WO2015098750A1 - 複層フィルム及びその製造方法 - Google Patents
複層フィルム及びその製造方法 Download PDFInfo
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- WO2015098750A1 WO2015098750A1 PCT/JP2014/083702 JP2014083702W WO2015098750A1 WO 2015098750 A1 WO2015098750 A1 WO 2015098750A1 JP 2014083702 W JP2014083702 W JP 2014083702W WO 2015098750 A1 WO2015098750 A1 WO 2015098750A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Definitions
- the present invention relates to a multilayer film and a method for producing the same.
- optical films are used for various image display devices such as liquid crystal display devices, organic EL display devices, and plasma displays. Such an optical film is used by being bonded to any other member having various functions such as a polarizer, a hard coat layer, an antireflection layer, an antistatic layer, an antiglare layer, and an antifouling layer. There are many. Therefore, such an optical film is desired to have high adhesive force with a member to be bonded.
- the easy-adhesion layer is a layer having a function to reinforce the adhesive force of the film and adhere more firmly when the film including the easy-adhesion layer is bonded to an arbitrary member via an adhesive as necessary. It is. About the easily bonding layer, what was formed with the urethane resin is proposed (refer patent document 1).
- the present invention was devised in view of the above-mentioned problems, and an object thereof is to provide a multilayer film including an easy-adhesion layer that has excellent adhesiveness and can maintain the adhesiveness for a long time in a high-humidity environment, and a method for producing the same.
- the inventor is a multilayer film including a base film and an easy-adhesion layer provided on the base film, and the easy-adhesion layer is polyurethane, crosslinked.
- Made of a cured product of a composition containing an agent and a non-volatile base, and having a polyurethane having a tensile modulus of elasticity in a predetermined range has excellent adhesion and can maintain the adhesion for a long time in a high humidity environment.
- the present invention was completed. That is, the present invention is as follows.
- a base film and an easy-adhesion layer provided on the base film comprises a cured product of a composition containing polyurethane, a crosslinking agent capable of crosslinking the polyurethane, and a non-volatile base.
- the tensile modulus of polyurethane is 1000 N / mm 2 or more 5000N / mm 2 or less, multilayer film.
- the multilayer film according to [1] wherein the base film includes a layer made of a resin containing an alicyclic structure-containing polymer.
- the crosslinking agent contains an epoxy compound.
- a step of forming a film of a composition comprising a polyurethane, a crosslinking agent capable of crosslinking the polyurethane, and a nonvolatile base on the base film; Curing the film of the composition, Tensile elastic modulus of the polyurethane is 1000 N / mm 2 or more 5000N / mm 2 or less, the production method of the multilayer film.
- a multilayer film including an easy-adhesion layer that is excellent in adhesiveness and can maintain the adhesiveness for a long time in a high-humidity environment, and a manufacturing method thereof.
- (meth) acryl includes both acrylic and methacrylic.
- (Meth) acrylate includes both acrylate and methacrylate.
- the particle size distribution is measured by laser diffraction method, and the cumulative volume calculated from the small diameter side in the measured particle size distribution is 50%. Adopt particle size.
- the in-plane retardation of the film or layer is a value represented by (nx ⁇ ny) ⁇ d unless otherwise specified.
- nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the film or layer and giving the maximum refractive index.
- ny represents the refractive index in the in-plane direction of the film or layer and perpendicular to the nx direction.
- d represents the film thickness of the film or layer.
- the retardation measurement wavelength is 550 nm.
- the retardation can be measured using a commercially available phase difference measuring apparatus (for example, “KOBRA-21ADH” manufactured by Oji Scientific Instruments, “WPA-micro” manufactured by Photonic Lattice) or the Senarmon method.
- the “polarizing plate” includes not only a rigid member but also a flexible member such as a resin film.
- the multilayer film of this invention is equipped with a base film and the easily bonding layer provided on this base film.
- the easy adhesion layer is a layer made of a cured product of a composition containing polyurethane, a crosslinking agent capable of crosslinking the polyurethane, and a nonvolatile base.
- the composition containing the polyurethane, the crosslinking agent, and the nonvolatile base is appropriately referred to as a “urethane composition”.
- a resin film is usually used.
- resin which comprises a base film resin containing arbitrary polymers can be used.
- a thermoplastic resin is preferable and it is especially preferable to use resin containing an alicyclic structure containing polymer.
- the resin containing the alicyclic structure-containing polymer is appropriately referred to as “alicyclic structure-containing polymer resin”.
- the alicyclic structure-containing polymer resin is excellent in transparency, low hygroscopicity, dimensional stability and light weight, and is suitable for an optical film.
- the base film may be a single layer structure film including only one layer, or may be a multilayer structure film including two or more layers.
- the base film has a multilayer structure, it is preferable that one or more layers included in the base film are made of an alicyclic structure-containing polymer resin, and at least one outermost layer of the base film is alicyclic.
- the resin comprises a structure-containing polymer resin.
- the alicyclic structure-containing polymer resin tends to have low adhesion, but this low adhesion can be compensated by the easy-adhesion layer. Therefore, when a base film is provided with the layer which consists of alicyclic structure containing polymer resin, the advantage of this invention that adhesiveness can be improved can be utilized effectively.
- the alicyclic structure-containing polymer is a polymer having an alicyclic structure in the structural unit of the polymer, a polymer having an alicyclic structure in the main chain, and an alicyclic structure in the side chain. Any of the polymers may be used. Moreover, an alicyclic structure containing polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Among these, a polymer containing an alicyclic structure in the main chain is preferable from the viewpoint of mechanical strength, heat resistance, and the like.
- Examples of the alicyclic structure include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structure.
- a saturated alicyclic hydrocarbon cycloalkane
- an unsaturated alicyclic hydrocarbon cycloalkene, cycloalkyne
- a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is particularly preferable.
- the number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, particularly preferably per alicyclic structure. Is a range of 15 or less. Thereby, the mechanical strength, heat resistance, and moldability of the base film are highly balanced and suitable.
- the proportion of the structural unit having an alicyclic structure in the alicyclic structure-containing polymer may be appropriately selected depending on the purpose of use, preferably 55% by weight or more, more preferably 70% by weight or more, particularly preferably. Is 90% by weight or more.
- the ratio of the structural unit having an alicyclic structure in the alicyclic structure-containing polymer is in this range, it is preferable from the viewpoint of the transparency and heat resistance of the base film.
- alicyclic structure-containing polymers examples include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Can be mentioned. Among these, norbornene-based polymers are preferable because of their good transparency and moldability.
- Examples of the norbornene-based polymer include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and an arbitrary monomer, or a hydride thereof; An addition polymer of a monomer having a norbornene structure, an addition copolymer of a monomer having a norbornene structure and an arbitrary monomer, or a hydride thereof.
- 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. It is.
- the “(co) polymer” includes both a polymer and a copolymer.
- Examples of the monomer having a norbornene 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 . 1 7,10 ] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring).
- 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 thereof may be bonded to the ring. Moreover, the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- Examples of the polar group include heteroatoms or atomic groups having heteroatoms.
- 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 sulfonic acid group.
- optional monomers capable of ring-opening copolymerization with a monomer having a norbornene structure include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; and cyclic conjugates such as cyclohexadiene and cycloheptadiene. Dienes and derivatives thereof; and the like.
- the optional monomer capable of ring-opening copolymerization with a monomer having a norbornene structure one type may be used alone, or two or more types may be used in combination at any ratio.
- a ring-opening polymer of a monomer having a norbornene structure, and a ring-opening copolymer of any monomer copolymerizable with a monomer having a norbornene structure are, for example, a known ring-opening monomer. It can be produced by polymerization or copolymerization in the presence of a polymerization catalyst.
- ⁇ -olefin is preferable, and ethylene is more preferable.
- the arbitrary monomer which can carry out addition copolymerization with the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- An addition copolymer of a monomer having a norbornene structure and an addition copolymer of any monomer that can be copolymerized with a monomer having a norbornene structure include, for example, a monomer of a known addition polymerization catalyst. It can be produced by polymerization or copolymerization in the presence.
- Examples of monocyclic olefin polymers include addition polymers of cyclic olefin monomers having a single ring such as cyclohexene, cycloheptene, and cyclooctene.
- cyclic conjugated diene polymer examples include polymers obtained by cyclization reaction of addition polymers of conjugated diene monomers such as 1,3-butadiene, isoprene and chloroprene; cyclic conjugated such as cyclopentadiene and cyclohexadiene. And 1,2- or 1,4-addition polymers of diene monomers; and their hydrides.
- vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides; vinyl aromatic hydrocarbons such as styrene and ⁇ -methylstyrene. Hydrogenated product obtained by hydrogenating an aromatic ring part contained in a polymer obtained by polymerizing monomers; vinyl alicyclic hydrocarbon monomer, or vinyl aromatic hydrocarbon monomer and vinyl aromatic hydrocarbon monomer And an aromatic ring hydride of a copolymer such as a random copolymer or a block copolymer with an arbitrary copolymerizable monomer.
- the block copolymer include a diblock copolymer, a triblock copolymer or a multi-block copolymer having more than that, a gradient block copolymer, and the like.
- the weight average molecular weight (Mw) of the polymer contained in the resin constituting the base film is usually 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, and usually 100,000 or less. Preferably it is 80,000 or less, More preferably, it is 50,000 or less.
- the weight average molecular weight is a polyisoprene or polystyrene converted weight average molecular weight measured by gel permeation chromatography using cyclohexane as a solvent. However, when the sample does not dissolve in cyclohexane, toluene may be used as a solvent for gel permeation chromatography. When the weight average molecular weight is in such a range, the mechanical strength and moldability of the multilayer film are highly balanced, which is preferable.
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer contained in the resin constituting the base film is usually 1.2 or more, preferably 1.5 or more, more preferably 1. It is 8 or more, usually 3.5 or less, preferably 3.0 or less, more preferably 2.7 or less.
- productivity of a polymer can be improved and cost can be suppressed.
- a low molecular weight component can be reduced by making it below an upper limit, relaxation time can be lengthened. Therefore, relaxation at high temperature exposure can be suppressed, and the stability of the base film can be enhanced.
- the polymer contained in the resin constituting the base film preferably has an absolute value of the photoelastic coefficient C of 10 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, preferably 7 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less. More preferably, it is 4 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less.
- the saturated water absorption rate of the polymer contained in the resin constituting the base film 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.
- the saturated water absorption is within the above range, the temporal change of the in-plane retardation Re and the thickness direction retardation Rth of the base film can be reduced.
- deterioration of the polarizing plate and the liquid crystal display device including the multilayer film of the present invention can be suppressed, and the display on the display can be kept stable and favorable for a long period.
- the saturated water absorption is a value obtained by expressing the mass increased by immersing the test piece in water at a constant temperature for a certain time as a percentage of the mass of the test piece before immersion. Usually, it is measured by immersing in 23 ° C. water for 24 hours.
- the saturated water absorption in the polymer can be adjusted to the above range, for example, by reducing the amount of polar groups in the polymer. From the viewpoint of lowering the saturated water absorption rate, the polymer preferably does not have a polar group.
- the resin constituting the base film may contain an optional component other than the polymer as long as the effects of the present invention are not significantly impaired.
- the optional components include colorants such as pigments and dyes; plasticizers; fluorescent brighteners; dispersants; thermal stabilizers; light stabilizers; ultraviolet absorbers; antistatic agents; An additive such as a surfactant. These components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the amount of the polymer contained in the resin constituting the base film is generally 50% to 100%, or 70% to 100%.
- the alicyclic structure-containing polymer resin has high hydrophobicity, but any hydrophilicity can be increased by the easy adhesion layer. It has the advantage that it can be firmly bonded to the member. From the viewpoint of effectively utilizing this advantage, the amount of the polymer contained in the alicyclic structure-containing polymer resin is, for example, 80% to 100%, more specifically, 90% to 100%. It is preferable to adjust the amount of these components.
- the alicyclic structure-containing polymer resin does not substantially contain particles.
- substantially free of particles means that even if particles are included in the resin, the amount of increase in haze of the base film from a state in which no particles are included is in a range of 0.05% or less. Means acceptable.
- the alicyclic structure-containing polymer tends to lack affinity with many organic particles and inorganic particles. Therefore, when an alicyclic structure-containing polymer resin containing particles in an amount exceeding the above range is stretched, voids are easily generated, and as a result, the haze may be significantly increased.
- the base film may be a film layer having a single layer structure including only one layer, or may be a film layer having a multilayer structure including two or more layers.
- polarizing plates having various characteristics can be produced.
- the base film includes two or more layers, one or more types of film layers may be included, or two or more different types of film layers may be included.
- the layer made of other than the alicyclic structure-containing polymer resin include a film layer having functions such as scratch prevention, antireflection, antistatic, antiglare and antifouling.
- the base film preferably has a total light transmittance in terms of 1 mm thickness of 80% or more, more preferably 90% or more.
- the total light transmittance can be measured using a spectrophotometer (manufactured by JASCO Corporation, ultraviolet-visible near-infrared spectrophotometer “V-570”) in accordance with JIS K0115.
- the base film preferably has a haze at a thickness of 1 mm of 0.3% or less, and more preferably 0.2% or less.
- the haze is an average value obtained from five points measured using “turbidimeter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7361-1997.
- the average thickness of the base film is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less.
- the thickness variation width of the base film is preferably within ⁇ 3% of the average thickness over the longitudinal direction and the width direction.
- the amount of the volatile component contained in the base film is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and further preferably 0.02% by weight or less.
- the amount of the volatile component is a substance having a molecular weight of 200 or less. Examples of volatile components include residual monomers and solvents.
- the amount of volatile components can be quantified by analyzing by gas chromatography as the sum of substances having a molecular weight of 200 or less.
- the base film is obtained by molding a resin for forming the base film by a known film forming method.
- the film forming method include a cast forming method, an extrusion forming method, and an inflation forming method.
- a 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, the working environment, and the manufacturing efficiency.
- the melt extrusion method include an inflation method using a die, and among them, a method using a T die is preferable in terms of excellent productivity and thickness accuracy.
- a base film When a base film is provided with two or more layers, there is no restriction
- adhesives examples include acrylic adhesives, urethane adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives , Ethylene-vinyl acetate adhesive, vinyl chloride-vinyl acetate adhesive, SEBS (styrene-ethylene-butylene-styrene copolymer) adhesive, SIS (styrene-isoprene-styrene block copolymer) adhesive And ethylene adhesives such as ethylene-styrene copolymers, and acrylic acid ester adhesives such as ethylene-methyl (meth) acrylate copolymers and ethylene- (meth) ethyl acrylate copolymers.
- An adhesive agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the average thickness of the adhesive layer formed by the adhesive is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
- coextrusion molding methods such as coextrusion T-die method, coextrusion inflation method, coextrusion lamination method, and dry lamination
- a film lamination molding method or the like can be used.
- a base film having two or more layers may be produced by using a coating molding method in which a surface of a certain film layer is coated with a solution containing a resin constituting another film layer.
- the coextrusion method is preferable from the viewpoint of production efficiency and from the viewpoint of not leaving volatile components such as a solvent in the base film.
- the coextrusion T-die method is particularly preferable.
- the co-extrusion T-die method includes a feed block method and a multi-manifold method, but the multi-manifold method is more preferable from the viewpoint that variations in film layer thickness can be reduced.
- the base film may be an unstretched film that has not been stretched, or a stretched film that has been stretched. Moreover, when a base film is provided with two or more layers, a stretched film may be obtained by laminating a film layer that has been previously stretched, or a multi-layered film obtained by coextrusion or the like. The film may be stretched to obtain a stretched film.
- the stretching method is not particularly limited, and for example, either a uniaxial stretching method or a biaxial stretching method may be employed.
- a uniaxial stretching method a method of uniaxial stretching in the longitudinal direction using a difference in peripheral speed of a roll for film conveyance; uniaxial stretching in the width direction using a tenter stretching machine And the like.
- biaxial stretching method simultaneous biaxial stretching method that stretches in the width direction according to the spread angle of the guide rail at the same time as stretching in the longitudinal direction with an interval between the clips to be fixed; roll for film conveyance
- Biaxial stretching method such as sequential biaxial stretching method that stretches in the longitudinal direction using the difference in peripheral speed between the two, then grips both ends with clips and stretches in the width direction using a tenter stretching machine, etc.
- it is neither parallel nor perpendicular to the width direction of the film using, for example, a tenter stretching machine that can apply a feeding force, a pulling force, or a pulling force at different speeds in the width direction or the longitudinal direction.
- An oblique stretching method in which oblique stretching is continuously performed in the direction may be used.
- 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 stretching temperature is preferably (Tg-30 ° C) or higher, more preferably (Tg-10 ° C) or higher, preferably (Tg + 60 ° C) or lower, where Tg is the glass transition temperature of the resin constituting the film to be stretched. More preferably, it is (Tg + 50 ° C.) or less.
- the draw ratio can be appropriately selected according to the optical properties of the substrate film to be used.
- the specific draw ratio is usually 1.05 times or more, preferably 1.1 times or more, and usually 10.0 times or less, preferably 2.0 times or less.
- An easy-adhesion layer is a layer which consists of a hardened
- Tensile modulus of the polyurethane is usually 1000 N / mm 2 or more, preferably 1200 N / mm 2 or more, more preferably 1400 N / mm 2 or more, usually 5000N / mm 2 or less, preferably 4000 N / mm 2 or less, more preferably Is 3000 N / mm 2 or less.
- polyurethane having a tensile elastic modulus equal to or higher than the lower limit of the above range the adhesion of the easy-adhesion layer can be increased. Moreover, since it can prevent that an easily bonding layer becomes hard too much by making it below an upper limit, damage to an easily bonding layer can be prevented.
- the conventional easy-adhesion layer a polymer having a low tensile elastic modulus is generally used. This is because, from the viewpoint of improving the adhesiveness by contacting the adhesive surface with a larger area, it was considered that the easy-adhesive layer should be flexible enough to deform according to the unevenness of the adhesive surface. is there.
- high adhesiveness is realized by using polyurethane having a relatively high tensile elastic modulus, contrary to the conventional case.
- the tensile modulus of elasticity of the polyurethane described above is a value measured before being mixed with a component such as a crosslinking agent and a non-volatile base.
- a specific method for measuring the tensile modulus of polyurethane is as follows. First, an aqueous dispersion of polyurethane (a solution may be used if necessary) is prepared as a sample. This aqueous dispersion is poured into a glass container so that the film thickness after drying is 100 ⁇ m. After leaving at room temperature for 24 hours, it is dried at 50 ° C. for 3 hours and at 120 ° C. for 20 minutes to obtain a polyurethane sheet.
- the obtained polyurethane sheet is punched into a dumbbell according to JIS K7162, and a test piece is obtained.
- This test piece is subjected to a tensile test using a tensile tester at a tensile speed of 5 mm / min, and the tensile elastic modulus is measured from the slope of the obtained stress-strain curve (SS curve).
- the tensile modulus of polyurethane can be controlled, for example, by adjusting the type and ratio of the polyurethane monomer.
- Specific examples of the method for controlling the tensile modulus include: (2) polyether polyol, (3) polyester polyol, (4) polyether ester polyol, and (5) polycarbonate, which will be described later, among monomers used as raw materials for polyurethane.
- the tensile elastic modulus of the polyurethane can be adjusted by adjusting the type and charging ratio of the macropolyol such as polyol.
- polyurethane for example, polyurethane obtained by reacting (i) a component containing an average of 2 or more active hydrogens in one molecule and (ii) a polyisocyanate component can be used.
- a polyisocyanate component for example, an isocyanate group-containing prepolymer obtained by urethanizing the component (i) and the component (ii) is chain-extended using a chain extender, and water is added to the dispersion.
- the polyurethane produced by the above can be used.
- the prepolymer can be obtained by subjecting the component (i) and the component (ii) to a urethanization reaction under an excess of isocyanate groups.
- the urethanization reaction can be performed in an organic solvent that is inert to the reaction and has a high affinity for water.
- the prepolymer may be neutralized before the chain extension of the prepolymer.
- Examples of the chain extension method of the isocyanate group-containing prepolymer include a method in which the isocyanate group-containing prepolymer and the chain extender are reacted in the presence of a catalyst as necessary. In this case, water, water-soluble polyamine, glycols, etc. can be used as the chain extender.
- component (i) those having hydroxylic active hydrogen are preferable, and for example, compounds having an average of two or more hydroxyl groups in one molecule are preferable.
- Specific examples of the component (i) include the following (1) polyol compound, (2) polyether polyol, (3) polyester polyol, (4) polyether ester polyol, and (5) polycarbonate polyol.
- polyol compound examples include 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 -Cyclohexanedimethanol, 2,2-dimethylpropanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, glycerin, trimethylolpropane and the like.
- polyether polyols examples include alkylene oxide adducts of the above polyol compounds; ring-opening (co) polymers of alkylene oxides and cyclic ethers (eg, tetrahydrofuran); polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymers 1,4-butanediol copolymer; glycols such as glycol, polytetramethylene glycol, polyhexamethylene glycol, polyoctamethylene glycol; and the like.
- Specific examples of the polyether polyol include poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol, and the like.
- polyester polyol examples include those obtained by polycondensation of a polyvalent carboxylic acid or an anhydride thereof and the above (1) polyol compound under hydroxyl-excess conditions.
- polyvalent carboxylic acid examples include dicarboxylic acids such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid; and tricarboxylic acids such as trimellitic acid. Is mentioned.
- polyester polyols include ethylene glycol-adipic acid condensate, butanediol-adipine condensate, hexamethylene glycol-adipic acid condensate, ethylene glycol-propylene glycol-adipic acid condensate, or glycol as an initiator.
- polylactone diol obtained by ring-opening polymerization of lactone.
- Polyether ester polyol for example, an ether group-containing polyol or a mixture of this and another glycol is mixed with a polyvalent carboxylic acid or anhydride thereof as exemplified in the above (3) and reacted with an alkylene oxide. And the like.
- the ether group-containing polyol include (2) polyether polyol and diethylene glycol.
- Specific examples of the polyether ester polyol include polytetramethylene glycol-adipic acid condensate.
- Polycarbonate polyol examples include a general formula HO—R— (O—C (O) —O—R) X —OH (wherein R represents a saturated fatty acid polyol residue having 1 to 12 carbon atoms). X represents the number of structural units of the molecule, and is usually an integer of 5 to 50).
- transesterification method in which a saturated aliphatic polyol and a substituted carbonate (for example, diethyl carbonate, diphenyl carbonate, etc.) are reacted under the condition that the hydroxyl group becomes excessive; the saturated aliphatic polyol and phosgene are reacted, or If necessary, it can be obtained by a method of further reacting a saturated aliphatic polyol thereafter.
- a saturated aliphatic polyol and a substituted carbonate for example, diethyl carbonate, diphenyl carbonate, etc.
- Examples of the component (ii) to be reacted with the component (i) include compounds containing an average of 2 or more isocyanate groups in one molecule.
- This compound may be an aliphatic compound, an alicyclic compound, or an aromatic compound.
- the aliphatic polyisocyanate compound is preferably an aliphatic diisocyanate having 1 to 12 carbon atoms, and examples thereof include hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, and hexane diisocyanate (HDI).
- the alicyclic polyisocyanate compound is preferably an alicyclic diisocyanate having 4 to 18 carbon atoms, such as 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), etc. Is mentioned.
- aromatic polyisocyanate include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and the like.
- the components (i) and (ii) can be arbitrarily selected and used depending on the use of the multilayer film of the present invention.
- the component (i) it is preferable to use a component having a bond that is difficult to hydrolyze.
- (2) polyether polyol and (5) polycarbonate polyol are preferable, and (2) polyether polyol is particularly preferable.
- Polyurethane using (2) polyether polyol as component (i) is called “polyether polyurethane”.
- polyurethane using (5) polycarbonate polyol as component (i) is called “polycarbonate polyurethane”.
- polyether-based polyurethane and polycarbonate-based polyurethane have an ether bond or a carbonate bond that is difficult to hydrolyze. Therefore, since polyurethane hardly deteriorates in a high-humidity environment, it is possible to suppress a temporal decrease in the tensile elastic modulus of the easily adhesive layer. Therefore, it is possible to effectively suppress a decrease in adhesiveness in a high humidity environment.
- polyurethanes may contain an acid structure in the molecular structure. Since polyurethane containing an acid structure can be dispersed in water without using a surfactant or with a small amount of surfactant, it is expected to improve the water resistance of the easily adhesive layer. . This is called a self-emulsifying type, and means that polyurethane particles can be dispersed and stabilized in water with only molecular ionicity even without a surfactant. Moreover, since the polyurethane containing an acid structure does not require or requires a small amount of a surfactant, it has excellent adhesion to a base film and can maintain high transparency.
- the acid structure examples include acid groups such as a carboxyl group (—COOH) and a sulfo group (—SO 3 H).
- the acid structure may be present in the side chain or at the terminal in the polyurethane.
- One type of acid structure may be used, or two or more types may be used in combination at any ratio.
- the amount of the acid structure is preferably 20 mgKOH / g or more, more preferably 25 mgKOH / g or more, preferably 250 mgKOH / g or less, more preferably 150 mgKOH / g or less as the acid value in the urethane composition.
- a polyether polyol or a polyester may be used in advance.
- transducing a carboxyl group into a polyol, polyetherester polyol, etc. is mentioned.
- the dimethylol alkanoic acid used here include dimethylol acetic acid, dimethylol propionic acid, and dimethylol butyric acid.
- a dimethylol alkanoic acid may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- part or all of the acid structure contained in the polyurethane is neutralized by a nonvolatile base. Due to the neutralization of the acid structure, the multilayer film maintains its properties as an optical material even when it has a thermal history exposed to high temperatures, and adheres to any member with a strong adhesive force. It is possible to Further, even if the acid structure is neutralized, the polyurethane particles can be dispersed in water without using a surfactant or even if the amount of the surfactant is small.
- the proportion of the acid structure to be neutralized is preferably 20% or more, particularly preferably 50% or more.
- the proportion of the acid structure to be neutralized is preferably 20% or more, particularly preferably 50% or more.
- Polyurethane preferably contains a polar group in order to enable reaction with a crosslinking agent.
- 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 sulfo group.
- a methylol group, a hydroxyl group, a carboxyl group, and an amino group are preferable, a hydroxyl group and a carboxyl group are more preferable, and a carboxyl group is particularly preferable.
- the amount of polar groups in the polyurethane is preferably 0.0001 equivalent / 1 kg or more, more preferably 0.001 equivalent / 1 kg or more, and preferably 1 equivalent / 1 kg or less.
- the polyurethane As the polyurethane, a commercially available water-based urethane resin may be used.
- the water-based urethane resin is a composition containing polyurethane and water, and is usually a composition in which polyurethane and optional components contained as necessary are dispersed in water.
- Examples of water-based urethane resins include the “ADEKA BONTITER” series manufactured by ADEKA, the “Olestar” series manufactured by Mitsui Chemicals, the “Bondic” series manufactured by DIC, and the “Hydran (WLS201, WLS202, etc.)” series.
- Bayer's "Imprunil” series, Kao's “Poise” series, Sanyo Kasei's “Samprene” series, Daiichi Kogyo Seiyaku's “Superflex” series, Enomoto Kasei's “ NEOREZ (Neoreds) series, “Sancure” series manufactured by Lubrizol, and the like can be used.
- one type of polyurethane may be used alone, or two or more types may be used in combination at any ratio.
- the state of the polyurethane is arbitrary, and may be dispersed in the form of particles, or may be dissolved in other components such as a solvent. Among these states, polyurethane is often dispersed in the form of particles.
- the average particle diameter of the polyurethane particles is preferably 0.01 ⁇ m to 0.4 ⁇ m from the viewpoint of the optical properties of the multilayer film of the present invention.
- the crosslinking agent can crosslink the polyurethane by reacting with a reactive group of the polyurethane to form a bond. This cross-linking can improve the mechanical strength, adhesiveness, and heat-and-moisture resistance of the easy-adhesion layer.
- the crosslinking agent is contained in the polyurethane such as a carboxyl group and its anhydride group contained as the acid structure, and a hydroxyl group left unreacted after the reaction between the component (i) and the component (ii). It can react with polar groups to form a crosslinked structure.
- crosslinking agent for example, a compound having two or more functional groups that can form a bond by reacting with a reactive group of polyurethane can be used.
- a crosslinking agent the compound which has a functional group which can react with the carboxyl group which a polyurethane has, or its anhydride group is preferable.
- Specific examples of the crosslinking agent include epoxy compounds, carbodiimide compounds, oxazoline compounds, and isocyanate compounds.
- a crosslinking agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the epoxy compound a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used.
- the epoxy compound those that are soluble in water or can be emulsified by being dispersed in water are preferable. If the epoxy group is soluble in water or can be emulsified, when the urethane composition is a water-based resin, the coating property of the water-based resin is improved and the easy-adhesion layer is easily produced. It becomes possible.
- the aqueous resin refers to a composition containing a solid content of a polymer or the like dissolved or dispersed in an aqueous solvent such as water.
- Examples of the epoxy compound include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexane glycol, neopentyl glycol and the like glycols 1 Diepoxy compound obtained by etherification of 1 mol with 2 mol of epichlorohydrin; obtained by etherification of 1 mol of polyhydric alcohols such as glycerin, polyglycerin, trimethylolpropane, pentaerythritol, sorbitol and 2 mol or more of epichlorohydrin Polyepoxy compounds: die obtained by esterification of 1 mol of dicarboxylic acid such as phthalic acid, terephthalic acid, oxalic acid, adipic acid and 2 mol of epichlorohydrin Carboxymethyl compound; and the like.
- dicarboxylic acid such as phthalic acid, tere
- epoxy compound examples include 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- ( ⁇ -acetoxy- ⁇ -oxypropyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether, 1,3,5-triglycidyl (2-hydroxy) Ethyl) isocyanurate, glycerol polyglycerol ethers and trimethylolpropane polyglycidyl ethers.
- epoxy compounds are commercially available products such as “Denacol (Denacol EX-521, EX-614B, etc.)” series manufactured by Nagase ChemteX Corporation.
- An epoxy compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the amount of the epoxy compound is usually 2 parts by weight or more, preferably 5 parts by weight or more, more preferably 8 parts by weight or more, and usually 40 parts by weight or less, preferably 35 parts by weight or less, with respect to 100 parts by weight of polyurethane. More preferably, it is 30 parts by weight or less.
- the amount of the epoxy compound is preferably 0.2 times or more, more preferably 0.4 times or more, particularly preferably 0.6 times, based on the weight, with respect to the amount of the epoxy compound equivalent to the polar group of polyurethane. It is more than double, preferably 5.0 times or less, more preferably 4.0 times or less, and particularly preferably 3.0 times or less.
- the amount of the epoxy compound equivalent to the polar group of polyurethane means the theoretical amount of the epoxy compound that can react with the total amount of polar group of polyurethane without excess or deficiency.
- the polar group of the polyurethane can react with the epoxy group of the epoxy compound. Therefore, by keeping the amount of the epoxy compound within the above range, the reaction between the polar group and the epoxy compound can be advanced to an appropriate level, and the mechanical strength of the easy adhesion layer can be effectively improved.
- the carbodiimide compound a compound having two or more carbodiimide groups in one molecule can be used.
- This carbodiimide compound is produced using an organic isocyanate such as organic monoisocyanate, organic diisocyanate, or organic triisocyanate as a raw material.
- organic isocyanates include aromatic isocyanates, aliphatic isocyanates, and mixtures thereof. Therefore, as the organic group possessed by the organic isocyanate, either aromatic or aliphatic may be used, or an aromatic organic group and an aliphatic organic group may be used in combination. Among these, from the viewpoint of reactivity, an organic isocyanate having an aliphatic organic group is particularly preferable.
- a carbodiimide compound is synthesized by a condensation reaction of an organic diisocyanate.
- organic isocyanate examples include 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexa Organic diisocyanates such as methylene diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate; isophorone isocyanate, phenyl isocyanate, cyclohexyl isocyanate, Examples thereof include organic monoisocyanates such as butyl isocyanate and naphthyl isocyanate.
- carbodiimide compounds are commercially available products such as “Carbodilite (Carbodilite V-02, V-02-L2, SV-02, V-04, E-02, etc.)” manufactured by Nisshinbo Chemical Co., Ltd. Is possible.
- a carbodiimide compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the amount of the carbodiimide compound is usually 1 part by weight or more, preferably 3 parts by weight or more, and usually 40 parts by weight or less, preferably 30 parts by weight or less based on 100 parts by weight of the polyurethane.
- oxazoline compound a polymer having an oxazoline group represented by the following formula (I) can be used.
- R 4 , R 5 , R 6 and R 7 are the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group and a substituted phenyl group.
- This oxazoline compound can be produced, for example, by subjecting a monomer component containing an addition-polymerizable oxazoline and optionally containing an unsaturated monomer to solution polymerization in an aqueous medium by a known polymerization method.
- a monomer component containing an addition-polymerizable oxazoline and optionally containing an unsaturated monomer to solution polymerization in an aqueous medium by a known polymerization method.
- the addition-polymerizable oxazoline include compounds represented by the following formula (II).
- R 4 , R 5 , R 6 and R 7 are the same as defined in formula (I).
- R 8 represents an acyclic organic group having an addition polymerizable unsaturated bond.
- addition polymerizable oxazoline are 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Examples thereof include oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. Moreover, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
- the amount of the addition-polymerizable oxazoline is preferably 3 parts by weight or more and preferably 100 parts by weight or less with respect to 100 parts by weight of all monomer components used for producing the oxazoline compound.
- any monomer that can be copolymerized with an addition-polymerizable oxazoline and does not react with an oxazoline group can be used.
- Such an arbitrary unsaturated monomer can be arbitrarily selected from the monomers described above.
- oxazoline compounds commercially available products include Epocross WS-500 and WS-700 manufactured by Nippon Shokubai Co., Ltd. Further, for example, for the emulsion type, Epocros K-2010, K-2020 and K-2030 manufactured by Nippon Shokubai Co., Ltd. can be mentioned. Among these, a water-soluble type having high reactivity with polyurethane is preferable. Moreover, an oxazoline compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the amount of the oxazoline compound can be set so that the molar ratio of the polar group of the polyurethane and the oxazoline group of the oxazoline compound (number of moles of polar group / number of moles of oxazoline group) falls within a predetermined range.
- the molar ratio can be set to 100/20 to 100/100.
- the reaction between the polyurethane and the oxazoline compound makes it difficult for the oxazoline group and the carboxylate to react. Therefore, the reactivity can be controlled by adjusting the kind of nonvolatile base used for neutralization and the degree of nonvolatileity.
- isocyanate compound a compound containing two or more isocyanate groups in one molecule can be used.
- These isocyanate compounds may be aliphatic compounds, alicyclic compounds, or aromatic compounds.
- Specific examples of the isocyanate compound include the same examples as the component (ii) described as the raw material for polyurethane.
- epoxy compounds and carbodiimide compounds are preferable, and epoxy compounds are particularly preferable.
- an epoxy compound is used as a cross-linking agent, the adhesion of the easy-adhesion layer can be particularly greatly improved.
- the pot life of a urethane composition can be improved when a carbodiimide compound is used as a crosslinking agent.
- Nonvolatile base examples include a base that is substantially non-volatile under the treatment conditions when the urethane composition is applied to the base film and then dried.
- being substantially non-volatile means that a decrease in non-volatile base is usually 80% or less.
- coating a urethane composition to a base film, leaving to stand at 80 degreeC for 1 hour is mentioned, for example.
- Such a non-volatile base can function as a neutralizing agent that neutralizes the acid structure of the polyurethane.
- an inorganic base or an organic base may be used as the nonvolatile base.
- an organic base having a boiling point of 100 ° C. or higher is preferable, an amine compound having a boiling point of 100 ° C. or higher is more preferable, and an amine compound having a boiling point of 200 ° C. or higher is particularly preferable.
- the organic base may be a low molecular compound or a polymer.
- examples of the non-volatile base examples include sodium hydroxide and potassium hydroxide.
- examples of the organic base include 2-amino-2-methyl-1-propanol (AMP), triethanolamine, triisopropanolamine (TIPA), monoethanolamine, diethanolamine, and tri [(2-hydroxy) -1 -Propyl] amine, 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-hydroxymethyl-1,3-propane potassium hydroxide, zinc ammonium complex, copper ammonium complex, silver Ammonium complex, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)
- the amount of the non-volatile base is usually 0.5 parts by weight or more, preferably 1 part by weight or more, more preferably 2 parts by weight or more, and usually 30 parts by weight or less, preferably 20 parts by weight with respect to 100 parts by weight of polyurethane. Part or less, more preferably 10 parts by weight or less.
- the urethane composition preferably contains particles.
- the surface roughness of the easy-adhesion layer formed by the cured product of the urethane composition can be increased. Thereby, since the slipperiness of the surface of an easily binding layer can be improved, it becomes possible to prevent blocking of the multilayer film and to suppress generation of wrinkles when the multilayer film is wound.
- inorganic particles either inorganic particles or organic particles may be used. However, it is preferable to use water-dispersible particles.
- inorganic particles include inorganic oxides such as silica, titania, alumina, zirconia; calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate Etc.
- a silicone resin, a fluororesin, an acrylic resin etc. will be mentioned, for example.
- silica is preferable.
- Silica particles are excellent in ability to suppress the generation of wrinkles and transparency, hardly cause haze, and have no coloration, so that the influence on the optical characteristics of the multilayer film of the present invention is small. Silica has good dispersibility and dispersion stability in the urethane composition. Among the silica particles, amorphous colloidal silica particles are particularly preferable.
- the average particle diameter of the particles is usually 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and usually 500 nm or less, preferably 300 nm or less, more preferably 200 nm or less.
- the amount of the particles is usually 1 part by weight or more, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and usually 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 100 parts by weight of polyurethane. Is 30 parts by weight or less.
- the urethane composition preferably contains a wetting agent.
- a wetting agent By using a wetting agent, the applicability when applying the urethane composition to the base film can be improved.
- an acetylene surfactant for example, an acetylene surfactant, a fluorine surfactant, or the like can be used.
- acetylene-based surfactant for example, Surfynol series, Dynol series manufactured by Air Products and Chemicals, Inc. can be used.
- fluorine-type surfactant DIC Corporation mega-fac series, Neos company's tangent series, AGC company's Surflon series, etc.
- the blending amount of the wetting agent is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more with respect to the solid content of the urethane composition (coating liquid). Usually, it is 5% by weight or less, preferably 4 parts by weight or less, more preferably 3% by weight or less. Sufficient applicability can be obtained by setting the amount of the wetting agent to be equal to or greater than the lower limit of the above range. Moreover, by making it into the upper limit value or less, bleeding out of the wetting agent can be suppressed, and further, the overcoatability can be improved.
- the urethane composition usually contains a solvent.
- a solvent water or a water-soluble solvent is used.
- 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.
- water is preferably used as the solvent.
- a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- the amount of the solvent can be set so that the viscosity of the urethane composition can be in a range suitable for coating.
- the amount of the solvent is set so that the solid content concentration of the urethane composition falls within a desired range.
- the desired range is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 15% by weight or less, more preferably 10% by weight or less.
- the urethane composition may contain a curing accelerator in combination with the crosslinking agent.
- a hardening accelerator the well-known hardening accelerator used for formation of an easily bonding layer can be used.
- the curing accelerator may be a tertiary amine compound (excluding compounds having a 2,2,6,6-tetramethylpiperidyl group having a tertiary amine at the 4-position). ), Boron trifluoride complex compounds and the like are suitable.
- a hardening accelerator may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
- the amount of the curing accelerator is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, more preferably 0.03 part by weight or more, usually 30 parts by weight or less, relative to 100 parts by weight of polyurethane.
- the amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
- the urethane composition may contain a curing aid in combination with the crosslinking agent.
- a curing aid used for forming the easy-adhesion layer can be used.
- Specific examples of curing aids include oxime / nitroso curing aids such as quinonedioxime, benzoquinonedioxime and p-nitrosophenol; maleimide curing aids such as N, Nm-phenylenebismaleimide; diallyl Allyl curing aids such as phthalate, triallyl cyanurate and triallyl isocyanurate; Methacrylate curing aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; Curing aids; and the like.
- a hardening adjuvant may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
- the amount of the curing aid is usually 1 part by weight or more, preferably 10 parts by weight or more, and usually 100 parts by weight or less, preferably 50 parts by weight or less with respect to 100 parts by weight of the crosslinking agent.
- urethane composition significantly impairs the effects of the present invention, for example, a heat stabilizer, a weather stabilizer, a leveling agent, a surfactant, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and an antifogging agent.
- a heat stabilizer for example, a heat stabilizer, a weather stabilizer, a leveling agent, a surfactant, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and an antifogging agent.
- Lubricants dyes, pigments, natural oils, synthetic oils, waxes and the like.
- these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- the urethane composition is usually a fluid composition.
- the viscosity of the urethane composition is preferably 15 mPa ⁇ s or less, and particularly preferably 10 mPa ⁇ s or less.
- the urethane composition can be uniformly applied to the surface of the base film.
- the viscosity is a value measured under a condition of 25 ° C. with a tuning fork type vibration viscometer.
- the viscosity of a urethane composition can be adjusted with the ratio of the solvent in a urethane composition, the particle size of particle
- the easy adhesion layer is a layer made of a cured product of the urethane composition.
- the easy-adhesion layer is usually provided directly on the base film without any other layer such as an adhesive layer.
- the easy adhesion layer may be provided only on one side of the base film, or may be provided on both sides. However, it is preferable to provide an easy-adhesion layer only on one side of the base film from the viewpoint of easily winding a multilayer film having an easy-adhesion layer into a roll.
- An easily bonding layer can be manufactured with the manufacturing method including the process of forming the film
- a coating method When forming a film of a urethane composition on a base film, a coating method is usually used.
- a coating method a known coating method can be adopted. Specific coating methods include, for example, a wire bar coating method, a dip method, a spray method, a spin coating method, a roll coating method, a gravure coating method, an air knife coating method, a curtain coating method, a slide coating method, and an extrusion coating method. Etc.
- the urethane composition forming the film is cured to obtain an easy-adhesion layer as a layer made of a cured product of the urethane composition.
- a solvent is dried and removed.
- the drying method is arbitrary, and for example, the drying may be performed by any method such as reduced pressure drying or heat drying.
- the crosslinking reaction of polyurethane usually proceeds.
- the heating temperature is appropriately set within a range in which the solvent can be dried to cure the polymer component in the urethane composition.
- the heating temperature may be set to a temperature at which no orientation relaxation occurs in the base film.
- the heating temperature is preferably (Tg ⁇ 30 ° C.) or higher, more preferably (Tg ⁇ 10 ° C.) or higher, where Tg is the glass transition temperature of the material forming the base film. Yes, preferably (Tg + 60 ° C.) or less, more preferably (Tg + 50 ° C.) or less.
- the surface modification treatment for the base film include energy ray irradiation treatment and chemical treatment.
- the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, etc., and from the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred.
- the chemical treatment include a saponification treatment, a method of immersing in an aqueous oxidizing agent solution such as potassium dichromate solution and concentrated sulfuric acid, and then washing with water.
- the surface of the easy-adhesion layer is preferably subjected to a hydrophilic surface treatment.
- the surface of the easy-adhesion layer is usually a bonding surface when the multilayer film of the present invention is bonded to an arbitrary member. Therefore, the adhesiveness of the multilayer film of this invention and arbitrary members can be improved notably by further improving the hydrophilic property of the surface of an easily bonding layer.
- hydrophilic surface treatment for the easy-adhesion layer examples include corona discharge treatment, plasma treatment, saponification treatment, and ultraviolet irradiation treatment. Among these, from the viewpoint of processing efficiency, corona discharge treatment and plasma treatment are preferable, and corona discharge treatment is more preferable. As the plasma treatment, atmospheric pressure plasma treatment is preferable.
- the average water contact angle on the surface of the easy-adhesion layer is in a desired range.
- the specific range of the average water contact angle is preferably 80 ° or less, more preferably 70 ° or less, particularly preferably 60 ° or less, and usually 20 ° or more.
- the standard deviation of the water contact angle is preferably 0.01 ° to 5 °.
- the water contact angle can be obtained by the ⁇ / 2 method using a contact angle meter.
- the average water contact angle is determined by, for example, measuring 20 water contact angles randomly selected within a range of 100 cm 2 on the surface of the easily adhesive layer subjected to the hydrophilized surface treatment, and calculating the average of the measured values. Calculated. The standard deviation of the water contact angle is calculated from this measured value.
- a functional group such as a hydroxy group, a carboxyl group, a carbonyl group, an amino group, or a sulfonic acid group can be introduced on the surface of the easy-adhesion layer.
- Corona discharge treatment is preferably a wire electrode, a plane electrode, or a roll electrode as the electrode structure.
- the material of the electrode include metals such as iron, copper, aluminum, and stainless steel.
- the electrode shape include a thin plate shape, a knife edge shape, and a brush shape.
- the corona discharge treatment it is preferable to carry out the treatment by sandwiching a dielectric between the film to be treated and the electrode in order to make the discharge uniform. It is preferable to use a dielectric having a relative dielectric constant of 10 or more.
- the dielectric structure is preferably a structure in which electrodes of both electrodes are sandwiched between dielectrics.
- the dielectric material include ceramics; plastics such as silicon rubber, polytetrafluoroethylene, and polyethylene terephthalate; glass; quartz; silicon dioxide; metal oxides such as aluminum oxide, zirconium dioxide, and titanium dioxide; barium titanate and the like. And the like.
- a solid dielectric having a relative dielectric constant of 10 or more under an environment of 25 ° C.
- 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 thickness of the dielectric is preferably in the range of 0.3 mm to 1.5 mm. Dielectric breakdown can be prevented by setting the thickness of the dielectric to be equal to or greater than the lower limit of the above range. Moreover, since it is not necessary to raise an applied voltage by making it below an upper limit, processing efficiency can be improved.
- the distance between the film to be treated and the electrode is preferably 0.5 mm to 10 mm.
- the interval is preferably 0.5 mm to 10 mm.
- the output of the corona discharge treatment is preferably performed under the condition that the damage to the surface to be treated is as small as possible. Specifically, it is preferably 0.02 kW or more, more preferably 0.04 kW or more, preferably 5 kW or less, more preferably Is 2 kW or less. Further, within this range, it is a preferable corona discharge treatment method to perform the corona discharge treatment several times at the lowest possible output.
- the density of the corona discharge treatment is preferably 1 W ⁇ min / m 2 or more, more preferably 5 W ⁇ min / m 2 or more, particularly preferably 10 W ⁇ min / m 2 or more, preferably 1000 W ⁇ min / m 2 or less. More preferably, it is 500 W ⁇ min / m 2 or less, and particularly preferably 300 W ⁇ min / m 2 or less.
- the frequency of the corona discharge treatment is preferably 5 kHz or more, more preferably 10 kHz or more, preferably 100 kHz or less, more preferably 50 kHz or less.
- the uniformity of the corona discharge treatment can be improved, so that unevenness of the corona discharge treatment can be prevented.
- the stable corona discharge process can be performed by making it below an upper limit.
- Corona discharge treatment can generate discharge in a finer state by surrounding the electrode with a casing, putting an inert gas inside the casing, and applying gas to the electrode part.
- an inert gas helium, argon, nitrogen etc. are mentioned, for example.
- An inert gas may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- examples of the plasma discharge treatment include glow discharge treatment and flame plasma treatment.
- glow discharge treatment either a vacuum glow discharge treatment performed under vacuum or an atmospheric pressure glow discharge treatment performed under atmospheric pressure can be used.
- atmospheric pressure glow discharge treatment performed under atmospheric pressure is preferable.
- the atmospheric pressure is in the range of 700 Torr to 780 Torr.
- a film to be treated is placed between opposing electrodes, a plasma-exciting gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes to excite the gas between the electrodes. Glow discharge is performed. This further increases the hydrophilicity of the treated surface.
- Plasma-excitable gas refers to a gas that can be plasma-excited under the above conditions.
- the plasma-exciting gas include rare gases such as argon, helium, neon, krypton, and xenon; nitrogen; carbon dioxide; chlorofluorocarbons such as tetrafluoromethane and mixtures thereof; and inert gases such as argon and neon.
- a reactive gas capable of imparting a polar functional group such as a carboxyl group, a hydroxyl group or a carbonyl group
- plasma excitation gas may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the frequency of the high frequency voltage in the plasma treatment is preferably in the range of 1 kHz to 100 kHz.
- the magnitude of the voltage is preferably in a range where the electric field strength when applied to the electrode is 1 kV / cm to 100 kV / cm.
- an alkali saponification treatment is suitable as the saponification treatment.
- the treatment method include an immersion method and an alkaline solution coating method, and the immersion method is preferable from the viewpoint of productivity.
- the dipping method in the saponification treatment is a technique in which a film to be treated is dipped in an alkaline solution under appropriate conditions, and all surfaces having reactivity with alkali on the entire surface of the film are saponified.
- the immersion method is preferable from the viewpoint of cost because it does not require special equipment.
- the alkaline liquid is preferably a sodium hydroxide aqueous solution.
- the concentration of the alkaline solution is preferably 0.5 mol / liter or more, more preferably 1 mol / liter or more, preferably 3 mol / liter or less, more preferably 2 mol / liter or less.
- the liquid temperature of the alkaline solution is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, preferably 70 ° C. or lower, more preferably 60 ° C. or lower.
- the dipping time is appropriately adjusted.
- the film After immersing the film in the alkaline solution, the film is thoroughly washed with water so that the alkali component does not remain in the treated film, or the alkali component is neutralized by immersing the film in dilute acid. It is preferable.
- the wavelength of the irradiated ultraviolet rays is usually 100 nm to 400 nm.
- the output value of the lamp which is an ultraviolet light source, is usually 120 W or more, preferably 160 W or more, and is usually 240 W or less, preferably 200 W or less.
- the irradiation amount of ultraviolet rays is preferably 100 mJ / cm 2 or more, more preferably 200 mJ / cm 2 or more, and particularly preferably 300 mJ / cm, when expressed as the total amount of accumulated ultraviolet light with respect to the object irradiated with ultraviolet rays.
- the total amount of integrated light amount is a value determined by the illuminance of the ultraviolet irradiation lamp and the line speed (film moving speed), and can be measured by, for example, an ultraviolet integrated illuminometer (EYEUV METER UVPF-A1).
- the thickness of the easy-adhesion layer is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, particularly preferably 0.02 ⁇ m or more, more preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
- the thickness of the easy adhesion layer is within the above range, sufficient adhesive strength between the base film and the easy adhesion layer can be obtained, and defects such as warpage of the multilayer film of the present invention can be eliminated.
- the ratio t 2 / t 1 with thickness t 2 of the thickness t 1 and the adhesion layer of the base film is preferably 0.0003 or more, more preferably more than 0.0010, particularly preferably 0.0025 or more, 0.0100 or less is preferable, 0.0080 or less is more preferable, and 0.0050 or less is particularly preferable.
- the transparency of the multilayer film of the present invention can be improved.
- the thickness of the base film becomes the thickness t1
- the multilayer film of the present invention includes two or more base film.
- the total thickness of these substrate films is the thickness t 1 .
- the multilayer film of the present invention comprises an easy-adhesion layer only one layer is provided the thickness of the thickness t 2 next to the adhesive layer, the multilayer film is readily adhesive layer of the present invention two or more layers thereof the total thickness of the adhesive layer is a thickness t 2 of the.
- the interface refractive index difference between the base film and the easy-adhesion layer is preferably 0.05 or less.
- the interface refractive index difference is within the above range, it is possible to suppress light loss when light is transmitted through the multilayer film of the present invention.
- the multilayer film of the present invention can have an arbitrary layer on the surface of the base film opposite to the easy adhesion layer.
- optional layers include an antireflection layer, a hard coat layer, an antistatic layer, an antiglare layer, an antifouling layer, and a separator film.
- the multilayer film of the present invention includes the easy-adhesion layer described above, the adhesive strength with any member is high. Furthermore, since the multilayer film of the present invention includes the above-described easy adhesion layer, the adhesive force can be maintained for a long time even in a high humidity environment. Therefore, even when it is left for a long time in a harsh environment such as during transportation and storage, it can be prevented that the multilayer film of the present invention peels from the bonded member.
- the multilayer film of the present invention has a total light transmittance of preferably 80% or more, more preferably 90% or more, from the viewpoint of stably exhibiting the function as an optical member.
- the multi-layer film of the present invention has a haze of preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less.
- a haze of preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less.
- the multilayer film of the present invention may be a retardation film having retardation in the plane or in the thickness direction.
- the specific retardation range can be set according to the use of the multilayer film of the present invention.
- the in-plane retardation Re is appropriately selected from the range of 10 nm to 500 nm
- the thickness direction retardation Rth is appropriately selected from the range of ⁇ 500 nm to 500 nm.
- the multilayer film of the present invention has an in-plane retardation Re variation of usually within 10 nm, preferably within 5 nm, and more preferably within 2 nm.
- the variation in the in-plane retardation Re is obtained when the in-plane retardation Re at the light incident angle of 0 ° (a state where the incident light beam and the film surface are orthogonal) is measured in the width direction of the film. This is the difference between the maximum value and the minimum value of the in-plane retardation Re.
- the amount of residual volatile components in the multilayer film of the present invention is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and further preferably 0.02% by weight or less.
- the multi-layer film of the present invention may have a width dimension of, for example, 1000 mm to 3000 mm.
- the multilayer film of this invention does not have a restriction
- the “long” film means a film having a length of 5 times or more, preferably 10 times or more, more specifically a roll shape. It has a length enough to be wound up and stored or transported.
- the multilayer film of this invention can be manufactured with the manufacturing method including the process of preparing a base film, and the process of manufacturing an easily bonding layer on the prepared base film.
- the process for producing the easy-adhesion layer on the base film includes a process for forming a film of the urethane composition on the base film and a process for curing the film of the urethane composition as described above. Including.
- the multilayer film of the present invention includes an optional layer other than the base film and the easy-adhesion layer
- the surface of the base film opposite to the easy-adhesion layer at any point in the method for producing the multilayer film A step of providing an arbitrary layer may be performed.
- the multilayer film of the present invention is usually used as an optical film.
- a protective film, retardation film, an optical compensation film, etc. will be mentioned.
- the multilayer film of the present invention is excellent in adhesiveness with an arbitrary member and has an advantage that the adhesiveness can be maintained for a long time under high humidity. From the viewpoint of effectively utilizing this advantage, the multilayer film of the present invention is preferably applied to an application used by being bonded to an arbitrary member. If the example of a specific use is given, it is preferable to use the multilayer film of this invention as a polarizing plate protective film.
- the polarizing plate usually includes a polarizer and a polarizing plate protective film. Therefore, when using the multilayer film of the present invention as a polarizing plate protective film, the multilayer film of the present invention is usually bonded to the polarizer on the easy adhesion layer side.
- the polarizing plate can be produced, for example, by laminating the easily adhesive layer of the multilayer film of the present invention and a polarizer.
- the polarizer may be directly bonded to the easy-adhesive layer without using the adhesive layer, or may be bonded through the adhesive layer.
- the multilayer film of the present invention may be bonded to only one surface of the polarizer, or may be bonded to both surfaces.
- another highly transparent film may be bonded to the other surface of the polarizer.
- the polarizer may be produced, for example, by adsorbing iodine or a dichroic dye to a polyvinyl alcohol film and then uniaxially stretching in a boric acid bath.
- iodine or a dichroic dye may be adsorbed and stretched on a polyvinyl alcohol film, and a part of the polyvinyl alcohol unit in the molecular chain may 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, may be used as the polarizer.
- a polarizer containing polyvinyl alcohol is preferable.
- the polarization degree of the polarizer is preferably 98% or more, more preferably 99% or more.
- the average thickness of the polarizer is preferably 5 ⁇ m to 80 ⁇ m.
- an optically transparent material can be used as the adhesive for adhering the polarizer and the multilayer film of the present invention.
- the adhesive include a water-based adhesive, a solvent-type adhesive, a two-component curable adhesive, a photo-curable adhesive, and a pressure-sensitive adhesive.
- a water-based adhesive is preferable, and a polyvinyl alcohol-based water-based adhesive is particularly preferable.
- an adhesive agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- an acrylate adhesive containing urethane (meth) acrylate, hydroxyalkyl (meth) acrylate, and an acrylamide derivative can be used.
- Urethane (meth) acrylate for example, after reacting a polyisocyanate and a polyol, further reacting a hydroxyl group-containing (meth) acryl compound and, if necessary, a hydroxyl group-containing allyl ether compound, thereby producing a radically polymerizable unsaturated group. It can be obtained as a containing oligomer.
- urethane (meth) acrylate can be obtained, for example, by reacting a hydroxyl group-containing (meth) acrylic compound with a polyol and further reacting with polyisocyanate.
- urethane (meth) acrylate use urethane (meth) acrylate having 2 to 3 double bonds per molecule and having a number average molecular weight of 500 to 3000 per double bond. However, it is preferable because it is easy to balance adhesive strength, flexibility, photocurability, viscosity, and the like.
- the amount of urethane (meth) acrylate in the photocurable adhesive is usually 30% to 50% by weight. By making the amount of urethane (meth) acrylate not less than the lower limit of the above range, the adhesive layer can be prevented from becoming brittle. Moreover, by making it into below an upper limit, the viscosity of an adhesive agent can be made low and adhesive strength can be made high.
- hydroxyalkyl (meth) acrylate examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Among these, hydroxyethyl methacrylate is particularly preferable.
- the amount of hydroxyalkyl (meth) acrylate in the photocurable adhesive is usually 13% to 40% by weight. By making the amount of hydroxyalkyl (meth) acrylate not less than the lower limit of the above range, the hydrophilicity of the entire adhesive can be increased, so that the adhesive strength especially for the polyvinyl alcohol polarizing film can be improved. Moreover, by making it into an upper limit or less, it can prevent that an adhesive bond layer becomes weak, and can make photocurability of an adhesive agent high.
- acrylamide derivatives include N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminopropylacrylamide, N-isopropylacrylamide, and N, N-dimethylamino.
- examples include propylacrylamide and N-hydroxyethylacrylamide. Of these, N, N-diethylacrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, and N-hydroxyethylacrylamide are particularly preferable.
- the amount of acrylamide in the photo-curing adhesive is usually in the range of 0 to 30% by weight, preferably 1 to 30% by weight.
- the photocurable adhesive preferably contains 30% to 40% by weight of isobornyl (meth) acrylate in addition to the components described above.
- isobornyl (meth) acrylate By including isobornyl (meth) acrylate, heat resistance is imparted to the adhesive layer. Furthermore, the viscosity for improving the coating performance can be adjusted without deteriorating the adhesive performance.
- the photocurable adhesive preferably contains a photopolymerization initiator.
- the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthiox
- the viscosity of the adhesive is usually 20 mPa or more, preferably 30 mPa or more, more preferably 50 mPa or more, and usually 5000 mPa or less, preferably 3000 mPa or less, more preferably 1500 mPa or less at 23 ° C.
- the average thickness of the adhesive layer is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
- the method of laminating the multilayer film and the polarizer there is no limitation on the method of laminating the multilayer film and the polarizer.
- the polarizer and the multilayer film of the present invention are bonded using a roll laminator, and if necessary, light such as drying or ultraviolet rays is applied.
- a method of performing irradiation is preferred.
- test piece was subjected to a tensile test at a tensile rate of 5 mm / min using a tensile tester (“Tensile Tester 5564” manufactured by Instron Japan), and the tensile modulus was measured from the slope of the obtained SS curve.
- Example 1 (1-1. Production of resin composition) 100 parts of an aqueous dispersion of polyether polyurethane (“Superflex 870” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in an amount of polyurethane, and 15 parts of an epoxy compound (“Denacol EX313” manufactured by Nagase ChemteX) as a crosslinking agent, 2 parts of adipic acid dihydrazide as a non-volatile base and 8 parts of silica particle water dispersion (Nissan Chemical “Snowtex MP1040”; average particle size 120 nm) as a lubricant and an amount of silica particles in water dispersion 8 parts of the liquid (Nissan Chemical “Snowtex XL”; average particle diameter of 50 nm) in the amount of silica particles, and solid acetylene surfactant (Air Products and Chemicals “Surfinol 440”) as a wetting agent
- a liquid resin composition 100
- the liquid resin composition 1 was applied to the surface of the base film subjected to the discharge treatment using a roll coater so that the dry thickness was 0.1 ⁇ m. Then, it heated at 130 degreeC for 60 second, and formed the easily bonding layer on the base film. Thereby, the multilayer film provided with a base film and an easily bonding layer was obtained.
- the multilayer film was subjected to an initial cutter peel test and a wet heat post-cutter peel test by the methods described above.
- Example 2 In the step (1-1), a carbodiimide compound (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- Carbodiimide compound (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- Example 3 In the step (1-1), an oxazoline compound (“Epocross WS700” manufactured by Nippon Shokubai Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- an oxazoline compound (“Epocross WS700” manufactured by Nippon Shokubai Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- Example 4 In the step (1-1), the type of the polyether-based polyurethane aqueous dispersion was changed to “Superflex 130” manufactured by Daiichi Kogyo Seiyaku. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- Example 5 In the step (1-1), the type of the polyether-based polyurethane aqueous dispersion was changed to “Superflex 130” manufactured by Daiichi Kogyo Seiyaku. In the step (1-1), a carbodiimide compound (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- a carbodiimide compound (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- Example 6 In the step (1-1), the type of the polyether-based polyurethane aqueous dispersion was changed to “Superflex 130” manufactured by Daiichi Kogyo Seiyaku. In the step (1-1), an oxazoline compound (“Epocross WS700” manufactured by Nippon Shokubai Co., Ltd.) was used in place of the epoxy compound as a crosslinking agent. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- step (1-1) an aqueous dispersion of polyether ester polyurethane (“Superflex 150HS” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of the aqueous dispersion of polyether polyurethane.
- the polyether ester-based polyurethane refers to a polyurethane produced using a polyether ester polyol as the component (i) among the monomers for producing the polyurethane.
- an epoxy compound as a crosslinking agent was not used. Except for the above, the multilayer film was produced and evaluated in the same manner as in Example 1.
- the results of the initial cutter peel test are all good in the examples. Therefore, it turns out that the easily bonding layer has high adhesiveness in the state before putting the multilayer film of this invention in a high-humidity environment. Moreover, in the Examples, the results of the post-wet heat cutter peeling test are all good. Therefore, it can be seen that the multilayer film of the present invention is excellent in durability in a high-humidity environment and can maintain high adhesion over a long period of time even when placed in a high-humidity environment.
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Abstract
Description
すなわち、本発明は以下の通りである。
前記易接着層は、ポリウレタンと、前記ポリウレタンを架橋させうる架橋剤と、不揮発性塩基とを含む組成物の硬化物からなり、
前記ポリウレタンの引っ張り弾性率が、1000N/mm2以上5000N/mm2以下である、複層フィルム。
〔2〕 前記基材フィルムが、脂環式構造含有重合体を含む樹脂からなる層を備える、〔1〕記載の複層フィルム。
〔3〕 前記架橋剤が、エポキシ化合物を含む、〔1〕又は〔2〕記載の複層フィルム。
〔4〕 前記組成物が、粒子を含む、〔1〕~〔3〕のいずれか一項に記載の複層フィルム。
〔5〕 前記組成物が、濡れ剤を含む、〔1〕~〔4〕のいずれか一項に記載の複層フィルム。
〔6〕 前記ポリウレタンが、ポリエーテル系ポリウレタンである、〔1〕~〔5〕のいずれか一項に記載の複層フィルム。
〔7〕 基材フィルム上に、ポリウレタンと、前記ポリウレタンを架橋させうる架橋剤と、不揮発性塩基とを含む組成物の膜を形成する工程と、
前記組成物の膜を硬化させる工程とを含み、
前記ポリウレタンの引っ張り弾性率が、1000N/mm2以上5000N/mm2以下である、複層フィルムの製造方法。
本発明の複層フィルムは、基材フィルムと、この基材フィルム上に設けられた易接着層とを備える。また、易接着層は、ポリウレタンと、このポリウレタンを架橋させうる架橋剤と、不揮発性塩基とを含む組成物の硬化物からなる層である。前記のポリウレタン、架橋剤及び不揮発性塩基を含む組成物を、以下、適宜「ウレタン組成物」と呼ぶ。
基材フィルムとしては、通常、樹脂フィルムを用いる。基材フィルムを構成する樹脂としては、任意の重合体を含む樹脂を用いうる。中でも、基材フィルムを構成する樹脂としては、熱可塑性樹脂が好ましく、脂環式構造含有重合体を含む樹脂を用いることが特に好ましい。脂環式構造含有重合体を含む樹脂を、以下、適宜「脂環式構造含有重合体樹脂」と呼ぶ。脂環式構造含有重合体樹脂は、透明性、低吸湿性、寸法安定性および軽量性などに優れ、光学フィルムに適している。
また、基材フィルムは、1mm厚でのヘイズが、0.3%以下であることが好ましく、0.2%以下であることがより好ましい。ここで、ヘイズは、JIS K7361-1997に準拠して、日本電色工業社製「濁度計 NDH-300A」を用いて、5箇所測定し、それから求めた平均値である。
接着剤は、貼り合わせるフィルム層を形成する樹脂の種類により適切なものを選択しうる。接着剤の例としては、アクリル系接着剤、ウレタン系接着剤、ポリエステル系接着剤、ポリビニルアルコール系接着剤、ポリオレフィン系接着剤、変性ポリオレフィン系接着剤、ポリビニルアルキルエーテル系接着剤、ゴム系接着剤、エチレン-酢酸ビニル系接着剤、塩化ビニル-酢酸ビニル系接着剤、SEBS(スチレン-エチレン-ブチレン-スチレン共重合体)系接着剤、SIS(スチレン-イソプレン-スチレンブロック共重合体)系接着剤、エチレン-スチレン共重合体などのエチレン系接着剤、エチレン-(メタ)アクリル酸メチル共重合体、エチレン-(メタ)アクリル酸エチル共重合体などのアクリル酸エステル系接着剤などが挙げられる。接着剤は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
接着剤により形成される接着剤層の平均厚みは、好ましくは0.1μm以上、より好ましくは0.5μm以上であり、好ましくは10μm以下、より好ましくは5μm以下である。
易接着層は、ポリウレタン、架橋剤及び不揮発性塩基を含むウレタン組成物の硬化物からなる層である。このようなウレタン組成物の硬化物からなる易接着層を用いることにより、本発明の複層フィルムを任意の部材に貼り合せる場合に、接着性を高めることができる。また、この易接着層は、優れた接着性を高湿度環境において長期間維持できる。
ポリウレタンの引っ張り弾性率は、通常1000N/mm2以上、好ましくは1200N/mm2以上、より好ましくは1400N/mm2以上であり、通常5000N/mm2以下、好ましくは4000N/mm2以下、より好ましくは3000N/mm2以下である。前記範囲の下限値以上の引張弾性率を有するポリウレタンを用いることにより、易接着層の接着性を高めることができる。また、上限値以下にすることにより、易接着層が過度に硬くなることを防止できるので、易接着層の破損を防止できる。
まず、試料としてポリウレタンの水分散体(必要に応じて溶液を用いてもよい)を用意する。この水分散体を、乾燥後膜厚が100μmになるように、ガラス容器に流しいれる。室温で24時間放置した後、50℃で3時間、及び、120℃で20分間乾燥させて、ポリウレタンのシートを得る。
得られたポリウレタンのシートを、JIS K7162に従い、ダンベル型に打ち抜いて、試験片を得る。
この試験片について引張り試験器を用いて引張り速度5mm/分で引っ張り試験を行い、得られた応力-歪み曲線(SSカーブ)の傾きから引っ張り弾性率を測定する。
また、ポリウレタンとしては、例えば、前記(i)成分及び前記(ii)成分をウレタン化反応させて得たイソシアネート基含有プレポリマーを、鎖延長剤を用いて鎖延長し、水を加えて分散体とすることによって製造されるポリウレタンを用いうる。前記のプレポリマーは、前記(i)成分及び前記(ii)成分を、イソシアネート基過剰の条件下でウレタン化反応させることで得られうる。また、前記のウレタン化反応は、反応に不活性で水との親和性の大きい有機溶媒中で行いうる。さらに、前記プレポリマーの鎖延長の前には、該プレポリマーを中和させてもよい。また、イソシアネート基含有プレポリマーの鎖延長方法としては、イソシアネート基含有プレポリマーと鎖延長剤とを、必要に応じて触媒の存在下で反応させる方法が挙げられる。この際、鎖延長剤としては、水、水溶性ポリアミン、グリコール類などを用いうる。
ポリオール化合物としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、1,2-ブチレングリコール、1,3-ブチレングリコール、2,3-ブチレングリコール、1,4-ブチレングリコール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサングリコール、2,5-ヘキサンジオール、ジプロピレングリコール、2,2,4-トリメチル-1,3-ペンタンジオール、トリシクロデカンジメタノール、1,4-シクロヘキサンジメタノール、2,2-ジメチルプロパンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,8-オクタメチレンジオール、グリセリン、トリメチロールプロパンなどが挙げられる。
ポリエーテルポリオールとしては、前記のポリオール化合物のアルキレンオキシド付加物;アルキレンオキシドと環状エーテル(例えばテトラヒドロフランなど)との開環(共)重合体;ポリエチレングリコール、ポリプロピレングリコール、エチレングリコール-プロピレングリコール共重合体、1,4-ブタンジオール共重合体;グリコール、ポリテトラメチレングリコール、ポリヘキサメチレングリコール、ポリオクタメチレングリコールなどのグリコール類;などが挙げられる。ポリエーテルポリオールの具体例としては、ポリ(オキシプロピレンエーテル)ポリオール、ポリ(オキシエチレン-プロピレンエーテル)ポリオール等が挙げられる。
ポリエステルポリオールとして、例えば、多価カルボン酸又はその無水物と前記(1)ポリオール化合物とを、水酸基過剰の条件で重縮合させて得られたものなどが挙げられる。ここで、多価カルボン酸としては、例えば、アジピン酸、コハク酸、セバシン酸、グルタル酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸等のジカルボン酸;トリメリット酸等のトリカルボン酸が挙げられる。ポリエステルポリオールの具体例としては、エチレングリコール-アジピン酸縮合物、ブタンジオール-アジピン縮合物、ヘキサメチレングリコール-アジピン酸縮合物、エチレングリコール-プロピレングリコール-アジピン酸縮合物、或いは、グリコールを開始剤としてラクトンを開環重合させたポリラクトンジオール、などが挙げられる。
ポリエーテルエステルポリオールとして、例えば、エーテル基含有ポリオールまたは、これと他のグリコールとの混合物を上記(3)で例示したような多価カルボン酸又はその無水物と混合してアルキレンオキシドを反応させてなるものなどが挙げられる。前記エーテル基含有ポリオールとしては、例えば、前記(2)ポリエーテルポリオールやジエチレングリコール等が挙げられる。また、ポリエーテルエステルポリオールの具体例としては、ポリテトラメチレングリコール-アジピン酸縮合物などが挙げられる。
ポリカーボネートポリオールとしては、例えば、一般式HO-R-(O-C(O)-O-R)X-OH(ただし、式中、Rは炭素原子数1~12の飽和脂肪酸ポリオール残基を示す。また、Xは分子の構造単位の数を示し、通常5~50の整数である。)で示される化合物などが挙げられる。これらは、飽和脂肪族ポリオールと置換カーボネート(例えば、炭酸ジエチル、ジフェニルカーボネートなど)とを、水酸基が過剰となる条件で反応させるエステル交換法;前記飽和脂肪族ポリオールとホスゲンとを反応させるか、または必要に応じて、その後さらに飽和脂肪族ポリオールを反応させる方法;などにより得ることができる。
脂肪族ポリイソシアネート化合物としては、炭素原子数1~12の脂肪族ジイソシアネートが好ましく、例えばヘキサメチレンジイソシアネート、2,2,4-トリメチルヘキサンジイソシアネート、ヘキサンジイソシアネート(HDI)などが挙げられる。
脂環式ポリイソシアネート化合物としては、炭素原子数4~18の脂環式ジイソシアネートが好ましく、例えば、1,4-シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、イソホロンジイソシアネート(IPDI)、ジシクロヘキシルメタンジイソシアネート(HMDI)などが挙げられる。
芳香族ポリイソシアネートとしては、例えば、トリレンジイソシアネート(TDI)、4,4’-ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどが挙げられる。
架橋剤は、ポリウレタンが有する反応性の基と反応して結合を形成することにより、ポリウレタンを架橋させうる。この架橋により、易接着層の機械的強度、接着性及び耐湿熱性を向上させることができる。通常、架橋剤は、前記酸構造として含まれるカルボキシル基及びその無水物基、並びに、(i)成分と(ii)成分との反応後に未反応で残った水酸基などのような、ポリウレタンに含まれる極性基と反応して架橋構造を形成しうる。
架橋剤の具体例を挙げると、エポキシ化合物、カルボジイミド化合物、オキサゾリン化合物、イソシアネート化合物等が挙げられる。また、架橋剤は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
また、エポキシ化合物の例を市販品で挙げると、ナガセケムテックス社製の「デナコール(デナコールEX-521,EX-614Bなど)」シリーズ等を挙げることができる。
エポキシ化合物は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
カルボジイミド化合物は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
また、オキサゾリン化合物は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
不揮発性塩基としては、ウレタン組成物を基材フィルムに塗布した後に乾燥させる際の処理条件下において、実質的に不揮発性である塩基が挙げられる。ここで実質的に不揮発性であるとは、通常、不揮発性塩基の減少分が80%以下であることをいう。また、ウレタン組成物を基材フィルムに塗布した後に乾燥させる際の処理条件としては、例えば、80℃で1時間放置することが挙げられる。このような不揮発性塩基は、ポリウレタンの酸構造を中和する中和剤として機能しうる。
ウレタン組成物は、粒子を含むことが好ましい。ウレタン組成物が粒子を含むことにより、そのウレタン組成物の硬化物によって形成される易接着層の表面粗さを大きくできる。これにより、易結着層の表面の滑り性を向上させることができるので、複層フィルムのブロッキングの防止、及び、複層フィルムを巻回する際のシワの発生の抑制が可能となる。
ウレタン組成物は、濡れ剤を含むことが好ましい。濡れ剤を用いることにより、ウレタン組成物を基材フィルムに塗布する際の塗布性を良好にできる。
また、これらは、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
ウレタン組成物は、通常、溶媒を含む。溶媒としては、水又は水溶性の溶媒を用いる。水溶性の溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、アセトン、テトラヒドロフラン、N-メチルピロリドン、ジメチルスルホキシド、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテルなどが挙げられる。中でも、溶媒としては、水を用いることが好ましい。また、溶媒は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
ウレタン組成物は、前記の架橋剤に組み合わせて、硬化促進剤を含んでいてもよい。硬化促進剤としては、易接着層の形成に用いられる公知の硬化促進剤を用いうる。例えば、架橋剤としてエポキシ化合物を用いる場合、硬化促進剤としては、第3級アミン系化合物(4-位に3級アミンを有する2,2,6,6-テトラメチルピペリジル基を有する化合物を除く)、三弗化ホウ素錯化合物などが好適である。また、硬化促進剤は、1種類を単独で用いてもよく、2種以上を任意の比率で組み合わせて用いてもよい。
硬化促進剤の量は、ポリウレタン100重量部に対して、通常0.001重量部以上、好ましくは0.01重量部以上、より好ましくは0.03重量部以上であり、通常30重量部以下、好ましくは10重量部以下、より好ましくは5重量部以下である。
硬化助剤の量は、架橋剤100重量部に対して、通常1重量部以上、好ましくは10重量部以上であり、通常100重量部以下、好ましくは50重量部以下である。
ウレタン組成物は、通常、流体状の組成物となっている。このウレタン組成物の粘度は、15mPa・s以下であることが好ましく、10mPa・s以下であるのが特に好ましい。ウレタン組成物の粘度が前記範囲内にあると、基材フィルムの表面にウレタン組成物を均一に塗布することができる。ウレタン組成物の粘度の下限に特段の制限は無いが、好ましくは0.25mPa・s以上である。ここで、前記の粘度は、音叉型振動式粘度計により25℃の条件下で測定した値である。
ウレタン組成物の粘度は、例えば、ウレタン組成物における溶媒の割合及び粒子の粒径などによって調整できる。
易接着層は、前記のウレタン組成物の硬化物からなる層である。この易接着層は、通常、基材フィルム上に、接着剤の層等の他の層を介することなく、直接に設けられる。易接着層は、基材フィルムの片面にのみ設けてもよいし、両面に設けてもよい。ただし、易接着層を有する複層フィルムをロール状に巻回しやすいとの観点から、基材フィルムの片面にのみ易接着層を設けることが好ましい。易接着層は、基材フィルム上にウレタン組成物の膜を形成する工程と、このウレタン組成物の膜を硬化させる工程とを含む製造方法により、製造できる。
平均水接触角は、例えば、親水化表面処理を施した易接着層の表面において、100cm2の範囲内で無作為に選んだ20点の水接触角を測定し、この測定値の加算平均により算出される。水接触角の標準偏差は、この測定値から算出される。
易接着層の厚みは、0.005μm以上が好ましく、0.01μm以上がより好ましく、0.02μm以上が特に好ましく、また、5μm以下が好ましく、2μm以下がより好ましく、1μm以下が特に好ましい。易接着層の厚みが前記範囲内にあると、基材フィルムと易接着層との十分な接着強度が得られ、かつ、本発明の複層フィルムの反りなどの欠陥を無くすことができる。
本発明の複層フィルムは、基材フィルムの易接着層とは反対側の表面に、任意の層を備えうる。任意の層の例を挙げると、反射防止層、ハードコート層、帯電防止層、防眩層、防汚層、セパレーターフィルム等が挙げられる。
本発明の複層フィルムは、上述した易接着層を備えるので、任意の部材との接着力が高い。さらに、本発明の複層フィルムは、上述した易接着層を備えるので、高湿度環境であっても、その接着力を長期間維持できる。したがって、例えば運搬及び保存時など、過酷な環境において長期間置かれる場合でも、本発明の複層フィルムが貼り合わせた部材から剥離することを防止できる。
本発明の複層フィルムは、基材フィルムを用意する工程と、用意した基材フィルム上に易接着層を製造する工程とを含む製造方法により、製造できる。ここで、基材フィルム上に易接着層を製造する工程は、上述したように、基材フィルム上にウレタン組成物の膜を形成する工程と、このウレタン組成物の膜を硬化させる工程とを含む。
さらに、複層フィルムの製造方法における任意の時点において、基材フィルム、易接着層及び複層フィルムを延伸する工程を行なってもよい。
本発明の複層フィルムは、通常、光学フィルムとして使用される。複層フィルムの用途となる光学フィルムの例を挙げると、保護フィルム、位相差フィルム、光学補償フィルムなどが挙げられる。
ウレタン(メタ)アクリレートとしては、一分子当たり2個~3個の二重結合を有し、且つ、二重結合1個当たりの数平均分子量が500~3000であるウレタン(メタ)アクリレートを用いることが、接着強度、柔軟性、光硬化性及び粘度等をバランスさせやすいので、好ましい。
光硬化型接着剤におけるウレタン(メタ)アクリレートの量は、通常30重量%~50重量%である。ウレタン(メタ)アクリレートの量を前記範囲の下限値以上にすることにより、接着剤層が脆くなることを防止できる。また、上限値以下にすることにより、接着剤の粘度を低くでき、また、接着強度を高くできる。
光硬化型接着剤におけるヒドロキシアルキル(メタ)アクリレートの量は、通常13重量%~40重量%である。ヒドロキシアルキル(メタ)アクリレートの量を前記範囲の下限値以上にすることにより、接着剤全体の親水性を高くできるので、特にポリビニルアルコール系偏光フィルムに対する接着強度を向上させることができる。また、上限値以下にすることにより、接着剤層が脆くなることを防止でき、また、接着剤の光硬化性を高くできる。
光硬化型接着剤におけるアクリルアミドの量は、通常0~30重量%、好ましくは1重量%~30重量%の範囲である。
また、以下の説明において、量を示す「部」及び「%」は、別に断らない限り、重量基準である。また、以下に説明する操作は、別に断らない限り、常温及び常圧の条件において行った。
(ポリウレタンの弾性率の測定方法)
ポリウレタンの水分散体を、乾燥後膜厚が100μmになるように、ガラス容器に流しいれた。室温で24時間放置した。その後、50℃で3時間、及び、120℃で20分間乾燥させて、ポリウレタンのシートを得た。
得られたポリウレタンのシートを、JIS K7162に従い、ダンベル型に打ち抜いて、試験片を得た。
この試験片について引張り試験器(インストロンジャパン社製「引っ張り試験機5564」)を用いて引張り速度5mm/分で引っ張り試験を行い、得られたSSカーブの傾きから引っ張り弾性率を測定した。
各実施例及び比較例で製造した複層フィルムの易接着層の表面と、製造例2で製造した偏光子の片面とを、製造例3で製造した接着液を用いてロールラミネーターで貼り合わせた。さらに、偏光子のもう片面に、保護フィルム(コニカミノルタ社製トリアセチルセルロースフィルム、商品名「KC4UYW」、厚み:40μm)を、製造例3で製造した接着液を用いて貼り合せることにより、偏光板を製造した。
次いで、この偏光板の複層フィルムの易接着層とは反対側の面とガラス基板とを、粘着シート(日東電工社製「LUCIACS CS9621T」)を介して貼り合わせて、サンプルを作製した。
その結果、複層フィルムとガラス基板との間で剥離が生じる場合は、易接着層及び接着液は十分な接着強度を有しており、初期カッター剥離試験の結果を「良」と評価した。また、偏光子と複層フィルムとの間で剥離が起きる場合は、接着強度が不十分であり、初期カッター剥離試験の結果を「不良」と評価した。
前記(初期カッター剥離試験)と同様にして、ガラス基板、複層フィルム、偏光子及び保護フィルムをこの順で備えるサンプルを作製した。
このサンプルの一部を60℃90%RHの恒温恒湿槽中で静置した。このサンプルの一部を一定時間毎に恒温恒湿槽から取り出し、前記(初期カッター剥離試験)と同様にして、基材フィルムの剥離を試みた。
また、恒温恒湿槽中での静置の開始後200時間~500時間において、偏光子と複層フィルムとの間で剥離が生じないで複層フィルムとガラス基板との間で剥離が起きる場合、湿熱後カッター剥離試験の結果を「良」と評価した。
さらに、恒温恒湿槽中での静置の開始後200時間が経過する前において偏光子と複層フィルムとの間で剥離が起きる場合、湿熱後カッター剥離試験の結果を「不良」と評価した。
脂環式構造含有重合体樹脂(日本ゼオン社製「ZEONOR1430」;ガラス転移温度135℃)のペレットを、空気を流通させた熱風乾燥器を用いて、70℃で2時間乾燥した。その後、65mm径のスクリューを備えた樹脂溶融混練機を有するTダイ式のフィルム溶融押出し成形機を使用し、溶融樹脂温度270℃、Tダイの幅500mmの成形条件で、厚み100μm、長さ1000mのフィルムを製造した。このフィルムは、脂環式構造含有重合体樹脂からなる基材フィルムである。
厚み80μmのポリビニルアルコールフィルムを、0.3%のヨウ素水溶液中で染色した。その後、染色したポリビニルアルコールフィルムを4%のホウ酸水溶液及び2%のヨウ化カリウム水溶液中で5倍まで延伸した後、50℃で4分間乾燥させて、偏光子を製造した。
アセトアセチル基を含むポリビニルアルコール(日本合成化学工業製「ゴーセファイマーZ410」)に水を加えて固形分3%に希釈し、接着液を製造した。
(1-1.樹脂組成物の製造)
ポリエーテル系ポリウレタンの水分散体(第一工業製薬社製「スーパーフレックス870」)をポリウレタンの量で100部と、架橋剤としてエポキシ化合物(ナガセケムテックス社製「デナコールEX313」)15部と、不揮発性塩基としてアジピン酸ジヒドラジド2部と、滑材としてシリカ粒子の水分散液(日産化学社製「スノーテックスMP1040」;平均粒子径120nm)をシリカ粒子の量で8部及びシリカ粒子の水分散液(日産化学社製「スノーテックスXL」;平均粒子径50nm)をシリカ粒子の量で8部と、濡れ剤としてアセチレン系界面活性剤(エアープロダクツアンドケミカルズ社製「サーフィノール440」)を固形分合計量に対して0.5重量%と、水とを配合して、固形分濃度2%の液状の樹脂組成物1を得た。
コロナ処理装置(春日電機社製)を用いて、出力300W、電極長240mm、ワーク電極間3.0mm、搬送速度4m/minの条件で、製造例1で得た基材フィルムの表面に放電処理を施した。
この複層フィルムについて、上述した方法で、初期カッター剥離試験及び湿熱後カッター剥離試験を行なった。
前記工程(1-1)において、架橋剤としてエポキシ化合物の代わりにカルボジイミド化合物(日清紡ケミカル社製「カルボジライトV-02」)を用いた。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
前記工程(1-1)において、架橋剤としてエポキシ化合物の代わりにオキサゾリン化合物(日本触媒社製「エポクロスWS700」)を用いた。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
前記工程(1-1)において、ポリエーテル系ポリウレタンの水分散液の種類を第一工業製薬社製「スーパーフレックス130」に変更した。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
前記工程(1-1)において、ポリエーテル系ポリウレタンの水分散液の種類を第一工業製薬社製「スーパーフレックス130」に変更した。
また、前記工程(1-1)において、架橋剤としてエポキシ化合物の代わりにカルボジイミド化合物(日清紡ケミカル社製「カルボジライトV-02」)を用いた。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
前記工程(1-1)において、ポリエーテル系ポリウレタンの水分散液の種類を第一工業製薬社製「スーパーフレックス130」に変更した。
前記工程(1-1)において、架橋剤としてエポキシ化合物の代わりにオキサゾリン化合物(日本触媒社製「エポクロスWS700」)を用いた。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
前記工程(1-1)において、ポリエーテル系ポリウレタンの水分散液の代わりに、ポリエーテルエステル系ポリウレタンの水分散液(第一工業製薬社製「スーパーフレックス150HS」)を用いた。ここで、ポリエーテルエステル系ポリウレタンとは、ポリウレタンを製造するモノマーのうち(i)成分としてポリエーテルエステルポリオールを用いて製造されたポリウレタンのことをいう。
また、前記工程(1-1)において、架橋剤としてのエポキシ化合物を用いなかった。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
前記工程(1-1)において、架橋剤としてのエポキシ化合物及び不揮発性塩基としてのアジピン酸ジヒドラジドを用いなかった。
以上の事項以外は実施例1と同様にして複層フィルムの製造及び評価を行なった。
実施例及び比較例の結果を、下記の表に示す。また、下記の表において、「ADH」とはアジピン酸ジヒドラジドのことを表す。
前記の表から分かるように、実施例においてはいずれも初期カッター剥離試験の結果が良好である。したがって、本発明の複層フィルムは、高湿環境に置かれる前の状態において易接着層が高い接着性を有することが分かる。
また、実施例においては、いずれも湿熱後カッター剥離試験の結果が良好である。したがって、本発明の複層フィルムは、高湿環境おける耐久性に優れ、高湿環境に置かれた場合でも長期間にわたって高い接着性を維持できることがわかる。
Claims (7)
- 基材フィルムと、前記基材フィルム上に設けられた易接着層とを備え、
前記易接着層は、ポリウレタンと、前記ポリウレタンを架橋させうる架橋剤と、不揮発性塩基とを含む組成物の硬化物からなり、
前記ポリウレタンの引っ張り弾性率が、1000N/mm2以上5000N/mm2以下である、複層フィルム。 - 前記基材フィルムが、脂環式構造含有重合体を含む樹脂からなる層を備える、請求項1記載の複層フィルム。
- 前記架橋剤が、エポキシ化合物を含む、請求項1又は2記載の複層フィルム。
- 前記組成物が、粒子を含む、請求項1~3のいずれか一項に記載の複層フィルム。
- 前記組成物が、濡れ剤を含む、請求項1~4のいずれか一項に記載の複層フィルム。
- 前記ポリウレタンが、ポリエーテル系ポリウレタンである、請求項1~5のいずれか一項に記載の複層フィルム。
- 基材フィルム上に、ポリウレタンと、前記ポリウレタンを架橋させうる架橋剤と、不揮発性塩基とを含む組成物の膜を形成する工程と、
前記組成物の膜を硬化させる工程とを含み、
前記ポリウレタンの引っ張り弾性率が、1000N/mm2以上5000N/mm2以下である、複層フィルムの製造方法。
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KR20240072123A (ko) | 2021-09-29 | 2024-05-23 | 니폰 제온 가부시키가이샤 | 복층 필름, 광학 복층 필름, 및 제조 방법 |
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US20160312076A1 (en) | 2016-10-27 |
KR20160102421A (ko) | 2016-08-30 |
JPWO2015098750A1 (ja) | 2017-03-23 |
TW201529797A (zh) | 2015-08-01 |
EP3088181A1 (en) | 2016-11-02 |
EP3088181A4 (en) | 2017-08-16 |
TWI635155B (zh) | 2018-09-11 |
JP6565681B2 (ja) | 2019-08-28 |
CN105829106A (zh) | 2016-08-03 |
KR102267426B1 (ko) | 2021-06-18 |
CN105829106B (zh) | 2018-06-05 |
EP3088181B1 (en) | 2018-09-05 |
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