏光膜の厚さは、特に限定されるものではないが、 10〜50 m、好ましくは 15〜45 μ mであることが望ましい。  [0137] The thickness of the polarizing film used in the present invention is not particularly limited, but is 10 to 50 m, preferably 15 to 45 μm.
[0138] これらの偏光膜は、そのまま本発明に係る偏光板の製造に用いてもよいが、接着剤 層と接する面に、コロナ放電処理、プラズマ処理を施して用いることもできる。  [0138] These polarizing films may be used as they are for the production of the polarizing plate according to the present invention, but the surfaces in contact with the adhesive layer can also be used after being subjected to corona discharge treatment or plasma treatment.
[0139] <偏光板>  [0139] <Polarizing plate>
本発明の偏光板は、上記ノルボルネン系榭脂フィルムと上記偏光膜とを、上記接着 剤を介して接着された偏光板である。  The polarizing plate of the present invention is a polarizing plate in which the norbornene-based resin film and the polarizing film are bonded via the adhesive.
[0140] このような偏光板の製造方法は特に制限されず、たとえば、ノルボルネン系榭脂フ イルムまたは偏光膜の一表面に接着剤を均一に塗布し、塗布面に他方のフィルム（ 膜)を重ね合わせてロール等により貼合し、乾燥する方法などが挙げられる。  [0140] The method for producing such a polarizing plate is not particularly limited. For example, an adhesive is uniformly applied to one surface of a norbornene-based resin film or a polarizing film, and the other film (film) is applied to the coated surface. For example, a method of overlapping and bonding with a roll or the like and drying may be used.
[0141] このとき、接着剤は、乾燥後の接着剤層の厚さが好ましくは 0. 01〜50 m、より好 ましくは 0. 1〜30 /ζ πι、特に好ましくは 1〜5 /ζ πιとなるように塗布することが好ましい 。乾燥後の接着剤層の厚さが上記範囲にあると、偏光板の透明性が維持され、かつ 十分な接着力でノルボルネン系榭脂フィルムと偏光膜とが接着され、これらの層間剥 離が起こりにくい。  [0141] At this time, the thickness of the adhesive layer after drying is preferably 0.01 to 50 m, more preferably 0.1 to 30 / ζ πι, and particularly preferably 1 to 5 /. It is preferable to apply so that ζπι. When the thickness of the adhesive layer after drying is in the above range, the transparency of the polarizing plate is maintained, and the norbornene-based resin film and the polarizing film are bonded with sufficient adhesive force, and the delamination of these layers is prevented. Hard to happen.
[0142] 上記接着剤塗布時の温度は、通常 15〜40°Cの範囲であり、貼合温度は通常 15 〜30°C程度の範囲である。貼合後は乾燥処理を行い、接着剤中に含まれる水など の溶媒を除去する。この際の乾燥温度は、通常 30〜85°C、好ましくは 40〜80°Cの 範囲である。その後、通常 15〜85°C、好ましくは 20〜50°C、より好ましくは 35〜45 °Cの温度環境下で、通常 0. 1〜： LOO日、好ましくは 0. 5〜30日程度、より好ましくは 1〜7日間養生して、接着剤を硬化させる。 [0143] このようにして形成された接着剤層には、ポリウレタン系榭脂とポリビニルアルコー ル系榭脂とが、固形分重量比 (ポリウレタン系榭脂 Zポリビュルアルコール系榭脂） 力 S95/5〜50/50、好ましくは 90/10〜70/30の範囲で含まれる。ただし、ポリウ レタン系樹脂とポリビニルアルコール系榭脂との合計重量（固形分)を 100とする。 [0142] The temperature at the time of applying the adhesive is usually in the range of 15 to 40 ° C, and the bonding temperature is usually in the range of about 15 to 30 ° C. After pasting, dry treatment is performed to remove water and other solvents contained in the adhesive. The drying temperature at this time is usually in the range of 30 to 85 ° C, preferably 40 to 80 ° C. Thereafter, usually in a temperature environment of 15 to 85 ° C, preferably 20 to 50 ° C, more preferably 35 to 45 ° C, usually 0.1 to: LOO days, preferably about 0.5 to 30 days, More preferably, the adhesive is cured by curing for 1 to 7 days. [0143] In the adhesive layer thus formed, the polyurethane-based resin and the polyvinyl alcohol-based resin have a solids weight ratio (polyurethane-based resin Z-polybulal alcohol-based resin). It is included in the range of 5-50 / 50, preferably 90 / 10-70 / 30. However, the total weight (solid content) of the polyurethane resin and the polyvinyl alcohol resin is 100.
[0144] 本発明にお 、て、偏光膜の両面にノルボルネン系榭脂フィルムを積層する場合は 、偏光膜の両面に上記接着剤を塗布してノルボルネン系榭脂フィルムを接着する。  In the present invention, when the norbornene-based resin film is laminated on both surfaces of the polarizing film, the above-mentioned adhesive is applied to both surfaces of the polarizing film to adhere the norbornene-based resin film.
[0145] 一方、偏光膜の片面にノルボルネン系榭脂フィルムを積層し、他方の面には他の 榭脂からなるフィルム（たとえば、保護フィルム）を積層する場合は、偏光フィルムの両 面に上記接着剤を塗布してノルボルネン系榭脂フィルムおよび他の榭脂からなるフィ ルムを接着してもよ ヽし、偏光膜とノルボルネン系榭脂フィルムとの接着に上記接着 剤を使用し、偏光膜と他の樹脂からなるフィルムとの接着には異なる接着剤を使用し てもよい。たとえば、他の榭脂からなるフィルムとしてァセチルセルロース系榭脂から なる保護フィルムを接着する場合、実質的にポリビニルアルコール系榭脂からなる接 着剤を用いてもよい。  [0145] On the other hand, when a norbornene-based resin film is laminated on one surface of the polarizing film and a film (for example, a protective film) made of other resin is laminated on the other surface, the above-mentioned film is formed on both surfaces of the polarizing film. A norbornene-based resin film and other film made of a resin may be adhered by applying an adhesive, and the above-mentioned adhesive is used for bonding the polarizing film and the norbornene-based resin film. Different adhesives may be used for bonding the film to other resin films. For example, when a protective film made of acetyl cellulose-based resin is bonded as a film made of other resin, an adhesive substantially made of polyvinyl alcohol-based resin may be used.
[0146] 本発明に係る偏光板は、良好な偏光機能を有し、ノルボルネン系榭脂フィルムと偏 光膜とが強固に接着されており、耐熱性、耐薬品性などの特性にも優れており、長期 使用においても剥離、変形、位相差変化などが生じにくぐ高い信頼性を有し、耐久 性に優れている。このような偏光板は、液晶表示装置などの用途に好適に用いること ができる。  [0146] The polarizing plate according to the present invention has a good polarizing function, and the norbornene-based resin film and the polarizing film are firmly bonded to each other, and has excellent characteristics such as heat resistance and chemical resistance. In addition, it has high reliability that resists peeling, deformation, phase change, etc. even during long-term use, and has excellent durability. Such a polarizing plate can be suitably used for applications such as a liquid crystal display device.
[0147] [実施例]  [0147] [Example]
以下、本発明を実施例により説明するが、本発明は、この実施例により何ら限定さ れるものではない。なお、以下において、「部」は、特に断りのない限り「重量部」を意 味する。  EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In the following description, “part” means “part by weight” unless otherwise specified.
[0148] また、ガラス転移温度、全光線透過率、偏光度、透過光の位相差、純水接触角、密 着性、耐湿試験、乾熱試験は、下記の方法により測定した。  [0148] The glass transition temperature, total light transmittance, polarization degree, retardation of transmitted light, pure water contact angle, adhesion, moisture resistance test, and dry heat test were measured by the following methods.
[0149] <ガラス転移温度 (Tg) > [0149] <Glass transition temperature (Tg)>
セイコーインスツルメンッ社製の示差走査熱量計 (DSC)を用い、窒素雰囲気で昇 温速度が 20°CZ分の条件でガラス転移温度 (以下、「Tg」とも 、う）を測定した。 [0150] く全光線透過率 > Using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc., the glass transition temperature (hereinafter also referred to as “Tg”) was measured under the condition of a temperature rising rate of 20 ° C.Z in a nitrogen atmosphere. [0150] Total light transmittance>
スガ試験機社製のヘイズメーター (HGM— 2DP型）を用い、全光線透過率を測定 した。  Total light transmittance was measured using a haze meter (HGM-2DP type) manufactured by Suga Test Instruments Co., Ltd.
[0151] <偏光度 >  [0151] <degree of polarization>
王子計測機器 (株)製の「KOBRA— 21ADHZPR」を用いて波長 547. 7nmの偏 光度を測定した。  The polarization at a wavelength of 547.7 nm was measured using “KOBRA-21ADHZPR” manufactured by Oji Scientific Instruments.
[0152] <透過光の位相差 > [0152] <Phase difference of transmitted light>
王子計測機器 (株）製の「KOBRA— 21ADH」を用い、波長 480nm、 550nm、 59 Onm、 630nm、 750nmでの位相差値を測定し、これらの波長以外の位相差値につ Vヽては前記波長での位相差値に基づ 、てコーシ一（Cauchy)の分散式を用いて算 出した。  Measure the phase difference values at wavelengths of 480 nm, 550 nm, 59 Onm, 630 nm, and 750 nm using “KOBRA-21ADH” manufactured by Oji Scientific Instruments Co., Ltd. Based on the retardation value at the wavelength, the calculation was performed using the Cauchy dispersion formula.
[0153] <純水接触角 > [0153] <Pure water contact angle>
直径 1. 5mmの水滴を針先に形成し、それをノルボルネン榭脂フィルムの表面に接 触させてノルボルネン榭脂フィルムに水滴を移し、水滴とノルボルネン榭脂フィルム 表面の純水接触角を接触角計 (協和界面化学 (株)製、 AD— 31 )を用 、て測定した  A water droplet with a diameter of 1.5 mm is formed at the tip of the needle, and it is brought into contact with the surface of the norbornene resin film. The water droplet is transferred to the norbornene resin film, and the contact angle is determined by the contact angle between the water droplet and the pure water contact surface of the norbornene resin film. Measured using a total (Kyowa Interface Chemical Co., Ltd., AD-31)
[0154] <接着性 (偏光子と保護フィルムとの接着性） > [0154] <Adhesiveness (Adhesiveness between polarizer and protective film)>
偏光板の偏光子と保護フィルムとの層間剥離を手で試み、層間剥離および材料破 壊の発生程度を目視にて以下の基準で評価した。  The delamination between the polarizer and the protective film of the polarizing plate was attempted by hand, and the degree of delamination and material destruction was visually evaluated according to the following criteria.
ランク 1 :層間剥離は生じず、材料破壊のみが生じた。  Rank 1: No delamination occurred, only material destruction occurred.
ランク 2 :—部材料破壊が生じ、同時に層間剥離も部分的に生じた。  Rank 2: The material destruction occurred, and at the same time, partial delamination occurred.
ランク 3：層間剥離のみが生じ、材料破壊は生じな!/、。  Rank 3: Only delamination occurs, and no material destruction occurs! /.
ランク 4：偏光板の製造工程にお 、て、層間剥離が生じた。  Rank 4: Delamination occurred in the manufacturing process of the polarizing plate.
[0155] <湿熱試験 > [0155] <Wet heat test>
偏光板を温度 40°C、相対湿度 95%の環境下にて 500時間保存した後、各種評価 を行った。  The polarizing plate was stored for 500 hours in an environment of a temperature of 40 ° C and a relative humidity of 95%, and then various evaluations were performed.
[乾熱試験]  [Dry heat test]
偏光板を温度 80°Cの環境下にて 500時間保存した後、各種評価を行った。 [0156] [合成例 1] Various evaluations were made after the polarizing plate was stored in an environment at a temperature of 80 ° C. for 500 hours. [0156] [Synthesis Example 1]
(ノルボルネン系榭脂の合成）  (Synthesis of norbornene-based resin)
窒素置換した反応容器に、 8—メチル—8—カルボキシメチルテトラシクロ [4. 4. 0 . 12, 5. 17, 10]ドデ力— 3 ェン 225部と、ビシクロ [2. 2. 1]ヘプト— 2 ェン 25 部と、分子量調節剤として 1—へキセン 18部と、溶媒としてトルエン 750部とを仕込み 、この溶液を 60°Cに加熱した。次いで、反応容器内の溶液に、重合触媒としてトリエ チルアルミニウムを含有するトルエン溶液 (濃度 1. 5モル ZL) 0. 62部と、 tーブタノ ールおよびメタノールで変性した六塩化タングステン（t ブタノール：メタノール：タン グステン =0. 35モル： 0. 3モル： 1モル）を含有するトルエン溶液（濃度 0. 05モル Z L) 3. 7部とを添加し、この溶液を 80°Cで 3時間加熱しながら攪拌することにより開環 共重合反応させて開環共重合体を含む溶液を得た。  In a reaction vessel purged with nitrogen, 8-methyl-8-carboxymethyltetracyclo [4.4.0.12,5,17,10] dede force-3 225 parts and bicyclo [2.2.1 ] 25 parts of hept-2-ene, 18 parts of 1-hexene as a molecular weight regulator, and 750 parts of toluene as a solvent were charged, and this solution was heated to 60 ° C. Next, in the solution in the reaction vessel, 0.66 parts of a toluene solution containing triethylaluminum as a polymerization catalyst (concentration: 1.5 mol ZL), tungsten hexachloride modified with t-butanol and methanol (t butanol: Methanol: Tungsten = 0.35 mol: 0.3 mol: 1 mol) Toluene solution (concentration 0.05 mol ZL) 3. Add 7 parts and heat this solution at 80 ° C for 3 hours While stirring, a ring-opening copolymerization reaction was performed to obtain a solution containing the ring-opening copolymer.
[0157] この共重合反応における重合転ィ匕率は 97%であり、得られた開環共重合体の 30 °Cのクロ口ホルム中における固有粘度（ 7? )を測定したところ、 0. 65dlZgであった [0157] The polymerization conversion rate in this copolymerization reaction was 97%, and the intrinsic viscosity (7?) Of the obtained ring-opening copolymer in 30 ° C of chloroform was measured. It was 65dlZg
uih  uih
[0158] 得られた開環共重合体溶液 4000部をオートクレープに仕込み、この開環共重合 体溶液に、カルボユルクロロヒドリドトリス（トリフエ-ルホスフィン)ルテニウム〔RuHCl ( CO) [P (C H ) ]〕0. 48部を添加し、水素ガス圧 100kgZcm2、反応温度 165°Cの [0158] 4000 parts of the resulting ring-opening copolymer solution was charged into an autoclave, and carbochlorochlorohydridotris (triphenylphosphine) ruthenium [RuHCl (CO) [P (CH ]]] 0.48 parts added, hydrogen gas pressure 100kgZcm 2 , reaction temperature 165 ° C
6 5 3 3  6 5 3 3
条件下で 3時間加熱攪拌することにより水素添加反応を行った。  The hydrogenation reaction was performed by heating and stirring under the conditions for 3 hours.
[0159] 得られた水素添加重合体を含む溶液を冷却した後、水素ガスを放圧した。この溶 液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添カロ 重合体 (以下、「樹脂 (a— 1)」ともいう）を得た。 [0159] After cooling the solution containing the obtained hydrogenated polymer, the hydrogen gas was released. This solution was poured into a large amount of methanol to separate and recover the coagulated product, which was dried to obtain a hydrogenated caropolymer (hereinafter also referred to as “resin (a-1)”).
[0160] 得られた榭脂（a— 1)について、水素添加率を、 400MHzの条件で1 H— NMRス ベクトルにより測定したところ、 99. 9%であった。 [0160] With respect to the obtained resin (a-1), the hydrogenation rate was measured by 1 H-NMR spectrum under the condition of 400 MHz, and it was 99.9%.
[0161] また、榭脂（a— 1)について、ゲルパーミエーシヨンクロマトグラフィー（GPC、カラム[0161] In addition, gel permeation chromatography (GPC, column)
：東ソ一（株）製 TSKgel G7000H X l : Tosohichi Co., Ltd. TSKgel G7000H X l
XL 、TSKgel GMH X 2および TSKgel G  XL, TSKgel GMH X 2 and TSKgel G
XL  XL
2000H X 1の 4本直列、溶媒:テトラヒドロフラン）により、ポリスチレン換算の数平均 2000H X 1 in series, solvent: tetrahydrofuran), polystyrene equivalent number average
XL XL
分子量 (Mn)および重量平均分子量 (Mw)を測定したところ、数平均分子量 (Mn) は 39, 000、重量平均分子量（Mw)は 116, 000、分子量分布（MwZMn)は 2. 9 7であった。 When the molecular weight (Mn) and the weight average molecular weight (Mw) were measured, the number average molecular weight (Mn) was 39,000, the weight average molecular weight (Mw) was 116,000, and the molecular weight distribution (MwZMn) was 2.9. It was 7.
[0162] また、榭脂（a— 1)のガラス転移温度 (Tg)は 130°Cであり、 23°Cにおける飽和吸水 率は 0. 3重量0 /0であった。さらに、榭脂（a— 1)の SP値を測定したところ、 19MPa1 2 であり、 30°Cのクロ口ホルム中で固有粘度（ 7? )を測定したところ 0. 67dlZgであつ [0162] Further,榭脂(a- 1) Glass transition temperature (Tg) of a 130 ° C, the saturated water absorption at 23 ° C was 0.3 wt 0/0. Furthermore, the measured SP value of榭脂(a- 1), a 19 MPa 1 2, filed in 0. 67DlZg was measured intrinsic viscosity (7?) In black port Holm 30 ° C
inh  inh
た。  It was.
[0163] [作製例 1]  [0163] [Production Example 1]
(位相差フィルムの作製）  (Production of retardation film)
榭脂（a— 1)をトルエンに濃度が 30重量％となるように溶解した。得られた溶液の室 温における溶液粘度は 30, OOOmPa' sであった。この溶液に、酸化防止剤としてべ ンタエリスリチルテトラキス [3— (3, 5—ジ一 t—ブチル 4—ヒドロキシフエニル）プロ ピオネート]を、榭脂（a— 1) 100重量部に対して 0. 1重量部添加し、得られた溶液を 日本ポール製の孔径 5 /z mの金属繊維焼結フィルターを用い、差圧が 0. 4MPa以 内に収まるように溶液の流速をコントロールしながら濾過した。その後、クラス 1000の クリーンルーム内に設置した井上金属工業製の「INVEXラボコーター」を用い、ァク リル酸系表面処理剤により親水化 (易接着性化)処理された、厚みが 100 /z mの PE Tフィルム (東レ (株)製の「ルミラー U94」）上に塗布した。次いで、得られた液層を、 5 0°Cで一次乾燥処理し、さらに、 90°Cで二次乾燥処理した後、 PETフィルム力も剥離 させて、厚さ 100 mの榭脂フィルム（以下、「榭脂フィルム (a— 2)」ともいう）を形成し た。得られた榭脂フィルム（a— 2)の残留溶媒量は 0. 5重量％であり、全光線透過率 は 93%以上であった。  Coffin (a-1) was dissolved in toluene to a concentration of 30% by weight. The solution viscosity at room temperature of the obtained solution was 30, OOOmPa's. In this solution, benzoerythrityltetrakis [3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate] as an antioxidant is added to 100 parts by weight of rosin (a-1). 0.1 part by weight was added, and the obtained solution was filtered using a metal fiber sintered filter made by Nippon Pole with a pore diameter of 5 / zm while controlling the flow rate of the solution so that the differential pressure was within 0.4 MPa. did. Then, using the INVEX Lab Coater made by Inoue Metal Industry installed in a Class 1000 clean room, it was hydrophilized with an acrylic acid-based surface treatment agent (easy-to-adhesive), and its thickness was 100 / zm. It was applied on a T film ("Lumirror U94" manufactured by Toray Industries, Inc.). Next, the obtained liquid layer was subjected to a primary drying treatment at 50 ° C., and further subjected to a secondary drying treatment at 90 ° C., and then the PET film force was also peeled off to obtain a 100 m thick resin film (hereinafter referred to as “the resin film”). “Resin film (a-2)”) was formed. The obtained resin film (a-2) had a residual solvent amount of 0.5% by weight and a total light transmittance of 93% or more.
[0164] また、上記と同様の手法により、残留溶媒量が 0. 4重量％であり、厚みが 80 mの 榭脂フィルム (以下、「榭脂フィルム (a— 3)」ともいう）、および残留溶媒量が 0. 3重量 %であり、厚みが 50 mの榭脂フィルム（以下、「榭脂フィルム（a— 4)」ともいう）を形 成した。得られた榭脂フィルム (a— 3)および榭脂フィルム (a— 4)の全光線透過率は いずれも 93%以上であった。  [0164] A resin film having a residual solvent amount of 0.4 wt% and a thickness of 80 m (hereinafter, also referred to as "wax film (a-3)"), and a method similar to the above, A resin film having a residual solvent amount of 0.3% by weight and a thickness of 50 m (hereinafter also referred to as “resin film (a-4)”) was formed. The total light transmittances of the obtained resin film (a-3) and resin film (a-4) were both 93% or more.
[0165] 得られた榭脂フィルム（a— 2)をテンター内で、 140°C (Tg+ 10°C)に加熱し、延伸 速度 300%Z分でフィルム面内の縦方向に 1. 3倍に延伸した後、フィルム面内の横 方向に 1. 3倍に延伸し、その後、 110°C (Tg— 20°C)の雰囲気下で 1分間この状態 を保持しながら冷却し、さらに室温で冷却した後、テンター内から取り出すことにより、 位相差フィルム（以下、「位相差フィルム (a— 5)」ともいう。）を得た。 [0165] The obtained resin film (a-2) was heated in a tenter to 140 ° C (Tg + 10 ° C) and stretched in the longitudinal direction in the film plane at a stretch rate of 300% Z. Then, the film is stretched 1.3 times in the transverse direction in the film plane, and then in this state for 1 minute under an atmosphere of 110 ° C (Tg—20 ° C) The film was cooled while being held, further cooled at room temperature, and then taken out from the tenter to obtain a retardation film (hereinafter also referred to as “retardation film (a-5)”).
[0166] 得られた位相差フィルム（a— 5)について、位相差 α (550)、位相差 j8 (550)、フィ ルム厚みを測定した。結果を表 1に示す。  [0166] With respect to the obtained retardation film (a-5), retardation α (550), retardation j8 (550), and film thickness were measured. The results are shown in Table 1.
[0167] 得られた榭脂フィルム（a— 3)をテンター内で、 140°C (Tg+ 10°C)に加熱し、延伸 速度 300%Z分でフィルム面内の横方向の幅を一定に保ちながら縦方向に 1. 3倍 に延伸した後、 110°C (Tg- 20°C)の雰囲気下で 1分間この状態を保持しながら冷 却し、さらに室温で冷却した後、テンター内から取り出すことにより、位相差フィルム（ 以下、「位相差フィルム (a— 6)」ともいう。）を得た。  [0167] The obtained resin film (a-3) was heated in a tenter to 140 ° C (Tg + 10 ° C), and the lateral width in the film plane was kept constant at a stretching rate of 300% Z. While maintaining this state for 1.3 minutes in an atmosphere of 110 ° C (Tg-20 ° C), while maintaining this state for 1 minute, and further cooling at room temperature, By taking out, a retardation film (hereinafter also referred to as “retardation film (a-6)”) was obtained.
[0168] 得られた位相差フィルム（a— 6)について、位相差 α (550)、位相差 j8 (550)、フィ ルム厚みを測定した。結果を表 1に示す。  [0168] With respect to the obtained retardation film (a-6), retardation α (550), retardation j8 (550), and film thickness were measured. The results are shown in Table 1.
[0169] 得られた榭脂フィルム（a— 4)をテンター内で、 140°C (Tg+ 10°C)に加熱し、延伸 速度 300%Z分でフィルム面内の縦方向に 1. 1倍に延伸した後、フィルム面内の横 方向に 1. 1倍に延伸し、その後、 110°C (Tg— 20°C)の雰囲気下で 1分間この状態 を保持しながら冷却し、さらに室温で冷却した後、テンター内から取り出すことにより、 位相差フィルム（以下、「位相差フィルム (a— 7)」ともいう。）を得た。  [0169] The obtained resin film (a-4) was heated to 140 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the longitudinal direction of the film at a stretch rate of 300% Z. Then, the film is stretched 1.1 times in the lateral direction in the film plane, and then cooled in an atmosphere of 110 ° C. (Tg—20 ° C.) for 1 minute, and further at room temperature. After cooling, the film was taken out from the tenter to obtain a retardation film (hereinafter also referred to as “retardation film (a-7)”).
[0170] 得られた位相差フィルム（a— 7)について、位相差 α (550)、位相差 (550)、フィ ルム厚みを測定した。結果を表 1に示す。  [0170] With respect to the obtained retardation film (a-7), the retardation α (550), the retardation (550), and the film thickness were measured. The results are shown in Table 1.
[0171] [作製例 2]  [0171] [Production Example 2]
(位相差フィルムの作製）  (Production of retardation film)
作製例 1と同様にして位相差フィルム (a— 5)、 (a- 6)および (a— 7)をそれぞれ作 製した後、得られた位相差フィルム (a— 5)、 （a— 6)および (a— 7)のそれぞれの両 面に対し、コロナ放電電子の照射量が 100WZm2Zminとなる条件で、大気下でコ ロナ処理をおこない、位相差フィルム（a— 5，）、 （& 6，）ぉょび(&ー7，）を得た。これ らの位相差フィルム表面の純水接触角は 40degであった。得られた位相差フィルム（ a— 5，）、 （a— 6，）および（a— 7，）の位相差 α (550)、位相差 j8 (550)、フィルム厚 みを測定した。結果を表 1に示す。 After producing retardation films (a-5), (a-6) and (a-7) in the same manner as in Production Example 1, the obtained retardation films (a-5), (a-6) ) And (a-7) are subjected to corona treatment in the atmosphere under the condition that the corona discharge electron dose is 100 WZm 2 Zmin, and the retardation film (a-5,), ( & 6,) I got a joy (& -7). The pure water contact angle on the surface of these retardation films was 40 deg. Retardation α (550), retardation j8 (550), and film thickness of the obtained retardation films (a-5,), (a-6,) and (a-7,) were measured. The results are shown in Table 1.
[0172] [比較作製例 1] (比較用位相差フィルムの作製） [0172] [Comparative Production Example 1] (Production of comparative retardation film)
榭脂（a— 1)に代えて出光石油化学製のポリカーボネート榭脂「A2700」（Tg= 15 5°C)を用い、トルエンに代えて塩化メチレンを用いた以外は作製例 1と同様にして、 残留溶媒量が 0. 4重量％であり、厚みが 100 mの榭脂フィルム（以下、「榭脂フィ ルム（f 2)」ともいう）、残留溶媒量が 0. 3重量％であり、フィルム厚みが 80 mの榭 脂フィルム (以下、「榭脂フィルム (f— 3)」ともいう）、および残留溶媒量が 0. 3重量0 /0 であり、フィルム厚みが 50 mの榭脂フィルム（以下、「榭脂フィルム（f 4)」ともいう） を得た。得られた榭脂フィルム (f— 2)〜 (f— 4)の全光線透過率は!、ずれも 91%で めつに。 As in Preparation Example 1, except that polycarbonate resin “A2700” (Tg = 155 ° C) made by Idemitsu Petrochemical was used instead of resin (a-1), and methylene chloride was used instead of toluene. Residual solvent amount is 0.4% by weight, 100 m thick resin film (hereinafter also referred to as “fat film (f 2)”), residual solvent amount is 0.3% by weight,榭fat film of the film thickness of 80 m (hereinafter, "榭脂film (f- 3)" also referred to), and the residual solvent amount is 0.3 wt 0/0, 榭脂film of the film thickness of 50 m (Hereinafter also referred to as “resin film (f4)”). The total light transmittance of the obtained resin films (f-2) to (f-4) is!
[0173] 得られた榭脂フィルム (f— 2)をテンター内で、 165°C (Tg+ 10°C)に加熱し、延伸 速度 300%Z分でフィルム面内の縦方向に 1. 03倍に延伸した後、フィルム面内の 横方向に 1. 03倍に延伸し、その後、 135°C (Tg— 20°C)の雰囲気下で 1分間この 状態を保持しながら冷却し、さらに室温で冷却した後、テンター内から取り出すことに より、位相差フィルム（以下、「位相差フィルム (f 5)」とも 、う）を得た。  [0173] The obtained resin film (f-2) was heated in a tenter to 165 ° C (Tg + 10 ° C) and stretched in the longitudinal direction in the film plane at a stretching rate of 300% Z for 1.03 times. Then, the film was stretched 1.03 times in the transverse direction in the film plane, and then cooled in an atmosphere of 135 ° C (Tg—20 ° C) for 1 minute while maintaining the temperature at room temperature. After cooling, a retardation film (hereinafter also referred to as “retardation film (f5)”) was obtained by taking it out from the tenter.
[0174] 得られた位相差フィルム (f 5)について、位相差 α (550)、位相差 |8 (550)、フィ ルム厚みを測定した。結果を表 1に示す。  [0174] With respect to the obtained retardation film (f5), retardation α (550), retardation | 8 (550), and film thickness were measured. The results are shown in Table 1.
[0175] 得られた榭脂フィルム (f— 3)をテンター内で、 165°C (Tg+ 10°C)に加熱し、延伸 速度 300%Z分でフィルム面内の横方向の幅を一定に保ちながら縦方向に 1. 03倍 に延伸した後、 135°C (Tg-20°C)の雰囲気下で 1分間この状態を保持しながら冷 却し、さらに室温で冷却した後、テンター内から取り出すことにより、位相差フィルム（ 以下、「位相差フィルム (f— 6)」とも 、う）を得た。  [0175] The obtained resin film (f-3) is heated in a tenter to 165 ° C (Tg + 10 ° C), and the transverse width in the film plane is kept constant at a stretching rate of 300% Z. While maintaining this state, the film was stretched 1.03 times in the longitudinal direction, cooled in this condition for 1 minute in an atmosphere of 135 ° C (Tg-20 ° C), further cooled at room temperature, and then from the inside of the tenter. By taking out, a retardation film (hereinafter, also referred to as “retardation film (f-6)”) was obtained.
[0176] 得られた位相差フィルム (f 6)について、位相差 α (550)、位相差 |8 (550)、フィ ルム厚みを測定した。結果を表 1に示す。得られた榭脂フィルム (f 4)をテンター内 で、 165°C (Tg+ 10°C)に加熱し、延伸速度 300%Z分でフィルム面内の縦方向に 1. 01倍に延伸した後、フィルム面内の横方向に 1. 01倍に延伸し、その後、 135°C ( Tg-20°C)の雰囲気下で 1分間この状態を保持しながら冷却し、さらに室温で冷却 した後、テンター内から取り出すことにより、位相差フィルム（以下、「位相差フィルム（ ί— 7)」ともいう）を得た。 [0177] 得られた位相差フィルム (f 7)について、位相差 α (550)、位相差 |8 (550)、フィ ルム厚みを測定した。結果を表 1に示す。 [0176] With respect to the obtained retardation film (f6), retardation α (550), retardation | 8 (550), and film thickness were measured. The results are shown in Table 1. The obtained resin film (f 4) was heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched 1.01 times in the longitudinal direction in the film plane at a stretching rate of 300% Z. Then, the film was stretched 1.01 times in the lateral direction in the film plane, and then cooled in this state for 1 minute in an atmosphere of 135 ° C (Tg-20 ° C), and further cooled at room temperature, By removing from the inside of the tenter, a retardation film (hereinafter, also referred to as “retardation film (ί-7)”) was obtained. [0177] With respect to the obtained retardation film (f7), retardation α (550), retardation | 8 (550), and film thickness were measured. The results are shown in Table 1.
[0178] [表 1] [0178] [Table 1]
表 1 table 1
Figure imgf000039_0001
Figure imgf000039_0001
P C：ボリカーボネート樹脂 （A 2700) PC: Polycarbonate resin (A 2700)
[0179] [合成例 2] [0179] [Synthesis Example 2]
(ポリウレタン系榭脂の合成）  (Synthesis of polyurethane resin)
ポリテトラメチレングリコール（分子量 2000) 500部、ポリメタクリル酸 36部、イソホロ ンジイソシァネート 206部、 80重量0 /0水力口ヒドラジン 13部、トリエチルァミン 27部を反 応させることにより、 GPCにより測定したポリスチレン換算の重量平均分子量が 12万 、不揮発分が 35重量％のポリウレタン榭脂ェマルジヨン (以下、「ポリウレタン榭脂（B - 1)」ともいう）を得た。 Polytetramethylene glycol (molecular weight 2000) 500 parts, 36 parts of polymethyl methacrylate, isophorone Nji iso Xia sulfonate 206 parts, 80 weight 0/0 hydroelectric port hydrazine 13 parts by reaction with Toriechiruamin 27 parts by GPC A polyurethane resin emulsion (hereinafter also referred to as “polyurethane resin (B-1)”) having a polystyrene-reduced weight average molecular weight of 120,000 and a nonvolatile content of 35% by weight was obtained.
[0180] [合成例 3] [0180] [Synthesis Example 3]
(ポリウレタン系榭脂の合成）  (Synthesis of polyurethane resin)
イソホロンジイソシァネートの代わりに、メチレンビス（4—シクロへキシノレイソシァネ ート） 206部を使用した以外は合成例 2と同様にして、 GPCにより測定したポリスチレ ン換算の重量平均分子量が 10万、不揮発分が 35重量％のポリウレタン榭脂ェマル ジョン (以下、「ポリウレタン榭脂 (B— 2)」とも 、う）を得た。  In the same manner as in Synthesis Example 2 except that 206 parts of methylene bis (4-cyclohexylenoisocyanate) was used instead of isophorone diisocyanate, the weight average molecular weight in terms of polystyrene measured by GPC was A polyurethane resin emulsion (hereinafter also referred to as “polyurethane resin (B-2)”) having a nonvolatile content of 35% by weight was obtained.
[0181] [調製例 1] [0181] [Preparation Example 1]
(接着剤の調製）  (Preparation of adhesive)
ポリビニルアルコール系榭脂である和光純薬工業 (株)製の 163— 03045 (分子量 22000、ケンィ匕度 88モル％)に、水を加えて固形分濃度が 7重量％の水溶液を調製 した。一方、ポリウレタン系榭脂である大日本インキ化学工業 (株)製の WLS— 201 ( 固形分濃度 35重量％) 100部に、ポリエポキシ系硬化剤である大日本インキ工業（ 株)製の CR— 5L (有効成分 100%品） 5部を配合し、水で希釈して固形分濃度が 20 重量％の水溶液を調製した。得られたポリウレタン系榭脂水溶液とポリビニルアルコ 一ル系榭脂水溶液とを、重量比で 1： 1 (固形分重量比で 80： 20)の割合で混合し、 固形分濃度が 15重量％の混合接着剤 (b— 1)を調製した。  Water was added to 163-03045 (molecular weight 22000, Kenya degree 88 mol%) manufactured by Wako Pure Chemical Industries, Ltd., which is a polyvinyl alcohol-based resin, to prepare an aqueous solution having a solid content concentration of 7% by weight. On the other hand, 100 parts of WLS-201 (solid concentration 35% by weight) manufactured by Dainippon Ink & Chemicals, Inc., which is a polyurethane resin, is added to CR manufactured by Dainippon Ink Industries, Ltd., a polyepoxy curing agent. — 5 L (100% active ingredient) 5 parts was mixed and diluted with water to prepare an aqueous solution with a solid content of 20% by weight. The obtained polyurethane-based resin aqueous solution and polyvinyl alcohol-based resin aqueous solution are mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and the solid content concentration is 15% by weight. A mixed adhesive (b-1) was prepared.
[0182] [調製例 2]  [0182] [Preparation Example 2]
大日本インキ化学工業 (株)製の WLS - 201の代わりに、ポリウレタン榭脂（B— 1) 100部を使用した以外は、調製例 1と同様にして、固形分濃度が 15重量％の混合接 着剤 (b— 2)を調製した。  Mixing with a solid content concentration of 15% by weight in the same manner as Preparation Example 1, except that 100 parts of polyurethane resin (B-1) was used instead of WLS-201 manufactured by Dainippon Ink and Chemicals, Inc. Adhesive (b-2) was prepared.
[0183] [調製例 3] 大日本インキ化学工業 (株)製の WLS - 201の代わりに、ポリウレタン榭脂（B— 2) 100部を使用した以外は、調製例 1と同様にして、固形分濃度が 15重量％の混合接 着剤 (b— 3)を調製した。 [0183] [Preparation Example 3] Mixing with a solid content concentration of 15% by weight in the same manner as in Preparation Example 1, except that 100 parts of polyurethane resin (B-2) was used instead of WLS-201 manufactured by Dainippon Ink & Chemicals, Inc. Adhesive (b-3) was prepared.
[0184] [調製例 4] [0184] [Preparation Example 4]
大日本インキ化学工業 (株)製の WLS - 201とポリビニルアルコール系榭脂とを固 形分重量比で 95： 5の割合で混合した以外は調製例 1と同様にして、固形分濃度が 15重量％の混合接着剤 (b— 4)を調製した。  The solids concentration was 15 in the same manner as in Preparation Example 1 except that WLS-201 manufactured by Dainippon Ink & Chemicals, Inc. and polyvinyl alcohol-based resin were mixed at a solid weight ratio of 95: 5. A weight percent mixed adhesive (b-4) was prepared.
[0185] [調製例 5] [Preparation Example 5]
大日本インキ化学工業 (株)製の WLS - 201とポリビニルアルコール系榭脂とを固 形分重量比で 50 : 50の割合で混合した以外は調製例 1と同様にして、固形分濃度 が 15重量％の混合接着剤 (b 5)を調製した。  The solids concentration is 15 in the same manner as in Preparation Example 1 except that WLS-201 manufactured by Dainippon Ink & Chemicals, Inc. and polyvinyl alcohol-based resin are mixed at a solid weight ratio of 50:50. A weight percent mixed adhesive (b 5) was prepared.
[0186] [比較調製例 1] [0186] [Comparative Preparation Example 1]
(比較用接着剤の調製）  (Preparation of comparative adhesive)
大日本インキ化学工業ィ匕学 (株)製の WLS— 201 (固形分濃度 35重量％の水溶 液） 100部に、大日本インキ化学工業 (株)製の CR— 5L (有効成分 100%品） 5部を 配合し、さらに水を加えて固形分濃度が 15重量％となるように希釈し、接着剤 (g—l )を調製した。  Dainippon Ink & Chemicals, Inc. WLS-201 (Solid content 35% by weight aqueous solution) 100 parts, Dainippon Ink & Chemicals CR-5L (100% active ingredient) ) 5 parts was added, and water was further added to dilute to a solid content concentration of 15% by weight to prepare an adhesive (g-l).
[0187] [比較調製例 2] [0187] [Comparative Preparation Example 2]
(比較用接着剤の調製）  (Preparation of comparative adhesive)
和光純薬工業 (株）製の 163— 03045 (分子量 22000、ケン化度 88モル0 /。）に、水 を加えて固形分濃度が 15重量％となるように希釈し、接着剤 (g— 2)を調製した。 Wako Pure Chemical Industries, Ltd. 163—03045 (molecular weight 22000, saponification degree 88 mol 0 /.) Was diluted with water to a solid content concentration of 15% by weight. 2) was prepared.
[0188] [比較調製例 3] [0188] [Comparative Preparation Example 3]
(比較用接着剤の調製）  (Preparation of comparative adhesive)
大日本インキ化学工業 (株)製の WLS - 201とポリビニルアルコール系榭脂とを固 形重量比で 50 : 50の割合で混合した以外は調製例 1と同様にして、固形分濃度が 1 5重量％の混合接着剤 (g- 3)を調製した。  The solids concentration is 15 as in Preparation Example 1 except that WLS-201 manufactured by Dainippon Ink and Chemicals, Inc. and polyvinyl alcohol-based resin are mixed at a solid weight ratio of 50:50. A weight percent mixed adhesive (g-3) was prepared.
[0189] [比較調製例 4] [0189] [Comparative Preparation Example 4]
(比較用接着剤の調製） ポリウレタン系榭脂として、ポリエステル骨格を有する大日本インキ化学工業 (株)製 の AP - 40N (固形分濃度 35重量％の水溶液） 100部を用 、た以外は調製例 1と同 様にして、固形分濃度が 15重量％の混合接着剤 (g-4)を調製した。 (Preparation of comparative adhesive) The same procedure as in Preparation Example 1 except that 100 parts of AP-40N (aqueous solution with a solid content of 35% by weight) manufactured by Dainippon Ink & Chemicals, Inc. having a polyester skeleton was used as the polyurethane resin. A mixed adhesive (g-4) having a solid content concentration of 15% by weight was prepared.
[0190] [比較調製例 5] [0190] [Comparative Preparation Example 5]
(比較用接着剤の調製）  (Preparation of comparative adhesive)
大日本インキ化学工業 (株)製の CR— 5Lの添加量を 5部にした以外は調製例 1と 同様にして、固形分濃度が 15重量％の混合接着剤 (g— 5)を調製した。  A mixed adhesive (g-5) having a solid content concentration of 15% by weight was prepared in the same manner as Preparation Example 1 except that the amount of CR-5L manufactured by Dainippon Ink & Chemicals, Inc. was changed to 5 parts. .
[0191] [実施例 1〜3] [0191] [Examples 1 to 3]
(a)偏光フィルムの作製  (a) Production of polarizing film
ポリビニルアルコール（以下、「PVA」と略す）を、ヨウ素濃度が 0. 03重量％であり、 ヨウ化カリウム濃度が 0. 5重量％である水溶液力 なる温度 30°Cの染色浴中で、延 伸倍率 3倍で前延伸加工し、次いで、ホウ酸濃度が 5重量％であり、ヨウ化カリウム濃 度が 8重量％である水溶液からなる温度 55°Cの架橋浴中で、延伸倍率 2倍で後延伸 加工した後、乾燥処理することにより、偏光膜 (以下、「偏光子（1)」ともいう）を得た。  Polyvinyl alcohol (hereinafter abbreviated as “PVA”) is spread in a dyeing bath at a temperature of 30 ° C. with an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight. Pre-stretched at a stretch ratio of 3 times, and then stretched at a stretch ratio of 2 times in a 55 ° C crosslinking bath consisting 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 post-stretched at, and then dried to obtain a polarizing film (hereinafter also referred to as “polarizer (1)”).
[0192] (b)保護フィルム付偏光板の作製  [0192] (b) Preparation of polarizing plate with protective film
上記 (a)で得た偏光子（1)の両面に、調製例 1〜3で得られた混合接着剤 (b— 1)、 (b— 2)または (b— 3)を介して、作製例 1で得られた位相差フィルム（a— 5)、 (a-6) および (a— 7)を表 2に示す組み合わせで接着して偏光板を得た。  Fabricated on both sides of the polarizer (1) obtained in (a) above via the mixed adhesive (b-1), (b-2) or (b-3) obtained in Preparation Examples 1 to 3. The retardation films (a-5), (a-6) and (a-7) obtained in Example 1 were bonded in the combinations shown in Table 2 to obtain polarizing plates.
[0193] 得られた偏光板の全光線透過率はすべて 44. 0%、偏光度は 99. 9%であった。ま た、得られた偏光板についてそれぞれ接着性を評価したところ、接着強度はすべて ランク 2であった。さらに、得られた各偏光板を湿熱下または乾熱下で保存した後、接 着性を評価した。結果を表 2に示す。  [0193] All the light transmittances of the obtained polarizing plates were 44.0%, and the degree of polarization was 99.9%. Further, when the adhesive properties of the obtained polarizing plates were evaluated, the adhesive strength was all rank 2. Furthermore, after each obtained polarizing plate was stored under wet heat or dry heat, the adhesion was evaluated. The results are shown in Table 2.
[0194] また、得られた各偏光板を湿熱下または乾熱下で保存した後、眼科用医療用刀 (フ ヱザ一安全剃刀 (株)製)で偏光子と位相差フィルムとを分離し、偏光子および位相 差フィルムのそれぞれにつ 、て位相差を測定した。結果を表 3に示す。  [0194] After each polarizing plate obtained was stored under wet heat or dry heat, the polarizer and the retardation film were separated with an ophthalmic medical sword (manufactured by Fusaichi Safety Razor Co., Ltd.). Then, the retardation was measured for each of the polarizer and the retardation film. The results are shown in Table 3.
[0195] [実施例 4、 5]  [0195] [Examples 4 and 5]
接着剤として、調製例 4または 5で得られた混合接着剤 (b-4)または (b— 5)を用 いた以外は、実施例 1と同様にして偏光板を得た。 [0196] 得られた偏光板につ!ヽてそれぞれ接着性を評価したところ、接着強度はすべてラ ンク 2であった。さらに、得られた各偏光板を湿熱下または乾熱下で保存した後、接 着性を評価した。結果を表 2に示す。 A polarizing plate was obtained in the same manner as in Example 1 except that the mixed adhesive (b-4) or (b-5) obtained in Preparation Example 4 or 5 was used as the adhesive. [0196] When the obtained polarizing plate was evaluated for adhesiveness, the adhesive strength was all rank 2. Furthermore, after each obtained polarizing plate was stored under wet heat or dry heat, the adhesion was evaluated. The results are shown in Table 2.
[0197] また、得られた各偏光板を湿熱下または乾熱下で保存した後、眼科用医療用刀 (フ ヱザ一安全剃刀 (株)製)で偏光子と位相差フィルムとを分離し、偏光子および位相 差フィルムのそれぞれにつ 、て位相差を測定した。結果を表 3に示す。  [0197] After each polarizing plate obtained was stored under wet heat or dry heat, the polarizer and the retardation film were separated with an ophthalmic medical sword (manufactured by Fusaichi Safety Razor Co., Ltd.). Then, the retardation was measured for each of the polarizer and the retardation film. The results are shown in Table 3.
[0198] [実施例 6]  [0198] [Example 6]
位相差フィルムとして、作製例 2で得られた位相差フィルム (a— 5，）、（a— 6，）およ び (a— 7 ' )を表 2に示す組み合わせで接着した以外は実施例 1と同様にして偏光板 を得た。  As the retardation film, the retardation films (a-5,), (a-6,) and (a-7 ') obtained in Preparation Example 2 were bonded together in the combinations shown in Table 2. A polarizing plate was obtained in the same manner as in 1.
[0199] 得られた偏光板の全光線透過率はすべて 44. 0%、偏光度は 99. 9%であった。ま た、得られた偏光板についてそれぞれ接着性を評価したところ、接着強度はすべて ランク 1であった。さらに、得られた各偏光板を湿熱下または乾熱下で保存した後、接 着性を評価した。結果を表 2に示す。  [0199] All the light transmittances of the obtained polarizing plates were 44.0%, and the degree of polarization was 99.9%. Also, when the adhesive properties of the obtained polarizing plates were evaluated, the adhesive strength was all rank 1. Furthermore, after each obtained polarizing plate was stored under wet heat or dry heat, the adhesion was evaluated. The results are shown in Table 2.
[0200] 本発明の偏光板の接着強度はランク 1または 2であり、使用可能なレベルであった。  [0200] The adhesive strength of the polarizing plate of the present invention was rank 1 or 2, which was a usable level.
また、ランク 2の偏光板はコロナ処理を施すことによりランク 1に向上した。  The rank 2 polarizing plate was improved to rank 1 by corona treatment.
[0201] また、得られた各偏光板を湿熱下または乾熱下で保存した後、眼科用医療用刀 (フ ヱザ一安全剃刀 (株)製)で偏光子と位相差フィルムとを分離し、偏光子および位相 差フィルムのそれぞれにつ 、て位相差を測定した。結果を表 3に示す。  [0201] Further, after each polarizing plate obtained was stored under wet heat or dry heat, the polarizer and the retardation film were separated with an ophthalmic medical sword (manufactured by Fusaichi Safety Razor Co., Ltd.). Then, the retardation was measured for each of the polarizer and the retardation film. The results are shown in Table 3.
[0202] [比較例 1]  [0202] [Comparative Example 1]
位相差フィルムとして、比較作製例 1で得られた位相差フィルム (f 5)、 （f—6)お よび (f 7)を表 2に示す組み合わせで接着した以外は実施例 1と同様にして偏光板 を得た。  As the retardation film, the same as in Example 1 except that the retardation films (f 5), (f-6) and (f 7) obtained in Comparative Preparation Example 1 were bonded in the combinations shown in Table 2. A polarizing plate was obtained.
[0203] 得られた偏光板の全光線透過率はすべて 44. 0%、偏光度は 99. 9%であった。ま た、得られた偏光板についてそれぞれ接着性を評価したところ、全ての偏光板にお いて、偏光子と位相差フィルムを剥離することができた。結果を表 2に示す。  [0203] All the light transmittances of the obtained polarizing plates were 44.0%, and the degree of polarization was 99.9%. Moreover, when the adhesiveness of each of the obtained polarizing plates was evaluated, the polarizer and the retardation film could be peeled from all the polarizing plates. The results are shown in Table 2.
[0204] [比較例 2〜6]  [0204] [Comparative Examples 2 to 6]
接着剤として、比較調製例 1〜5で得られた接着剤 (g—1)もしくは (g 2)、または 混合接着剤 (g— 3)、（g— 4)もしくは (g— 5)を用いた以外は、実施例 1と同様にして 偏光板を得た。 As an adhesive, the adhesive (g-1) or (g 2) obtained in Comparative Preparation Examples 1 to 5, or A polarizing plate was obtained in the same manner as in Example 1 except that the mixed adhesive (g-3), (g-4) or (g-5) was used.
[0205] 得られた偏光板につ!ヽてそれぞれ接着性を評価したところ、偏光子と位相差フィル ムを剥離することができた。結果を表 2に示す。  [0205] When the obtained polarizing plate was evaluated for adhesiveness, the polarizer and the retardation film could be peeled off. The results are shown in Table 2.
[0206] [表 2] 表 2 [0206] [Table 2] Table 2
Figure imgf000044_0001
Figure imgf000044_0001
1 ) 偏光板の構成：位相差フィルム 1 Z偏光子 （ 1 ) Z位相差フィルム 2  1) Polarizing plate composition: retardation film 1 Z polarizer (1) Z retardation film 2
：測定せず 3] : Not measured 3]
表 3 Table 3
Figure imgf000045_0001
Figure imgf000045_0001
偏光板の構成：位相差フィルム 1/偏光子 （1) /位相差フィルム 2 Composition of polarizing plate: retardation film 1 / polarizer (1) / retardation film 2

Claims

請求の範囲 The scope of the claims
[1] ノルボルネン系榭脂フィルムと偏光膜とが接着剤層を介して積層された偏光板であ つて、前記接着剤層がポリエーテルポリオールとポリイソシァネートイ匕合物とを反応さ せてなるポリウレタン系榭脂とポリビュルアルコール系榭脂との混合物力も形成され、 該接着剤層中のポリウレタン系榭脂とポリビニルアルコール系榭脂との合計 100重量 部に対して固形分重量比（ポリウレタン系榭脂 Zポリビニルアルコール系榭脂）が 90 ZlO〜70Z30であることを特徴とする偏光板。  [1] A polarizing plate in which a norbornene-based resin film and a polarizing film are laminated via an adhesive layer, and the adhesive layer reacts a polyether polyol and a polyisocyanate compound. A mixture force of polyurethane-based resin and polybulal alcohol-based resin is also formed, and the solid content weight ratio (100 parts by weight of the total of polyurethane-based resin and polyvinyl alcohol-based resin in the adhesive layer ( A polarizing plate characterized in that the polyurethane-based resin (Z-polyvinyl alcohol-based resin) is 90 ZlO to 70Z30.
[2] 前記ノルボルネン系榭脂フィルム力 下記式（1)で表される少なくとも 1種の化合物 を含む単量体を (共)重合して得られた榭脂からなるフィルムであることを特徴とする 請求項 1に記載の偏光板。 [2] The norbornene-based resin film strength is a film comprising a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1): The polarizing plate according to claim 1.
[化 1]  [Chemical 1]
Figure imgf000046_0001
Figure imgf000046_0001
(式（1)中、 Ri〜R4は、各々独立に水素原子;ハロゲン原子;または酸素、窒素、ィォ ゥもしくはケィ素を含有していてもよい 1価の基を表す。 R1と R2、または R3と R4とが相 互に結合してアルキリデン基を形成していてもよぐあるいは、 R1と R2、 R3と R4、または R2と R3とが相互に結合して単環または多環の炭素環または複素環を形成してもよい 。 Xは 0または 1〜3の整数、 yは 0または 1を表す。ただし、 Xが 0のとき、 yも 0である。） (In the formula (1), Ri to R 4 each independently represent a hydrogen atom, a halogen atom, or a monovalent group that may contain oxygen, nitrogen, ion, or key. R 1 and R 2 , or R 3 and R 4 may be bonded to each other to form an alkylidene group, or R 1 and R 2 , R 3 and R 4 , or R 2 and R 3 may be To form a monocyclic or polycyclic carbocyclic or heterocyclic ring, X is 0 or an integer of 1 to 3, y is 0 or 1, provided that when X is 0, y is also 0.)
[3] 前記ノルボルネン系榭脂フィルムが位相差フィルムであることを特徴とする請求項 1 に記載の偏光板。 [3] The polarizing plate according to claim 1, wherein the norbornene-based resin film is a retardation film.
[4] 前記接着剤層が、さらに水溶性エポキシィ匕合物を含有し、該接着剤層中のポリウレ タン樹脂と水溶性エポキシィ匕合物との合計 100重量部に対して、固形分重量比 (ポリ ウレタン榭脂 Z水溶性エポキシィ匕合物）が 97Z3〜82Z18であることを特徴とする 請求項 1に記載の偏光板。  [4] The adhesive layer further contains a water-soluble epoxy compound, and the solid content weight ratio with respect to a total of 100 parts by weight of the polyurethane resin and the water-soluble epoxy compound in the adhesive layer. The polarizing plate according to claim 1, wherein (polyurethane resin Z water-soluble epoxy compound) is 97Z3 to 82Z18.
[5] ノルボルネン系榭脂フィルムを、ポリエーテルポリオールとポリイソシァネートイ匕合物 とを反応させてなるポリウレタン系榭脂とポリビニルアルコール系榭脂との混合物から 形成され、ポリウレタン系榭脂とポリビュルアルコール系榭脂との合計 100重量部に 対して固形分重量比（ポリウレタン系榭脂 Zポリビュルアルコール系榭脂）が 90Z10 〜70Z30である接着剤層を介して偏光膜と接着することを特徴とする偏光板の製造 方法。 [5] A norbornene-based resin film is formed from a mixture of a polyurethane-based resin and a polyvinyl alcohol-based resin obtained by reacting a polyether polyol and a polyisocyanate compound. An adhesive layer having a solid weight ratio (polyurethane-based resin Z-polybulal alcohol-based resin) of 90Z10 to 70Z30 with respect to a total of 100 parts by weight of the polyurethane-based resin and the polybulle alcohol-based resin is formed. A polarizing plate is bonded to the polarizing film through a method for producing a polarizing plate.
前記ノルボルネン系榭脂フィルム表面を、予めコロナ放電電子の照射量 70〜： LOO WZm2/minでコロナ処理することを特徴とする請求項 5に記載の偏光板の製造方 法。 6. The method for producing a polarizing plate according to claim 5, wherein the surface of the norbornene-based resin film is previously subjected to corona treatment with a corona discharge electron dose of 70 to: LOO WZm 2 / min.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008096694A1 (en) * 2007-02-05 2008-08-14 Jsr Corporation Phase difference film, polarizing plate using the phase difference film, and liquid crystal panel
JP2009157160A (en) * 2007-12-27 2009-07-16 Sekisui Chem Co Ltd Thermoplastic resin film and polarizing plate using the same
JP2009241283A (en) * 2008-03-28 2009-10-22 Nippon Zeon Co Ltd Method for manufacturing laminated film and laminated film
JP2009242464A (en) * 2008-03-28 2009-10-22 Nippon Zeon Co Ltd Method for manufacturing laminate film, and laminate film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001350018A (en) * 2000-06-05 2001-12-21 Nitto Denko Corp Optical compensation film, polarizing plate and liquid crystal display device using the same
JP2004037841A (en) * 2002-07-03 2004-02-05 Sekisui Chem Co Ltd Manufacturing method of polarizer
JP2004198952A (en) * 2002-12-20 2004-07-15 Jsr Corp Optical film and its use
JP2004212848A (en) * 2003-01-08 2004-07-29 Jsr Corp Optical film and its manufacture method as well as application product thereof
JP2004334168A (en) * 2003-04-16 2004-11-25 Sumitomo Chem Co Ltd Polarizing plate and its manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001350018A (en) * 2000-06-05 2001-12-21 Nitto Denko Corp Optical compensation film, polarizing plate and liquid crystal display device using the same
JP2004037841A (en) * 2002-07-03 2004-02-05 Sekisui Chem Co Ltd Manufacturing method of polarizer
JP2004198952A (en) * 2002-12-20 2004-07-15 Jsr Corp Optical film and its use
JP2004212848A (en) * 2003-01-08 2004-07-29 Jsr Corp Optical film and its manufacture method as well as application product thereof
JP2004334168A (en) * 2003-04-16 2004-11-25 Sumitomo Chem Co Ltd Polarizing plate and its manufacturing method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008096694A1 (en) * 2007-02-05 2008-08-14 Jsr Corporation Phase difference film, polarizing plate using the phase difference film, and liquid crystal panel
JP2009157160A (en) * 2007-12-27 2009-07-16 Sekisui Chem Co Ltd Thermoplastic resin film and polarizing plate using the same
JP2009241283A (en) * 2008-03-28 2009-10-22 Nippon Zeon Co Ltd Method for manufacturing laminated film and laminated film
JP2009242464A (en) * 2008-03-28 2009-10-22 Nippon Zeon Co Ltd Method for manufacturing laminate film, and laminate film

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