JP6007829B2 - Gas barrier film and method for producing gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film and a method for producing a gas barrier film. More specifically, the present invention relates to a gas barrier film that uses a retardation film as a substrate and can be suitably used for flexible lighting and displays using an organic electroluminescence element (organic EL element).

  A display device using an organic EL light-emitting element has a metal electrode on the back side of the light-emitting layer with respect to an observer, and the presence of external light generates reflected light from the metal electrode. There is a problem in that the display quality is remarkably lowered by the fact that the scenery on the observer side is reflected. In order to prevent the metal reflection, a technique using a circularly polarizing plate as an antireflection film on a front substrate of a light emitting element is known. The circularly polarizing plate is composed of a retardation film which is a polarizing plate and a quarter-wave plate (hereinafter also referred to as a λ / 4 plate). As this retardation film, a polymer alignment formed by stretching a polymer film. A technique using a film or the like is known.

  When such a conventional retardation film is used as a circularly polarizing plate, a good antireflection effect can be obtained only at a specific wavelength where the retardation is a quarter wavelength. However, there has been a problem that good reflection prevention cannot be obtained in visible light, for example, in a wide band of wavelengths of 400 nm to 700 nm, and as a result, the reflected light is colored.

  The following Patent Document 1 describes a method for solving the above colored problem. However, when the retardation film is exposed to a high temperature, the retardation film, which is a resin, expands, causing a phase shift.

  Moreover, it is calculated | required for organic EL light emitting element to interrupt | block permeation | transmission of water vapor | steam and oxygen for durability, and what is called a gas barrier film which has such a property is required. In order to improve the gas barrier property of the gas barrier film, an inorganic layer is formed by a method such as sputtering or plasma CVD (Patent Document 2 below). However, in the prior art described in Patent Document 2, a gas barrier layer (hereinafter also simply referred to as a barrier layer) is directly laminated on a substrate. Moreover, the example using the retardation film as a base material is not described. However, when a retardation film is used as the base material, due to the difference in thermal expansion between the base material that is a resin and the inorganic barrier layer, during the high temperature treatment (200 ° C. or higher) during device fabrication, It has been found that there is a problem in that a difference in expansion coefficient occurs between the material and the barrier layer, and the film peels off and cracks in the barrier layer occur.

  Moreover, the following patent document 3 is known as a technique combining a retardation film and a barrier layer. Patent Document 3 describes a technique in which a resin having cholesteric regularity is sandwiched between a base material and a barrier layer, and a retardation film is attached on the resin layer with an adhesive layer. However, a resin layer having cholesteric regularity is vulnerable to heat, and there is a problem that a difference in expansion coefficient from the barrier layer occurs at a high temperature such as when a device is produced, resulting in film peeling and cracking of the barrier layer. Moreover, with the crack of the barrier layer, the retardation film expands and the phase shifts, and the function as the retardation film may not be sufficiently achieved.

JP 2012-226996 A International Publication No. 2012/046767 JP 2009-104065 A

  However, the gas barrier film according to the prior art as described in Patent Document 2 is not intended for application to a retardation film. Accordingly, there has been no gas barrier film that can be used as a retardation film imparted with gas barrier properties while maintaining the retardation even at high temperatures.

  The present invention has been made in view of the above-described problems of the prior art, has a sufficient gas barrier property, does not cause a phase shift at high temperatures, and uses a retardation film as a base material. The object is to provide a film.

  The above-mentioned problem according to the present invention is solved by the following means.

1 Retardation Re550 in the in-plane direction with respect to light having a wavelength of 550 nm is a retardation film having a retardation film of 110 to 150 nm, and the film thickness is 1.0 to 2.5 times that of Re550 on the retardation film. A gas barrier film having a gas barrier layer.
2 The gas barrier film as described in 1 above, wherein the retardation film is a cellulose ester film.

3. The gas barrier film as described in 1 or 2 above, wherein an intermediate resin layer having an in-plane retardation Re550 of 0 to 20 nm with respect to light having a wavelength of 550 nm is provided between the retardation film and the gas barrier layer.
4 The gas barrier film according to 3, wherein the intermediate resin layer contains a resin and oxide metal fine particles.

5. The gas barrier film according to 3 or 4 , wherein the retardation film has a pencil hardness of HB to H, the intermediate resin layer has a pencil hardness of H to 3H, and the gas barrier layer has a pencil hardness of 4H to 6H.
6 The gas barrier film according to any one of 1 to 5, wherein the retardation film is long and an orientation angle is in a range of 40 ° to 50 ° with respect to the long direction.

7 The gas barrier film according to any one of 1 to 6 , wherein the gas barrier layer is composed of at least two layers, and one of the at least two layers is a polysilazane film.

By performing a plasma discharge while supplying a film forming gas by winding a base material that is a retardation film having a retardation Re550 of 110 to 150 nm in an in-plane direction with respect to light having 8 wavelengths of 550 nm between 110 nm and 150 nm. The method according to any one of 1 to 7 above, further comprising a step of forming a gas barrier layer having a thickness of 1.0 to 2.5 times Re550 of the retardation film on the retardation film. A method for producing a gas barrier film.
9 Before the step of forming the gas barrier layer,
The orientation angle is 40 ° or more and 50 ° or less with respect to the longitudinal direction by stretching the long resin film in the direction in which the stretching direction is 40 ° or more and 50 ° or less with respect to the longitudinal direction. 9. The production method according to 8 above, further comprising a step of forming the retardation film which is in the range.
10 The gas barrier layer is composed of at least two layers, and one of the at least two layers is a polysilazane film,
Before the step of forming the gas barrier layer, a step of forming the intermediate resin layer by applying a coating liquid containing a resin on the substrate;
Forming a first gas barrier layer on the intermediate resin layer by plasma vapor deposition;
A step of forming a second gas barrier layer on the first gas barrier layer by applying a coating liquid containing polysilazane on the first gas barrier layer and drying, followed by irradiation with vacuum ultraviolet rays;
In the step of forming the first gas barrier layer and the step of forming the second gas barrier layer, the first gas barrier layer and the second gas barrier layer include the first gas barrier layer and The total film thickness of the second gas barrier layer is formed to be 1.0 to 2.5 times the Re550 of the retardation film,
10. The method for producing a gas barrier film as described in 9 above.

  According to the present invention, it is possible to provide a gas barrier film that has a sufficient gas barrier property and that does not cause a phase shift at high temperatures even when a retardation film is used as a substrate. Become.

It is the schematic of the plasma CVD apparatus used in the Example.

  Hereinafter, modes for carrying out the present invention will be described. The gas barrier film of the present invention basically has a base material and a gas barrier layer on the base material, and particularly uses a retardation film as the base material. That is, the retardation Re550 (hereinafter also simply referred to as Re550) in the in-plane direction with respect to light having a wavelength of 550 nm is a retardation film having a retardation film of 110 to 150 nm, and 1.0 of the Re550 on the retardation film. A gas barrier film having a gas barrier layer having a film thickness of ˜2.5 times. As a preferred embodiment, a resin intermediate layer can be provided between the substrate and the gas barrier layer. Further, the gas barrier layer can be composed of two or more layers of a gas barrier layer formed by plasma CVD and a second gas barrier layer including a polysilazane film. Hereafter, each element which comprises the gas barrier film of this invention is demonstrated.

<Base material>
In the gas barrier film of the present invention, a retardation film is used as a substrate. The retardation film used in the present invention has a retardation Re550 in the in-plane direction at a measurement wavelength of 550 nm of 110 nm to 150 nm. Thereby, a retardation film can be functioned as a quarter wavelength plate, it can be set as a circularly-polarizing plate by laminating | stacking with a polarizing film, and can be used conveniently for an organic EL element etc.

  The retardation (Re550) in the in-plane direction at each measurement wavelength is | nx−ny | × d (where nx represents the refractive index in the slow axis direction in the plane of the retardation film, and ny represents the retardation film). Represents the refractive index in the fast axis direction in the plane of d, and d represents the film thickness.). Here, the in-plane refers to the in-plane of the retardation film and the in-plane perpendicular to the thickness direction of the film. Retardation can be measured by the parallel Nicol rotation method using a birefringence meter as used in the examples.

  The retardation film used in the present invention has an Nz coefficient of −0.25 to −0.05, preferably −0.18 to −0.10 at a wavelength of 550 nm. Here, the Nz coefficient is a value represented by (nx−nz) / (nx−ny) (wherein nx and ny are the same as described above, and nz represents the refractive index in the thickness direction of the retardation film). ). A retardation film having an Nz coefficient in this range can be easily produced by oblique stretching, and can have excellent viewing angle characteristics when used in an organic EL display device.

  From the viewpoint of use as an optical film, the retardation film preferably has a total light transmittance of 85% or more, more preferably 92% or more. Here, the total light transmittance is an average value obtained by measuring five locations using “Durbidity Meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997. .

  The haze of the retardation film is preferably 1% or less, more preferably 0.8% or less, and particularly preferably 0.5% or less. By setting the haze to a low value, the sharpness of the display image of the display device incorporating the retardation film can be improved. Here, haze is an average value obtained by measuring five locations using, for example, “Durbidity Meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997.

  In the retardation film of the present invention, ΔYI is preferably 5 or less, and more preferably 3 or less. When this ΔYI is in the above range, there is no coloring and visibility can be improved. Here, ΔYI is obtained as an arithmetic average value by performing the same measurement five times using, for example, “Spectral Color Difference Meter SE2000” manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM E313.

  The thickness of the retardation film is usually 5 μm or more, preferably 8 μm or more, more preferably 10 μm or more, particularly preferably 20 μm or more, and usually 500 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

  The material constituting the retardation film is not particularly limited, and a material having a layer made of styrene resin, alicyclic olefin polymer, methacrylic resin, cellulose acylate, cellulose acetate, polycarbonate resin, or the like can be used. . These materials may be used alone or in combination of two or more.

  Styrenic resin is a polymer resin having a styrene structure as a part or all of repeating units, and is polystyrene, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-chlorostyrene, p -Styrenic monomers such as nitrostyrene, p-aminostyrene, p-carboxystyrene, p-phenylstyrene, ethylene, propylene, butadiene, isoprene, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, methyl acrylate, Examples thereof include copolymers with other monomers such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, and vinyl acetate. Among these, polystyrene or a copolymer of styrene and maleic anhydride can be suitably used.

  The alicyclic olefin polymer is an amorphous olefin polymer having a cycloalkane structure or a cycloalkene structure in the main chain and / or side chain. Specifically, (1) norbornene polymer, (2) monocyclic olefin polymer, (3) cyclic conjugated diene polymer, (4) vinyl alicyclic hydrocarbon polymer, and these A hydride etc. are mentioned. Among these, norbornene-based polymers are more preferable from the viewpoints of transparency and moldability. Examples of the resin having these alicyclic structures include those described in JP-A No. 05-310845, JP-A No. 05-097978, and US Pat. No. 6,511,756.

  Specific examples of norbornene-based polymers include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization, hydrides thereof, and norbornene-based monomers. And addition copolymers with other monomers copolymerizable with norbornene monomers.

  The methacrylic resin is a polymer having a methacrylic acid ester as a main component, and includes a methacrylic acid ester homopolymer and a copolymer of a methacrylic acid ester and other monomers. Usually, alkyl methacrylate is used. In the case of a copolymer, acrylic acid esters, aromatic vinyl compounds, vinylcyan compounds, etc. are used as other monomers copolymerized with methacrylic acid esters.

  As the cellulose ester, a cellulose ester having cellulose ester as a main component and a mixture of additives such as a plasticizer and an ultraviolet absorber is preferable. The cellulose ester is a carboxylic acid ester having about 2 to 22 carbon atoms or an aromatic carboxylic acid ester, and particularly preferably a lower fatty acid ester having 6 or less carbon atoms.

  When using a cellulose ester as a retardation film, it is preferable that 60-100 mass% of cellulose esters are contained. The total acyl group substitution degree of the cellulose ester is preferably 2.1 to 2.9.

  The acyl group bonded to the hydroxyl group may be linear or branched or may form a ring. Furthermore, another substituent may be substituted. When the degree of substitution is the same, birefringence decreases when the number of carbon atoms is large, and therefore, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms. The cellulose ester preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.

  Specific cellulose esters include cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate as well as cellulose having propionate group, butyrate group or phthalyl group bonded thereto. The mixed fatty acid ester can be used. The butyryl group forming butyrate may be linear or branched.

  As the cellulose ester preferably used for the retardation film, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are particularly preferably used. Of these, cellulose acetate propionate is most preferred. A film prepared by adding a retardation increasing agent as described in, for example, JP-A-2002-22944 to cellulose acetate having an average acetylation degree (acetylation degree) of 45.0 to 62.5% Although effectively used in the present invention, cellulose acetate propionate is more preferable in that it hardly causes quality deterioration due to bleed-out on the film surface under high temperature and high humidity storage.

  The polycarbonate resin can be produced by melt polymerization of a full orange hydroxy component, an aliphatic diol component and a carbonic acid diester.

  Examples of the carbonic acid diester include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, and bis (m-cresyl) carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total of dihydroxy compounds.

  In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

<Resin intermediate layer>
In the gas barrier film of this invention, it is preferable to have the resin intermediate | middle layer containing resin between the phase difference film which is a base material, and a gas barrier layer. This is because the adhesiveness between the retardation film and the gas barrier layer is improved by providing the resin intermediate layer. Further, the resin intermediate layer preferably has an in-plane retardation Re550 of 0 to 20 nm with respect to light having a wavelength of 550 nm. When Re550 is within this range, the phase shift due to the retardation film as a substrate can be more effectively prevented, as well as the phase shift due to the resin intermediate layer itself can be eliminated.

  In particular, in the present invention, the resin intermediate layer may contain a particulate metal oxide. In the case of fine particles, the compatibility between the retardation film and the resin intermediate layer and the compatibility between the gas barrier layer, which is an inorganic layer, and the fine particle metal oxide are good, and the adhesion between the retardation film and the gas barrier layer is greatly improved. To do. Furthermore, in the case of high-temperature processing (200 ° C.) at the time of manufacturing an electronic device by providing a resin intermediate layer having an intermediate hardness or a resin intermediate layer containing a particulate metal oxide between a soft retardation film and a hard gas barrier layer In addition, film peeling can be further prevented by relaxing the difference in expansion coefficient between the retardation film and the barrier layer by the resin layer of the intermediate layer. When providing a resin intermediate layer, it is preferable that the pencil hardness of a base material, a resin intermediate layer, and a gas barrier layer is HB-H, H-3H, and 4H-6H, respectively. By inclining the hardness in this way, the gas barrier layer is more effective in suppressing the expansion of the retardation film even when a softer and more easily heat-extensible base material is exposed to a high temperature environment. Slippage and film deformation can be prevented.

  The film thickness of the resin intermediate layer is preferably 1 to 20 μm, more preferably 2 to 7 μm. If it is the said range, the desired effect of this invention can be achieved more reliably.

(resin)
The resin in the resin intermediate layer of the present invention may contain an actinic ray curable resin that is cured by irradiation with actinic rays such as ultraviolet rays and electron beams, and is a thermosetting resin that is cured by heat treatment. May be. As the curable resin, for example, the types of resins listed below can be preferably used.

(1.1) Silicone Resin A silicone resin having a siloxane bond with Si—O—Si as the main chain can be used. As the silicone resin, a silicone resin made of a predetermined amount of polyorganosiloxane resin can be used (for example, see JP-A-6-9937).

  The thermosetting polyorganosiloxane resin is not particularly limited as long as it becomes a three-dimensional network structure with a siloxane bond skeleton by a continuous hydrolysis-dehydration condensation reaction by heating. It exhibits curability and has the property of being hard to be re-softened by heating once cured.

  Such a polyorganosiloxane resin includes the following general formula (A) as a structural unit, and the shape thereof may be any of a chain, a ring, and a network.

Formula (A) ((R1) (R2) SiO) _n
In the general formula (A), “R1” and “R2” represent the same or different substituted or unsubstituted monovalent hydrocarbon groups. Specifically, as “R1” and “R2”, an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkenyl group such as a vinyl group and an allyl group, an aryl group such as a phenyl group and a tolyl group, A cycloalkyl group such as a cyclohexyl group and a cyclooctyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or the like, such as a chloromethyl group, 3, 3, 3- Examples include trifluoropropyl group, cyanomethyl group, γ-aminopropyl group, N- (β-aminoethyl) -γ-aminopropyl group, and the like. “R1” and “R2” may be a group selected from a hydroxyl group and an alkoxy group. In the general formula (A), “n” represents an integer of 50 or more.

  The polyorganosiloxane resin is usually used after being dissolved in a hydrocarbon solvent such as toluene, xylene or petroleum solvent, or a mixture of these with a polar solvent. Moreover, you may mix | blend and use what differs in a composition in the range which mutually melt | dissolves.

  The method for producing the polyorganosiloxane resin is not particularly limited, and any known method can be used. For example, it can be obtained by hydrolysis or alcoholysis of one or a mixture of two or more organohalogenosilanes, and polyorganosiloxane resins generally contain hydrolyzable groups such as silanol groups or alkoxy groups. A group is contained in an amount of 1 to 10% by mass in terms of a silanol group.

  These reactions are generally performed in the presence of a solvent capable of melting the organohalogenosilane. It can also be obtained by a method of synthesizing a block copolymer by cohydrolyzing a linear polyorganosiloxane having a hydroxyl group, an alkoxy group or a halogen atom at the molecular chain terminal with an organotrichlorosilane. The polyorganosiloxane resin thus obtained generally contains the remaining HCl, but in the composition of the present embodiment, the storage stability is good, so that the one having 10 ppm or less, preferably 1 ppm or less is used. Is good.

(1.2) Epoxy resin An alicyclic epoxy resin (see International Publication No. 2004/031257) such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate can be used. An epoxy resin containing a spiro ring or a chain aliphatic epoxy resin can also be used.

(1.3) Resin containing allyl ester compound Bromine-containing (meth) allyl ester not containing an aromatic ring (see JP-A-2003-66201), allyl (meth) acrylate (see JP-A-5-286896) , Allyl ester resins (see JP-A-5-286896 and JP-A-2003-66201), copolymer compounds of acrylate esters and epoxy group-containing unsaturated compounds (see JP-A-2003-128725), acrylate compounds (Refer to Unexamined-Japanese-Patent No. 2003-147072), an acrylic ester compound (refer to Unexamined-Japanese-Patent No. 2005-2064), etc. can be used preferably.

(1.4) Acrylate Resin The curable resin used for the resin intermediate layer may be an acrylate resin that is a polycyclic hydrocarbon compound composed of an alicyclic hydrocarbon skeleton, such as acrylic acid, methacrylic acid, and methyl methacrylate. can give.

  As monomers constituting the acrylic resin, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate , N-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate , Glycidyl acrylate, 2-hydride Xylethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, Diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2, 2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate Glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion oxide modified pentaerythritol Triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2,4-trimethyl- 1,3-pentadi All diacrylate, diallyl fumarate, 1,10-decandiol dimethyl acrylate, pentaerythritol hexaacrylate, and those obtained by replacing the above acrylate with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone Etc. The above monomers can be used as one or a mixture of two or more or as a mixture with other compounds.

(1.5) Cyclic azasilane It reacts with OH of silicon dioxide such as cyclic azasilane, and the amine remaining after ring-opening reacts with the resin to be polymerized, so that the surface of nano-silicon dioxide particles can be modified. Something is also mentioned.

  The resins (1.1) to (1.5) may be used alone or in combination of two or more.

  In addition, the resin curing agent is not particularly limited, and examples thereof include an acid anhydride curing agent and a phenol curing agent.

  Specific examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride. Examples thereof include an acid, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride and the like.

  The polymerization initiator is a polymerization of an acrylic monomer, and is preferably an initiator that generates radicals. An azo initiator or a peroxide initiator can be used.

  Oil-soluble peroxide-based or azo-based initiators are preferred. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxide initiators such as peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2' Azobis (2,3,3-trimethyl Butyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvalero) Nitrile), 2- (carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobisisobutyrate and the like.

  In particular, organic peroxides such as tertiary isobutyl hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, hydrogen peroxide, and the like are preferable.

  These polymerization initiators are preferably used in an amount of 0.01 to 20% by mass, particularly 0.1 to 10% by mass, based on the polymerizable monomer.

  Moreover, a hardening accelerator is contained as needed. The curing accelerator is not particularly limited as long as it has good curability, is not colored, and does not impair the transparency of the thermosetting resin. For example, 2-ethyl-4-methylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2E4MZ) imidazoles, tertiary amines, quaternary ammonium salts, diazabicycloundecene and other bicyclic amidines and their derivatives, phosphines, phosphonium salts, etc. can be used. You may use these 1 type or in mixture of 2 or more types.

  In addition, resin other than actinic-light curable resin may be contained in the resin of a resin intermediate | middle layer in the range which does not impair the effect of this invention.

(Fine particle metal oxide)
The fine particle metal oxide has an average primary particle diameter in the range of 1 to 100 nm, and examples thereof include fine particle silicon dioxide, fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and fine particle iron oxide. Among these, silicon dioxide is particularly preferable in order to achieve the desired effect of the present invention. One or more, preferably two or more of these particulate metal oxides may be combined. Further, the shape of the fine particle metal oxide is not particularly limited such as spherical, needle-like, rod-like, spindle-like, indefinite shape, or plate shape, and the crystal form is not particularly limited such as amorphous, rutile type, or anatase type.

  Furthermore, these fine particle metal oxides are conventionally known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylation. It is preferable that the surface treatment is performed in advance by lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment or the like. Of these, water repellent treatment is particularly preferred with one or more surface treatment agents selected from silicone, silane, fluorine compounds, amino acid compounds, and metal soaps.

  Examples of silicone treatment include coating and heat treatment of methyl hydrogen polysiloxane, examples of silane include alkylsilane treatment, and examples of fluorine compounds include perfluoroalkyl phosphate ester, perfluoropolyether, perfluoroalkyl silicone, perfluoro Alkyl / polyether co-modified silicones, perfluoroalkylsilanes, and the like are mentioned. Examples of amino acid compounds include N-lauroyl-L-lysine, and examples of metal soaps include aluminum stearate.

  Examples of commercially available resins containing fine particle oxides include, for example, Rio Duras (registered trademark) LCH1559 (manufactured by Toyo Ink Co., Ltd.), OPSTAR (registered trademark) Z7501 (manufactured by JSR Corp.), Z842. -1 (manufactured by Aika Kogyo Co., Ltd.), as fine particle zinc oxide, "FINEX-25", "FINEX-50", "FINEX-75" (above, Sakai Chemical Industry Co., Ltd.); "MZ500" series "MZ700" series (above, manufactured by Teika Co., Ltd.) "ZnO-350", "Sumifine" series (above, manufactured by Sumitomo Osaka Cement Co., Ltd.), "TYN" series (above, manufactured by Toyo Ink Co., Ltd.) ) And the like. As fine particle titanium oxide, “TTO-55, 51, S, M, D” series (above, manufactured by Ishihara Sangyo Co., Ltd.); “JR” series, “JA” series (above, manufactured by Teika Co., Ltd.), “TYT” series (above, manufactured by Toyo Ink Co., Ltd.) and the like. The fine cerium oxide includes high-purity cerium oxide sold by Nikki Co., Ltd. or Seimi Chemical Co., Ltd. Of these, silicon dioxide, titanium oxide, and zinc oxide are particularly preferable.

  The fine particle metal oxide is preferably contained in the resin intermediate layer in an amount of 10 to 70% by mass, more preferably 30 to 50% by mass.

<Gas barrier layer>
The gas barrier layer is formed on the above-mentioned base material directly or through a resin intermediate layer, and protects display elements and the like to which a retardation film and a gas barrier film are attached from moisture and oxygen in the outside air. Have Usually, the above-mentioned retardation film as a base material is softer and easily stretched by heat, but the gas barrier layer formed by the plasma CVD method is harder and hardly stretched by heat. In the present invention, even when the gas barrier film is exposed to a high temperature environment by laminating the gas barrier layer on the retardation film as 1.0 to 2.5 times the Re550 of the retardation film, the retardation is increased. The gas barrier layer can effectively suppress expansion and contraction due to heat of the film. By suppressing the expansion and contraction due to the environmental temperature, the phase shift of the retardation film is also suppressed. In addition, since the retardation film is usually produced by stretching a resin film, the retardation film has a property of being easily torn in the stretching direction, but the present invention can also suppress such ease of tearing. These effects are more remarkable when the resin intermediate layer is further provided between the retardation film and the gas barrier film.

  Therefore, the gas barrier film of the combination of the gas barrier layer having the above specific thickness and the retardation film can be used as a retardation film having excellent gas barrier properties and reduced phase shift, and is not easily stretched by heat. It becomes. For example, in the case where there is a soldering process after the gas barrier film is attached to an object for producing an electronic device, the gas barrier film is exposed to a high temperature of 200 to 250 ° C. for several minutes. Even in such a case, the gas barrier film of the present invention can suppress expansion and contraction of the retardation film and phase shift.

  If the thickness of the gas barrier layer is less than 1.0 times Re550 of the retardation film, the gas barrier layer is too thin, and the gas barrier layer may be cracked due to expansion and contraction of the base material. On the other hand, if the film thickness of the gas barrier layer exceeds 2.5 times Re550 of the retardation film, the hard gas barrier layer is too thick, so that problems such as difficulty in making the gas barrier film difficult to roll easily occur. . The thickness of the gas barrier layer is preferably 1.5 to 2.5 times, more preferably 1.9 to 2.5 times Re550 of the retardation film. The thickness of the gas barrier layer can be measured by observing the cross section of the gas barrier film with a transmission electron microscope (TEM) at 5000 to 10,000 times. Further, since the retardation Re550 of the gas barrier film is not substantially different from the Re550 of the retardation film of the base material, the Re550 of the gas barrier film may be measured and regarded as the Re550 of the base material.

  Further, the gas barrier layer may be composed of two or more layers. In this case, the total film thickness of the two or more gas barrier layers is 1.0 to 2.5 times Re550 of the retardation film. Just do it. The gas barrier layer is more preferably composed of two layers. In this case, it is preferable to have a polysilazane film as the second gas barrier layer on the gas barrier layer formed by the plasma CVD method. The polysilazane film will be described later.

In the present invention, to exhibit gas barrier properties means that the gas barrier film as a whole exhibits a water vapor transmission rate of 0.01 g / m ² / day or less and an oxygen transmission rate of 0.01 ml / m ² / day / atm or less. Say. The water vapor transmission rate can be measured by a method described in JIS K 7126B or Japanese Patent Application Laid-Open No. 2004-333127 (g / m ² / day). Similarly, the oxygen permeability can be measured by the method described in JIS K 7126B (ml / m ² / day / atm). In order to have the above gas barrier properties, the gas barrier film is preferably formed so as to have a water vapor transmission coefficient of 1 × 10 ⁻¹⁴ g · cm / (cm ² · sec · Pa) or less. The water vapor transmission coefficient can be measured by the following method. A sample film is formed on a known support (for example, cellulose triacetate film; thickness: 100 μm), and two containers on the primary side and the secondary side separated by sandwiching the sample film are evacuated. Water vapor having a relative humidity of 92% RH is introduced to the primary side, and the amount of water vapor that has permeated the sample film and has emerged to the secondary side is measured at 250 ° C. using a vacuum gauge. This is measured over time, and a transmission curve is created by taking the secondary water vapor pressure (Pa) on the vertical axis and time (seconds) on the horizontal axis. The water vapor transmission coefficient (g · cm · cm ⁻² · sec ⁻¹ · Pa ⁻¹ ) is determined using the slope of the straight line portion of this permeation curve. Since the water vapor transmission coefficient of the support is known, the water vapor transmission coefficient can be calculated from this thickness and the thickness of the sample film formed on the support.

  In the present invention, the gas barrier layer is preferably a film obtained by the following plasma CVD method. That is, the gas barrier layer according to the present invention is a plasma chemical vapor deposition method in which a substrate is wound between a pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. A thin film layer formed on the substrate is preferred.

  Such a gas barrier layer preferably uses a source gas containing an organosilicon compound and an oxygen gas as a film forming gas, and contains carbon, silicon, and oxygen as constituent elements of the gas barrier layer. Further, in the carbon distribution curve showing the relationship between the distance from the surface of the gas barrier layer in the film thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atom ratio) The carbon atom ratio of the gas barrier layer is within the range of 8 to 20 at% as an average value of the entire layer, and the carbon distribution curve continuously changes with a concentration gradient in the layer. From the viewpoint of achieving both high gas barrier properties and flexibility. The average value of the entire carbon atom ratio layer can be obtained from data obtained by measurement of an XPS depth profile described later.

In addition, the gas barrier layer of the present invention preferably satisfies the following condition (A). The gas barrier layer contains carbon, silicon, and oxygen, and the distance from the surface of the layer in the thickness direction of the layer and the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms, and carbon atoms In the silicon distribution curve, oxygen distribution curve and carbon distribution curve showing the relationship between the ratio (silicon atom ratio), the oxygen atom ratio (oxygen atom ratio) and the carbon atom ratio (carbon atom ratio), respectively.
[Condition (A)]
(I) In a region where the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio are 90% or more of the film thickness of the layer, the following formula (1):
(Oxygen atom ratio)> (silicon atom ratio)> (carbon atom ratio) (1)
Or the following expression (2):
(Carbon atom ratio)> (silicon atom ratio)> (oxygen atom ratio) (2)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) It is preferable that the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 5 at% or more from the viewpoint of achieving both high gas barrier properties and flexibility.

  Hereinafter, the details of the gas barrier layer according to the present invention will be further described.

(Gas barrier layer-element extreme value)
The gas barrier layer according to the present invention contains carbon, silicon, and oxygen as constituent elements of the gas barrier layer, and the distance from the surface of the layer in the film thickness direction of the layer and the sum of silicon atoms, oxygen atoms, and carbon atoms In the carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the amount (carbon atom ratio), the carbon atom ratio of the gas barrier layer is in the range of 8 to 20 at% as an average value of the entire layer. More preferably, it is the range of 10-20 at%. By setting it within this range, it is possible to form a gas barrier layer that sufficiently satisfies gas barrier properties and flexibility.

  In addition, it is preferable that the carbon atom ratio continuously changes with a concentration gradient from the viewpoint of achieving both gas barrier properties and flexibility. In such a gas barrier layer, it is preferable that the carbon distribution curve in the layer has at least one extreme value. Furthermore, it is more preferable to have at least two extreme values, it is more preferable to have at least three extreme values, and it is particularly preferable to have at least four extreme values, but five or more extreme values may be included. Since the number of extreme values is also caused by the film thickness of the barrier layer, it cannot be specified unconditionally. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film is bent is insufficient. In the case of having at least two or three extreme values as described above, the gas barrier layer in the film thickness direction of the gas barrier layer at one extreme value and the extreme value adjacent to the extreme value included in the carbon distribution curve. The absolute value of the difference in distance from the surface is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present invention, the extreme value refers to the maximum value or the minimum value of the atomic ratio of each element.

(Definition of maximum and minimum values)
In the present invention, the maximum value is a point where the value of the atomic ratio of an element changes from increase to decrease when the distance from the surface of the gas barrier layer is changed, and is more than the value of the atomic ratio of the element at that point. This means that the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer is further changed in the range of 4 to 20 nm is reduced by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element should be reduced by 3 at% or more in any range.

  Furthermore, in the present invention, the minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the gas barrier layer is changed, and from the value of the atomic ratio of the element at that point This also means that the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer is further changed by 4 to 20 nm from this point increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range.

(Definition of substantially continuous)
In the present invention, the carbon distribution curve is preferably substantially continuous. In this specification, that the carbon distribution curve is substantially continuous means that it does not include a portion where the carbon atom ratio in the carbon distribution curve changes discontinuously. Specifically, from the etching rate and the etching time, In the relationship between the distance (x, unit: nm) from the surface of the layer in the film thickness direction of at least one of the gas barrier layers calculated and the carbon atom ratio (C, unit: at%), Formula (F1):
(DC / dx) ≦ 0.5 (F1)
This means that the condition represented by

(Relationship between maximum and minimum carbon atom ratio)
Further, in such a gas barrier layer, it is further preferable that (iii) the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 5 at% or more. In such a gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, and particularly preferably 7 at% or more. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient.

(Relationship between maximum and minimum oxygen atom ratio)
In the present invention, the oxygen distribution curve of the gas barrier layer preferably has at least one extreme value, more preferably has at least two extreme values, and further preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the film thickness of the gas barrier layer, and it cannot be defined unconditionally. In the case of having at least three extreme values, the difference in distance from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer at one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value. Are preferably 200 nm or less, more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, but considering the improvement effect of crack generation suppression / prevention when the gas barrier film is bent, the thermal expansion property, etc. The thickness is preferably 10 nm or more, and more preferably 30 nm or more.

  In the present invention, the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve of the gas barrier layer is preferably 3 at% or more, more preferably 5 at% or more, and further preferably 6 at% or more. Preferably, it is particularly preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient.

(Relationship between maximum and minimum silicon atom ratio)
In the present invention, the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve of the gas barrier layer is preferably less than 5 at%, more preferably less than 4 at%, and less than 3 at%. Particularly preferred. When the absolute value is less than 5 at%, the gas barrier property and mechanical strength of the obtained gas barrier film are sufficient.

(Ratio of the total amount of oxygen atoms + carbon atoms)
In the present invention, the distance from the surface of the layer in the film thickness direction of at least one of the gas barrier layers and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms In the oxygen-carbon total distribution curve (also referred to as oxygen-carbon distribution curve) which is (referred to as oxygen-carbon total atomic ratio), the absolute value of the difference between the maximum value and the minimum value of the oxygen-carbon total atomic ratio. Is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is sufficient.

(About XPS depth profile)
The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon total distribution curve in the film thickness direction of the gas barrier layer are measured by X-ray photoelectron spectroscopy (XPS) and a rare gas such as argon. By using together with ion sputtering, it can be created by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time is roughly correlated with the distance from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer in the film thickness direction. As the “distance from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer”, it is possible to adopt the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. it can. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  In addition, from the viewpoint of forming a gas barrier layer having a uniform and excellent gas barrier property over the entire film surface, the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer). Is preferred. In this specification, that the gas barrier layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the film surface of the gas barrier layer by XPS depth profile measurement. When an oxygen-carbon total distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum atomic ratio of carbon in each carbon distribution curve The absolute value of the difference between the value and the minimum value is the same as each other or within 5 at%.

  The gas barrier film of the present invention preferably includes at least one gas barrier layer that satisfies all of the above conditions (i) to (iii), but may include two or more layers that satisfy such conditions. Furthermore, when two or more such gas barrier layers are provided, the materials of the plurality of gas barrier layers may be the same or different. Further, when two or more such gas barrier layers are provided, such a gas barrier layer may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Moreover, as such a plurality of gas barrier layers, a gas barrier layer not necessarily having a gas barrier property may be included.

  In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atom ratio, the oxygen atom ratio, and the carbon atom ratio are expressed by the formula (1) in a region where 90% or more of the film thickness of the layer. When the conditions to be satisfied are satisfied, the silicon atomic ratio in the gas barrier layer is preferably in the range of 25 to 45 at%, and more preferably in the range of 30 to 40 at%. The oxygen atomic ratio in the gas barrier layer is preferably in the range of 33 to 67 at%, more preferably in the range of 45 to 67 at%. Furthermore, the carbon atom ratio in the gas barrier layer is preferably in the range of 3 to 33 at%, and more preferably in the range of 3 to 25 at%.

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, the silicon atom ratio, the oxygen atom ratio, and the carbon atom ratio are expressed by the formula (2) in a region where 90% or more of the film thickness of the layer. When the conditions to be satisfied are satisfied, the silicon atomic ratio in the gas barrier layer is preferably in the range of 25 to 45 at%, and more preferably in the range of 30 to 40 at%. The oxygen atomic ratio in the gas barrier layer is preferably in the range of 1 to 33 at%, and more preferably in the range of 10 to 27 at%. Furthermore, the carbon atom ratio in the gas barrier layer is preferably in the range of 33 to 66 at%, and more preferably in the range of 40 to 57 at%.

  Here, the term “at least 90% or more of the film thickness of the gas barrier layer” does not need to be continuous in the gas barrier layer.

(Gas barrier layer thickness)
The thickness of the gas barrier layer is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 1000 nm, and particularly preferably in the range of 100 to 500 nm. When the thickness of the gas barrier layer is within the above range, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are excellent, and no deterioration of the gas barrier properties due to bending is observed.

(Second gas barrier layer)
The gas barrier film of the present invention may be composed of two or more gas barrier layers. In this case, in addition to the gas barrier layer formed by plasma CVD, at least a second gas barrier layer can be provided thereon. The second gas barrier layer is not limited to this, but a polysilazane film formed by coating is preferable. That is, a coating film of a coating-type polysilazane-containing liquid is provided on the gas barrier layer formed by plasma CVD, and is formed by irradiating vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less and performing a modification treatment. It is preferable to have two gas barrier layers. By providing the second gas barrier layer on the gas barrier layer provided by the CVD method, minute defects remaining in the gas barrier layer can be filled with the gas barrier component of polysilazane from above, and further gas barrier property and flexibility Can be improved. There may be a plurality of the gas barrier layers and polysilazane films formed by the above-mentioned CVD, but each layer is preferably composed of two layers from the viewpoint of simplicity of the manufacturing process and cost.

(Polysilazane)
“Polysilazane” that can be used for the second gas barrier layer is a polymer having a silicon-nitrogen bond in the structure and is a polymer that is a precursor of silicon oxynitride, and those having the following structure are preferably used.

In the formula, each of R ¹ , R ² , and R ³ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or carbon. An aryl group having 6 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms is represented.

In the present invention, perhydropolysilazane in which all of R ¹ , R ^2, and R ³ are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the resulting gas barrier layer.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. Examples of commercially available polysilazane solutions include AQUAMICA (registered trademark) NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials.

(Other layers)
The gas barrier film of the present invention may have a layer in addition to the gas barrier layer and the resin intermediate layer. For example, the surface of the substrate opposite to the resin intermediate layer may have a pressure-sensitive adhesive layer and other layers for the production of display elements and the like.

<Method for producing gas barrier film>
Next, the manufacturing method of the gas barrier film of the present invention will be described separately for each element manufacturing method.

(Manufacturing method of substrate)
As the base material of the gas barrier film of the present invention, the above retardation film is used. The retardation film is usually obtained by forming the above resin composition to produce a long unstretched film, and subjecting the obtained unstretched film to a stretching treatment. Here, the term “long” means that the film has a length of at least 5 times the width, preferably 10 times or more, specifically a roll. It has a length enough to be wound up into a shape and stored or transported. Such a long film can be obtained by continuously performing the production process in the length direction on the production line. For this reason, when manufacturing a phase difference film, it is possible to carry out a part or all of each process simply and efficiently in-line.

  For example, a casting method or the like may be used as a method for producing a film before stretching, but melt extrusion is preferred from the viewpoint of production efficiency and from the viewpoint that volatile components such as a solvent do not remain in the film. The melt extrusion molding can be performed by, for example, a T-die method.

  The thickness of the film before stretching is preferably 10 μm or more, more preferably 50 μm or more, preferably 800 μm or less, more preferably 200 μm or less. By setting it to the lower limit value or more of the above range, sufficient retardation and mechanical strength can be obtained, and by setting it to the upper limit value or less, flexibility and handling properties can be improved.

  Examples of the stretching operation include a method of uniaxial stretching in the longitudinal direction using a difference in peripheral speed between rolls (longitudinal uniaxial stretching); a method of uniaxial stretching in the width direction using a tenter (lateral uniaxial stretching); A method of performing longitudinal uniaxial stretching and lateral uniaxial stretching in order (sequential biaxial stretching); a method of stretching in an oblique direction with respect to the longitudinal direction of the film before stretching (oblique stretching); In particular, when oblique stretching is employed, a long retardation film having a slow axis in an oblique direction is usually obtained, so there is little waste when cutting out a rectangular product from a long retardation film, and a large area is obtained. It is preferable because a retardation film can be produced efficiently. Here, “oblique direction” means a direction that is neither parallel nor orthogonal.

  As a specific example of the oblique stretching method, a stretching method using a tenter stretching machine can be exemplified. As such a tenter stretching machine, for example, on the left and right of the pre-stretched film (that is, the left and right of the film width direction when the pre-stretched film transported horizontally is observed from the MD direction), Examples include a tenter stretching machine that can add a take-up force. In addition, for example, a tenter that can achieve oblique stretching by adding a feed force, pulling force, or pulling force at equal speeds in the left and right directions in the TD direction or the MD direction to make the trajectory non-linear with the same distance to move left and right. A stretching machine is also mentioned. In addition, for example, a tenter stretching machine that can achieve stretching in an oblique direction by setting the moving distance to be different on the left and right.

  When extending | stretching in the diagonal direction, it is preferable to extend | stretch in the direction from which the angle which a extending | stretching direction makes with respect to the elongate direction of the film before extending | stretching becomes 40 to 50 degree. Thereby, the retardation film which has an orientation angle in the range of 40 degrees or more and 50 degrees or less with respect to the elongate direction is obtained. Here, the “orientation angle” is an angle formed by the MD direction of the long retardation film and the in-plane slow axis of the retardation film.

  When the retardation film is used as a rectangular film piece, it preferably has a slow axis in the range of 40 ° to 50 ° with respect to the side direction of the rectangle. In such a case, if the orientation angle is in the range of 40 ° or more and 50 ° or less with respect to the longitudinal direction, when a rectangular product is cut out from the long retardation film, it is parallel to the longitudinal direction or Since it is sufficient to cut out a rectangular film piece having sides in an orthogonal direction, the production efficiency is good and the area can be easily increased.

  The film temperature at the time of stretching is preferably (Tg-3) ° C. or higher, more preferably (Tg-1) ° C. or higher, where the glass transition temperature of the resin composition of the present invention is Tg. Moreover, it is preferable that it is (Tg + 3) degrees C or less, and it is more preferable that it is (Tg + 2) degrees C or less.

  The draw ratio is preferably 1.1 to 6 times, more preferably 1.2 to 5.5 times, and particularly preferably 1.5 to 4.0 times. In addition, the frequency | count of extending | stretching may be 1 time and may be 2 times or more.

  Furthermore, when manufacturing the retardation film of this invention, you may perform processes other than the above-mentioned. For example, a preheated film may be preheated before being stretched. Furthermore, if necessary, another film such as a masking film may be bonded to the retardation film in order to protect the retardation film and improve the handleability.

(Method for producing resin intermediate layer)
The resin intermediate layer can be formed by applying a coating solution in which a resin is dissolved or dispersed in a solvent on a substrate. When the resin further contains a fine metal oxide, it can be mixed with the coating solution by the following method. As a density | concentration of resin, 10-70 mass% is preferable in a coating liquid, More preferably, it is 30-50 mass%.

  The solvent is not particularly limited, and ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and butyl acetate, aromatic compounds such as toluene and xylene, diethyl ether, tetrahydrofuran and the like And ethers such as methanol, ethanol, isopropanol and the like. Dissolve resins such as aromatic solvents such as toluene and xylene, chlorine solvents such as dichloromethane and carbon tetrachloride, hydrocarbon solvents such as n-hexane and cyclohexane, ketone solvents such as cyclohexanone and methyl isobutyl ketone, A solvent that swells is used.

  Any appropriate method can be adopted as a coating method. Specific examples include a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a cast film forming method, a bar coating method, and a gravure printing method.

(Method of mixing fine metal oxide and resin)
The fine particle metal oxide used in the present invention is mixed with the resin by a known technique. Usually, the resin is used as a solution, and the fine metal oxide is mixed into the solution while stirring with a stirrer. The dispersant and other additives that may be added at the time of stirring are added and stirred before or after the addition of the metal oxide fine particles as necessary. In the case where the resin has a high viscosity or is in a solid state, a solvent may be appropriately added. If the dispersion is not easy, the metal oxide fine particles, the resin and the solvent are added and mixed uniformly using a high shear mixer such as a Henschel mixer or a super mixer.

  The concentration of the particulate metal oxide in the coating solution varies depending on the film thickness of the resin intermediate layer and the pot life of the coating solution, but is 20% by mass or more and 80% by mass or less based on the mass of the particulate metal oxide and the resin. . Preferably, it is 30 mass% or more and 70 mass% or less.

(Method for producing gas barrier layer)
The gas barrier layer according to the present invention is preferably a layer formed by plasma enhanced chemical vapor deposition. In the present invention, as a method for producing a gas barrier film, a substrate which is a retardation film having a retardation Re550 of 110 to 150 nm in the in-plane direction with respect to light having a wavelength of 550 nm is wound between a pair of film forming rollers to form a film. There is also provided a manufacturing method including a step of forming a gas barrier layer having a film thickness of 1.0 to 2.5 times that of Re550 on the retardation film by performing plasma discharge while supplying a gas. The gas barrier layer is a layer formed by such a plasma chemical vapor deposition method. Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma chemical vapor deposition method preferably contains an organosilicon compound and oxygen, and the content of oxygen in the film forming gas is the same as that in the film forming gas. It is preferable that the amount of oxygen be less than or equal to the theoretical oxygen amount required for complete oxidation of the entire amount of the organosilicon compound. In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

  Next, a method for producing the gas barrier film of the present invention will be described. The gas barrier film of the present invention can be produced by forming the gas barrier layer on the stress absorbing layer surface of the resin substrate. As a method for forming such a gas barrier layer according to the present invention on the surface of the resin base material, from the viewpoint of gas barrier properties, a plasma chemical vapor deposition method (plasma CVD method) is adopted. The plasma chemical vapor deposition method may be a Penning discharge plasma type plasma chemical vapor deposition method.

  In order to form a layer in which the carbon atomic ratio has a concentration gradient and continuously changes in the layer, as in the gas barrier layer according to the present invention, when plasma is generated in the plasma chemical vapor deposition method, The plasma discharge is preferably generated in the space between the plurality of film forming rollers. In the present invention, a pair of film forming rollers is used, and the resin base material is wound around each of the pair of film forming rollers, It is preferable to generate a plasma by discharging between a pair of film forming rollers. Thus, by using a pair of film forming rollers, winding the resin base material on the pair of film forming rollers, and performing plasma discharge between the pair of film forming rollers, the resin base material and the film forming roller By changing the distance between the gas barrier layer, it is possible to form a gas barrier layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer.

  It is also possible to form a film on the surface part of the resin substrate that exists on the other film forming roller while forming a film on the surface part of the resin substrate that exists on one film formation roller. In addition to producing a thin film efficiently, the film formation rate can be doubled compared to the plasma CVD method without using a normal roller, and a film having substantially the same structure can be formed. It becomes possible to at least double the extreme value, and it is possible to efficiently form a layer that satisfies all of the above conditions (i) to (iii).

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

  Moreover, it is preferable that the gas barrier film which concerns on this invention forms the said gas barrier layer on the surface of the said base material by a roll-to-roll system from a viewpoint of productivity. Further, an apparatus that can be used when producing a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film formation rollers and a plasma power source, and the pair of film formations. It is preferable that the apparatus has a configuration capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible.

  Hereinafter, the method for forming a gas barrier layer according to the present invention will be described in more detail with reference to FIG. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the gas barrier layer according to the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  1 includes a feed roller 32, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form the gas barrier layer 3 on the surface of the base material 2 by the CVD method, and the gas barrier layer component is formed on the surface of the base material 2 on the film forming roller 39. Further, the gas barrier layer component can be deposited on the surface of the base material 2 on the film forming roller 40 while being deposited, so that the gas barrier layer can be efficiently formed on the surface of the base material 2.

  Inside the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the gas barrier layer 3 as a vapor deposition film can be efficiently formed.

  As the film forming roller 39 and the film forming roller 40, known rollers can be appropriately used. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 39 and 40 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  In such a manufacturing apparatus 31, the base material 2 is arrange | positioned on a pair of film-forming roller (The film-forming roller 39 and the film-forming roller 40) so that the surface of the base material 2 may respectively oppose. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, the gas barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 39 by the plasma CVD method, and the gas barrier layer component is further deposited on the film forming roller 40. Therefore, the gas barrier layer can be efficiently formed on the surface of the substrate 2.

  As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. The winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 in which the gas barrier layer 3 is formed on the substrate 2, and a known roller may be used as appropriate. it can.

  Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used.

  The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

  Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, as such a plasma generating power source 42, it becomes possible to perform plasma CVD more efficiently, so that the applied power can be set to 100 W to 10 kW, and the AC frequency is set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the gas barrier layer 3 is previously formed can be used. As described above, the gas barrier layer 3 can be made thicker by using the substrate 2 in which the gas barrier layer 3 is previously formed.

  Using such a manufacturing apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport of the film (base material) The gas barrier layer according to the present invention can be produced by appropriately adjusting the speed. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. As a result, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer 3 is formed on the surface of the base material 2 on the film-forming roller 39 and the surface of the base material 2 on the film-forming roller 40 by plasma CVD. Formed by law. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field. For this reason, when the base material 2 passes through the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 1, the maximum value of the carbon distribution curve is formed in the gas barrier layer. On the other hand, when the substrate 2 passes through the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. It is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the gas barrier layer (the difference between the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (base material transport speed). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. Then, the gas barrier layer 3 is formed.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas may be used alone or in combination of two or more. The source gas in the film-forming gas used for forming the gas barrier layer 3 can be appropriately selected and used according to the material of the gas barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of properties such as the handleability of the compound and the gas barrier properties of the resulting gas barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, appropriate source gases are selected according to the type of the gas barrier layer 3.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not excessively increasing the ratio of the reaction gas, the formed gas barrier layer 3 is excellent in that excellent barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reactive gas are used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the raw material gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen system When the thin film is produced, a reaction represented by the following reaction formula 1 occurs by the film forming gas, and silicon dioxide is generated.

  In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form a gas barrier layer that satisfies all the above conditions (i) to (iii). Therefore, in the present invention, when the gas barrier layer is formed, the oxygen amount is set to a stoichiometric ratio of 12 with respect to 1 mol of hexamethyldisiloxane so that the reaction of the above reaction formula 1 does not proceed completely. It is preferable to make it less than a mole. In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane). Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer, and the above conditions (i) to (iii) It is possible to form a gas barrier layer satisfying all of the above), and to exhibit excellent gas barrier properties and bending resistance in the obtained gas barrier film. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The electric power to be applied to the power source can be adjusted as appropriate according to the type of the raw material gas, the pressure in the vacuum chamber, etc. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

  Although the conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of raw material gas, the pressure in the vacuum chamber, and the like, it is preferably in the range of 0.25 to 100 m / min. More preferably, it is in the range of 5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a gas barrier layer, without impairing productivity.

  As described above, as a more preferable aspect of the present embodiment, the gas barrier layer according to the present invention is formed by plasma CVD using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is characterized by doing. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce a gas barrier layer having both the barrier performance and the barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

(Second gas barrier layer)
The second gas barrier layer can be formed by applying a coating liquid containing polysilazane on the gas barrier layer formed by the CVD method and drying it, followed by irradiation with vacuum ultraviolet rays.

  As the organic solvent for preparing the coating solution, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. For example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, ethers such as alicyclic ethers can be used, specifically, There are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.

  The concentration of polysilazane in the coating liquid containing polysilazane varies depending on the thickness of the second gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.

  In order to promote the modification to silicon oxynitride, the coating solution is coated with a metal catalyst such as an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, or an Rh compound such as Rh acetylacetonate. It can also be added. In the present invention, it is particularly preferable to use an amine catalyst. Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.

  The amount of these catalysts added to the polysilazane is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.2 to 5% by mass, and 0.5 to More preferably, it is in the range of 2% by mass. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

  Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane. Specific examples include a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a cast film forming method, a bar coating method, and a gravure printing method.

(Excimer processing)
In the second gas barrier layer according to the present invention, at least a part of the polysilazane is modified into silicon oxynitride in the step of irradiating the layer containing polysilazane with vacuum ultraviolet rays. Here, an estimation mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation process to obtain a specific composition of SiOxNy will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. In the case of SiOxNy, x = 0 and y = 1. In order to satisfy x> 0, an external oxygen source is required. This is because (i) oxygen and moisture contained in the polysilazane coating solution, and (ii) oxygen taken into the coating film from the atmosphere during the coating and drying process. As an outgas from the substrate side due to oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process, (iv) heat applied in the vacuum ultraviolet irradiation process, etc. Oxygen and moisture moving into the coating film, (v) When the vacuum ultraviolet irradiation process is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, Oxygen, moisture, etc. taken into the coating film become oxygen sources.

  On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.

  Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

  The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below.

(1) Dehydrogenation and associated Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, it is cured as a SiNy composition without being oxidized. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(2) Formation of Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated as outgas from the base material by the heat of irradiation is considered to be the main moisture source. When the moisture is excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO2.1 to 2.3 is obtained.

(3) Direct oxidation by singlet oxygen, formation of Si-O-Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet rays, singlet oxygen having a very strong oxidizing power is formed. H or N in the perhydropolysilazane is replaced with O to form a Si—O—Si bond and harden. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

(4) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation / excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved, and oxygen, It is considered that when an oxygen source such as ozone or water is present, it is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

  Adjustment of the composition of the silicon oxynitride of the layer subjected to vacuum ultraviolet irradiation on the layer containing polysilazane can be performed by appropriately controlling the oxidation state by appropriately combining the above oxidation mechanisms (1) to (4). .

In vacuum ultraviolet irradiation step in the present invention, it is preferable that the illuminance of the vacuum ultraviolet rays in the coating film surface for receiving the polysilazane coating film is in the range of 30~200mW / cm ^2, in the range of 50~160mW / cm ² It is more preferable. When it is 30 mW / cm ² or more, there is no concern that the reforming efficiency is lowered, and when it is 200 mW / cm ² or less, the coating film is not ablated and the substrate is not damaged.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in the range of 500~5000mJ / cm ^2. 200 mJ / cm ² or more, the performed modification sufficiently, cracking and not excessive modification is 10000 mJ / cm ² or less, there is no thermal deformation of the substrate.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a gas space that is generated in a gas space by applying a high frequency high voltage of several tens of kHz to the electrode by placing a gas space between both electrodes via a dielectric such as transparent quartz. It is a discharge called a thin micro discharge. When the micro discharge streamer reaches the tube wall (derivative), electric charges accumulate on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and disappeared. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall is accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as those of dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so that the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to discharge in the entire discharge space. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. The outer diameter of the tube of the thin tube lamp is about 6 nm to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time. Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration during vacuum ultraviolet irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 to 4500 ppm.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to a following example.

  First, a method for evaluating the obtained gas barrier film will be described.

1. Measurement of pencil hardness The pencil hardness of the base material, the underlayer and the gas barrier layer was measured by the JIS K5600-5-4 method (1999 version). The results are shown in Table 2.

2. Evaluation of adhesion Cross-cut adhesion is evaluated according to the description of 5.6 of the JIS K 5600 (2004 edition) by using a cutter knife from one side of the laminate with a 1 mm square that penetrates the gas barrier layer and reaches the substrate. Apply 100 grid cuts with 1mm interval cutter guide, and paste cellophane adhesive tape (Nichiban Co., Ltd. “CT405AP-18”; 18mm width) on the cut surface and rub it completely with an eraser. After the tape was attached, it was peeled off in the vertical direction, and the amount of the gas barrier layer remaining on the substrate surface was visually confirmed.

  The number of peels in 100 pieces was examined and evaluated according to the following criteria.

◎: The number of peels in the cross cut test is 5 or less ○: The number of peels in the cross cut test is 10 or less Δ: The number of peels in the cross cut test is 11 to 20 ×: The number of peels in the cross cut test In addition, 21 or more pieces were subjected to the cross-cut evaluation after being exposed to an oven at 200 ° C. for 15 minutes for heat resistance evaluation. The results are shown in Table 2.

3. Measurement of retardation The retardation was measured by a parallel Nicol rotation method using a birefringence meter KOBRA-WR manufactured by Oji Scientific Instruments.
In addition, as an evaluation of heat resistance, the retardation was evaluated after exposure to 200 ° C. for 15 minutes in an oven. The results are shown in Table 2.

(Examples 1-13 and Comparative Examples 1-8)
(1) Base material In Examples 1-13 and Comparative Examples 1-8, what was described in following Table 1 with the film produced with the following method was used as a base material, respectively.

<Polystyrene>
(Manufacture of unstretched film)
74 parts of amorphous polystyrene (manufactured by PS Japan, trade name “HF77”, glass transition temperature 78 ° C.) and poly (2,6-dimethyl-1,4-phenylene oxide) (Aldrich catalog No. 18242-7) 26 parts and 1 part of an antioxidant were kneaded with a twin screw extruder to produce transparent resin composition pellets. The glass transition temperature was 113 ° C. The resin composition pellets were melted by a single screw extruder, supplied to an extrusion die, and extruded to obtain an unstretched film having a thickness of 150 μm.

(Manufacture of stretched film)
Next, the unstretched film was stretched obliquely with a tenter stretching machine so that the slow axis was in a direction inclined by 45 ° with respect to the MD direction. The temperature during stretching was 115 ° C., which is 2 ° C. higher than the glass transition temperature of the resin composition, and the stretching ratio was 3.6 times. As a result, a long retardation film A having a thickness of 60 μm was obtained. When the orientation of the obtained retardation film was confirmed, the slow axis was inclined 45 ° with respect to the MD direction. This retardation film had a Re550 of 140 nm and was a λ / 4 plate.

<Cellulose ester>
A cellulose ester film (trade name “KA”, manufactured by Kaneka Corporation) was obliquely stretched to obtain a long retardation film B having a thickness of 100 μm. When the orientation of the obtained retardation film was confirmed, the slow axis was inclined 45 ° with respect to the MD direction. This retardation film had a Re550 of 140 nm and was a λ / 4 plate.

<Polycarbonate>
(Melting extrusion)
An optical grade polycarbonate resin (trade name AD-5503, Tg; 145 ° C., viscosity average molecular weight M; 15,200), which is a homopolymer of bisphenol A, manufactured by Teijin Chemicals Ltd. is dehumidified by Matsui Manufacturing Co., Ltd. The pellets were dried at 120 ° C. for 4 hours using a hot air dryer. The extruder used was a single screw. The dried resin pellets were put into a heating hopper of a melt extruder heated to 110 ° C. The extruder cylinder temperature was 270 ° C., and a leaf disk filter made of SUS non-woven fabric with an average opening of 10 μm was used between the extruder and the T-die. The molten resin immediately after discharge was extruded onto the rotating cooling roll surface with a T-die set at 260 ° C. The extrusion die had a lip width of 1,800 mm and a lip opening of 1 mm. The die lip was flat with no irregularities on its lower surface. The cooling roll has a configuration of three, a diameter of 360 mmφ, a roll surface length of 1,900 mm, and a structure in which the coolant is circulated and controlled so that the surface temperature of the roll is uniform.

  The air gap between the die lip tip and the cooling roll surface is 15 mm, the first cooling roll temperature is 130 ° C., the second cooling roll temperature is 125 ° C., the third cooling roll temperature is 120 ° C., and the peripheral speed of the first cooling roll is When R1, the peripheral speed of the second cooling roll is R2, and the peripheral speed of the third cooling roll is R3, R1 = 8 m / min, the ratio R2 / R1 is 1.005, and the ratio R3 / R2 is 1. .000. The first cooling roll, the second cooling roll, the third cooling roll and the film were sequentially circumscribed, and the film was wound up via a take-off roll. Regarding the thickness in the width direction of the film, it is adjusted in a mountain shape so that the center of the film is thick, and then both ends of the film are edge-cut by 100 mm to obtain a film having a width of 1,500 mm and a thickness of about 74 μm. The masking film and 1,000 m were co-wound to obtain a wound layer of an unstretched film.

(Stretching)
Next, this film wound layer is set in a feeding machine of a longitudinal stretching machine that stretches between zone lengths of 7 m and between nip rolls in a drying furnace, and is passed through a longitudinal stretching machine while peeling off the masking film. The film was longitudinally stretched 1.07 times at 150 ° C., a polyethylene masking film having a thickness of 30 μm was attached, edge-cut and wound to obtain a roll-shaped stretched film. This film was a λ / 4 plate having a retardation of 140 nm.

(2) Production of resin intermediate layer In Comparative Example 2, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 (acrylate-based ultraviolet curable resin, fine particle metal oxide, manufactured by JSR Corporation) on one side of the substrate Material: silicon dioxide), and after drying with a wire bar so that the film thickness after drying is 4 μm, drying conditions; after drying at 80 ° C. for 3 minutes, in an air atmosphere, using a high-pressure mercury lamp, curing conditions; Curing was performed at 1.0 J / cm ² to form a resin intermediate layer. Moreover, in Examples 1-4, 7-13, and Comparative Examples 3-5, 7-8, except having changed resin into the material of Table 1, the resin intermediate | middle layer was produced by the same method.

(3) Gas barrier layer (lower layer) production apparatus:
In Examples 1-5, 7-12, and Comparative Examples 3-6, 7-8, the substrate was mounted on a plasma CVD apparatus, and the substrate described in Table 1 under the following film forming conditions (plasma CVD conditions) A gas barrier layer (lower layer) having a thickness shown in Table 1 was formed on the base layer.

<Film forming conditions>
Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.8 m / min.

  The film thickness shown in Table 1 was controlled by adjusting the supply amount of the source gas.

(4) Second gas barrier layer (upper layer) PHPS
In Examples 4, 6, and 11 to 13, the second gas barrier layer (upper layer) was formed as follows.

(Polysilazane layer coating solution)
A 10 mass% dibutyl ether solution of perhydropolysilazane (Aquamica (registered trademark) NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a polysilazane layer coating solution.

(Formation of polysilazane layer)
The polysilazane layer coating solution is applied with a wireless bar so that the (average) film thickness after drying is 300 nm, dried by treatment for 1 minute in an atmosphere at a temperature of 85 ° C. and a humidity of 55% RH, A polysilazane layer was formed by holding for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) to perform dehumidification.

(Formation of gas barrier layer: Silica conversion treatment of polysilazane layer by ultraviolet light)
Next, the following ultraviolet device was installed in the vacuum chamber for the polysilazane layer formed above, and the pressure in the device was adjusted to carry out a silica conversion treatment.

(UV irradiation device)
Apparatus: M.com Co., Ltd. excimer irradiation apparatus MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
(Reforming treatment conditions)
The base material on which the polysilazane layer fixed on the operation stage was formed was modified under the following conditions to form a gas barrier layer.
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds.

(Comparative Example 9)
(Preparation of brightness enhancement film having one cholesteric resin layer)
(1-1: Preparation of transparent resin substrate having alignment film)
Both surfaces of a film made of an alicyclic olefin polymer (manufactured by ZEON Corporation; trade name “ZEONOR (registered trademark) film ZF14-100”) were subjected to corona discharge treatment. An aqueous solution of 5% modified polyamide (FR105 / CM4000 70/30 mixture, FR105: methoxymethylated nylon manufactured by Lead City Co., Ltd. CM4000: copolymerized polyamide manufactured by Toray Industries, Inc.) is coated with # 2 wire bar on one side of the film. It was used and applied, and the coating film was dried to form an alignment film having a thickness of 0.1 μm. Next, the alignment film was rubbed to prepare a transparent resin substrate having the alignment film.

(1-2: Formation of first cholesteric resin layer)
A cholesteric liquid crystal composition (the following general formula A1) was applied to the surface of the transparent resin substrate having the alignment film prepared above having the alignment film using a # 10 wire bar. The coating film is subjected to an orientation treatment at 100 ° C. for 5 minutes, and the coating film is subjected to a process of irradiation with weak ultraviolet rays of 0.1 to 45 mJ / cm ² followed by a heating treatment at 100 ° C. for 1 minute. After repeating twice, 800 mJ / cm ² ultraviolet rays were irradiated in a nitrogen atmosphere to obtain a first cholesteric resin layer having a dry film thickness of 5 μm.

(1-3: Formation of gas barrier layer, preparation of circularly polarized light separating sheet)
In a solvent comprising pure water / isopropyl alcohol = 90/10 (weight ratio), PVA (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA226, polymerization degree 2600, saponification degree 88%), and silane coupling agent (manufactured by Shin-Etsu Chemical; KBM603 (N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, molecular weight 222) and KBE903 (1-aminopropyl triethoxysilane, molecular weight 221) 1; 1 mixture) 80/20 (weight) The gas barrier layer material composition having a viscosity of 27 to 30 cp (23 ° C.) was obtained.

  On the cholesteric resin layer prepared in (1-2) above, the gas barrier layer material composition is applied using a # 4 wire bar, dried and cured at 110 ° C. for 2 to 3 minutes, and dried film thickness A gas barrier layer of 0.1 μm ± 0.05 μm was obtained, and a laminate (1-a) having a base layer, an alignment film, a first cholesteric resin layer, and a gas barrier layer in this order was obtained, and this was a circularly polarized light separating sheet As used below.

(1-4: Preparation of retardation film)
A monomer composition composed of 97.8% by weight of methyl methacrylate and 2.2% by weight of methyl acrylate was polymerized by a bulk polymerization method to obtain resin pellets.

  Rubber particles were produced according to Example 3 of JP-B-55-27576. The rubber particles have a spherical three-layer structure, the core inner layer is a cross-linked polymer of methyl methacrylate and a small amount of allyl methacrylate, and the inner layer is composed of butyl acrylate and styrene as main components and a small amount of acrylic acid. It is a soft elastic copolymer obtained by crosslinking and copolymerizing allyl, and the outer layer is a hard polymer of methyl methacrylate and a small amount of ethyl acrylate. The average particle size of the inner layer was 0.19 μm, and the particle size including the outer layer was 0.22 μm.

  70 parts by weight of the resin pellets and 30 parts by weight of the rubber particles were mixed and melt kneaded with a twin screw extruder to obtain a methacrylic acid ester polymer composition A (glass transition temperature 105 ° C.).

  By coextruding the methacrylic ester polymer composition A (b layer) and the styrene maleic anhydride copolymer (glass transition temperature 130 ° C.) (a layer) at a temperature of 280 ° C., a b layer / a layer A multilayer film having an average thickness of 45/70/45 (μm) with a three-layer structure of / b layers was obtained. The laminated film is stretched obliquely at a stretching temperature of 134 ° C. and a stretching ratio of 1.8 times so that the slow axis is in a direction inclined by 45 degrees with respect to the MD direction by a tenter stretching machine. Got.

  The retardation in the front direction of the optically anisotropic layer was 140 nm, and the retardation in the thickness direction was −85 nm (each numerical value is a measured value after stretching). Further, one side of the optically anisotropic layer was subjected to corona discharge treatment so that the wetting index was 56 dyne / cm. This optically anisotropic layer was used as a retardation film in the following.

(1-5: Production of brightness enhancement film)
The circularly polarized light separating sheet (laminate 1-a) obtained in (1-3) and the retardation film obtained in (1-4) are so adhesive that the gas barrier layer and the retardation film face each other. The laminate (1-b) was obtained by laminating with (Daido Chemicals; acrylic adhesive, E-5301). The same alicyclic ring as that used in (1-1) is further bonded to the retardation film surface of this laminate (1-b) via an adhesive (manufactured by Daido Kasei; acrylic adhesive, E-5301). A film made of the formula olefin polymer was attached. Thereby, the first base material layer, the first alignment film, the first cholesteric resin layer, the first gas barrier layer, the adhesive layer, the retardation film, the adhesive layer, and the second base material layer are laminated in this order. An eight-layer brightness enhancement film was obtained. In Comparative Example 9, the thickness of the gas barrier layer with respect to Re550 of the retardation film was 0.71 times.

1 gas barrier film,
2 base material,
3 gas barrier layer,
31 manufacturing equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 Take-up roller.

Claims (10)

A substrate whose retardation Re550 in the in-plane direction with respect to light having a wavelength of 550 nm is a retardation film having a thickness of 110 to 150 nm;
On the retardation film, a gas barrier layer having a thickness of 1.0 to 2.5 times that of Re550,
Gas barrier film having The gas barrier film according to claim 1, wherein the retardation film is a cellulose ester film. The gas barrier film according to claim 1 or 2 , further comprising an intermediate resin layer having an in-plane retardation Re550 of 0 to 20 nm with respect to light having a wavelength of 550 nm between the retardation film and the gas barrier layer. The gas barrier film according to claim 3, wherein the intermediate resin layer contains a resin and oxide metal fine particles. The gas barrier film according to claim 3 or 4 , wherein the retardation film has a pencil hardness of HB to H, the intermediate resin layer has a pencil hardness of H to 3H, and the gas barrier layer has a pencil hardness of 4H to 6H. 6. The gas barrier film according to claim 1, wherein the retardation film is long and an orientation angle is in a range of 40 ° to 50 ° with respect to the long direction. The gas barrier film according to any one of claims 1 to 6 , wherein the gas barrier layer comprises at least two layers, and one of the at least two layers is a polysilazane film. By performing a plasma discharge while supplying a film formation gas by winding a base material that is a retardation film having a retardation Re550 of 110 to 150 nm in the in-plane direction with respect to light having a wavelength of 550 nm between a pair of film formation rollers, Forming a gas barrier layer having a thickness of 1.0 to 2.5 times Re550 of the retardation film on the retardation film;
Having a method for producing a gas barrier film according to any one of claims 1-7. Before the step of forming the gas barrier layer,
The orientation angle is 40 ° or more and 50 ° or less with respect to the longitudinal direction by stretching the long resin film in the direction in which the stretching direction is 40 ° or more and 50 ° or less with respect to the longitudinal direction. The manufacturing method of Claim 8 which further has the process of forming the said retardation film which is the range of these. The gas barrier layer is composed of at least two layers, and one of the at least two layers is a polysilazane film;
Before the step of forming the gas barrier layer, a step of forming the intermediate resin layer by applying a coating liquid containing a resin on the substrate;
Forming a first gas barrier layer on the intermediate resin layer by plasma vapor deposition;
A step of forming a second gas barrier layer on the first gas barrier layer by applying a coating liquid containing polysilazane on the first gas barrier layer and drying, followed by irradiation with vacuum ultraviolet rays;
In the step of forming the first gas barrier layer and the step of forming the second gas barrier layer, the first gas barrier layer and the second gas barrier layer include the first gas barrier layer and The total film thickness of the second gas barrier layer is formed to be 1.0 to 2.5 times the Re550 of the retardation film,
The manufacturing method of the gas-barrier film of Claim 9.