JP2009242464A - Method for manufacturing laminate film, and laminate film - Google Patents

Abstract

A method for producing a laminated film having good adhesion between a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin and a urethane resin layer while maintaining the properties as an optical material, and the method Providing a laminated film manufactured by
SOLUTION: A method for producing a laminated film having a base film having a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin on the outermost surface and a urethane resin layer, and having an average surface water A step of forming a base film having a contact angle (Da) of 20 to 50 degrees and a standard deviation (Ds) of a water contact angle of 0.01 to 5, and an aqueous dispersion of an aqueous urethane resin on the base film The manufacturing method of the laminated | multilayer film characterized by including the process to apply | coat, and the laminated | multilayer film manufactured by this method.
[Selection figure] None

Description

  The present invention relates to a method for producing a laminated film and a laminated film produced by this method. More specifically, the present invention can be used for various image display devices such as a liquid crystal display device, an organic EL display device and a plasma display, and as an optical material. Method for producing a laminated film having good adhesion between a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin and a urethane resin layer while maintaining the above properties, and a laminated film produced by this method About.

  As films used in various image display devices such as liquid crystal display devices, organic EL display devices, and plasma displays, films containing alicyclic structure-containing polymers such as norbornene polymers or (meth) acrylic resins are known. ing. Since these films are excellent in heat resistance, transparency and optical properties, for example, an electrode substrate of a liquid crystal cell constituting a liquid crystal display element, a polarizing plate, a protective film for polarizing plate, a retardation film, a viewing angle widening film Development of optical films such as brightness enhancement films and films with transparent electrodes for touch panels, optical applications such as light guide plates and optical disks is being attempted. These films are often used by being laminated on a film or substrate having various other functions such as a polarizing film, a hard coat layer, an antireflection layer, an antistatic layer, an antiglare layer, and an antifouling layer. Therefore, it is preferable that the adhesiveness with the laminated | stacked film or board | substrate is favorable. Until now, various attempts have been made to improve the adhesion between an alicyclic structure-containing polymer film or a film containing a (meth) acrylic resin and a film or substrate containing another resin on which the film is laminated. ing.

  For example, claim 1 of Patent Document 1 describes “a polarizing plate protective film characterized in that a polyurethane resin layer is formed on a thermoplastic saturated norbornene-based resin film”.

  Further, claim 1 of Patent Document 2 describes “a polarizing plate characterized in that a norbornene-based resin film, a polyurethane layer, an adhesive layer, and a polarizing film are laminated”.

Japanese Patent Laid-Open No. 2001-174637 JP 2006-201736 A

  The subject of this invention is the manufacturing method of the laminated | multilayer film with favorable adhesiveness of the film layer containing a cycloaliphatic structure containing polymer or (meth) acrylic-type resin, and a urethane resin layer, maintaining the characteristic as an optical material. And a laminated film produced by this method, and even when another resin material, particularly a polarizer, is laminated on the laminated film, an alicyclic structure-containing polymer or a (meth) acrylic resin is provided. It is providing the manufacturing method of the laminated | multilayer film with which the film layer and urethane resin layer to contain do not peel, and the laminated | multilayer film manufactured by this method.

As means for solving the problems,
Claim 1
A method for producing a laminated film having a base film having a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin on the outermost surface and a urethane resin layer,
Based on a step of forming a base film having a surface average water contact angle (Da) of 20 to 50 degrees and a water contact angle standard deviation (Ds) of 0.01 to 5, and an aqueous dispersion of an aqueous urethane resin The process of applying on the material film,
A method for producing a laminated film, comprising:
Claim 2
The aqueous dispersion of the water-based urethane resin has a viscosity of 15 mPa · s or less, and is a method for producing a laminated film according to claim 1,
Claim 3
The surface of the base film is subjected to at least one treatment selected from the group consisting of corona treatment, plasma treatment and saponification treatment,
The average water contact angle (Da) is 20 to 50 degrees, and the standard deviation (Ds) of the water contact angle is 0.01 to 5, wherein the laminated film according to claim 1 or 2 Manufacturing method,
Claim 4
The water-based urethane resin is a self-emulsifying water-based urethane resin, the production method according to any one of claims 1 to 3,
Claim 5
The aqueous dispersion of the water-based urethane resin contains a crosslinking agent, and is the production method according to any one of claims 1 to 4,
Claim 6
It is a laminated film manufactured by the manufacturing method as described in any one of Claims 1-5.

  According to the method for producing a laminated film of the present invention, it is possible to provide a laminated film having good adhesion between a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin and a urethane resin layer, and Even if another resin material, especially a polarizer is laminated on this laminated film, a laminated film in which the film layer containing the alicyclic structure-containing polymer or (meth) acrylic resin and the urethane resin layer are not peeled off. Can be provided. Therefore, the laminated film manufactured by the manufacturing method of the present invention can be suitably used for an optical apparatus such as a liquid crystal display device.

  The method for producing a laminated film of the present invention is a method for producing a laminated film having a base film having a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin on the outermost surface and a urethane resin layer. And forming a base film having an average surface water contact angle (Da) of 20 to 50 degrees and a water contact angle standard deviation (Ds) of 0.01 to 5, and an aqueous dispersion of an aqueous urethane resin. A step of coating the substrate film on the substrate film.

  The base film may be formed only by a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin (hereinafter, this film layer is referred to as a film layer (A)), A plurality of films may be laminated. When the base film is formed of a plurality of films, the film layer (A) may be provided on at least one side of the film layer (B) formed by laminating at least one film. It may be formed by providing a film layer (A) on both sides of (B). The urethane resin layer is provided on the surface on which the film layer (A) is formed.

  The film layer (B) may be a kind of film, or two or more kinds of films may be laminated. When this film layer (B) is formed by laminating a plurality of films, a film having various functions is appropriately selected as the film forming each layer according to the performance required for the laminated film of the present invention. Examples of the film layer (B) include films having functions such as polarized light, reflected polarized light, scratch prevention, antireflection, antistatic, antiglare and antifouling.

  The film layer (A) contains an alicyclic structure-containing polymer or a (meth) acrylic resin.

  The alicyclic structure-containing polymer has an alicyclic structure in the repeating unit of the polymer, a polymer having an alicyclic structure in the main chain and a polymer having an alicyclic structure in the side chain. Any of these can be used. Examples of the alicyclic structure include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength, heat resistance, etc., the cycloalkane structure. Or a cycloalkene structure is preferable, and a cycloalkane structure is most preferable. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The heat resistance and the moldability of the film are highly balanced and suitable. The ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, preferably 55% by weight or more, Preferably it is 70 weight% or more, Most preferably, it is 90 weight% or more. It is preferable from the viewpoint of the transparency and heat resistance of the film layer (A) that the ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is in this range.

  Examples of the alicyclic structure-containing polymer include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof. it can. Among these, norbornene-based resins can be suitably used because of their good transparency and moldability.

  Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure. An addition polymer of a monomer having a monomer, an addition copolymer of a monomer having a norbornene structure and another monomer, or a hydride thereof. Among these, a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.

Examples of the monomer having a rubornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7. -Diene (common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4. 0.1 ^2,5 . ^{17, 10} ] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. Moreover, these substituents may be the same or different and a plurality may be bonded to the ring. Monomers having a norbornene structure can be used singly or in combination of two or more.

  Examples of the polar group include a hetero atom or an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

  Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like.

  A ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.

  Examples of other monomers that can be addition copolymerized with a monomer having a norbornene structure include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, And cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and the like. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable and ethylene is more preferable.

  An addition polymer of a monomer having a norbornene structure and an addition copolymer of a monomer having a norbornene structure with another monomer copolymerizable with a monomer having a norbornene structure are prepared in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.

Among norbornene-based resins, as repeating units, X: bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 ^2,5 ] decane-7 , 9-diyl-ethylene structure, the content of these repeating units is 90% by weight or more based on the entire repeating units of the norbornene-based resin, and the content ratio of X and the content ratio of Y Is preferably 100: 0 to 40:60 by weight ratio of X: Y. By using such a resin, it is possible to obtain an optical film that has no dimensional change in the long term and is excellent in stability of optical characteristics.

  Examples of the monocyclic olefin resin include addition polymers of cyclic olefin monomers having a single ring such as cyclohexene, cycloheptene, and cyclooctene.

  As the cyclic conjugated diene polymer, a polymer obtained by cyclization reaction of an addition polymer of a conjugated diene monomer such as 1,3-butadiene, isoprene, chloroprene or chloroprene; cyclic conjugated such as cyclopentadiene or cyclohexadiene Mention may be made of 1,2- or 1,4-addition polymers of diene monomers; and their hydrides.

  Examples of vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides; vinyl aromatic hydrocarbon monomers such as styrene and α-methylstyrene. Hydrogenated product obtained by hydrogenating the aromatic ring part contained in the polymer obtained by polymerization; copolymerization of vinyl alicyclic hydrocarbon monomers or vinyl aromatic hydrocarbon monomers with these vinyl aromatic hydrocarbon monomers Examples include a hydride of an aromatic ring of a copolymer such as a random copolymer with other possible monomers or a block copolymer. Examples of the block copolymer include diblock, triblock or higher multiblock, and gradient block copolymer.

  The hydrogenation method in the case of using a hydride as the alicyclic structure-containing polymer used in the present invention is not particularly limited and can be performed according to a known method. In order to obtain a hydride, a known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the polymer solution, and hydrogen is usually added to the reaction system at −10 to + 250 ° C., preferably 0 to 200 ° C. , 0.01 to 10 MPa, preferably 0.05 to 8 MPa, and allowed to react for 0.1 to 50 hours. The hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more. The higher the hydrogenation rate, the better the fluidity and heat resistance of the polymer.

  The molecular weight of the alicyclic structure-containing polymer used in the present invention is appropriately selected according to the purpose of use, but gel permeation chromatography using cyclohexane as a solvent or toluene when the polymer resin does not dissolve. The polyisoprene or polystyrene-equivalent weight average molecular weight (Mw) measured in (1) is usually 10,000 to 100,000, preferably 15,000 to 80,000, more preferably 20,000 to 50,000. When the weight average molecular weight is in such a range, the mechanical strength and molding processability of the laminated film are highly balanced and suitable.

  The glass transition temperature of the alicyclic structure-containing polymer may be appropriately selected according to the purpose of use, but is preferably in the range of 130 to 150 ° C, more preferably 135 to 145 ° C. When the glass transition temperature is lower than 130 ° C., the durability at high temperatures is deteriorated. When the glass transition temperature is higher than 150 ° C., the durability is improved, but normal stretching is difficult.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alicyclic structure-containing polymer is 1.2 to 3.5, preferably 1.5 to 3.0, more preferably 1.8. ~ 2.7. If this value exceeds 3.5, the low-molecular component increases, so the component with a short relaxation time increases, and even when the film has the same in-plane retardation Re at first glance, the relaxation during high-temperature exposure increases in a short time. The stability of the film may be reduced. On the other hand, those having a molecular weight distribution lower than 1.2 lead to a decrease in resin productivity and an increase in cost, which is not practical as a display member.

The alicyclic structure-containing polymer used in the present invention preferably has an absolute value of photoelastic coefficient of 10 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 7 × 10 ⁻¹² Pa ⁻¹ or less. 4 × 10 ⁻¹² Pa ⁻¹ or less is particularly preferable. The photoelastic coefficient C is expressed as follows: birefringence is Δn and stress is σ.
C = Δn / σ
It is a value represented by When the photoelastic coefficient of the alicyclic structure-containing polymer exceeds 10 × 10 ⁻¹² Pa ⁻¹ , the in-plane letter Re of the film layer (A) may vary greatly.

  The alicyclic structure-containing polymer used in the present invention preferably contains substantially no particles. Here, “substantially free of particles” means that even if particles are added to a film containing an alicyclic structure-containing polymer, the increase in haze from the non-added state is 0.05% or less. It means that the amount is acceptable. In particular, since the alicyclic structure-containing polymer lacks affinity with many organic particles and inorganic particles, when a film containing the alicyclic structure-containing polymer to which the amount of particles exceeding the above range is added is stretched. , Voids are likely to occur, and as a result, there is a risk that a significant decrease in haze may occur.

  The saturated water absorption of the alicyclic structure-containing polymer of the present invention is preferably 0.03% by weight or less, more preferably 0.02% by weight or less, and particularly preferably 0.01% by weight or less. When the saturated water absorption is within the above range, the change over time of Re and Rth of the film layer (A) in the present invention can be reduced, and further, the deterioration of the polarizing plate and liquid crystal display device provided with the film layer (A) can be reduced. It can be suppressed and the display on the display can be kept stable and good in the long term. The saturated water absorption is a value expressed as a percentage of the mass of the test piece before immersion after the test piece is immersed in water at a constant temperature for a fixed time. Usually, it is measured by immersing in 23 ° C. water for 24 hours. The saturated water absorption rate in the alicyclic structure-containing polymer of the present invention can be adjusted to the above value, for example, by reducing the amount of polar groups in the alicyclic structure-containing polymer. A resin having no group is desired.

  The alicyclic structure-containing polymer used in the present invention includes coloring agents such as pigments and dyes, fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, antioxidants, You may add well-known additives, such as a lubricant, in the range which does not impair the effect of invention.

  The film layer (A) containing the alicyclic structure-containing polymer is not particularly limited by the production method. A film layer (A) is obtained by shape | molding the above-mentioned resin etc. with a well-known film shaping | molding method. Examples of the film forming method include a cast forming method, an extrusion forming method, and an inflation forming method. Among these, the melt extrusion method that does not use a solvent can reduce the amount of residual volatile components efficiently, and is preferable from the viewpoints of the global environment and work environment, and excellent manufacturing efficiency. Examples of the melt extrusion method include an inflation method using a die, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.

  When the base film is formed by a plurality of films of the film layer (A) and the film layer (B), the base film is manufactured from the manufactured film layer (A) and the manufactured film layer (B ) May be bonded together using an adhesive, or may be manufactured by a coextrusion method or the like without using an adhesive.

  In the case of bonding using an adhesive, the adhesive may be appropriately selected depending on the type of resin forming the film layer (A) and the film layer (B). For example, an acrylic adhesive, a urethane adhesive , Polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, ethylene-vinyl acetate adhesives, vinyl chloride-vinyl acetate adhesives Agent, SEBS (styrene-ethylene-butylene-styrene copolymer) adhesive, SIS (styrene-isoprene-styrene block copolymer) adhesive, ethylene-based adhesives such as ethylene-styrene copolymer, ethylene- (Meth) methyl acrylate copolymer, ethylene- (meth) ethyl acrylate copolymer, etc. Such as acrylic acid ester-based adhesives.

  0.1-10 micrometers is preferable and, as for the average thickness of the contact bonding layer formed with the said adhesive agent, it is more preferable that it is 0.5-5 micrometers.

  When the base film is produced without using an adhesive, preferably, a coextrusion T-die method, a coextrusion inflation method, a coextrusion lamination method or the like; a film lamination molding method such as dry lamination, And well-known methods, such as a coating molding method which coats the resin solution which comprises a film layer (A) on the surface of a film layer (B), can be utilized suitably. Among these, the coextrusion molding method is preferable from the viewpoint of manufacturing efficiency and not leaving a volatile component such as a solvent in the base film.

  Among the coextrusion molding methods, the coextrusion T-die method is preferable. Further, examples of the coextrusion T-die method include a feed block method and a multi-manifold method, but the multi-manifold method is more preferable in that variation in the thickness of the film layer (B) can be reduced.

  The film layer (A) used in the present invention may be a stretched film (hereinafter also referred to as a stretched film layer (A)) by subjecting an unstretched film to a stretch treatment.

  The stretching method of the film layer (A) for obtaining the stretched film layer (A) used in the present invention is not particularly limited, and may be stretched by either a uniaxial stretching method or a biaxial stretching method. Stretching methods include a method of uniaxial stretching in the longitudinal direction using the difference in peripheral speed on the roll side; a uniaxial stretching method such as a method of uniaxial stretching in the transverse direction using a tenter stretching machine; At the same time as stretching in the longitudinal direction using the guide rail, the biaxial stretching method that stretches in the transverse direction depending on the spread angle of the guide rail, and the longitudinal direction using the difference in the peripheral speed between the rolls, and both ends thereof A biaxial stretching method such as a sequential biaxial stretching method in which a clip is gripped and stretched in the transverse direction using a tenter stretching machine; a feed force, a pulling force, or a pulling force at different speeds can be applied in the lateral or longitudinal direction. And a method of continuously and obliquely stretching in the direction of an arbitrary angle θ with respect to the width direction of the film using a tenter stretching machine.

  Examples of the apparatus used for stretching include a longitudinal uniaxial stretching machine, a tenter stretching machine, a bubble stretching machine, and a roller stretching machine.

  The temperature during stretching is preferably between (Tg-30 ° C) and (Tg + 60 ° C), more preferably (Tg-10 ° C), where Tg is the glass transition temperature of the material constituting the unstretched film. It is selected from temperatures between (Tg + 50 ° C.).

  What is necessary is just to select a draw ratio suitably according to the optical characteristic of the stretched film (A) to be used, and is 1.05-10.0, Preferably, it is 1.1-2.0.

  Examples of (meth) acrylic resins include thermoplastic resins and ultraviolet curable resins.

  When the (meth) acrylic resin is a thermoplastic resin, a polymer resin containing a (meth) acrylic acid ester as a main component is preferably used as the thermoplastic resin. This polymer resin may be a homopolymer or copolymer consisting only of (meth) acrylic acid ester, and is a copolymer of (meth) acrylic acid ester and a monomer copolymerizable therewith. May be. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid. Similarly, (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester.

  The (meth) acrylic acid ester used as the main component of the (meth) acrylic resin preferably has a structure derived from (meth) acrylic acid, an alkanol having 1 to 15 carbon atoms, and a cycloalkanol. More preferably, it is a structure derived from an alkanol having 1 to 8 carbon atoms. When there are too many carbon numbers, the elongation at the time of the fracture | rupture of the brittle film obtained will become large too much.

  Specific examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate. , T-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate; methyl methacrylate, ethyl methacrylate, methacryl N-propyl acid, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, methacrylic acid 2 -Ethylhexyl, methacrylic acid n- Sill, and the like methacrylic acid n- dodecyl.

  Moreover, these (meth) acrylic acid esters may have an arbitrary substituent such as a hydroxyl group or a halogen atom. Examples of the (meth) acrylic acid ester having such a substituent include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-methacrylic acid 2- Examples include hydroxypropyl, 4-hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, glycidyl methacrylate, and the like. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  The (meth) acrylic resin used in the present invention has a (meth) acrylic acid ester content of preferably 50% by weight or more, more preferably 85% by weight or more, and particularly preferably 90% by weight or more. .

  The monomer copolymerizable with the (meth) acrylic acid ester is not particularly limited, but α, β-ethylenically unsaturated carboxylic acid ester monomers other than the (meth) acrylic acid ester described above, α, β-ethylenically unsaturated carboxylic acid monomer, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, unsaturated carboxylic acid amide monomer, Examples thereof include carboxylic acid unsaturated alcohol esters and olefin monomers.

  Specific examples of the α, β-ethylenically unsaturated carboxylic acid ester monomer other than the (meth) acrylic acid ester described above include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, etc. Can be mentioned.

  The α, β-ethylenically unsaturated carboxylic acid monomer may be any of monocarboxylic acid, polyvalent carboxylic acid, partial ester of polyvalent carboxylic acid, and polyvalent carboxylic acid anhydride. Examples include acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, monoethyl maleate, mono n-butyl fumarate, maleic anhydride, itaconic anhydride and the like.

  Specific examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl α-methylstyrene, vinyl toluene and divinylbenzene.

  Specific examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1. , 3-butadiene, cyclopentadiene and the like. Specific examples of the non-conjugated diene monomer include 1,4-hexadiene, dicyclopentadiene, and ethylidene norbornene.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.

  Specific examples of the α, β-ethylenically unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylacrylamide and the like. Specific examples of the carboxylic acid unsaturated alcohol ester monomer include vinyl acetate. Specific examples of the olefin monomer include ethylene, propylene, butene, pentene and the like.

  As the monomer copolymerizable with (meth) acrylic acid ester, one type may be used alone, or two or more types may be used in combination. As a monomer copolymerizable with (meth) acrylic acid ester, an alkenyl aromatic monomer is preferable, and styrene is particularly preferable.

  In the (meth) acrylic resin used in the present invention, the content of the monomer copolymerizable with the (meth) acrylic ester is 50% by weight or less, preferably 15% by weight or less, more preferably 10% by weight. It is as follows.

  Preferable specific examples of the (meth) acrylic resin used in the present invention include methyl methacrylate / methyl acrylate / butyl acrylate / styrene copolymer, methyl methacrylate / methyl acrylate copolymer, methyl methacrylate / Examples thereof include styrene / butyl acrylate copolymers. One type of acrylic resin may be used alone, or two or more types may be used in combination. In the present invention, among these, a polymethacrylate resin is preferable, and among them, a polymethyl methacrylate resin is more preferable.

  Although the molecular weight of (meth) acrylic-type resin is not specifically limited, Usually, it is 50,000-500,000 in a weight average molecular weight. When the molecular weight is within this range, a homogeneous film can be easily produced by the melt casting method.

  The (meth) acrylic resin used in the present invention preferably has an elongation at break in the tensile test in the range of 10 to 180%, and more preferably in the range of 50 to 170%. When the elongation at break is within the above range, the bristle film has good dregs. When two or more kinds of (meth) acrylic resins are used in combination, the elongation at break of the mixture is preferably within the above range. The elongation at break is a value obtained under the conditions of test piece type 1B (W10, L100, t0.1 mm) and speed of 5 mm / min according to JIS K 7127.

  The film layer (A) containing the thermoplastic (meth) acrylic resin is not particularly limited by the production method. The film layer (A) containing a thermoplastic acrylic resin is obtained by molding by the same film forming method as the film layer (A) containing the alicyclic structure-containing polymer. Moreover, when the base film is formed of a plurality of films of the film layer (A) and the film layer (B), the base film is manufactured with the manufactured film layer (A) and the manufactured film layer. (B) may be bonded together using an adhesive, or may be manufactured by a coextrusion method or the like without using an adhesive. When the base film is formed of a plurality of films, the base film is obtained by molding by the above-described film forming method as in the case of the film layer (A) containing the alicyclic structure-containing polymer. It is done.

  When the (meth) acrylic resin is an ultraviolet curable resin, examples of the ultraviolet curable resin component include urethane acrylate, epoxy acrylate, and polyester acrylate that have an affinity with a urethane resin layer described later. An ultraviolet curable resin component is preferred.

  Moreover, as a suitable ultraviolet curable resin component used by this invention, the resin which contains the prepolymer, oligomer, and / or monomer which have a polymerizable unsaturated bond or an epoxy group in a molecule | numerator, and is hardened | cured by ultraviolet irradiation is mentioned. . Examples of prepolymers and oligomers having polymerizable unsaturated bonds or epoxy groups in the molecule include unsaturated polyesters such as a condensation product of unsaturated dicarboxylic acid and polyhydric alcohol; polyester methacrylate, polyether methacrylate, polyol methacrylate, Examples thereof include methacrylates such as melamine methacrylate, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylates such as melamine acrylate, and cationic polymerization type epoxy compounds.

Examples of monomers having a polymerizable unsaturated bond or epoxy group in the molecule include styrene monomers such as styrene and α-methylstyrene; methyl acrylate, ethyl acrylate, -2-ethylhexyl acrylate, methoxyethyl acrylate Acrylates such as butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate Methacrylic acid esters such as lauryl methacrylate; acrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N- Dibenzylamino) methyl, acrylic acid -Unsaturated substituted amino alcohol esters such as (N, N-diethylamino) propyl; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, ethylene Glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and other multifunctional acrylates; trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol Polythiols having two or more thiol groups in the molecule, such as tetrathioglycolate; glycidyl acrylate, glycidyl methacrylate, glycidyl phenyl ether, glycidyl ethyl ether, epichlorohydrin, allyl glycidyl ether, ethylene oxide, propylene oxide , Neopentyl glycol diglycidyl ether, trimethylolpropane diglycidyl ether, Roll diglycidyl ether, diglycerol triglycidyl ether, diglycerol triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, phenol novolac polyglycidyl ether, cresol Epoxy compounds such as novolac polyglycidyl ether can be mentioned.
In the present invention, these prepolymers, oligomers and / or monomers can be used singly or in combination of two or more.

  The content of the prepolymer, oligomer and / or monomer in the ultraviolet curable resin component used in the present invention is preferably 5% by weight to 95% by weight from the viewpoint of obtaining excellent coating suitability. A suitable ultraviolet curable resin component used in the present invention contains a photopolymerization initiator and a photopolymerization accelerator. As photopolymerization initiators, radical polymerizable initiators such as acetophenones, benzophenones, thioxanthones, acylphosphine oxides, benzoin ethers, oxime esters; aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium And cationic polymerization initiators such as salts, metathelone compounds, and benzoin sulfonates. These can be used individually by 1 type or in combination of 2 or more types. The content of the photopolymerization initiator is usually 0.1% by weight to 10% by weight in the ultraviolet curable resin component.

  The ultraviolet curable resin component is usually applied as a solution. Examples of the solvent that can be used in the coating liquid include alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monobutyl ether Glycols such as diacetone glycol and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; oximes such as methyl ethyl ketoxime; and combinations of two or more thereof.

  In order to add various functions to the film layer (A) in an auxiliary manner, the ultraviolet curable resin component includes an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant such as a dye or pigment, a plasticizer, a lubricant, A surfactant or the like may be mixed.

  The method for coating the ultraviolet curable resin component on the film layer (B) is not particularly limited, and a known coating method can be employed. Specific coating methods include wire bar coating, dipping, spraying, spin coating, roll coating, gravure coating, air knife coating, curtain coating, slide coating, and extrusion coating. Can be mentioned. The coating amount of the ultraviolet curable resin component is not particularly limited, but the thickness after curing is usually 0.05 to 50 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm.

  As the film layer (B) used in the present invention, it is preferable to use a film layer subjected to surface modification treatment on one side or both sides. By performing the surface modification treatment, the adhesion with the film layer (A) can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment. Examples of the energy ray irradiation treatment include corona treatment, plasma treatment, electron beam irradiation treatment, and ultraviolet ray irradiation treatment. From the viewpoint of processing efficiency, corona treatment and plasma treatment are preferred, and corona treatment is particularly preferred. Examples of the chemical treatment include a method of immersing in an aqueous solution of an oxidizing agent such as potassium dichromate solution or concentrated sulfuric acid and then washing with water.

The ultraviolet rays irradiated by the ultraviolet irradiation device may be those having a wavelength of usually 100 to 400 nm. The output value of the lamp is usually 120 to 240 w, and preferably 160 to 200 w. The dose of ultraviolet rays is against ultraviolet irradiation object, when expressed in a total amount of integrated light quantity of ultraviolet light, preferably 100~2,000mJ / cm ^2, more preferably, 200~1,500mJ / cm ^2, and most preferably Is 300 to 1,000 mJ / cm ² . The total amount of integrated light is a value determined by the illuminance of the ultraviolet irradiation lamp and the line speed (film moving speed), and is measured by, for example, an ultraviolet integrated illuminometer (EYEUV METER UVPF-A1 manufactured by Eye Graphic).

  The ultraviolet irradiation is preferably performed in an inert gas atmosphere, for example, in a nitrogen gas atmosphere in which the oxygen concentration is 500 ppm or less, preferably 100 ppm or less. When UV irradiation is performed in an inert gas atmosphere, the photopolymerization initiator can be greatly reduced compared to the curing of UV curable resin components in the air, and a film layer (A) with excellent weather resistance must be designed. Is possible. In addition, since photopolymerization initiators are generally expensive, reducing the amount used is effective in reducing costs.

  Moreover, in this invention, you may apply | coat an ultraviolet curable resin component, after forming a primer layer in a film layer (B). Thereby, the adhesiveness of a film layer (A) can be improved further. The material constituting the primer layer includes polyester urethane resin, polyether urethane resin, polyisocyanate resin, polyolefin resin, resin having hydrocarbon skeleton and / or polybutadiene skeleton in the main chain, polyamide resin, acrylic resin, polyester resin, chloride Examples thereof include vinyl-vinyl acetate copolymer, chlorinated rubber, cyclized rubber, and modified products in which polar groups are introduced into these polymers. The thickness of the primer layer is not particularly limited, and is usually 0.3 to 5 μm, preferably 0.5 to 2 μm.

  The film layer (A) used in the present invention preferably has a total light transmittance of 80% or more in terms of 1 mm thickness. More preferably, the total light transmittance is 90% or more. Further, the film layer (A) used in the present invention preferably has a haze at a thickness of 1 mm of 0.3% or less. More preferably, the haze is 0.2% or less. If the haze exceeds 0.3%, the transparency of the film layer (A) may be lowered.

  The film layer (A) used in the present invention has in-plane retardation Re and thickness direction retardation Rth depending on the design of the display, but in-plane retardation Re is 10 to 500 nm, and thickness direction retardation Rth is It is appropriately selected from the range of about −500 to 500 nm. The in-plane retardation Re in the present invention is the refractive index nx in the slow axis direction of the film, the refractive index ny in the direction perpendicular to the slow axis in the plane, the refractive index nz in the thickness direction, and the average thickness of the film. D is a value defined by (nx−ny) × D, and the thickness direction retardation Rth in the present invention is a value defined by ((nx + ny) / 2−nz) × D. .

  The average thickness of the film layer (A) used for this invention can be suitably selected by the relationship with the thickness of a film layer (B), and is 5 micrometers-500 micrometers normally, Preferably it is 20-300 micrometers. The thickness variation is preferably within ± 3% of the average thickness over the longitudinal direction and the width direction. By setting the thickness variation within the above range, variations in optical characteristics such as Re of the film layer (A) of the present invention can be reduced.

  The film layer (A) used in the present invention has an in-plane retardation Re variation within 10 nm, preferably within 5 nm, and more preferably within 2 nm. By setting the variation of the in-plane retardation Re within the above range, the display quality can be improved when used as a retardation film for a liquid crystal display device. Here, the variation in the in-plane retardation Re is obtained when the in-plane retardation Re is measured in the width direction of the film when the light incident angle is 0 ° (incident light beam and the stretched polyolefin film surface of the present invention are orthogonal). Is the difference between the maximum value and the minimum value of the in-plane retardation Re.

  The content of the residual volatile component in the film layer (A) used in the present invention is not particularly limited, but is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and further preferably 0.02% by weight. It is as follows. If the content of the residual volatile component exceeds 0.1% by weight, the optical characteristics of the film layer (A) in the present invention may change over time. By making the content of the volatile component in the above range, the dimensional stability is improved, the in-plane retardation Re or Rth of the film layer (A) can be reduced, and the film layer (A ), The deterioration of the polarizing plate and the liquid crystal display device can be suppressed, and the display on the display can be kept stable and good for a long time. The volatile component is a substance having a molecular weight of 200 or less contained in a trace amount in the film layer (A) in the present invention, and examples thereof include residual monomers and solvents. The content of the volatile component can be quantified by analyzing the film layer (A) in the present invention by gas chromatography as a total of substances having a molecular weight of 200 or less.

  It is preferable that the film layer (A) used for this invention is elongate. The long shape means one having a length of at least about 5 times the width direction of the film, preferably 10 times or more, and specifically wound in a roll shape. It has a length that can be stored or transported.

The base film or stretched base film used in the present invention is subjected to surface modification treatment before providing the urethane resin layer, and the average water contact angle of the surface of the base film or stretched base film is 20 to 50 degrees. Within the range, the standard deviation of the water contact angle is 0.01-5. The water contact angle is determined by the θ / 2 method using a contact angle meter. The average water contact angle was determined by measuring the 20 water contact angles randomly selected within the range of 100 cm ² in the surface-treated base film or stretched base film, and adding the average of these measured values. Is calculated by The standard deviation of the water contact angle is calculated from this measured value. By performing the surface modification treatment, functional groups such as a hydroxy group, a carboxyl group, a carbonyl group, an amino group, and a sulfone group can be introduced on the surface of the base film or the stretched base film. Therefore, when the aqueous dispersion of the aqueous urethane resin is applied to the surface of the film layer (A), the aqueous dispersion of the aqueous urethane resin is adapted to the surface of the film layer (A) and can be applied uniformly. Therefore, a urethane resin layer having a uniform thickness can be formed on the surface of the film layer (A). Examples of the surface modification treatment include corona treatment, plasma treatment, ultraviolet irradiation treatment, and saponification treatment. From the viewpoint of processing efficiency, corona treatment and plasma treatment are preferred, and corona treatment is particularly preferred. When the film layer (A) is formed of an acrylic resin, it is preferable to saponify the surface of the film layer (A).

  The corona treatment used in the present invention is preferably a wire electrode, a plane electrode, or a roll electrode as the electrode structure, but in order to make the discharge uniform, a dielectric is sandwiched between the base film and the electrode. It is preferable to carry out the treatment at

  As the material of the electrode, metals such as iron, copper, aluminum, and stainless steel can be used. As the electrode shape, electrodes such as a thin plate shape, a knife edge shape, and a brush shape can be used.

  The dielectric preferably has a relative dielectric constant of 10 or more, and has a structure in which a dielectric is sandwiched between upper and lower electrodes. Dielectric materials include ceramics, silicone rubber, polytetrafluoroethylene, polyethylene terephthalate and other plastics, glass, quartz, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide and other metal oxides, and compounds such as barium titanate. Is mentioned. In particular, interposing a solid dielectric having a relative dielectric constant of 10 or more (in an environment of 25 ° C.) is advantageous in that corona treatment can be performed at a high speed with a low voltage. Examples of the solid dielectric having a relative dielectric constant of 10 or more include metal oxides such as zirconium dioxide and titanium dioxide, oxides such as barium titanate, and silicon rubber. The dielectric thickness is preferably in the range of 0.3 to 1.5 mm. If the thickness of the dielectric is too thin, dielectric breakdown is likely to occur, and if it is too thick, the applied voltage needs to be increased, resulting in poor efficiency.

  The distance between the base film and the electrode is preferably 0.5 to 10 mm. If the thickness is less than 0.5 mm, only a thin film of the base film can pass, and if there is a seam, the base film may hit the electrode when passing, and the base film may be damaged. Moreover, since an applied voltage will become high when it exceeds 10 mm, a power supply becomes large and discharge will become a streamer shape.

  The output of the corona treatment used in the present invention is preferably a condition for treating as little damage as possible on the surface of the film layer (A), specifically 0.02 to 5 kW, preferably 0.04 to 2 kW. More preferably. Also, the best corona treatment method is to perform the corona treatment several times within the above range at the lowest possible output.

The density of the corona treatment used in the present invention is not limited as long as the average water contact angle of the film layer (A) is 20 to 50 degrees and the standard deviation of the water contact angle is within a range of 0.01 to 5. Specifically, it is preferably a 1~1000W · min / m ^2, more preferably 5~500W · min / m ^2, further preferably 10~300W · min / m ^2. When the treatment density is low, the applicability of the aqueous dispersion of the water-based urethane resin is lowered. Moreover, when high, the surface of a film layer (A) will be destroyed and adhesiveness will fall.

  The frequency of the corona treatment used in the present invention is preferably 5 to 100 kHz, and more preferably 10 to 50 kHz. When the frequency is lowered, the uniformity of the corona discharge treatment is deteriorated, and unevenness of the corona discharge treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing a high-output corona discharge treatment, but when performing a low-output corona discharge treatment, it becomes difficult to perform a stable treatment. Unevenness occurs.

  In the corona treatment used in the present invention, the discharge can be generated in a finer state by surrounding the electrode with a casing, putting an inert gas inside the casing, and applying gas to the electrode portion. As the inert gas, helium, argon, or nitrogen can be used.

  Examples of the plasma treatment used in the present invention include glow discharge treatment and flame plasma treatment. As the glow discharge, either a vacuum glow discharge process performed under vacuum or an atmospheric pressure glow discharge process performed under atmospheric pressure can be used, but an atmospheric pressure glow discharge process performed under atmospheric pressure is preferable from the viewpoint of productivity. . In addition, the atmospheric pressure in this invention is the range of 700-780 Torr. In the glow discharge treatment, a stretched film is placed between opposing electrodes, a plasma-exciting gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes, thereby plasma-exciting the gas and glow discharge between the electrodes. Is to do. Thereby, the surface of a film layer (A) is processed and the hydrophilicity of the surface of a film layer (A) is improved.

  The plasma-excitable gas refers to a gas that is plasma-excited under the above conditions. Plasma-excitable gases include chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane and mixtures thereof, and inert gases such as argon and neon, carboxyl groups and hydroxyl groups. And a reactive gas capable of imparting a polar functional group such as a carbonyl group.

  The frequency of the high-frequency voltage is preferably in the range of 1 kHz to 100 kHz, and the magnitude of the voltage is preferably in a range in which the electric field strength when applied to the electrode is 1 to 100 kV / cm.

  The saponification treatment used in the present invention is an alkali saponification treatment. Examples of the treatment method include an immersion method and an alkaline solution coating method, but the immersion method is preferable from the viewpoint of productivity.

  The immersion method is a technique in which a base film is immersed in an alkaline solution under appropriate conditions, and all surfaces having reactivity with alkali on the entire surface of the base film are saponified, and special equipment is required. Therefore, it is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. The concentration is preferably from 0.5 to 3 mol / l, more preferably from 1 to 2 mol / l. The liquid temperature of the alkaline liquid is preferably 25 to 70 ° C, more preferably 30 to 60 ° C. The treatment time may be adjusted as appropriate as long as the average water contact angle of the film layer (A) is 20 to 50 degrees and the standard deviation of the water contact angle is within the range of 0.01 to 5.

  After being immersed in the alkali solution, it is preferable to sufficiently wash with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the base film.

  The urethane resin layer in the present invention can be obtained by directly applying an aqueous dispersion of a water-based urethane resin on the surface of a surface-modified base film or stretched base film. The aqueous dispersion of an aqueous urethane resin is formed by dispersing an aqueous urethane resin in water, and can take the form of an emulsion, a colloidal dispersion, an aqueous solution, or the like.

  The aqueous urethane resin is not particularly limited. For example, (i) an aqueous system obtained by reacting a component containing an average of two or more active hydrogens in one molecule and (ii) a polyvalent isocyanate component. The urethane resin, or the above component (i) and component (ii) is urethanated in an organic solvent that is inert to the reaction and has a high affinity for water under the condition of excess isocyanate group to obtain an isocyanate group-containing prepolymer. Then, there is an aqueous urethane resin produced by neutralizing the prepolymer, extending the chain with a chain extender, and adding water to form a dispersion. These water-based urethane resins may contain an acid component (acid residue).

  The chain extension method of the isocyanate group-containing prepolymer may be a known method. For example, water, a water-soluble polyamine, glycols or the like is used as the chain extender, and the isocyanate group-containing prepolymer and the chain extender component are used. May be reacted in the presence of a catalyst as necessary.

  The component containing two or more active hydrogens in average in one molecule of the component (i) is not particularly limited, but one having a hydroxyl active hydrogen is preferable. Specific examples of such compounds include the following.

(1) Diol compound:
Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol 1,6-hexane glycol, 2,5-hexanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tricyclodecane dimethanol, 1,4-cyclohexane dimethanol and the like.

(2) Polyether diol:
Alkylene oxide adducts of the above diol compounds, ring-opening (co) polymers such as alkylene oxides and cyclic ethers such as tetrahydrofuran, such as polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol-propylene glycol, glycol, polytetramethylene glycol , Polyhexamethylene glycol, polyoctamethylene glycol and the like.

(3) Polyester diol:
Dicarboxylic acid such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid or the like and ethylene glycol, propylene glycol, 1,4-butane as mentioned in (1) above Examples thereof include those obtained by polycondensation with a diol compound such as diol, 1,6-hexanediol, 1,8-octamethylenediol, neopentylglycol and the like under hydroxyl group-excess conditions. Specifically, ethylene glycol-adipic acid condensate, butanediol-adipine condensate, hexamethylene glycol-adipic acid condensate, ethylene glycol-propylene glycol-adipic acid condensate, or lactone ring opening using glycol as an initiator. Examples thereof include polymerized polylactone diol.

(4) Polyether ester diol:
An ether group-containing diol (polyether diol or diethylene glycol of (2) above) or a mixture of this with another glycol is added to the dicarboxylic acid or anhydride thereof exemplified in (3) above to react with the alkylene oxide. For example, polytetramethylene glycol-adipic acid condensate.

(5) Polycarbonate diol:
General formula HO-R- (OC (O) -O-R) x-O
Compounds represented by H (wherein R is a saturated fatty acid diol residue having 1 to 12 carbon atoms, x is the number of repeating units of the molecule, and is usually an integer of 5 to 50). These include a transesterification method in which a saturated aliphatic diol and a substituted carbonate (diethyl carbonate, diphenyl carbonate, etc.) are reacted under the condition that the hydroxyl group is excessive, the saturated aliphatic diol and phosgene are reacted, or as necessary. Then, it can be obtained by a method of further reacting with a saturated aliphatic diol.

  The compounds as exemplified in the above (1) to (5) can be used alone or in combination of two or more.

  As the polyisocyanate component (ii) to be reacted with the component (i), an aliphatic, alicyclic or aromatic compound containing an average of two or more isocyanate groups in one molecule can be used.

  As the aliphatic diisocyanate compound, an aliphatic diisocyanate having 1 to 12 carbon atoms is preferable, and examples thereof include hexamethylene diisocyanate and 2,2,4-trimethylhexane diisocyanate. The alicyclic diisocyanate compound is preferably an alicyclic diisocyanate having 4 to 18 carbon atoms, and examples thereof include 1,4-cyclohexane diisocyanate and methylcyclohexylene diisocyanate. Examples of the aromatic isocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.

  In addition, those containing an acid residue in the water-based urethane resin can be dispersed in water without using a surfactant (hereinafter also referred to as an emulsifier) or in a small amount. Therefore, it is expected that the water resistance of the coating film is improved. This is called a self-emulsifying type, and means a state in which the polyurethane resin is dispersed and stabilized in water only by molecular ionicity without using a surfactant. Since a surfactant is unnecessary, it is preferable because it has excellent adhesiveness with an alicyclic structure-containing polymer and can maintain high transparency. The content of the acid residue is preferably in the range of 25 to 150 mgKOH / g, preferably 30 to 100 mgKOH / g, as the acid value in the aqueous urethane resin. If the acid value is less than 25, water dispersibility tends to be insufficient, and it is often necessary to use a surfactant. On the other hand, if the acid value is greater than 150, the water resistance of the coating tends to be poor.

Method of introducing an acid group into the water-based urethane resin, a method which has been conventionally used can be used without particular limitation, for example, dimethylol alkanoic acid from the (2) of the glycol component described in (4) Single A method of introducing an acid group by introducing a carboxyl group into a polyether diol, a polyester diol, a polyether ester diol or the like in advance by substituting a part or all of them is preferable. Examples of the dimethylolalkanoic acid used here include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid.

Further, by neutralizing the acid components remaining in the water-based urethane resin, it is possible to improve the water-dispersibility of the water-based urethane resin, it is preferably neutralized. Examples of the neutralizing agent that neutralizes the acid component include organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and triethanolamine, and inorganic such as sodium hydroxide, potassium hydroxide, and ammonia. A base etc. can be mentioned.

  The water-based urethane resin used in the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 200,000 or less.

  As the water-based urethane resin, commercially available water-based urethane resins can be used as they are. For example, “Adekabon titer” series manufactured by Asahi Denka Kogyo Co., Ltd., “Made by Mitsui Toatsu Chemical Co., Ltd.” "Olestar" series, "Bondic" series by Dainippon Ink & Chemicals, Ltd., "Hydran" series, "Imperil" series by Bayer, "Sofranate" series by Sofran Japan, Kao Corporation ) "Poise" series, Sanyo Chemical Industries "Samprene" series, Hodogaya Chemical Co., Ltd. "IZerax" series, Daiichi Kogyo Seiyaku "Superflex" series The “Neolets” series manufactured by Zeneca Corporation can be used.

The aforementioned water-based urethane resin, if necessary, heat stabilizer, weathering stabilizer, leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging, lubricants, dyes, pigments, natural oils, An appropriate amount of other compounding agents such as synthetic oil, wax and crosslinking agent may be added.

  When the thickness of the urethane resin layer formed on the film layer (A) is 1 μm or less, it is preferable to further add a crosslinking agent for the purpose of improving the mechanical strength of the urethane resin layer. As a crosslinking agent that can be used in the present invention, any compound having a functional group that reacts with a reactive group of an aqueous urethane resin can be used without particular limitation, but an aqueous epoxy compound, an aqueous amino compound, an aqueous isocyanate, and the like. It is preferable to use a compound or an aqueous carbodiimide compound from the viewpoint of versatility of the material, and particularly preferable to use an aqueous epoxy compound or an aqueous amino compound from the viewpoint of adhesiveness.

  The water-based epoxy compound may be any compound that is soluble in water or has two or more epoxy groups emulsified. For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol; 1 mol of glycol such as 1,4-butanediol, 1,6-hexane glycol, neopentyl glycol and 2 mol of epichlorohydrin Diepoxy compounds obtained by etherification, polyepoxy compounds obtained by etherification of 1 mol of polyhydric alcohols such as glycerin, polyglycerin, trimethylolpropane, pentaerythritol, sorbitol and 2 mol or more of epichlorohydrin, phthalic acid, terephthalic acid Epoxy compounds such as diepoxy compounds obtained by esterification of 1 mol of dicarboxylic acid such as oxalic acid and adipic acid and 2 mol of epichlorohydrin. It is.

  The aqueous amino compound may be any compound that is soluble in water or has two or more amino groups emulsified. For example, carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, acrylic acid dihydrazide, etc. A compound, a melamine resin, a urea resin, a guanamine resin, etc. are mentioned.

  The water-based isocyanate compound may be a compound that has solubility in water or has two or more non-blocked isocyanate groups and block-type isocyanate groups emulsified. Examples of the non-blocking isocyanate compound include compounds obtained by reacting a polyfunctional isocyanate compound with a monovalent or polyvalent nonionic polyalkylene ether alcohol. As the block type isocyanate compound, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diene Isocyanate (XDI), isophorone diisocyanate (IPDI), methylcyclohexyl diisocyanate (H6TDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), hexamethylene diisocyanate (HDI), norbornene diisocyanate (NBDI), 2, 4,6-triisopropylphenyl diisocyanate (TIDI), 1,12-diisocyanatododecane (DDI), 2,4, -bis- (8-isocyanatooctyl) -1,3-dioctylcyclobutane (OCDI), n-pentane- 1,4-diisocyanates and their isocyanurate-modified products, adduct-modified products, burette-modified products, allophanate-modified products, and polymers having one or more isocyanate groups are modified with polyoxyalkylene groups, carboxyl groups, etc. And a compound obtained by making it water-soluble and / or water-dispersible and masking an isocyanate group with a blocking agent (phenol, ε-caprolactam, etc.).

  The water-based carbodiimide compound may be a compound compound that is soluble in water or has two or more carbodiimide bonds (—N═C═N—) emulsified. A compound having two or more carbodiimide bonds is obtained by a method in which two isocyanate groups are decarboxylated to form -N = C = N- using two or more molecules of polyisocyanate and a carbodiimidization catalyst. be able to. The polyisocyanate and the carbodiimidization catalyst used when producing a compound having two or more carbodiimide bonds are not particularly limited, and conventionally known ones can be used.

  The ratio of the water-based urethane resin and the crosslinking agent may be 1 to 30 parts by weight, preferably 5 to 15 parts by weight (solid content) of the cross-linking agent with respect to 100 parts by weight (solid content) of the water-based urethane resin. preferable. By blending, the strength of the coating film and the stability of the coating solution can be achieved.

  From the viewpoint of film optical properties, the particle diameter of the aqueous urethane resin particles dispersed in the aqueous dispersion of the aqueous urethane resin in the present invention is preferably 0.01 μm to 0.4 μm. The particle size of the water-based urethane resin particles can be measured by a dynamic light scattering method, and for example, can be measured by a light scattering photometer DLS-8000 series manufactured by Otsuka Electronics Co., Ltd. The aqueous dispersion of the water-based urethane resin in the present invention may contain a water-soluble solvent. Examples of the water-soluble solvent include methanol, ethanol, isopropyl alcohol, acetone, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like.

  The viscosity of the aqueous dispersion of the aqueous urethane resin in the present invention is preferably 15 mPa · s or less, and particularly preferably 10 mPa · s or less. When the viscosity of the dispersion is within the above range, an aqueous dispersion of an aqueous urethane resin can be uniformly applied to the surface of the film layer (A). The viscosity of the aqueous dispersion of the aqueous urethane resin is a value measured at 25 ° C. with a tuning fork type vibration viscometer. The ratio of the aqueous urethane resin in the aqueous dispersion of the aqueous urethane resin and the particles of the aqueous urethane resin By changing the diameter and the like, the viscosity of the aqueous dispersion of the water-based urethane resin can be adjusted.

  The urethane resin layer in the present invention preferably has a pencil hardness of H or more at a thickness of 20 μm. By setting it in the above range, scratch resistance can be imparted to the laminated film.

  The urethane resin layer can be formed by coating an aqueous dispersion of an aqueous urethane resin on one or both surfaces of the film layer (A) that has undergone surface modification treatment.

  The method for applying the aqueous dispersion of the water-based urethane resin on the film layer (A) is not particularly limited, and a known application method can be employed. Specific coating methods include wire bar coating, dipping, spraying, spin coating, roll coating, gravure coating, air knife coating, curtain coating, slide coating, and extrusion coating. Can be mentioned. The coating amount of the aqueous dispersion of the water-based urethane resin is not particularly limited, but the thickness after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and particularly preferably 0.03 to 1 μm. Within the above range, sufficient adhesive strength between the film layer (A) and the urethane resin layer can be obtained, and a laminated film free from defects such as warping of the film can be provided.

  The film layer (A) and the urethane resin layer in the present invention preferably have an interface refractive index difference of 0.05 or less. When the interface refractive index difference is within the above range, it is possible to suppress light loss when light is transmitted through the laminated film of the present invention.

  When the film layer (A) is provided on one side of the base film, the urethane resin layer is provided on the surface of the film layer (A), and the film layer (A) is provided on both sides of the base film. Can be provided on both sides of the substrate film. By providing it on both sides of the base film, web handling can be improved in the case of a long film.

  The laminated film according to the present invention is produced into a polarizing plate by further laminating a polarizer on the surface of the urethane resin layer in the laminated film, and the present invention is provided via an adhesive on at least one surface of the polarizer. It can manufacture by laminating | stacking this laminated film. When the laminated film of the present invention is laminated only on one side of the polarizer, a highly transparent film may be laminated on the other side of the polarizer. The polarizing plate is also referred to as a polarizing film or a polarizing sheet.

  The polarizer can be obtained by adsorbing iodine or dichroic dye on a polyvinyl alcohol film and then uniaxially stretching in a boric acid bath, and adsorbing iodine or dichroic dye on a polyvinyl alcohol film. And stretching, and a part of the polyvinyl alcohol unit in the molecular chain can be modified to a polyvinylene unit. A polarizer having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer, a multilayer polarizer, and a cholesteric liquid crystal polarizer, can also be used as the polarizer. Among these, a polarizer comprising polyvinyl alcohol is preferable. The polarization degree of the polarizer is preferably 98% or more, more preferably 99% or more. The thickness (average thickness) of the polarizer is preferably 5 μm to 80 μm.

  The adhesive for adhering the polarizer and the laminated film of the present invention is not particularly limited as long as it is optically transparent, and is an aqueous adhesive, a solvent-type adhesive, a two-component curable adhesive, an ultraviolet curable type. Examples thereof include an adhesive and a pressure-sensitive adhesive. Among these, a water-based adhesive is preferable, and a polyvinyl alcohol-based water-based adhesive is particularly preferable.

  The average thickness of the adhesive layer is preferably 0.05 to 5 μm, and more preferably 0.1 to 1 μm.

  As a method of laminating the laminated film of the present invention on the polarizer, a normal method can be used. After applying an adhesive to one surface of the polarizer, the polarizer and the present invention are used using a roll laminator. A method in which the laminated film is bonded to the surface on which the urethane resin layer is provided and dried. The drying time and the drying temperature are appropriately selected according to the type of adhesive.

  The laminated film of the present invention has good adhesion to a film, sheet or substrate formed of another resin and has excellent optical properties. Besides a plate, it can be formed on a film with an antireflection film, a protective film, a retardation film, a viewing angle widening film, a brightness enhancement film, and the like.

  The laminated film of the present invention is suitably used for various image display devices such as organic EL display devices and plasma displays.

Next, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to the following Example.
The test and evaluation in an Example and a comparative example were performed with the following method.

(Evaluation methods)
<Measurement of water contact angle>
Within a 100 cm ² range of the surface-modified film, 20 water contact angles are randomly measured, and an average of these measured values is calculated to obtain an average water contact angle (Da). Deviation (Ds) was calculated. The water contact angle was measured by using a contact angle meter DM500 manufactured by Kyowa Interface Chemical Co., Ltd., 3 μl of pure water was dropped on the measurement surface, and the water contact angle was measured by the θ / 2 method.
<Measurement of viscosity of coating liquid>
Using a tuning fork type vibration viscometer SV-10 (manufactured by A & D), the viscosity of the prepared coating solution was measured under the condition of 25 ° C.
<Pencil hardness of urethane resin layer>
Based on JIS K5600-5-4, measurement was performed with a load of 500 g at a thickness of 10 μm.
<Refractive index of urethane resin layer>
A urethane resin layer having a thickness of 200 nm is formed on a glass substrate, and using a high-speed spectroscopic ellipsometer (manufactured by JA Woollam, M-2000U), a measurement wavelength of 245 to 1000 nm, an incident angle of 55 °, 60 °, and The measurement was made at 65 °, and the value calculated based on the measured value was taken as the refractive index.
<Surface shape observation of the coated surface after coating the coating solution on the film layer (A) after the surface treatment>
The coated surface after coating the coating solution on the film layer (A) after the surface treatment was randomly sampled at 20 points with a size of 5 × 5 mm, and a field emission scanning electron microscope (S-4700, ( (Made by Hitachi, Ltd.), the presence or absence of repelling of the coating liquid was observed.
<Abrasion resistance test>
The entire surface of the laminated film was subjected to a load of 0.02 MPa on # 0000 steel wool and the surface after 10 reciprocations at a stroke width of 25 mm and a speed of 30 mm / sec was visually observed and evaluated according to the following criteria. .
(Double-circle): A crack is not recognized at all.
○: Slightly weak scratches are observed when carefully observed.
X: Scratches are observed.
<Optical properties of laminated film>
Based on JIS K7361-1997, the produced laminated film was measured for total light transmittance and haze of the laminated film using “Durbidity Meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. Moreover, the presence or absence of interference fringes on the surface of the laminated film was visually evaluated.
<Measurement of peel strength of polarizing plate>
The produced polarizing plate was cut into a width of 15 mm, the polarizer and the laminated film were pulled in the 180 ° direction, and the strength was measured (measurement of 180 ° peel strength). The measurement was made with a length of 50 mm, and the average peel strength and the peel strength R (maximum value-minimum value) at that time were measured. In addition, the test was implemented at the tensile speed of 50 mm / sec using the universal tension compression tester (TCM-500CR: Shinsei Tsushin Kogyo Co., Ltd. product) as a measuring machine.

(Production Example 1)
<Manufacture of base film (I)>
A pellet of an alicyclic structure-containing polymer (ZEONOR 1430, manufactured by Nippon Zeon Co., Ltd .; glass transition temperature 135 ° C.) was dried at 70 ° C. for 2 hours using a hot air dryer in which air was circulated, and then a 65 mmφ screw. A base film (I) having a thickness of 100 μm and a length of 1000 m under a molding condition of a melt resin temperature of 270 ° C. and a T die width of 500 mm, using a T-die type film melt extrusion molding machine having a resin melt kneader equipped with ) Was produced. As a result of measuring the refractive index of the produced base film (I), the refractive index was 1.52. The base film (I) is an example of the base film used in the present invention.

(Production Example 2)
<Manufacture of base film (II)>
As a film layer (B), a polystyrene resin, Daylark D332 (manufactured by Nova Chemical), and as a film layer (A), a pellet of ZEONOR 1430 (manufactured by Nippon Zeon Co., Ltd.), which is an alicyclic structure-containing polymer, is 5 at 100 ° C. After drying for a period of time, each was fed to a separate extruder. After the resin is melted in the extruder, it is merged in the feed block through the polymer pipe and the polymer filter, extruded in a sheet form from a T-die having a width of 500 mm onto the casting drum, and cooled on the cooling drum to obtain a thickness. A multilayer film composed of A layer-B layer-A layer having a length of 140 μm and a length of 1000 m was obtained. As a result of measuring the refractive index of the outermost part of the produced multilayer film, the refractive index was 1.52.
Next, the produced multi-layer film having a width of 500 mm is continuously uniaxially stretched at a stretching temperature of 140 ° C. and a stretching ratio of 2.0 times using a tenter-type lateral stretching machine, and further, the left and right ends are cut and removed. By doing this, the base film (II) in which the orientation axis coincided with the width direction was obtained. In addition, base film (II) is an example of the base film used for this invention, and is a film which has an alicyclic structure containing polymer layer in the outermost surface.

(Production Example 3)
<Manufacture of base film (III)>
A mixture comprising 90.0 parts of ditrimethylolpropane tetraacrylate (NK ester AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 10.0 parts of photoinitiator (Irgacure 907, manufactured by Ciba-Geigy), and 900.0 parts of butyl acetate. Was stirred and mixed, and then filtered through a 1 μm filter to prepare an ultraviolet curable resin solution.
Next, on both surfaces of the base film (I) produced in Production Example 1, using a corona treatment device (manufactured by Kasuga Denki Co., Ltd.), an output of 200 W, a frequency of 33.1 kHz, a wire electrode having a diameter of 1.2 mm, an electrode The discharge treatment is performed once under the conditions of a length of 240 mm, a work electrode distance of 3.0 mm, and a conveyance speed of 1 m / min, and then the dry film thickness is 2 μm using the previously prepared UV curable resin solution using a gravure coater. After being applied and dried at 80 ° C. for 5 minutes, ultraviolet ray irradiation (integrated light amount 400 mJ / cm 2) was performed using an ultrahigh pressure mercury lamp, and the resin was cured to obtain a base film (III). In addition, base film (III) is an example of the base film used for this invention, and is a film which has a (meth) acrylic resin layer in the outermost surface. As a result of measuring the refractive index of the outermost part of the produced base film (III), the refractive index was 1.49.

(Production Example 4)
<Manufacture of polarizer>
Polyvinyl alcohol film (trade name 9P75R, manufactured by Kuraray Co., Ltd.) having a thickness of 80 μm is dyed in a 0.3% iodine aqueous solution, and then 5 times in a 4% boric acid aqueous solution and a 2% potassium iodide aqueous solution. And then dried at 50 ° C. for 4 minutes to obtain a polarizer.

(Production Example 5)
<Production of aqueous dispersion of water-based urethane resin>
A 2000 ml four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser tube was charged with 317.2 g of 3-methyl-1,5-pentanediol, 174 g of terephthalic acid, and 146 g of adipic acid in a reactor. The esterification reaction was carried out while distilling off the water produced at 200 ° C. while passing nitrogen gas under pressure. When the acid value of the polyester reached 1.0 mgKOH / g, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. The obtained polyester polyol had a hydroxyl value of 56.1 mgKOH / g, an acid value of 0.2 mgKOH / g, and a number average molecular weight (calculated from the hydroxyl value) of 2000.
In a 2000 ml four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, 840 g of the polyester polyol, 119 g of tolylene diisocyanate, and 200 g of methyl ethyl ketone were added and reacted at 75 ° C. for 1 hour while introducing nitrogen. . After completion of the reaction, the mixture was cooled to 60 ° C., 41 g of dimethylolpropionic acid and 25 g of triethylamine were added and reacted at 75 ° C. to obtain a prepolymer solution having a terminal isocyanate group with NCO of 0.5%. Next, this prepolymer was cooled to 40 ° C., 1500 parts of water was added, and emulsification was performed by stirring at high speed with a homomixer. Methyl ethyl ketone was distilled off from the emulsion under heating and reduced pressure to obtain an aqueous dispersion of an aqueous urethane resin having a solid content of 40%.

(Production Example 6)
<Adjustment of coating liquid (A)>
The aqueous dispersion of the water-based urethane resin prepared in Production Example 5 was diluted with water to a solid content of 2% to prepare a coating liquid (A). The viscosity of the coating liquid (A) was 2.0 mPa · s, the pencil hardness of the urethane resin layer was H, and the refractive index was 1.52.

(Production Example 7)
<Adjustment of coating liquid (B)>
By adding 10 g of an aqueous urethane resin dispersion prepared in Production Example 5, 0.4 g of Denacol EX-810 (manufactured by Nagase ChemteX Corp.) and 136 g of water, which is an aqueous epoxy compound, the solid content is 3%. A coating liquid (B) was prepared. The viscosity of the coating liquid (B) was 2.3 mPa · s, the pencil hardness of the urethane resin layer was 2H, and the refractive index was 1.49.

(Production Example 8)
<Adjustment of coating liquid (C)>
By adding 10 g of an aqueous dispersion of an aqueous urethane resin produced in Production Example 5, 0.08 g of Duranate WB40-100 (manufactured by Asahi Kasei Chemicals Corporation) and 261.9 g of water, which is an aqueous isocyanate compound, the solid content is 1 A 5% coating solution (C) was prepared. The viscosity of the coating liquid (C) was 1.8 mPa · s, the pencil hardness of the urethane resin layer was 2H, and the refractive index was 1.54.

(Production Example 9)
<Adjustment of coating liquid (E)>
By adding 5 g of an aqueous dispersion of an aqueous urethane resin prepared in Production Example 5, 2.0 g of methylated melamine resin MW-30 (manufactured by Sanwa Chemical Co., Ltd.), which is an aqueous amino compound, and 126.3 g of water, and stirring. A coating liquid (E) having a solid content of 3.0% was prepared. The viscosity of the coating liquid (E) was 2.4 mPa · s, the pencil hardness of the urethane resin layer of the coating liquid (E) was 2H, and the refractive index was 1.60.

(Production Example 10)
<Adjustment of adhesive liquid>
Goseifamer Z410 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., PVA containing acetoacetyl group) was diluted with water to a solid content of 3% to prepare an adhesive solution.

Example 1
Using a corona treatment apparatus (manufactured by Kasuga Denki Co., Ltd.) equipped with an electrode whose electrode surface is covered with ceramic on both sides of the base film (I) produced in Production Example 1, an output of 200 W, an electrode length of 240 mm, The discharge treatment was performed once under the conditions of 1.5 mm between work electrodes and a conveyance speed of 5 m / min. The average water contact angle (Da) of the base film (I) subjected to the discharge treatment was 23 °, and the standard deviation (Ds) of the water contact angle was 4.7 °. Next, the coating liquid (A) prepared in Production Example 6 is applied to both sides of the discharge-treated base film (I) so that the film thickness after drying is 80 nm and dried at 80 ° C. for 10 minutes. Thus, a laminated film 1 was obtained. As a result of observing the coated surface of the produced laminated film 1, no repelling of the coated surface was observed. The evaluation results of the produced laminated film 1 are shown in Table 1.
Next, after applying the adhesive liquid produced in Production Example 10 to one surface of the laminated film 1, the polarizer produced in Production Example 4 was bonded to the polarizer using a roll laminator, and dried at 70 ° C. for 10 minutes to obtain polarized light. A plate 1 was produced. When the peel strength of the produced polarizing plate 1 was measured, the average peel strength was 567 g / 15 mm width, and R was 24 g / 15 mm.

(Example 2)
Using a remote atmospheric pressure plasma treatment apparatus (manufactured by E-Square), both sides of the base film (II) produced in Production Example 2 were output 1.8 kW, nitrogen flow rate 200 L / min, and conveyance speed 1 m / min. Surface treatment was carried out twice under conditions. The average water contact angle (Da) of the surface-treated substrate film (II) was 33 °, and the standard deviation (Ds) of the water contact angle was 0.02 °. Next, the coating liquid (B) prepared in Production Example 7 is applied to both surfaces of the surface-treated base film (II) so that the film thickness after drying becomes 90 nm, and dried at 80 ° C. for 10 minutes. Thus, a laminated film 2 was obtained. As a result of observing the coated surface of the produced laminated film 2, no repelling of the coated surface was observed. The evaluation results of the produced laminated film 2 are shown in Table 1.
Next, after applying the adhesive liquid produced in Production Example 10 to one side of the laminated film 2, the polarizer produced in Production Example 4 was bonded to the polarizer using a roll laminator, and dried at 70 ° C. for 10 minutes, thereby polarizing the film. Plate 2 was prepared. When the peel strength of the produced polarizing plate 2 was measured, the average peel strength was 510 g / 15 mm width, and R was 19 g / 15 mm width.

(Example 3)
The base film (III) produced in Production Example 3 was immersed in an aqueous sodium hydroxide solution having a weight of 5% by weight and a liquid temperature of 40 ° C. for 30 minutes to carry out a surface treatment. The average water contact angle (Da) of the surface-treated base film (III) was 47 °, and the standard deviation (Ds) of the water contact angle was 0.03 °. Next, the coating liquid (C) prepared in Production Example 8 is applied to one surface of the surface-treated base film (III) so that the film thickness after drying is 50 nm and dried at 80 ° C. for 10 minutes. Thus, a laminated film 3 was obtained. As a result of observing the coated surface of the produced laminated film 3, no repelling of the coated surface was observed. The evaluation results of the produced laminated film 3 are shown in Table 1.
Next, after applying the adhesive liquid produced in Production Example 10 to the treated surface of the laminated film 3, it was bonded to the polarizer produced in Production Example 4 using a roll laminator and dried at 70 ° C. for 10 minutes, A polarizing plate 3 was produced. When the peel strength of the produced polarizing plate 3 was measured, the average peel strength was 415 g / 15 mm width and R was 21 g / 15 mm width.

(Comparative Example 1)
The corona treatment conditions of Example 1 were as follows: using a corona treatment apparatus (manufactured by Kasuga Electric Co., Ltd.) equipped with wire electrodes, an output of 400 W, a wire electrode with a diameter of 1.2 mm, an electrode length of 240 mm, and a workpiece electrode of 1.5 mm The discharge treatment was performed twice under the condition of a conveyance speed of 5 m / min. The average water contact angle (Da) of the base film (I) subjected to the discharge treatment was 19 °, and the standard deviation (Ds) of the water contact angle was 5.5 °. Next, the coating liquid (A) prepared in Production Example 6 is applied to both sides of the discharge-treated base film (I) so that the film thickness after drying is 80 nm and dried at 80 ° C. for 10 minutes. Thus, a comparative laminated film 1 was obtained. As a result of observing the coated surface of the produced comparative example laminated film 1, repellency was observed over the entire coated surface. The evaluation results of the produced comparative example laminated film 1 are shown in Table 1.
Subsequently, after apply | coating the adhesive liquid produced in the manufacture example 10 to the process surface of the laminated film 1 of a comparative example, it bonds with the polarizer produced in the manufacture example 4 using a roll laminator, and dries at 70 degreeC for 10 minutes. Thus, a comparative polarizing plate 1 was produced. When the peel strength of the produced comparative polarizing plate 1 was measured, the average peel strength was 354 g / 15 mm width, and a decrease in adhesive strength was observed. Further, R was 44 g / 15 mm, and uneven adhesion was observed.

(Comparative Example 2)
When the water contact angle of the base film (III) produced in Production Example 3 was measured, the average water contact angle (Da) was 56 °, and the standard deviation (Ds) of the water contact angle was 0.01 °. By applying the coating liquid (C) produced in Production Example 8 on one side of the base film (III) so that the film thickness after drying is 50 nm and drying at 80 ° C. for 10 minutes, a comparative example A laminated film 2 was obtained. As a result of observing the coated surface of the produced comparative example laminated film 2, repellency was remarkably observed over the entire coated surface. The evaluation results of the produced comparative laminated film 2 are shown in Table 1.
Next, after applying the adhesive liquid produced in Production Example 10 to the treated surface of Comparative Example Laminated Film 2, it is bonded to the polarizer produced in Production Example 4 using a roll laminator and dried at 70 ° C. for 10 minutes. Thus, a comparative polarizing plate 2 was produced. When the peel strength of the produced comparative polarizing plate 2 was measured, the average peel strength was 120 g / 15 mm width, and a decrease in adhesive strength was observed.

(Comparative Example 3)
A comparative laminated film 3 was prepared in the same manner as in Comparative Example 1 except that the coating liquid (A) used in Comparative Example 1 was changed to the coating liquid (E) prepared in Production Example 9. As a result of observing the coated surface of the produced comparative laminated film 3, no repelling of the coated surface was observed. Although the evaluation result of the produced comparison laminated film 3 is described in Table 1, the fall of the total light transmittance and the interference fringe on the film surface were observed notably.

Claims (6)

A method for producing a laminated film having a base film having a film layer containing an alicyclic structure-containing polymer or a (meth) acrylic resin on the outermost surface and a urethane resin layer,
Based on a step of forming a base film having a surface average water contact angle (Da) of 20 to 50 degrees and a water contact angle standard deviation (Ds) of 0.01 to 5, and an aqueous dispersion of an aqueous urethane resin The process of applying on the material film,
The manufacturing method of the laminated | multilayer film characterized by including.   The method for producing a laminated film according to claim 1, wherein the aqueous dispersion of the water-based urethane resin has a viscosity of 15 mPa · s or less. The surface of the base film is subjected to at least one treatment selected from the group consisting of corona treatment, plasma treatment and saponification treatment,
The average water contact angle (Da) is 20 to 50 degrees, and the standard deviation (Ds) of the water contact angle is 0.01 to 5, wherein the laminated film according to claim 1 or 2 Production method.   The method according to any one of claims 1 to 3, wherein the water-based urethane resin is a self-emulsifying water-based urethane resin.   The manufacturing method according to claim 1, wherein the aqueous dispersion of the water-based urethane resin contains a crosslinking agent.   The laminated film manufactured by the manufacturing method as described in any one of Claims 1-5.