JP2003062943A - Resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate having a polarizing function excellent in durability and the stability of optical capacity under a severe using environment. SOLUTION: A layer of a film (A) comprising an alicyclic structure-containing polymer resin is formed on at least one surface of a polarizing film (B) through a layer (C) of an adhesive containing a polyether type polymer having a silyl group in its terminal or a polyolefinic polymer having a silyl group in its terminal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate in which a layer made of a polymer resin containing an alicyclic structure is adhered to a polarizing film and a method for producing the same, more specifically, a laminate suitable as a polarizing film and a method for producing the same. Regarding

[0002]

2. Description of the Related Art Polarizing films utilize various functions such as removal of reflected light and light lockability, and are used in, for example, sunglasses, camera filters, sports goggles, lighting gloves, antiglare headlights for automobiles, light-shielding window glass, It is used in a wide range of fields such as light intensity control filters, fluorescent display contrastars, translucency continuous change plates, and polarizing films for microscopes. Recently, it has been used in a liquid crystal display (LCD) and its functionality has been highlighted. A liquid crystal display is generally composed of a liquid crystal display element, a polarizing film, a retardation film, a backlight and the like. The polarizing film is composed of a thin film type polarizing film having a polarizing function and a protective layer for ensuring durability and mechanical strength of the polarizing film, and protective layers made of various films adhere to both sides of the polarizing film. It is laminated by the agent. As the protective layer, a solution cast film of cellulose triacetate (hereinafter abbreviated as TAC), which has low birefringence and good appearance, is mainly used. Recently, instead of TAC, a thermoplastic saturated norbornene-based resin sheet is laminated as a protective layer on a polarizing film to obtain a polarizing film excellent in moisture resistance, physical strength, heat resistance, transparency and low birefringence. It is reported that As a laminating method, a method has been reported in which a polarizing film and a thermoplastic saturated norbornene-based resin sheet are bonded together with an acrylic pressure-sensitive adhesive, and then heated and pressed to bond them (Japanese Patent Laid-Open No. 5-212828, JP Kaihei 6-511117).

By the way, LCDs are rapidly becoming widespread in thin and small notebook personal computers, car navigation systems, flat TVs, etc., and the polarizing films used therefor have durability in more severe environment than before,
Optical performance is required to be stable.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate having a polarizing function which is excellent in durability and optical performance stability under a severe environment of use.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a thermoplastic saturated norbornene is produced by a silicone-based adhesive containing a polyether having a substituted silyl group at the terminal as a main component. A laminated film formed by laminating a resin film on at least one surface of a polarizing film,
Even under severe environment such as long-term high temperature and high humidity environment, the occurrence of haze due to heat and moisture, discoloration, deformation, etc., found that the interface peeling of each layer and fine swelling, the occurrence of cracks does not occur, The present invention has been completed based on the findings.

Thus, according to the present invention, (1) an adhesive layer (C) containing a polyether polymer having a silyl group at the terminal or a polyolefin polymer having a silyl group at the terminal is used to provide a grease. The laminate (2) in which the layer of the film (A) made of a polymer resin having a cyclic structure is formed on at least one surface of the polarizing film (B), and the polyether polymer is polypropylene oxide. Laminate (3) The silyl group has an alkyl group or an alkoxy group as a substituent (1) or (2) The laminate (4) A film (A) comprising an alicyclic structure-containing polymer resin And an adhesive containing a polyether polymer having a silyl group at the terminal or a polyolefin polymer having a silyl group at the terminal is applied to at least one of the polarizing film (B), and then the adhesive There is provided a method for producing a laminate, which includes a step of bonding the film (A) and the polarizing film (B) with the coated surface inside and further heating and drying.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The laminate of the present invention comprises a layer (C) of an adhesive containing a polyether polymer having a silyl group at the terminal or a polyolefin polymer having a silyl group at the terminal, The layer of the film (A) made of a polymer resin containing an alicyclic structure is formed on at least one surface of the polarizing film (B). The layers of the film (A) may be formed on both sides of the polarizing film (B).

The alicyclic structure-containing polymer resin has an alicyclic structure in the repeating unit of the polymer and may have an alicyclic structure in either the main chain or the side chain. . Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and the cycloalkane structure is preferable from the viewpoint of thermal stability and the like. When the number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15, a sealing layer excellent in heat resistance and flexibility is obtained. can get. The proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer resin may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, and more preferably Is 9
It is 0% by weight or more. If the proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer resin is excessively low, heat resistance is reduced, which is not preferable. The balance other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin is appropriately selected according to the purpose of use.

Specific examples of the alicyclic structure-containing polymer resin include (1) norbornene-based polymers, (2) monocyclic cycloolefin-based polymers, (3) cyclic conjugated diene-based polymers,
(4) Vinyl alicyclic hydrocarbon polymers, hydrides thereof, and the like. Among these, from the viewpoint of heat resistance, mechanical strength, etc., a norbornene-based polymer hydride,
Vinyl alicyclic hydrocarbon polymers and hydrides thereof are preferred.

(1) Norbornene-based polymer The norbornene-based polymer used in the present invention includes a ring-opening polymer of a norbornene-based monomer and a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization. Examples thereof include polymers, hydrides thereof, addition polymers of norbornene-based monomers, and addition copolymers of norbornene-based monomers with other monomers copolymerizable therewith. Among these, the hydrogenated ring-opening polymer of the norbornene-based monomer is most preferable from the viewpoint of heat resistance, mechanical strength and the like.

The norbornene-based monomer includes bicyclo [2.2.1] -hept-2-ene (common name: norbornene) and its derivatives (having a substituent on the ring),
Tricyclo ^{[4.3.1 2,5.} 0 ^1,6 ] -deca-
3,7-Diene (common name dicyclopentadiene) and its derivatives, tetracyclo [7.4.11 ^10,13 . 0 ^{1
, 9} . 0 ^2,7 ] -trideca-2,4,6-11 tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene: trivial name methanotetrahydrofluorene) and its derivatives, tetracyclo [4 .4.
1 ^2,5 . 1 ^{7, 10} . 0] -dodec-3-ene (conventional name: tetracyclododecene) and its derivatives. Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and the like, and the norbornene-based monomer may have two or more kinds thereof. Specifically, 8-methoxycarbonyl - tetracyclo ^{[4.4.1 2,5.} 1 ^{7, 10} .
0] - dodeca-3-ene, 8-methyl-8-methoxycarbonyl - tetracyclo ^{[4.4.1 2,5.} 1
^7,10 . 0] -dodeca-3-ene and the like.
These norbornene-based monomers may be used alone or in combination of two or more.

The ring-opening polymer of these norbornene-based monomers, or the ring-opening copolymer of the norbornene-based monomer and other monomer capable of ring-opening copolymerization contains a monomer component in the presence of a known ring-opening polymerization catalyst. It can be obtained by polymerizing under. As the ring-opening polymerization catalyst, for example, ruthenium, a metal halide such as osmium, and a catalyst comprising a nitrate or an acetylacetone compound, and a reducing agent, or titanium, zirconium, tungsten,
A catalyst composed of a metal halide such as molybdenum or an acetylacetone compound and an organoaluminum compound can be used. Examples of the other monomer capable of ring-opening copolymerization with the norbornene-based monomer include monocyclic cycloolefin-based monomers such as cyclohexene, cycloheptene, and cyclooctene.

The hydrogenated ring-opening polymer of the norbornene-based monomer is usually carbon-carbon unsaturated by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization solution of the above ring-opening polymer. It can be obtained by hydrogenating the bond.

The addition polymer of the norbornene-based monomer or the addition (co) polymer of the norbornene-based monomer and another monomer copolymerizable with the norbornene-based monomer is obtained by adding these monomers to a known addition polymerization catalyst such as titanium, It can be obtained by (co) polymerization using a catalyst composed of a zirconium or vanadium compound and an organic aluminum compound.

Other monomers copolymerizable with the norbornene-based monomer include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene. , 1-hexadecene, 1-octadecene, 1-eicosene, and other α-olefins having 2 to 20 carbon atoms, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4, Cycloolefins such as 7-methano-1H-indene, and their derivatives; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
Non-conjugated dienes such as 1,4-hexadiene and 1,7-octadiene; and the like are used. Among these, α-
Olefins, especially ethylene, are preferred.

These other monomers copolymerizable with the norbornene-based monomer can be used alone or in combination of two or more kinds. In the case of addition-copolymerizing a norbornene-based monomer with another monomer copolymerizable with the norbornene-based monomer, the ratio of the structural unit derived from the norbornene-based monomer to the structural unit derived from the other copolymerizable monomer in the addition copolymer. However, the weight ratio is usually 30:70 to 99: 1, preferably 50:50 to 97 :.
3, more preferably, it is appropriately selected to be in the range of 70:30 to 95: 5.

(2) Monocyclic cycloolefin polymer As the monocyclic cycloolefin polymer, for example, an addition polymer of a monocyclic cycloolefin monomer such as cyclohexene, cycloheptene or cyclooctene is used. be able to.

(3) Cyclic Conjugated Diene Polymer As the cyclic conjugated diene polymer, for example, 1,2- or 1,4-addition polymerization of a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene is carried out. Polymers and hydrides thereof can be used.

The molecular weight of the norbornene-based polymer, monocyclic cyclic olefin-based polymer or cyclic conjugated diene-based polymer used in the present invention is appropriately selected according to the purpose of use, but cyclohexane solution (polymer resin Is not dissolved, the weight average molecular weight in terms of polyisoprene or polystyrene measured by gel permeation chromatography of a toluene solution) is usually 5,000 to 500,
000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, which is suitable because the mechanical strength of the molded product and the moldability are highly balanced. .

(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and hydrogens thereof. Compounds; hydrides of aromatic ring moieties of polymers of vinyl aromatic monomers such as styrene and α-methylstyrene; In this case, a copolymer such as a random copolymer or a block copolymer of a vinyl alicyclic hydrocarbon polymer or a vinyl aromatic monomer and another monomer copolymerizable with these monomers. It may be a polymer or a hydride thereof. Examples of the block copolymer include a diblock, a triblock, or a multiblock or a gradient block copolymer of more than that, and there is no particular limitation.

The molecular weight of the vinyl alicyclic hydrocarbon polymer used in the present invention is appropriately selected according to the purpose of use, but gel permeation of a cyclohexane solution (toluene solution if the polymer resin is not dissolved) is used. By weight average molecular weight in terms of polyisoprene or polystyrene measured by the cation chromatography method, usually 10,000 to 300,
000, preferably 15,000 to 250,000, and more preferably 20,000 to 200,000 is suitable because the mechanical strength and molding processability of the molded article are highly balanced.

The glass transition temperature (Tg) of the alicyclic structure-containing polymer resin used in the present invention may be appropriately selected depending on the purpose of use, but is usually 80 ° C. or higher, preferably 100 ° C. or higher. 250 ° C, more preferably 120 ° C to 200
It is in the range of ° C. Within this range, heat resistance and molding processability are highly balanced, which is preferable.

In the present invention, the alicyclic structure-containing polymer resin described above can be molded to obtain the film (A). As the method for molding the film (A), for example, either a heat melting molding method or a solution casting method can be used. The heat melt molding method can be classified in more detail into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, and the like. In order to obtain a film excellent in accuracy and the like, an extrusion molding method, an inflation molding method and a press molding method are preferable, and an extrusion molding method is most preferable. The molding conditions are appropriately selected depending on the purpose of use and the molding method, but in the case of the hot melt molding method, the cylinder temperature is usually 150 to 400 ° C., preferably 20.
The temperature is appropriately set in the range of 0 to 350 ° C, more preferably 230 to 330 ° C. If the resin temperature is too low, the fluidity deteriorates, causing sink marks and distortion in the film, and if the resin temperature is too high, voids and silver streaks occur due to thermal decomposition of the resin, or the film turns yellow. Defects may occur. The thickness of the film (A) is usually 10 to 300 μm, preferably 20 to 200 μm, more preferably 30 to 100 μm.

Adhesive The adhesive used in the present invention contains a polyether polymer having a silyl group at the terminal or a polyolefin polymer having a silyl group at the terminal. The polyether polymer is
Any polymer having an ether bond in the main chain can be used, but in the present invention, a polymer containing a repeating unit obtained by polymerizing an alkylene oxide such as ethylene oxide or propylene oxide is preferable.
The polymer may contain epichlorohydrin or allyl glycidyl ether as a copolymerization component,
Specifically, it is most preferable to use polyalkylene oxide such as polyethylene oxide, polypropylene oxide, and a copolymer of ethylene oxide and propylene oxide. As the polyolefin-based polymer, specifically, it is preferable to use a chain olefin polymer such as ethylene, propylene, or isobutylene. The above polyether-based polymer or polyolefin-based polymer,
Although it may be a polymer or an oligomer, it is more preferable that it is liquid at room temperature without containing a solvent. Among these, polypropylene oxide and isobutylene oligomer are particularly preferable from the viewpoint of adhesive strength, durability and the like.

The polyether polymer or the polyolefin polymer is required to have a silyl group at least at one end, but one having a silyl group at every end is more preferable. The silyl group is preferably one having an alkyl group or an alkoxy group as a substituent. The alkyl group or alkoxy group preferably has 1 or 2 carbon atoms. Specific examples of the silyl group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group and diethylmethylsilyl group; trimethoxysilyl group, triethoxysilyl group, dimethoxyethoxysilyl group, diethoxy. Trialkoxysilyl group such as methoxysilyl group; dimethoxymethylsilyl group, dimethoxyethylsilyl group, diethoxymethylsilyl group, diethoxyethylsilyl group, dimethylmethoxysilyl group, dimethylethoxysilyl group, diethylmethoxysilyl group, diethylethoxysilyl Examples of such groups include alkylalkoxysilyl groups, but from the viewpoint of reactivity and stability, alkylalkoxysilyl groups are preferable, dialkoxyalkylsilyl groups are more preferable, and dimethoxymethylsilyl groups are the most preferable. Preferred. The number average molecular weight (Mn) of the polyether-based polymer and the olefin-based polymer is preferably 1,000 to 100,
000, more preferably 2,000 to 50,000, and further preferably 3,000 to 30,000. Mn
Is within the above range, the viscosity of the adhesive and the strength of the adhesive layer are excellent. The viscosity of the above polyether polymer and olefin polymer is preferably in the range of 1 to 100 Pa · s at 23 ° C.

The adhesive used in the present invention is a curing catalyst (curing agent) capable of forming a siloxane bond by reacting silyl groups of these polymers in addition to the above polyether polymers and polyolefin polymers. The one containing As the curing agent, platinum-based, tin-based, bismuth-based, etc.
There are various types, but among them, tin-based curing agents are preferable in terms of compatibility with the olefin-based polymer, curing rate, reaction activity, and the like. Examples of the tin-based curing agent include stannous octoate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutylmalate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-
Dilauryloxycarbonyl-distannoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin diversate, dibutyltin di-2-ethylhexano And dibutyltin oxide. The amount of the curing agent is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyether polymer or the olefin polymer.
Parts by weight, more preferably 0.5 to 3 parts by weight.

The adhesive used in the present invention is generally used as a prepolymer of a curable resin such as a curable epoxy resin or a curable acrylic resin, and a curing agent for these prepolymers. By further containing, it is possible to improve the strength and the like of the adhesive layer. The amount of the prepolymer is preferably 2 to 50 parts by weight, more preferably 10 to 40 parts by weight, and the curing agent is preferably 1 to 100 parts by weight with respect to the polyether polymer or the olefin polymer. 30 parts by weight, more preferably 5 to 20 parts by weight.

The adhesive has a viscosity when applied to the film,
You may dilute with a solvent and use it in order to control the film thickness of a coating film, etc. Solvents used for dilution include alcohols such as isopropyl alcohol and isobutyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane; esters such as ethyl acetate and butyl acetate. Kinds; aromatic hydrocarbon compounds such as toluene and xylene. These solvents are
They may be used alone or in combination of two or more, and the mixing ratio, dilution ratio, etc. are appropriately selected depending on the type of substrate and the bonding method.

In addition to the above, the adhesives used in the present invention include fillers such as calcium carbonate and titanium oxide, reactive diluents such as (meth) acrylic monomers, plasticizers, surfactants (leveling agents), and ultraviolet absorbers. Agents, light stabilizers, antioxidants, dehydrating agents, adhesive agents, pot life extenders (acetylacetone, methanol, methyl orthoacetate, etc.),
It may also contain additives commonly incorporated in adhesives, such as cissing improvers.

Depending on the type of curing agent, the above-mentioned adhesive may be one which is cured by moisture in the air at room temperature or one which is cured by heating, but from the viewpoint of storage stability, the main agent containing an olefin polymer. It is preferable to use a two-component type in which (A liquid) and an auxiliary agent (B liquid) containing a curing agent are separated.

The polarizing film (B) a polarizing film used in the present invention (B) is not particularly limited as long as it functions as a polarizer. For example, polyvinyl alcohol (PVA) / iodine type polarizing film, PVA
A dye-based polarizing film in which a dichroic dye is adsorbed and oriented on a base film, or a polyene-based polarizing film in which a polyene is formed by inducing a dehydration reaction from a PVA-based film or a dehydrochlorination reaction of a polyvinyl chloride film, Examples thereof include a polarizing film having a dichroic dye on the surface and / or inside of a PVA-based film composed of a modified PVA containing a cationic group in the molecule. From the viewpoint of durability of the polarizing film, PVA is used.
-Iodine type polarizing film is preferable. The manufacturing method of the polarizing film is not particularly limited. For example, a method of adsorbing iodine ions after stretching the PVA-based film, a method of stretching the PVA-based film after dyeing with a dichroic dye, a method of stretching the PVA-based film after dyeing with a dichroic dye, and a dichroic dye Examples thereof include known methods such as a method of stretching after printing on a PVA-based film and a method of printing a dichroic dye after stretching the PVA-based film. For example, in more detail, the method of (1) dissolves iodine in a potassium iodide solution to form iodine ions, adsorbs the ions on a PVA film and stretches them, and then bathes in a 1 to 4% boric acid aqueous solution at a bath temperature of 30%. ~ 40
A polarizing film is manufactured by immersing at a temperature of ℃. More specifically, the PVA film is treated with boric acid in the same manner, and then stretched uniaxially by about 3 to 7 times, and then added to a 0.05 to 5% dichroic dye aqueous solution at a bath temperature of 30 to 40 ° C. And the dye is adsorbed, dried at 80 to 100 ° C., and heat-fixed to manufacture a polarizing film.

In the present invention, the adhesive is applied to at least one of the film (A) and the polarizing film (B) made of the alicyclic structure-containing polymer resin, and then the adhesive application surface is placed inside. A laminate can be obtained by bonding the film (A) and the polarizing film (B) together and further heating and drying. The adhesive may be applied to both the film (A) and the polarizing film (B). Further, the film (A) may be adhered to both surfaces of the polarizing film (B), in which case the adhesive may be applied to both surfaces of the polarizing film. Specifically, (1) at least one of the film (A) and the polarizing film (B) has an adhesive agent (may contain a solvent).
(2) at least the film (A) and the polarizing film (B) are adhered to each other before the adhesive is dried, and the adhesive is dried (and cured if necessary) to adhere. An adhesive (which may contain a solvent) is applied to either A) or the polarizing film (B), and the adhesive layer is in a semi-cured state (not cured but dried: a so-called B stage state). ), And then the film (A) and the polarizing film (B)
It is possible to use a method such as a method of bonding and bonding and curing and bonding the adhesive (so-called precoat method).

The method (1) can be used when the adhesive cures at room temperature due to moisture, and can be used when the adhesive is cured by heating, and the method (2) can be used when the adhesive cures by heating. it can. The drying temperature, the curing temperature, the respective times, etc. of the adhesive are set to the optimum ranges depending on the type of the curing agent. In addition, it is preferable to control the thickness of the adhesive layer by applying pressure after the film (A) and the polarizing film (B) are bonded together.

The laminate of the present invention obtained by the above method has a polarizing function, and therefore, for example, sunglasses, camera filters, sports goggles, lighting gloves,
It can be used in a wide range of fields such as anti-glare headlights for automobiles, light-shielding window glass, light quantity adjusting filters, fluorescent display contrastars, continuously variable transmissivity plates, and polarizing films for microscopes. Furthermore, since the laminate of the present invention has excellent optical performance and durability, it is particularly useful for liquid crystal displays (L
It can be suitably used for a polarizing film (CD) and a polarizing plate.

[0035]

EXAMPLES The present invention will be described more specifically below with reference to production examples, examples and comparative examples, but the scope of the present invention is not limited to these examples. In these examples, "part" is based on weight unless otherwise specified. The methods for measuring various physical properties are as follows.

(1) The glass transition temperature (Tg) was measured by a differential scanning calorimeter (DSC method). (2) Unless otherwise specified, the molecular weight was measured as a polyisoprene conversion value measured by gel permeation chromatography (GPC) using cyclohexane as a solvent. (3) The optical performance was evaluated by the following method. A test piece (laminated film) obtained by adhering a film of an alicyclic structure-containing polymer resin and an undyed PVA film with an adhesive is subjected to the following five types of reliability tests in sequence, and then laminated. The transparency of the film, the occurrence of haze, the presence or absence of coloring, etc. were visually observed and evaluated. High temperature test: 80 ° C, 50% humidity, 500 hours High temperature and high humidity test Part 1: Temperature 60 ° C, 90% humidity,
500 hours high temperature and high humidity test Part 2: temperature 80 ° C, humidity 90%,
100 hours Low temperature test: -30 ° C, humidity 10%, 500 hours Water resistance test: Place a wet tissue on the laminated film at a temperature of 80 ° C and humidity 90% and leave it for 30 minutes. (4) Durability was evaluated by observing the laminated film, which was subjected to all the reliability tests in (3) in sequence, with an optical microscope, and checked whether there was any interface defect such as peeling or swelling at the interface between the adhesive layer and both films. It was observed and evaluated.

[Production Example 1] In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane was mixed with 0.82 parts of 1-hexene, 0.15 parts of dibutyl ether and 0.30 parts of triisobutylaluminum at room temperature. Then, while maintaining at 45 ° C., 8-methyl-tetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -dodeca-3-ene (hereinafter, M
200 parts of TD) and tungsten hexachloride (0.7
% Toluene solution) was continuously added over 2 hours for polymerization. 1.06 parts of butyl glycidyl ether and 0.52 parts of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst to stop the polymerization reaction.

Then, to 100 parts of the reaction solution containing the obtained ring-opening polymer, 270 parts of cyclohexane was added, and further 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) as a hydrogenation catalyst was added, and hydrogen was added. Then, the pressure is increased to 5 MPa and the temperature is increased to 200 ° C. with stirring, and then the reaction is allowed to proceed for 4 hours to obtain 20% of the MTD ring-opening polymer hydrogenated polymer.
A containing reaction solution was obtained. After removing the hydrogenation catalyst by filtration, a soft polymer (Kuraray; Septon 200)
2) and an antioxidant (manufactured by Ciba Specialty Chemicals; Irganox 1010) were added and dissolved in each of the obtained solutions (each 0.1 part per 100 parts of the polymer). Next, cyclohexane as a solvent and other volatile components are removed from the solution by using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) while extruding the hydrogenated polymer in a molten state into a strand form from an extruder, and cooling the pellets. It was converted to and collected. The weight average molecular weight (Mw) of this hydrogenated ring-opening polymer was 35,000, and the hydrogenation rate was 9
It was 9.9% and Tg was 134 ° C.

Example 1 The pellets obtained in Production Example 1 were dried at 70 ° C. for 2 hours using a hot air dryer in which air was passed to remove water, and then a resin provided with a screw of 65 mmφ. Using a T-die type film melt extrusion molding machine having a melt-kneading machine, a film having a thickness of 50 μm was extruded under the conditions of a molten resin temperature of 220 ° C. and a T-die width of 300 mm. The obtained film is lengthwise 30
An adhesive that is cut to 0 mm and contains 100 parts of polypropylene oxide modified with methyldimethoxysilyl at both ends (Cyryl SAT200: manufactured by Kanebuchi Kagaku Kogyo) and 2 parts of a curing agent (dibutyltin acetate: Neostan U-220: manufactured by Nitto Kagaku). Is applied with a bar coater, and then the same size as the thickness of 100 μm is applied onto the adhesive application surface of the film.
The undyed PVA stretched film of No. 1 was laminated, pressed by a roll, and then heated and dried at 80 ° C. for 10 minutes to bond both films. The thickness of the adhesive layer was 5 μm. The reliability test was performed on the obtained laminated film and evaluated. The results are shown in Table 1.

Example 2 As an adhesive, 100 parts of a partially acryl-modified product of polypropylene oxide modified with methyldimethoxysilyl at both ends (Cyryl MA440: manufactured by Kanebuchi Kagaku Kogyo) and a curing agent (dibutyltin acetate: Neostan U-220). A laminated film was produced and evaluated in the same manner as in Example 1 except that an adhesive containing 2 parts by weight of Nitto Kagaku) was used. The results are shown in Table 1.

[Comparative Example 1] An adhesive having a mixture of a silicone resin and an epoxy resin (Super X, manufactured by Cemedine Co.) as a main component was applied to a film obtained by the same method as in Example 1 using a bar coater. To a thickness of 20 μm, and then the above PVA film similar to that used in Example 1 is pasted on one side with the adhesive layer interposed therebetween,
After pressure bonding with a roll, both films were adhered by heating and drying at 80 ° C. for 10 minutes. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0042]

[Table 1]

As described above, according to Table 1, the present invention in which the norbornene-based polymer film (A) and the polarizing film (B) are adhered using an adhesive containing a polypropylene oxide-based polymer having a silyl group at the terminal The laminated film (Example 1 and Example 2) has good transparency, has no haze and coloring, and has no change at the interface between the film (A) and the polarizing film (B) and the adhesive layer. Even though it has not occurred,
In the laminated film (Comparative Example 1) in which the film (A) of the norbornene-based polymer and the polarizing film (B) were adhered using another adhesive, a slight haze was generated in the adhesive layer portion, and the film (A ) And the polarizing film (B) and the interface between the adhesive layer and the adhesive layer and the polarizing film (B) were slightly swollen.

[0044]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a laminate suitable as a polarizing film, which is excellent in durability in a severe environment of use and stability of optical performance.

Continued front page    F term (reference) 2H049 BA02 BA27 BB11 BB22 BB43                       BB51 BC22 BC23 BC24                 4F100 AK02B AK02E AK03A AK03D                       AK03K AK21 AK54A AK54D                       AK54K AL06 AL08A AL08D                       AL09 BA05 BA06 BA10B                       BA10E CA02 CA06 EH46                       EJ42 GB90 JL11A JL11D                       JN10C

Claims (4)

[Claims] 1. From an alicyclic structure-containing polymer resin through a layer (C) of an adhesive containing a silyl group-terminated polyether polymer or a silyl group-terminated polyolefin polymer. A laminate formed by forming the layer of the film (A) on at least one surface of the polarizing film (B). 2. The laminate according to claim 1, wherein the polyether polymer is polypropylene oxide. 3. The laminate according to claim 1, wherein the silyl group has an alkyl group or an alkoxy group as a substituent. 4. A polyether polymer having a silyl group at the terminal or a polyolefin resin having a silyl group at the terminal on at least one of the film (A) and the polarizing film (B) made of a polymer resin containing an alicyclic structure. A method for producing a laminate, which comprises a step of applying an adhesive containing a polymer, then bonding the film (A) and the polarizing film (B) with the adhesive-applied surface inside, and further heating and drying.